CN105671319A - Mixed electroplating sludge treatment method - Google Patents
Mixed electroplating sludge treatment method Download PDFInfo
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- CN105671319A CN105671319A CN201610178426.5A CN201610178426A CN105671319A CN 105671319 A CN105671319 A CN 105671319A CN 201610178426 A CN201610178426 A CN 201610178426A CN 105671319 A CN105671319 A CN 105671319A
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- leachate
- electroplating sludge
- chromium
- filtering residue
- processing method
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a mixed electroplating sludge treatment method, and belongs to the technical field of waste treatment and utilization. The problem that in an existing mixed electroplating sludge treatment method, iron and chromium cannot be effectively separated can be solved. The mixed electroplating sludge treatment method comprises the steps that mixed electroplating sludge and mixed liquor are mixed, and the mixed liquor is composed of sodium containing neutral water and returning liquor generated in the previous treatment process; acid substances are added, if no sulfate radical exists in a system, substances containing the sulfate radical are added, and sodium jarosite sediment starts to be generated; alkali substances are slowly added to conduct neutralization till no sodium jarosite is generated, and leaching pulp is obtained; the leaching pulp is filtered to obtain filter liquor and filter residues, and the filter liquor is leachate; clean water is added in the filter residues to be stirred, then acid substances are added, filter liquor and filter residues are obtained through filtration, and the filter liquor is returning liquor; and chromium is extracted from the leachate. The method is used for treating the mixed electroplating sludge containing chromium and iron, especially for treating the high-chromium mixed electroplating sludge, and the method is furthermore used for treating the high-chromium mixed electroplating sludge with the low copper, nickel and zinc content.
Description
Technical field
The invention belongs to refuse process and utilize technical field, be specifically related to a kind of mixing electroplating sludge processing method.
Background technology
The waste water produced in electroplating process can become electroplating sludge after treatment, multiple different electroplating wastewaters the mud processing generation together is mixing electroplating sludge. Containing many useful metallic elements such as chromium, ferrum, copper, zinc, nickel in mixing electroplating sludge, its content is even up to rich ore level, therefore mixing electroplating sludge has the double attribute of contaminative and resource-type, therefore mix the innoxious of electroplating sludge and recycling is an important problem.
A kind of existing mixing electroplating sludge processing method is to make pollution metal phase inversion toxicity reduction by the curing technology such as burning method, ferrite process, fills afterwards. But this method is only temporarily avoid or reduce environmental pollution, pollutes metal and substantially yet suffer from, and the metals resources in mixing electroplating sludge cannot be utilized, cause a large amount of waste.
Additionally also having now the technology being reclaimed the metals such as mixing Copper in Electroplating Sludge, nickel, zinc by methods such as leachings, its response rate also can reach more than 90%. But chromium all can not be realized efficient recovery by existing method, and chromium is pollute the most serious element in mixing electroplating sludge, and Ye Shi China extremely lacks the precious metal resource of (China's chromium degree of self-sufficiency only 0.1%).
Why it is difficult to the recovery of chromium, being because substantially all can iron content in mixing electroplating sludge, and high ferro, ferrous iron, chromic chemical behavior are quite similar, the methods such as existing extraction, precipitation are all difficult to efficiently separate the two, also can cause the precipitation of a small amount of copper, nickel, zinc on the contrary, reduce the response rate of these metals. Although now with bibliographical informations such as phosphoric acid precipitates method, oxalate precipitation method, freeze crystallizations, but these methods also all can not realize effective ferrochrome in real industrial treatment process and separate.
Summary of the invention
The present invention is directed to the problem that existing mixing electroplating sludge processing method can not realize ferrum, chromium efficiently separates, it is provided that one can realize siderochrome and be kept completely separate, thus realizing the mixing electroplating sludge processing method that chromium 100% is recycled.
Solve the technical scheme one mixing electroplating sludge processing method that the technology of the present invention problem adopts, containing chromium and ferrum in described mixing electroplating sludge, the treating method comprises following steps:
Step (1), comprising:
Step (11), mix mixing electroplating sludge with mixed liquor, and wherein, mixed liquor is made up of the rework solution containing the middle generation of following step (2) in sodium neutral water and last time processing procedure;
Step (12), adding acidic materials to pH value is 1～1.5, if sulfate radical-free in system, adds the material of containing sulfate radicals, starts to produce sodium jarosite precipitation;
Step (13), is slowly added to alkaline matter and is neutralized, and to no longer having sodium jarosite to generate, must leach slurry;
Step (2), comprising:
Step (21), filters leaching and starches to obtain filtrate and filtering residue, and filtrate is leachate;
Step (22), adding acidic materials after adding clear water stirring to the filtering residue of step (21) gained is 1～1.5 to pH value, filters to get filtrate and filtering residue, and filtrate is rework solution;
Step (3), extracts chromium from leachate.
Preferably, in described step (11), the mass ratio of mixing electroplating sludge and mixed liquor is 1: 1～1.5.
Preferably, described step is additionally added ripe slurry in (11), described ripe slurry is the leaching slurry of step (13) gained in processing procedure last time, and the quality of described ripe slurry accounts for the 1/4～1/3 of the gross mass of the mixture of mixing electroplating sludge, mixed liquor, ripe slurry.
Preferably, the acidic materials added in described step (12) are sulphuric acid; The acidic materials added in described step (22) are sulphuric acid.
Preferably, between described step (11) and step (12), and between step (12) and step (13), all include: be slowly added to hydrogen peroxide to solution ferrous ions content less than 0.1g/L.
Preferably, the alkaline matter added in described step (13) is sodium carbonate and/or sodium bicarbonate.
Preferably, gained filtering residue is also rinsed in (21) by described step, and gained rinsing liquid adds in leachate; Gained filtering residue is also rinsed in (22) by described step, and gained rinsing liquid adds in rework solution.
Preferably, after described step (22), also including: step (23), adding calcic alkaline matter to pH value after adding clear water stirring to the filtering residue of step (22) gained is 7～8, obtaining filtrate and filtering residue after filtration, filtering residue includes semi-hydrated gypsum.
It may further be preferable that the calcic alkaline matter added in described step (23) is calcium oxide.
Preferably, described mixing electroplating sludge goes back cupric; The step extracting copper from leachate is also included between described step (2) and step (3).
It may further be preferable that the described step extracting copper from leachate for extract copper by extraction process from leachate.
Preferably, also nickeliferous and zinc in described mixing electroplating sludge; The step extracting nickel and zinc from leachate is also included between described step (2) and step (3).
It may further be preferable that the described step extracting nickel and zinc from leachate includes: be slowly added to sodium sulfide in leachate to pH value not higher than the pH value of gained leachate in step (13), make nickel and zinc precipitation; Filtering to get filtrate and filtering residue, filtrate is leachate, and filtering residue is nickel zinc vulcanizing mine concentrate.
Preferably, described step (3) specifically includes: step (31), and adding alkaline matter to leachate is 7～8 to pH value, makes chromium precipitate;Step (32), filters to get filtrate and filtering residue, and filtering residue includes chromic oxide gel.
It may further be preferable that the alkaline matter added in described step (31) is sodium hydroxide; In described step (32), the filtrate of gained is containing sodium neutral water.
Ferrum and chromium can be efficiently separated by the mixing electroplating sludge processing method of the present invention, realize the efficient recovery of to chromium 100%, thus ensureing that its copper, nickel, zinc etc. extract in product without chromium, the recovery utilization rate of these elements being all promoted to 100%, improving resource utilization; And, the emission of this processing method is not high-risk material, and simply general refuse, pollutes little; Additionally, the precipitation that uses in this processing method, leaching, the technique such as filtration are all adapted for the conventional process of industrialized production, the raw materials such as used sulphuric acid, hydrogen peroxide, sodium carbonate, Calx, liquid caustic soda, sodium sulfide are also all the conventional materials of low cost, and also have a lot of intermediate products to can be used in other steps, therefore its materials are economized, cost is low, it is simple to actual industrial applications.
As can be seen here, the mixing electroplating sludge processing method of the present invention can realize the recycling of to multiple resources such as chromium, copper, nickel, zinc 100%, and resource utilization is high, and pollutes little, and the feature of environmental protection is good, and materials are economized, and cost is low, is suitable to industrialized production.
The mixing electroplating sludge processing method of the present invention is for processing the mixing electroplating sludge containing chromium and ferrum, it is particularly suited for processing high chromium mixing electroplating sludge, is more further suitable to process the high chromium mixing electroplating sludge that the copper being representative with region, Wuxi, nickel, Zn content are relatively low.
Detailed description of the invention
For making those skilled in the art be more fully understood that technical scheme, below in conjunction with detailed description of the invention, the present invention is described in further detail.
Embodiments of the invention provide one mixing electroplating sludge processing method.
The mixing electroplating sludge processing method of the present invention is for processing at least mixing electroplating sludge containing chromium and ferrum, it is particularly suited for processing high chromium mixing electroplating sludge, is more further suitable to process the high chromium mixing electroplating sludge that the copper being representative with region, Wuxi, nickel, Zn content are relatively low. This processing method can realize chromium, being kept completely separate of ferrum in mixing electroplating sludge, thus the various metals such as chromium, ferrum, copper, nickel, zinc can all be realized the recycling close to 100%, makes full use of resource, and makes products therefrom innoxious, does not produce to pollute.
S1, this step are that sodium jarosite leaches, for being separated by ferrum; It specifically includes following steps:
S101, being mixed with mixed liquor by mixing electroplating sludge, wherein, mixed liquor is formed by containing the rework solution of generation in following steps S2 in sodium neutral water and last time processing procedure; Preferably, mixing electroplating sludge is 1: 1～1.5 with the mass ratio of mixed liquor.
That is, the rework solution containing chromium produced in step S2 in last time processing procedure is mixed with the neutral water containing sodium, obtain mixed liquor, then mixing electroplating sludge is mixed according to mud liquor ratio (mass ratio) stirring of 1: 1～1.5 with mixed liquor, obtain the mixture of similar suspension. Wherein, the all rework solutions produced in processing last time all should add in mixed liquor, and containing sodium neutral water can adopt in following steps produce containing sodium neutral water, may be used without individually configuration containing sodium neutral water (such as aqueous sodium persulfate solution), the Na ion concentration condition generated due to sodium jarosite readily satisfies, therefore its concrete consumption does not limit, as long as ensureing that the mass ratio of mixing electroplating sludge and mixed liquor is 1: 1～1.5, and in mixed liquor, the amount of sodium can make whole ferrum all be changed into sodium jarosite to precipitate.
Preferably, being additionally added ripe slurry in this step, ripe slurry is the leaching slurry that in processing procedure last time, step S1 obtains, and its quality accounts for the 1/4～1/3 of the gross mass of raw material (namely mixing the mixture of electroplating sludge, mixed liquor, ripe slurry).
That is, the product that this step in last time processing procedure is obtained leaches slurry, it is not fully enter subsequent step to process, but staying a part to add in this secondary raw material carrying out processing as ripe slurry, this ripe slurry quality accounts for the 1/4 to 1/3 of this raw material (namely mixing the mixture of electroplating sludge, mixed liquor, ripe slurry) gross mass. The advantage using ripe slurry is in that: on the one hand containing sodium jarosite crystal in ripe slurry, as the nucleus generating sodium jarosite, can accelerate response speed; Meanwhile, the processing procedure of this step can produce nature and heat up, therefore gained leachate is high temperature, and its part is returned the initial temperature that can improve raw material in this step, save the energy, speed up processing.
S102, optional, it is slowly added to hydrogen peroxide to solution ferrous ions content less than 0.1g/L.
Owing to mixing electroplating sludge being likely to containing a large amount of ferrous, therefore need in system, to add hydrogen peroxide (i.e. hydrogen peroxide) as strong oxidizer, the ferrous ion in solution to be converted into ferric ion (because ferric ion could generate sodium jarosite precipitation).
Certainly, as long as ensureing not affect processing procedure, it is also possible to other strong oxidizers replace hydrogen peroxide (such as hydrogen peroxide).
Certainly, if this is just without ferrous iron in mixing electroplating sludge, then this step can not also be carried out.
S103, addition acidic materials to pH value are 1～1.5, if sulfate radical-free in system, add the material of containing sulfate radicals, start to produce sodium jarosite precipitation; Preferably, acidic materials are sulphuric acid.
It is to say, with the pH value of sulphuric acid (such as concentrated sulphuric acid) regulation system to 1～1.5, start to produce sodium jarosite crystal.
Wherein, sulphuric acid can simultaneously work as the effect of sulfate radical needed for regulating pH value and introducing sodium jarosite, therefore is preferred.
S104, optional, it is slowly added to hydrogen peroxide to system ferrous ions content less than 0.1g/L.
Add after sulphuric acid in step S103, it is possible to make more ferrous iron in mixing electroplating sludge be dissolved out and become ion, therefore if it is required, can again be oxidized as ferric ion with hydrogen peroxide (i.e. hydrogen peroxide).
Certainly, as long as ensureing not affect processing procedure, it is also possible to other strong oxidizers replace hydrogen peroxide (such as hydrogen peroxide).
Certainly, if not dissolving more ferrous ion after adding sulphuric acid, then this step also can not be carried out.
S105, it is slowly added to alkaline matter and is neutralized, to no longer having sodium jarosite to generate, slurry must be leached; Preferably, alkaline matter is sodium carbonate and/or sodium bicarbonate.
It is acid process owing to generating the process of sodium jarosite, therefore needs to be continuously added sodium carbonate (or sodium bicarbonate) and be neutralized, to ensure that ferrum continues to precipitate with sodium jarosite form. In this step, the ferrum of more than 90% can precipitate with the formation of sodium jarosite, poised state can be reached when the content of ferrum drops to very low, for ensureing that ferrum precipitates completely, continuously adding alkaline matter makes remaining ferrum precipitate (its amount is little certainly) completely with forms such as bloodstone, goethitum, ferric subsulfates, but it is corresponding, also having a small amount of chromium to precipitate with the form of co-precipitation, the rework solution (containing each) therefore produced in following S2 step needs to return in this step and continues with.
Wherein, the cost of sodium carbonate (or sodium bicarbonate) is low, neutralising capacity strong, also can supplement the sodium in system, therefore be preferred.
The product of this step gained is for leaching slurry, and its part is retained as in next production the ripe slurry used, and remains leaching slurry then entrance following steps and continues with. System heats up naturally in this step, the total iron content leached in slurry when General reactions terminates can be down to below 0.1g/L (so low content can be considered and is kept completely separate), pH value is between 1.8～2.8, temperature is then at 85～95 DEG C, and record now leaches the pH value of slurry in order to follow-up use.
Iron content leached mud is easily separated, processes by S2, this step, and produces rework solution; It specifically includes following steps:
Filtrate and filtering residue are starched to obtain in S201, filtration leaching, and filtrate is leachate.
It is to say, the leaching slurry that step S1 is obtained is filtered, separate filtering residue (i.e. leached mud) and filtrate (i.e. leachate). Wherein, filtering residue is mainly sodium jarosite, continues with in this step; Leachate then not iron content, but containing chromium, copper, nickel, zinc etc., continue with in subsequent step.
Preferably, also filtering residue being rinsed in this step, gained rinsing liquid adds leachate.
On filtering residue, inevitably contamination has the leachate containing chromium, therefore it is carried out rinsing to colourless by available clear water (such as tap water or neutral water), and is added in leachate by rinsing liquid and be uniformly processed.
S202, to step S201 gained filtering residue add clear water stirring, afterwards add acidic materials be 1～1.5 to pH value, filter to get filtrate and filtering residue, filtrate is rework solution; Wherein, acidic materials are preferably sulphuric acid.
It is to say, filtering residue is processed with sulphuric acid (such as concentrated sulphuric acid), after again filtering, the filtering residue of gained enters subsequent step, and filtrate is then as rework solution, in the mixed liquor of the step S1 processed next time. As it was previously stated, for ensureing that complete deironing is likely to have part chromium to be also deposited in filtering residue (i.e. leached mud) in step S1, owing to chromium is high malicious pollutant, as long as therefore deposit filtering residue and just cannot be utilized, and only as high-risk refuse. Therefore, chromium a small amount of in filtering residue acid adding thoroughly to be dissolved by this step again, for ensureing the dissolving of chromium, it is likely to have part ferrum also again to be dissolved, therefore its gained filtrate (rework solution) to return in step S1 and again to process, so the filtering residue after this step process is no longer containing chromium, it is achieved thereby that being completely separated of ferrum and chromium.
Wherein, the sulfate radical that sulphuric acid brings can be used for generating in step sl sodium jarosite, therefore is preferred.
Preferably, also gained filtering residue being rinsed in this step, gained rinsing liquid adds rework solution.
On filtering residue, inevitably contamination has filtrate, therefore it is carried out rinsing to colourless by available clear water (such as tap water), and rinsing liquid adds rework solution is unified is used for step S1.
S203, preferred, in the filtering residue of step S202 gained, add clear water stirring, adding calcic alkaline matter afterwards is 7～8 to pH value, after filtration filtrate and filtering residue, filtering residue includes semi-hydrated gypsum; Preferably, calcic alkaline matter is calcium oxide.
The stirring it is to say, sodium jarosite filtering residue is added water, and adjust pH value to neutral or alkalescence with Calx (calcium oxide), Calx acts the effect neutralizing remaining sulphuric acid, makes the acid-base value of slag meet the national standard of Ordinary solid waste discharge; Owing to it is mainly composed of semi-hydrated gypsum, therefore the raw material of cement can be made. Certainly, because being typically necessary ferrum in cement, therefore the ferrum in sodium jarosite (bloodstone, goethitum, ferric subsulfate etc.) does not affect it as cement raw material use;Sodium in sodium jarosite content in sodium jarosite molecule is very low, just lower in leached mud, cleans free sodium (sodium sulfate) with clear water, and remaining sodium would not exceed the sodium content industry standard that leached mud allows as cement raw material use.
Preferably, also gained filtering residue being rinsed in this step, gained rinsing liquid and filtrate are together as containing sodium neutral water.
On filtering residue, inevitably contamination has filtrate, therefore it is suitably rinsed by available clear water (such as tap water), and the filtrate in rinsing liquid and this step is used in other steps together as containing sodium neutral water.
S3, preferred, if mixing electroplating sludge goes back cupric, then from leachate, extract copper; It concretely extracts copper by extraction process from leachate.
Separated the leachate not iron content obtained by step S201, containing only chromium, copper, zinc, nickel etc., therefore by copper extractants such as M5640, copper therein can be extracted, obtain metallic copper product again through back extraction, electrodeposition etc. afterwards, it is achieved the copper of 100% reclaims. Owing to the extraction of copper is conventional hydrometallurgical technology, therefore it is not described in detail at this.
Certainly, if not cupric in mixing electroplating sludge, then this step can not also be carried out. Or, it is possible to from leachate, copper is extracted by other means (as replaced with zinc).
S4, preferred, if also nickeliferous and zinc in mixing electroplating sludge, then extraction nickel and zinc from leachate; It concretely vulcanizes heavy nickel zinc, and the heavy nickel zinc of sulfuration comprises the steps that
S401, in leachate, it is slowly added to sodium sulfide to pH value not higher than the pH value of gained leachate in step S1, makes nickel and zinc precipitation.
It is to say, be slowly added to sodium sulfide in the leachate (i.e. liquid more than extraction copper) carry copper through extraction, make nickel, zinc with the form Precipitation of nickel sulfide, zinc sulfide. Wherein, preferential and nickel ion, zinc ion chemical combination after being hydrolyzed in dilute acid soln due to sodium sulfide, as long as addition is slowly suitable, stirring fully, can avoid sulphion to overflow with the form of hydrogen sulfide and cause pH value to raise substantially. When adding excessive sodium sulfide after reacting completely (because we cannot directly judge whether reaction is complete), owing to the sulphion in sodium sulfide can be hydrolyzed, then pH value necessarily rises, and (even pH value begins to ramp up, then representing and react completely, whole nickel, zinc are all precipitated). Now, as long as ensureing the final pH value of the leachate initial pH value (should at being front recorded) not higher than the leachate produced in step S1; Because the necessarily ionic state of the chromium in leachate under this pH value, as long as therefore ensure that pH value final in this step is lower than it, so that it may avoid the precipitation of chromium, it is ensured that without chromium in gained precipitate. Certainly, according to principles above, the pH value starting leachate before treatment (more than extraction copper liquid) lower than the initial pH value of the leachate produced in above step S1, so must could provide sufficient pH value excursion for sulfide precipitation; If the pH value of leachate (more than extraction copper liquid) is beyond above original ph, then recall to sulphuric acid.
Wherein, use the method for the heavy nickel zinc of sulfuration maximally effective can realize separating of nickel zinc and chromium when low nickel zinc at high chromium, and the sodium in sodium sulfide can increase the sodium ion amount in leachate, it is simple to it is as containing sodium neutral water, and therefore the mode with sodium sulfide extraction nickel zinc is preferred.
S402, filtering to get filtrate and filtering residue, filtrate is leachate, and filtering residue is nickel zinc vulcanizing mine concentrate.
The product of above step S401 is filtered, filtrate is only leachate containing chromium (i.e. liquid after heavy nickel zinc), and filtering residue is with nickel sulfide, zinc sulfide for main component, conventional smelting process can be used for as nickel zinc vulcanizing mine concentrate and carry nickel zinc, thus realizing the nickel zinc recovering of 100%.
Preferably, also gained filtering residue being rinsed in this step, rinsing liquid adds leachate.
On filtering residue, inevitably contamination has the filtrate in this step, therefore it is carried out rinsing to colourless by available clear water (such as tap water), and rinsing liquid adds unified subsequent treatment in leachate.
Certainly, if not nickeliferous zinc in mixing electroplating sludge, then this step can not also be carried out; Or, it is also possible to additive method extracts nickel zinc; But when extracting copper and also to extract nickel zinc, then this step must carry out after extracting the step of copper, in order to avoid sulphion makes copper precipitate.
Certainly, if possibly together with other metallic element in mixing electroplating sludge, then, after also can separating realizing ferrochrome, by other known method, these elements are carried out extracting and developing, be not described in detail at this.
S5, from leachate extract chromium; It specifically comprises the steps that
S501, to add alkaline matter be 7～8 to leachate to pH value, makes chromium precipitate; Preferably, alkaline matter is sodium hydroxide.
That is, the alkaline matters such as liquid caustic soda (i.e. sodium hydroxide) can be added in the leachate remove copper, nickel, zinc, make leachate reach neutrality or alkalescence, make chromium (i.e. trivalent chromium) precipitate with the form of chromium sulfate basic and the mixture of chromic oxide gel.
Wherein, sodium hydroxide can provide sodium in solution, and the sulphuric acid used in each step before also allows for the generation of chromium sulfate basic. Therefore be preferred.
S502, filtering to get filtrate and filtering residue, filtering residue includes chromic oxide gel.
It is to say, the product of step S501 is filtered again, filtering residue is the mixture of chromium sulfate basic and chromic oxide gel, can be used for the industry such as process hides, printing and dyeing, reclaims thus realizing the 100% of chromium; And filtrate can be used in other steps of this method as containing sodium neutral water. For excess containing sodium neutral water, it is also only containing the conventional ion such as sodium, sulfate radical, and pollutes metal without chromium, copper, nickel, zinc etc., therefore has reached common industrial wastewater discharge standard, can be delivered directly to sewage treatment plant.
Ferrum and chromium can be efficiently separated by the mixing electroplating sludge processing method of the present invention, realize 100% efficient recovery to chromium, thus ensureing that its copper, nickel, zinc etc. extract in product without chromium, the recovery utilization rate of these elements being all promoted to 100%, improving resource utilization; And, the emission of this processing method is not high-risk material, and simply general refuse, pollutes little; Additionally, the precipitation that uses in this processing method, leaching, the technique such as filtration are all adapted for the conventional process of industrialized production, the raw materials such as used sulphuric acid, hydrogen peroxide, sodium carbonate, Calx, liquid caustic soda, sodium sulfide are also all the conventional materials of low cost, and also have a lot of intermediate products to can be used in other steps, therefore its materials are economized, cost is low, it is simple to actual industrial applications.
As can be seen here, the mixing electroplating sludge processing method of the present invention can realize the recycling of to multiple resources such as chromium, copper, nickel, zinc 100%, and resource utilization is high, and pollutes little, and the feature of environmental protection is good, and materials are economized, and cost is low, is suitable to industrialized production.
Adopting different design parameters that mixing electroplating sludge is processed, it is concrete such as following example.
Embodiment 1:
Being mixed according to the mass ratio of 1: 1 with mixed liquor by the high chromium mixing electroplating sludge that Wuxi Yong Da sewage treatment plant produces, mixed liquor is made up of the rework solution produced in processing containing sodium neutral water and last time; Leachate (the i.e. ripe slurry) stirring that in being processed with last time by mixture, this step produces again mixes, and ripe slurry accounts for the 1/3 of whole raw material (namely mixing electroplating sludge, mixed liquor, ripe slurry) gross mass. Then being slowly dropped into hydrogen peroxide, to solution, ferrous iron concentration is 0.08g/L. Being slow added into concentrated sulphuric acid to pH value is 1, and the sodium jarosite crystal beginning with yellow produces. Slowly adding hydrogen peroxide, to solution, ferrous iron concentration is 0.08g/L. Process is continuously added sodium carbonate be neutralized, to no longer having sodium jarosite to generate, slurry must be leached. Now leach total iron content in slurry solution and be down to 0.02g/L, pH most 2.5, leach slurry and warm naturally to 95 DEG C.
This shows, by this step, substantially can all be precipitated by ferrum (now chromium is in the solution), it is achieved ferrochrome is kept completely separate.
Filtering and leach slurry, filtrate is leachate, and the rinsing of filtering residue clear water is to colourless, and rinsing liquid adds in leachate (i.e. filtrate) together. Filtering residue adding clear water stirring afterwards, adjusts pH value to 1.5 with concentrated sulphuric acid, again filter, the rinsing of filtering residue clear water is to colourless, and filtrate and rinsing liquid are as the rework solution used in process next time. Filtering residue adds water stirring again, adjusts pH value to 8 with Calx, and third time filters, and filtering residue, through toxicity detection pass the test, is used for producing cement as semi-hydrated gypsum, and filtrate is then incorporated to containing sodium neutral water.
To chromium in filtering residue (leached mud is mainly composed of semi-hydrated gypsum) now, copper, nickel, zinc element content detect, result is as follows:
Table 1, leached mud detection of content of element result
| Chromium (mg/kg) | Copper (mg/kg) | Nickel (mg/kg) | Zinc (mg/kg) |
| 119 | 88.4 | 92.4 | 163 |
As can be seen here, in first time isolated leached mud, the constituent content such as chromium, copper, nickel, zinc is extremely low, all below 2/10000ths, it is believed that without, therefore chromium, copper, nickel, zinc etc. are inevitable is all present in filtrate (leachate); And as it was previously stated, total iron content is at below 0.02g/L in leaching slurry solution (i.e. leachate), this shows that ferrum has nearly all been deposited in leached mud and has suffered, and ferrum, chromium are kept completely separate.
Filtering residue (leached mud is mainly composed of semi-hydrated gypsum) now is carried out toxicity characteristic leaching procedure, and result is as follows:
Table 2, leached mud toxicity leach testing result
Visible, after leached mud is leached, total chrome content is reduced to 4.08mg/L, pollutes the heaviest Cr VI and does not then detect, this show in leached mud this with regard to the chromium of denier be also substantially at can not the state of dissolution, further reduce its contaminative.
With M5640, leachate (namely above first time filters the filtrate of gained) is extracted, back extraction afterwards, electrodeposition, produce metallic copper.
Add sodium sulfide to the leachate (i.e. liquid more than extraction copper) through extracting to precipitate completely to nickel zinc, and ensure the endpoint pH pH value 2.5 not higher than initial leachate before. Filtering, the rinsing of filtering residue clear water is to colourless, and it is nickel zinc vulcanizing mine concentrate, and smelting process extracts nickel zinc routinely, and rinsing liquid then enters next step together with filtrate (i.e. leachate).
Leachate (i.e. liquid after heavy nickel zinc) adjusts pH value to 8 with liquid caustic soda, makes chromium (i.e. trivalent chromium) formula precipitate, and filtered filtration residue is the mixture of chromium sulfate basic and chromic oxide gel, for process hides and printing and dyeing; Filtrate is incorporated to step before returning containing sodium neutral water and uses, and the unnecessary detection containing sodium neutral water is up to standard, is directly discharged to sewage treatment plant as commonly industrial wastewater.
Finally, above (mixing containing sodium neutral water repeatedly obtained) containing sodium neutral water being detected, its testing result is as follows:
Table 3, testing result containing sodium neutral water
Visible, the content containing pollution elements various in sodium neutral water produced in the present embodiment is lower, complies fully with the standard of ordinary industrial sewage.
Wherein, above each testing result has examining report by Jiangsu new master's environmental monitoring company limited.
As can be seen here, the processing method of the present invention can realize being kept completely separate of ferrum and chromium in mixing electroplating sludge, and realize chromium, copper, nickel, zinc etc. 100% extraction, it is ensured that all abundant recyclings of useful resources; Meanwhile, all without chromium in other products except carrying chromium product, not resulting in pollution, the feature of environmental protection is fine.
Embodiment 2:
The mixing electroplating sludge of the Gao Ge produced at wastewater treatment center, Treatment of Metal Surface sci-tech industrial park, Wuxi mixes according to the mass ratio of 1: 1.5 with mixed liquor, and mixed liquor is made up of the rework solution produced in processing containing sodium neutral water and last time; Leachate (the i.e. ripe slurry) stirring that in being processed with last time by mixture, this step produces again mixes, and ripe slurry accounts for the 1/4 of whole raw material (namely mixing electroplating sludge, mixed liquor, ripe slurry) gross mass. Then being slowly dropped into hydrogen peroxide, to solution, ferrous iron concentration is 0.1g/L. Being slowly added to concentrated sulphuric acid to pH value is 1.5, and the sodium jarosite crystal beginning with yellow produces. Slowly adding hydrogen peroxide, to solution, ferrous iron concentration is 0.1g/L. Process is continuously added sodium carbonate be neutralized, to no longer having sodium jarosite to generate, slurry must be leached. Now leach total iron content in the solution of slurry and be down to 0.05g/L, pH most 2.8, leach slurry and warm naturally to 85 DEG C.
This shows, by this step, substantially can all be precipitated by ferrum (now chromium is in the solution), it is achieved ferrochrome is kept completely separate.
Filtering and leach slurry, filtrate is leachate, and the rinsing of filtering residue clear water is to colourless, and rinsing liquid adds in leachate (i.e. filtrate) together. Filtering residue adding clear water stirring afterwards, adjusts pH value to 1 with concentrated sulphuric acid, again filter, the rinsing of filtering residue clear water is to colourless, and filtrate and rinsing liquid are as the rework solution used in process next time. Filtering residue adds water stirring again, adjusts pH value to 7 with Calx, and third time filters, and filtering residue detects pass the test through toxicity, is used for producing cement as semi-hydrated gypsum, and filtrate is then incorporated to containing sodium neutral water.
With M5640, leachate (namely above first time filters the filtrate of gained) is extracted, back extraction afterwards, electrodeposition, produce metallic copper.
Add sodium sulfide to the leachate (i.e. liquid more than extraction copper) through extracting to precipitate completely to nickel zinc, and ensure the endpoint pH pH value 2.8 not higher than initial leachate before. Filtering, the rinsing of filtering residue clear water is to colourless, and it is nickel zinc vulcanizing mine concentrate, and smelting process extracts nickel zinc routinely, and rinsing liquid then enters next step together with filtrate (leachate).
Leachate (after heavy nickel zinc liquid) adjusts pH value to 7 with liquid caustic soda, makes chromium (i.e. trivalent chromium) precipitate, and filtered filtration residue is the mixture of chromium sulfate basic and chromic oxide gel, for process hides and printing and dyeing; Filtrate is incorporated to step before returning containing sodium neutral water and uses, and the unnecessary detection containing sodium neutral water is up to standard, is directly discharged to sewage treatment plant as commonly industrial wastewater.
Wherein, to the carrying out multielement detection in the leached mud (filtering residue being namely main component with semi-hydrated gypsum) produced in journey processed above, country's non-ferrous metal and electronic material Institute of Analysis having examining report, result is as follows:
Table 4, leached mud composition detection result
| SO3(w/%) | CaO (w/%) | SiO2(w/%) | Fe2O3(w/%) |
| 56.04 | 37.77 | 2.53 | 1.89 |
| Cr2O3(w/%) | Al2O3(w/%) | Na2O (w/%) | P2O5(w/%) |
| 0.34 | 0.30 | 0.28 | 0.22 |
| TiO2(w/%) | SnO2(w/%) | ZnO (w/%) | CuO (w/%) |
| 0.12 | 0.11 | 0.08 | 0.05 |
| Cl (w/%) | K2O (w/%) | NiO (w/%) | MgO (w/%) |
| 0.05 | 0.05 | 0.05 | 0.04 |
| I (w/%) | PbO (w/%) | Ag2O (w/%) | |
| 0.03 | 0.03 | 0.01 |
Wherein, SO3Being the representation of sulfate radical, its reality constitutes semi-hydrated gypsum together with CaO.
Visible, in leached mud, the content of chromium, copper, nickel, zinc etc. is extremely low, substantially can be considered without.
As can be seen here, the processing method of the present invention can realize being kept completely separate of ferrum and chromium in mixing electroplating sludge, and realize chromium, copper, nickel, zinc etc. 100% extraction, it is ensured that all abundant recyclings of useful resources; Meanwhile, all without chromium in other products except carrying chromium product, not resulting in pollution, the feature of environmental protection is fine.
It is understood that the principle that is intended to be merely illustrative of the present of embodiment of above and the illustrative embodiments that adopts, but the invention is not limited in this. For those skilled in the art, without departing from the spirit and substance in the present invention, it is possible to make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (15)
1. a mixing electroplating sludge processing method, containing chromium and ferrum in described mixing electroplating sludge, it is characterised in that the treating method comprises following steps:
Step (1), comprising:
Step (11), mix mixing electroplating sludge with mixed liquor, and wherein, mixed liquor is made up of the rework solution containing the middle generation of following step (2) in sodium neutral water and last time processing procedure;
Step (12), adding acidic materials to pH value is 1～1.5, if sulfate radical-free in system, adds the material of containing sulfate radicals, starts to produce sodium jarosite precipitation;
Step (13), is slowly added to alkaline matter and is neutralized, and to no longer having sodium jarosite to generate, must leach slurry;
Step (2), comprising:
Step (21), filters leaching and starches to obtain filtrate and filtering residue, and filtrate is leachate;
Step (22), adding acidic materials after adding clear water stirring to the filtering residue of step (21) gained is 1～1.5 to pH value, filters to get filtrate and filtering residue, and filtrate is rework solution;
Step (3), extracts chromium from leachate.
2. processing method according to claim 1, it is characterised in that
In described step (11), mixing electroplating sludge is 1: 1～1.5 with the mass ratio of mixed liquor.
3. processing method according to claim 1, it is characterised in that
Being additionally added ripe slurry in described step (11), described ripe slurry is the leaching slurry of step (13) gained in processing procedure last time, and the quality of described ripe slurry accounts for the 1/4～1/3 of the gross mass of the mixture of mixing electroplating sludge, mixed liquor, ripe slurry.
4. processing method according to claim 1, it is characterised in that
The acidic materials added in described step (12) are sulphuric acid;
The acidic materials added in described step (22) are sulphuric acid.
5. processing method according to claim 1, it is characterised in that
Between described step (11) and step (12), and between step (12) and step (13), all include: be slowly added to hydrogen peroxide to solution ferrous ions content less than 0.1g/L.
6. processing method according to claim 1, it is characterised in that
The alkaline matter added in described step (13) is sodium carbonate and/or sodium bicarbonate.
7. processing method according to claim 1, it is characterised in that
Gained filtering residue is also rinsed in (21) by described step, and gained rinsing liquid adds in leachate;
Gained filtering residue is also rinsed in (22) by described step, and gained rinsing liquid adds in rework solution.
8. processing method according to claim 1, it is characterised in that after described step (22), also include:
Step (23), adding calcic alkaline matter after adding clear water stirring to the filtering residue of step (22) gained is 7～8 to pH value, obtains filtrate and filtering residue after filtration, and filtering residue includes semi-hydrated gypsum.
9. processing method according to claim 8, it is characterised in that
The calcic alkaline matter added in described step (23) is calcium oxide.
10. processing method according to claim 1, it is characterised in that
Described mixing electroplating sludge goes back cupric;
The step extracting copper from leachate is also included between described step (2) and step (3).
11. processing method according to claim 10, it is characterised in that
The described step extracting copper from leachate for extract copper by extraction process from leachate.
12. processing method according to claim 1, it is characterised in that
Also nickeliferous and zinc in described mixing electroplating sludge;
The step extracting nickel and zinc from leachate is also included between described step (2) and step (3).
13. processing method according to claim 12, it is characterised in that the described step extracting nickel and zinc from leachate includes:
In leachate, it is slowly added to sodium sulfide to pH value not higher than the pH value of gained leachate in step (13), makes nickel and zinc precipitation;
Filtering to get filtrate and filtering residue, filtrate is leachate, and filtering residue is nickel zinc vulcanizing mine concentrate.
14. processing method according to claim 1, it is characterised in that described step (3) specifically includes:
Step (31), adding alkaline matter to leachate is 7～8 to pH value, makes chromium precipitate;
Step (32), filters to get filtrate and filtering residue, and filtering residue includes chromic oxide gel.
15. processing method according to claim 14, it is characterised in that
The alkaline matter added in described step (31) is sodium hydroxide;
In described step (32), the filtrate of gained is containing sodium neutral water.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114517261A (en) * | 2021-12-06 | 2022-05-20 | 生态环境部华南环境科学研究所 | Method and device for selectively extracting and recovering chromium element in electroplating sludge |
| CN115626773A (en) * | 2022-11-01 | 2023-01-20 | 盛隆资源再生（无锡）有限公司 | Comprehensive utilization method of calcium-iron-chromium-containing sludge |
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| CN115626773B (en) * | 2022-11-01 | 2024-02-06 | 盛隆资源再生（无锡）有限公司 | Comprehensive utilization method of sludge containing calcium, iron and chromium |
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