CN102660687A - Method for recycling heavy metal resources of stainless steel pickling waste water neutralization sludge - Google Patents
Method for recycling heavy metal resources of stainless steel pickling waste water neutralization sludge Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000010802 sludge Substances 0.000 title claims abstract description 36
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 35
- 239000010935 stainless steel Substances 0.000 title claims abstract description 35
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 29
- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- 238000006386 neutralization reaction Methods 0.000 title claims abstract description 12
- 238000004064 recycling Methods 0.000 title abstract 8
- 238000005554 pickling Methods 0.000 title abstract 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000011651 chromium Substances 0.000 claims abstract description 39
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 238000002386 leaching Methods 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 239000012492 regenerant Substances 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 238000005349 anion exchange Methods 0.000 claims abstract description 3
- 238000011084 recovery Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910000628 Ferrovanadium Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 230000029087 digestion Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000012267 brine Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 14
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract 1
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 238000009738 saturating Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 229910018487 Ni—Cr Inorganic materials 0.000 description 6
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000010801 sewage sludge Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- -1 metals ion Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses a method for recycling heavy metal resources of stainless steel pickling waste water neutralization sludge and belongs to the technical field of recycling of sludge after sewage treatment. The method comprises the following steps of: 1) performing acid pickling, namely extracting the stainless steel pickling waste water neutralization sludge by using sulfuric acid as extractant, and adding an additive to inhibit the leaching of ferrum; 2) oxidizing, namely adding oxidant into a leaching solution to oxidize Mn(II) into manganese dioxide; 3) performing ion exchange, allowing a solution obtained after oxidation to pass through an anion exchange column, enriching and recycling hexavalent chromium, adsorbing and saturating, regenerating by using regenerant, and recycling chromate from a regeneration solution; and 4) performing neutralization precipitation, namely recycling nickelous hydroxide from ion exchange effluent by a neutralization precipitation method. By the method, ferrum is inhibited at an acid pickling section, the acid pickling is performed while ferrum is removed, the multi-stage multi-step recycling of manganese, chromium, and nickel metal resources can be realized, the innocent treatment of sludge and recycling of heavy metal are realized, and the method has comprehensive benefit of economic benefit, environmental benefit and social benefit.
Description
Technical field
The surface treatment industry waste water that the present invention relates to stainless steel, Wire Rope Production and be correlated with is after neutralizing treatment; Manganese, nickel, chromium resource recovery method in the heavy metal sewage sludge that produces; More particularly, relate in a kind of stainless steel acid cleaning waste water and the sludge heavy-metal its recovery method as resource.
Background technology
The acid waste water that stainless steel produces in surface treatment process is generally handled through the neutralization precipitation method, and heavy metal sewage sludge such as nickeliferous in a large number, the chromium of generation, manganese belongs to the industrial hazard waste.Heavy metal exists with forms such as carbonate, precipitations of hydroxide in the mud, if not treated random stacking or simple landfill, heavy metal very easily leaches and is diffused in the physical environment, and soil and surface water are produced great effect, is detrimental to health.
At present, the treatment process of this type of stainless steel sludge mainly concentrates on the harmless treatment aspect, comprises stacking, landfill, burns, fills out sea etc., and these treatment processs are easy to cause secondary pollution because of dealing with improperly; Simultaneously, processing costs is expensive, and general enterprise is difficult to accept.In addition; Containing heavy metals such as a large amount of nickel, chromium, manganese in the acid-washing stainless steel mud, is a kind of potential renewable resource, if recycle effectively; Realize the resource utilization of mud; Not only solve problem of environmental pollution, can also obtain considerable economic, solve the problem of shortage of resources to a certain extent.Thereby metals resources harmless resource utilization treatment and disposal technology more and more becomes the focus of domestic and international concern in the heavy metal sewage sludge.
In recent years, many investigators have studied the innoxious and resource treatment technique of heavy metal in the acid-washing stainless steel mud.The Liu Fu of Nanjing University waits the people by force, and (publication number: CN101982433A) developed a kind of stainless steel sludge treatment and disposal integrated technology based on chemical method and ion exchange method, the heavy metal resources separating effect is obvious, and the recovery is high; But its weak point is: (1) is because the recovery value of iron is little, in this application case; Adopt hydrometallurgical technology to reclaim iron; Not only increased facility investment, and technical process is complicated, is difficult to effective linking; And positively charged ion nickel, chromium lose seriously in the iron removal, and resource recovery reduces; (2) in this application case, adopt IX to reclaim nickel, increased facility investment and running cost.
In addition; People such as the Song Min of Southeast China University (publication number: CN101618896A) studied the technology that a kind of extraction process reclaims nickel in the mud leach liquor, precipitator method recovery chromium; Loss is serious but there is in the iron removal nickel chromium triangle in this method, and extraction agent is carried loss secretly, produces secondary pollution problem.Chen Qisong (publication number: 101235439A) wait the people to disclose a kind of method that from stainless steel sludge, reclaims nickel salt, chromic salts; Zhou Caiyong (publication number: 101863516A) wait the people to disclose a kind of stainless steel sludge that utilizes and reclaim the method that contains the chromium Ni ferrite; All exist nickel, chromium recovery ratio low; Shortcomings such as metals resources is recovered as work in-process, and value of the product is low.
Summary of the invention
The technical problem that invention will solve
The objective of the invention is to overcome in the prior art complicated in the stainless steel acid cleaning waste water with sludge treatment technique; And nickel, the deficiency that chromium recovery ratio is low provide in a kind of stainless steel acid cleaning waste water and the sludge heavy-metal its recovery method as resource, and the present invention is according to heavy metal ion existence form characteristics in the mud; Suppress the leaching of iron; Emphasis reclaims valuable resources such as nickel, manganese, chromium, and flow process is compact, it is easy to control, and manganese, chromium, nickel valuable metal resource realize that multistage substep reclaims; Efficient is high, effective; The present invention has realized that the resource utilization of sewage sludge harmlessness disposing, process water qualified discharge and heavy metal reclaims, and has the comprehensive benefit of economic benefit, environmental benefit and social benefit, and popularizing application prospect is wide.
Technical scheme
For achieving the above object, technical scheme provided by the invention is:
With the sludge heavy-metal its recovery method as resource, the steps include: in a kind of stainless steel acid cleaning waste water of the present invention
1) acidleach: adopt sulfuric acid as digestion agent with mud in the stainless steel acid cleaning waste water, and through adding the leaching of additive inhibition iron, excess sludge is innoxious mud discharging after washing, this step can realize the leaching of manganese, nickel, chromium;
2) oxidation: in the leaching liquid that step 1) obtains, add oxygenant; Mn (II) is oxidized to Manganse Dioxide; Filtered filtration residue gets Manganse Dioxide after brine wash and drying, Cr in this step (III) is oxidized to Cr (VI) simultaneously, is convenient to IX and realizes that nickel chromium triangle separates;
3) IX: step 2) after the oxidation solution through anion-exchange column, the enriching and recovering sexavalent chrome, adsorb saturated after, the employing regenerator is regenerated, and from regenerated liquid, reclaims chromic salt;
4) neutralization precipitation: step 3) intermediate ion exchange effluent adopting neutralization precipitation method reclaims nickel hydroxide.
Preferably, the sulfuric acid that adopts 50-90% with mud in the stainless steel acid cleaning waste water of step 1) is as digestion agent, and the condition of controlling is that the pH value is 1.0-2.5, is warming up to 75-95 ℃ behind the leaching 10-80min.Adopt the sulfuric acid of 50-90% to help destroying the mud structure in this step, improve the metals ion leaching yield.
Preferably, adopting sodium sulfate earlier in the step 1) is additive, reacts required sodium salt so that ihleite to be provided; The mass ratio of dewatered sludge and sodium sulfate is 5-25:1; Add yellow sodium ferrovanadium crystal seed then, promote the siderotil crystalline to generate, the dosage of yellow sodium ferrovanadium crystal seed is 1-10g/L; Control pH value is 1.5-2.5, and the reaction times is 1.0-5.0 h; At last, add the pyrrhosiderite crystal seed, the dosage of this pyrrhosiderite crystal seed is 1-10g/L, and control pH value is 2.5-3.5, reaction times 1.0-5.0 h.
Preferably, step 2) adopts potassium permanganate as oxygenant in, and add oxidization time 1.0-5.0 h by the 100-130% of contained manganese, the theoretical oxidation aequum of chromium in the leaching liquid.
Preferably, adopt the resin anion(R.A) exchange column to separate in the step 3) and remove chromium, the exchange flow velocity is 1-5 BV/h; Treatment capacity is 10-30 BV/ batch; Regenerator is the NaOH of 0.2-2.0 mol/L, and regenerant flow rate is 1-5 BV/h, and regenerant consumption is 10-20 BV/ batch.
Preferably, adopt in the step 4) with the sodium hydroxide deposition and reclaim nickel, temperature is 20-80 ℃, improves the sedimentation that temperature helps nickel hydroxide, and the pH value is 9.0-13.0, reaction times 0.5-5 h.
Beneficial effect
The present invention takes into full account the metals ion recovery value, and iron is suppressed in the acidleach excess sludge, optionally leaches manganese, nickel, chromium; Simplify technical process, reduce facility investment, overcome the deficiency of technology in the past; It is effective that IX and neutralization precipitation reclaim nickel chromium triangle; Product purity is high, compares with existing known technology, has following unusual effect:
(1) in a kind of stainless steel acid cleaning waste water of the present invention with the sludge heavy-metal its recovery method as resource; Iron is suppressed at acidleach workshop section, the outstanding noble metal resources such as nickel, chromium that reclaim, the acidleach deironing is carried out in same reaction kettle; Improved organic efficiency; Simplified technical process, minimizing equipment and medicament investment, convenient operation and management;
(2) in a kind of stainless steel acid cleaning waste water of the present invention with the sludge heavy-metal its recovery method as resource, adopt simple chemical precipitation method, add common soda acid medicament; Pharmacy security is reliable, and technological principle is simple, technology maturation; The sludge treatment recovering effect is good, has the flexibility of wide spectrum;
(3) in a kind of stainless steel acid cleaning waste water of the present invention with the sludge heavy-metal its recovery method as resource, in its technological process, nickel chromium triangle loss is less, the valuable metal organic efficiency is high, the total yield of manganese, nickel is greater than 95%, chromium recovery ratio reaches 80-90%;
(4) in the whole process flow of the present invention, temperature, pH value are connected good, and the integrated artistic integrated level is high, and heavy metal resources realizes that substep reclaims, and excess sludge is innoxious, and economic benefit, environmental benefit and obvious social benefit are very significantly.
Embodiment
This law Benq handles in the stainless steel acid cleaning waste water and mud in Wet technique, for further understanding content of the present invention, below in conjunction with embodiment the present invention is further described.
Embodiment 1
In the stainless steel acid cleaning waste water in the present embodiment with mud from Da Feng stainless steel industrial zone, Jiangsu sewage work, mud is handled stainless steel acid cleaning waste water by calcium chloride, lime and PAM and is obtained, wherein the major metal ion content is as shown in table 1.
Among table 1 embodiment 1 in the stainless steel acid cleaning waste water with the major metal ion content of mud
| Element | Fe | Mn | Ni | Cr |
| Content g/kg | 157.2 | 2.8 | 30 | 23.3 |
With the sludge heavy-metal its recovery method as resource, its concrete steps are in a kind of stainless steel acid cleaning waste water of present embodiment:
(1) acidleach: get above-mentioned mud 40 g in 500 mL there-necked flasks, add 200 mL water, after stirring, drip 80% sulfuric acid and stablize about 2.0, be warming up to 95 ℃ after leaching 50 min, add the Na of 8mL, 360 g/L then until pH
2SO
4Solution (dewatered sludge in the present embodiment: sodium sulfate quality is than being 13.9:1); Three-necked flask is placed 95 ℃ of water-baths; And constantly stir, add 2.5mL, the yellow modumite crystal seed (this crystal seed dosage is 2.84 g/L) of 250 g/L high densitys again, simultaneously through dripping 10% Na
2CO
3Solution control pH value 2.0 after carrying out the ihleite deironing and reacting 2h, continues to add 10% Na
2CO
3, regulate control pH value 3.0, and add 2.5mL, 250 g/L pyrrhosiderite crystal seeds (this crystal seed dosage is 2.84 g/L); Carry out the pyrrhosiderite reaction, after continuing to react 2h, cold filtration; And after filter residue carried out carrying out washing treatment; Leach toxicity test, the leaching toxicity of nickel chromium triangle all is lower than the toxicity criterion, and this excess sludge is innoxious mud.The major metal ionic concn is in the leaching liquid: iron 58.15mg/L, manganese 466mg/L, nickel 4970mg/L, chromium 3700mg/L.
(2) oxidation: get the deferrization leach liquor that 200mL step (1) obtains; Carry out the potassium permanganate oxidation reaction, add potassium permanganate 2.43g by 100% of contained manganese, the theoretical oxidation aequum of chromium in the leaching liquid, under 50-60 ℃; Stirring reaction 1h; Filtration drying obtains the thick product 1.3g of Manganse Dioxide, and the oxidation ratio of Manganse Dioxide reaches more than 99%, and Cr in this step (III) is oxidized to Cr (VI) simultaneously.
(3) IX: adopt the DEX-Cr dechromisation resin dedicated, solution entering ion exchange column carries out the chromium exchange after the middle oxidation of step (2), and resin makes the transition into the sulfate radical type through sulfuric acid, resin demand 2g.Solution gets into exchange column with 14mL/h (about 3.5BV/h) after the oxidation, and treatment capacity reaches 25BV, and resin dynamic adsorption amount is 250mg/g.Adopt 1.0 mol/L NaOH as regenerator, regenerate with the 3.5BV/h flow velocity under 35 ℃, regenerant consumption is 15 BV, and the resin regeneration rate reaches more than 98%.Collect regenerated liquid 80mL, the chromium maximum concentration reaches 15000mg/L in the regenerated liquid.
(4) neutralization precipitation: nickel adopts 10%NaOH to precipitate recovery in the step 3) intermediate ion exchange water outlet, and control deposition pH is under 10.0,50 ℃ of conditions behind the stirring reaction 1h, staticly settle, behind the 1h promptly deposition fully, nickel concentration is lower than 0.05mg/L in the water outlet.
Embodiment 2
Used mud and basic step are with embodiment 1 in the present embodiment, and difference is: drip 90% sulfuric acid in the step (1) and stablize about 2.5 until pH, be warming up to 85 ℃ after leaching 10 min, add Na then
2SO
4Solution (dewatered sludge in the present embodiment: sodium sulfate quality is than being 5:1) places 85 ℃ of water-baths with three-necked flask, and constantly stirs, and adds yellow modumite crystal seed (this crystal seed dosage is 10g/L) again, simultaneously through dripping 10% Na
2CO
3Solution control pH value 2.5 after carrying out the ihleite deironing and reacting 5 h, continues to add 10% Na
2CO
3, regulate control pH value 3.5, and add pyrrhosiderite crystal seed (this crystal seed dosage is 1 g/L); Carry out the pyrrhosiderite reaction, continue reaction 5 h, improve the leaching that pH helps suppressing iron; But can cause the leaching yield of nickel, chromium to reduce, concentration of metal ions is in the filtrating at last: iron 20.05mg/L, manganese 453mg/L; Nickel 4830mg/L, chromium 3510mg/L; Get 200mL step (1) in the step (2) and add potassium permanganate 2.82g by 120% of contained manganese, the theoretical oxidation aequum of chromium in the leaching liquid, stirring reaction 5 h cross and filter thick product 1.4 g of Manganse Dioxide; Solution gets into exchange column with 5BV/h after the middle oxidation of step (3); Treatment capacity reaches 30 BV, adopts 2.0 mol/L NaOH as regenerator, regenerates with 5 BV/h flow velocitys under 35 ℃; Regenerant consumption is 10 BV, and final chromium regenerated liquid maximum concentration reaches 14500mg/L; Control deposition pH is stirring reaction 5 h under 9.0,20 ℃ of conditions in the step (4), and the water outlet nickel concentration can not detect.Experimental result is basically with embodiment 1.
Embodiment 3
Used mud and basic step are with embodiment 1 in the present embodiment, and difference is: Dropwise 5 0% sulfuric acid stablizes 1.0 until pH in the step (1), is warming up to 75 ℃ after leaching 80 min, adds Na then
2SO
4Solution (dewatered sludge in the present embodiment: sodium sulfate quality is than being 25:1) places 75 ℃ of water-baths with three-necked flask, and constantly stirs, and adds yellow modumite crystal seed (this crystal seed dosage is 1 g/L) again, simultaneously through dripping 10% Na
2CO
3Solution control pH value 1.5 after carrying out the ihleite deironing and reacting 1 h, continues to add 10% Na
2CO
3, regulate control pH value 2.5, and add pyrrhosiderite crystal seed (this crystal seed dosage is 10 g/L), carry out the pyrrhosiderite reaction, continue reaction 1.0 h; Get 200mL step (1) in the step (2) and add potassium permanganate by 130% of contained manganese, the theoretical oxidation aequum of chromium in the leaching liquid, stirring reaction 3 h cross and filter thick product 1.4 g of Manganse Dioxide; Solution gets into exchange column with 1BV/h after the middle oxidation of step (3), and treatment capacity reaches 10 BV, adopts 0.2 mol/L NaOH as regenerator, regenerates with 1 BV/h flow velocity, and regenerant consumption is 20 BV, and final chromium regenerated liquid maximum concentration reaches 14400mg/L; Control deposition pH is stirring reaction 0.5 h under 13.0,80 ℃ of conditions in the step (4), and the water outlet nickel concentration can not detect.Experimental result is basically with embodiment 1.
Embodiment 1 ~ 3, and the present invention is suppressed at acidleach workshop section with iron, the outstanding noble metal resources such as nickel, chromium that reclaim, and the acidleach deironing is carried out in same reaction kettle, has simplified technical process, minimizing equipment and medicament investment; Nickel chromium triangle loss of the present invention is less, and the valuable metal organic efficiency is high, and the total yield of manganese, nickel is greater than 95%, and chromium recovery ratio reaches 80-90%; In the whole process flow, temperature, pH value are connected good, and the integrated artistic integrated level is high, and heavy metal resources realizes that substep reclaims, and excess sludge is innoxious, and economic benefit, environmental benefit and obvious social benefit are very significantly.
Claims (6)
- In the stainless steel acid cleaning waste water with the sludge heavy-metal its recovery method as resource, the steps include:1) acidleach: adopt sulfuric acid as digestion agent with mud in the stainless steel acid cleaning waste water, and through adding the leaching of additive inhibition iron, excess sludge is innoxious mud discharging after washing;2) oxidation: in the leaching liquid that step 1) obtains, add oxygenant, Mn (II) is oxidized to Manganse Dioxide, filtered filtration residue gets Manganse Dioxide after brine wash and drying, and Cr in this step (III) is oxidized to Cr (VI) simultaneously;3) IX: step 2) after the oxidation solution through anion-exchange column, the enriching and recovering sexavalent chrome, adsorb saturated after, the employing regenerator is regenerated, and from regenerated liquid, reclaims chromic salt;4) neutralization precipitation: step 3) intermediate ion exchange effluent adopting neutralization precipitation method reclaims nickel hydroxide.
- 2. in a kind of stainless steel acid cleaning waste water according to claim 1 with the sludge heavy-metal its recovery method as resource; It is characterized in that: the sulfuric acid that adopts 50-90% with mud in the stainless steel acid cleaning waste water of step 1) is as digestion agent; The condition of controlling is that the pH value is 1.0-2.5, is warming up to 75-95 ℃ behind the leaching 10-80min.
- 3. with the sludge heavy-metal its recovery method as resource, it is characterized in that in a kind of stainless steel acid cleaning waste water according to claim 1 and 2: adopting sodium sulfate earlier in the step 1) is additive, and the mass ratio of dewatered sludge and sodium sulfate is 5-25:1; Add yellow sodium ferrovanadium crystal seed then; The dosage of yellow sodium ferrovanadium crystal seed is 1-10g/L, and control pH value is 1.5-2.5, and the reaction times is 1.0-5.0 h; Add the pyrrhosiderite crystal seed at last; The dosage of this pyrrhosiderite crystal seed is 1-10g/L, and control pH value is 2.5-3.5, reaction times 1.0-5.0 h.
- 4. in a kind of stainless steel acid cleaning waste water according to claim 3 with the sludge heavy-metal its recovery method as resource; It is characterized in that: step 2) in adopt potassium permanganate as oxygenant; And add oxidization time 1.0-5.0 h by the 100-130% of contained manganese in the leaching liquid, the theoretical oxidation aequum of chromium.
- 5. in a kind of stainless steel acid cleaning waste water according to claim 4 with the sludge heavy-metal its recovery method as resource; It is characterized in that: adopt the resin anion(R.A) exchange column to separate in the step 3) and remove chromium; The exchange flow velocity is 1-5 BV/h, and treatment capacity is 10-30 BV/ batch, and regenerator is the NaOH of 0.2-2.0 mol/L; Regenerant flow rate is 1-5 BV/h, and regenerant consumption is 10-20 BV/ batch.
- 6. with the sludge heavy-metal its recovery method as resource, it is characterized in that in a kind of stainless steel acid cleaning waste water according to claim 5: adopt in the step 4) with the sodium hydroxide deposition and reclaim nickel, temperature is 20-80 ℃, and the pH value is 9.0-13.0, reaction times 0.5-5 h.
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