CN102618726A - Treatment method for detoxifying and recycling chromium slag - Google Patents
Treatment method for detoxifying and recycling chromium slag Download PDFInfo
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- CN102618726A CN102618726A CN2012100710904A CN201210071090A CN102618726A CN 102618726 A CN102618726 A CN 102618726A CN 2012100710904 A CN2012100710904 A CN 2012100710904A CN 201210071090 A CN201210071090 A CN 201210071090A CN 102618726 A CN102618726 A CN 102618726A
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 80
- 239000011651 chromium Substances 0.000 title claims abstract description 80
- 239000002893 slag Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004064 recycling Methods 0.000 title claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 226
- 238000000605 extraction Methods 0.000 claims abstract description 103
- 239000002253 acid Substances 0.000 claims abstract description 50
- 239000007921 spray Substances 0.000 claims abstract description 46
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012141 concentrate Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 21
- 238000005070 sampling Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 114
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 238000012545 processing Methods 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 11
- 238000004458 analytical method Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005554 pickling Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 150000001844 chromium Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012492 regenerant Substances 0.000 claims description 3
- 238000012958 reprocessing Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010029240 Neuritis Diseases 0.000 description 1
- 206010040943 Skin Ulcer Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- PXLIDIMHPNPGMH-PJWPDVOUSA-N disodium;dioxido(dioxo)chromium-51 Chemical compound [Na+].[Na+].[O-][51Cr]([O-])(=O)=O PXLIDIMHPNPGMH-PJWPDVOUSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 238000009736 wetting Methods 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
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a treatment method for detoxifying chromium-containing (VI) waste slag and recycling chromium (VI). The treatment method for detoxifying and recycling the chromium slag is characterized by comprising the following steps of: 1) sampling and analyzing content, acidity and particle diameter of main components in the chromium-containing waste slag; 2) establishing 3 to 6 leaching tanks; 3) piling the chromium-containing waste slag with the particle diameter of less than or equal to 20 meshes in the leaching tanks; 4) preparing 0.01 to 1 weight percent dilute acid; 5) spraying the dilute acid to the chromium-containing waste slag in the No. 1 leaching tank through a spray pipe, spraying the leachate in the No. 1 leaching tank to the No. 2 leaching tank, spraying the leachate in the No. 2 leaching tank to the No. 3 leaching tank, and so on, collecting the leachate in the last leaching tank, and entering the next procedure; and 6), regulating the pH of the collected leachate to 1.5-2 by using 10 weight percent dilute sulfuric acid, filtering, performing countercurrent multistage extraction-back extraction concentration, and thus obtaining 20 to 30 weight percent chromium-containing concentrate. The method is low in cost and environment-friendly, and can be used for recovering chromium.
Description
Technical field
The invention belongs to the environmental pollution improvement field, be specifically related to the treatment process of the recycling of a kind of detoxifcation that contains chromium (VI) waste residue and chromium (VI).
Background technology
In the process of chromium salt production, can produce the waste residue that contains hypertoxic chromium (VI).Because historical reasons contain chromium (VI) waste residue in a large number and are effectively disposed.Chromium (VI) is one of high toxicity element, and directly the discharging meeting causes severe contamination to environment, and human body contact or absorption can cause grievous injuries such as skin ulceration, respiratory inflammation, anaemia, neuritis, and it still is one of known carcinogenic substance.
At present, containing the harmless treatment of chromium (VI) waste residue, mainly is that the chromium (VI) that toxicity is higher is reduced into lower chromium of toxicity (III) or chromium metal (0).The method that adopts mainly contains high temperature reduction roasting, electrochemical reduction, chemical reduction, absorbing and reducing etc.The employing aforesaid method is handled, the recycling more complicated of chromium, and cost recovery is higher, reduction is not thorough.Discharge or landfill if contain the waste residue of chromium (III) after will handling, in the long run, also can pollute environment.
Summary of the invention
The objective of the invention is to the treatment process that a kind of chromium residue detoxifying is recycled, this method cost is low, environmental protection, can reclaim chromium.
To achieve these goals, the technical scheme that the present invention taked is: the treatment process that chromium residue detoxifying is recycled is characterized in that it comprises the steps:
1) at first sampling analysis contains staple content in chromium (VI) waste residue (staple is a chromium content), acidity, particle diameter;
2) (or claim cement pit, what of chromium content to select what of leaching ponds according to, chromium content is little to build 3～6 leaching ponds; The quantity in leaching pond is few; And carry out antiseepage and handle), above the leaching pond, build movably shower, the bottom in leaching pond is provided with leaching liquid vent pipe (pvc pipe); Install line strainer additional in the leaching liquid vent pipe, the leaching liquid vent pipe is provided with by-pass valve control (ball valve); Leaching liquid vent pipe be connected with collecting tank (collecting tank is built in the exit in the leaching pond, collects leaching liquid);
3) at first carry out sub-sieve according to size (can know) by sampling analysis; Through sieving (reach and fit the particle diameter that is prone to leaching) with 20 order vibratory screening apparatuss behind the wet ball grinding, the chromium residue (or claiming the chromium slag) of particle diameter≤20 orders (for meeting the chromium residue of particle diameter requirement) is piled in the leaching pond;
4) compound concentration is the diluted acid of 0.01～1wt%;
5) at first the chromium residue in the 1# leaching pond is sprayed (one-level leaching) diluted acid and (be sprayed onto the chromium residue surface uniformly through shower through shower; And infilter) to chromium residue inside; The leach liquor in 1# leaching pond is used for 2# leaching pond spray (secondary leaching), the leach liquor spray 3# leaching pond (three grades of leachings) in 2# leaching pond, and the rest may be inferred; Collect the leach liquor in last leaching pond, get into subsequent processing [entering step 6)];
After chromium (VI) content of the leach liquor (or claiming effluent) in 1# leaching pond is less than 0.2mg/L (GB21900-2008 discharging limit the quantity of requirement); Slag tap in 1# leaching pond; The back 1# that slags tap leaches the pond and stacks new chromium residue; As last step leaching pond leaching and collection leaching liquid, get into subsequent processing [entering step 6)]; The pond is leached as one-level in 2# leaching pond, sprays with diluted acid; The pond is leached as secondary in 3# leaching pond, with leach liquor (collection liquid) spray (spray 3# leaching pond) in 2# leaching pond; The rest may be inferred, and the pond is leached as final stage in 1# leaching pond, with the leach liquor spray of prime;
After chromium (VI) content of the leach liquor (or claiming effluent) in 2# leaching pond is less than 0.2mg/L (GB21900-2008 discharging limit the quantity of requirement); Slag tap in 2# leaching pond; The back 2# that slags tap leaches the pond and stacks new chromium residue; As last step leaching pond (level leaching last pond) leaching and collection leaching liquid, get into subsequent processing [entering step 6)]; The pond is leached as one-level in 3# leaching pond, and 3# leaching pond sprays with diluted acid; The pond is leached as penultimate stage in 1# leaching pond, sprays with the leach liquor (collection liquid) of the leaching pond of prime when adopting 6 leaching ponds (if, leach the pond with the 6th); The rest may be inferred, and the pond is leached as final stage in 2# leaching pond, with the leach liquor spray of prime; Circulation leaching according to this;
6) it is 1.5～2 (acid adjustments) that the leaching liquid of collecting uses the dilute sulphuric acid adjustment pH about 10wt%, filters, and obtains the leaching liquid after the acid adjustment; Leaching liquid after the acid adjustment is carried out counter current multi-stage extraction-reextraction concentrate (or claiming that multi-stage counter current extraction-reextraction concentrates), obtain content and contain chromium (VI) liquid concentrator (recyclable utilization) at 20～30wt%.
This contains chromium (VI) liquid concentrator can produce multiple chromic salts products such as potassiumchromate, Sodium chromate-51Cr, SRM 935a or sodium dichromate 99 through evaporative crystallization, realizes the recycling of resource.
It is said that to contain chromium (VI) waste residue be the waste residue that produces in the process of chromium salt production.
The volume in said leaching pond is 500m
3The bottom in said leaching pond tilts to the mouth of pipe of leaching liquid vent pipe with the gradient of 2～3 degree.
The said diluted acid of step 4) is with 25m
3The speed of/h is sprayed onto the chromium residue surface.
Said counter current multi-stage extraction-reextraction concentrates and comprises the steps:
1), the preparation of extraction feed
1. be extraction agent with the tertiary amine, kerosene is solvent, is made into tertiary amine-kerosene extraction liquid of containing the 30wt% tertiary amine (organic phase, or be called the O phase),
2. the leaching liquid that set by step 6) obtains after the acid adjustment is as by collection liquid (water is also referred to as the A phase),
3. sodium hydroxide or the potassium hydroxide solution of preparing 5～10wt% are as reverse-extraction agent;
4. be regenerator with 10wt% sulfuric acid;
2), extraction liquid, come together liquid, reverse-extraction agent, regenerator are placed respectively in the corresponding high-level container, through under meter control flow velocity;
3), extraction
Extraction section adopts the four-stage counter-current extraction, and (counter-current extraction is extraction means commonly used; The professional should be understood that extraction process is two to advance scene 2, and the counter-current extraction liquid that come together goes out from first progressive final stage; In the process of the extraction of flowing step by step; Be extracted into gradually in the organic phase by the collection material, just do not contained by the collection material in the effluent, be called raffinate.Fresh extraction liquid advances from final stage; This moment, extraction liquid did not contain by the collection material, in the process of the extraction of flowing step by step, and gradually will be in organic phase by the collection extracting substances; From elementary outflow the time, be full of by the collection material; Be called the extraction liquid that contains certain material), extraction liquid with compared (volume ratio) O: A=1 by collection liquid: 5～10 (comparing is one of key concept of extraction chemistry, the ratio of expression biphase volume); Through counter-current extraction, chromium is extracted in the extraction liquid, obtains raffinate by collection liquid, and the concentration of chromium in the raffinate (VI) is less than 0.2mg/L; Qualified discharge or recycling; Chromium (VI) in organic phase, is obtained containing chromium extraction liquid by enrichment method, gets into the section of stripping and strips;
4), strip
Stripping section adopts the Pyatyi countercurrent reextraction to get; Contain the comparing of chromium extraction liquid (O phase) and reverse-extraction agent (A mutually) (volume ratio) and be O: A=2～10: 1; The chromium that contains in the chromium extraction liquid is arrived water by back extraction; Obtain strip liquor, strip liquor concentration is 20～30wt%, collects after concentrate and carry out crystallization and obtain solid-stately containing the chromaking chemical product or preparation contains liquid prods such as chromium passivating agent, tanning agent; The extraction agent that does not contain chromium that obtains gets into RS Regenerator Section and carries out reprocessing cycle;
5), regeneration
RS Regenerator Section adopts one-level regeneration, and the extraction liquid after the back extraction and regenerator are by 1～2: 1 compare (volume ratio) mixed pickling and regenerated, and the extraction liquid after pickling is regenerated returns extraction section and recycles; Sulfuric acid regenerant is carrying out obtaining spent acid after the pickling to extraction agent, and spent acid is used to prepare diluted acid.
Extraction equipment adopts mixing-clarification formula extraction tank, seals, and prevents that solvent evaporates from causing the consumption of secondary pollution and reagent; Mixing pit stirs with 1.1KW driven by motor stirring rake, and rotating speed of agitator is 95r/min.
The advantage of circulated in countercurrent dump leaching method is:
1, chromium slag treatment capacity is big, and flexibly.Can require according to the total amount of chromium slag, day output, the parameters such as content of chromium (VI) in the chromium slag, build the pond of corresponding volume and quantity, the equipment construction cost is low.
2, single-stage leaching starting point concentration is high, and subsequent concn reduces gradually, and it is big not only to leach liquid measure, and fluctuation of concentration is big.Reagent consumption is big.The leaching of employing multi-stage countercurrent, the concentration of leach liquor chromium (VI) is high, and stable content, helps the subsequent recovery utilization.Reagent consumption is few.Chromium (VI) content is well below the emission standard of country in the chromium slag of leaching back.
3, concentrate through multi-stage counter current extraction-reextractions after, contain the chromium leaching liquid be further purified, concentrated, generally can concentrate 20～30 times.Reduced the cost that extracts chromium (VI) preparation chromic salts from chromium slag leaching liquid significantly, made the recycle of chromium have feasibility economically.Thoroughly remove the pollution of chromium on the one hand, can be made into the product of multiple chromium (VI) on the other hand, realized the utilization again of chromium.
The invention has the beneficial effects as follows: utilize chromium (VI) to be easy to become solution in the characteristic of water and diluted acid,, the chromium (VI) in the chromium residue (being the chromium slag) is leached in the aqueous solution, through counter-current extraction, chromium (VI) is recycled again with the method for diluted acid or the dump leaching of spent acid employing adverse current; Reach the chromium residue detoxifcation, the purpose of simultaneously chromium being recycled.Low, the environmental protection of cost of the present invention can be recycled chromium.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
The treatment process that chromium residue detoxifying is recycled, it comprises the steps:
1) at first sampling analysis contains staple content in chromium (VI) waste residue (staple is a chromium content), acidity, granularity:
Contain in chromium (VI) waste residue through analyzing one; Butt chromium (VI) content is 2.6wt%; Insoluble silicate, aluminosilicate content 83wt%; The content of the oxysalt of acid-solubility iron, sodium, magnesium, calcium, oxide compound and oxyhydroxide is between 0.5～5wt%, and other constituent contents are all less than 0.1wt%.Acidity is PH=6.5.The above macrobead content of 20 orders is 8wt%, the about 1.5cm of largest particle diameter.Chromium slag average moisture content 19wt%.
2) building four volumes is 500m
3Leaching pond (cement pit), movably shower is built in leaching pond top.1500 tons of chromium slags can be adorned in each leaching pond.Pvc pipe (leaching liquid vent pipe) and the ball valve that a φ 80mm loads spun glass installed in bottom in the leaching pond, and the bottom in leaching pond tilts to the mouth of pipe with the gradient of 2～3 degree.The leaching liquid vent pipe is connected with collecting tank.
3) chromium (VI) waste residue (chromium slag, or claim chromium residue) sieves with 20 order vibratory screening apparatuss, macrobead with the ball mill ball milling after after 20 order vibratory screening apparatuss, the chromium residue (or title chromium slag) of particle diameter≤20 orders (for meeting the chromium residue of particle diameter requirement) is piled and is leached in the pond.The wetting chromium slag of all spraying water when the ball milling that sieves prevents that the chromium slag from flying upward.
4) dilute sulphuric acid of preparation 0.01% mass concentration is with 25m
3The speed of/h evenly sprays above the chromium slag.
5) at first the chromium slag in 1# pond is sprayed (one-level leaching).Leach liquor is used for 2# pond spray (secondary leaching), the leach liquor spray 3# pond (three grades of leachings) in 2# pond, the leach liquor spray 4# pond (level Four leaching) in 3# pond.The leach liquor of collecting the 4# pond filters, acid adjustment, carries out counter current multi-stage extraction-reextraction and concentrates.
The leach liquor color in 1# pond is by orange--and Huang-yellowish-colourless gradually changing, when leach liquor became colorless, sampling was carried out chromic detection by the analytical procedure of GB7467-1987.Stop the spray [chromium (VI) content is less than 0.2mg/L (GB21900-2008 discharges the requirement of limiting the quantity of)] in 1# pond after up to standard, slag tap, stack new slag.
The pond is leached as one-level in 2# leaching pond; With dilute sulphuric acid the 2# pond is sprayed (one-level leaching); Leach liquor spray 3# pond (secondary leaching), 2# pond, 3# pond leach liquor spray 4# pond (three grades of leachings), 4# pond leach liquor spray 1# pond (level Four leaching); The leach liquor of collecting the 1# pond filters, acid adjustment, carries out counter current multi-stage extraction-reextraction and concentrates.
After 2# pond leach liquor is up to standard, slag tap, stack new slag.Leach as level Four.3# leaches as one-level in the pond, leaches with dilute sulphuric acid.With this leaching that circulates.
6) leaching time of each pond chromium slag is about 32h, about 1000 tons of day output.Final stage leach liquor concentration is about about 1～2%.It is 1.5 that the leaching liquid of collecting uses the dilute sulphuric acid adjustment pH about 10wt%, filters, and obtains the leaching liquid after the acid adjustment; Leaching liquid after the acid adjustment is carried out counter current multi-stage extraction-reextraction concentrate (or claiming that multi-stage counter current extraction-reextraction concentrates), obtain content and contain chromium (VI) liquid concentrator (recyclable utilization) at 20～30wt%.
Said counter current multi-stage extraction-reextraction concentrates and comprises the steps:
1), the preparation of extraction feed
1. be extraction agent with tertiary amine (N-235), kerosene is solvent, is made into tertiary amine-kerosene extraction liquid of containing the 30wt% tertiary amine (organic phase, or be called the O phase), carries out the four-stage counter-current extraction.
2. the leaching liquid that set by step 6) obtains after the acid adjustment is as by collection liquid (water is also referred to as the A phase),
3. the potassium hydroxide solution of preparing 10wt% is as reverse-extraction agent;
4. be regenerator with 10wt% sulfuric acid;
2), extraction liquid (tertiary amine-kerosene extraction liquid), come together liquid, reverse-extraction agent, regenerator are placed respectively in the corresponding high-level container, through under meter control flow velocity;
3), extraction
Extraction section adopts the four-stage counter-current extraction, and (counter-current extraction is extraction means commonly used; The professional should be understood that extraction process is two to advance scene 2, and the counter-current extraction liquid that come together goes out from first progressive final stage; In the process of the extraction of flowing step by step; Be extracted into gradually in the organic phase by the collection material, just do not contained by the collection material in the effluent, be called raffinate.Fresh extraction liquid advances from final stage; This moment, extraction liquid did not contain by the collection material, in the process of the extraction of flowing step by step, and gradually will be in organic phase by the collection extracting substances; From elementary outflow the time, be full of by the collection material; Be called the extraction liquid that contains certain material), extraction liquid with compared (volume ratio) O: A=1 by collection liquid: 10 (comparing is one of key concept of extraction chemistry, the ratio of expression biphase volume); Through counter-current extraction, chromium is extracted in the extraction liquid, obtains raffinate by collection liquid, and the concentration of chromium in the raffinate (VI) is less than 0.2mg/L; Qualified discharge or recycling; Chromium (VI) in organic phase, is obtained containing chromium extraction liquid by enrichment method, gets into the section of stripping and strips;
Raffinate carries out chromic detection by the analytical procedure of GB7467-1987.Reach GB21900-2008 and discharge the requirement back discharging of limiting the quantity of, or circulation is used to prepare dilute sulphuric acid.
4), strip: carry out Pyatyi and strip containing the chromium organic phase, with chromium from organic phase back extraction to water.
Stripping section adopts the Pyatyi countercurrent reextraction to get; Contain chromium extraction liquid (O phase) and be O: A=2 with compare (volume ratio) of reverse-extraction agent (A is mutually): 1, the chromium that contains in the chromium extraction liquid is arrived water by back extraction, obtains strip liquor; Strip liquor concentration is 30wt% (contain chromium be 30% potassium chromate solution); Contain chromium and be 30% potassium chromate solution, through heating evaporation concentrate, crystallization, filtration, drying obtain the potassiumchromate product, 1/2 mother liquor mixes with leaching liquid and extracts; 1/2 mother liquor mixes with strip liquor, carries out condensing crystal (solid-state contain the chromaking chemical product or preparation contains liquid prods such as chromium passivating agent, tanning agent); The extraction agent that does not contain chromium that obtains gets into RS Regenerator Section and carries out reprocessing cycle;
5), regeneration
RS Regenerator Section adopts one-level regeneration, and the extraction agent after the back extraction (extraction agent that does not contain chromium) and regenerator are by 1～2: 1 compare (volume ratio) mixed pickling and regenerated, and the extraction liquid after pickling is regenerated returns extraction section and recycles; Sulfuric acid regenerant is carrying out obtaining spent acid after the pickling to extraction agent, and spent acid is used to prepare diluted acid.
Extraction equipment adopts mixing-clarification formula extraction tank, seals, and prevents that solvent evaporates from causing the consumption of secondary pollution and reagent; Mixing pit stirs with 1.1KW driven by motor stirring rake, and rotating speed of agitator is 95r/min.
Embodiment 2:
The treatment process that chromium residue detoxifying is recycled, it comprises the steps:
1) at first sampling analysis contains staple content in chromium (VI) waste residue (staple is a chromium content), acidity, particle diameter;
Contain in chromium (VI) waste residue through analyzing one; Butt chromium (VI) content is 3.2wt%; Insoluble silicate, aluminosilicate content 83wt%; The content of the oxysalt of acid-solubility iron, sodium, magnesium, calcium, oxide compound and oxyhydroxide is between 0.5～5wt%, and other constituent contents are all less than 0.1wt%.Acidity is PH=6.5.The above macrobead content of 20 orders is 8wt%, the about 1.5cm of largest particle diameter.Chromium slag average moisture content 19wt%.
2) build 3 leaching ponds (and carry out antiseepage and handle), above the leaching pond, build movably shower, the bottom in leaching pond is provided with leaching liquid vent pipe (pvc pipe), installs line strainer additional in the leaching liquid vent pipe, and the leaching liquid vent pipe is provided with by-pass valve control (ball valve); Leaching liquid vent pipe be connected with collecting tank (collecting tank is built in the exit in the leaching pond, collects leaching liquid);
3) at first carry out sub-sieve according to size (can know) by sampling analysis; Through sieving (reach and fit the particle diameter that is prone to leaching) with 20 order vibratory screening apparatuss behind the wet ball grinding, the chromium residue (or claiming the chromium slag) of particle diameter≤20 orders (for meeting the chromium residue of particle diameter requirement) is piled in the leaching pond;
4) compound concentration is the diluted acid of 0.01～1wt%; With 25m
3The speed of/h evenly sprays above the chromium slag;
5) at first the chromium residue in the 1# leaching pond is sprayed (one-level leaching) diluted acid and (be sprayed onto the chromium residue surface uniformly through shower through shower; And infilter) to chromium residue inside; The leach liquor in 1# leaching pond is used for 2# leaching pond spray (secondary leaching); The leach liquor in last leaching pond is collected in the leach liquor spray 3# leaching pond (three grades of leachings) in 2# leaching pond, gets into subsequent processing [entering step 6)];
After chromium (VI) content of the leach liquor (or claiming effluent) in 1# leaching pond is less than 0.2mg/L (GB21900-2008 discharging limit the quantity of requirement); Slag tap in 1# leaching pond; The back 1# that slags tap leaches the pond and stacks new chromium residue; As last step leaching pond leaching and collection leaching liquid, get into subsequent processing [entering step 6)]; The pond is leached as one-level in 2# leaching pond, sprays with diluted acid; The pond is leached as secondary in 3# leaching pond, with leach liquor (collection liquid) spray (spray 3# leaching pond) in 2# leaching pond; The pond is leached as final stage in 1# leaching pond, with the leach liquor spray of prime;
After chromium (VI) content of the leach liquor (or claiming effluent) in 2# leaching pond is less than 0.2mg/L (GB21900-2008 discharging limit the quantity of requirement); Slag tap in 2# leaching pond; The back 2# that slags tap leaches the pond and stacks new chromium residue; As last step leaching pond (level leaching last pond) leaching and collection leaching liquid, get into subsequent processing [entering step 6)]; The pond is leached as one-level in 3# leaching pond, and 3# leaching pond sprays with diluted acid; The pond is leached as penultimate stage in 1# leaching pond, sprays with the leach liquor (collection liquid) in the leaching pond (leaching the pond with 3#) of prime; The pond is leached as final stage in 2# leaching pond, with the leach liquor spray of prime; Circulation leaching according to this;
6) it is 1.5 (acid adjustments) that the leaching liquid of collecting uses the dilute sulphuric acid adjustment pH about 10wt%, filters, and obtains the leaching liquid after the acid adjustment; Leaching liquid after the acid adjustment is carried out counter current multi-stage extraction-reextraction concentrate (or claiming that multi-stage counter current extraction-reextraction concentrates), obtain content and contain chromium (VI) liquid concentrator (recyclable utilization) at 20～30wt%.
Said counter current multi-stage extraction-reextraction concentrates with embodiment 1 basic identical, and difference is: during extraction, and O: A=1: 5; The sodium hydroxide solution of preparation 5wt% is as reverse-extraction agent; The chromium extraction liquid (O phase) that contains of stripping section is O: A=10 with compare (volume ratio) of reverse-extraction agent (A mutually): 1.
Embodiment 3 (building 6 leaching ponds):
The treatment process that chromium residue detoxifying is recycled, it comprises the steps:
1) at first sampling analysis contains staple content in chromium (VI) waste residue (staple is a chromium content), acidity, particle diameter;
Contain in chromium (VI) waste residue through analyzing one; Butt chromium (VI) content is 1.8wt%; Insoluble silicate, aluminosilicate content 83wt%; The content of the oxysalt of acid-solubility iron, sodium, magnesium, calcium, oxide compound and oxyhydroxide is between 0.5～5wt%, and other constituent contents are all less than 0.1wt%.Acidity is PH=13.0.The above macrobead content of 20 orders is 8wt%, the about 10cm of largest particle diameter.Chromium slag average moisture content 19wt%.
2) build 6 leaching ponds (and carry out antiseepage and handle), above the leaching pond, build movably shower, the bottom in leaching pond is provided with leaching liquid vent pipe (pvc pipe), installs line strainer additional in the leaching liquid vent pipe, and the leaching liquid vent pipe is provided with by-pass valve control (ball valve); Leaching liquid vent pipe be connected with collecting tank (collecting tank is built in the exit in the leaching pond, collects leaching liquid);
3) at first carry out sub-sieve according to size (can know) by sampling analysis; Through sieving (reach and fit the particle diameter that is prone to leaching) with 20 order vibratory screening apparatuss behind the wet ball grinding, the chromium residue (or claiming the chromium slag) of particle diameter≤20 orders (for meeting the chromium residue of particle diameter requirement) is piled in the leaching pond;
4) compound concentration is the diluted acid of 0.01～1wt%; With 25m
3The speed of/h evenly sprays above the chromium slag;
5) at first the chromium residue in the 1# leaching pond is sprayed (one-level leaching) diluted acid and (be sprayed onto the chromium residue surface uniformly through shower through shower; And infilter) to chromium residue inside; The leach liquor in 1# leaching pond is used for 2# leaching pond spray (secondary leaching), the leach liquor spray 3# leaching pond (three grades of leachings) in 2# leaching pond, and the rest may be inferred; Collect the leach liquor in last leaching pond, get into subsequent processing [entering step 6)];
After chromium (VI) content of the leach liquor (or claiming effluent) in 1# leaching pond is less than 0.2mg/L (GB21900-2008 discharging limit the quantity of requirement); Slag tap in 1# leaching pond; The back 1# that slags tap leaches the pond and stacks new chromium residue; As last step leaching pond leaching and collection leaching liquid, get into subsequent processing [entering step 6)]; The pond is leached as one-level in 2# leaching pond, sprays with diluted acid; The pond is leached as secondary in 3# leaching pond, with leach liquor (collection liquid) spray (spray 3# leaching pond) in 2# leaching pond; The rest may be inferred, and the pond is leached as final stage in 1# leaching pond, with the leach liquor spray of prime;
After chromium (VI) content of the leach liquor (or claiming effluent) in 2# leaching pond is less than 0.2mg/L (GB21900-2008 discharging limit the quantity of requirement); Slag tap in 2# leaching pond; The back 2# that slags tap leaches the pond and stacks new chromium residue; As last step leaching pond (level leaching last pond) leaching and collection leaching liquid, get into subsequent processing [entering step 6)]; The pond is leached as one-level in 3# leaching pond, and 3# leaching pond sprays with diluted acid; The pond is leached as penultimate stage in 1# leaching pond, sprays with the leach liquor (collection liquid) in the leaching pond (leaching the pond with the 6th) of prime; The rest may be inferred, and the pond is leached as final stage in 2# leaching pond, with the leach liquor spray of prime; Circulation leaching according to this;
6) it is 2 (acid adjustments) that the leaching liquid of collecting uses the dilute sulphuric acid adjustment pH about 10wt%, filters, and obtains the leaching liquid after the acid adjustment; Leaching liquid after the acid adjustment is carried out counter current multi-stage extraction-reextraction concentrate (or claiming that multi-stage counter current extraction-reextraction concentrates), obtain content and contain chromium (VI) liquid concentrator (recyclable utilization) at 20～30wt%.
Said counter current multi-stage extraction-reextraction concentrates with embodiment 1.
Claims (6)
1. the treatment process of chromium residue detoxifying recycling is characterized in that it comprises the steps:
1) at first staple content, acidity, particle diameter in the sampling analysis chromium residue;
2) build 3～6 leaching ponds, above the leaching pond, build movably shower, the bottom in leaching pond is provided with the leaching liquid vent pipe, installs line strainer additional in the leaching liquid vent pipe, and the leaching liquid vent pipe is provided with by-pass valve control; The leaching liquid vent pipe is connected with collecting tank;
3) at first carry out sub-sieve,, particle diameter≤20 purpose chromium residues are piled in the leaching pond through sieving with 20 order vibratory screening apparatuss behind the wet ball grinding according to size;
4) compound concentration is the diluted acid of 0.01～1wt%;
5) at first the chromium residue in the 1# leaching pond is sprayed diluted acid through shower; The leach liquor in 1# leaching pond is used for 2# leaching pond spray, the leach liquor spray 3# leaching pond in 2# leaching pond, and the rest may be inferred; Collect the leach liquor in last leaching pond, get into subsequent processing;
After the chromium content of the leach liquor in 1# leaching pond is less than 0.2mg/L, slag tap in 1# leaching pond, and new chromium residue is stacked in the 1# leaching pond, back of slagging tap, and as last step leaching pond leaching and collect leaching liquid, gets into subsequent processing; The pond is leached as one-level in 2# leaching pond, sprays with diluted acid; The pond is leached as secondary in 3# leaching pond, with the leach liquor spray in 2# leaching pond; The rest may be inferred, and the pond is leached as final stage in 1# leaching pond, with the leach liquor spray of prime;
After the chromium content of the leach liquor in 2# leaching pond is less than 0.2mg/L, slag tap in 2# leaching pond, and new chromium residue is stacked in the 2# leaching pond, back of slagging tap, and as last step leaching pond leaching and collect leaching liquid, gets into subsequent processing; The pond is leached as one-level in 3# leaching pond, and 3# leaching pond sprays with diluted acid; The pond is leached as penultimate stage in 1# leaching pond, sprays with the leach liquor in the leaching pond of prime; The rest may be inferred, and the pond is leached as final stage in 2# leaching pond, with the leach liquor spray of prime; Circulation leaching according to this;
6) it is 1.5～2 that the leaching liquid of collecting uses the dilute sulphuric acid adjustment pH of 10wt%, filters, and obtains the leaching liquid after the acid adjustment; Leaching liquid after the acid adjustment is carried out counter current multi-stage extraction-reextraction concentrate, obtain content and contain the chromium liquid concentrator at 20～30wt%.
2. the treatment process that chromium residue detoxifying according to claim 1 is recycled is characterized in that: said to contain chromium (VI) waste residue be the waste residue that produces in the process of chromium salt production.
3. the treatment process that chromium residue detoxifying according to claim 1 is recycled, it is characterized in that: the volume in said leaching pond is 500m
3
4. the treatment process that chromium residue detoxifying according to claim 1 is recycled is characterized in that: the bottom in said leaching pond tilts to the mouth of pipe of leaching liquid vent pipe with the gradient of 2～3 degree.
5. the treatment process that chromium residue detoxifying according to claim 1 is recycled, it is characterized in that: the said diluted acid of step 4) is with 25m
3The speed of/h is sprayed onto the chromium residue surface.
6. the treatment process that chromium residue detoxifying according to claim 1 is recycled is characterized in that: said counter current multi-stage extraction-reextraction concentrates and comprises the steps:
1), the preparation of extraction feed
1. be extraction agent with the tertiary amine, kerosene is solvent, is made into the tertiary amine-kerosene extraction liquid that contains the 30wt% tertiary amine,
2. the leaching liquid that set by step 6) obtains after the acid adjustment is as by collection liquid,
3. sodium hydroxide or the potassium hydroxide solution of preparing 5～10wt% are as reverse-extraction agent;
4. be regenerator with 10wt% sulfuric acid;
2), extraction liquid, come together liquid, reverse-extraction agent, regenerator are placed respectively in the corresponding high-level container, through under meter control flow velocity;
3), extraction
Extraction section adopts the four-stage counter-current extraction, extraction liquid with compared O: A=1 by collection liquid: 5～10; Through counter-current extraction, chromium is extracted in the extraction liquid, obtains raffinate by collection liquid, and the concentration of chromium is less than 0.2mg/L in the raffinate; Qualified discharge or recycling; Chromium in organic phase, is obtained containing chromium extraction liquid by enrichment method, gets into the section of stripping and strips;
4), strip
Stripping section adopts the Pyatyi countercurrent reextraction to get; The O that is in a ratio of that contains chromium extraction liquid and reverse-extraction agent: A=2～10: 1; The chromium that contains in the chromium extraction liquid is arrived water by back extraction; Obtain strip liquor, strip liquor concentration is 20～30wt%, collects after concentrate and carry out crystallization and obtain solid-stately containing the chromaking chemical product or preparation contains chromium passivating agent or tanning agent; The extraction agent that does not contain chromium that obtains gets into RS Regenerator Section and carries out reprocessing cycle;
5), regeneration
RS Regenerator Section adopts one-level regeneration, and the extraction agent after the back extraction and regenerator are by 1～2: 1 compare mixed pickling and regenerated, and the extraction liquid after pickling is regenerated returns extraction section and recycles; Sulfuric acid regenerant is carrying out obtaining spent acid after the pickling to extraction agent, and spent acid is used to prepare diluted acid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851511A (en) * | 2012-08-29 | 2013-01-02 | 江西自立资源再生有限公司 | Method for reducing contents of zinc and copper in smelting ash acid leaching residues |
| CN104787952A (en) * | 2015-03-25 | 2015-07-22 | 湖南永清环保研究院有限责任公司 | Process for recovering chromium from hexavalent chromium-containing wastewater |
| CN104959369A (en) * | 2015-05-20 | 2015-10-07 | 湖南永清环保研究院有限责任公司 | Method used for recycling chromium from chromium-polluted soil |
| CN106929698A (en) * | 2015-12-30 | 2017-07-07 | 核工业北京化工冶金研究院 | A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101116767A (en) * | 2007-07-03 | 2008-02-06 | 重庆长江环保建设有限公司 | Novel method of zero discharging of chromium and absolute utilization of resource |
| CN101138670A (en) * | 2006-09-08 | 2008-03-12 | 隋智通 | Novel process of the high temperature reduction and detoxication of industrial chromic slag |
| CN101816829A (en) * | 2010-04-09 | 2010-09-01 | 河南金谷环保工程设备有限公司 | Chromium residue detoxifying process |
-
2012
- 2012-03-16 CN CN2012100710904A patent/CN102618726B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101138670A (en) * | 2006-09-08 | 2008-03-12 | 隋智通 | Novel process of the high temperature reduction and detoxication of industrial chromic slag |
| CN101116767A (en) * | 2007-07-03 | 2008-02-06 | 重庆长江环保建设有限公司 | Novel method of zero discharging of chromium and absolute utilization of resource |
| CN101816829A (en) * | 2010-04-09 | 2010-09-01 | 河南金谷环保工程设备有限公司 | Chromium residue detoxifying process |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851511A (en) * | 2012-08-29 | 2013-01-02 | 江西自立资源再生有限公司 | Method for reducing contents of zinc and copper in smelting ash acid leaching residues |
| CN104787952A (en) * | 2015-03-25 | 2015-07-22 | 湖南永清环保研究院有限责任公司 | Process for recovering chromium from hexavalent chromium-containing wastewater |
| WO2016150022A1 (en) * | 2015-03-25 | 2016-09-29 | 湖南永清环保研究院有限责任公司 | Process for recovering chromium from hexavalent chromium-containing wastewater |
| US10577676B2 (en) * | 2015-03-25 | 2020-03-03 | Hunan Yonker Environmental Protection Research Institute Co., LTD | Process for recycling chromium from waste water containing hexavalent chromium |
| CN104959369A (en) * | 2015-05-20 | 2015-10-07 | 湖南永清环保研究院有限责任公司 | Method used for recycling chromium from chromium-polluted soil |
| CN106929698A (en) * | 2015-12-30 | 2017-07-07 | 核工业北京化工冶金研究院 | A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome |
| CN106929698B (en) * | 2015-12-30 | 2019-02-26 | 核工业北京化工冶金研究院 | A kind of processing method of chromium slag nitration mixture enhanced leaching-extraction and recovery siderochrome |
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