CN102618726B - Treatment method for detoxifying and recycling chromium slag - Google Patents
Treatment method for detoxifying and recycling chromium slag Download PDFInfo
- Publication number
- CN102618726B CN102618726B CN2012100710904A CN201210071090A CN102618726B CN 102618726 B CN102618726 B CN 102618726B CN 2012100710904 A CN2012100710904 A CN 2012100710904A CN 201210071090 A CN201210071090 A CN 201210071090A CN 102618726 B CN102618726 B CN 102618726B
- Authority
- CN
- China
- Prior art keywords
- leaching
- chromium
- pond
- extraction
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 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 30
- 238000004064 recycling Methods 0.000 title claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 228
- 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 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 20
- 239000012141 concentrate Substances 0.000 claims abstract description 19
- 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
- 238000004458 analytical method Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 11
- 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
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 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
- 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
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 42
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 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
- 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
- 239000012263 liquid product 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
- 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
- 239000003365 glass fiber 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
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 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
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 the 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 solution used in the present invention is: the treatment process that chromium residue detoxifying is recycled is characterized in that it comprises the steps:
1) at first sampling analysis contains main component content in chromium (VI) waste residue (main component is chromium content), acidity, particle diameter;
2) build 3～6 leaching ponds and (or claim cement pit, what of chromium content to select what of leaching ponds according to, chromium content is little, 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 (by sampling analysis as can be known), by sieving (reach and fit the easily particle diameter of leaching) with 20 order vibratory screening apparatuss behind the wet ball grinding, the chromium residue (or claiming 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 by shower the chromium residue in the 1# leaching pond is sprayed (one-level leaching) diluted acid and (be sprayed onto the chromium residue surface uniformly by 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, the rest may be inferred, collect the leach liquor in last leaching pond, enter subsequent processing [entering step 6)];
After chromium (VI) content of the leach liquor (or claiming effluent liquid) 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, enter 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 liquid) 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, enter 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) to adjust pH be 1.5～2 (acid adjustments) to the dilute sulphuric acid of the leaching liquid of Shou Jiing about with 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 multi-stage counter current extraction-reextraction to concentrate), obtain content and contain chromium (VI) concentrated solution (recyclable utilization) at 20～30wt%.
This contains chromium (VI) concentrated solution can produce multiple chromic salts products such as potassiumchromate, Sodium chromate, potassium bichromate or sodium dichromate 99 through evaporative crystallization, realizes the recycling of resource.
It is described that to contain chromium (VI) waste residue be the waste residue that produces in the process of chromium salt production.
The volume in described leaching pond is 500m
3The bottom in described leaching pond tilts with the mouth of pipe of 2～3 gradients of spending to the leaching liquid vent pipe.
The described diluted acid of step 4) is with 25m
3The speed of/h is sprayed onto the chromium residue surface.
Described 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. set by step 6) leaching liquid that obtains after the acid adjustment is as by collection liquid (water is also referred to as the A phase),
3. prepare the sodium hydroxide of 5～10wt% or potassium hydroxide solution 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, by 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 will be appreciated that, extraction process is two to advance scene 2, 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 liquid, 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, gradually will be by the collection extracting substances in organic phase, 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 the volume of expression two-phase); By 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) is concentrated and is enriched in the organic phase, obtains containing chromium extraction liquid, enters 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 phase) (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 by concentrating and carries out crystallization and obtain solid-stately containing the chromaking chemical product or preparation contains liquid products such as chromium passivating agent, tanning agent; The extraction agent that does not contain chromium that obtains enters 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 for the preparation diluted acid.
Extraction equipment adopts and mixes-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 height, 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 height of leach liquor chromium (VI), and stable content are conducive to 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 by 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 recycling 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, adopt the method for adverse current dump leaching with diluted acid or spent acid, the leaching of chromium (VI) in the chromium residue (being the chromium slag) in the aqueous solution, by counter-current extraction, is recycled chromium (VI) again; Reach the chromium residue detoxifcation, simultaneously the purpose that chromium is 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 the following examples.
Embodiment 1:
The treatment process that chromium residue detoxifying is recycled, it comprises the steps:
1) at first sampling analysis contains main component content in chromium (VI) waste residue (main component is chromium content), acidity, granularity:
One contains in chromium (VI) waste residue by analysis, 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 glass fibre 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, with chromium residue (or claiming chromium slag) heap of particle diameter≤20 orders (for meeting the chromium residue of particle diameter requirement) to leaching in the pond.The wetting chromium slag that sieves and all spray water during ball milling 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, leach liquor spray 4# pond (three grades of leachings), 3# pond, leach liquor spray 1# pond (level Four leaching), 4# pond, 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 dilute sulphuric acid of the leaching liquid of collecting about with 10wt% adjusted pH, and filtration 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 multi-stage counter current extraction-reextraction to concentrate), obtain content and contain chromium (VI) concentrated solution (recyclable utilization) at 20～30wt%.
Described 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. set by step 6) leaching liquid that obtains after the acid adjustment is as by collection liquid (water is also referred to as the A phase),
3. prepare the potassium hydroxide solution of 10wt% 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, by 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 will be appreciated that, extraction process is two to advance scene 2, 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 liquid, 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, gradually will be by the collection extracting substances in organic phase, 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 the volume of expression two-phase); By 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) is concentrated and is enriched in the organic phase, obtains containing chromium extraction liquid, enters 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 for preparing 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 phase): 1, the chromium that contains in the chromium extraction liquid is arrived water by back extraction, obtain strip liquor, strip liquor concentration is 30wt% (contain chromium be 30% potassium chromate solution), contain chromium and be 30% potassium chromate solution, concentrate through heating evaporation, crystallization, filter, drying obtains 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 and (solid-stately contains the chromaking chemical product or preparation contains the chromium passivating agent, liquid products such as tanning agent); The extraction agent that does not contain chromium that obtains enters 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 for the preparation diluted acid.
Extraction equipment adopts and mixes-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 main component content in chromium (VI) waste residue (main component is chromium content), acidity, particle diameter;
One contains in chromium (VI) waste residue by analysis, 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 (by sampling analysis as can be known), by sieving (reach and fit the easily particle diameter of leaching) with 20 order vibratory screening apparatuss behind the wet ball grinding, the chromium residue (or claiming 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 by shower the chromium residue in the 1# leaching pond is sprayed (one-level leaching) diluted acid and (be sprayed onto the chromium residue surface uniformly by 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, collect the leach liquor in last leaching pond, enter subsequent processing [entering step 6)];
After chromium (VI) content of the leach liquor (or claiming effluent liquid) 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, enter 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 liquid) 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, enter 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) to adjust pH be 1.5 (acid adjustments) to the dilute sulphuric acid of the leaching liquid of Shou Jiing about with 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 multi-stage counter current extraction-reextraction to concentrate), obtain content and contain chromium (VI) concentrated solution (recyclable utilization) at 20～30wt%.
Described counter current multi-stage extraction-reextraction concentrates substantially the same manner as Example 1, 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 phase): 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 main component content in chromium (VI) waste residue (main component is chromium content), acidity, particle diameter;
One contains in chromium (VI) waste residue by analysis, 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 (by sampling analysis as can be known), by sieving (reach and fit the easily particle diameter of leaching) with 20 order vibratory screening apparatuss behind the wet ball grinding, the chromium residue (or claiming 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 by shower the chromium residue in the 1# leaching pond is sprayed (one-level leaching) diluted acid and (be sprayed onto the chromium residue surface uniformly by 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, the rest may be inferred, collect the leach liquor in last leaching pond, enter subsequent processing [entering step 6)];
After chromium (VI) content of the leach liquor (or claiming effluent liquid) 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, enter 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 liquid) 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, enter 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, uses leach liquor (collection liquid) spray in the leaching pond (with the 6th 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) to adjust pH be 2 (acid adjustments) to the dilute sulphuric acid of the leaching liquid of Shou Jiing about with 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 multi-stage counter current extraction-reextraction to concentrate), obtain content and contain chromium (VI) concentrated solution (recyclable utilization) at 20～30wt%.
Described 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 main component content, acidity, particle diameter in the sampling analysis chromium residue;
2) build 3～6 leaching ponds, build movably shower above the leaching pond, 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 according to size, by sieving with 20 order vibratory screening apparatuss behind the wet ball grinding, particle diameter≤20 purpose chromium residues are piled in the leaching pond;
4) compound concentration is the diluted acid of 0.01～1wt%;
5) at first by shower the chromium residue in the 1# leaching pond is sprayed diluted acid, 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, enter 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, enters 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, enters 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, uses the leach liquor spray 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) to adjust pH with the dilute sulphuric acid of 10wt% be 1.5～2 to the leaching liquid of Shou Jiing, 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 concentrated solution at 20～30wt%.
2. the treatment process recycled of chromium residue detoxifying according to claim 1 is characterized in that: described chromium residue be produce in the process of chromium salt production contain the sexavalent chrome waste residue.
3. the treatment process recycled of chromium residue detoxifying according to claim 1, it is characterized in that: the volume in described leaching pond is 500m
3
4. the treatment process recycled of chromium residue detoxifying according to claim 1 is characterized in that: the bottom in described leaching pond tilts with the gradients of 2～3 degree mouth of pipe to the leaching liquid vent pipe.
5. the treatment process recycled of chromium residue detoxifying according to claim 1, it is characterized in that: the described diluted acid of step 5) is with 25m
3The speed of/h is sprayed onto the chromium residue surface.
6. the treatment process recycled of chromium residue detoxifying according to claim 1, it is characterized in that: described counter current multi-stage extraction-reextractions is concentrated to be comprised 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. set by step 6) leaching liquid that obtains after the acid adjustment is as by collection liquid,
3. prepare the sodium hydroxide of 5～10wt% or potassium hydroxide solution 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, by under meter control flow velocity;
3), extraction
Extraction section adopts the four-stage counter-current extraction, extraction liquid with compared O:A=1:5～10 by collection liquid; By 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 is concentrated and is enriched in the organic phase, obtains containing chromium extraction liquid, enters the section of stripping and strips;
4), strip
Stripping section adopts the Pyatyi countercurrent reextraction to get, O:A=2～the 10:1 that is in a ratio of that contains chromium extraction liquid and reverse-extraction agent, 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 by concentrating and carries 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 enters 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 mixes pickling regeneration with regenerator by comparing of 1～2:1, and the extraction liquid after pickling regeneration 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 for the preparation diluted acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100710904A CN102618726B (en) | 2012-03-16 | 2012-03-16 | Treatment method for detoxifying and recycling chromium slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100710904A CN102618726B (en) | 2012-03-16 | 2012-03-16 | Treatment method for detoxifying and recycling chromium slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102618726A CN102618726A (en) | 2012-08-01 |
| CN102618726B true CN102618726B (en) | 2013-08-14 |
Family
ID=46558927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100710904A Expired - Fee Related CN102618726B (en) | 2012-03-16 | 2012-03-16 | Treatment method for detoxifying and recycling chromium slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102618726B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851511B (en) * | 2012-08-29 | 2014-01-08 | 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 |
| CN104787952B (en) * | 2015-03-25 | 2016-04-27 | 湖南永清环保研究院有限责任公司 | A kind of from containing the technique reclaiming chromium hexavalent chromium wastewater |
| CN104959369B (en) * | 2015-05-20 | 2017-03-29 | 湖南永清环保研究院有限责任公司 | A kind of technique that chromium is reclaimed from chromium-polluted soil |
| 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 |
Family Cites Families (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 |
| CN101816829B (en) * | 2010-04-09 | 2011-08-31 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN102618726A (en) | 2012-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103849774B (en) | A kind of method that discarded SCR catalyst is recycled | |
| CN103194615B (en) | Lead hydrometallurgical technology through utilizing lead sulfate | |
| CN107299223B (en) | A kind of compound alkaline-leaching and vanadium extraction method of bone coal and its system | |
| CN105695751B (en) | A kind of purification technique of electrolytic manganese anode mud | |
| CN101597073B (en) | Method for preparing sodium thiocyanate by using desulphurization waste liquid of coke oven gas | |
| CN104178632B (en) | A kind of method of titanium white waste acid comprehensive utilization | |
| CN102618726B (en) | Treatment method for detoxifying and recycling chromium slag | |
| CN106744721A (en) | The recovery separation method and application of sulfuric acid and dissolubility titanium in titanium white waste acid | |
| CN106745193A (en) | The method that iron content zinc-containing sludge recovery prepares zinc hydroxide and dyestuff level iron oxide red | |
| CN107699695A (en) | It is a kind of that tungsten, the method for vanadium are reclaimed from useless SCR denitration | |
| CN101012500A (en) | Method for separating highly-pure rare-earth oxide from low-yttrium middle-heavy rare earth mine | |
| CN101509070A (en) | Method for acid leaching extraction of vanadium from vanadium-containing raw material | |
| CN106435197A (en) | Process and device for alkaline extraction and recovery from waste catalysts in SCR (selective catalytic reduction) denitrification | |
| CN108866337B (en) | A method of processing metal sludge | |
| CN114634189A (en) | Method and system for recovering aluminum electrolysis overhaul slag | |
| CN110436585A (en) | A kind of method of water soluble salt removing and recycling in Quadratic aluminum dust | |
| CN106185953B (en) | A kind of large-scale quartz sand pickling impurity removal whitening process | |
| CN108706844A (en) | Iron, chromium, the separation and recovery method of aluminium and its application in more metal hazardous wastes | |
| CN105461140B (en) | A kind of Tungsten smelting ion-exchange waste water integrated treatment recovery system and method | |
| CN107182281B (en) | The technique of uranium-bearing liquid waste processing in a kind of uranium enrichment technique | |
| CN203284447U (en) | System used for recovering lithium, rubidium and / or cesium from lepidolite ore | |
| CN107604163A (en) | A kind of technique of no scorification processing electroplating sludge | |
| CN207451636U (en) | The system that MgZn ferrite is prepared using pickling sludge and pickle liquor | |
| CN109516443A (en) | A kind of processing method of the Waste Sulfuric Acid containing aluminium | |
| CN102943178B (en) | Method for recovering titanium in wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: WUHAN WEICHUAN ENVIRONMENTAL PROTECTION TECHNOLOGY Free format text: FORMER OWNER: JIANGXI JIEYIYUAN ENVIRONMENTAL TECHNOLOGY CO., LTD. Effective date: 20130509 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 330025 NANCHANG, JIANGXI PROVINCE TO: 430000 WUHAN, HUBEI PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20130509 Address after: 430000, Hubei District, Wuhan, Wuchang Linjiang Avenue 55, Jinjiang international city 5, 1 units, 3, 302 Applicant after: WUHAN WEICHUAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: 602 room 330025, building B, building 6, Chaoyang oasis, No. 669 Fu Sheng Road, Nanchang, Jiangxi, Xihu District Applicant before: JIANGXI JIEYIYUAN ENVIRONMENTAL TECHNOLOGY Co.,Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130814 |