CN106929698A - A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome - Google Patents
A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome Download PDFInfo
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- CN106929698A CN106929698A CN201511023816.7A CN201511023816A CN106929698A CN 106929698 A CN106929698 A CN 106929698A CN 201511023816 A CN201511023816 A CN 201511023816A CN 106929698 A CN106929698 A CN 106929698A
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- chromium
- slag
- recovery
- nitration mixture
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- 239000011651 chromium Substances 0.000 title claims abstract description 107
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 90
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000002893 slag Substances 0.000 title claims abstract description 71
- 238000000605 extraction Methods 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 238000006396 nitration reaction Methods 0.000 title claims abstract description 27
- 238000011084 recovery Methods 0.000 title claims abstract description 26
- 238000003672 processing method Methods 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 238000002386 leaching Methods 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000012074 organic phase Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 235000001727 glucose Nutrition 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 3
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract description 2
- 235000014413 iron hydroxide Nutrition 0.000 abstract description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 6
- 150000001844 chromium Chemical class 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 salts compound Chemical class 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ANFIEGWCRSNVFS-UHFFFAOYSA-N [Na].OCl(=O)=O Chemical compound [Na].OCl(=O)=O ANFIEGWCRSNVFS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000002419 base digestion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2200/00—Recycling of non-gaseous waste material
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome technical field, and in particular to a kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome；The present invention uses nitration mixture Strengthen education, leaches the Cr VI in later stage addition reducing agent reducing leaching liquid and slag, and iron and trivalent chromium in leachate carry out extract and separate recovery, reaches the purpose of the harmless treatment of chromium slag and the synthetical recovery of iron.Chromium slag is processed using this method, the Cr VI in chromium slag and trivalent chromium dissolution as far as possible can again be occurred the risk of brightness reversion after reducing chromic wastes disposal.And synthetical recovery iron and chromium, Fe (OH)3With Cr (OH)3Purity is more than 99.0%, and the product iron hydroxide for obtaining is high with chromium hydroxide purity.
Description
Technical field
The invention belongs to chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome technical field, and in particular to a kind of chromium slag
The processing method of nitration mixture Strengthen education-extraction and recovery siderochrome.
Background technology
The metal simple-substance and compound of chromium are in plating casting, chemical industry metallurgical, leather manufacture, bio-pharmaceuticals
And the conglomerate such as Aero-Space is widely used, ranks one of 8 kinds of raw materials of most competitiveness.Chromic salts is at me
State status is even more very important, and 15% product is all inseparable with its in national economy, China's chromic salts compound
Industrial annual value of production about 4,000,000,000 in 2006.External chromium salt production history more than 200 years, annual production more than 1200kt,
Mainly there are the countries such as the United States, Russia, English, day, moral in producing region.Chinese chromic salts development only 50 years, but development is swift and violent,
Current chromium salt production amount and the 1st, the consumption figure Jun Ju worlds.Chromic salts is huge to pull economy to increase performance rapidly
While big effect, the severe toxicity for also bringing the title of " city bomb " and " fearful city malignant tumor " is secondary
Product-chromium slag.Generally, the product quantity of slag of crome metal is 10 times of its output, and it is that its finished product is produced that chromic salts produces the quantity of slag
3-5 times of amount.Total chrome content is 1-7% in chromium slag, and Cr (VI) content accounts for 1-3%, wherein water-soluble and acid is molten
The ratio of property Cr (VI) is about 2:3.Soluble Cr (VI) is with strong oxidizing property, mutagenicity and carcinogenicity
One of internationally recognized 3 kinds of carcinogenic metallic compounds.According to statistics, once there were 70 Duo Ge chromium salt productions factories in the whole nation,
National production capacity is about 300kt/a, and burden is administered greatly with chromium slag contaminated because technique falls behind, and stops production and changes the line of production
Family about more than 40, national existing chromium salt factory 25.Because production technology falls behind and environmental consciousness weakness, I
State's left over by history chromium slag muck deposits total amount in 4500kt or so, and annual also with the quantity increasing more than 800kt
Plus.At present, chromium slag is arbitrarily stored up, and not only takes a large amount of land resources, and containing the leachate contamination of Cr (VI)
Surface water and groundwater, tiny flying dust can also pollute air, ecological environment and people's life health are caused
Significant damage.Early in October, 2005, joint is formulated and announced《Chromium slag contaminated comprehensive improvement action scheme》
The target of improvement and recovery that chromium slag contaminated site was basically completed in 2012 is formulated.To cut-off at present, this
One target is not yet realized.Therefore, the innoxious and Resource analysis for carrying out chromium slag have extremely important reality
Meaning.
The content of the invention
For above-mentioned prior art, present invention aim at a kind of chromium slag nitration mixture Strengthen education-extraction and recovery of offer
The processing method of siderochrome, harmless treatment is carried out to chromium slag.
In order to achieve the above object, the treatment side of a kind of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome of the invention
Method, comprises the following steps：
Step one, by chromium slag certain liquid-solid ratio and at a temperature of, add a certain amount of sulfuric acid and hydrochloric acid by chromium slag
In Cr VI be dissolved out with trivalent chromium；
After step 2, nitration mixture dissolving chromium slag, a certain amount of reducing agent is added to carry out the reduction of Cr VI；
Step 3, reduction add a certain amount of polyethers to stir and stand the regular hour after terminating, then
Carry out solid-liquor separation；
Step 4, the leachate that will be obtained extract ferric iron with TBP；
Step 5, the organic phase that will extract iron are washed with hydrochloric acid, wash away the impurity of entrainment, and hydrochloric acid is dense
It is 3~6mol/L to spend, and cleaning solution returns to carry out the leaching of chromium slag；Load iron organic phase after washing is entered with water
Row back extraction, 1~20min of time of contact, 10~40 DEG C of temperature is 1 compared to O/A:1~50:1, series
2~10 grades, obtain ferric chloride solution；
Step 6, will extract iron after raffinate with NaOH adjust pH value be 2~5, with P204 extract trivalent
Chromium；
Step 7, the organic phase that will extract chromium are washed with the solution that pH value is 2~4, wash away residual
Impurity, wash water returns to carry out the leaching of chromium slag；
Step 8, will wash after load chromium organic phase acid back extraction.
The liquid-solid ratio that chromium slag described in further step one is leached is 3:1~20:1, temperature is 60~100 DEG C,
Time is 20~120min；The nitration mixture of addition is sulfuric acid and hydrochloric acid, and sulphuric acid is the 0.1~1 of the chromium quantity of slag
Times, hydrochloric acid addition is 0.5~3 times of the chromium quantity of slag.
The addition of the reducing agent described in further step 2 is the 0.1%~5% of the chromium quantity of slag, and the reaction time is
0.5~5h.
Reducing agent described further is glucose, sodium sulfite, sodium pyrosulfite, sodium thiosulfate any one
Kind.
Polyethers addition described in further step 3 is the 0.3%~3% of the chromium quantity of slag, the reaction time is 0.5~
2h, filters after standing 12~48h.
Extractant concentration described in further step 4 is 10~30%, and diluent is sulfonated kerosene；Extraction is former
Liquid is by adding hydrochloric acid and sodium chloride, it is ensured that acidity is more than 0.5mol/L, and chloride content is more than 100g/L；TBP
Extraction iron time of contact be 1~20min, 10~40 DEG C of extraction temperature, extraction phase compares O/A=1:5~5:1, extraction
3~9 grades of series.
P204 concentration described in further step 6 is 10%~30%, and diluent is sulfonated kerosene, P204 soaps
Change degree is 20%~80%；Extraction time of contact is 1~20min, 10~40 DEG C of extraction temperature, extraction phase ratio
O/A=1:5~5:1, extract 3~9 grades of series.
Back extraction time of contact described in further step 8 is 5~30min, and temperature is 20~40 DEG C, phase
It is 1 than O/A:1~50:1, extraction series is 2~10 grades.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome of the present invention strengthens leaching using nitration mixture
Go out, leach the Cr VI in later stage addition reducing agent reducing leaching liquid and slag, iron and trivalent chromium in leachate
Extract and separate recovery is carried out, the method for reaching the harmless treatment of chromium slag and the synthetical recovery of iron.
A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome of the present invention and existing other method phases
Than again with Cr VI dissolution thoroughly, also major part is dissolved trivalent chromium, is returned after reducing chromic wastes disposal
Yellow risk, and synthetical recovery iron and chromium, the product iron hydroxide for obtaining are high with chromium hydroxide purity.
Specific embodiment
The present invention is elaborated with reference to specific embodiment.
A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome of the present invention, comprises the following steps：
Step one, by chromium slag certain liquid-solid ratio and at a temperature of, add a certain amount of sulfuric acid and hydrochloric acid by chromium slag
In Cr VI be dissolved out with trivalent chromium；
The liquid-solid ratio that chromium slag is leached is 3:1~20:1, temperature is 60~100 DEG C, and the time is 20~120min；
The nitration mixture of addition is sulfuric acid and hydrochloric acid, and sulphuric acid is 0.1~1 times of the chromium quantity of slag, and hydrochloric acid addition is chromium
0.5~3 times of the quantity of slag；
After step 2, nitration mixture dissolving chromium slag, a certain amount of reducing agent is added to carry out the reduction of Cr VI；
Reducing agent used be glucose, sodium sulfite, sodium pyrosulfite, sodium thiosulfate etc. any,
Addition is the 0.1%~5% of the chromium quantity of slag, and the reaction time is 0.5~5h；
Step 3, reduction add a certain amount of polyethers to stir and stand the regular hour after terminating, then
Carry out solid-liquor separation；
Polyethers addition is the 0.3%~3% of the chromium quantity of slag, and the reaction time is 0.5~2h, after standing 12~48h
Filtering；
Step 4, the leachate that will be obtained extract ferric iron with TBP；
Extractant concentration is 10~30%, and diluent is sulfonated kerosene；Extraction stoste is by adding hydrochloric acid and chlorination
Sodium, it is ensured that acidity is more than 0.5mol/L, chloride content is more than 100g/L；TBP extraction iron time of contact be 1~
20min, 10~40 DEG C of extraction temperature, extraction phase compares O/A=1:5~5:1, extract 3~9 grades of series；
Step 5, the organic phase that will extract iron are washed with hydrochloric acid, wash away the impurity of entrainment, and hydrochloric acid is dense
It is 3~6mol/L to spend, and cleaning solution returns to carry out the leaching of chromium slag；
Load iron organic phase after washing is stripped with water, 1~20min of time of contact, temperature 10~
40 DEG C, be 1 compared to O/A:1~50:1,2~10 grades of series obtains ferric chloride solution；
Step 6, will extract iron after raffinate with NaOH adjust pH value be 2~5, with P204 extract trivalent
Chromium, P204 concentration is 10~30%, and diluent is sulfonated kerosene, and P204 saponification degrees are 20%~80%；
Extraction time of contact be 1~20min, 10~40 DEG C of extraction temperature, extraction phase compares O/A=1:5~5:1,
3~9 grades of series of extraction；
Step 7, the organic phase that will extract chromium are washed with the solution that pH value is 2~4, wash away residual
Impurity, wash water returns to carry out the leaching of chromium slag；
Step 8, will wash after load chromium organic phase acid back extraction, it is used acid be hydrochloric acid or sulfuric acid, concentration
0.5mol/L~3mol/L；
Back extraction time of contact is 5~30min, and temperature is 20~40 DEG C, is 1 compared to O/A:1~50:1,
Extraction series is 2~10 grades.
Embodiment one
Certain chromium slag contain total chromium 3.12%, Cr VI 0.85%, 1kg chromium slag add 6L water, the 200ml concentrated sulfuric acids,
1500ml hydrochloric acid, after reacting 60min at 60~80 DEG C, adds 40g glucose to be reduced at 80~90 DEG C
3h, adds polyethers 15g stirring 30min, stops stirring, is filtered after standing 24h, obtains containing total chromium 3.56g/L,
Cr VI 0.5mg/L, iron 8.7g/L.The leachate of silica 0.4g/L.Remaining slag dry weight 950g, contains
Total chromium 0.23%, " hazardous waste judging standard-leaching characteristic identification " is pressed to the slag after washing
(GB5085.3-2007), HJ687-2014 alkali digestion procedure, is dissolved and is detected, water soluble hexavalent chromium
Content meet " chromic salts industry pollutant emission standard " regulation, water soluble hexavalent chromium is less than in waste residue
The second level discharge standard of 8mg/kg.
Extraction Fe3+Condition：Extractant is 30%TBP, and diluent is sulfonated kerosene.First material liquid is adjusted with hydrochloric acid
Acidity is 0.5mol, and adds a certain amount of NaCl so that Cl in solution-Reach 100g/L.Add chloric acid
Sodium aoxidizes 60min at 80 DEG C, and sodium chlorate addition is 0.3%, by it is ferrous oxidising be ferric iron.Extraction
Compared to O/A=2, time of contact 5min, extraction series is 6 grades, and raffinate contains Fe3+10mg/L.Carrying iron has
Machine mutually uses 5mol/L salt acid elutions, and compared to O/A=5/1, washing series is 4 grades, and wash water returns to carry out chromium
The leaching of slag.Load iron organic phase after washing is stripped iron with pure water, and O/A=10, time of contact are compared in back extraction
3min, back extraction series is 5 grades, obtains the strip liquor of iron content 30g/L.
Cr3+Extraction：Extractant is 10%P204+10% n-octyl alcohols+sulfonated kerosene, saponification degree 50%.Use hydrogen
Sodium oxide molybdena regulation has extracted ferric remaining phase, and regulation pH value is 3.Extraction phase than O/A=2, time of contact 5min,
Extraction series is 10 grades, and raffinate contains Cr3+1.5mg/L.The water washing that chromium organic phase pH value is 3 is carried,
Compared to O/A=3, series is 3 grades.Load chromium organic phase after washing is stripped with 1mol/L sulfuric acid, is compared
O/A=1/20, series is 4 grades, obtains the Cr of 35g/L3+Solution.
Claims (8)
1. a kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome, it is characterised in that the method
Comprise the following steps：
Step one, by chromium slag certain liquid-solid ratio and at a temperature of, add a certain amount of sulfuric acid and hydrochloric acid by chromium slag
In Cr VI be dissolved out with trivalent chromium；
After step 2, nitration mixture dissolving chromium slag, a certain amount of reducing agent is added to carry out the reduction of Cr VI；
Step 3, reduction add a certain amount of polyethers to stir and stand the regular hour after terminating, then
Carry out solid-liquor separation；
Step 4, the leachate that will be obtained extract ferric iron with TBP；
Step 5, the organic phase that will extract iron are washed with hydrochloric acid, wash away the impurity of entrainment, and hydrochloric acid is dense
It is 3~6mol/L to spend, and cleaning solution returns to carry out the leaching of chromium slag；Load iron organic phase after washing is entered with water
Row back extraction, 1~20min of time of contact, 10~40 DEG C of temperature is 1 compared to O/A:1~50:1, series
2~10 grades, obtain ferric chloride solution；
Step 6, will extract iron after raffinate with NaOH adjust pH value be 2~5, with P204 extract trivalent
Chromium；
Step 7, the organic phase that will extract chromium are washed with the solution that pH value is 2~4, wash away residual
Impurity, wash water returns to carry out the leaching of chromium slag；
Step 8, will wash after load chromium organic phase acid back extraction.
2. the processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome according to claim 1, its
It is characterised by, the liquid-solid ratio that the chromium slag described in step one is leached is 3:1~20:1, temperature is 60~100 DEG C,
Time is 20~120min；The nitration mixture of addition is sulfuric acid and hydrochloric acid, and sulphuric acid is the 0.1~1 of the chromium quantity of slag
Times, hydrochloric acid addition is 0.5~3 times of the chromium quantity of slag.
3. the processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome according to claim 1, its
It is characterised by, the addition of the reducing agent described in step 2 is the 0.1%~5% of the chromium quantity of slag, the reaction time is
0.5~5h.
4. the processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome according to claim 2, its
It is characterised by, the reducing agent is glucose, sodium sulfite, sodium pyrosulfite, sodium thiosulfate any one
Kind.
5. the processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome according to claim 1, its
Be characterised by, the polyethers addition described in step 3 for the chromium quantity of slag 0.3%~3%, the reaction time be 0.5~
2h, filters after standing 12~48h.
6. the processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome according to claim 1, its
It is characterised by, the extractant concentration described in step 4 is 10~30%, and diluent is sulfonated kerosene；Extraction is former
Liquid is by adding hydrochloric acid and sodium chloride, it is ensured that acidity is more than 0.5mol/L, and chloride content is more than 100g/L；TBP
Extraction iron time of contact be 1~20min, 10~40 DEG C of extraction temperature, extraction phase compares O/A=1:5~5:1, extraction
3~9 grades of series.
7. the processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome according to claim 1, its
It is characterised by, the P204 concentration described in step 6 is 10%~30%, and diluent is sulfonated kerosene, P204 soaps
Change degree is 20%~80%；Extraction time of contact is 1~20min, 10~40 DEG C of extraction temperature, extraction phase ratio
O/A=1:5~5:1, extract 3~9 grades of series.
8. the processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome according to claim 1, its
It is characterised by, the back extraction time of contact described in step 8 is 5~30min, temperature is 20~40 DEG C, phase
It is 1 than O/A:1~50:1, extraction series is 2~10 grades.
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