CN102409165A - Gradient arsenic removing method for high-arsenic metallurgical wastes - Google Patents
Gradient arsenic removing method for high-arsenic metallurgical wastes Download PDFInfo
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- CN102409165A CN102409165A CN2011103795100A CN201110379510A CN102409165A CN 102409165 A CN102409165 A CN 102409165A CN 2011103795100 A CN2011103795100 A CN 2011103795100A CN 201110379510 A CN201110379510 A CN 201110379510A CN 102409165 A CN102409165 A CN 102409165A
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 89
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 32
- 238000002386 leaching Methods 0.000 claims abstract description 28
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims abstract description 19
- 229940000489 arsenate Drugs 0.000 claims abstract description 18
- 229960002594 arsenic trioxide Drugs 0.000 claims description 32
- 239000002893 slag Substances 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims 2
- 229910052802 copper Inorganic materials 0.000 abstract description 12
- 239000010949 copper Substances 0.000 abstract description 12
- 239000011133 lead Substances 0.000 abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052787 antimony Inorganic materials 0.000 abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 8
- 239000000428 dust Substances 0.000 abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052718 tin Inorganic materials 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 239000004332 silver Substances 0.000 abstract description 4
- 238000011282 treatment Methods 0.000 abstract description 4
- 239000000779 smoke Substances 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 abstract 3
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 abstract 1
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 abstract 1
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 abstract 1
- 229940047047 sodium arsenate Drugs 0.000 abstract 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000001698 pyrogenic effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 150000001495 arsenic compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229940000488 arsenic acid Drugs 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- -1 white arsenic Chemical class 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- GVPLVOGUVQAPNJ-UHFFFAOYSA-M potassium;hydron;trioxido(oxo)-$l^{5}-arsane Chemical compound [K+].O[As](O)([O-])=O GVPLVOGUVQAPNJ-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- DBQFKMXHMSMNRU-UHFFFAOYSA-N [Zn].[Co].[Cu] Chemical compound [Zn].[Co].[Cu] DBQFKMXHMSMNRU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CVXNLQMWLGJQMZ-UHFFFAOYSA-N arsenic zinc Chemical compound [Zn].[As] CVXNLQMWLGJQMZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- RKYSWCFUYJGIQA-UHFFFAOYSA-H copper(ii) arsenate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RKYSWCFUYJGIQA-UHFFFAOYSA-H 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention provides a gradient arsenic removing method for high-arsenic metallurgical wastes, which is generally suitable for comprehensive arsenic removing treatments of high-arsenic smoke dust generated in the smelting process of lead, zinc, antimony, copper, tin and the like, high-arsenic anode mud generated in the electrolytic process of wet lead, silver, copper and the like and other metallurgical wastes. The method comprises two stages of water leaching arsenic removal and oxidizing acid leaching arsenic removal and specifically comprises the following steps of: first, selectively dissolving out free arsenic trioxide and water soluble arsenate (like sodium arsenate and potassium arsenate) through water leaching; and then further leaching out indissolvable arsenate and arsenic sulfide in the water leaching residue as well as little incomplete arsenic trioxide dissolved out by water by using a mixed leaching liquor of acid and water soluble oxidizing agent. The method provided by the invention has the advantages of low consumption of acid and alkali, high arsenic removing efficiency, safety, environment friendliness and suitability for arsenic removing treatment of various arsenic contained metallurgical wastes, in particular for arsenic removing treatment of the smoke dust with high content of free arsenic trioxide.
Description
Technical field
The present invention relates to the arsenic removing method of the high arsenic metallurgical waste that a kind of pyrogenic process or hydrometallurgy process produce, like the comprehensive dearsenification processing of the metallurgical wastes such as the high arsenic anode sludge that produce in the electrolytic processes such as the high-arsenic dust that produces in the smelting processes such as lead, zinc, antimony, copper, tin and lead bullion, silver, copper; Being particularly related to the high dearsenification that contains the arsenic metallurgical waste of free white arsenic content handles.
Background technology
Arsenic normal and precious metal associations such as lead, zinc, antimony, copper, tin and gold and silver, indium, platinum, rhodium, palladium in the earth's crust.Because arsenic compound fusing point such as arsenic and white arsenic and sublimation temperature are relatively low, in pyrometallurgical processes, thereby arsenic compound is easy to produce a large amount of high-arsenic dusts with flue gas form volatilizing and enriching; Arsenate ion and heavy metal ion form high arsenic slag charge (like the high arsenic anode sludge of electrolysis generation) in the hydrometallurgy process.At present, it is the high arsenic metallurgical waste of representative with the cigarette ash and the anode sludge that market exists a large amount of, except arsenic content very high (3-30%), also contains valuable metals such as a large amount of lead, zinc, antimony, copper, gold and silver, indium simultaneously in these waste materials, and recovery value is high.Yet arsenic is a kind of toxic substance, and high-load arsenic is to the environment huge harm and be difficult to factors such as processing, greatly reduces the marketable value of these high arsenic metallurgical wastes.Therefore, the efficient dearsenic technique of developing high arsenic metallurgical waste has become extremely urgent instantly demand.
Arsenic usually exists with the form of white arsenic, arsenate and red arsenic in metallurgical waste, and the arsenic removing method of report comprises two kinds of pyrogenic process and wet methods at present.
The pyrogenic process dearsenification is to utilize the low-boiling characteristics of arsenic compound such as white arsenic, carries out dearsenification through the mode of intensification volatilized arsenic compound.Because compounds such as the lead that part is higher slightly than arsenic compound boiling point, antimony, tin also can volatilize along with white arsenic, the separating effect of pyrogenic process dearsenification is relatively poor, and the white arsenic flue gas that produces causes serious secondary pollution.Chinese patent CN101942567A " a kind of contain the method that the compound arsenic antimony compounds of the multivalence attitude anode sludge removes arsenic and antimony " has reported a kind of method of carrying out the pyrogenic process dearsenification through the dynamic vacuum evaporation; This method can reduce pyrogenic process dearsenification temperature to alleviate the volatilization of compounds such as lead, antimony, tin; But very high to equipment requirements, the domestic and international at present high-temperature vacuum furnace that does not all also satisfy scale operation.
The present bibliographical information of wet method dearsenication is maximum, mainly utilizes the soda acid both sexes characteristic of white arsenic, through acidleach or the alkali process of soaking arsenic element is contained the mode that the arsenic waste material transfers to the aqueous solution from solid and carries out dearsenification.Alkali soaks dearsenification and normally through alkaline solutions such as sodium hydroxide, the molten sodium sulphite of yellow soda ash arsenic is converted into water miscible sodium arseniate; Regulate pH of leaching solution like Chinese patent CN101200776A " a kind of method of dearsenification from trioxygen-containingization two arsenic flue dust " with sodium hydroxide, yellow soda ash or ammoniacal liquor, add ydrogen peroxide 50 again and leach dearsenification; Chinese patent CN1375565A " a kind of copper zinc cobalt material removes the method for arsenic " then directly adopts the sodium hydroxide concentrated alkali solution to leach dearsenification, and Chinese patent CN1312392 and CN101328539A then adopt sodium sulphite and sodium hydroxide processing contains arsenic smoke dust as leach liquor.But solubleness is very little in alkaline solution for indissoluble arsenate (like cupric arsenate, ferric arsenate and Tricalcium arsenate), and therefore to containing the waste material of indissoluble arsenate, alkali soaks and do not reach ideal dearsenification effect.
The acidleach dearsenification normally is converted into water miscible arsenic acid or arsenus acid through sulfuric acid, hydrochloric acid or the like acid solution with arsenic, even also have good dissolving ability for the indissoluble arsenate.Therefore through regulating appropriate acidity, acidleach contains the arsenic waste material to various solids can reach ideal dearsenification effect.If but there are a large amount of arsenides (like arsenic zinc, lead arsenide etc.) in the waste material, strong acid and containing can produce the arsine gas of severe toxicity under reducing metal (like the zinc) condition.Hydrogen arsenide and the arsenus acid solubleness in acid solution is less relatively, produces potential safety hazard thereby volatilize easily under the high density.
For high arsenic metallurgical waste, the content of indissoluble arsenate is generally all than higher, and alkali soaks dearsenification and is difficult to reach ideal effect, and the acidleach dearsenification is effective but have potential safety hazard.Based on this contradiction; Liang Rongxuan etc. (" coloured mining and metallurgy "; 2006,22 (6): 27-29) adopt the sodium-salt calcination method, through the indissoluble arsenate in the waste material being converted into water miscible sodium arseniate with sodium salt is baking mixed; Thereby reach ideal dearsenification effect, similarly patent such as Chinese patent CN1093755A " safety dearsenicating technology for high-arsenic material ".But this method produces in mixing, roasting and furnace charge cargo handling process and contains the arsenic dust in a large number, its secondary pollution degree even more serious than the white arsenic flue gas of pyrogenic process dearsenification generation.Thereby, do not have also at present in the prior art that a kind of method can satisfy efficiently simultaneously, a dearsenification requirement of safety, environmental protection.
Summary of the invention
It is low that the object of the invention aims to provide a kind of production cost, selects stripping property good, the high arsenic metallurgical waste gradient arsenic removing method of efficient, safety, environmental protection.
Technical scheme of the present invention comprises water logging and two steps of oxidation acid leaching:
(1) water logging: at first high arsenic metallurgical waste is adopted 50～100 ℃ of hot water stripping free state white arsenics and water miscible arsenate, filter and obtain water logging slag and leach liquor;
(2) oxidation acid leaching: with the incomplete white arsenic of stripping in arsenate, red arsenic and the water logging step of water logging slag employing acid and water-soluble oxidizers mixing leach liquor stripping indissoluble;
The mass percent of arsenic is not less than 3 in the said high arsenic metallurgical waste.
Leach liquor condensation-crystallization in said (1) step is separated out white arsenic, and mother liquor continues to return the leaching that circulates of water logging step, to reduce the arsenic-containing waste water amount of whole technology.
The crux of process innovation of the present invention is that the present invention proposes the method for first water logging rear oxidation acidleach coupling first and carries out gradient dearsenification processing for high arsenic metallurgical waste.Promptly earlier free white arsenic in the high arsenic metallurgical waste (arsenic as in the high arsenic metallurgical dust waste material mainly exists with the white arsenic form) and water miscible arsenate (like sodium arseniate and potassium dihydrogen arsenate) are removed, because white arsenic has bigger solubleness (as 98.5 ℃ time solubleness reach 8.18g/100g) in hot water through hot water; Slag after the water logging and then through acidleach stripping indissoluble arsenate; And under oxidizing condition, red arsenic are removed, and hydrogen arsenide can be converted into white arsenic fast under oxidizing condition, continue to obtain to remove.
The contrast traditional method, the advantage of this method is:
1) production cost is low: water logging is consumption acids, alkali not, has reduced production cost;
2) select stripping property: water logging has extraordinary selectivity to white arsenic, and other heavy metal ion can stripping like lead, antimony, copper, tin etc.
3) environment friendly: traditional alkali soak or method leach liquor such as acidleach in arsenic element exist with arsenic acid or arsenous anion ion; Need to adopt lime treatment also to produce a large amount of Tricalcium arsenate waste residues, and Tricalcium arsenate is leached easily again and produce secondary pollution by acidic medium.White arsenic in the water logging leach liquor of the present invention is mainly physical dissolution, can separate out highly purified white arsenic product through simple crystallisation by cooling, has avoided the generation of Tricalcium arsenate waste residue.In addition, the metal ion content in the leach liquor of water logging very low (little potassium ion and sodium ion), the mother liquor salinity behind the heavy arsenic of leach liquor is low, can recycle for a long time, greatly reduces wastewater discharge.
4) production security: the dissolving of white arsenic in water can not produce and contain the arsenic toxic gas; Total arsenic amount can remove (free white arsenic content Gao Yuegao through water logging in the high arsenic metallurgical waste more than 50%; The water soaking dearsenication amount is big more), arsenic content reduces greatly in the water logging slag; Oxidation acid leaching adds excessive oxidant can be oxidized to arsenic acid with arsenus acid, and hydrogen arsenide then is oxidized to white arsenic, thereby guarantees the production security of acidleach process.
5) applied widely: water logging is to free white arsenic and water miscible arsenate, and oxidation acid leaching is to indissoluble arsenate and red arsenic.After water logging-oxidation acid leaching coupling, dearsenification efficient can satisfy the at present all kinds of processing requirements that the dearsenification of arsenic metallurgical waste is handled that contain, and the dearsenification that is particularly useful for the high metallurgical waste of free white arsenic content is handled; Thereby realize the recovery marketable value of high arsenic metallurgical waste.
The contriver finds that through further research the present invention can comprise following preferred version:
Liquid-solid ratio in said (1) step in the water logging process is 1: 3～8g/mL.
Adopt the mode that stirs to leach in the water logging process in said (1) step, extraction time is 2～8 hours.
The concentration of acid is between 0.1～4.0mol/L described in said (2) step.
Acid is sulfuric acid, hydrochloric acid or nitric acid described in said (2) step.
The water logging slag is 1: 3～8g/mL with the solid-to-liquid ratio of mixing leach liquor.
The amount of the water-soluble oxidizers that said (2) were added in the step is 1～4 times that arsenic reacts required molar weight in the oxidation water logging slag.
Water-soluble oxidizers is a potassium permanganate in said (2) step, perchloric acid is received or ydrogen peroxide 50.
Method of the present invention specifically may further comprise the steps:
1, water logging: the water soluble that utilizes white arsenic; And the water-fast character of compound of heavy metal ion such as lead, antimony, tin, zinc and copper is carried out the selectivity stripping through water logging with free white arsenic and water miscible arsenate (like sodium arseniate and potassium dihydrogen arsenate).For improving leaching efficiency, adopt 50-100 ℃ hot water, liquid-solid ratio 1: 3～8, extraction time was advisable in 2～8 hours.High arsenic metallurgical waste through water logging after, the 50%-85% of its total arsenic amount can remove.Solid-liquid mixtures filtered while hot after the water logging obtains the water logging slag of one section dearsenification, and the leach liquor crystallisation by cooling is separated out the white arsenic product, and crystalline mother solution returns and leaches new waste material, recycles for a long time.
2, oxidation acid leaching: indissoluble arsenate in the water logging slag and red arsenic and a small amount of incomplete white arsenic of water logging stripping, adopt the mixing leach liquor of " acid+oxygenant " to leach once more.Mixing leach liquor with " sulfuric acid+potassium permanganate " is an example; Sulfuric acid concentration is 0.1～4mol/L, and the addition of potassium permanganate is added doubly by 1～4 of last arsenic mol in the slag and added, and extraction temperature is 20～80 ℃; Liquid-solid ratio is 1: 3～8, and extraction time is to be advisable in 2～8 hours.The dearsenification slag that solid-liquid mixtures filtered while hot after the acidleach obtains, its arsenic content are lower than 2% (usually between 0.5-1.5%).
Description of drawings
Accompanying drawing is the inventive method particular flow sheet.
Embodiment
Following examples are intended to explain the present invention rather than to further qualification of the present invention.
Embodiment 1
Raw material, the high-arsenic dust of certain copper smelting plant institute output of first ground, its staple is (%): As 25.38%, and Cu 4.41%, and Pb 45.28%.Get above-mentioned raw materials 100g, add water 400mL, be warmed up to 95 ℃ then, constant temperature stirred after 3 hours, and heat filtering obtains the 86.43g arsenic content and be 13.88% water logging slag, and arsenic-removing rate is 52.73%.The leach liquor crystallisation by cooling is separated out white arsenic 11.27g.The water logging slag continues to adopt oxidation acid leaching, and oxygenant is a ydrogen peroxide 50, and leach liquor consists of: (2mol/L H
2SO
4Solution 200mL)+(30%H
2O
2100mL), 70 ℃ of extraction temperatures, constant temperature stirred 4 hours.Gained filter residue arsenic content is 1.61% behind the oxidation acid leaching, and leaching yield is 90.4%.Comprehensive water logging and acidleach, total arsenic-removing rate is 95.35%.It is 98.3% that filtrating condensation-crystallization after the water logging is separated out the white arsenic product gas purity.
Embodiment 2
Raw material, the high-arsenic dust of certain institute of lead-zinc smelting factory output of second ground, its staple (%): As 21.25%, and Pb 20.43%, and Cu 3.14%, and Zn 7.28%.Get above-mentioned raw materials 100g, add water 300mL, be warmed up to 85 ℃ then, constant temperature stirred after 4 hours, heat filtering, and arsenic content is 11.54% in the water logging slag, leaching yield is 54.30%.The water logging slag continues to adopt oxidation acid leaching, and oxygenant is a ydrogen peroxide 50, and leach liquor consists of: (1mol/L H
2SO
4Solution 300mL)+(15%KMn
2O
4100mL), 70 ℃ of extraction temperatures, constant temperature stirred 4 hours.Gained filter residue arsenic content is 1.42% behind the oxidation acid leaching, and leaching yield is 91.3%.Comprehensive water logging and acidleach, total arsenic-removing rate is 95.10%.It is 98.5% that filtrating condensation-crystallization after the water logging is separated out the white arsenic product gas purity.
Embodiment 3
Raw material, the high arsenic anode sludge of the third ground electrolysis plant institute output, its staple (%): As 13.28%, Pb22.15%, Cu 3.23%.Get above-mentioned raw materials 100g, add water 500mL, be warmed up to 90 ℃ then, constant temperature stirred after 3 hours, heat filtering, and arsenic content is 7.89% in the water logging slag, leaching yield is 43.43%.The water logging slag continues to adopt oxidation acid leaching, and oxygenant is a ydrogen peroxide 50, and leach liquor consists of: (0.8mol/L H
2SO
4Solution 300mL)+(15%NaClO
4100mL), 27 ℃ of extraction temperatures (room temperature) stirred 4 hours.Gained filter residue arsenic content is 1.23% behind the oxidation acid leaching.Comprehensive water logging and acidleach, total arsenic-removing rate is 93.21%.It is 92.2% that filtrating condensation-crystallization after the water logging is separated out the white arsenic product gas purity.
Claims (10)
1. the gradient arsenic removing method of a high arsenic metallurgical waste comprises water logging and two steps of oxidation acid leaching:
(1) water logging: at first high arsenic metallurgical waste is adopted 50～100 ℃ of hot water stripping free state white arsenics and water miscible arsenate, filter and obtain water logging slag and leach liquor;
(2) oxidation acid leaching: with the incomplete white arsenic of stripping in arsenate, red arsenic and the water logging step of water logging slag employing acid and water-soluble oxidizers mixing leach liquor stripping indissoluble;
The mass percent of arsenic is not less than 3 in the said high arsenic metallurgical waste.
2. method according to claim 1, the leach liquor condensation-crystallization in said (1) step is separated out white arsenic, and mother liquor continues to return the leaching that circulates of water logging step.
3. method according to claim 1 and 2 is characterized in that: the liquid-solid ratio in said (1) step in the water logging process is 1: 3～8g/mL.
4. method according to claim 3 is characterized in that: adopt the mode that stirs to leach in the water logging process in said (1) step, extraction time is 2～8 hours.
5. method according to claim 1 and 2, the concentration of acid is between 0.1～4.0mol/L described in said (2) step.
6. method according to claim 5, acid is sulfuric acid, hydrochloric acid or nitric acid described in said (2) step.
7. method according to claim 5, the water logging slag is 1: 3～8g/mL with the solid-to-liquid ratio of mixing leach liquor.
8. method according to claim 1 and 2, the amount of the water-soluble oxidizers that said (2) were added in the step is 1～4 times that arsenic reacts required molar weight in the oxidation water logging slag.
9. method according to claim 8, water-soluble oxidizers is a potassium permanganate in said (2) step, perchloric acid is received or ydrogen peroxide 50.
10. method according to claim 1 and 2, extraction temperature is 20～80 ℃ in said (2) step.
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| CN102634672A (en) * | 2012-04-17 | 2012-08-15 | 金川集团有限公司 | Method for treating arsenic-containing waste copper slag |
| CN103555952A (en) * | 2013-11-04 | 2014-02-05 | 青川县天运金属开发有限公司 | Harmless treatment method for multi-metal coexisting arsenic-containing waste |
| CN103894240A (en) * | 2014-04-01 | 2014-07-02 | 李灏呈 | Regeneration method for arsenic poisoning selective catalytic reduction denitration catalyst |
| CN105039722A (en) * | 2015-06-29 | 2015-11-11 | 中南大学 | Method for preferably removing arsenic in lead and antimony smoke |
| CN106636657A (en) * | 2016-11-14 | 2017-05-10 | 中南大学 | Method for pre-removing arsenic in arsenic-containing soot |
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| CN110468282A (en) * | 2019-09-20 | 2019-11-19 | 北方铜业股份有限公司 | The alkali of arsenic-containing material soaks arsenic removing method |
| CN113930628A (en) * | 2021-09-03 | 2022-01-14 | 湖南有色金属研究院有限责任公司 | Comprehensive recovery method of arsenic-antimony smoke |
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| CN103894240B (en) * | 2014-04-01 | 2016-01-20 | 李灏呈 | A kind of renovation process of arsenic poisoning denitrifying catalyst with selective catalytic reduction |
| CN103894240A (en) * | 2014-04-01 | 2014-07-02 | 李灏呈 | Regeneration method for arsenic poisoning selective catalytic reduction denitration catalyst |
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