CN109354149A - A kind of processing method of the waste water containing heavy metal-polluted acid - Google Patents
A kind of processing method of the waste water containing heavy metal-polluted acid Download PDFInfo
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- CN109354149A CN109354149A CN201811336802.4A CN201811336802A CN109354149A CN 109354149 A CN109354149 A CN 109354149A CN 201811336802 A CN201811336802 A CN 201811336802A CN 109354149 A CN109354149 A CN 109354149A
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- acid
- heavy metal
- waste
- waste water
- water containing
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- 239000002253 acid Substances 0.000 title claims abstract description 73
- 239000002351 wastewater Substances 0.000 title claims abstract description 21
- 238000003672 processing method Methods 0.000 title claims abstract description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002699 waste material Substances 0.000 claims abstract description 50
- 239000002893 slag Substances 0.000 claims abstract description 20
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 238000004073 vulcanization Methods 0.000 claims abstract description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003546 flue gas Substances 0.000 claims abstract description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 13
- 239000005864 Sulphur Substances 0.000 claims abstract description 12
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 230000033116 oxidation-reduction process Effects 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 229910021543 Nickel dioxide Inorganic materials 0.000 claims description 2
- 229910001570 bauxite Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 41
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 241001062472 Stokellia anisodon Species 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 18
- 229910052785 arsenic Inorganic materials 0.000 description 14
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 9
- 235000001508 sulfur Nutrition 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- YZLDZQVPPLMHGJ-UHFFFAOYSA-N iron(2+);sulfane Chemical compound S.[Fe+2] YZLDZQVPPLMHGJ-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- -1 sulfide hydrogen Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000004272 Eragrostis cilianensis Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FGIWMSAVEQNPPQ-UHFFFAOYSA-N arsenic;hydrate Chemical compound O.[As] FGIWMSAVEQNPPQ-UHFFFAOYSA-N 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/73—After-treatment of removed components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention discloses a kind of processing method of waste water containing heavy metal-polluted acid, belongs to technical field of waste water processing.The method of the invention is that will smelt the purified rear resulting sulfur dioxide of furnace flue gas to carry out catalysis reduction treatment, obtains the sulphur product such as sulfide hydrogen；The sulphur product is introduced into waste acid, sulfide precipitation is carried out with heavy metal ion in waste acid and arsenic ion and reacts；Waste acid solution after vulcanization reaction is separated by solid-liquid separation, products therefrom arsenic sulfide slag and heavy metal vulcanized slag precipitating are recycled.The method of the present invention relies on the cleaning equipment of the produced high-concentration sulfur dioxide flue gas acid preparing technique of sulphide ore smelting, using the purified sulfur dioxide of high-sulfur flue gas acid preparing as raw material, sulphur product processing waste acid is produced through catalysis reduction, the waste acid of the sector generation can not only efficiently be handled, it also can be recycled to arsenic sulfide slag, the method administers the waste acid of its acid manufacturing processes generation using the self-produced raw material sulfur dioxide of enterprise, reduces the cost of enterprise governance waste acid, has significant economy, environmental benefit.
Description
Technical field
The present invention relates to a kind of processing methods of waste water containing heavy metal-polluted acid, belong to technical field of waste water processing.
Background technique
After the high-concentration sulfur dioxide flue gas that smelting industry generates is purified, it can be used for preparing sulfuric acid, in high-sulfur flue gas acid
During cleanization, the waste acid largely containing heavy metals such as arsenic, lead can be generated.Waste acid is one kind by troilite and metallurgical off-gas acid-making
The acid waste water containing a large amount of arsenic that process generates.Such waste water often has the characteristics that acid height, arsenic content are high.Its pollution tool
There is generality, i.e. major pollutants are heavy metal (arsenic, cadmium, copper, lead etc.).Such acidic arsenic-containing waste water has stronger corrosion
Property, on the one hand pipeline and structures are caused to corrode, on the other hand, due in waste water there are a large amount of arsenic, can to people, animals and plants,
Water body and soil cause damages.
The chemical method of processing acid water has very much, mainly includes lime neutralisation, coagulant sedimentation and vulcanization etc..
Lime neutralisation handles waste acid, and since the solubility of calcium arsenate and calcium arsenite is lower, which is not able to satisfy arsenic qualified discharge
It is required that and water outlet pH higher, generate a large amount of solid waste, easily cause secondary pollution.Coagulant sedimentation, which is also easy to produce, largely to be contained
Arsenic waste residue easily causes secondary pollution to ambient enviroment if the storage of these waste residues is improper.Vulcanization administers waste acid, and process uses
Vulcanizing agent price costly, and when using vulcanized sodium, potassium sulfide etc. as vulcanizing agent, great amount of soluble metal cation enters
Waste acid, so increase solid waste in and slag quality and yield；And because of the readily soluble characteristic of soluble metal cationic (sodium, potassium etc.),
With the dissolution for solidifying solable matter in slag, secondary pollution is easily brought.
Waste acid is since arsenic content is high, strong toxicity, and arsenic has metal and nonmetallic duality and intractability, always
It is the hot spot of Heavy Metals in Waters contamination control area research.For such waste water, researchers also proposed corresponding processing
Method and technique.Chinese patent CN103553248B discloses a kind of heavy metal-polluted acid waste water reclaiming recovery method and device,
Waste acid separation is realized by electrodialysis anions and canons film.The technique generates intractable neutralization slag, and it is improper to store, and easily causes two
Secondary pollution, anions and canons film is expensive, handles such waste water and easily blocks, is damaged, and additionally introduces vulcanizing agent in the technique,
Also improve corresponding cost；Chinese patent CN106830275A discloses a kind of ferrous sulfide (FeS) oxidation dissolution and goes to remove water
The method of body middle and high concentration As (III) is synthesized FeS by chemical precipitation, is reacted using its oxidation dissolution to remove in waste water
Arsenic.But after the method ferrous sulfide enters waste acid, iron content chemical reaction waste residue can be generated, the yield of dangerous solid waste is increased.It is Chinese special
Sharp CN107619068A discloses a kind of iron sulfonium and prepares method of the hydrogen sulfide for waste acid processing, leaching broken by iron sulfonium solid
Enter Acidic Liquid and prepare hydrogen sulfide, uses the hydrogen sulfide treatment waste acid of preparation.The method can generate a large amount of ferric sulfate etc. and neutralize slag, increase
Add the yield of dangerous solid waste, and the acid solution that the technique immerses, as what reaction carried out recycles, acid concentration is thinning, meeting
Make to react slack-off or can not carry out, therefore acid solution need to be rejoined, a large amount of acid solution improves processing cost.
Summary of the invention
The purpose of the present invention is to provide a kind of processing methods of waste water containing heavy metal-polluted acid, rely on flue gas acid preparing process,
Using the sulfur dioxide after high-sulfur gas cleaning as raw material, the sulphur product such as sulfide hydrogen processing waste acid is produced through catalysis reduction, not only
The waste acid of the sector generation can efficiently be handled, moreover it is possible to be recovered to arsenic sulfide slag, realize efficient, the low-cost processes of waste acid, have
There is significant economic and environmental benefit.
This invention is through the following steps that realize:
(1) the purified rear resulting sulfur dioxide of furnace flue gas will be smelted and carry out catalysis reduction treatment, obtain the sulphur such as sulfide hydrogen
Product；
(2) sulphur product obtained in step (1) is introduced into waste acid, it is heavy to carry out vulcanization with heavy metal ion in waste acid and arsenic ion
It forms sediment and reacts；
(3) the waste acid solution after vulcanization reaction in step (2) is separated by solid-liquid separation, recycles products therefrom arsenic sulfide slag and a huge sum of money
Belong to vulcanized slag precipitating.
In catalysis reduction treatment process described in step (1) of the present invention: used reducing agent can be H2, H2It restored
Catalyst employed in journey is V2O5, bauxite, Ru/Al2O3、Co/Al2O3、Co-Mo/Al2O3、Ru/TiO2Or load NiO
R- Al2O3, catalysis reduction temperature is 300 ~ 550 DEG C, H2With SO2Volume ratio: V(H2)/V(SO2)=1 ~ 4.
In step (1) of the present invention in catalysis reduction treatment process: used reducing agent can also be CH4, CH4It restored
Catalyst employed in journey is Ce (La) Ox or adulterates Ce (La) Ox of Cu or Ni, and catalysis reduction temperature is 600 ~ 800
DEG C, CH4With SO2Volume ratio: V(CH4)/V(SO2)=1 ~ 3.
In step (1) of the present invention in catalysis reduction treatment process: used reducing agent can also be NH3, NH3It restored
Catalyst employed in journey is TiO2The sulfide catalyst of carrying transition metal Mn, Fe, Co, Ni or Cu, catalysis reduction
Temperature is 600 ~ 800 DEG C, NH3With SO2Volume ratio: V(NH3)/V(SO2)=(3 ~ 5): (2 ~ 4).
Preferably, the introduction volume of step (2) hydrogen sulfide of the present invention is 0.5 ~ 3ml/s.
Preferably, the oxidation-reduction potential of step (2) vulcanization reaction of the present invention is 6 ~ 76mV.
Waste acid in step (2) of the present invention can be pre-processed first, and the impurity in waste acid is removed；As's contains in waste acid
Amount is in 4000 ~ 20000mg/L.
Be separated by solid-liquid separation in step (3) of the present invention to be filtering, screening, sedimentation, centrifugation etc..
Advantages of the present invention and effect:
(1) present invention is raw material using sulfur dioxide after purification, and catalysis reduction prepares the sulphur product such as sulfide hydrogen, avoids traditional gold
The problem of belonging to adding for sulfide, leading to the increase of sediment solid waste.Not only high-efficient purification waste acid, but also can be recovered to valuable in waste acid
Metal.The method sulfur dioxide and waste acid self-produced using smelting industry, are combined improvement, the dioxy after relying on the sector relieving haperacidity
Change sulfur catalysis reduction, obtain sulphur product high-efficient purification waste acid, simultaneously, moreover it is possible to be recovered to corresponding resource, be controlled for enterprise pollution object
Reason alleviates financial burden, has significant economic and environmental benefit.
(2) the method for the invention is not required to additionally introduce vulcanizing agent, and the sulphur such as sulfide hydrogen generated by catalysis reduction produce
Object administers waste acid, can not only efficiently, low-cost processes waste acid, moreover it is possible to recycling wherein valuable metal；It is controlled using the self-produced raw material of the factory
The waste acid of its generation is managed, there is significant resource benefit.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the present invention；
Fig. 2 is H2Reduction method SO2Removal rate and sulfide yield；
Fig. 3 is CH4Reduction method SO2Removal rate and sulfide yield；
Fig. 4 is NH3Reduction method SO2Removal rate and sulfide yield.
Specific embodiment
Invention is further described in detail combined with specific embodiments below, but protection scope of the present invention is not limited to
The content.
Embodiment 1
Using purified sulfur dioxide flue gas in smelting lead acid-making process as raw material, using H2For reducing agent, with Co-Mo/
Al2O3It is 300 DEG C in temperature for catalyst, V(H2): V(SO2Catalytic reduction reaction is carried out under conditions of)=3, obtains Containing Sulfur
The reduced sulfurs product such as hydrogen is introduced into the waste acid for being 10000mg/L containing arsenic concentration by product hydrogen sulfide with the introduction volume of 1ml/s
Vulcanization reaction is carried out, the oxidation-reduction potential for controlling vulcanization reaction is 50mV, to products therefrom arsenic sulfide slag and a huge sum of money after reaction
Belong to vulcanized slag precipitating and is filtered recycling.
As can be seen from Figure 2, H2Reduction method is with Co-Mo/Al2O3When for catalyst, SO2Removal rate be 98%, vulcanize produce
Amount is 88%, shows that the method can a large amount of output sulfide removal waste acids.
After the processing of 1 the present embodiment of table in waste acid heavy metal content
Embodiment 2
Using purified sulfur dioxide flue gas in pyrite flue gas acid preparing technique as raw material, using H2For reducing agent, with NiO/r-
Al2O3(the r- Al of load NiO2O3) it is catalyst, it is 320 DEG C in temperature, V(H2): V(SO2It carries out being catalyzed under conditions of)=2 also
Original reaction, obtains the reduced sulfurs product such as sulfide hydrogen, by product hydrogen sulfide with the introduction volume of 1.5ml/s, introduces and contains arsenic concentration
To carry out vulcanization reaction in the waste acid of 9000mg/L, the oxidation-reduction potential for controlling vulcanization reaction is 20mV, to gained after reaction
Product arsenic sulfide slag and heavy metal vulcanized slag precipitating carry out screening recycling.
As can be seen from Figure 2, H2Reduction method is with NiO/r-Al2O3When for catalyst, SO2Removal rate be 98%, vulcanize produce
Amount is 68%, shows that the method can a large amount of output sulfide removal waste acids.
After the processing of 2 the present embodiment of table in waste acid heavy metal content
Embodiment 3
Using purified sulfur dioxide flue gas in copper blast furnace off-gas acid-making process as raw material, using CH4For reducing agent, adulterated with Cu
Ce (La) Ox be catalyst, temperature be 675 DEG C, V(H2): V(SO2Catalytic reduction reaction is carried out under conditions of)=2, is contained
The reduced sulfurs product such as hydrogen sulfide introduces the dirt for being 15000mg/L containing arsenic concentration by product hydrogen sulfide with the introduction volume of 2ml/s
Vulcanization reaction is carried out in acid, the oxidation-reduction potential for controlling vulcanization reaction is 60mV, to products therefrom arsenic sulfide slag after reaction and
Heavy metal vulcanized slag precipitating is filtered recycling.
From figure 3, it can be seen that CH4When reduction method is using Cu/Ni-Ce (La) Ox as catalyst, SO2Removal rate be 100%, vulcanization
Produce amount is 83%, shows that the method can a large amount of output sulfide removal waste acids.
After the processing of 3 the present embodiment of table in waste acid heavy metal content
Embodiment 4
Using purified sulfur dioxide flue gas in smelting lead acid-making process as raw material, using NH3For reducing agent, with CoS2-
TiO2It is 700 DEG C in temperature for catalyst, V(H2): V(SO2Catalytic reduction reaction is carried out under conditions of)=4:3, obtains Containing Sulfur
The reduced sulfurs product such as hydrogen introduces the waste acid for being 20000mg/L containing arsenic concentration by product hydrogen sulfide with the introduction volume of 2.5ml/s
Middle carry out vulcanization reaction, the oxidation-reduction potential for controlling vulcanization reaction is 70mV, to products therefrom arsenic sulfide slag after reaction and again
Metal vulcanized slag precipitating carries out sedimentation recycling.
As can be seen from Figure 4, NH3Reduction method is with CoS2-TiO2When for catalyst, SO2Removal rate be 100%, vulcanize produce
Amount is 85%, shows that the method can a large amount of output sulfide removal waste acids.
After the processing of 4 the present embodiment of table in waste acid heavy metal content
Claims (6)
1. a kind of processing method of waste water containing heavy metal-polluted acid, which is characterized in that specifically includes the following steps:
(1) the purified rear resulting sulfur dioxide of furnace flue gas will be smelted and carry out catalysis reduction treatment, obtain the sulphur such as sulfide hydrogen
Product；
(2) sulphur product obtained in step (1) is introduced into waste acid, it is heavy to carry out vulcanization with heavy metal ion in waste acid and arsenic ion
It forms sediment and reacts；
(3) the waste acid solution after vulcanization reaction in step (2) is separated by solid-liquid separation, recycles products therefrom arsenic sulfide slag and a huge sum of money
Belong to vulcanized slag precipitating.
2. the processing method of the waste water containing heavy metal-polluted acid according to claim 1, it is characterised in that: catalysis is gone back in step (1)
During the reason of original place: used reducing agent is H2, catalyst V2O5, bauxite, Ru/Al2O3、Co/Al2O3、Co-Mo/
Al2O3、Ru/TiO2Or the r- Al of load NiO2O3, catalysis reduction temperature is 300 ~ 550 DEG C, V(H2)/V(SO2)=1 ~ 4.
3. the processing method of the waste water containing heavy metal-polluted acid according to claim 1, it is characterised in that: catalysis is gone back in step (1)
During the reason of original place: used reducing agent is CH4, catalyst is Ce (La) Ox or Ce (La) Ox of doping Cu or Ni,
Being catalyzed reduction temperature is 600 ~ 800 DEG C, V(CH4)/V(SO2)=1 ~ 3.
4. the processing method of the waste water containing heavy metal-polluted acid according to claim 1, it is characterised in that: catalysis is gone back in step (1)
During the reason of original place: used reducing agent is NH3, used catalyst is TiO2Carrying transition metal Mn, Fe, Co, Ni or
The sulfide catalyst of Cu, catalysis reduction temperature are 600 ~ 800 DEG C, V(NH3)/V(SO2)=(3 ~ 5): (2 ~ 4).
5. the processing method of the waste water containing heavy metal-polluted acid according to claim 1, it is characterised in that: step (2) sulphur product
Introduction volume is 0.5 ~ 3ml/s.
6. the processing method of the waste water containing heavy metal-polluted acid according to claim 1, it is characterised in that: step (2) vulcanization reaction
Oxidation-reduction potential be 6 ~ 76mV.
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