CN105417767B - A method of going arsenic removal from sulfuric acid acid water - Google Patents
A method of going arsenic removal from sulfuric acid acid water Download PDFInfo
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- CN105417767B CN105417767B CN201510771985.2A CN201510771985A CN105417767B CN 105417767 B CN105417767 B CN 105417767B CN 201510771985 A CN201510771985 A CN 201510771985A CN 105417767 B CN105417767 B CN 105417767B
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- arsenic
- sulfuric acid
- acid
- water
- acid water
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 79
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002253 acid Substances 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 44
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 36
- 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 claims abstract description 25
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000005189 flocculation Methods 0.000 claims abstract description 11
- 230000016615 flocculation Effects 0.000 claims abstract description 11
- 239000013049 sediment Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 31
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 30
- 239000002699 waste material Substances 0.000 claims description 17
- 239000010440 gypsum Substances 0.000 claims description 13
- 229910052602 gypsum Inorganic materials 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 239000002893 slag Substances 0.000 abstract description 19
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 10
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 10
- 239000004571 lime Substances 0.000 abstract description 10
- 238000006386 neutralization reaction Methods 0.000 abstract description 7
- 239000006071 cream Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 18
- 235000019738 Limestone Nutrition 0.000 description 10
- 239000006028 limestone Substances 0.000 description 10
- 239000003643 water by type Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 7
- 235000014413 iron hydroxide Nutrition 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- BMSYAGRCQOYYMZ-UHFFFAOYSA-N [As].[As] Chemical compound [As].[As] BMSYAGRCQOYYMZ-UHFFFAOYSA-N 0.000 description 3
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 3
- 229940103357 calcium arsenate Drugs 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- -1 and therefore Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- UYZMAFWCKGTUMA-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane;dihydrate Chemical compound O.O.[Fe+3].[O-][As]([O-])([O-])=O UYZMAFWCKGTUMA-UHFFFAOYSA-K 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material 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
- 238000009941 weaving Methods 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- 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
- C02F2101/101—Sulfur 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
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention belongs to technical field of industrial sewage treatment, a kind of method that arsenic removal is gone in the acid water from sulfuric acid is specifically disclosed, it includes following steps：1, it is neutralized with the calcium carbonate suspension of 5wt% 8wt% and sulfuric acid acid water, is separated by solid-liquid separation after neutralization.2, the filtrate after neutralization is neutralized again with the lime cream soliquoid of 5wt% 8wt%, is separated by solid-liquid separation, be more than that 98% arsenic is removed during this.3, ferric sulfate or bodied ferric sulfate flocculation sediment carry out the remaining arsenic of flocculation sediment removal to the filtrate in step 2.The method of the present invention processing cost is low, operating condition is simple, and treated, and waste water can reach corresponding discharging standards, while can obtain the arsenic slag of high concentration, is conducive to recycling or the stabilization/solidification of arsenic.
Description
Technical field
The present invention relates to the sides that arsenic removal is gone in technical field of industrial sewage treatment more particularly to a kind of acid water from sulfuric acid
Method, the method for the present invention are suitably applied the processing of arsenic content height, the big waste water of acidity.
Background technology
Sulfuric acid is raw material important in Chemical Manufacture, it is widely used in agricultural, metallurgy industry, national defence, weaving row
Industry etc..China has become global sulfuric acid production capacity highest, yield maximum, the maximum country of consumption figure.It is worth mentioning that it is expected that
In 2015, Chinese sulphuric acid output can reach 100,000,000 tons/year, and wherein flue gas during smelting is made sulfuric acid and accounts for 30%.In flue gas during smelting process
In, the arsenic-containing acid waste water of high concentration is known as sulfuric acid acid water, is its major pollutants.In sulfuric acid acid water containing 6~
10% sulfuric acid and the heavy metal of high level such as arsenic.In general arsenic content is special up to 2~15g/L in sulfuric acid acid water
Different situation is up to 20g/L.It can all be generated in a large amount of acidic arsenic-containing discharge of wastewater to environment every year in industrial production, if be not added with
Very serious pollution can be then caused to environment with processing.It is well known that even if a small amount of arsenic if can be carcinogenic.Therefore arsenic in water
Removal is all an important theme in worldwide.If a kind of new, efficient, economic sulfuric acid waste acid can be developed
Wastewater processing technology, will be with great society, environmental protection and economic dispatch meaning.
The method of processing sulfuric acid acid water mainly has lime method, iron salt method, vulcanization etc. at present.
Lime method is to react to generate calcium arsenate or calcium arsenite precipitation with arsenic in waste water using lime.In order to make arsenic poison subtract
It is low or preferably go arsenic removal, the process of aeration is industrially also added, trivalent arsenic is oxidized to pentavalent arsenic.But only lean on lime stone
Waste water can not be made to be up to state standards.Therefore it needs that molysite generation iron hydroxide or ferrous hydroxide colloid arsenic-adsorbing is added.
The minimum ferric arsenate of solubility (scorodite) can also be generated under certain conditions.Vulcanization is that sulphion forms vulcanization with arsenic
Arsenic precipitates, and arsenic is made to be removed from water.
The equal Shortcomings of the above method：(1) lime method or iron salt method are required to that a large amount of chemical agent is added；(2) it generates
The solid waste object amount of danger containing arsenic it is big；(3) in slag containing arsenic, arsenic content is low, is unfavorable for recycling or the stabilization/solidification of arsenic slag；
(4) although vulcanization can obtain the higher arsenic sulfide slag of arsenic content, the method can only carry out in acid condition, and
The very strong hydrogen sulfide gas of toxicity is easy tod produce, operating cost is also sufficiently expensive；(5) treatment process the degree of automation is relatively low, pH
Value is not easy to control, and calcium ion is more in solution be easy to cause line clogging etc..
Invention content
The purpose of the present invention is being directed to the deficiencies in the prior art, propose in a kind of slave sulfuric acid acid water newly
The method of arsenic removal, the sulfuric acid acid water are gas washing spent acid in sulfuric acid industry, and the phenolphthalein acidity of the sulfuric acid acid water is
The arsenic content of 60-100g/L, sulfuric acid acid water are 2-15g/L.
The present invention, which adopts the following technical scheme that, realizes its goal of the invention.
A method of arsenic removal being gone from sulfuric acid acid water, its step are as follows：
(1) calcium carbonate neutralizes：The calcium carbonate that calcium carbonate mass fraction is 5%-8% is added into sulfuric acid acid water to suspend
Liquid, the sulfuric acid in neutralisation of sulphuric acid acid water adjust pH to 1.8~1.9, are separated by solid-liquid separation after the reaction was continued 0.5h, solid is stone
Cream product can be sold (as forms such as cement additives), and filtrate enters in next step.
For the consumption of the calcium carbonate in 60~100kg/ tons of sulfuric acid acid waters, the yield of gypsum is 80~140kg/ tons
Sulfuric acid acid water.
(2) milk of lime neutralizes：The lime that calcium hydroxide mass fraction is 5%-8% is added into filtrate obtained by step (1)
Breast adjusts pH to 11.9~12.1, is separated by solid-liquid separation after the reaction was continued 2h, in this step milk of lime in filtrate obtained by step (1)
Arsenic reaction generate unformed calcium arsenate and calcium arsenite precipitation, be more than that 98% arsenic is removed during this.
In the milk of lime that step (2) is consumed in calcium and sulfuric acid acid water the molar ratio of arsenic 1.5~2：1.
What this step generated is precipitated as arsenic-containing waste residue, and wherein 25%~30%, this step generates useless containing arsenic arsenic content
The quality of slag is 15~30kg/ tons of sulfuric acid acid waters.
(3) ferric sulfate flocculation sediment：Be added in the filtrate obtained by the step (2) ferric sulfate that mass fraction is 8%-10% or
Polymeric ferrous sulphate solution adjusts pH to 8~9, is separated by solid-liquid separation after reacting 10min.Obtained solid belongs to unhazardous waste, and filtrate is straight
Run in and puts.
Under this alkaline condition, the effects that generating iron hydroxide, catching, bridge by absorption, net, removes remaining arsenic, and sulphur
Acid group then generates calcium sulfate with the calcium binding in filtrate obtained by step (2).
In this step, the ferric sulfate of consumption or the quality of bodied ferric sulfate are 2~4kg/ tons of sulfuric acid acid waters, generation
Precipitation quality is 3~6kg/ tons of sulfuric acid acid waters.
Compared with prior art, the processing method of sulfuric acid acid water of the invention has the following advantages that：
1, first segment slag arsenic content is low, is not dangerous solid waste.
Sulfuric acid acid water is handled in traditional three-stage process processing procedure, and first segment is calcium oxide or calcium hydroxide,
And terminal is handled in first segment, pH value is 1.9 or so, at this point, calcium oxide or calcium hydroxide can adsorb more arsenic, causes solid
Arsenic content is higher in slag；In the present invention, in first segment, traditional calcium oxide or calcium hydroxide, lime stone are substituted with lime stone
Will not arsenic-adsorbing, the slag arsenic content of gained is low, slag be not dangerous solid waste, can be used for construction material etc., handle disposition
Expense is also low.The experimental results showed that the content of arsenic is less than 0.1% in gypsum tailings, belong to not dangerous waste.
2, required treatment agent amount reduction, the quantity of slag are few.
Sulfuric acid acid water is handled in traditional three-stage process processing procedure, and first segment is calcium oxide or calcium hydroxide,
Products therefrom is calcium sulfate, the experimental results showed that, calcium sulfate can wrap up calcium oxide or calcium hydroxide, cause calcium oxide or hydroxide
Calcium dosage increases, and the gained quantity of slag also increases；In the present invention, traditional calcium oxide or hydroxide are substituted with lime stone in first segment
Calcium, lime stone are reacted with acid, generate carbon dioxide, because of the effusion of carbon dioxide, lime stone will not be wrapped up by calcium sulfate so that its
Dosage is small, and the production quantity of slag is also small.The experimental results showed that being compared with conventional method, the quantity of slag reduces 10-20%.
3, medicament expense reduces, and processing cost reduces.
Lime or milk of lime are made of lime stone, and therefore, sulfuric acid acid water is handled in three-stage process technique, in first segment
Substituting lime or milk of lime, pharmaceutical quantities, medicament expense with lime stone reduces, and processing cost reduces.The experimental results showed that and often
Rule method is compared, and medicament expense reduces 20-35%.
4, gained gypsum pattern is relatively preferable, is more convenient later use.
The experimental results showed that substituting lime or milk of lime, the topographical surface light of gained calcium sulfate (gypsum) slag with lime stone
It is sliding, without micro-crack, be conducive to increase gypsum intensity (《The relationship of gypsum hardenite defect and intensity》In explicitly point out micro-crack
Gypsum intensity can be reduced with fracture), increase gypsum later use value.
5, second segment slag arsenic content is high, is convenient for recycling.
After substituting lime or milk of lime using lime stone, first segment slag arsenic content is low, and arsenic is concentrated mainly in second segment slag.
The experimental results showed that the content of arsenic greatly improves in second segment arsenic slag, reach as high as 29.3%, be conducive to arsenic resource reclaim or
Stabilization/solidification.
Description of the drawings
Fig. 1 goes the technological process of the method for arsenic removal in a kind of acid water from sulfuric acid for the present invention.
Specific implementation mode
It is sulfuric acid that the process object sulfuric acid acid water of the method for arsenic removal is removed in a kind of acid water from sulfuric acid of the present invention
Gas washing spent acid in industrial production, phenolphthalein acidity are 60-100g/L, and arsenic content is 2-15g/L, and the step of the method is as follows：
(1) calcium carbonate neutralizes：The calcium carbonate that calcium carbonate mass fraction is 5%-8% is added into sulfuric acid acid water to suspend
Liquid, the sulfuric acid in neutralisation of sulphuric acid acid water adjust pH to 1.8~1.9, are separated by solid-liquid separation after the reaction was continued 0.5h, solid is stone
Cream product can be sold (as forms such as cement additives), and filtrate enters in next step.
For the consumption of the calcium carbonate in 60~100kg/ tons of sulfuric acid acid waters, the yield of gypsum is 70~130kg/ tons
Sulfuric acid acid water.
(2) milk of lime neutralizes：The milk of lime that mass fraction is 5%-8% is added into filtrate obtained by step (1), adjusts pH
To 11.9~12.1, it is separated by solid-liquid separation after the reaction was continued 2h, milk of lime reacts life with the arsenic in filtrate obtained by step (1) in this step
It is precipitated at unformed calcium arsenate and calcium arsenite, this has 99% arsenic to be removed in the process.
In the milk of lime that step (2) is consumed in calcium and sulfuric acid acid water the molar ratio of arsenic 1.5~2：1.
What this step generated is precipitated as arsenic-containing waste residue, and wherein 25%~30%, this step generates useless containing arsenic arsenic content
The quality of slag is 15~30kg/ tons of sulfuric acid acid waters.
(3) ferric sulfate flocculation sediment：Be added in the filtrate obtained by the step (2) ferric sulfate that mass fraction is 8%-10% or
Polymeric ferrous sulphate solution adjusts pH to 8~9, is separated by solid-liquid separation after reacting 10min.Under this alkaline condition, iron hydroxide is generated,
The effects that catching, bridge by absorption, net removes remaining arsenic, and sulfate radical then with the calcium ion knot in step (2) gained filtrate
Symphysis is at calcium sulfate.
In this step, the ferric sulfate of consumption or the quality of bodied ferric sulfate are 2~4kg/ tons of sulfuric acid acid waters, generation
Precipitation quality is 3~6kg/ tons of sulfuric acid acid waters.
It is three specific embodiments of the present invention below：
Embodiment 1
The present embodiment is process object, phenol with the sulfuric acid acid water that Daye, hubei Province copper smelting plant sulfuric acid plant is discharged
Phthalic acidic is 65g/L, and arsenic content is 8.8g/L.Process flow is carried out using the method for the present invention and relevant parameter is as follows：
Handle the sulfuric acid acid water of 1L (about 1.01kg), the stage of sum in calcium carbonate, the carbon for being 8% with mass fraction
Sour calcium suspension adjusts pH to 1.9, needs the calcium carbonate for consuming about 66g, generates the gypsum of about 90g, and arsenic content is 0.08%,
Belong to unhazardous waste.
In milk of lime neutralization stage, the milk of lime for being 8% with mass fraction adjusts pH to 11.9, needs to consume about 20g's
Calcium hydroxide generates the arsenic-containing waste residue of about 30g, and arsenic content is 29.1%, needs stable curing.Have 99.2% during this
Arsenic is removed.
During ferric sulfate flocculation sediment, the ferrum sulfuricum oxydatum solutum that mass fraction is 10% is added, passes through the iron of ferric sulfate
Ion hydrolyzes to reduce pH to 9, consumes the ferric sulfate of about 2.5g, generates the iron hydroxide of 4g and the mixture of calcium sulfate, and arsenic
Content is 0.007%, belongs to unhazardous waste.After ferric sulfate flocculation sediment, the content of arsenic is 0.2mg/L in filtrate, low
0.5mg/L is limited in national standard, while also below professional standard 0.3mg/L, it can be with direct emission.
Embodiment 2
The present embodiment is process object, phenol with the sulfuric acid acid water that Tongling, Anhui Province copper smelting plant sulfuric acid plant is discharged
Phthalic acidic is 90g/L, and arsenic content is 13.7g/L.Process flow is carried out using the method for the present invention and relevant parameter is as follows：
Handle the sulfuric acid acid water of 1L (about 1.01kg), the stage of sum in calcium carbonate, the carbon for being 5% with mass fraction
Sour calcium suspension adjusts pH to 1.9, needs the calcium carbonate for consuming about 92g, generates the gypsum of about 124g, and arsenic content is
0.09%, belong to unhazardous waste.
In milk of lime neutralization stage, the milk of lime for being 5% with mass fraction adjusts pH to 11.9, needs to consume about 28g's
Calcium hydroxide generates the arsenic-containing waste residue of about 46g, and arsenic content is 29.3%, needs stable curing.Have 98.4% during this
Arsenic is removed.
During ferric sulfate flocculation sediment, the ferrum sulfuricum oxydatum solutum that mass fraction is 8% is added, by the iron of ferric sulfate from
Son hydrolyzes to reduce pH to 8, consumes the ferric sulfate of about 2.7g, generates the iron hydroxide of 4.3g and the mixture of calcium sulfate, and arsenic
Content is 0.008%, belongs to unhazardous waste.After ferric sulfate flocculation sediment, the content of arsenic is 0.21mg/L in filtrate, low
0.5mg/L is limited in national standard, while also below professional standard 0.3mg/L, it can be with direct emission.
Embodiment 3
The present embodiment is process object, phenol with the sulfuric acid acid water that Jiangxi Guixi copper smelting plant sulfuric acid plant is discharged
Phthalic acidic is 75g/L, and arsenic content is 3.8g/L.Process flow is carried out using the method for the present invention and relevant parameter is as follows：
Handle the sulfuric acid acid water of 1L (about 1.01kg), the stage of sum in calcium carbonate, the carbon for being 6% with mass fraction
Sour calcium suspension adjusts pH to 1.9, needs the calcium carbonate for consuming about 76g, generates the gypsum of about 104g, and arsenic content is
0.05%, belong to unhazardous waste.
In milk of lime neutralization stage, the milk of lime for being 7% with mass fraction adjusts pH to 11.9, needs to consume about 17g's
Calcium hydroxide generates the arsenic-containing waste residue of about 14g, and arsenic content is 26.7%, needs stable curing.Have 98.6% during this
Arsenic is removed.
During ferric sulfate flocculation sediment, the polymeric ferrous sulphate solution that mass fraction is 9% is added, passes through iron ion water
Solution reduces pH to 9, consumes the bodied ferric sulfate of about 2.4g, generates the iron hydroxide of 3.9g and the mixture of calcium sulfate, and arsenic
Content is 0.006%, belongs to unhazardous waste.After ferric sulfate flocculation sediment, the content of arsenic is 0.2mg/L in filtrate, low
0.5mg/L is limited in national standard, while also below professional standard 0.3mg/L, it can be with direct emission.
Specific embodiments are merely illustrative of the spirit of the present invention described in this specification.Skill belonging to the present invention
The technical staff in art field can make various modifications or additions to the described embodiments or using similar side
Formula substitutes, and however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (3)
1. a kind of method for going arsenic removal in acid water from sulfuric acid, its step are as follows：
（1）Calcium carbonate neutralizes：The calcium carbonate suspension that calcium carbonate mass fraction is 5%-8% is added into sulfuric acid acid water, in
With the sulfuric acid in sulfuric acid acid water, pH to 1.8 ~ 1.9 is adjusted, is separated by solid-liquid separation after the reaction was continued 0.5 h, solid is gypsum production
Product, filtrate enter in next step；
The phenolphthalein acidity of the sulfuric acid acid water is 60-100 g/L, and the arsenic content of sulfuric acid acid water is 2-15 g/L；
（2）Milk of lime neutralizes：Toward step（1）The milk of lime that calcium hydroxide mass fraction is 5%-8% is added in gained filtrate, adjusts
It is separated by solid-liquid separation after pH to 11.9 ~ 12.1, the reaction was continued 2 h；
Step（2）What is generated is precipitated as arsenic-containing waste residue, and wherein arsenic content is 25% ~ 30%；
（3）Ferric sulfate flocculation sediment：Toward step（2）The ferric sulfate or polymerised sulphur that mass fraction is 8%-10% are added in gained filtrate
Sour ferrous solution adjusts pH to 8 ~ 9, is separated by solid-liquid separation after reacting 10min, obtained solid belongs to unhazardous waste, filtrate direct emission.
2. according to the method described in claim 1, it is characterized in that：Step（2）Calcium and sulfuric acid waste acid in the milk of lime consumed
The molar ratio of arsenic in waste water is 1.5 ~ 2：1.
3. according to the method described in claim 1, it is characterized in that：Step（3）In, the ferric sulfate of consumption or bodied ferric sulfate
Quality is 2 ~ 4 kg/ tons of sulfuric acid acid water, and the precipitation quality of generation is 3 ~ 6 kg/ tons of sulfuric acid acid water.
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