CN108191031A - A kind of no sulphur figure water hydroxyl sarmientite and its application in trivalent arsenic waste water is purified - Google Patents

A kind of no sulphur figure water hydroxyl sarmientite and its application in trivalent arsenic waste water is purified Download PDF

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Publication number
CN108191031A
CN108191031A CN201810008659.XA CN201810008659A CN108191031A CN 108191031 A CN108191031 A CN 108191031A CN 201810008659 A CN201810008659 A CN 201810008659A CN 108191031 A CN108191031 A CN 108191031A
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trivalent arsenic
waste water
water
sulphur
trivalent
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CN108191031B (en
Inventor
李青竹
柴立元
杨锦琴
颜宇琛
胡可人
王庆伟
杨志辉
闵小波
梁彦杰
刘恢
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Central South University
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Central South University
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • 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

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  • 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)
  • Inorganic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention relates to a kind of no sulphur figure water hydroxyl sarmientite and its application in trivalent arsenic waste water is purified, wherein, the method for purification trivalent arsenic waste water includes：Trivalent arsenic waste water and trivalent ferrous solution are fed simultaneously, adjust the pH value of mixed solution to 1.41 2.45, stirring at normal temperature, precipitation and separation to obtain the final product, wherein drug used and reagent not containing sulfate radicals.The precipitation that this method obtains is i.e. without sulphur figure water hydroxyl sarmientite, chemical formula Fe6(AsO3)4(HAsO3)(OH)4·4H2O, crystal structure is identical with the crystal structure characteristic of figure water hydroxyl sarmientite, also belongs to a kind of mineral crystal structure, can be applied in the trivalent arsenic waste water of not containing sulfate radicals, forms precipitation and achievees the purpose that remove trivalent arsenic.

Description

A kind of no sulphur figure water hydroxyl sarmientite and its application in trivalent arsenic waste water is purified
Technical field
The present invention relates to field of environment engineering technology, more particularly, to a kind of no sulphur figure water hydroxyl sarmientite and its net Change the application in trivalent arsenic waste water.
Background technology
With the continuous development of China's non-ferrous metal metallurgy industry, the wastewater discharge containing trivalent arsenic is also increasing, but The compound for being arsenic and arsenic is generally acknowledged strong carcinogen, it is therefore desirable to carry out ability after strictly handling to the waste water containing trivalent arsenic Discharge.
In the prior art, generally trivalent arsenic is removed using the precipitation method.Publication number CN107010704A discloses a kind of processing Waste water containing trivalent arsenic, trivalent ferrous solution and sulfate liquor are reacted generation figure water hydroxyl arsenic iron by the method for the waste water containing trivalent arsenic Alum crystal, so as to achieve the effect that remove trivalent arsenic, but this method will add in two kinds of medicaments, pharmaceutical quantities are big, and by-product is more.It is open Number CN106006754A discloses a kind of method that hydro-thermal method synthesizes high-purity figure water hydroxyl sarmientite, is existed using ferric sulfate and trivalent arsenic Reaction generation figure water hydroxyl sarmientite at 100-130 DEG C, primarily to the high figure water hydroxyl sarmientite of purity is obtained for studying, Be not suitable for industrial extensive processing waste water containing trivalent arsenic.
Therefore, it develops a kind of no sulphur figure water hydroxyl sarmientite and removal applied to trivalent arsenic is meaningful, it can be anti- It should not add mildly, under conditions of sulfate and remove trivalent arsenic.
Invention content
In view of the deficienciess of the prior art, the present invention provides a kind of no sulphur figure water hydroxyl sarmientite and its in purification trivalent arsenic Application in waste water.Sulfate need not be added in, will only contain trivalent arsenic waste water and ferric iron solution reaction obtains no sulphur figure water hydroxyl Sarmientite crystal settling, so as to remove trivalent arsenic.
The technical solution adopted by the present invention is as follows：
A kind of method for purifying trivalent arsenic waste water, including：Trivalent arsenic waste water and trivalent ferrous solution are fed simultaneously, adjusted mixed The pH value of solution is closed to 1.41-2.45, stirring at normal temperature, precipitation and separation to obtain the final product, wherein drug used and reagent not containing sulfate radicals.
In the above-mentioned technical solutions, drug and reagent used not containing sulfate radicals, will contain trivalent arsenic waste water and ferric iron is molten Liquid is fed simultaneously, is come into full contact with and is mixed, and is adjusted mixed liquor pH value to 1.41-2.45, is stirred is obtained by the reaction at normal temperatures It precipitates (no sulphur figure water hydroxyl sarmientite), so as to fulfill removal trivalent arsenic.When pH value is more than 2.45, what is obtained is amorphous hydrogen-oxygen Change iron, do not form no sulphur figure water hydroxyl sarmientite precipitation；When pH value is less than 1.41, what is obtained is unformed solid phase.The technology Scheme reaction condition is mild, without additionally adding in sulfate radical, can also obtain crystal precipitation, so as to remove trivalent arsenic, is suitble to work Industry application, it is at low cost.
In the above-mentioned technical solutions, the pH value is preferably 1.56~2.08.On this condition, no sulphur figure water can be improved The yield and purity of hydroxyl sarmientite.
In the above-mentioned technical solutions, the molar concentration of trivalent arsenic is 0.015mol/L~0.15mol/ in the mixed solution L, preferably 0.15mol/L.The concentration the high more is conducive to be formed without sulphur figure water hydroxyl sarmientite crystal.
In the above-mentioned technical solutions, trivalent arsenic and ferric molar concentration rate are 0.3~1.5 in the mixed solution: 1, preferably 1:1.It is that Fe supply forms the hydroxide of iron to adsorb in order to prevent to control trivalent arsenic and ferric molar ratio Form takes away arsenic.
In the above-mentioned technical solutions, the room temperature is 15~30 DEG C, preferably 25 DEG C.
In the above-mentioned technical solutions, the time being stirred to react is 3~10 days, preferably 5 days.
Trivalent arsenic waste water and the generation of ferric iron solution reaction are precipitated without sulphur figure water hydroxyl sarmientite, reaction temperature and time pair The speed and purity for forming crystal have an impact, and after considering, temperature is preferably 25 DEG C, and the reaction time is preferably 5 days.
In the above-mentioned technical solutions, it is preferred that the ferric iron is ferric nitrate, and the trivalent arsenic is sodium arsenite.Because Nitrate including ferric nitrate is soluble easily in water, can promote reaction, small without the influence of sulphur figure water hydroxyl sarmientite crystal on being formed.Separately Outside, what the present invention obtained is with the object after sulfate radical in arsenite ion substitution figure water hydroxyl sarmientite without sulphur figure water hydroxyl sarmientite Matter, therefore be more advantageous to reacting with sodium arsenite.
The second object of the present invention is to provide a kind of no sulphur figure water hydroxyl sarmientite, and the no sulphur figure water hydroxyl sarmientite is above-mentioned Purify the precipitation being prepared in the method for trivalent arsenic waste water.
Without sulphur figure water hydroxyl sarmientite, chemical formula Fe6(AsO3)4(HAsO3)(OH)4·4H2O, crystal structure and figure Water hydroxyl sarmientite Fe6(AsO3)4(SO4)(OH)4·4H2The crystal structure characteristic of O is identical.
The present invention has the advantage that relative to the prior art：
No sulphur figure water hydroxyl sarmientite Fe provided by the invention6(AsO3)4(HAsO3)(OH)4·4H2O is to use arsenite ion Replace the substance after the sulfate radical in figure water hydroxyl sarmientite crystal structure, can pass through under conditions of it need not add in sulfate radical It is stirred to react obtained under ferric iron and trivalent arsenic solution room temperature, reaction condition is mild, can be applied to the trivalent of not containing sulfate radicals It is formed in arsenic waste water without sulphur figure water hydroxyl sarmientite, is that the environment of exploded view water hydroxyl sarmientite should so as to fulfill the removal of trivalent arsenic With having very important significance.
Description of the drawings
Fig. 1 is the XRD comparing results without sulphur figure water hydroxyl sarmientite Yu sulfur-bearing figure water hydroxyl sarmientite in the embodiment of the present invention 1 Figure；
Fig. 2 is that the infrared spectrum without sulphur figure water hydroxyl sarmientite and sulfur-bearing figure water hydroxyl sarmientite in the embodiment of the present invention 1 compares Result figure；
Fig. 3 is without sulphur figure water hydroxyl sarmientite and sulfur-bearing figure water hydroxyl sarmientite, the Raman light of scorodite in the embodiment of the present invention 1 Compose comparing result figure；
Fig. 4 XRD result figures of gained without sulphur figure water hydroxyl sarmientite in the range of 1.27~2.45 for reacting solution pH value；
Fig. 5 is the microscopic appearance picture without sulphur figure water hydroxyl sarmientite that reaction solution obtains at various ph values；
Fig. 6 is that arsenic, iron when reacting solution pH value is formed in the range of 1.27~2.45 without sulphur figure water hydroxyl sarmientite remove Rate result；
Fig. 7 is that trivalent arsenic and the XRD of ferric iron molar concentration rate obtained solid in the range of 0.3~15 are tied in reaction solution Fruit is schemed.
Specific embodiment
With reference to the accompanying drawings and examples, the specific embodiment of the present invention is described in further detail.Implement below Example is merely to illustrate the present invention, is not intended to limit protection scope of the present invention.
Embodiment 1
A kind of method for purifying trivalent arsenic waste water is present embodiments provided, including：By waste water and nitric acid containing sodium arsenite Ferrous solution feeds mixing simultaneously, in mixed solution the molar concentration of Fe (III) and As (III) be respectively 0.15mol/L, 0.15mol/L adjusts the pH value of mixed solution to 1.56, is reacted 5 days using magnetic agitation at 25 DEG C, then solid-liquid is carried out Separation is filtered, wherein drug used and reagent not containing sulfate radicals.
As (III) and Fe (III) concentration in filtrate are detected, so as to calculate removal rate.
After being washed with deionized 3 times to gained filter residue, dried at 80 DEG C.XRD results such as Fig. 1 institutes of obtained solid sample Show, infrared spectrogram is as shown in Fig. 2, Raman spectrogram is as shown in Figure 3.
Infrared spectrogram (Fig. 2) illustrates that sulphate-containing ion, Raman spectrogram (Fig. 3) do not illustrate in the solid in the solid Without pentavalent arsenic but contain trivalent arsenic, can determine that the present embodiment has obtained a kind of arsenous anion substituted sulfuric acid with reference to Fig. 1 to Fig. 3 Root without sulphur figure water hydroxyl sarmientite, and its have the crystal structure identical with sulfur-bearing figure water hydroxyl sarmientite.
The pH value of reaction solution is adjusted by nitric acid and sodium hydroxide, when pH value is adjusted at 1.27~2.45 models When enclosing interior, the results are shown in Figure 4 by the XRD of obtained solid, and gained is unformed solid phase in the solution of pH value 1.27, in pH value Also there is on a small quantity without sulphur figure water hydroxyl sarmientite, in the solution that pH is 1.41~2.08 the existing unformed solid phase of gained in 2.45 solution In obtain is no sulphur figure water hydroxyl sarmientite, microscopic appearance is as shown in Figure 5.
In addition, arsenic, the removal rate of iron are as shown in Figure 6 in the range of pH is 1.27~2.45.Wherein ferric removal rate Increase, such as pH value is increased to 2.45 from 1.27 as pH is increased, ferric removal rate increases to 98.26% from 5.1%. The removal rate of trivalent arsenic pH value be less than 1.56 when it is relatively low, such as pH be 1.27~1.56 when, the removal rate of trivalent arsenic is about 40%；When pH value is more than 1.56, the removal rate of trivalent arsenic is increased with pH and is increased, such as when pH value is increased to 2.08 from 1.62 When again to 2.45, the removal rate of trivalent arsenic correspondingly increases to 82% from 50.2% and is further added by 92%.Although trivalent arsenic and three The removal rate of valency iron is all highest when pH is 2.45, but fixed containing a large amount of nothings in the figure water hydroxyl sarmientite formed under this condition The hydroxide of shape iron, so being not suitable as the optimal conditions of no sulphur figure water hydroxyl sarmientite arsenic removal application.
In adjustment initial reaction solution trivalent arsenic and ferric ratio from 0.3 be changed to 15 and control ph be 1.60, Obtained solid detects (Fig. 7) confirmation through XRD can obtain no sulphur figure water hydroxyl in trivalent arsenic and ferric ratio for 0.3~1.5 Sarmientite, the solid obtained after trivalent arsenic and ferric ratio are more than 1.5 is unformed phase.
To control trivalent arsenic and ferric iron ratio be 1.0, pH value 1.60, adjust in initial reaction solution trivalent arsenic concentration from 1.5×10-3Mol/L increases to 1.5 × 10-1Mol/L is less than 1.5 × 10 in trivalent arsenic concentration-2It is generated during mol/L without solid, Higher than 1.5 × 10-2It has been obtained during mol/L without sulphur figure water hydroxyl sarmientite.
Finally, it these are only the preferred embodiment of the present invention, be not intended to limit the scope of the present invention.It is all this Within the spirit and principle of invention, any modification, equivalent replacement, improvement and so on should be included in the protection model of the present invention Within enclosing.

Claims (9)

  1. A kind of 1. method for purifying trivalent arsenic waste water, which is characterized in that including：By trivalent arsenic waste water and trivalent ferrous solution simultaneously into Material adjusts the pH value of mixed solution to 1.41-2.45, stirring at normal temperature, precipitation and separation to obtain the final product, wherein drug used and reagent are not Containing sulfate radicals.
  2. 2. a kind of method for purifying trivalent arsenic waste water according to claim 1, which is characterized in that the pH value for 1.56~ 2.08。
  3. 3. a kind of method for purifying trivalent arsenic waste water according to claim 1, which is characterized in that three in the mixed solution The molar concentration of valency arsenic is 0.015mol/L~0.15mol/L, preferably 0.15mol/L.
  4. 4. a kind of method for purifying trivalent arsenic waste water according to claim 1, which is characterized in that three in the mixed solution Valency arsenic is 0.3~1.5 with ferric molar concentration rate:1, preferably 1:1.
  5. 5. according to a kind of method for purifying trivalent arsenic waste water of claim 1-4 any one of them, which is characterized in that the room temperature It is 15~30 DEG C, preferably 25 DEG C.
  6. 6. according to a kind of method for purifying trivalent arsenic waste water of claim 1-4 any one of them, which is characterized in that the stirring Time be 3~10 days, preferably 5 days.
  7. 7. according to a kind of method for purifying trivalent arsenic waste water of claim 1-4 any one of them, which is characterized in that the trivalent Iron is ferric nitrate, and the trivalent arsenic is sodium arsenite.
  8. 8. a kind of no sulphur figure water hydroxyl sarmientite, which is characterized in that the no sulphur figure water hydroxyl sarmientite is to appoint in claim 1~7 The precipitation being prepared in the method for the one purification trivalent arsenic waste water.
  9. A kind of 9. no sulphur figure water hydroxyl sarmientite according to claim 8, which is characterized in that chemical formula Fe6(AsO3)4 (HAsO3)(OH)4·4H2O, crystal structure and figure water hydroxyl sarmientite Fe6(AsO3)4(SO4)(OH)4·4H2The crystal structure of O Feature is identical.
CN201810008659.XA 2018-01-04 2018-01-04 Sulfur-free arsenical chalcanthite and application thereof in purifying trivalent arsenic wastewater Active CN108191031B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108101115A (en) * 2018-01-04 2018-06-01 中南大学 A kind of hydro-thermal method prepares the method without sulphur figure water hydroxyl sarmientite

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107010704A (en) * 2017-05-02 2017-08-04 中南大学 A kind of method for handling the waste water containing trivalent arsenic
CN107500362A (en) * 2017-09-15 2017-12-22 中南大学 A kind of new figure water hydroxyl sarmientite and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107010704A (en) * 2017-05-02 2017-08-04 中南大学 A kind of method for handling the waste water containing trivalent arsenic
CN107500362A (en) * 2017-09-15 2017-12-22 中南大学 A kind of new figure water hydroxyl sarmientite and its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108101115A (en) * 2018-01-04 2018-06-01 中南大学 A kind of hydro-thermal method prepares the method without sulphur figure water hydroxyl sarmientite
CN108101115B (en) * 2018-01-04 2019-09-03 中南大学 A kind of method of the hydro-thermal method preparation without sulphur figure water hydroxyl sarmientite

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