CN106823234A - A kind of method that hydro-thermal method prepares the solid arsenic mineral of high stability - Google Patents
A kind of method that hydro-thermal method prepares the solid arsenic mineral of high stability Download PDFInfo
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- CN106823234A CN106823234A CN201611192966.5A CN201611192966A CN106823234A CN 106823234 A CN106823234 A CN 106823234A CN 201611192966 A CN201611192966 A CN 201611192966A CN 106823234 A CN106823234 A CN 106823234A
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- arsenic
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
Abstract
The present invention relates to a kind of method that hydro-thermal method prepares the solid arsenic mineral of high stability, arsenic solution dearsenification high will be contained and solidified, and arsenic containing solution is obtained harmless treatment.After trivalent arsenic in arsenic containing solution is pentavalent arsenic by the present invention through catalysis oxidation, oxidated solution synthesizes the solid arsenic mineral of high stable using the heavy arsenic method hydro-thermal method of lime, can directly store up.First pass through the heavy arsenic method of lime and obtain calcium arsenate, then calcium arsenate is changed into the solid arsenic mineral of high stability using hydro-thermal method, toxicity is leached and meets GB5085.3 2007 (solid waste judging standard leaching characteristic identification) regulations.Present invention process flow is short, and arsenic effect of sinking is good, and liquid can be discharged directly after heavy arsenic, and the solid arsenic mineral stability of synthesis is high, stabilization can be stored up under the conditions of wide ph range 2~11 and strong reducing property.
Description
Technical field
The invention belongs to mineral As retention field, it is related to a kind of preparation method of the solid arsenic mineral of high stability.
Background technology
Arsenic is a kind of hypertoxic element, and has high carcinogenic, and extensive association is in various non-ferrous metal metallurgy process systems.Closely
Over 30 years, as China's non-ferrous metal industry is developed rapidly, arsenic pollution problem is more severe, seriously threatens the life of people
Health.Therefore, it is a urgent and relevant problem to carry out arsenic pollution Controlling research.
Current As retention mainly includes encapsulating and the solid class of arsenic two of mineral.Encapsulating is exactly with materials such as cement, glass, to containing
Arsenic material is coated, and can be stablized and be stored up.This method solid waste amount is big, high cost, it is difficult to extensive use.The solid arsenic of mineral
Will arsenic be converted into stability arsenic-containing ores high and store up.Gu the selection of arsenic mineral, should from leach stability, mineral arsenic content,
Leach product toxicity, prepare many-sided choosing comprehensively such as complexity and cost.Primary and secondary arsenic mineral, although sum is up to
More than 300 plant, but it is rare to be wherein used for " choosing of satisfaction " reality category of solid arsenic.In Ca (II)-As (V)-H2In O systems, different bars
A series of calcium arsenate mineral can be synthesized under part, its stability is higher；But, solubility is larger in acid condition for calcium arsenate, and
Ca (II) ion therein can be with solubilised state CO2Reaction, generates calcium carbonate and discharges arsenic again.Therefore, calcium arsenate class mineral
And solid arsenic mineral should not be used as.In Fe (III)-As (V)-H2In O systems, change reaction condition can prepare a series of compositions,
Crystal formation and the different precipitated ferric arsenate of crystallinity.Wherein, scorodite (FeAsO4·2H2O), because its stability is high, theoretical arsenic content
Up to 32%, it is easy to the aqueous low advantage of solid-liquor separation, slag in crystalline state, is the optimal arsenic mineral admittedly generally acknowledged at present.
The preparation method of current scorodite is broadly divided into three major types：Hydro-thermal method, non-pressure process and improvement non-pressure process.Wherein hydro-thermal
, due to the HTHP for needing, energy consumption is larger, it is difficult to commercial Application for method；Non-pressure process prepares scorodite, but its cycle at ambient pressure
It is more long；Non-pressure process is improved in normal pressure, degree of supersaturation is controlled by slow iron protoxide ion under the conditions of 75~90 DEG C, at 7 hours
High-crystallinity scorodite is inside prepared for, is optimal preparation method generally acknowledged at present.Scorodite has stronger stability, conventional
Research in arsenic leaching concentration it is minimum up to 0.5mg/L, but this is only limitted under faintly acid (pH value 2~6) and oxidizing condition, and
Highly acid or basic region or under reductive condition, it leaches less stable.Therefore, further research is prepared to alkalescence
Scorodite with strong reducing property ambient stable is extremely necessary.
In the patent announced at present, Japan same and mining industry Co., Ltd patent of invention (CN 102153145 A, CN
101952204 A) first proposition ferrous iron be source of iron, process arsenic containing solution, and prepare scorodite and iron arsenate powder,
The heavy arsenic of the method is thoroughly, simple and convenient, but the scorodite and ferric arsenate that prepare are only steady in narrower pH (2~6) scope interior energy
Surely store up, the toxicity of arsenic leaches the limit for exceeding well over GB5085.3-2007 national Specifications under the conditions of alkalescence or strong reducing property
Value (<5mg/L).
The content of the invention
It is an object of the invention to provide a kind of preparation method of the solid arsenic mineral of high stability, one kind can be prepared and existed
The solid arsenic mineral of stabilization under the conditions of pH scopes wide and strong reducing property.Process is simple of the invention, easy to operate, the solid arsenic minerals of preparation
Thing arsenic content is higher, and toxicity leaching concentration is very low, and stable region field width, stabilization can be stored up under the conditions of strong reducing property.
To realize the purpose of the present invention, there is provided following technical scheme：
A kind of preparation method of the solid arsenic mineral of high stability, comprises the following steps：
(1) arsenic containing solution catalysis oxidation
By way of catalysis oxidation, to oxidizing gas and catalyst is added in arsenic containing solution, by the As in solution3+Turn
Become As5+；
(2) the heavy arsenic of oxidated solution
Solution ph after step (1) gained oxidation is adjusted to 1.5~3, CaO, Ca are added in the way of continuous charging
(OH)2In one or two as heavy arsenical, the mol ratio for making Ca and As in the solution is 2~8:1, the sedimentation time is 5
~10 hours, reaction temperature was 10 DEG C~90 DEG C；
(3) the solid arsenic mineral of hydro-thermal method synthesis
Step (2) products therefrom is placed in reactor carries out solid arsenic treatment, to iron salt solutions are added in reaction system, makes
The mol ratio of Fe and As is controlled 1~5:1, regulation and control reaction is carried out under the conditions of pH value 1.5~3, makes Fe3+With AsO4 3-Reaction life
Into the solid arsenic mineral of high stability.
In step (1), the main component of the arsenic containing solution includes：As 5~100g/L, Sb 0.5g/L~3g/L, Pb
10~120g/L of 50ppm~800ppm, Sn 2ppm~200ppm, Te 10~500ppm, NaOH.
Oxidizing gas described in step (1) are oxygen, air or oxygen-enriched air；Preferably, the oxidizing gas
Gas flow is controlled in 1~20L/min.
Catalyst described in step (1) is KMnO4；Preferably, the mol ratio of As and Mn is controlled 5:1~50:1.
The temperature that catalytic oxidation system is controlled described in step (1) is 30 DEG C~120 DEG C.
Preferably, the condition that the hydro-thermal method described in step (3) is controlled is that reaction temperature is 100 DEG C~200 DEG C, during reaction
Between be 2h~10h, mixing speed 50r/min~500r/min.
Iron salt solutions described in step (3) include：In ferrum sulfuricum oxydatum solutum, ferric chloride solution or iron nitrate solution at least
One kind is preferably ferrum sulfuricum oxydatum solutum.
Preferably, the addition speed of the iron salt solutions described in step (3) is 5-30ml/min.
Preferably, the reaction time described in step (3) is 2~10h.
The present invention adds iron salt solutions as heavy arsenical in the way of continuous charging, and height is synthesized surely with the arsenic in solution
Qualitatively consolidate arsenic mineral.
As a kind of specific embodiment of the invention：
Specifically include following steps (flow is referred to shown in Fig. 1)：
1st, arsenic containing solution catalysis oxidation operation, by way of catalysis oxidation, to adding oxidizing gas in arsenic containing solution
And catalyst, by the As in solution3+It is transformed into As5+；
2nd, the solid arsenic operation of oxidated solution, is adjusted to 1.5~3, with continuous charging by the solution ph after step (1) gained oxidation
Mode add CaO, Ca (OH)2In one or two as heavy arsenical, make the mol ratio of Ca and As in the solution for 2~
8:1, the sedimentation time is 5~10 hours, and reaction temperature is 10 DEG C~90 DEG C；
3rd, the solid arsenic mineral operation of hydro-thermal method synthesis, step (2) products therefrom is placed in reactor carries out solid arsenic treatment, to
Iron salt solutions are added in reaction system, the mol ratio of Fe and As is controlled 1~5:1, regulation and control reaction is in the condition of pH value 1.5~3
Under carry out, make Fe3+With AsO4 3-The solid arsenic mineral of high stability is synthesized；The iron salt solutions are ferrum sulfuricum oxydatum solutum, iron chloride
At least one in solution or iron nitrate solution.The addition speed of described iron salt solutions is 5-30ml/min.
Advantages of the present invention:
(1) present invention process is simple, and easy to operate, agents useful for same molysite, oxygen is laboratory common experimental material, instead
Mild condition is answered, it is low for equipment requirements.
(2) the solid arsenic mineral crystallinity that prepared by the present invention is high, it is easy to solid-liquor separation.
(3) the solid arsenic mineral that the present invention is prepared is because its crystallinity is high, BET specific surface area is small, stable region field width, and has
Standby high stability.And the leaching concentration of its arsenic be less than 0.5mg/L, less than GB5085.3-2007 (solid waste judging standard-
Leaching characteristic identification) regulation, can store up safely, solve solid arsenic mineral and be difficult to stablize under alkalescence and reductive condition and store up this
One problem.
In a word, the rational operation collocation of the present invention, by strictly controlling the conditional parameter in each operation, synthesize highly crystalline
The solid arsenic mineral of degree, bulky grain, high stability, Gu arsenic mineral stability is high, and can be in wide ph range (2~11) and strong reducing property bar
Stabilization is stored up under part, reduces the cost of arsenic treatment, has reached the purpose of environmental protection, economy, energy-conservation, high security, realizes the nothing of arsenic
Evilization.
Brief description of the drawings
Fig. 1 the inventive method process flow diagrams.
Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
Main component includes in arsenic containing solution：As 60g/L, Sb 1.1g/L, Pb 235ppm, Sn 38.5ppm, Te
24.4ppm, NaOH 30g/L.
A kind of preparation method of the solid arsenic mineral of high stability, comprises the following steps:Arsenic containing solution uses the side of catalysis oxidation
Method is by As3+It is oxidized to As5+, the condition for controlling is that oxygen flow is 5L/min, adds KMnO4For catalyst makes As/Mn mol ratios
Control is 10:1, as a result catalytic oxidation system temperature control shows at 90 DEG C, As3+Conversion ratio be 98.45%.
The pH value of oxidated solution is adjusted to 1.5, CaO and Ca (OH) is added in the way of continuous charging2As heavy arsenical,
Ca/As mol ratios are 5, and the sedimentation time is 6 hours, and reaction temperature is 60 DEG C, generates calcium arsenate.The solid arsenic mineral of synthesis uses hydro-thermal
Method, control condition is that calcium arsenate is placed in reactor, to ferrum sulfuricum oxydatum solutum is added in kettle, is controlled to its Fe/As mol ratio
2.5, make Fe3+With AsO4 3-The solid arsenic mineral of high stability is synthesized；Other control conditions are that reaction temperature is 120 DEG C, instead
It is 6h, mixing speed 400r/min between seasonable.The solid arsenic mineral of the high stability of synthesis, according to GB5085.3-2007 (solid waste
Judging standard-leaching characteristic identification) toxicity leaching is carried out, the leaching concentration of arsenic is 0.41mg/L, less than the limit value of the standard,
Can safety and stability store up.
Embodiment 2
Main component includes in arsenic containing solution：As 76g/L, Sb 0.8g/L, Pb 96.7ppm, Sn 27.5ppm, Te
38.7ppm, NaOH 25g/L.
A kind of preparation method of the solid arsenic mineral of high stability, comprises the following steps：Arsenic containing solution uses the side of catalysis oxidation
Method is by As3+It is oxidized to As5+, the condition for controlling is that oxygen flow is 10L/min, adds KMnO4For catalyst makes As/Mn moles
Than controlling 40：1, as a result catalytic oxidation system temperature control shows at 30 DEG C, As3+Conversion ratio be 92.31%；
The pH value of oxidated solution is adjusted to 2, CaO and Ca (OH) is added in the way of continuous charging2As heavy arsenical, Ca/
As mol ratios are 8, and the sedimentation time is 8 hours, and reaction temperature is 90 DEG C, generates calcium arsenate.The solid arsenic mineral of synthesis uses hydro-thermal method,
Control condition is that calcium arsenate is placed in reactor, to ferrum sulfuricum oxydatum solutum is added in kettle, its Fe/As mol ratio is controlled to 5,
Fe3+With AsO4 3-The solid arsenic mineral of high stability is synthesized；Other control conditions are that reaction temperature is 150 DEG C, reaction time
It is 7h, mixing speed 100r/min.The solid arsenic mineral of the high stability of synthesis, according to GB5085.3-2007, (solid waste differentiates mark
Standard-leaching characteristic identification) toxicity leaching is carried out, the leaching concentration of arsenic is 0.67mg/L, less than the limit value of the standard, can be safe
Stabilization is stored up.
Embodiment 3
Main component includes in arsenic containing solution：As 50g/L, Sb 1.8g/L, Pb 186ppm, Sn 34.7ppm, Te
27.8ppm, NaOH 5g/L.
A kind of preparation method of the solid arsenic mineral of high stability, comprises the following steps：Arsenic containing solution uses the side of catalysis oxidation
Method is by As3+It is oxidized to As5+, the condition for controlling is that oxygen flow is 1L/min, adds KMnO4For catalyst makes As/Mn mol ratios
Control is 20：1, as a result catalytic oxidation system temperature control shows at 120 DEG C, As3+Conversion ratio be 89.36%
The pH value of oxidated solution is adjusted to 1.5, CaO and Ca (OH) is added in the way of continuous charging2As heavy arsenical,
Ca/As mol ratios are 5, and the sedimentation time is 10 hours, and reaction temperature is 60 DEG C, generates calcium arsenate.The solid arsenic mineral of synthesis uses water
Hot method, control condition is that calcium arsenate is placed in reactor, to ferrum sulfuricum oxydatum solutum is added in kettle, controls its Fe/As mol ratio
It is 3, Fe3+With AsO4 3-The solid arsenic mineral of high stability is synthesized；Other control conditions are that reaction temperature is 120 DEG C, reaction
Time is 4h, mixing speed 350r/min.The solid arsenic mineral of the high stability of synthesis, according to GB5085.3-2007, (solid waste reflects
Other standard-leaching characteristic identification) toxicity leaching is carried out, the leaching concentration of arsenic is 0.54mg/L, less than the limit value of the standard, can
Safety and stability is stored up.
Although above having used general explanation, specific embodiment and experiment, the present invention is made to retouch in detail
State, but on the basis of the present invention, it can be made some modifications or improvements, this is to those skilled in the art apparent
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Scope.
Claims (7)
1. a kind of high stability consolidates the preparation method of arsenic mineral, it is characterised in that comprise the following steps：
(1) arsenic containing solution catalysis oxidation
By way of catalysis oxidation, to oxidizing gas and catalyst is added in arsenic containing solution, by the As in solution3+It is transformed into
As5+；
(2) the heavy arsenic of oxidated solution
Solution ph after step (1) gained oxidation is adjusted to 1.5~3, CaO, Ca (OH) are added in the way of continuous charging2In
One or two as heavy arsenical, the mol ratio for making Ca and As in the solution is 2~8:1, the sedimentation time is 5~10 small
When, reaction temperature is 10 DEG C~90 DEG C；
(3) the solid arsenic mineral of hydro-thermal method synthesis
Step (2) products therefrom is placed in reactor carries out solid arsenic treatment, to iron salt solutions are added in reaction system, makes reaction
The mol ratio of Fe and As is controlled 1~5 in system:1, regulation and control reaction is carried out under the conditions of pH value 1.5~3, makes Fe3+With AsO4 3-
The solid arsenic mineral of reaction generation high stability；The iron salt solutions are in ferrum sulfuricum oxydatum solutum, ferric chloride solution or iron nitrate solution
At least one.
2. high stability according to claim 1 consolidates the preparation method of arsenic mineral, it is characterised in that：It is described in step (1)
The main component of arsenic containing solution includes：As 5~100g/L, Sb 0.5g/L~3g/L, Pb 50ppm~800ppm, Sn 2ppm
10~120g/L of~200ppm, Te 10~500ppm, NaOH.
3. high stability according to claim 1 and 2 consolidates the preparation method of arsenic mineral, it is characterised in that institute in step (1)
Oxidizing gas are stated for oxygen, air or oxygen-enriched air；Preferably, the gas flow control of the oxidizing gas 1~
20L/min。
4. the preparation method of the solid arsenic mineral of high stability according to claim any one of 1-3, it is characterised in that step
(1) catalyst described in is KMnO4；Preferably, the mol ratio of As and Mn is controlled 5:1~50:1.
5. the preparation method of the solid arsenic mineral of high stability according to claim any one of 1-4, it is characterised in that step
(1) temperature that catalytic oxidation system described in is controlled is 30 DEG C~120 DEG C.
6. the preparation method of the solid arsenic mineral of high stability according to claim any one of 1-5, it is characterised in that step
(3) condition that the hydro-thermal method described in is controlled is that reaction temperature is 100 DEG C~200 DEG C, and the reaction time is 2h~10h, mixing speed
50r/min~500r/min.
7. the preparation method of the solid arsenic mineral of high stability according to claim any one of 1-6, it is characterised in that step
(3) the addition speed of the iron salt solutions described in is 5-30ml/min.
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| CN114836636A (en) * | 2022-05-24 | 2022-08-02 | 江西理工大学 | Method for separating arsenic from arsenic-containing alkali liquor and recovering alkali |
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