CN107312928B - A kind of method that arsenic sulfide slag prepares pentavalent arsenic leachate - Google Patents

A kind of method that arsenic sulfide slag prepares pentavalent arsenic leachate Download PDF

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CN107312928B
CN107312928B CN201710500670.3A CN201710500670A CN107312928B CN 107312928 B CN107312928 B CN 107312928B CN 201710500670 A CN201710500670 A CN 201710500670A CN 107312928 B CN107312928 B CN 107312928B
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arsenic
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sulfide slag
leachate
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CN107312928A (en
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贾永锋
马旭
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Institute of Applied Ecology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
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Abstract

The present invention provides a kind of arsenic sulfide slags for the method for pentavalent arsenic leachate, comprising the following steps: (1) is successively alternately added alkaline solution and oxidant into arsenic sulfide slag, is dissolved and aoxidized, be separated by solid-liquid separation, obtain filtrate；The pH value of the dissolution and oxidation process system is 7~14；(2) filtrate and oxidant are mixed and carries out oxidation reaction, be separated by solid-liquid separation, obtain pentavalent arsenic leachate；The endpoint pH of the oxidation reaction is 1~7.The present invention is successively alternately added alkaline solution and oxidant into arsenic sulfide slag, so that the arsenones in arsenic sulfide slag is constantly dissolved and is aoxidized, then obtain pentavalent arsenic leachate by deep oxidation.Embodiment the result shows that, arsenic content is high in the resulting leachate of the present invention, is easy to consolidate arsenic method by scorodite and fixes the arsenic in leachate, arsenic content is only 0.5wt% or so in remaining filter residue.

Description

A kind of method that arsenic sulfide slag prepares pentavalent arsenic leachate
Technical field
The present invention relates to a kind of technical field of Solid state fermentation, in particular to a kind of arsenic sulfide slag prepares pentavalent arsenic leachate Method.
Background technique
In the production processes such as metallurgical industry, chemical industry, solution dearsenification processing usually uses sulphide precipitation, thus Generate arsenic sulfide slag.Arsenide is extremely toxic substance, and stability is very poor, and arsenic-containing waste, which mostly uses greatly, for a long time hoards storage Method processing, cause high concentration arsenic-containing waste cumulative, generate secondary pollution in order to prevent, to arsenic sulfide slag carry out it is harmless The problem of change is treated as urgent need to resolve.
Currently, the processing technique of arsenic sulfide slag mainly has: arsenones produce the technology of arsenic trioxide, arsenones produce arsenic The technology of hydrochlorate.Wherein arsenones produce the process complexity of arsenic trioxide, and processing cost is high, and arsenic trioxide market at present Atrophy, demand are low；The process flow that arsenones produce arsenate is short, is easy to control, but Leach reaction under alkaline condition The dosage for the arsenate for being not thorough, and preparing is limited, and sodium hydroxide consumption is big in preparation process and higher cost.
Scorodite precipitation technique be generally used for processing arsenious waste solution, the arsenic-containing waste residue amount stability with higher of generation, But the precursor liquid of scorodite crystallization must be pentavalent arsenic solution, and arsenic sulfide slag dissolubility is low, arsenic is not easy to leach, and is not easy to be prepared into Solution, thus be not available scorodite precipitation technique and handled.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of method that arsenic sulfide slag prepares pentavalent arsenic leachate, the present invention The method arsenic leaching rate of offer is high, and obtained pentavalent arsenic leachate is suitble to the synthesis of scorodite, consolidates arsenic method by scorodite and is easy By the pentavalent arsenic removing in leachate.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of methods that arsenic sulfide slag prepares pentavalent arsenic leachate, comprising the following steps:
(1) it is successively alternately added alkaline solution and oxidant into arsenic sulfide slag, dissolved and is aoxidized, is separated by solid-liquid separation, Obtain filtrate；The pH value of the dissolution and oxidation process system is 7~14；
(2) filtrate and oxidant are mixed and carries out oxidation reaction, be separated by solid-liquid separation, obtain pentavalent arsenic leachate；It is described The endpoint pH of oxidation reaction is 1~7.
Preferably, the alkaline solution is alkaline hydrated oxide solution.
Preferably, the alkaline hydrated oxide solution is sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution.
Preferably, the concentration of the alkaline hydrated oxide solution is 100~1000g/L.
Preferably, the oxidant in the step (1) and step (2) is independently hydrogen peroxide, ozone, oxygen, permanganic acid One or more of potassium and perchloric acid.
Preferably, the molar ratio of total arsenic is 1~10:1 in oxidant and arsenic sulfide slag in the step (1).
Preferably, the pH value of step (1) dissolution and oxidation process system is 8~13.
Preferably, the molar ratio of total arsenic is 1~10:1 in oxidant and filtrate in the step (2).
Preferably, the endpoint pH of oxidation reaction is 2~6 in the step (2).
Preferably, alkaline solution and oxidant are successively alternately added in the step (1) specifically:
Alkaline solution is added into arsenic sulfide slag, obtains the first mixed system, the pH of the first mixed system of control is no more than 14；
Oxidant is added into first mixed system, obtains the second mixed system, controls the pH of the second mixed system Value is not less than 7；
Continue that alkaline solution and oxidant are successively alternately added into system, until the arsenones in arsenic sulfide slag are completely molten Solution.
The present invention provides a kind of processing methods of arsenic sulfide slag, comprising the following steps: (1) successively hands over into arsenic sulfide slag It for alkaline solution and oxidant is added, is dissolved and is aoxidized, be separated by solid-liquid separation, obtain filtrate；The dissolution and oxidation process body The pH value of system is 7~14；(2) filtrate and oxidant are mixed and carries out oxidation reaction, be separated by solid-liquid separation, obtain pentavalent arsenic leaching Liquid；The endpoint pH of the oxidation reaction is 1~7.The present invention is successively alternately added alkaline solution and oxidation into arsenic sulfide slag Agent makes the arsenones in arsenic sulfide slag constantly dissolve and aoxidize, and converts pentavalent arsenic for most of trivalent arsenic therein, then lead to It crosses deep oxidation and obtains pentavalent arsenic leachate.Embodiment the result shows that, pentavalent arsenic contains in the pentavalent arsenic leachate that the present invention obtains Amount is high, and the arsenic content in remaining filter residue is only 0.5wt%~0.6wt%, illustrates that most arsenic in arsenic sulfide slag enter In leachate.In addition, the resulting leachate of the present invention is easy to consolidate arsenic method by scorodite and fixes the arsenic in leachate, so as to It enough avoids the problem that generating a large amount of harmful solid wastes during conventional vulcanized arsenic Slag treatment, avoids and secondary pollution is caused to environment.
Detailed description of the invention
Fig. 1 is the XRD spectrum for the scorodite precipitation that the embodiment of the present invention 4 obtains；
Fig. 2 is the SEM figure for the scorodite precipitation that the embodiment of the present invention 4 obtains.
Specific embodiment
The present invention provides a kind of processing methods of arsenic sulfide slag, comprising the following steps:
(1) it is successively alternately added alkaline solution and oxidant into arsenic sulfide slag, dissolved and is aoxidized, is separated by solid-liquid separation, Obtain filtrate；The pH value of the dissolution and oxidation process system is 7~14；
(2) filtrate and oxidant are mixed and carries out oxidation reaction, be separated by solid-liquid separation, obtain pentavalent arsenic leachate；It is described The endpoint pH of oxidation reaction is 1~7.
In the present invention, the arsenic sulfide slag is in the production processes such as metallurgical industry, chemical industry, using sulfide precipitation Method dearsenification and generate arsenic sulfide slag, the main component in arsenic sulfide slag is arsenones, also miscellaneous containing the heavy metals such as Pb, Zn, Cd, Cu Matter.
The present invention is successively alternately added alkaline solution and oxidant into arsenic sulfide slag, is dissolved and is aoxidized, solid-liquid point From obtaining filtrate；The pH value of system is 7~14 in dissolution and oxidation process.In the present invention, dissolution and system in oxidation process PH value be preferably 8~13, more preferably 9~12；The alkaline solution is preferably alkaline hydrated oxide solution, more preferably hydrogen Sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution；The concentration of the alkaline hydrated oxide solution is preferably 100~ 1000g/L, more preferably 400~800g/L；The oxidant is preferably hydrogen peroxide, ozone, sulfur dioxide, oxygen, permanganic acid One or more of potassium and perchloric acid；The concentration of the hydrogen peroxide is preferably 1~30wt%, more preferably 25~29wt%； The molar ratio of total arsenic is preferably 1~10:1 in the oxidant and arsenic sulfide slag, more preferably 2~6:1.
Alkaline solution and oxidant are successively alternately added in arsenic sulfide slag mixing slurry by the present invention to be dissolved and aoxidizes, In the present invention, the process of alkaline solution and oxidant is alternately added in the step (1) specifically:
Alkaline solution is added into arsenic sulfide slag, obtains the first mixed system, the pH of the first mixed system of control is no more than 14；
Oxidant is added into first mixed system, obtains the second mixed system, controls the pH of the second mixed system Value is not less than 7；
As described in above-mentioned steps, continue successively to be alternately added alkaline solution and oxidant into system, until arsenic sulfide slag Arsenones in mixing slurry are completely dissolved.
In a specific embodiment of the present invention, judge that the standard that arsenones are completely dissolved becomes deep for the color of mixed system When blackish green or mixed system pH value is more sensitive to alkaline solution, that is, it can determine whether that arsenones are completely dissolved.
Alkaline solution is added into arsenic sulfide slag by the present invention, obtains the first mixed system, controls the pH of the first mixed system No more than 14, preferably more than 13.5, more preferably no more than 13；Then oxidant is added into first mixed system, obtains To the second mixed system, the pH value for controlling the second mixed system is not less than 7, preferably not less than 7.5, more desirably not less than 8.At this In field, arsenones are not readily dissolved, and the present invention is partly dissolved the arsenones in arsenic sulfide slag by the way that alkaline solution is added, trivalent Arsenic enters in liquid phase, adds oxidant for trivalent arsenic and is oxidized to pentavalent arsenic, breaks the dissolution equilibrium of arsenones, then adds Alkaline solution makes arsenones continue to dissolve, and replaces repeatedly, dissolves arsenones constantly, until dissolution is complete.The present invention is logical The pH value for crossing system in control dissolution and oxidation process, comes out the heavy metal precipitation in arsenic sulfide slag, while making arsenic and difference The sulphion of form enters in liquid phase, obtains sulphur simple substance by-product subsequently through oxidation.
Arsenic sulfide slag is preferably configured to arsenic sulfide slag mixing slurry and adds alkaline solution and oxidant by the present invention；The sulphur Change arsenic slag mixing slurry preferably to be mixed by arsenic sulfide slag and water, the present invention mixes middle arsenic sulfide slag the arsenic sulfide slag Quality does not have particular/special requirement, and arsenic sulfide slag content is higher in arsenic sulfide slag mixing slurry, five in final gained pentavalent arsenic leachate Valence arsenic content is higher, and the concentration of arsenic sulfide slag in arsenic sulfide slag mixing slurry can be selected according to required pentavalent arsenic concentration；At this In the specific embodiment of invention, in the arsenic sulfide slag mixing slurry quality of arsenic sulfide slag and the volume ratio of water be preferably 1~ 20g:10mL, more preferably 2~3g:10mL；The present invention does not have particular/special requirement to the hybrid mode of arsenic sulfide slag and water, uses this The technical solution mixed known to the technical staff of field.In the present invention, the arsenones that arsenic sulfide slag and water mix Slag mixing slurry is acidity, and pH value is 3 or so.
The present invention dissolves arsenic sulfide slag and the temperature of oxidation process does not have particular/special requirement, in specific embodiments of the present invention In, preferably promote the dissolution of arsenones by heating；The temperature of the heating is preferably 10~150 DEG C, more preferably 30~90 DEG C, most preferably 70~80 DEG C.
After arsenones dissolution completely, dissolved system is separated by solid-liquid separation by the present invention, obtains filtrate.The present invention is to solid The specific method of liquid separation does not have particular/special requirement, using solid-liquid separating method well known to those skilled in the art, specifically Such as filtering.In the present invention, gained filter residue is the dirt rich in heavy metals such as Pb, Zn, Cd, Cu after the step (1) is separated by solid-liquid separation Mud can be used for the recycling of heavy metal；Leading ion in the filtrate is the sulphion of trivalent arsenic, pentavalent arsenic and different shape, Only minimal amount of heavy metal ion can enter in filtrate.
After obtaining filtrate, the filtrate and oxidant are mixed and carry out oxidation reaction by the present invention, are separated by solid-liquid separation, are obtained pentavalent Arsenic leachate；The endpoint pH of the oxidation reaction is 1~7.In the present invention, the endpoint pH of the oxidation reaction is preferably 2~6, more preferably 3~5；The type of the oxidant is consistent with above scheme, and details are not described herein；The oxidant and filter The molar ratio of total arsenic is preferably 1~10:1, more preferably 2~6:1 in liquid；The present invention is not special to the time of oxidation reaction It is required that the terminal pH of reaction system reaches 1~7.
Trivalent arsenic remaining in filtrate is oxidized to pentavalent arsenic by oxidation reaction by the present invention, while will be present in filtrate Different morphologic sulphur ionic oxide formation is elemental sulfur.
After the completion of the oxidation reaction, the system after oxidation reaction is separated by solid-liquid separation by the present invention, obtains pentavalent arsenic leaching Liquid out.The present invention does not have particular/special requirement to the specific method of separation of solid and liquid, uses separation of solid and liquid well known to those skilled in the art Method, it is specific as filtered.In the present invention, the step (2) is separated by solid-liquid separation obtained solid matter main component and is Elemental sulfur, test result show that arsenic content is only 0.6wt% or so in elemental sulfur that the present invention obtains, can be used for producing sulfuric acid.
Arsenic content can achieve 1~50g/L in the pentavalent arsenic leachate that the present invention obtains, and be suitable for the synthesis of scorodite, In a specific embodiment of the present invention, it scorodite can be used to consolidate arsenic method the arsenic in pentavalent arsenic leachate is fixed, reach and remove The purpose of arsenic.
The concrete operation method that the present invention consolidates arsenic method for scorodite does not have particular/special requirement, ripe using those skilled in the art The scorodite known consolidates arsenic method.In a specific embodiment of the present invention, the scorodite consolidates the fixed pentavalent arsenic leachate of arsenic method Preferably include following steps:
It will be mixed after the acidification of pentavalent arsenic leachate with trivalent iron salt, heavy arsenic carried out at 80~95 DEG C.
In the present invention, acidification acid is preferably one or more of sulfuric acid, hydrochloric acid and nitric acid；The acidification Endpoint pH is preferably 1~3, and more preferably 1.5~2.5；The present invention does not have particular/special requirement, energy to the concentration and dosage of the acid It is enough that pentavalent arsenic leachate is acidified to required pH value；The present invention makes the pH value of system be suitble to the conjunction of scorodite by acidification At.
In the present invention, the trivalent iron salt is preferably one or more of ferric sulfate, iron chloride and ferric nitrate；It is described The molar ratio of total arsenic is preferably 1~2:1 in trivalent iron salt and pentavalent arsenic leachate, more preferably 1.5:1；The temperature of the heavy arsenic It is 80~95 DEG C, preferably 85~90 DEG C；The time of the heavy arsenic is preferably 5~9h, more preferably 6~8h, most preferably 7h.
In the present invention, the chemical reaction that the heavy arsenic process occurs is as follows:
Fe3++AsO4 3-+2H2O→FeAsO4·2H2O (scorodite).
Pentavalent arsenic is fixed in scorodite by the present invention by heavy arsenic, and scorodite is that a kind of stability is high, safe and harmless Solid containing arsenic.
After the heavy arsenic, heavy arsenic products therefrom system is preferably separated by solid-liquid separation by the present invention, obtains scorodite and filtrate. The present invention does not have particular/special requirement to the specific method of separation of solid and liquid, is using solid-liquid separating method well known to those skilled in the art Can, it is specific as filtered.
In the present invention, Gu arsenic content is lower in gained filtrate after arsenic reaction, the arsenic content in filtrate can be detected, If arsenic content does not meet the requirement of GB8978-1996 " in sewage and discharge standard " still, iron arsenic coprecipitation can be further used Carry out deeply removing arsenic.
The present invention does not have particular/special requirement to the concrete operation method of iron arsenic coprecipitation, using known to those skilled in the art Iron arsenic coprecipitation.
It is carried out below with reference to the method that embodiment prepares pentavalent arsenic leachate to arsenic sulfide slag provided by the invention detailed Illustrate, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Arsenic sulfide slag: containing As:20g/100g, and arsenic sulfide slag 100g and 100mL water is mixed, and obtains arsenic sulfide slag mixing Slurry, is heated to 60 DEG C for arsenic sulfide slag mixing slurry under mechanical stirring, and 500g/LNaOH is added in arsenic sulfide slag mixing slurry, is obtained To the first mixed system, the pH value for controlling the first mixed system is no more than 14, quality point is then added into the first mixed system The H that number is 30%2O2, obtain the second mixed system, the pH value of the second mixed system of control is not less than 8.5, continue alternately and repeatedly to NaOH solution and H are added in arsenic sulfide slag mixing slurry2O2, until mixing slurry color transition is that depth is blackish green, it is separated by solid-liquid separation, Obtain filtrate and heavy metal sewage sludge；
30%H is continuously added into gained filtrate2O2, reaction end pH control is separated by solid-liquid separation 3.5, obtains pentavalent arsenic leaching Liquid and elemental sulfur out.
Detected that (detection method is as follows: As test method: As concentration uses boron hydrogen to the arsenic content in heavy metal sewage sludge Change potassium, atomic fluorescence spectrum measurement, atomic fluorescence spectrophotometer (AFS-2202E) is carried out after 5 samples of every survey Single-point verification), can obtain the arsenic content in heavy metal sewage sludge is 0.58wt%, illustrates that the arsenic of the overwhelming majority all enters in filtrate.
4 sample points are randomly selected during alternately dissolution oxidation, detect total arsenic content and trivalent arsenic content in solution, And total arsenic content (As (T)) and trivalent when dissolving oxidation terminal and step (2) oxidation reaction terminal to step (1) in filtrate Arsenic content (As (III)) is detected, and gained testing result is as shown in table 1:
During the dissolution oxidation of table 1 As (T) and As (III) content with pH value variation
In table 1, the sample point of pH value 11.38,10.18,9.94,11.58 is grab sample point, the sampling that pH is 9.96 Sample point when point is step 1 dissolution oxidation terminal (i.e. mixing slurry becomes deep blackish green), it is that step (2) oxidation is anti-that pH, which is 5.5, Answer sample point when terminal.
According to table 1 as can be seen that during dissolution oxidation, with the progress of dissolution oxidation, the total arsenic content in liquid phase is got over Come higher, and trivalent arsenic content is fewer and fewer, and when step (2) oxidation reaction terminal, the trivalent arsenic content in solution is only 0.222g/L illustrates that the trivalent arsenic of the overwhelming majority is oxidized for pentavalent arsenic.
Arsenic content in by-product elemental sulfur obtained by step (2) is detected, the arsenic content that can be obtained in elemental sulfur is only 0.61wt% can be used to produce sulfuric acid.
Embodiment 2
Arsenic sulfide slag: containing As:20g/100g, and arsenic sulfide slag 100g and 100mL water is mixed, and obtains arsenic sulfide slag mixing Slurry, is heated to 90 DEG C for arsenic sulfide slag mixing slurry under mechanical stirring, by the Ca (OH) of 250g/L2Arsenic sulfide slag mixing slurry is added In, the first mixed system is obtained, the pH value of the first mixed system of control is no more than 12, is then passed through oxygen to the first mixed system Gas obtains the second mixed system, and the pH value of the second mixed system of control is not less than 8.5, continues alternately and repeatedly mixed to arsenic sulfide slag It closes in slurry and Ca (OH) is added2Solution and H2O2, until mixing slurry color transition is that depth is blackish green, it is separated by solid-liquid separation, is filtered Liquid；
The liquor potassic permanganate that mass fraction is 30% is continuously added into gained filtrate, reaction end pH control 5.0, It is separated by solid-liquid separation, obtains pentavalent arsenic leachate and elemental sulfur.
The arsenic content in heavy metal sewage sludge is detected according to the method in embodiment 1, can be obtained in heavy metal sewage sludge Arsenic content is 0.60wt%, illustrates that the arsenic of the overwhelming majority all enters in filtrate.
Total arsenic content and trivalent arsenic content during aoxidizing according to the method in embodiment 1 to dissolution in solution are examined It surveys, gained testing result is as shown in table 2:
During the dissolution oxidation of table 2 As (T) and As (III) content with pH value variation
In table 2, the sample point of pH value 11.20,10.35,11.2,10.59 is grab sample point, the sampling that pH is 9.85 Sample point when point is step 1 dissolution oxidation terminal (i.e. mixing slurry becomes deep blackish green), it is that step (2) oxidation is anti-that pH, which is 5.0, Answer sample point when terminal.
According to table 2 as can be seen that during dissolution oxidation, with the progress of dissolution oxidation, the total arsenic content in liquid phase is got over Come higher, and trivalent arsenic content is fewer and fewer, and when step (2) oxidation reaction terminal, the trivalent arsenic content in solution is only 0.21g/L illustrates that the trivalent arsenic of the overwhelming majority is oxidized for pentavalent arsenic.
Arsenic content in by-product elemental sulfur obtained by step (2) is detected, the arsenic content that can be obtained in elemental sulfur is only 0.60wt% can be used to produce sulfuric acid.
Embodiment 3
(1) arsenic sulfide slag: containing As:30g/100g, and arsenic sulfide slag 100g and 100mL water is mixed, and it is mixed to obtain arsenic sulfide slag Slurry is closed, arsenic sulfide slag mixing slurry is heated to 80 DEG C under mechanical stirring, 300g/LNaOH is added in arsenic sulfide slag mixing slurry, The first mixed system is obtained, the pH value of the first mixed system of control is no more than 12, quality then is added into the first mixed system The H that score is 30%2O2, the second mixed system is obtained, the pH value of the second mixed system of control is not less than 8.5, continues alternately and repeatedly NaOH solution and H are added into arsenic sulfide slag mixing slurry2O2, until mixing slurry color transition is deep blackish green, progress solid-liquid point From obtaining filtrate and heavy metal sewage sludge；
(2) 30%H is continuously added into gained filtrate2O2, reaction end pH control is separated by solid-liquid separation, obtains pentavalent 6.0 Arsenic leachate and elemental sulfur.
The arsenic content in heavy metal sewage sludge is detected according to the method in embodiment 1, can be obtained in heavy metal sewage sludge Arsenic content is 0.61wt%, illustrates that the arsenic of the overwhelming majority all enters in filtrate.
Total arsenic content and trivalent arsenic content during aoxidizing according to the method in embodiment 1 to dissolution in solution are examined It surveys, gained testing result is as shown in table 3:
During the dissolution oxidation of table 3 As (T) and As (III) content with pH value variation
In table 3, the sample point of pH value 11.35,11.28,10.95,10.58 is grab sample point, and pH is 9.66 to take Sample point when sampling point is step 1 dissolution oxidation terminal (i.e. mixing slurry becomes deep blackish green), it is step (2) oxidation that pH, which is 6.0, Sample point when reaction end.
According to table 3 as can be seen that during dissolution oxidation, with the progress of dissolution oxidation, the total arsenic content in liquid phase is got over Come higher, and trivalent arsenic content is fewer and fewer, and when step (2) oxidation reaction terminal, the trivalent arsenic content in solution is only 0.204g/L illustrates that the trivalent arsenic of the overwhelming majority is oxidized for pentavalent arsenic.
Arsenic content in by-product elemental sulfur obtained by step (2) is detected, the arsenic content that can be obtained in elemental sulfur is only 0.59wt% can be used to produce sulfuric acid.
Embodiment 4
The pentavalent arsenic leachate that Example 1 obtains, sulfuric acid acidification, which is added, makes pH of leaching solution be down to 2.0, heating mixing Object is to 95 DEG C and the trivalent iron salt that Fe/As molar ratio is 1 is added, and the time is added as 2h in control, and (200rpm) is held under mechanical stirring Continuous 8h, continues to be separated by solid-liquid separation, obtains stable scorodite, is separated by solid-liquid separation, obtains filtrate and scorodite, and Fe is pressed into filtrate (III)/As molar ratio is 4 addition ferric sulfate, continues to neutralize to pH=7 with calcium oxide, is separated by solid-liquid separation, obtains final filtrate.
Obtained scorodite precipitation is detected using X-ray diffraction method, gained XRD spectrum is as shown in Figure 1；According to figure 1 as can be seen that scorodite precipitation and scorodite standard card PDF00-018-0654 matching degree that the present invention obtains are good, it is known that There is higher crystallinity by resulting scorodite.
Gained scorodite precipitation is observed using scanning electron microscope, gained SEM figure is as shown in Figure 2；According to fig. 2 As can be seen that gained scorodite is crystal grain of the partial size less than 10 μm.
By the hazardous waste leach toxicity test method of USEPA (TCLP) to the stability of obtained scorodite precipitation into Row measurement, the TCLP arsenic concentration that can obtain scorodite is only 1.985ppm, far below 5ppm specified in USEPA.
The arsenic content of the final filtrate of gained is detected, can obtain arsenic content is only 0.19mg/L, is far below GB8978- 0.5mg/L specified in 1996 " in sewage and discharge standards ".
As seen from the above embodiment, arsenic sulfide slag can effectively be dissolved and be aoxidized by method provided by the invention, be prepared into Pentavalent arsenic leachate, can remove the heavy metal and sulphur of the overwhelming majority in preparation process, in finally obtained pentavalent arsenic leachate Arsenic concentration is high, is easy to consolidate arsenic method or iron arsenic coprecipitation arsenic removal by scorodite, so as to avoid conventional vulcanized arsenic Slag treatment A large amount of harmful solid wastes are led to the problem of in the process, avoid and secondary pollution is caused to environment.
As seen from the above embodiment, the present invention is the above is only a preferred embodiment of the present invention, it is noted that for For those skilled in the art, without departing from the principle of the present invention, can also make it is several improvement and Retouching, these modifications and embellishments should also be considered as the scope of protection of the present invention.

Claims (9)

1. a kind of method that arsenic sulfide slag prepares pentavalent arsenic leachate, comprising the following steps:
(1) it is successively alternately added alkaline solution and oxidant into arsenic sulfide slag, dissolved and is aoxidized, is separated by solid-liquid separation, obtains Filtrate；The pH value of the dissolution and oxidation process system is 7~14；
It is described to be successively alternately added alkaline solution and oxidant specifically:
Alkaline solution is added into arsenic sulfide slag, obtains the first mixed system, the pH of the first mixed system of control is no more than 14；
Oxidant is added into first mixed system, obtains the second mixed system, controls the pH value of the second mixed system not Lower than 7；
Continue that alkaline solution and oxidant are successively alternately added into system, until the arsenones in arsenic sulfide slag are completely dissolved；
(2) filtrate and oxidant are mixed and carries out oxidation reaction, be separated by solid-liquid separation, obtain pentavalent arsenic leachate；The oxidation The endpoint pH of reaction is 1~7.
2. the method according to claim 1, wherein the alkaline solution is alkaline hydrated oxide solution.
3. according to the method described in claim 2, it is characterized in that, the alkaline hydrated oxide solution be sodium hydroxide solution, Potassium hydroxide solution or calcium hydroxide solution.
4. according to the method in claim 2 or 3, which is characterized in that the concentration of the alkaline hydrated oxide solution be 100~ 1000g/L。
5. the method according to claim 1, wherein the oxidant in the step (1) and step (2) is independent For one or more of hydrogen peroxide, ozone, oxygen, potassium permanganate and perchloric acid.
6. method according to claim 1 or 5, which is characterized in that total in oxidant and arsenic sulfide slag in the step (1) The molar ratio of arsenic is 1~10:1.
7. the method according to claim 1, wherein the pH value of the step (1) dissolution and oxidation process system It is 8~13.
8. the method according to claim 1, wherein total arsenic rubs in oxidant and filtrate in the step (2) You are than being 1~10:1.
9. the method according to claim 1, wherein in the step (2) oxidation reaction endpoint pH be 2~ 6。
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CN103388076A (en) * 2013-07-23 2013-11-13 中南民族大学 Method for recovering elementary substance arsenic from arsenic sulfide slag
CN106180138A (en) * 2016-07-15 2016-12-07 深圳市危险废物处理站有限公司 A kind of processing method of arsenic-containing waste
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CN103030233A (en) * 2011-09-30 2013-04-10 深圳市明灯科技有限公司 Treatment method for high-concentration arsenic waste water
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