CN116199320B - A method for optimizing crystal seeds and stabilizing arsenic in high-acid, protein-containing and arsenic-containing wastewater - Google Patents
A method for optimizing crystal seeds and stabilizing arsenic in high-acid, protein-containing and arsenic-containing wastewater Download PDFInfo
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Abstract
An optimized seed crystal for high-acid protein-containing arsenic-containing wastewater and a method for stabilizing solid arsenic thereof belong to the technical field related to environmental protection water pollution treatment. Adding a pH regulator into the high-acid protein-containing arsenic-containing wastewater, regulating the pH value to be 1.5-2.5, carrying out solid-liquid separation, heating and stirring the primary solution, and carrying out solid-liquid separation again to obtain the crystal form scorodite; mixing crystal form scorodite and neutralizer to obtain slurry; and (3) reacting the slurry with high-acid protein-containing arsenic-containing wastewater, performing solid-liquid separation, and pickling, drying and grinding the obtained arsenic slag to obtain the optimized seed crystal. Mixing the optimized seed crystal and the neutralizer, adding the high-acid protein-containing arsenic-containing wastewater seed, and carrying out an arsenic removal reaction to obtain stable arsenic-fixing slag, wherein the arsenic removal rate is up to more than 99.99%. The method has simple process, reduces the arsenic slag quantity to 1/3-1/2 of the prior art, and can realize the recycling of resources.
Description
Technical Field
The invention belongs to the technical field of environmental protection water pollution treatment, relates to a wastewater purification treatment method for high-arsenic refractory gold ore generated in a biological metallurgy process, and in particular relates to a high-acid protein-containing arsenic-containing wastewater optimization seed crystal and a method for stabilizing and fixing arsenic.
Background
Arsenic-containing gold ores are the most studied ore type at present because of the greatest reserves and the highest economic value of recovery. Arsenic is widely used as a class I pollutant in industrial wastewater, and causes great pollution to water resources and soil. Gao Shen refractory gold ores can oxidize arsenic in ores into low-toxicity pentavalent arsenic in a biological metallurgy process, so that a biological oxidation method has become a method with wide application prospect. Gao Shen refractory gold ores can generate a large amount of high-acid protein-containing arsenic-containing wastewater in the biological metallurgy process, and besides low-toxicity pentavalent arsenic, arsenic in the wastewater still contains trace highly toxic trivalent arsenic and arsenic combined with protein, and if the wastewater is not treated, direct discharge can bring serious harm to the environment and human health. Therefore, the high-acid protein-containing arsenic-containing wastewater can be discharged after reaching the standard.
At present, the arsenic-containing wastewater treatment method is more, and mainly comprises a chemical precipitation method, a flocculation method, an extraction method, an adsorption method, a microbiological method and the like, but the chemical precipitation method is most widely applied and has the best effect in engineering practice. Sulfidation and lime neutralization are the most commonly used chemical precipitation methods. The vulcanizing method has the advantages of high reaction speed, large treatment capacity and simple process, but arsenic can be dissolved into solution again due to the change of pH value, toxic gas H 2 S can be generated to pollute the atmosphere, and the defects of high medicament treatment cost and large residual sulfur content of discharged water exist. The lime neutralization method is simple in process, convenient to implement, obvious in cost advantage, stable in wastewater discharge and up to the standard, and is the most widely applied arsenic removal method in the industry at present.
In addition, in view of the water quality uniqueness of the high-acid protein-containing arsenic-containing wastewater (high-acid protein-containing), the lime neutralization method is also a method for treating the high-acid protein-containing arsenic-containing wastewater of a biological metallurgy enterprise. Although the method can remove most of arsenic in the high-acid protein-containing arsenic-containing wastewater, the arsenic content in the backwater is still higher than 0.5mg/L, and the growth of bacteria is adversely affected by the gradual accumulation of arsenic for a long time; meanwhile, the main phases of arsenic slag generated by a lime neutralization method are amorphous ferric arsenate and calcium arsenate with high solubility, the slag quantity is very large, the existing arsenic slag disposal method is to pile up the arsenic slag in a tailing pond, secondary pollution is easily caused after long-term placement, and great environmental hidden trouble exists.
The patent with publication No. CN111170510A discloses a method for treating arsenic-containing wastewater and solidifying arsenic, and the invention solidifies all the precipitated arsenic in the form of scorodite although the precipitation rate of arsenic in the wastewater reaches 99.78%, but the process is very complicated and industrial application is difficult to realize.
Therefore, developing a method which has simple process, high arsenic removal efficiency, small arsenic slag quantity, good arsenic fixing effect and capability of realizing resource recycling is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide the optimized seed crystal of the high-acid protein-containing arsenic-containing wastewater and the method for stabilizing and fixing arsenic by the same, which have simple process, the arsenic slag quantity is reduced to 1/3-1/2 of that of the prior art, the arsenic removal rate is up to more than 99.99%, and the resource recycling can be realized.
The technical scheme adopted for solving the technical problems is as follows:
The invention relates to an optimized seed crystal for high-acid protein-containing arsenic-containing wastewater, which is prepared by the following steps:
S1: adding a pH regulator into the high-acid protein-containing arsenic-containing wastewater, and regulating the pH value of the high-acid protein-containing arsenic-containing wastewater to be 1.5-2.5 to obtain a primary slag mixed solution; solid-liquid separation is carried out to obtain a slag phase and a primary solution;
Heating the primary solution, stirring for 100-150 min, performing solid-liquid separation again, and pickling and drying the obtained solid product to obtain the crystal form scorodite;
s2: mixing crystal form scorodite and neutralizer to obtain slurry;
Reacting the slurry with high-acid protein-containing arsenic-containing wastewater, and carrying out solid-liquid separation to obtain filtrate and arsenic slag;
S3: and (3) pickling, drying and grinding the arsenic slag to obtain the high-acid protein-containing arsenic-containing wastewater optimized seed crystal.
In the technical scheme, the high-acid protein-containing arsenic-containing wastewater is characterized in that the arsenic content is higher than 3g/L, the iron content is higher than 18g/L, the sulfate radical content is 60-120 g/L, pH, the bacterial content is 10 3～1012/mL, and the protein content accounts for 60% -70% of the bacterial content.
In the technical scheme, the pH regulator in the step S1 is one or two of calcium oxide and calcium hydroxide, and water is mixed to prepare the slurry with the mass fraction of 5-15%. The pH regulator is added to regulate pH value and reduce Fe-As ratio and sulfate radical content.
In the step S1, the slag phase is a mixture of calcium sulfate, ferric hydroxide, amorphous calcium arsenate and ferric arsenate;
in the step S1, the heating temperature is 90-98 ℃;
In the step S1, the stirring speed is 800-1000 rpm, and the high-speed stirring is used for forming the crystal form scorodite.
In the above technical scheme, in the step S2, the neutralizing agent is a compound of calcium oxide and magnesium oxide, or calcium hydroxide and magnesium hydroxide according to the mass ratio of calcium: the magnesium compound is 1: (10-3) preparing into emulsion with mass concentration of 5% -30%.
In the S2, the addition amount of the crystal form scorodite is 0.0001-0.05% of the arsenic mass concentration in the high-acid protein-containing arsenic-containing wastewater.
In the step S2, the adding ratio of the crystal form scorodite to the neutralizer is controlled according to the pH value of the slurry, and the pH value is preferably 3.5-4.5;
In the step S2, the reaction of the slurry and the high-acid protein-containing arsenic-containing wastewater is as follows: reacting for 15-40 min at the stirring speed of 600-800 rpm and the pH value of 3.5-4.5;
the arsenic content in the filtrate is lower than 0.5mg/L, the iron content is lower than 50mg/L, the sulfate radical content is 30-60 g/L, and the pH value is 3.5-5; the arsenic slag contains 25-30% of arsenic, 15-25% of iron and 4-8% of sulfur.
In the above technical scheme, in the step S3, the grain size of the optimized seed crystal after mechanical grinding is more than 80% and is greater than 400 mesh;
The optimized seed crystal is a mixture of ferric hydroxide, crystalline ferric arsenate (crystalline form scorodite), magnesium arsenate and denatured protein precipitate.
The invention discloses a method for stabilizing and fixing arsenic by optimizing seed crystals in high-acid protein-containing arsenic-containing wastewater, which comprises the following steps:
Mixing the prepared high-acid protein-containing arsenic-containing wastewater optimized seed crystal with a neutralizer, adding the high-acid protein-containing arsenic-containing wastewater seed crystal, and carrying out an arsenic removal reaction to obtain stable arsenic-fixing slag, wherein the arsenic removal rate is up to more than 99.99%.
In the technical scheme of the method for stabilizing and fixing arsenic by optimizing seed crystals in the high-acid protein-containing arsenic-containing wastewater, the neutralizing agent is calcium oxide and magnesium oxide or a compound of calcium hydroxide and magnesium hydroxide according to calcium: the mass ratio of the magnesium compound is 1: (10-3) preparing into emulsion with mass concentration of 5% -30%. The pH value of the high-acid protein-containing arsenic-containing wastewater can be regulated by calcium oxide and magnesium oxide or calcium hydroxide and magnesium hydroxide, the reaction energy of the calcium oxide and magnesium hydroxide and the acid can release heat, the reaction rate can be improved, the magnesium oxide can realize the selective separation of arsenic and sulfur in the high-acid protein-containing arsenic-containing wastewater, the arsenic slag quantity can be reduced, and meanwhile, the stability of arsenic slag can be improved. In the reaction process, the too low concentration (lower than 5%) of the emulsion can cause the increase of the addition amount, reduce the reaction efficiency and increase the water treatment cost after purification; the emulsion concentration is too high (higher than 30%), which can lead to the failure of effective control of the reaction pH value, and the generated calcium sulfate is easy to wrap the medicament, resulting in medicament waste.
The optimized seed crystal addition amount of the high-acid protein-containing arsenic-containing wastewater is 0.0005% -0.1% of the arsenic mass concentration in the high-acid protein-containing arsenic-containing wastewater.
The addition amount of the optimized seed crystal and the neutralizer of the high-acid protein-containing arsenic-containing wastewater is controlled by the pH value of the solution, namely 3.5-5. In the above reaction process, the pH value control is very important to provide a reaction environment for generating the crystal form scorodite with stable structure.
The dearsenifying reaction condition is that stirring speed is 600-800 rpm, pH is 3.5-5, and reaction is carried out for 40-60 min;
The arsenic content in the arsenic-fixing slag is 5.5-7.5%, the iron content is 25-32%, the sulfur content is 7.5-10%, and the arsenic content in the arsenic-fixing slag is lower than 1.2mg/L as a result of toxic dissolution, thereby meeting the related requirements of GB 18598-2019.
The invention provides a method for stabilizing and fixing arsenic by optimizing seed crystals in high-acid protein-containing arsenic-containing wastewater, which has the beneficial effects that compared with the prior art:
(1) The high-acid protein-containing arsenic-containing wastewater is rapid and complete in arsenic removal and stable in arsenic fixation, so that the arsenic content in the acid wastewater with the molar ratio of iron (III) to arsenic (V) of more than 8 is lower than 0.5mg/L (the arsenic removal rate is more than 99.98 percent), the iron content is lower than 50mg/L (the iron removal rate is more than 99.72 percent), the arsenic content of the arsenic fixation slag toxic leaching result is lower than 1.2mg/L, and the arsenic fixation slag meets the related requirements of GB18598-2019 on hazardous waste landfill.
(2) The invention utilizes arsenic, iron and protein in the high-acid protein-containing arsenic-containing wastewater to synthesize the crystal form scorodite and optimize the seed crystal, thereby laying a foundation for generating arsenic slag with high crystallinity and good arsenic fixing effect in the subsequent process of neutralizing and dearsenifying and stabilizing the arsenic.
(3) The invention provides a set of simple treatment process, which has the advantages of simple equipment, easy operation, mild condition, low cost, small slag quantity, easy separation of solid and liquid, stable property of the solid arsenic slag, selective precipitation of arsenic and sulfur, high arsenic removal efficiency, small arsenic slag quantity and good arsenic fixing effect, and avoids secondary pollution.
Drawings
FIG. 1 shows XRD of arsenic fixing slag obtained in accordance with an embodiment of the present invention.
FIG. 2 is XRD of arsenic fixing slag obtained in comparative example of the first embodiment of the present invention.
FIG. 3 is a schematic process flow diagram of the method for optimizing seed crystal stabilization and arsenic fixation of high-acid protein-containing arsenic-containing wastewater.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples. It should be noted that the following examples are illustrative of the present invention, but are not intended to limit the scope of the present invention.
Example 1
400ML of high-acid protein-containing arsenic-containing wastewater from a biological oxidation smelting plant is placed in a beaker, wherein the arsenic concentration is 6280mg/L, the iron concentration is 22.3g/L, the sulfate radical is 112.3g/L, the pH value is 0.9, the bacterial number is 1000/mL, and the protein accounts for 60% of the bacteria. The process flow diagram of the method for stabilizing and fixing arsenic by optimizing seed crystals of high-acid protein-containing arsenic-containing wastewater is shown in fig. 3, and specifically comprises the following steps:
(1) Adding calcium oxide slurry with the mass concentration of 5% into high-acid protein-containing arsenic-containing wastewater, adjusting the pH value of the solution to be 1.5, filtering to remove slag, heating the residual solution to 90 ℃ and reacting at 800rpm for 120min, filtering, and pickling and drying the filtered solid product to obtain the crystal form scorodite;
(2) Taking the crystal form scorodite obtained in the step (1) according to 0.05% of the arsenic mass concentration in the high-acid protein-containing arsenic-containing wastewater, regulating the crystal form scorodite and calcium oxide and magnesium oxide (1+10) to form slurry with the concentration of 5%, adding the slurry into the high-acid protein-containing arsenic-containing wastewater, regulating the pH value of the solution to 4.5, reacting at 600rpm for 40min, filtering to obtain filtrate and arsenic slag, detecting that the arsenic content in the filtrate is 0.41mg/L (the arsenic removal rate is 99.993%), the iron content is 43mg/L (the iron removal rate is 99.807%), the sulfate content is 58.9g/L, and the arsenic content in the arsenic slag is 25% by mass, and the sulfur content in the arsenic slag is 4% by mass; wherein arsenic exists in the form of arsenate, iron phase contains ferric hydroxide, sulfur exists in the form of sulfate radical, and some crystal water, calcium, magnesium and the like can be also generated.
(3) Pickling the arsenic slag obtained in the step (2), drying, mechanically grinding, and using the arsenic slag as an optimized seed crystal of high-acid protein-containing arsenic-containing wastewater, wherein the granularity is 80% of +400 meshes;
(4) Taking the slurry with the concentration of 5% prepared by the optimized seed crystal and calcium oxide and magnesium oxide (1+10) of the high-acid protein-containing arsenic-containing wastewater obtained in the step (3) according to the mass concentration of 0.0005% of arsenic in the high-acid protein-containing arsenic-containing wastewater as a new dearsenification agent, regulating the pH value of the solution to be 5, reacting for 60min at 600rpm to obtain stable arsenic-fixing slag, wherein the arsenic removal rate is as high as 99.99%, the XRD of the obtained arsenic-fixing slag is as shown in figure 1, the mass percentage of arsenic in the arsenic-fixing slag is 7.5%, the mass percentage of iron is 32%, the mass percentage of sulfur is 7.5%, and the toxic leaching result of the arsenic-fixing slag is 0.12mg/L, thereby meeting the related requirements of GB 18598-2019.
Comparative example one
In contrast, the process of treating the high-acid protein-containing arsenic-containing wastewater in the first embodiment is directly carried out in the step (4) without adding the optimized seed crystal of the high-acid protein-containing arsenic-containing wastewater, and the conditions are the same as those in the first embodiment. As shown in figure 2, XRD of the obtained arsenic slag is poor in crystallinity, the mass percentage of arsenic in the arsenic slag is 5.13%, the mass percentage of iron is 29.26%, the mass percentage of sulfur is 8.51%, toxicity dissolution experiments are carried out on the arsenic slag according to HJ766, and through detection, the arsenic content is 1.12mg/L, and the stability of the arsenic slag meets the related requirements of GB18598-2019, but is close to the limit value of 1.2mg/L.
Example two
400ML of high-acid protein-containing arsenic-containing wastewater from a biological oxidation smelting plant is placed in a beaker, wherein the arsenic concentration is 4160mg/L, the iron concentration is 18.3g/L, pH, the value is 1.0, the sulfate radical content is 62.3g/L, the bacterial number is 10 12/mL, and the protein accounts for 70% of the bacteria.
(1) Adding calcium hydroxide slurry with the mass concentration of 15% into high-acid protein-containing arsenic-containing wastewater, adjusting the pH value of the solution to 2.5, filtering to remove slag, heating the residual solution to 98 ℃, reacting at 1000rpm for 120min, filtering, and pickling and drying the filtered solid product to obtain the crystal form scorodite;
(2) Taking the crystal form scorodite obtained in the step (1) according to 0.0001% of the arsenic mass concentration in the high-acid protein-containing arsenic-containing wastewater, preparing the crystal form scorodite and calcium oxide and magnesium oxide (1+3) into slurry with the mass concentration of 30%, adding the slurry into the high-acid protein-containing arsenic-containing wastewater, adjusting the pH value of the solution to 3.5, reacting for 15min at 800rpm, filtering to obtain filtrate and arsenic slag, detecting that the arsenic content in the filtrate is 0.34mg/L (arsenic removal rate 99.992%), the iron content is 35mg/L (iron removal rate 99.81%), the sulfate content is 30.1g/L, the arsenic mass percentage in the arsenic slag is 30%, the iron mass percentage is 15%, and the sulfur mass percentage in the arsenic slag is 8%;
(3) Pickling the arsenic slag obtained in the step (2), drying, mechanically grinding, and using the arsenic slag as an optimized seed crystal of high-acid protein-containing arsenic-containing wastewater, wherein the granularity is 90% of +400 meshes;
(4) Taking the high-acid protein arsenic-containing wastewater obtained in the step (3) according to 0.1% of the arsenic mass concentration in the high-acid protein arsenic-containing wastewater, adjusting the pH value of the solution to 4.5 by taking slurry with the mass concentration of 30% prepared by optimizing seed crystals and calcium oxide and magnesium oxide (1+3) as a new dearsenifying agent, and reacting for 40min at 600rpm to obtain stable arsenic-fixing slag, wherein the arsenic removal rate is up to more than 99.99%, the arsenic mass percentage in the arsenic-fixing slag is 5.5%, the iron mass percentage is 25%, the sulfur mass percentage is 10%, and the arsenic content of the toxicity leaching result of the arsenic-fixing slag is 0.82mg/L, thereby meeting the related requirements of GB 18598-2019.
Example III
400ML of high-acid protein-containing arsenic-containing wastewater from a biological oxidation smelting plant is placed in a beaker, wherein the arsenic concentration is 3100mg/L, the iron concentration is 20.3g/L, pH, the sulfate radical content is 78.1g/L, the bacterial number is 10 5/mL, and the protein accounts for 65% of the bacteria.
(1) Adding 10% calcium hydroxide slurry into high-acid protein-containing arsenic-containing wastewater, adjusting the pH value of the solution to 2, filtering to remove slag, heating the residual solution to 95 ℃ and 900rpm for reaction for 120min, filtering, and pickling and drying the solid product obtained by filtering to obtain the crystal form scorodite;
(2) Taking the crystal form scorodite obtained in the step (1) according to 0.001% of the arsenic mass concentration in the high-acid protein-containing arsenic-containing wastewater, preparing the crystal form scorodite and calcium oxide and magnesium oxide (1+5) into slurry with the mass concentration of 10%, adding the slurry into the high-acid protein-containing arsenic-containing wastewater, adjusting the pH value of the solution to be 4.0, reacting at 700rpm for 25min, filtering to obtain filtrate and arsenic slag, detecting that the arsenic content in the filtrate is 0.11mg/L (the arsenic removal rate is 99.996%), the iron content is 23mg/L (the iron removal rate is 99.886%), the sulfate content is 41g/L, and the arsenic content in the arsenic slag is 26.9%, the iron mass percentage is 20% and the sulfur mass percentage is 5.9%;
(3) Pickling the arsenic slag obtained in the step (2), drying, mechanically grinding, and using the arsenic slag as an optimized seed crystal of high-acid protein-containing arsenic-containing wastewater, wherein the granularity is 85% of +400 meshes;
(4) Taking the high-acid protein arsenic-containing wastewater obtained in the step (3) according to the mass concentration of 0.005% of arsenic in the high-acid protein arsenic-containing wastewater, adjusting the pH value of the solution to be 3.5 by taking slurry with the mass concentration of 10% prepared by optimizing seed crystals and calcium oxide and magnesium oxide (1+5) as a novel dearsenifying agent, reacting for 50min at 700rpm to obtain stable arsenic-fixing slag, wherein the arsenic removal rate is up to more than 99.99%, the mass percentage of arsenic in the arsenic-fixing slag is 6.1%, the mass percentage of iron is 27.4%, the mass percentage of sulfur is 8.3%, and the toxicity leaching result of the arsenic-fixing slag is 0.52mg/L, thereby meeting the related requirements of GB 18598-2019.
Example IV
400ML of high-acid protein-containing arsenic-containing wastewater from a biological oxidation smelting plant is placed in a beaker, wherein the arsenic concentration is 5090mg/L, the iron concentration is 30.7g/L, pH, the sulfate radical content is 90.1g/L, the bacterial number is 10 7/mL, and the protein accounts for 63% of the bacteria.
(1) Adding calcium hydroxide slurry with the mass concentration of 7.5% into high-acid protein-containing arsenic-containing wastewater, adjusting the pH value of the solution to be 1.8, filtering to remove slag, heating the residual solution to 93 ℃ and at 750rpm for reaction for 120min, filtering, and pickling and drying the solid product obtained by filtering to obtain the crystal form scorodite;
(2) Taking the crystal form scorodite obtained in the step (1) according to 0.01% of the mass concentration of arsenic in the high-acid protein-containing arsenic-containing wastewater, preparing slurry with the mass concentration of 15% by mixing the crystal form scorodite with calcium oxide and magnesium oxide (1+7), adding the slurry into the high-acid protein-containing arsenic-containing wastewater, adjusting the pH value of the solution to 3.75, reacting at 650rpm for 20min, filtering to obtain filtrate and arsenic slag, detecting the arsenic content in the filtrate to be 0.44mg/L (arsenic removal rate 99.991%), the iron content to be 49.7mg/L (iron removal rate 99.83%), the sulfate content to be 37.3g/L, and the arsenic content in the arsenic slag to be 28.6%, the iron content to be 18.1% and the sulfur content to be 5%;
(3) Pickling the arsenic slag obtained in the step (2), drying, mechanically grinding, and using the arsenic slag as an optimized seed crystal of high-acid protein-containing arsenic-containing wastewater, wherein the granularity is 87% of the granularity of +400 meshes;
(4) Taking the optimized seed crystal of the high-acid protein arsenic-containing wastewater obtained in the step (3) and calcium oxide and magnesium oxide (1+7) to prepare slurry with the mass concentration of 15 percent as a novel dearsenifying agent, adjusting the pH value of the solution to be 4.0, and reacting at 650rpm for 45min to obtain stable arsenic-fixing slag, wherein the arsenic removal rate is up to more than 99.99%, the mass percentage of arsenic in the arsenic-fixing slag is 6.9%, the mass percentage of iron is 26.8%, the mass percentage of sulfur is 7.9%, and the toxicity leaching result of the arsenic-fixing slag is 0.67mg/L, thereby meeting the related requirements of GB 18598-2019.
Example five
400ML of high-acid protein-containing arsenic-containing wastewater from a biological oxidation smelting plant is placed in a beaker, wherein the arsenic concentration is 3210mg/L, the iron concentration is 21.7g/L, pH, the sulfate radical content is 107.5g/L, the bacterial number is 10 9/mL, and the protein accounts for 68% of the bacteria.
(1) Adding calcium hydroxide slurry with the mass concentration of 12.5% into high-acid protein-containing arsenic-containing wastewater, adjusting the pH value of the solution to be 2.3, filtering to remove slag, heating the residual solution to 96.5 ℃ and reacting at 950rpm for 120min, filtering, and pickling and drying the filtered solid product to obtain the crystal form scorodite;
(2) Taking the crystal form scorodite obtained in the step (1) according to 0.03% of the arsenic mass concentration in the high-acid protein-containing arsenic-containing wastewater, preparing the crystal form scorodite and calcium oxide and magnesium oxide (1+9) into slurry with the mass concentration of 20%, adding the slurry into the high-acid protein-containing arsenic-containing wastewater, adjusting the pH value of the solution to be 4.25, reacting for 30min at 750rpm, filtering to obtain filtrate and arsenic slag, detecting that the arsenic content in the filtrate is 0.17mg/L (the arsenic removal rate is 99.994%), the iron content is 47mg/L (the iron removal rate is 99.78%), the sulfate content is 41.2g/L, and the arsenic content in the arsenic slag is 26%, the iron content is 22.5% and the sulfur content is 7%;
(3) Pickling the arsenic slag obtained in the step (2), drying, mechanically grinding, and taking the arsenic slag as an optimized seed crystal of high-acid protein-containing arsenic-containing wastewater, wherein the granularity is 83% of +400 meshes;
(4) Taking the optimized seed crystal of the high-acid protein arsenic-containing wastewater obtained in the step (3) and calcium oxide and magnesium oxide (1+9) to prepare slurry with the mass concentration of 20 percent as a novel dearsenifying agent, adjusting the pH value of the solution to be 4.7, and reacting at 750rpm for 55min to obtain stable arsenic-fixing slag, wherein the arsenic removal rate is up to more than 99.99 percent, the mass percent of arsenic in the arsenic-fixing slag is 5.7 percent, the mass percent of iron is 29.3 percent, the mass percent of sulfur is 9.1 percent, and the toxicity leaching result of the arsenic-fixing slag is 0.32mg/L, thereby meeting the related requirements of GB 18598-2019.
Comparative example two
The difference from the first embodiment is that in the step (1), the stirring speed is 100rpm, so that the obtained optimized seed crystal has large crystal grains, and is not easy to perform crystallization reaction in the process of stabilizing the arsenic.
Comparative example three
The difference of the first embodiment is that the concentration of the emulsion in the neutralizing agent is 2%, which can increase the adding amount, reduce the reaction efficiency and increase the water treatment cost after purification.
Comparative example four
The difference of the first embodiment is that the concentration of the emulsion in the neutralizing agent is 50%, which can not effectively control the pH value of the reaction, and the generated calcium sulfate is easy to wrap the medicament, so that the medicament is wasted.
Comparative example five
The difference of the first embodiment is that after the neutralizing agent is added, when the pH value is lower than 3.5, the arsenic content in the filtrate obtained after the reaction is 1310mg/L (the arsenic removal rate is 79.14%), which is far higher than the arsenic emission amount in the industrial wastewater by 0.5mg/L.
Claims (6)
1. The optimized seed crystal for the high-acid protein-containing arsenic-containing wastewater is characterized by being prepared by the following steps:
S1: adding a pH regulator into the high-acid protein-containing arsenic-containing wastewater, and regulating the pH value of the high-acid protein-containing arsenic-containing wastewater to be 1.5-2.5 to obtain a primary slag mixed solution; solid-liquid separation is carried out to obtain a slag phase and a primary solution;
heating and stirring the primary solution, performing solid-liquid separation again, and pickling and drying the obtained solid product to obtain the crystal form scorodite;
s2: mixing crystal form scorodite and neutralizer to obtain slurry;
Reacting the slurry with high-acid protein-containing arsenic-containing wastewater, and carrying out solid-liquid separation to obtain filtrate and arsenic slag;
s3: pickling, drying and grinding arsenic slag to obtain high-acid protein-containing arsenic-containing wastewater optimized seed crystal;
Wherein the high-acid protein-containing arsenic-containing wastewater is wastewater with arsenic content higher than 3g/L, iron content higher than 18g/L, sulfate radical content of 60-120 g/L, pH less than or equal to 1, bacterial content of 10 3～1012/mL and protein content of 60-70% of the bacterial content;
In the step S1, one or two of calcium oxide and calcium hydroxide are mixed with water to prepare slurry with the mass fraction of 5-15%; the slag phase is a mixture of calcium sulfate, ferric hydroxide, amorphous calcium arsenate and ferric arsenate; the heating temperature is 90-98 ℃; the stirring speed is 800-1000 rpm, and the stirring time is 100-150 min;
In the step S2, the neutralizer is calcium oxide and magnesium oxide or a compound of calcium hydroxide and magnesium hydroxide according to the mass ratio of calcium: the magnesium compound is 1: (10-3) preparing an emulsion with the mass concentration of 5-30%; the addition amount of the crystal form scorodite is 0.0001-0.05% of the arsenic mass concentration in the high-acid protein-containing arsenic-containing wastewater; the adding ratio of the crystal form scorodite and the neutralizer is controlled according to the pH value of the slurry, and the pH value of the slurry is 3.5-4.5;
In the step S2, the reaction of the slurry and the high-acid protein-containing arsenic-containing wastewater is as follows: reacting for 15-40 min at the stirring speed of 600-800 rpm and the pH value of 3.5-4.5.
2. The optimized seed crystal for the high-acid protein-containing arsenic-containing wastewater, according to claim 1, wherein the arsenic content in the filtrate is lower than 0.5mg/L, the iron content is lower than 50mg/L, the sulfate content is 30-60 g/L, and the pH value is 3.5-5; the arsenic slag contains 25-30% of arsenic, 15-25% of iron and 4-8% of sulfur.
3. The optimized seed crystal for high-acid protein-containing arsenic-containing wastewater according to claim 1, wherein in S3, the optimized seed crystal has a grain size of >400 mesh accounting for 80% or more after mechanical grinding; the optimized seed crystal is a mixture of ferric hydroxide, crystalline ferric arsenate, magnesium arsenate and denatured protein precipitate.
4. A method for optimizing seed stabilization of arsenic from high acid protein-containing arsenic-containing wastewater according to any one of claims 1 to 3, comprising the steps of:
Mixing the optimized seed crystal of the high-acid protein-containing arsenic-containing wastewater and the neutralizer, adding the seed crystal of the high-acid protein-containing arsenic-containing wastewater, and carrying out an arsenic removal reaction to obtain stable arsenic-fixing slag, wherein the arsenic removal rate is as high as more than 99.99%.
5. The method for optimizing seed crystal stabilization of arsenic-containing wastewater with high acid and protein according to claim 4, wherein the neutralizing agent is calcium oxide and magnesium oxide or calcium hydroxide and magnesium hydroxide according to calcium compound: the mass ratio of the magnesium compound is 1: (10-3) preparing an emulsion with the mass concentration of 5-30%;
The optimized seed crystal addition amount of the high-acid protein-containing arsenic-containing wastewater is 0.0005% -0.1% of the arsenic mass concentration in the high-acid protein-containing arsenic-containing wastewater;
the addition amount of the optimized seed crystal and the neutralizer of the high-acid protein-containing arsenic-containing wastewater is controlled by the pH value of the solution;
the dearsenifying reaction condition is that the stirring speed is 600-800 rpm, and the pH value is 3.5-5, and the reaction is carried out for 40-60 min.
6. The method for stabilizing solid arsenic by optimizing seed crystal for high acid protein-containing arsenic-containing wastewater according to claim 4, wherein the solid arsenic slag contains 5.5-7.5% by mass of arsenic, 25-32% by mass of iron and 7.5-10% by mass of sulfur, and the solid arsenic slag toxic leaching result is less than 1.2mg/L and meets the related requirements of GB 18598-2019.
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