CN111620481B - Recycling treatment method of industrial wastewater containing chlorine and arsenic - Google Patents
Recycling treatment method of industrial wastewater containing chlorine and arsenic Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Abstract
The invention discloses a resource treatment method of industrial wastewater containing chlorine and arsenic, which comprises the following steps: adding a preset amount of adsorbing material into the wastewater solution, and simultaneously starting heating operation and stirring operation; filtering the adsorption slag in the stirred solution; adding a preset amount of sulfuric acid into the filtering solution, adding a preset amount of the adsorbing material again, and simultaneously starting heating operation and stirring operation; filtering the adsorption slag in the stirred solution; detecting the concentration of chloride ions and/or arsenic ions in the filtered solution, and judging whether the detection result meets the treatment requirement; when the detection result meets the treatment requirement, the filtered solution is recycled or discharged after reaching the standard; collecting the adsorption slag in the previous step, adding a preset amount of resolution liquid, adding an alkaline material and stirring until the pH value keeps alkaline and does not decrease; filtering out the adsorption material after desorption and regeneration; so as to realize the recycling of the adsorption material.
Description
Technical Field
The invention relates to the technical field of environmental protection equipment, in particular to a resource treatment method of industrial wastewater containing chlorine and arsenic.
Background
If industrial wastewater enters natural water without being treated, the ecosystem in the water can be seriously damaged. The continuous decline of water quality can lead to fishery to be seriously influenced, and even pollute the underground water when the water quality exceeds a certain degree.
Particularly, chlorine and arsenic in industrial wastewater are seriously damaged, chlorine ions and arsenic ions in the industrial wastewater are respectively separated out by a chemical precipitation method commonly used at home and abroad, and then the separated chlorine and arsenic ions are respectively sent into professional equipment or plants for treatment so as to prevent the chlorine ions and the arsenic ions from being directly discharged to the nature.
However, the existing precipitation method needs to consume a large amount of precipitant for treating the wastewater, does not consider the recycling of the precipitant, and greatly increases the treatment cost.
Therefore, there is a need to provide a new method for recycling industrial wastewater containing arsenic chloride to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a recycling treatment method of industrial wastewater containing chlorine and arsenic, which is used for solving the technical problems that the consumption of a precipitator for wastewater treatment is too high and the recycling is not considered in the related art.
In order to solve the technical problem, the resource treatment method of the industrial wastewater containing the chlorine and the arsenic, which is provided by the invention, comprises the following steps:
s10, adding a preset amount of active calcium bismuth antimony-based combination group inorganic adsorption material into the wastewater solution, and simultaneously starting heating operation and stirring operation; so as to react with chloride ions and/or arsenic ions in the solution to generate adsorption slag;
s20, filtering the adsorption slag in the stirred solution; to leave the adsorbent material to be desorbed for regeneration;
s30, adding a preset amount of sulfuric acid into the filtering solution, adding a preset amount of the adsorbing material again, and simultaneously starting heating operation and stirring operation; the residual chloride ions and/or arsenic acid ions in the solution react again to generate adsorption slag;
s40, filtering the adsorption slag in the stirred solution; to leave the adsorbent material to be desorbed for regeneration;
s50, detecting the concentration of chloride ions and/or arsenic ions in the filtered solution, and judging whether the detection result meets the processing requirement;
s51, when the detection result meets the processing requirement, the filtered solution is recycled or discharged after reaching the standard;
s52, when the detection result does not meet the processing requirement, the step of adding the sulfuric acid with the preset amount into the filtering solution again, adding the adsorbing material with the preset amount again, and starting the heating operation and the stirring operation simultaneously;
in this embodiment, the processing requirement may be: the concentration of chloride ions is less than or equal to 2.4g/L and/or the concentration of arsenate ions is less than or equal to 4.7 g/L. The user can carry out appropriate adjustment to the processing requirement according to the actual production situation and the requirement of market, only need satisfy production and normally go on can.
S60, collecting the adsorption slag in the previous step, adding a preset amount of analysis solution, adding an alkaline material and stirring until the pH value keeps alkaline and does not decrease; so as to analyze and regenerate the adsorption slag into the adsorption material and a solution containing chloride ions and/or arsenic acid ions;
in this embodiment, the alkaline material is sodium carbonate and/or sodium hydroxide.
S70, filtering the adsorption material after analysis and regeneration; so as to realize the recycling of the adsorption material.
In a preferred embodiment of the present invention, the analysis liquid is water; alternatively, the analysis solution is a solution obtained by filtering the adsorbent.
As a preferable mode of the invention, the resource treatment method of the industrial wastewater containing the chlorine and the arsenic further comprises the following steps:
s80, detecting the concentration of chloride ions and/or arsenic ions in the desorption solution after the adsorption material is filtered, and judging whether the detection result meets the enrichment condition;
and S81, when the detection result meets the enrichment condition, extracting the chloride ions and/or the arsenic acid ions in the solution to extract corresponding chemical products.
In this embodiment, the enrichment condition may be that the concentration of the chloride ions and/or the arsenate ions is greater than or equal to 230 g/L. The user can carry out appropriate adjustment to the enrichment condition according to the actual production situation and the market requirement, and only need satisfy production and go on normally.
As a preferred embodiment of the present invention, the step S81 specifically includes the following steps:
s811, when the chloride ions meet the enrichment conditions, obtaining a chloride salt product by adopting a chemical crystallization method;
and/or;
and S812, adding a precipitator when the arsenic acid ions meet the enrichment conditions to obtain arsenic acid precipitation products.
In a preferred embodiment of the present invention, before the step S10, the method further includes the steps of:
s11, adding a preset amount of concentrated sulfuric acid into the industrial wastewater, and introducing a preset amount of nitrogen gas to cool the industrial wastewater to a first temperature range, and crystallizing to separate out a first crystal;
s12, filtering the first crystal, cooling the solution after filtering the first crystal to a second temperature range, and crystallizing and separating out a second crystal;
s13, filtering the second crystal to obtain the waste water solution.
In a preferred embodiment of the present invention, the first temperature range is 5 to 20 ℃ and the second temperature range is 1 to 5 ℃.
In a preferred mode of the invention, the heating operation is performed to 30-60 ℃; in the stirring operation, the stirring operation time is 1-3 hours.
The present invention provides an adsorbent material; the adsorption material comprises calcium oxide, bismuth oxide and antimony oxide.
The invention provides a preparation method of an adsorbing material; the preparation method of the adsorbing material comprises the following steps:
s1, mixing calcium oxide, bismuth oxide and antimony oxide according to the proportion of 1:1: 8-1: 3:20 to form a solid mixture;
s2, mixing the solid mixture and clear water according to the solid-liquid ratio of 1:2, and adding the mixture into a stirrer;
s3, starting the stirrer to stir for 2-3 hours at the temperature of 25-55 ℃; in addition, during stirring, dilute sulfuric acid with the concentration of 1-5% is added every 20-30 minutes to play a role in activating the material;
s4, after stirring is finished and an intermediate material is formed in the stirrer, filtering the intermediate material;
s5, mixing the intermediate material and clear water according to a solid-liquid ratio of 1:2, and adding the mixture into a reactor;
s6, adding alkali liquor into the reactor to adjust the pH value to 8-12;
s7, starting the reactor to stir for 1-2 hours at the temperature of 55-75 ℃, finally obtaining a finished product, and filtering to obtain the finished product.
In the resource treatment method of the industrial wastewater containing chlorine and arsenic, the adsorption slag in the previous step is collected, after a preset amount of analysis solution is added, alkaline materials are added while stirring until the pH value keeps alkaline and does not decrease any more; so as to analyze and regenerate the adsorption slag into the adsorption material and a solution containing chloride ions and/or arsenic acid ions; filtering out the adsorption material after desorption and regeneration so as to realize the recycling of the adsorption material; thereby solving the technical problems that the consumption of the wastewater treatment precipitator is too high and the recycling is not considered in the related technology.
In a further preferred mode, the resource treatment method for the industrial wastewater containing chlorine and arsenic provided by the invention also has the following advantages:
(1) the adsorbing material can react with chloride ions and arsenic ions in the solution to generate adsorbing slag; the problem of purifying the wastewater solution containing chlorine and arsenic simultaneously is solved;
(2) when the detection result meets the enrichment condition, extracting chloride ions and/or arsenic acid ions in the solution to extract corresponding chemical products; chloride ions and arsenic ions can be enriched and then used as resource products;
(3) when the detection result does not meet the treatment requirement, adding a preset amount of sulfuric acid into the filtered solution again, adding a preset amount of the adsorption material again, and simultaneously starting heating operation and stirring operation; in the reaction vessel, the space of the reaction vessel is limited, and when too much adsorbing material is put into the reaction vessel, the adsorbing material and the solution can not be fully mixed and reacted; removing chloride ions and arsenic ions in the solution by adopting a multi-section combination mode, and flexibly adjusting the process flow;
so that the wastewater solution with ultrahigh chloride ion content can be treated step by step, for example, the chloride ion content is more than 150 g/l; and can reduce the chloride ion concentration to a target value according to the chloride ion concentration and requirements.
(4) Adding a preset amount of concentrated sulfuric acid into industrial wastewater, and introducing a preset amount of nitrogen gas simultaneously to cool the industrial wastewater to a first temperature range, and crystallizing to separate out a first crystal; filtering the first crystal, cooling the solution after filtering the first crystal to a second temperature range, and crystallizing to separate out a second crystal;
the waste water containing two kinds of chlorine salt can be skillfully separated into two kinds of resource crystallized products through process combination.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an active calcium bismuth antimony based combined group inorganic adsorption material.
In one embodiment of the present invention, the activated calcium bismuth antimony based combination group inorganic adsorbent material comprises calcium oxide, bismuth oxide and antimony oxide.
Adding an active calcium bismuth antimony-based combined group inorganic adsorption material (material group) into a wastewater solution, and adjusting the pH value of the solution to a specific condition; thereby adsorbing and recovering chloride ions or/and arsenic ions in the industrial wastewater, and leading the chloride ions or/and arsenic ions not to be directly discharged along with the wastewater.
In this embodiment, the pH value is adjusted to a specific condition, which may be pH 8 to 14 or pH 1 to 6.
Chloride ions or/and arsenic ions in industrial wastewater are absorbed and recovered through an active calcium bismuth antimony-based combined group inorganic adsorption material (material group), and the active calcium bismuth antimony-based combined group inorganic adsorption material (material group) is recovered, and the reaction is carried out step by step or one step through the reaction steps:
the active calcium bismuth antimony-based combined group inorganic adsorption material provided by the invention has the following beneficial effects:
firstly, chlorine ions or/and arsenic ions can be adsorbed under different pH conditions;
secondly, after adsorbing chlorine or/and arsenic ions, releasing the adsorbed ions after adjusting the pH value by adding alkali;
thirdly, with the release of the adsorbed ions, the adsorption material realizes desorption and regeneration, so that the adsorption material can be recycled;
fourthly, the groups formed by the adsorption material after adsorbing ions have compounds and mixtures;
and fifthly, the adsorption material has various bond bonds in the structure, and the adsorption efficiency can be flexibly adjusted through the combination of parameters such as temperature, stirring strength, stirring time, pH value, container pressure and the like.
Sixthly, the adsorbing material is not easy to dissolve in liquid, has good filterability after adsorbing ions and after analyzing and regenerating, and has little residual adsorbing material in the adsorbed solution.
The invention provides a preparation method of an active calcium bismuth antimony based combined group inorganic adsorption material.
In an embodiment of the present invention, a method for preparing an activated calcium bismuth antimony based combination group inorganic adsorption material comprises the following steps:
s1, mixing calcium oxide, bismuth oxide and antimony oxide; mixing according to the ratio of 1:1: 8-1: 3:20 to form a solid mixture; wherein the calcium oxide may be CaO or Ca (OH)2(ii) a The bismuth oxide may be Bi2O3Or Bi2O4(ii) a The antimony oxide may be Sb2O5、Sb2O3Or Sb2O4。
S2, mixing the solid mixture and clear water according to the solid-liquid ratio of 1:2, and adding the mixture into a stirrer;
s3, starting the stirrer to stir for 2-3 hours at the temperature of 25-55 ℃; in addition, during stirring, dilute sulfuric acid with the concentration of 1-5% is added every 20-30 minutes to play a role in activating the material;
s4, after stirring is finished and an intermediate material is formed in the stirrer, filtering the intermediate material;
s5, mixing the intermediate material and clear water according to the solid-liquid ratio of 1:2, and adding the mixture into a reactor;
s6, adding alkali liquor into the reactor to adjust the pH value to 8-12;
s7, starting the reactor to stir for 1-2 hours at the temperature of 55-75 ℃, finally obtaining a finished product, and filtering to obtain the finished product.
The invention also provides a recycling treatment method of the industrial wastewater containing the chlorine and the arsenic.
Example one
S10, taking 1L of chlorine-containing wastewater discharged by an iron and steel plant, and detecting that the chlorine ions in the wastewater are 25g/L and the PH is 6; adding 100g of the adsorbing material prepared by the method into chlorine-containing wastewater;
simultaneously heating and stirring the wastewater solution for 1.5 hours at a stirring speed of 300 revolutions per minute; heating to 40 ℃;
s20, filtering the adsorption slag in the stirred solution;
s30, adding a preset amount of sulfuric acid into the filtering solution, adding a preset amount of the adsorbing material again, and simultaneously starting heating operation and stirring operation;
s40, filtering the adsorption slag in the stirred solution;
s50, detecting the concentration of chloride ions in the filtered solution, and judging whether the detection result meets the processing requirement;
in this embodiment, the processing requirement may be: the concentration of the chloride ions is less than or equal to 2.4 g/L.
Detecting that the content of chloride ions in the filtered solution is 2.4g/l, and the removal rate of the chloride ions is 90.4%;
s51, the detection result meets the treatment requirement, and the filtered solution is recycled or discharged after reaching the standard;
s60, adding 500ml of clear water into the adsorption slag; adding sodium carbonate while stirring, maintaining pH at 10, and stirring at 350 r/min for about 1.5 hr
S70, filtering the adsorption material after analysis and regeneration;
and filtering the solution after stirring, wherein filter residues are the resolved adsorption material and can be recycled.
S80, detecting the concentration of chloride ions in the desorption solution after the adsorption material is filtered, and judging whether the detection result meets the enrichment condition;
in this embodiment, the concentration of the chloride ions is greater than or equal to 230 g/L.
S811, when the detection result meets the enrichment condition, extracting the chloride ions in the solution to extract the corresponding chemical product.
Specifically, the solution after the first filtration is detected, wherein the concentration of chloride ions is 43g/l, the net content in the folded solution is 21.5g, 22.6g of chloride ions in the stock solution (taken in S10) are removed, and the solution is basically resolved into a resolving solution after being absorbed by an absorbent;
the desorption solution can be used for continuously desorbing and regenerating the adsorbing material under the condition of supplementing alkaline materials until the chloride ions are enriched to be more than 230 g/l.
And (5) the detection result meets the enrichment condition, and a chemical crystallization method is used for crystallizing the NaCl.
Example two
S10, taking 1l of arsenic-containing wastewater discharged by a certain gold smelting company, and detecting that the concentration of arsenic acid ions is 20.3g/l and the PH is 1;
taking 25g of the adsorption material which is analyzed and regenerated in the first step, adding 35g of the adsorption material prepared according to the preparation method, and adding the adsorption material into arsenic-containing wastewater;
heating the solution at 55 deg.C while stirring for about 100 min at a rotation speed of 400 rpm;
s20, filtering the adsorption slag in the stirred solution;
s30, adding a preset amount of sulfuric acid into the filtering solution, adding a preset amount of the adsorbing material again, and simultaneously starting heating operation and stirring operation;
s40, filtering the adsorption slag in the stirred solution;
s50, detecting the concentration of arsenic acid ions in the filtered solution, and judging whether the detection result meets the processing requirement;
in this implementation, the processing requirement may be: the concentration of arsenic acid ions is less than or equal to 4.7 g/L.
S51, when the detection result meets the processing requirement, the filtered solution is recycled or discharged after reaching the standard;
detecting that the concentration of arsenic in the filtered solution is 3.8g/l, and the removal rate of arsenic is 81.3%;
s60, collecting the adsorption slag in the previous step, adding a preset amount of analysis solution, adding an alkaline material and stirring until the pH value keeps alkaline and does not decrease; so as to analyze and regenerate the adsorption slag into the adsorption material and a solution containing arsenic acid ions;
specifically, filter residues are added into the resolution solution; heating the solution to about 70 deg.C while stirring for 2.5 hr, adding sodium hydroxide, and stirring at 300 r/min while maintaining pH at 10 or higher'
S70, filtering the adsorption material after analysis and regeneration;
the filter residue is an adsorption material regenerated by analysis and can be retained for use.
S80, detecting the concentration of arsenic acid ions in the desorption solution after the adsorption material is filtered, and judging whether the detection result meets the enrichment condition;
in this embodiment, the enrichment condition may be that the concentration of arsenate ions is greater than or equal to 230 g/L.
And S812, adding a precipitator when the arsenic acid ions meet the enrichment conditions to obtain arsenic acid precipitation products.
Specifically, similar to step S811 in the first embodiment, the desorption solution may be used to regenerate the adsorbent by further desorption in the case where the alkaline material is replenished until the arsenic ions are enriched to 230g/l or more.
The detection result meets the enrichment condition, Ca (OH) is added2As a precipitant, calcium arsenate precipitate (arsenic acid precipitate product) is generated; the filtered solution may be retained for continued desorption of the adsorbent material.
EXAMPLE III
S10, taking 1L of wastewater containing chlorine and arsenic discharged from an iron and steel plant, and detecting that the chlorine content of chloride ions is 25g/L, the concentration of arsenic acid ions is 20.3g/L, and the PH is 1; adding 200g of the adsorbing material prepared by the method into wastewater containing chlorine and arsenic;
simultaneously heating and stirring the wastewater solution for 1.5 hours at a stirring speed of 300 revolutions per minute; heating to 40 deg.C;
s20, filtering the adsorption slag in the stirred solution;
s30, adding a preset amount of sulfuric acid into the filtering solution, adding a preset amount of the adsorbing material again, and simultaneously starting heating operation and stirring operation;
s40, filtering the adsorption slag in the stirred solution;
s50, detecting the concentrations of chloride ions and arsenic ions in the filtered solution, and judging whether the detection result meets the processing requirement;
in this embodiment, the processing requirement may be: the concentration of chloride ions is less than or equal to 2.4g/L and the concentration of arsenate ions is less than or equal to 4.7 g/L.
Detecting that the content of chloride ions in the filtered solution is 2.4g/l, and the removal rate of the chloride ions is 90.4%;
detecting that the concentration of arsenic in the filtered solution is 3.8g/l, and the removal rate of arsenic is 81.3%;
s51, when the detection result meets the treatment requirement, the filtered solution is recycled or discharged after reaching the standard;
s60, adding 500ml of clear water into the adsorption slag; adding sodium carbonate and sodium hydroxide while stirring, maintaining pH at 10, and stirring at 400 rpm for about 1.5 hr
S70, filtering the adsorption material after analysis and regeneration;
and filtering the solution after stirring, wherein filter residues are the resolved adsorption material and can be recycled.
S80, detecting the concentrations of chloride ions and arsenic ions in the desorption solution after the adsorption material is filtered, and judging whether the detection result meets the enrichment condition;
in this embodiment, the concentration of the chloride ions and the concentration of the arsenate ions are both greater than or equal to 230 g/L.
S811, when the detection result meets the enrichment condition, extracting the chloride ions in the solution to extract the corresponding chemical product.
Specifically, when the alkaline material can be replenished with the desorption solution, the desorption solution is continuously used for desorbing and regenerating the adsorbent until the chloride ions are enriched to 230g/l or more.
And (5) the detection result meets the enrichment condition, and a chemical crystallization method is used for crystallizing the NaCl.
And S812, adding a precipitator when the arsenic acid ions meet the enrichment conditions to obtain arsenic acid precipitation products.
Specifically, similar to step S811, the desorption solution may be used to regenerate the adsorbent by further desorption until the arsenic ions are enriched to 230g/l or more, in the case where the basic material is replenished.
The detection result meets the enrichment condition, Ca (OH) is added2As a precipitant, calcium arsenate precipitate (arsenic acid precipitate product) is generated; the filtered solution may be retained for continued desorption of the adsorbent material.
Example four
S11, adding a certain amount of H into a solution containing KCL with concentration of more than 10% and NaCl with concentration of more than 5%2SO4(ii) a While introducing a certain amount of nitrogen to cool the solution to 5-20 deg.C2SO4Crystallizing out and filtering out K2SO4；
S12, cooling the filtered solution in S1 to 1-5 ℃ and Na2SO4Crystallizing out;
s13, filtering Na2SO4Then, the wastewater solution is obtained.
S10, adding a preset amount of active calcium bismuth antimony-based combination group inorganic adsorption material into the wastewater solution, and simultaneously starting heating operation and stirring operation;
simultaneously heating and stirring the wastewater solution for 1.5 hours at a stirring speed of 300 revolutions per minute; heating to 40 ℃;
s20, filtering the adsorption slag in the stirred solution;
s30, adding a preset amount of sulfuric acid into the filtering solution, adding a preset amount of the adsorbing material again, and simultaneously starting heating operation and stirring operation;
s40, filtering the adsorption slag in the stirred solution;
s50, detecting the concentration of chloride ions in the filtered solution, and judging whether the detection result meets the processing requirement;
in this embodiment, the processing requirement may be: the concentration of the chloride ions is less than or equal to 2.4 g/L.
Detecting that the content of chloride ions in the filtered solution is 2.4g/l, and the removal rate of the chloride ions is 90.4%;
s51, the detection result meets the treatment requirement, and the filtered solution is recycled or discharged after reaching the standard;
s60, adding 500ml of clear water into the adsorption slag; adding sodium carbonate while stirring, maintaining pH at 10, and stirring at 400 rpm for about 1.5 hr
S70, filtering the adsorption material after analysis and regeneration;
and filtering the solution after stirring, wherein filter residues are the resolved adsorption material and can be recycled.
S80, detecting the concentration of chloride ions in the desorption solution after the adsorption material is filtered, and judging whether the detection result meets the enrichment condition;
in this embodiment, the concentration of the chloride ions is greater than or equal to 230 g/L.
S811, when the detection result meets the enrichment condition, extracting the chloride ions in the solution to extract the corresponding chemical product.
Specifically, the solution after the first filtration is detected, wherein the concentration of chloride ions is 43g/l, the net content in the folded solution is 21.5g, 22.6g of chloride ions in the stock solution (taken in S10) are removed, and the solution is basically resolved into a resolving solution after being absorbed by an absorbent;
when the alkaline material can be replenished with the desorption solution, the desorption and regeneration of the adsorbent are continued until the chloride ion concentration is 230g/l or more.
And (5) the detection result meets the enrichment condition, and a chemical crystallization method is used for crystallizing the NaCl.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (7)
1. A resource treatment method of industrial wastewater containing chlorine and arsenic is characterized by comprising the following steps:
adding a preset amount of an active calcium bismuth antimony-based combination group inorganic adsorption material into the wastewater solution, and simultaneously starting heating operation and stirring operation; so as to react with chloride ions and/or arsenic ions in the solution to generate adsorption slag;
filtering the adsorption slag in the stirred solution, and reserving the adsorption slag for resolving and regenerating the adsorption material;
adding a preset amount of sulfuric acid into the filtered solution, adding a preset amount of the adsorption material again, and simultaneously starting heating operation and stirring operation to react with the residual chloride ions and/or arsenic acid ions in the solution again to generate adsorption slag;
filtering the adsorption slag in the stirred solution, and reserving the adsorption slag for resolving and regenerating the adsorption material;
detecting the concentration of chloride ions and/or arsenic ions in the filtered solution, and judging whether the detection result meets the treatment requirement;
when the detection result meets the treatment requirement, the filtered solution is recycled or discharged after reaching the standard;
when the detection result does not meet the treatment requirement, adding a preset amount of sulfuric acid into the filtered solution again, adding a preset amount of the adsorption material again, and simultaneously starting heating operation and stirring operation;
collecting the adsorption slag in the previous step, adding a preset amount of resolution liquid, adding an alkaline material and stirring until the pH value keeps alkaline and does not decrease; so as to analyze and regenerate the adsorption slag into the adsorption material and a solution containing chloride ions and/or arsenic acid ions;
filtering out the adsorption material after desorption and regeneration; so as to realize the recycling of the adsorption material;
wherein the adsorption material comprises calcium oxide, bismuth oxide and antimony oxide;
the preparation method of the adsorbing material comprises the following steps:
mixing the calcium oxide, the bismuth oxide and the antimony oxide in a ratio of 1:1: 8-1: 3:20 to form a solid mixture;
mixing the solid mixture and clear water according to a solid-liquid ratio of 1:2, and adding the mixture into a stirrer;
starting the stirrer to stir for 2-3 hours at the temperature of 25-55 ℃; in addition, during stirring, dilute sulfuric acid with the concentration of 1-5% is added every 20-30 minutes to play a role in activating the material;
after stirring is finished, filtering out the intermediate material after the intermediate material is formed in the stirrer;
mixing the intermediate material and clear water according to a solid-liquid ratio of 1:2, and adding the mixture into a reactor;
adding alkali liquor into the reactor to adjust the pH value to 8-12;
starting the reactor to stir for 1-2 hours at the temperature of 55-75 ℃, finally obtaining a finished product, and filtering to obtain the finished product.
2. The method for recycling industrial wastewater containing chlorine and arsenic according to claim 1, wherein the desorption solution is water; alternatively, the analysis solution is a solution obtained by filtering the adsorbent.
3. The method for recycling industrial wastewater containing chlorine and arsenic as claimed in claim 2, further comprising the following steps:
detecting the concentration of chloride ions and/or arsenic ions in the desorption solution after the adsorption material is filtered, and judging whether the detection result meets the enrichment condition;
and when the detection result meets the enrichment condition, extracting the chloride ions and/or the arsenic acid ions in the solution to extract corresponding chemical products.
4. The method for recycling industrial wastewater containing chlorine and arsenic according to claim 3, wherein when the detection result meets the enrichment condition, the step of extracting and treating the chloride ions and/or arsenic ions in the solution comprises the following steps:
when the inspection result shows that the chloride ions meet the enrichment condition, a chemical crystallization method is adopted to obtain a chloride salt product;
and/or adding a precipitator when the arsenic acid ions meet the enrichment conditions to obtain arsenic acid precipitation products.
5. The method for recycling industrial wastewater containing chlorine and arsenic as claimed in claim 1, wherein before the step of adding a preset amount of the activated calcium, bismuth and antimony based combined group inorganic adsorption material into the wastewater solution and simultaneously starting the heating operation and the stirring operation, the method further comprises the following steps:
adding a preset amount of concentrated sulfuric acid into industrial wastewater, and introducing a preset amount of nitrogen gas simultaneously to cool the industrial wastewater to a first temperature range, and crystallizing to separate out a first crystal;
filtering the first crystal, cooling the solution after filtering the first crystal to a second temperature range, and crystallizing to separate out a second crystal;
and filtering the second crystal to obtain the wastewater solution.
6. The method for recycling industrial wastewater containing chlorine and arsenic according to claim 5, wherein the first temperature range is 5-20 ℃, and the second temperature range is 1-5 ℃.
7. The method for recycling industrial wastewater containing chlorine and arsenic according to claim 1, wherein in the heating operation, the temperature is heated to 30-60 ℃; in the stirring operation, the stirring operation time is 1-3 hours.
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| CN114380433A (en) * | 2021-12-15 | 2022-04-22 | 湖南省特种设备检验检测研究院 | Arsenic-containing wastewater treatment process and system based on waste heat utilization |
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| WO2010017652A1 (en) * | 2008-08-11 | 2010-02-18 | Hernandez Pavez Jose Octavio | Process and system for separation, recycling and sustainable environmental stabilisation of acid effluents with arsenic (as) and/or heavy metals which form insoluble sulphides |
| CN104831067A (en) * | 2015-04-03 | 2015-08-12 | 中南大学 | Method for separating and recovering arsenic from metallurgical material acid leaching liquid |
| CN205892968U (en) * | 2016-06-27 | 2017-01-18 | 长沙赛恩斯环保工程技术有限公司 | High fluorine chlorine effluent disposal system |
| CN109173340A (en) * | 2018-11-08 | 2019-01-11 | 中南大学 | A method of the adsorbing and removing chlorine from strongly acidic solution |
| CN110304757A (en) * | 2019-05-28 | 2019-10-08 | 白银有色集团股份有限公司 | It is a kind of for handling the technique of arsenic-containing waste water |
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| WO2010017652A1 (en) * | 2008-08-11 | 2010-02-18 | Hernandez Pavez Jose Octavio | Process and system for separation, recycling and sustainable environmental stabilisation of acid effluents with arsenic (as) and/or heavy metals which form insoluble sulphides |
| CN104831067A (en) * | 2015-04-03 | 2015-08-12 | 中南大学 | Method for separating and recovering arsenic from metallurgical material acid leaching liquid |
| CN205892968U (en) * | 2016-06-27 | 2017-01-18 | 长沙赛恩斯环保工程技术有限公司 | High fluorine chlorine effluent disposal system |
| CN109173340A (en) * | 2018-11-08 | 2019-01-11 | 中南大学 | A method of the adsorbing and removing chlorine from strongly acidic solution |
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