阅读说明：本技术 一种含砷废弃试剂的无害化处理方法 (Harmless treatment method for arsenic-containing waste reagent ) 是由 范增华 王金博 洪常亮 何礼龙 张花娟 康建 李宇 文锐 李俊阳 于 2020-12-16 设计创作，主要内容包括：本发明公开了一种含砷废弃试剂的无害化处理方法,属于危险废物剧毒试剂无害化处置技术领域。该方法包括：将含砷废弃试剂溶解,得到第一溶液；将硫酸亚铁与第一双氧水充分反应,得到第二溶液；将第二溶液缓慢加入至第一溶液中,反应,得到第三溶液；在第三溶液中加入氧化钙、水泥和砂砾。本发明中,主要通过向含砷废弃试剂中加入一定量硫酸亚铁、双氧水及氧化钙,使得含砷废弃试剂通过氧化还原、络合共沉降反应将As～(3+)与Fe～(2+)分别转化为As～(5+)与Fe～(3+),从而生成砷铁络合物沉淀,以达到降低其毒性及迁移性的稳定化效果；最后通过加入水泥、沙子等稳定剂、固化剂对其进行固化处理,从而有效避免有害成分向环境中迁移扩散,降低对人体及环境的污染与危害。(The invention discloses a harmless treatment method of arsenic-containing waste reagents, belonging to the technical field of harmless treatment of virulent reagents of hazardous wastes. The method comprises the following steps: dissolving the arsenic-containing waste reagent to obtain a first solution; fully reacting ferrous sulfate with first hydrogen peroxide to obtain a second solution; slowly adding the second solution into the first solution, and reacting to obtain a third solution; calcium oxide, cement and gravel are added to the third solution. In the invention, a certain amount of ferrous sulfate, hydrogen peroxide and calcium oxide are mainly added into the arsenic-containing waste reagent, so that the arsenic-containing waste reagent can react with As through oxidation reduction and complexing codeposition 3+ With Fe 2+ Respectively converted into As 5+ With Fe 3+ Thereby generating arsenic iron complex precipitation to achieve the stabilization effect of reducing the toxicity and the mobility of the arsenic iron complex precipitation; finally, the cement, sand and other stabilizing agents and curing agents are added to carry out curing treatment, thereby effectively avoiding harmful componentsThe product can migrate and diffuse into the environment, and the pollution and harm to human bodies and the environment are reduced.)

1. A method for the innocent treatment of arsenic-containing waste reagents, which is characterized by comprising the following steps:

dissolving the arsenic-containing waste reagent to obtain a first solution;

fully reacting ferrous sulfate with first hydrogen peroxide to obtain a second solution;

slowly adding the second solution into the first solution, and reacting to obtain a third solution;

and adding calcium oxide, cement and gravel into the third solution, and reacting to obtain the water-insoluble ferric arsenate complex.

2. The method as claimed in claim 1, wherein the waste reagent containing arsenic is one of sodium arsenite, trisodium arsenate and arsenic trioxide.

3. The method as claimed in claim 2, wherein when the arsenic-containing waste reagent is arsenic trioxide, the second hydrogen peroxide solution is added to the first solution to perform redox reaction before the second solution is slowly added to the first solution.

4. The method as claimed in claim 3, wherein when the waste reagent containing arsenic is the sodium arsenite or the trisodium arsenate, the waste reagent containing arsenic is dissolved in water.

5. The method according to claim 3, wherein when the arsenic-containing waste reagent is arsenic trioxide, the arsenic-containing waste reagent is dissolved in a sodium hydroxide solution having a concentration of 10% or more.

6. The method of claim 4, wherein when the arsenic-containing waste reagent is the sodium arsenite or the trisodium arsenate, the mass ratio of the arsenic-containing waste reagent to the water to the ferrous sulfate to the first oxydol to the calcium oxide to the cement to the gravel is 1:7:2:4:0.5:5: 10.

7. The method of claim 5, wherein when the arsenic-containing waste reagent is arsenic trioxide, the mass ratio of the arsenic-containing waste reagent, sodium hydroxide solution of not less than 10%, ferrous sulfate, first hydrogen peroxide, second hydrogen peroxide, calcium oxide, cement and gravel is 1:1:1:0.7:3:0.5:5: 10.

8. The method as claimed in claim 1, wherein the reaction time of the ferrous sulfate and the first hydrogen peroxide solution is 20-40 min.

9. The method as claimed in claim 3, wherein the reaction time of the first solution and the second hydrogen peroxide solution is 15-30 min.

Technical Field

The invention relates to the technical field of harmless treatment of highly toxic reagents for hazardous wastes, in particular to a harmless treatment method of arsenic-containing waste reagents.

Background

The arsenic-containing agent is a highly toxic substance, such as arsenic trioxide, sodium arsenite, trisodium arsenate, etc., and enters into human body through respiratory tract or digestive tract, mainly affects permeability of human nervous system and capillary, and has irritation effect on skin and mucosa. Therefore, the reagent containing arsenic or the package containing arsenic must be reasonably disposed of to effectively prevent harm to human, animals, plants and environment.

The first prior art is as follows: a method for treating arsenic-containing waste, application number is CN106180138A, the invention leaches the high arsenic-containing material through alkaline, get the high-concentration sodium arsenite or sodium arsenate solution, make it turn into sodium arsenate completely through oxidizing; adding a small amount of seed crystal lepidocrocite (gamma FeOOH) slurry into a reaction kettle, slowly adding an arsenic-containing solution, simultaneously adding a slightly excessive high-concentration ferrite solution, adding a neutralizer, maintaining the reaction pH to be 3.5-5.5, controlling the temperature in the reaction process, enabling the arsenic in the solution to be completely reacted and completely enter precipitation, easily filtering the obtained precipitation slag, and realizing harmless and stable treatment of the arsenic-containing solution.

The second prior art is: a method for treating arsenic-containing waste, with application number CN108706763A, comprises the following steps: (1) adjusting the pH value: adding sodium hydroxide and hydrogen chloride into the arsenic-containing waste solution, and adjusting the pH value to 6-8; (2) primary precipitation: adding ferric trichloride into the arsenic-containing waste solution after the pH value is adjusted, so that the ratio of Fe in the arsenic-containing waste: as is 5-7: 1, stirring for 30min, standing for 60min, and separating water and slag; (3) secondary precipitation: adding lime milk into the separated water solution, stirring for 10min, introducing oxygen, oxidizing for 20-25 min at an oxygen supply rate of 0.5-0.6L/min, and separating water and slag; (4) filtering and detecting the arsenic content: and (4) filtering the solution in the step (3) through activated carbon, and detecting the arsenic content, wherein the arsenic content can be discharged when being less than 5%.

In summary, the prior art can only treat arsenic slag, arsenic-containing waste with low arsenic content, and pure sodium arsenite, trisodium arsenate and arsenic trioxide cannot be treated.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a harmless treatment method of arsenic-containing waste reagents. The method comprises the following steps:

dissolving the arsenic-containing waste reagent in water to obtain a first solution;

fully reacting ferrous sulfate with first hydrogen peroxide to obtain a second solution;

slowly adding the second solution into the first solution, and reacting to obtain a third solution;

and adding calcium oxide, cement and gravel into the third solution, and reacting to obtain the water-insoluble ferric arsenate complex.

Further, the arsenic-containing waste reagent is one of sodium arsenite, trisodium arsenate and arsenic trioxide.

Further, when the arsenic-containing waste reagent is the arsenic trioxide, before the second solution is slowly added into the first solution, second hydrogen peroxide is added into the first solution to perform redox reaction.

Further, when the arsenic-containing waste reagent is the sodium arsenite or the trisodium arsenate, the arsenic-containing waste reagent is dissolved in water.

Further, when the arsenic-containing waste reagent is the arsenic trioxide, the arsenic-containing waste reagent is dissolved in a sodium hydroxide solution with the concentration of more than or equal to 10%.

Further, when the arsenic-containing waste reagent is the sodium arsenite or the trisodium arsenate, the mass ratio of the arsenic-containing waste reagent to the water to the ferrous sulfate to the first oxydol to the calcium oxide to the cement to the gravel is 1:7:2:4:0.5:5: 10.

Further, when the arsenic-containing waste reagent is the arsenic trioxide, the mass ratio of the arsenic-containing waste reagent, a sodium hydroxide solution with the concentration of not less than 10%, ferrous sulfate, first hydrogen peroxide, second hydrogen peroxide, calcium oxide, cement and gravel is 1:1:1:0.7:3:0.5:5: 10.

Further, the reaction time of the ferrous sulfate and the first hydrogen peroxide is 20-40 min.

Further, the reaction time of the first solution and the second hydrogen peroxide is 15-30 min.

Further, the third solution was reacted with the calcium oxide, cement and gravel for 2 hours.

Further, the pH value of the third solution after the third solution reacts with the calcium oxide, the cement and the gravel is 10-11.

The technical scheme provided by the embodiment of the invention has the following beneficial effects: in the invention, a certain amount of ferrous sulfate, hydrogen peroxide and calcium oxide are mainly added into the arsenic-containing waste reagent, so that the arsenic-containing waste reagent can react with As through oxidation reduction and complexing codeposition³⁺With Fe²⁺Respectively converted into As⁵⁺With Fe³⁺Thereby generating arsenic iron complex precipitation to achieve the stabilization effect of reducing the toxicity and the mobility of the arsenic iron complex precipitation; and finally, the cement, sand and other stabilizing agents and curing agents are added to carry out curing treatment, so that the harmful components are effectively prevented from migrating and diffusing into the environment, and the pollution and harm to human bodies and the environment are reduced. In addition, the invention has wide treatment range, comprises trisodium arsenate, sodium arsenite, arsenic trioxide and the like, and has simple steps and low cost.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a flow chart of a method for the harmless treatment of arsenic-containing waste reagents according to an embodiment of the present invention;

FIG. 2 is a flow chart of a method for harmless treatment of arsenic-containing waste reagents according to a second embodiment of the present invention;

FIG. 3 is a flow chart of a method for harmless treatment of arsenic-containing waste reagents according to a third embodiment of the present invention;

FIG. 4 is a flow chart showing a method for detoxifying a waste reagent containing arsenic according to a fourth embodiment of the present invention.

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Example one

A method for the innocent treatment of arsenic-containing waste reagents, see fig. 1, comprising the steps of:

step (1): and dissolving the arsenic-containing waste reagent to obtain a first solution.

Step (2): and fully reacting ferrous sulfate with first hydrogen peroxide to obtain a second solution.

And (3): slowly adding the second solution into the first solution, and reacting to obtain a third solution;

and (4): and adding calcium oxide, cement and gravel into the third solution, and reacting to obtain the water-insoluble ferric arsenate complex.

Example two

Referring to fig. 2, the method for detoxifying arsenic-containing waste reagent shown in fig. 1 is discussed in detail, and includes the following steps:

a step (101): 1000g of sodium arsenite was dissolved in 7000g of water to give a first solution.

A step (102): and (3) fully reacting 2000g of ferrous sulfate with 4000g of first hydrogen peroxide for 20-40 min to obtain a second solution.

Step (103): and slowly adding the second solution into the first solution, and reacting for 1h to obtain a third solution.

A step (104): and adding 500g of calcium oxide, 5000g of cement and 10000g of gravel into the third solution, reacting for 2 hours, and obtaining the water-insoluble ferric arsenate complex, wherein the pH value is 10-11 after the reaction.

The staff performs three tests according to the method to obtain three groups of treated samples of sodium arsenite, and detects the three groups of treated samples of sodium arsenite, wherein the detection items and data refer to table one:

watch 1

As can be seen from the detection data in the table, Cd, Tcr, Cu, Ni, Pb, Zn and Cr are not detected in the three groups of sodium arsenite treated samples⁶⁺And F^-And the content of As is within the acceptable range.

EXAMPLE III

Referring to fig. 3, the method for detoxifying arsenic-containing waste reagent shown in fig. 1 is discussed in detail, and the method includes the following steps:

step (201): 1000g trisodium arsenate was dissolved in 7000g water to give a first solution.

Step (202): and (3) fully reacting 2000g of ferrous sulfate with 4000g of first hydrogen peroxide for 20-40 min to obtain a second solution.

Step (203): and slowly adding the second solution into the first solution, and reacting for 1h to obtain a third solution.

A step (204): and adding 500g of calcium oxide, 5000g of cement and 10000g of gravel into the third solution, reacting for 2 hours, and obtaining the water-insoluble ferric arsenate complex, wherein the pH value is 10-12 after the reaction.

In addition, the staff performs three groups of tests according to the method to obtain three groups of trisodium arsenate treated samples, and detects the three groups of trisodium arsenate treated samples, and the detection items and data are shown in the second table:

watch two

As can be seen from the detection data in the table, Cd, Tcr, Cu, Ni, Pb, Zn and Cr are not detected in the three groups of trisodium arsenate treated samples⁶⁺And F^-And the content of As is within the acceptable range.

Example four

Referring to fig. 4, the method for detoxifying arsenic-containing waste reagent shown in fig. 1 is discussed in detail, and the method includes the following steps:

step (301): 1000g of arsenic trioxide is dissolved in 1000g of sodium hydroxide solution with the concentration of more than or equal to 10 percent to obtain a first solution.

Step (302): fully reacting 1000g of ferrous sulfate with 700g of first hydrogen peroxide for 20-40 min to obtain a second solution.

Step (303): adding 3000g of second hydrogen peroxide into the first solution, and fully reacting for 15-30 min.

Step (304): and slowly adding the second solution into the first solution subjected to the oxidation-reduction reaction with second hydrogen peroxide, and reacting for 1h to obtain a third solution.

Step (305): and adding 500g of calcium oxide, 5000g of cement and 10000g of gravel into the third solution, reacting for 2 hours, and obtaining the water-insoluble ferric arsenate complex, wherein the pH value is 10-12 after the reaction.

It should be noted that, according to the above method, the worker performs three tests to obtain three sets of arsenic trioxide treatment samples, and detects the three sets of arsenic trioxide treatment samples, where the detection items and data are shown in table three: watch III

As can be seen from the detection data in the table, Cd, Tcr, Cu, Ni, Pb, Zn and Cr are not detected in the three groups of arsenic trioxide treatment samples⁶⁺And F^-And the content of As is within the acceptable range.

It is worth to be noted that, in the invention, a certain amount of ferrous sulfate, hydrogen peroxide and calcium oxide (or directly adding polymeric ferric sulfate) are mainly added into the arsenic-containing waste reagent, so that the arsenic-containing waste reagent can react with As through oxidation reduction and complexing codeposition reaction³⁺With Fe²⁺Respectively converted into As⁵⁺With Fe³⁺Thereby generating arsenic iron complex precipitation to achieve the stabilization effect of reducing the toxicity and the mobility of the arsenic iron complex precipitation; and finally, the cement, sand and other stabilizing agents and curing agents are added to carry out curing treatment, so that the harmful components are effectively prevented from migrating and diffusing into the environment, and the pollution and harm to human bodies and the environment are reduced. In addition, the invention has wide treatment range, comprises trisodium arsenate, trisodium arsenite, arsenic trioxide and the like, and has simple steps and low cost.

The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.