CN111544822A - Barium slag stabilizing treatment method - Google Patents

Barium slag stabilizing treatment method Download PDF

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Publication number
CN111544822A
CN111544822A CN202010283211.6A CN202010283211A CN111544822A CN 111544822 A CN111544822 A CN 111544822A CN 202010283211 A CN202010283211 A CN 202010283211A CN 111544822 A CN111544822 A CN 111544822A
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Prior art keywords
barium
slag
barium slag
solution
sulfate solution
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Inventor
李绍华
丁贞玉
杨博文
周欣
张宗文
刘锋平
刘晋凯
田源
刘红雷
史蕊
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Environmental Planning Institute Of Ministry Of Ecology And Environment
Shanghai Shenglong Environment Remediation Technologies Co ltd
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Environmental Planning Institute Of Ministry Of Ecology And Environment
Shanghai Shenglong Environment Remediation Technologies Co ltd
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Priority to CN202010283211.6A priority Critical patent/CN111544822A/en
Publication of CN111544822A publication Critical patent/CN111544822A/en
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40

Abstract

The invention relates to a barium slag stabilizing treatment method, which comprises the following steps: 1) adding a hydrogen peroxide solution into the barium slag, uniformly stirring, standing and maintaining; 2) adding a sulfate solution and EDTA powder into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining. The invention combines the hydrogen peroxide, the sulfate and the EDTA for use, combines the advantages of all the components together, establishes an economic, efficient, green and environment-friendly method for stabilizing the barium slag, and greatly improves the effect of stabilizing the barium slag.

Description

Barium slag stabilizing treatment method
Technical Field
The invention belongs to the field of soil remediation in the technical field of environmental engineering, and particularly relates to a stabilizing treatment method for barium slag.
Background
The barium residue is residue left after barite is roasted and reduced at high temperature and then leached by hot water in the barium carbonate production process, and is hazardous waste listed in Ming dynasty in the national hazardous waste records. The harmful component of barium residue is mainly Ba2+、S2-The hazardous waste storage material has damage to respiratory tract, muscle cells, cardiovascular function, mucous membrane and the like of a human body, if the hazardous waste storage material is directly stockpiled, the hazardous waste standard management requirements cannot be met, a large amount of land is occupied, and the environment attractiveness is influenced. Heavy metal barium in barium slag mainly exists in acid soluble barium and water soluble barium, leaching rate of barium ions in an acid solution environment is up to more than 92%, and compared with hazardous waste leaching toxicity standard limit value of GB5085.3-2007 hazardous waste identification Standard-leaching toxicity identification, heavy metal barium in barium slag sample exceeds standard limit value by 2-20 times, so that the barium slag needs to be stabilized before landfill or regeneration and reuse, and Ba in leaching solution2+The content of (A) meets the requirement of environmental protection.
A large amount of barium sulfide is remained in barium residues of a pollution source, the water solubility is strong, and the barium leaching concentration is high, in the prior art, a slow release sulfate precipitation mechanism, a synergistic precipitation mechanism, an adsorption stabilization mechanism, a complexing mechanism and the like are mainly used for treating barium, leachable barium ions in polluted soil enter a liquid phase and then act with an adsorption material and a complexing material to play a primary role in adsorption blocking and buffer stabilization, the release rate of the barium ions is slowed down, further the slow release sulfate and the like are gradually released and precipitate with the barium ions, and stable and harmless barium sulfate precipitates and the like are generated. The reaction mechanism is as follows:
1. the sulfate precipitation mechanism takes sulfate as a main repair component, and sulfide contained in the sulfate is converted into SO4 through rapid conversion2-Ions, may react with Ba2+Combined to generate BaSO4And precipitating the insoluble matters.
Ba2+(aq)+SO4 2-(aq)→BaSO4(s)
2. Mechanism of syngeneic precipitation
Sulfate and phosphate are used as main repairing components, and the sulfate and the phosphate can cooperatively precipitate soluble barium in the soil phase, so that harmlessness of leaching toxicity of the barium is realized.
Ba2+(aq)+SO4 2-(aq)+PO4 3-/HPO4 2-/H2PO4 -(aq)→BaSO4(s) + BaP-based stabilized product(s)
3. Adsorption-based stabilization mechanism
Ba2++ high efficiency adsorption adjuvant → Ba-Solid phase stabilized product
4. Complex precipitation mechanism Ba2++ complexing agent → Ba precipitate phase
5. Morphotropic regulation mechanism
Soluble Ba phase + morphology regulator → carbonate bound Ba phase/ferromanganese bound Ba phase/residual Ba phase
Naturally piled up barium slag, BaCl on surface of barium slag2Is already washed by rainwater and almost no BaSO is generated4Thus, most of Ba2+Coated with other substances, the barium residue can only be ground to more than 200 meshes, and HCl or HNO is added3Dissolving, and adding SO4 2-The method is time-consuming, labor-consuming and high in cost, and cannot be industrially applied in a large scale.
In the prior harmless treatment method of barium slag, sulfate such as sodium sulfate and ferrous sulfate is singly mixed with the barium slag to fix soluble barium in the barium slag, so that the sulfur ion component of the barium slag can not be utilized, and sodium ions or ferrous ions are brought into the barium slag, so that the barium slag is not beneficial to comprehensive utilization after harmless treatment.
CN102189099A discloses the group Na in the prior art2SO3The method for treating the chromium-barium composite polluted soil only uses Na2SO3As a treatment agent for synchronously treating Ba in the polluted soil2+，Cr6+And BaCrO4And the like, but the technology does not pay attention to sulfur ions in barium slag and the problem of improving the stability of the medicament. CN107597801B provides a method for innocent treatment of barium slag by using phosphogypsum, wherein soluble barium in the barium slag mainly exists in the form of sulfide or hydrosulfide, and soluble sulfur and phosphorus (sulfate radical and phosphate radical) in the phosphogypsum are used for precipitating and solidifying the soluble barium, but the scheme also introduces the sulfate radical without considering the use of sulfide ions existing in the barium slag. Aiming at the defects in the prior art, the inventor provides a stabilizing treatment method for barium slag through a large number of experiments and explorations, makes full use of substances contained in the barium slag, solves the technical problem that soluble barium is difficult to fix in the prior art, and can greatly improve the treatment efficiency and the stabilizing rate of the barium slag.
Disclosure of Invention
The invention combines the hydrogen peroxide, the sulfate and the EDTA for use, combines the advantages of all the components together, establishes an economic, efficient, green and environment-friendly method for stabilizing the barium slag, and greatly improves the effect of stabilizing the barium slag.
In order to achieve the aim, the invention provides a barium slag stabilizing treatment method, which comprises the following steps:
1) adding a hydrogen peroxide solution into the barium slag, uniformly stirring, standing and maintaining;
2) adding a sulfate solution into the barium residue obtained in the step 1), uniformly stirring, and standing and maintaining.
Preferably, the concentration of the hydrogen peroxide solution is 2 wt% to 5 wt%.
Preferably, the addition amount of the hydrogen peroxide solution is 5-10% of the weight of the barium slag.
Preferably, the sulfate solution is a sodium sulfate solution or a ferrous sulfate solution.
Preferably, the concentration of the sodium sulfate solution is 2 wt% to 10 wt%.
Preferably, the concentration of the ferrous sulfate solution is 5 wt% -15 wt%.
Preferably, the addition amount of the sulfate solution is 5-10% of the weight of the barium slag.
Preferably, the curing time in step 1) is 2-4 h.
Preferably, the curing time in step 2) is 2-48 h.
Preferably, the method for stabilizing barium slag according to the present invention further comprises:
3) adding calcium sulfate into the barium residue obtained in the step 2), uniformly stirring, and standing and maintaining. Standing and maintaining for 2-48h, and adding calcium sulfate to absorb water to make the water content of barium residue lower than 60% to reach the landfill standard.
Furthermore, EDTA is added while the hydrogen peroxide solution and the sulfate solution are added to control the volume of barium sulfate particles, so that the situation that the surface of barium slag is blocked by a channel on the surface of the barium slag after the barium slag is rapidly reacted is avoided, subsequent reaction is hindered, and the long-acting property of the medicament is realized.
Compared with the prior barium slag stabilizing technology, the invention has the following advantages:
(1) the invention adds hydrogen peroxide, the oxidability of which can rapidly destroy a large amount of organic matter structures in the waste residue, so that barium wrapped by organic matters such as humus can be converted into exchangeable state, and then the barium is easily combined with sulfate radicals to form stable barium sulfate, thereby accelerating the stabilization of barium ions.
(2) The invention fully utilizes the original sulfur ions and hydroxyl ions contained in the barium slag, and the hydrogen peroxide is added in the first step to enable the hydrogen peroxide to react with the sulfur ions in the barium slag to generate elemental sulfur and hydroxyl ions (H)2O2+S2-＝S+2OH-)，The generated sulfur simple substance can generate disproportionation reaction with hydroxide ions under the alkaline environment to generate sulfur ions and sulfite ions (3S +6 OH)-＝2S2-+SO3 2-+3H2O), the sulfite and barium ions will generate barium sulfite precipitate (SO)3 2-+Ba2+BaSO3 ↓), secondly, the composition of barium sediment is comparatively complicated, and the trace part heavy metal material that contains such as copper, iron, cobalt, nickel can play the catalytic effect, makes hydrogen peroxide can directly or indirectly oxidize the sulphide ion directly into sulphite ion or sulphate ion to the barium ion of stabilization solidification, makes it obtain better stabilization effect than the sulphate of independent use.
(3) The newly generated substance of the invention is only water, and the cleaning can not cause secondary pollution.
(4) In the second step, partial sodium sulfate or ferrous sulfate is added to prevent barium ions which are only dependent on sulfur ions in barium slag from being possibly stabilized and cured incompletely, and the stability of barium sulfate is better than that of barium sulfite, so that the barium ions are promoted to be precipitated completely, the stability of the barium ions is improved, the dosage of the barium ions matched with hydrogen peroxide is less, and the subsequently introduced sodium ions and iron ions are less and are cleaner.
(5) According to the invention, the hydrogen peroxide solution and the sulfate solution are added, and simultaneously, the EDTA is added to control the volume of barium sulfate particles, so that the situation that the surface of barium slag is blocked by a channel on the surface of the barium slag after the barium slag is subjected to rapid reaction is avoided, the subsequent reaction is hindered, and the long-acting property of the medicament is realized.
(6) Because the water content of the waste residue is adjusted by adding the calcium sulfate to meet the landfill requirement that the water content is lower than 60 percent, the defect that the water content is adjusted by adopting cement in the prior art is avoided, and the excessive sulfate ions are prevented from invading the cement to continue to react to generate a large amount of calcium sulphoaluminate, so that the cement is cracked and loses the solidification effect.
Detailed Description
The present invention is further described with reference to specific examples to enable those skilled in the art to better understand the present invention and to practice the same, but the examples are not intended to limit the present invention.
In the following examples of the invention, the barium slag sample is from a domestic enterprise slag yard. Randomly selecting 3 point positions in a slag field, taking hardened samples with the depth of (0-0.5m) and unboard knot samples with the depth of less than 0.5m, and mixing the hardened samples or the unboard knot samples at different point positions for a stabilization experiment.
Example 1
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 2 wt% sodium sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 hours.
Example 2
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 5 wt% sodium sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 hours.
Example 3
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 10 wt% sodium sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 h.
Example 4
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 5 wt% ferrous sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 hours.
Example 5
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 10 wt% ferrous sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 hours.
Example 6
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 15 wt% ferrous sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 hours.
Example 7
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 2 wt% hydrogen peroxide solution into the barium residue obtained in the step 1), uniformly stirring, and standing and maintaining for 2 hours.
3) Adding 500g of 10 wt% ferrous sulfate solution into the barium residue obtained in the step 2), uniformly stirring, standing and maintaining for 48 hours.
Example 8
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 5 wt% hydrogen peroxide solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 2 h.
3) Adding 500g of 10 wt% ferrous sulfate solution into the barium residue obtained in the step 2), uniformly stirring, standing and maintaining for 48 hours.
Example 9
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 2 wt% hydrogen peroxide solution into the barium residue obtained in the step 1), uniformly stirring, and standing and maintaining for 2 hours.
3) Adding 500g of 2 wt% sodium sulfate solution into the barium residue obtained in the step 2), uniformly stirring, and standing and maintaining for 48 hours.
Example 10
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 2 wt% hydrogen peroxide solution into the barium residue obtained in the step 1), uniformly stirring, and standing and maintaining for 2 hours.
3) Adding 500g of 5 wt% ferrous sulfate solution into the barium residue obtained in the step 2), uniformly stirring, standing and maintaining for 48 hours.
Example 11
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 5 wt% hydrogen peroxide solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 2 h.
3) Adding 500g of 5 wt% sodium sulfate solution into the barium residue obtained in the step 2), uniformly stirring, and standing and maintaining for 48 hours.
Example 12
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 2 wt% sodium sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 hours.
Example 13
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 5 wt% sodium sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 hours.
Example 14
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 10 wt% sodium sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 h.
Example 15
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 5 wt% ferrous sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 hours.
Example 16
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 10 wt% ferrous sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 hours.
Example 17
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 1kg of 15 wt% ferrous sulfate solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 48 hours.
Example 18
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 2 wt% hydrogen peroxide solution into the barium residue obtained in the step 1), uniformly stirring, and standing and maintaining for 2 hours.
3) Adding 500g of 10 wt% ferrous sulfate solution into the barium residue obtained in the step 2), uniformly stirring, standing and maintaining for 48 hours.
Example 19
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 5 wt% hydrogen peroxide solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 2 h.
3) Adding 500g of 10 wt% ferrous sulfate solution into the barium residue obtained in the step 2), uniformly stirring, standing and maintaining for 48 hours.
Example 20
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 2 wt% hydrogen peroxide solution into the barium residue obtained in the step 1), uniformly stirring, and standing and maintaining for 2 hours.
3) Adding 500g of 2 wt% sodium sulfate solution into the barium residue obtained in the step 2), uniformly stirring, and standing and maintaining for 48 hours.
Example 21
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 2 wt% hydrogen peroxide solution into the barium residue obtained in the step 1), uniformly stirring, and standing and maintaining for 2 hours.
3) Adding 500g of 5 wt% ferrous sulfate solution into the barium residue obtained in the step 2), uniformly stirring, standing and maintaining for 48 hours.
Example 22
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 5 wt% hydrogen peroxide solution into the barium residue obtained in the step 1), uniformly stirring, standing and maintaining for 2 h.
3) Adding 500g of 5 wt% sodium sulfate solution into the barium residue obtained in the step 2), uniformly stirring, and standing and maintaining for 48 hours.
Comparative example 1
1) Taking 10kg of hardened barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve; no drug stabilization treatment was performed.
Comparative example 2
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve; no drug stabilization treatment was performed.
The samples of examples 1-24 and comparative examples 1-2 were tested before and after treatment as follows:
the method for detecting the soluble barium is HJ766-2015, and comprises the steps of weighing 0.1g of sample, adding 4ml of perchloric acid, 10ml of nitric acid and 4ml of hydrofluoric acid, digesting, transferring and fixing the volume for detection.
The barium leaching method after the stabilization treatment is HJ299-2007, and the barium concentration test method is HJ 766-2015.
The barium leaching method comprises the steps of taking a nitric acid/sulfuric acid mixed solution (the mass ratio of concentrated sulfuric acid to concentrated nitric acid is 2: 1, about 2 drops of concentrated sulfuric acid are dropped into 1L of reagent water, the pH value is 3.20 +/-0.005) as a leaching agent, weighing 150-200g of sample, placing the sample in a 2L extraction bottle, and according to the water content of the sample, according to the liquid-solid ratio of 10: 1(L/kg) calculating the volume of the leaching agent required; adding an extracting agent, tightly covering a bottle cap, adjusting the rotating speed of an oscillating device to be 30 +/-2 r/min, and oscillating for 18 +/-2 hours at the temperature of 23 +/-2 ℃; releasing excessive pressure if gas is opened in the fume hood; the leachate for metal analysis is digested according to the requirements of the analysis method.
The stabilization method test results obtained by sampling test of examples 1 to 22 and comparative examples 1 to 2 are shown in Table 1
TABLE 1 stabilization method test results
Figure BDA0002447490010000071
Figure BDA0002447490010000081
The stability effect of the medicament is calculated by adopting a leaching stability efficiency formula recommended by a toxicity leaching method TCLP issued by the national environmental protection agency:
Figure BDA0002447490010000082
TABLE 2 stabilization treatment efficacy Table
Item Stable efficiency Item Stable efficiency
Example 1 77.78％ Example 12 69.77％
Example 2 80.45％ Example 13 75.99％
Example 3 84.92％ Example 14 79.48％
Example 4 65.32％ Example 15 63.72％
Example 5 79.50％ Example 16 71.98％
Example 6 83.73％ Example 17 75.64％
Example 7 90.31％ Example 18 88.14％
Example 8 91.01％ Example 19 89.13％
Example 9 92.46％ Example 20 90.76％
Example 10 94.96％ Example 21 96.49％
Example 11 95.99％ Example 22 97.80％
From the results of comparative examples 1-2, it can be seen that for the blank samples which were not treated with any stabilizing agent, the leached barium concentration was as high as 805000 μ g/L and 172000 μ g/L, which is required to be stabilized in accordance with "hazardous waste discrimination Standard-discrimination of leached toxicity GB 5085.3-2007" in order to exceed the requirement that the leached barium concentration far exceeds the leaching toxicity of barium ion by less than 100 mg/kg.
From the results of examples 1 to 3 and 12 to 14, it was found that the sodium sulfate solution alone can achieve the stabilization effect for both hardened and unboard barium residues, the stabilization rate for hardened barium residues increases with the concentration of the sodium sulfate solution from 2 wt% to 10 wt%, and is between 77.78% and 84.92%, and for unboard barium residues, the stabilization rate increases with the concentration of the sodium sulfate solution from 2 wt% to 10 wt%, and is between 69.77% and 79.48%.
From the results of examples 4-6 and 15-17, it can be seen that the stabilization effect can be obtained by adding the ferrous sulfate solution alone for the hardened and unboard barium slag, the stabilization rate increases with the ferrous sulfate solution concentration from 5 wt% to 15 wt% for the hardened barium slag, the stabilization rate is between 65.32% and 83.73%, the stabilization rate increases with the ferrous sulfate solution concentration from 5 wt% to 15 wt% for the unboard barium slag, the stabilization rate is between 63.72% and 75.64%, and the stabilization effect of the ferrous sulfate solution is slightly worse than that of the sodium sulfate solution.
In examples 7-11 and 18-22, firstly, 2-5 wt% of hydrogen peroxide solution is added, and then, sodium sulfate solution or ferrous sulfate solution is added for reaction, compared with the case of singly using sodium sulfate solution or ferrous sulfate solution, the stabilization rate is obviously improved and is between 88.14% and 97.80%, wherein in examples 10-11 and examples 21-22, the stabilization rates are all around 95%, and good treatment effect is obtained. As the barium slag contains a large amount of sulfur ions besides barium ions, the barium slag is alkaline, and the barium slag also shows that barium hydroxide and sulfur ions exist (if the sulfur ions exist under an acidic condition, the barium slag can be converted into hydrogen sulfide gas to be discharged), the inventor finds that hydrogen peroxide and the sulfur ions can react to generate a sulfur simple substance and hydrogen by adding hydrogen peroxide in the first stepOxygen radical ion (H)2O2+S2-＝S+2OH-) The generated sulfur simple substance can generate disproportionation reaction with hydroxide ions under the alkaline environment to generate sulfur ions and sulfite ions (3S +6 OH)-＝2S2-+SO3 2-+3H2O), the sulfite and barium ions will generate barium sulfite precipitate (SO)3 2-+Ba2+BaSO3 ↓), secondly, the composition of barium sediment is comparatively complicated, and the trace part heavy metal material that contains such as copper, iron, cobalt, nickel can play the catalytic effect, makes hydrogen peroxide can directly or indirectly oxidize the sulphide ion directly into sulphite ion or sulphate ion to the barium ion of stabilization solidification, makes it obtain better stabilization effect than the sulphate of independent use. In addition, the originally contained sulfur ions and hydroxide ions of the barium slag are fully utilized, and only water is newly generated, so that secondary pollution cannot be caused during cleaning. And in the second step, partial sodium sulfate or ferrous sulfate is added to prevent barium ions which are only dependent on sulfur ions in barium slag from being possibly not completely stabilized and solidified, and the stability of barium sulfate is more difficult to be compatible with barium sulfite, so that the barium ions are promoted to be completely precipitated, the stability of the barium ions is improved, the dosage of the barium ions is less when the barium ions are matched with hydrogen peroxide, and the sodium ions and the iron ions which are introduced subsequently are less and are cleaner.
In order to further observe the stability of the leached barium concentration after the curing, the samples of examples 14,17,21, and 22 were examined for 5 days, 10 days, 20 days, and 30 days, respectively, and the results are shown in Table 3.
Table 3 stability test table for concentration of leached barium
Figure BDA0002447490010000091
Figure BDA0002447490010000101
As can be seen from the data in the table, the average growth rate of the leached barium in the subsequent curing time in example 14 in which only sodium sulfate was added was 2.08%, the average growth rate of the leached barium in the subsequent curing time in example 17 in which only ferrous sulfate was added was 3.60%, example 21 in which 2 wt% hydrogen peroxide solution and 5 wt% ferrous sulfate solution were added, the average growth rate of the leached barium in the subsequent curing time was 1.54%, example 22 in which 5 wt% hydrogen peroxide solution and 5 wt% sodium sulfate solution were added, the average growth rate of the leached barium in the subsequent curing time was 1.23%, the concentration growth rate of the leached barium in the scheme in which hydrogen peroxide solution and sulfate solution were added was low, and the average value-added rate was significantly smaller than that in the scheme in which only sulfate was added, indicating that the persistence was good while maintaining the high stabilization effect on barium.
In order to further verify that the volume of barium sulfate particles can be controlled by adding EDTA, so that the situation that a channel on the surface of barium slag is blocked after the surface of the barium slag is subjected to rapid reaction to hinder subsequent reaction is avoided, the long-acting property of the medicament is realized, the embodiments 21 and 22 are improved, and the EDTA solution is added while the medicament is added.
Example 23
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 2 wt% hydrogen peroxide solution and 0.5L of 0.5mol/L EDTA solution into the barium residue obtained in the step 1), uniformly stirring, and standing and maintaining for 2 hours.
3) Adding 500g of 5 wt% ferrous sulfate solution and 0.5L of 0.5mol/L EDTA solution into the barium residue obtained in the step 2), uniformly stirring, and standing and maintaining for 48 hours.
Example 24
1) Taking 10kg of unblanked barium slag of a certain barium slag factory, crushing, uniformly mixing, air-drying and sieving by a 10-mesh sieve;
2) adding 500g of 5 wt% hydrogen peroxide solution and 0.5L of 0.5mol/L EDTA solution into the barium residue obtained in the step 1), uniformly stirring, and standing and maintaining for 2 hours.
3) Adding 500g of 5 wt% sodium sulfate solution and 0.5L of 0.5mol/L EDTA solution into the barium residue obtained in the step 2), uniformly stirring, and standing and maintaining for 48 hours.
Table 4 stability test table for leaching barium concentration after adding EDTA
Figure BDA0002447490010000102
Figure BDA0002447490010000111
The data in the table above show that the average growth rate of the leached barium is lower than 1% after the EDTA solution is added, which proves that EDTA can ensure that the surface channel of barium slag is smooth and the subsequent inversion is thorough by reducing the volume of barium sulfate particles, the pesticide effect is strong in persistence, and the growth rate of the leached barium is kept at a low and stable level.
The above tests show that the solutions of examples 22 to 24 can be used as a preferred pharmaceutical solution for the on-site remediation of barium residues, see examples 25 to 33.
Example 25
Injecting a treating agent into barium slag by adopting a high-pressure rotary jet grouting pile grouting method, firstly injecting a proper amount of hydrogen peroxide solution according to the amount of the barium slag, then injecting a proper amount of sodium sulfate solution, wherein the hydraulic cutting radius of a grouting area is 0.4-0.5 m, the injection pressure of 25-30 Mpa is adopted, the diameter of a nozzle is 2.0mm, the lifting speed in the high-pressure rotary jet grouting process is 15-30 cm/min, the dynamic pitch (the lifting speed to rotation speed ratio) is 1-2, and after repairing, the leaching concentration of the barium slag in the hydraulic cutting radius (r is 0.4m) is 102 mu g/L which is far lower than the target repairing value of 100 mg/L.
Example 26
The barium slag is treated by adopting an in-situ stirring method, according to the amount of the barium slag, a proper amount of hydrogen peroxide solution is added firstly, then a proper amount of sodium sulfate solution is added, the diameter of a stirring shaft is phi 800, the rotating speed is 25-45 r/min, the flow is 30L/min, the drilling speed is 0.236m/min, the lifting speed is 0.55m/min, and after repair, the leaching concentration of the barium slag in the stirring radius (r is 0.4m) is 53 mu g/L which is far lower than the repair target value of 100 mg/L.
Example 27
And (2) treating the barium slag by adopting an injection well method, firstly adding a proper amount of hydrogen peroxide solution according to the amount of the barium slag, then adding a proper amount of sodium sulfate solution, and after repairing, wherein the leaching concentration of the barium slag in a hydraulic fracturing radius range (r is 0.6m) injected by the injection well is far lower than a repairing target value of 100 mg/L.
Example 28
Other conditions are the same as the example 25, the sodium sulfate solution is replaced by the ferrous sulfate solution, and after the repair, the leaching concentration of the barium residue in the hydraulic cutting radius (r is 0.4m) is 223 mug/L which is far lower than the repair target value of 100 mg/L.
Example 29
The other conditions were the same as in example 26, the sodium sulfate solution was replaced with a ferrous sulfate solution, and after the repair, the leaching concentration of barium residue was 167 μ g/L, which was far below the target repair value of 100mg/L, within the stirring radius (r ═ 0.4 m).
Example 30
In the same manner as in example 27 except that the sodium sulfate solution was replaced with a ferrous sulfate solution, the barium residue leaching concentration in the range of the hydraulic fracture radius (r ═ 0.6m) injected from the injection well after the restoration was 233 μ g/L, which was far below the restoration target value of 100 mg/L.
Example 31
Under the same conditions as in example 25, the EDTA solution was added together with the hydrogen peroxide solution and the sodium sulfate solution, and after the repair, the leaching concentration of the barium residue in the hydraulic cutting radius (r ═ 0.4m) was 125 μ g/L, which was far below the target repair value of 100 mg/L.
Example 32
Under the same conditions as in example 26, the EDTA solution was added together with the hydrogen peroxide solution and the sodium sulfate solution, and after the repair, the leaching concentration of the barium residue was 113 μ g/L, which was much lower than the target repair value of 100mg/L, within the stirring radius (r ═ 0.4 m).
Example 33
Under the same conditions as in example 27, the EDTA solution was added together with the hydrogen peroxide solution and the sodium sulfate solution, and after the completion of the repair, the leaching concentration of the barium residue in the hydraulic fracture radius range (r ═ 0.6m) injected from the injection well was 97 μ g/L, which was far lower than the repair target value of 100 mg/L.
The on-site repair embodiment of the barium slag shows that after the preferable scheme of the invention is adopted, the leaching concentration of the barium slag is far lower than the target repair value, and a good treatment effect is obtained.
In the preferred embodiment, calcium sulfate is added to the obtained barium residue, and the mixture is stirred uniformly and kept still for 10 hours. Because cement is generally adopted to absorb water to adjust the water content in the prior art, but the method is not suitable for waste residues containing more sulfate ions, after the cement is hardened, excessive sulfate ions invade and continue to react to generate a large amount of calcium sulphoaluminate, and the calcium sulphoaluminate crystals expand to cause cracks in the cement, thereby causing great damage, and being incapable of being used for fixing the barium residue and adjusting the water content, in the invention, the calcium sulfate with sulfate radicals is selected to absorb water to adjust the water content, so that the water content of the barium residue is lower than 60 percent to reach the landfill standard.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (10)

1. A method for stabilizing treatment of barium slag comprises the following steps:
1) adding a hydrogen peroxide solution into the barium slag, uniformly stirring, standing and maintaining;
2) adding a sulfate solution into the barium residue obtained in the step 1), uniformly stirring, and standing and maintaining.
2. The method of claim 1, wherein the hydrogen peroxide solution has a concentration of 2 wt% to 5 wt%.
3. The method according to claim 2, wherein the hydrogen peroxide solution is added in an amount of 5-10% by weight of the barium residue.
4. The method of claim 1, wherein the sulfate solution is a sodium sulfate solution or a ferrous sulfate solution.
5. The method of claim 4, wherein the sodium sulfate solution has a concentration of 2 wt% to 10 wt%.
6. The method as claimed in claim 4, wherein the concentration of the ferrous sulfate solution is 5 wt% to 15 wt%.
7. The method according to any one of claims 4 to 6, wherein the sulphate solution is added in an amount of 5% to 10% by weight of the barium residue.
8. The method of claim 1, wherein the hydrogen peroxide solution and the sulfate solution are added simultaneously with the addition of EDTA.
9. The method of claim 1, further comprising:
3) adding calcium sulfate into the barium residue obtained in the step 2), uniformly stirring, and standing and maintaining.
10. The method as claimed in claim 1, wherein the curing time in step 1) is 2-4h and the curing time in step 2) is 2-48 h.
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CN114230240A (en) * 2021-11-15 2022-03-25 中化环境修复(上海)有限公司 Slow release material for stabilizing treatment of barium slag and stabilizing treatment method of barium slag
CN114349413A (en) * 2022-03-18 2022-04-15 中国科学院生态环境研究中心 Barium slag harmless recycling treatment method and prepared building material
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