CN112605101A - Stabilizing treatment method for barium-containing waste - Google Patents
Stabilizing treatment method for barium-containing waste Download PDFInfo
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- CN112605101A CN112605101A CN202011459396.8A CN202011459396A CN112605101A CN 112605101 A CN112605101 A CN 112605101A CN 202011459396 A CN202011459396 A CN 202011459396A CN 112605101 A CN112605101 A CN 112605101A
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- barium
- silicate
- containing waste
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- 229910052788 barium Inorganic materials 0.000 title claims abstract description 76
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 230000000087 stabilizing effect Effects 0.000 title abstract description 6
- 238000002386 leaching Methods 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 29
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000004568 cement Substances 0.000 claims abstract description 11
- 229910001422 barium ion Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract 2
- 239000007787 solid Substances 0.000 claims description 16
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 claims description 9
- 230000001988 toxicity Effects 0.000 claims description 9
- 231100000419 toxicity Toxicity 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002920 hazardous waste Substances 0.000 abstract description 13
- 229910052916 barium silicate Inorganic materials 0.000 abstract description 10
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000006641 stabilisation Effects 0.000 abstract description 5
- 238000011105 stabilization Methods 0.000 abstract description 5
- 230000020477 pH reduction Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910020489 SiO3 Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 150000001553 barium compounds Chemical class 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910003641 H2SiO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003487 anti-permeability effect Effects 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- -1 silicate ions Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000004927 wastewater treatment sludge Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
Abstract
The invention discloses a stabilizing disposal method of barium-containing waste, which mainly comprises the following steps: 1) adding a proper amount of water into the barium-containing waste, mixing and stirring the mixture into slurry to obtain a first mixture; 2) adding soluble silicate into the first mixture, uniformly stirring, adding an acid solution to adjust the pH, and stirring and mixing to be viscous to obtain a second mixture; 3) and adding cement into the second mixture, mixing and stirring, standing, and then curing and molding. The invention adopts the reaction of silicate and barium ions in waste to generate insoluble barium silicate, thereby realizing the stabilization of barium. Secondly, silicate gel with a three-dimensional net structure is rapidly generated through acidification and decomposition of silicate and can be coated on the surface of the formed barium silicate, so that the re-dissolution of the barium silicate is effectively prevented, and the leaching concentration of barium in the cured body after treatment is far lower than the requirement of the barium control limit of 85mg/l in hazardous waste landfill pollution control standard (GB 18598-2019).
Description
Technical Field
The invention relates to the field of safe landfill of hazardous wastes, in particular to a stabilizing treatment method of barium-containing wastes.
Background
The hazardous waste refers to solid waste with hazardous characteristics listed in national hazardous waste lists or identified according to the national hazardous waste identification standards and methods. The barium-containing waste is a common hazardous waste, mainly comes from industries such as basic chemical raw material manufacturing, metal surface treatment, heat treatment processing and the like, and mainly comprises slag generated in the production process of barium compounds (excluding barium sulfate), dust collected by a dust collection (removal) device, reaction residues, wastewater treatment sludge, barium-containing salt bath slag generated in a heat treatment process and the like.
The barium-containing waste has great harm to human health and ecological environment. Barium and its compounds can enter into body from respiratory tract, digestive tract and damaged skin, and can also be used for killing by intravenous administration. The ingestion of soluble barium compounds can cause barium poisoning, barium-containing waste entering the environment can also harm human health along with the enrichment of food chains, and on the other hand, most metals enter the soil and have obvious adverse effects on the physicochemical properties of the soil, the biological characteristics of the soil and the microbial community structure.
The barium-containing waste treatment method mainly comprises the methods of resource utilization, cement kiln cooperative treatment, safe landfill and the like. Wherein, the landfill disposal method has mature technology and can intensively dispose the barium-containing waste. However, in the prior art, the purpose of stabilization has been achieved by adding sulfate or carbonate or adjusting the pH value in the form of barium sulfate, barium carbonate or barium hydroxide. The disadvantages of the above method are: the barium concentration in the leaching solution is higher, and the leaching solution does not have long-term stability.
Disclosure of Invention
The invention provides a method for stably treating barium-containing waste, which aims to solve the problems in the prior art and has the advantages of remarkable stable curing effect, simplicity and convenience in operation, wide adaptability and low cost.
The invention is realized by the following technologies:
a method for firmly disposing barium-containing waste, comprising the following steps:
(1) adding water and mixing: adding a proper amount of water into the barium-containing waste, mixing and stirring the mixture into slurry to obtain a first mixture;
(2) adding silicate and mixing: adding soluble silicate into the first mixture, uniformly stirring, adding an acid solution to adjust the pH, and stirring and mixing to be viscous to obtain a second mixture;
(3) curing and forming: and adding cement into the second mixture, mixing and stirring, standing for a period of time, and then curing and forming.
Preferably, the mixing and stirring time in the step (1) is 5min to 10 min; the solid content of the first mixture is 50-70%.
Preferably, the soluble silicate in step (2) is added in solid form; the adding amount of the soluble silicate is calculated according to the molar ratio 1 (1.2-1.5) of barium ions in the barium-containing waste leachate to silicate groups of the soluble silicate, and the barium-containing waste leachate is obtained by leaching according to a leaching method of an industry standard HJ/T299-2007 solid waste-leaching toxicity leaching method sulfuric acid-nitric acid method.
Preferably, the soluble silicate is one or both of sodium silicate and potassium silicate.
Preferably, the stirring time for adding the soluble silicate in the step (2) is 10min to 15 min.
Preferably, the pH range in the step (2) is 5-7, and the stirring time for adding the acid solution is 10-15 min.
Preferably, the acid solution is one or more of sulfuric acid or phosphoric acid with the mass concentration of 30-50%.
Preferably, the adding amount of the cement in the step (3) is 10-15% of the total amount of the barium-containing waste.
Preferably, the mixing and stirring time of the step (3) is 5min to 10 min.
And (3) sampling and analyzing the solidified body after treatment, leaching and determining the total barium content of the leachate according to a solid waste-leaching toxicity leaching method sulfuric acid-nitric acid method 2007 HJ/T299-plus, and warehousing and burying after meeting the requirement of a barium stabilization control limit of 85mg/l in hazardous waste landfill pollution control standard (GB 18598-2019).
The invention achieves the following remarkable effects in the process of stabilizing and disposing the barium-containing waste:
(1) the method utilizes the reaction of free barium ions in the waste and silicate to generate insoluble barium silicate, thereby realizing the stabilization of barium.
(2) During the pH adjustment process, silicate gel with a three-dimensional network structure is rapidly generated through acidification and decomposition of silicate, and can be coated on the surface of the formed barium silicate, so that the barium silicate is effectively prevented from being dissolved out again.
(3) The silicate and sulfate and phosphate generated by neutralization have the effects of accelerating coagulation in the cement hydration process, enhancing the strength of a solidified body, improving better anti-permeability effect, and generating the secondary coating effect, so that the leaching concentration of barium in the solidified body after treatment is far lower than the requirement of hazardous waste landfill pollution control standard (GB 18598-2019).
(4) Can greatly reduce the consumption of the curing material cement and reduce the disposal cost of the stabilization curing.
(5) The treatment method can be used for treating barium-containing wastes with different barium leaching concentrations and has wide application range.
Drawings
FIG. 1 is a flow chart of the treatment process for stabilizing the solidification of the barium-containing waste according to the present invention.
Detailed Description
The invention adopts soluble silicate and barium to react to generate insoluble substance barium silicate, and the reaction principle is as follows:
Ba2++SiO3 2-＝BaSiO3↓
2H++SiO3 2-＝H2SiO3↓→SiO2↓+H2O
barium ions react with silicate ions to generate insoluble barium silicate, so that the barium is stabilized; during the pH adjustment process, the sodium silicate quickly generates silicic acid gel with a three-dimensional net structure due to acidification reaction, and the silicic acid gel can be coated on the surface of the formed barium silicate, so that the barium silicate is effectively prevented from being dissolved out again.
The present invention will be described in further detail with reference to examples.
Example 1:
leaching barium-containing sludge of a chemical enterprise according to HJ/T299-2007 sulfuric acid-nitric acid method for solid waste-leaching toxicity leaching method to obtain barium-containing leachate, and detecting that the total barium concentration in the barium-containing leachate is 598mg/L, which is far greater than the requirement that the barium leaching concentration in hazardous waste landfill pollution control standard is less than 85 mg/L. The stable solidification of the barium-containing waste is accomplished by the following steps: (1) 200g of barium-containing waste is put into a stainless steel container, and a proper amount of water is added to the barium-containing waste and stirred for 5 min. Obtaining a first mixture with the solid content of 70%; (2) the total barium concentration in the barium-containing waste leachate is 598mg/L according to Ba2+With SiO2 2-Sodium silicate (Na) was added to the first mix at a 1:1.5 molar ratio2SiO3·9H2O)3.71g, and mixing and stirring for 10 min; regulating the pH value to 5.0 by using sulfuric acid with the mass concentration of 30%, mixing and stirring for 10min to form a viscous paste to obtain a second mixture; (3) adding 25g of cement into the second mixture, and stirring for 5 min; standing for a period of time, and then curing and forming.
The treated solidified body is detected according to HJ/T299-2007 sulfuric acid-nitric acid method for solid waste-leaching toxicity leaching method, and the barium concentration in the leaching solution is 1.51mg/L, which is far lower than the requirement of hazardous waste landfill pollution control standard.
Example 2:
leaching barium-containing waste residue of a certain surface treatment enterprise according to HJ/T299-2007 sulfuric acid-nitric acid method for solid waste-leaching toxicity leaching method to obtain barium-containing leachate, detecting the total barium concentration in the barium-containing leachate to be 1520mg/L which is far greater than that in dangerous wasteThe barium leaching concentration is less than 85mg/L in the standard for controlling landfill pollution. The stable solidification of the barium-containing waste is accomplished by the following steps: (1) putting 200g of barium-containing waste into a stainless steel container, adding a proper amount of water, and fully stirring for 10min to obtain a first mixture with the solid content of 60%; (2) the total barium concentration in the barium-containing waste leachate is 1520mg/L, as Ba2+With SiO2 2-Adding potassium silicate (K) into the first mixture at a molar ratio of 1:1.22SiO3)4.10g, mixing and stirring for 15min, adjusting the pH to 6.5 by using a phosphoric acid solution with the mass concentration of 50%, mixing and stirring for 10min to obtain a viscous paste, and thus obtaining a second mixture; (3) adding 20g of cement into the second mixture, and stirring for 10 min; standing for a period of time, and then curing and forming.
The treated solidified body is detected according to HJ/T299-2007 sulfuric acid-nitric acid method for solid waste-leaching toxicity leaching method, and the barium concentration in the leaching solution is 5.40mg/L, which is far lower than the requirement of hazardous waste landfill pollution control standard.
Example 3:
barium-containing sludge of a certain barium salt production enterprise is leached according to HJ/T299-2007 'sulfuric acid-nitric acid method for solid waste-leaching toxicity leaching method' to obtain barium-containing leachate, and the total barium concentration in the barium-containing leachate is detected to be 3020mg/L, which is far greater than the requirement that the barium leaching concentration in 'hazardous waste landfill pollution control standard' is less than 85 mg/L. The stable solidification of the barium-containing waste is accomplished by the following steps: (1) putting 200g of barium-containing waste into a stainless steel container, adding a proper amount of water, and fully stirring for 10min to obtain a first mixture with the solid content of 50%; (2) the total barium concentration in the barium-containing waste leachate is 3020mg/L, as per Ba2+With SiO2 2-Sodium silicate (Na) was added to the first mix at a 1:1.4 molar ratio2SiO3·9H2O)8.75g and potassium silicate (K)2SiO3)4.76g, mixing and stirring for 15min, adjusting the pH to 7.0 by using a mixed solution of sulfuric acid and phosphoric acid with the mass concentration of 30%, mixing and stirring for 15 min; the mixture is viscous paste-like to obtain a second mixture; (3) adding 30g of cement into the second mixture, and mixing and stirring for 10 min; standing for a period of time, and then curing and forming.
The treated solidified body is detected according to HJ/T299-2007 sulfuric acid-nitric acid method for solid waste-leaching toxicity leaching method, and the barium concentration in the leaching solution is 5.30mg/L, which is far lower than the requirement of hazardous waste landfill pollution control standard.
Claims (9)
1. A method for firmly disposing barium-containing waste is characterized by comprising the following steps:
(1) adding water and mixing: adding a proper amount of water into the barium-containing waste, and mixing and stirring to obtain a first mixture;
(2) adding silicate and mixing: adding soluble silicate into the first mixture, uniformly stirring, adding an acid solution to adjust the pH, and uniformly mixing and stirring to obtain a second mixture;
(3) curing and forming: and adding cement into the second mixture, uniformly mixing and stirring, standing for a period of time, and then curing and molding.
2. The method for firmly disposing the barium-containing waste as claimed in claim 1, wherein the soluble silicate in the step (2) is one or both of sodium silicate and potassium silicate.
3. The method of claim 2, wherein the soluble silicate is added in solid form; the adding amount of the soluble silicate is calculated according to the molar ratio 1 (1.2-1.5) of barium ions in the barium-containing waste leachate to silicate groups of the soluble silicate, and the barium-containing waste leachate is obtained by leaching according to a leaching method of an industry standard HJ/T299-2007 solid waste-leaching toxicity leaching method sulfuric acid-nitric acid method.
4. The method for firmly disposing the barium-containing waste as claimed in claim 1, wherein the acid solution is one or both of sulfuric acid or phosphoric acid with a mass concentration of 30-50%.
5. The method for firmly disposing the barium-containing waste according to claim 1, wherein the mixing and stirring time in the step (1) is 5min to 10 min; the solid content of the first mixture is 50-70%.
6. The method for firmly disposing the barium-containing waste according to claim 1, wherein the pH value in the step (2) is 5-7, and the stirring time for adding the acid solution is 10-15 min.
7. The method for firmly disposing the barium-containing waste according to claim 1, wherein the stirring time for adding the soluble silicate in the step (2) is 10min to 15 min.
8. The stabilized disposal method of barium-containing waste as claimed in claim 1, wherein the cement is added in the amount of 10% -15% of the total amount of barium-containing waste in said step (3).
9. The method for firmly disposing the barium-containing waste as claimed in claim 1, wherein the mixing and stirring time of step (3) is 5min to 10 min.
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