CN103121730A - Method for treatment of low-concentration mercury containing wastewater by utilizing modified pelelith - Google Patents
Method for treatment of low-concentration mercury containing wastewater by utilizing modified pelelith Download PDFInfo
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- CN103121730A CN103121730A CN2013100927677A CN201310092767A CN103121730A CN 103121730 A CN103121730 A CN 103121730A CN 2013100927677 A CN2013100927677 A CN 2013100927677A CN 201310092767 A CN201310092767 A CN 201310092767A CN 103121730 A CN103121730 A CN 103121730A
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Abstract
The invention discloses a method for the treatment of low-concentration mercury containing wastewater by utilizing modified pelelith. The method comprises the following steps: (1) crushing the pelelith, putting the pelelith into a prepared traditional adsorbent solution for modification and filtering and drying, thereby obtaining a pelelith adsorbent; (2) treating the mercury containing wastewater by utilizing the pelelith adsorbent; and (3) detecting the wastewater and discharging the detection-qualified wastewater. As the method for the treatment of the mercury containing wastewater by utilizing the modified pelelith adsorbent is used, on the basis of controlling the cost, the problem that the mercury content in the low-concentration mercury containing wastewater exceeds the specified standard is solved. The method is low in cost, simple in equipment, simple and convenient to operate, short in treatment period, time-saving, labor-saving, environment-friendly and free of pollution in treatment process and good in treatment effect. In addition, the pelelith adsorbent can be repeatedly recycled for multiple times.
Description
Technical field
The present invention relates to a kind for the treatment of process of mercury-containing waste water, particularly relate to a kind of method that adopts the modification volcanized rock to process the lower concentration mercury-containing waste water.
Background technology
Mercury is the stronger metallic element of a kind of toxicity, and is larger to the harm of environment, classified as priority pollutant by a lot of international bodies.Mercury-containing waste water is one of the most serious trade effluent of a kind of environmental pollution, all produce a large amount of mercury-containing waste waters in the industry such as mercury smelting, lead-zinc smelting, electrochemistry, the waste water of the productions dischargings such as wherein amalgamate smelting, the smelting of regeneration mercury, chlorine industry, plastics industry, electronic industry is the main source that Mercury in Water Body pollutes.At present, the consumption of China's mercury increases year by year, and mercury pollution is very serious.Developing water technology easy, efficient, easy row is badly in need of at present take control water body mercury pollution as China.
Now developed a series of water body mercury pollution control techniquess, mercury-containing waste water treatment method commonly used has chemical precipitation method, electrolytic process, microbial method, metal deoxidization, ion exchange method etc., but these methods easily cause secondary pollution.Existing research and utilization gac, modified zeolite, volcanic ash, flyash, metallic zinc and Mycophyta etc. are as the mercurous trade effluent of sorbent treatment, can effectively prevent secondary pollution, but because of prices of raw and semifnished materials impact, processing costs is very high, is applicable to process and reclaim the higher trade effluent of mercury relative concentration.The mercury-containing waste water lower for relative concentration, exploitation cheapness and resourceful sorbent material have good prospect with the technology of removing Mercury in Wastewater.
The volcanized rock characteristic is similar to volcanic ash, all has the advantages such as specific surface area is large, loading capacity is large.Pozzuolanic particle diameter＜1mm is generally 0.2mm, needs the standing time longer in water technology, and more than generally needing 2h, and the particle diameter of volcanized rock is larger, and time of repose can significantly shorten.On the other hand, 1060 extinct volcano circumferential distribution of China have a large amount of volcanized rocks, and volcanic ash is seldom, and the ash field material require import of China, therefore, volcanized rock draw materials and expense aspect have a clear superiority in than volcanic ash.Up to now, not yet see the report that utilizes volcanized rock to process mercury-containing waste water, also there is no relevant patented technology.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of utilizing mercury ion in modification volcanized rock Adsorption lower concentration mercury-containing waste water, and described method cost is low, easy and simple to handle.
The present invention processes the method for lower concentration mercury-containing waste water with the modification volcanized rock, comprise the steps:
(1) pulverize volcanized rock, put it into modification in the traditional sorbent material solution for preparing, obtain the volcanized rock sorbent material after filtering drying;
(2) adopt volcanized rock sorbent treatment mercury-containing waste water;
(3) detect waste water, qualified rear discharging.
The method of processing the lower concentration mercury-containing waste water with the modification volcanized rock of the present invention, wherein step (3) also comprises step afterwards:
(4) recovery of volcanized rock sorbent material: will put into strippant desorb 1h after used described volcanized rock absorbent filtering, filter and dry described volcanized rock sorbent material, the recycling of volcanized rock sorbent material has reduced processing cost again, and reduced the waste that treating processes produces, environment friendly and pollution-free.
The method of processing the lower concentration mercury-containing waste water with the modification volcanized rock of the present invention, wherein described in step (1), the preparation method of volcanized rock sorbent material is as follows:
Powder after A, volcanized rock are pulverized is crossed 10 order scalpings, powder diameter＜1.8mm;
B, the preparation traditional sorbent material solution, described volcanized rock powder is put into described solution, oscillation treatment 12h, wash to pH be 6.5～7.5;
C, filtration are also dried described volcanized rock powder, namely get the volcanized rock sorbent material.
The volcanized rock characteristic is similar to volcanic ash, all has the advantages such as specific surface area is large, loading capacity is large, but pozzuolanic particle diameter＜1mm, be generally 0.2mm, need the standing time longer in water technology, more than generally needing 2h, and the particle diameter of volcanized rock is larger, and time of repose can significantly shorten; The preparation method of described volcanized rock sorbent material is simple, the cycle is short.Oscillation treatment is in order to make fully contacting of volcanized rock powder and traditional sorbent material solution, adsorption site position with the activation volcanized rock, improve absorption property, common pretreatment time according to mineral material, be set to 12h, then wash to water outlet nearly neutral (pH=6.5～7.5), with thorough removal sorbent material debris.It is acid that liquor ferri trichloridi is, and the washing modified adsorbent is to neutral, shows that iron trichloride residual on sorbent material removes substantially; Vibration 12h is the prime time of the adsorption site position activation of volcanized rock, and evidence reached balance in 10 hours substantially, in order to guarantee activation effect, stablized 2 hours.
The method of processing the lower concentration mercury-containing waste water with the modification volcanized rock of the present invention, wherein adopt the method for volcanized rock sorbent treatment mercury-containing waste water to be described in step (2): regulating waste water ph is 10.5～11.5, the addition of described volcanized rock sorbent material is 1.0～4.0g/500mL, oscillation treatment 1h, standing 15min.Modification volcanized rock sorbent material is subjected to impact that water body pH changes greatly on the adsorption rate of mercury, and under alkaline condition, adsorption rate is higher, and the modification volcanized rock has larger loading capacity to mercury when water body pH ≈ 11.1.0 the modification volcanized rock sorbent material addition of～4.0g/500mL is to consider Adsorption efficient and processing cost, surpasses the 4g processing cost too high, and is not enough lower than the 1g processing efficiency; Oscillation treatment 1h is definite according to experiment effect, and 15min has obvious adsorption effect, and 30min reaches adsorption equilibrium substantially, and in order to make it stable, oscillation treatment 30-60min is preferably absorption 1h; Standing is in order to process rear solid-liquid separation, and more than standing 15min, liquid does not have suspended particulate substantially.
The method of processing the lower concentration mercury-containing waste water with the modification volcanized rock of the present invention, wherein said traditional sorbent material is hydrochloric acid, sulfuric acid, sodium hydroxide or iron trichloride.
The method of processing the lower concentration mercury-containing waste water with the modification volcanized rock of the present invention, wherein said traditional sorbent material is iron trichloride, the concentration of solution is 1～1.5mol/L.Modification is exactly that the chemical group that absorption shows is changed, to strengthen ion adsorption capacity, at present commonly used have soda acid modification, an organic solvent modification, sulfuric acid as used in this method of the invention, hydrochloric acid, sodium hydroxide, ethanol, acetone, iron trichloride etc., wherein, sulfuric acid and hydrochloric acid belong to acid stronger material, sodium hydroxide and belong to that stronger material, ethanol and the acetone of alkalescence belongs to organic solvent, iron trichloride belongs to acidulous material.Different sorbent materials can be to differ to the adaptation of modified condition, and under weakly acidic ferric trichloride modified condition, the ion-exchange capacity of volcanized rock sorbent material is the strongest.Select ferric trichloride modified volcanized rock, it is mainly the absolute value that improves particle surface point position on principle, thereby produce very strong electrostatic double layer electrostatic repulsion effect, adsorption layer can also produce very strong steric exclusion effect simultaneously, thereby improve the particle agglomeration phenomenon, increase adsorptive power, therefore, iron trichloride is the preferred traditional sorbent material of modification volcanized rock.
The method of processing the lower concentration mercury-containing waste water with the modification volcanized rock of the present invention, wherein said strippant is HCl solution, concentration is 1mol/L.HCl solution is common chemical reagent, is easy to get, and choosing of concentration, the optimum concn that experiment obtains is 1mol/L, better configuration.
The method of processing the lower concentration mercury-containing waste water with the modification volcanized rock of the present invention, the bake out temperature in wherein said step (4) and step C is 100～105 ℃.
The method of processing the lower concentration mercury-containing waste water with the modification volcanized rock of the present invention, wherein said volcanized rock adopt electric mill to pulverize; Oscillation treatment adopts shaking table to carry out.
The method of processing the lower concentration mercury-containing waste water with the modification volcanized rock of the present invention, it is more than 10 times that wherein said volcanized rock sorbent circulation is utilized number of times.
The method difference from prior art that the present invention processes the lower concentration mercury-containing waste water with the modification volcanized rock is that the present invention adopts the modification volcanized rock to process the lower concentration mercury-containing waste water, and the volcanized rock specific surface area is 530～680m
2/ g through modification, has very strong adsorptive power, and mercury in mercury-containing waste water is had removal effect preferably; The volcanic ash particle diameter is less, needs the standing time longer in water technology, and more than generally needing 2h, and the particle diameter of volcanized rock is larger, and time of repose can significantly shorten; 1060 extinct volcano circumferential distribution of China have a large amount of volcanized rocks, and volcanic ash is seldom, and the ash field material require import of China, therefore, volcanized rock draw materials and expense aspect have a clear superiority in than volcanic ash.
Method with modification volcanized rock sorbent treatment mercury-containing waste water provided by the invention, on the basis of controlling cost, solve the problem that in the lower concentration mercury-containing waste water, mercury exceeds standard, the mercury of modification volcanized rock sorbent material in can the quick adsorption mercury-containing waste water, the mercury-containing waste water of right＜0.5mg/L, adsorption rate after 15min just can reach between 75%-85%, the basic adsorption equilibrium of 1h; By changing adsorption conditions such as dosage, pH, adsorption time etc., adsorption rate can reach more than 92%, the concentration＜0.04mg/L of mercury in water after processing; Realize qualified discharge, improve environmental quality; In the method for processing the lower concentration mercury-containing waste water with the modification volcanized rock of the present invention, volcanized rock is easy to get, and described sorbent material and strippant are also all common solution, and raw material sources are extensive; Described method cost is low, equipment is simple, easy and simple to handle, treatment cycle is short, time saving and energy saving, treating processes is environment friendly and pollution-free and treatment effect is good, and wherein said volcanized rock sorbent material can also repeat to recycle repeatedly, has again reduced cost.
Below in conjunction with accompanying drawing, the method with modification volcanized rock processing lower concentration mercury-containing waste water of the present invention is described further.
Description of drawings
Fig. 1 is that the use of different traditional sorbent materials in the method for the invention is on the impact of volcanized rock adsorptive power;
Fig. 2 is the impact of different pH values on modification volcanized rock adsorptive power in the method for the invention;
Fig. 3 is that modification volcanized rock sorbent material injected volume different in the method for the invention is on the impact of adsorption;
Fig. 4 is the adsorption isothermal line schematic diagram of modification volcanized rock to mercury in the method for the invention.
Embodiment
Embodiment 1
The impact of the use of different traditional sorbent materials on the volcanized rock adsorptive power:
As shown in Figure 1: adopt respectively traditional sorbent treatment techniques such as hydrochloric acid, sulfuric acid, ethanol, acetone, sodium hydroxide, iron trichloride to carry out modification to volcanized rock, then shaking table vibration 12h washs to water outlet closely neutrally, dries under 105 ℃ of conditions; 4g modification volcanized rock sorbent material is added in the mercury-containing waste water that the 500mL starting point concentration is 0.5mg/L, shaking table vibration 1h, water body pH is 10.86.As can be seen from Figure 1, modification volcanized rock sorbent material is subjected to the impact of modified condition larger on the adsorption rate of mercury, and the modification volcanized rock adsorption rate after iron trichloride is processed is the highest.
The impact of different pH values on modification volcanized rock adsorptive power:
As shown in Figure 2, be respectively at water body pH under 3.83,5.64,7.38,9.15,10.89 and 11.5 condition, 4g modification volcanized rock sorbent material is added in the mercury-containing waste water that the 500mL starting point concentration is 0.5mg/L, shaking table vibration 1h.As can be seen from Figure 2, modification volcanized rock sorbent material is subjected to impact that water body pH changes greatly on the adsorption rate of mercury, and under alkaline condition, adsorption rate is higher, and the modification volcanized rock has larger loading capacity to mercury when water body pH ≈ 11.
Embodiment 3
The impact of different modification volcanized rock sorbent material injected volumes on adsorption:
Respectively 1g, 2g and 4g modification volcanized rock sorbent material being added to the 500mL starting point concentration is 0.5mg/L, and pH is in 10.89 mercury-containing waste water, shaking table vibration 1h.In Fig. 3 curve, " zero " expression is that modification volcanized rock sorbent material injected volume is 1g, and namely accounting for mercurous effluent sewage mass percent is 0.2%; What " ▽ " represented is that modification volcanized rock sorbent material injected volume is 2g, and namely accounting for mercurous effluent sewage mass percent is 0.4%; What " " represented is that modification volcanized rock sorbent material injected volume is 4g, and namely accounting for mercurous effluent sewage mass percent is 0.8%.Can find out, modification volcanized rock dosage and wastewater quality ratio are in 0.2～0.8% interval, and adsorption rate changes little, still can reach more than 92%.Simultaneously, the adsorption rate after 15min just can reach between 75%-85%, the basic adsorption equilibrium of 1h.By changing adsorption conditions such as dosage, pH, adsorption time etc., adsorption rate all can reach more than 92%.
Embodiment 4
Fig. 4 is the adsorption isothermal line schematic diagram of modification volcanized rock to mercury in the method for the invention.It is 0.025mg/L, 0.05mg/L, 0.15mg/L, 0.25mg/L, 0.35mg/L and 0.5mg/L that 4g modification volcanized rock sorbent material is added to respectively 500mL mercury concentration, and pH is in 10.91 mercury-containing waste water, shaking table vibration 1h.As can be seen from Figure 4, adsorptive capacity increases with the increase of adsorption equilibrium concentration, and this increase tendency is obvious all the more along with the increase of equilibrium concentration, shows that the modification volcanized rock meets the Freundlich model to the absorption behavior of mercury.
Embodiment 5
Getting Huinan County, Liaoning extinct volcano mouth stone is raw material, and electric mill is pulverized, and crosses 10 order scalpings, processes 105 ℃ of dry for standby with the iron trichloride of 1mol/L.
Getting the mercury concentration of discharging on mercury ore district, Guizhou tailing dam is the waste water 500mL of 0.43mg/L, and the pH value of waste water is adjusted to 10.92, directly adds modification volcanized rock 4g, and shaking table vibration 1h is centrifugal, get supernatant liquor and measure total mercury concentration.Result is: the residual concentration of mercury is 0.032mg/L, clearance is 92.6%, result is lower than the sewage discharge limit value 0.05mg/L of total mercury in national sewage comprehensive emission standard GB8978-1996, and lower than the sewage discharge limit value 0.04mg/L of total mercury in national tin, antimony, mercury emission of industrial pollutants standard (exposure draft).
Embodiment 6
Method with modification volcanized rock processing lower concentration mercury-containing waste water of the present invention comprises the steps:
(1) electric mill is pulverized volcanized rock, and the powder after pulverizing is crossed 10 order scalpings, powder diameter＜1.8mm; Compound concentration is the liquor ferri trichloridi of 1.5mol/L, and described volcanized rock powder is put into described solution, shaking table oscillation treatment 12h, wash to pH be 6.5; Filter and at 100 ℃ of described volcanized rock powder of oven dry, namely get the volcanized rock sorbent material.
(2) regulating mercury-containing waste water pH value is 10.5, and the addition of described volcanized rock sorbent material is 4.0g/500mL, shaking table oscillation treatment 1h, standing 15min.
(3) detect waste water, qualified rear discharging.
Embodiment 7
(1) electric mill is pulverized volcanized rock, and the powder after pulverizing is crossed 10 order scalpings, powder diameter＜1.8mm; Compound concentration is the sulphuric acid soln of 1mol/L, and described volcanized rock powder is put into described solution, shaking table oscillation treatment 12h, wash to pH be 7.5; Filter and at 100 ℃ of described volcanized rock powder of oven dry, namely get the volcanized rock sorbent material.
(2) regulating mercury-containing waste water pH value is 11.5, and the addition of described volcanized rock sorbent material is 1.0g/500mL, shaking table oscillation treatment 1h, standing 15min.
(3) detect waste water, qualified rear discharging.
(1) recovery of volcanized rock sorbent material: will put into strippant desorb 1h after the used described volcanized rock absorbent filtering of embodiment 6 or 7, described strippant is HCl solution, and concentration is 1mol/L, filters and dry described volcanized rock sorbent material.
(2) regulating mercury-containing waste water pH value is 11, and the addition of described volcanized rock sorbent material is 3.0g/500mL, shaking table oscillation treatment 1h, standing 15min.
(3) detect waste water, qualified rear discharging.
Embodiment 9
(1) recovery of volcanized rock sorbent material: will put into strippant desorb 1h after the used described volcanized rock absorbent filtering of embodiment 8, described strippant is HCl solution, and concentration is 1mol/L, filters and dry described volcanized rock sorbent material.
(2) regulating mercury-containing waste water pH value is 11, and the addition of described volcanized rock sorbent material is 2.5g/500mL, shaking table oscillation treatment 1h, standing 15min.
(3) detect waste water, qualified rear discharging.
Consumption according to 2.5g modification volcanized rock sorbent material/500mL waste water is processed mercury-containing waste water, and after absorption 1h, then the state that reaches capacity is placed in 1mol/L HCl desorb 1h, filters, dries.The regeneration volcanized rock sorbent material that obtains is proceeded the adsorption and desorption experiment of continuous 10 times under the same terms, adsorption rate〉92.1%, can realize the recycle of sorbent material, reach good environmental benefit.
Above-described embodiment is described the preferred embodiment of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that those of ordinary skills make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (10)
1. a method of processing the lower concentration mercury-containing waste water with the modification volcanized rock, is characterized in that: comprise the steps:
(1) pulverize volcanized rock, put it into modification in the traditional sorbent material solution for preparing, obtain the volcanized rock sorbent material after filtering drying;
(2) adopt volcanized rock sorbent treatment mercury-containing waste water;
(3) detect waste water, qualified rear discharging.
2. use modification volcanized rock according to claim 1 is processed the method for lower concentration mercury-containing waste water, and it is characterized in that: step (3) also comprises step afterwards:
(4) recovery of volcanized rock sorbent material: with putting into strippant desorb 1h after used described volcanized rock absorbent filtering, filter and dry described volcanized rock sorbent material.
3. use modification volcanized rock according to claim 1 and 2 is processed the method for lower concentration mercury-containing waste water, and it is characterized in that: described in step (1), the preparation method of volcanized rock sorbent material is as follows:
Powder after A, volcanized rock are pulverized is crossed 10 order scalpings, powder diameter＜1.8mm;
B, the preparation traditional sorbent material solution, described volcanized rock powder is put into described solution, oscillation treatment 12h, wash to pH be 6.5～7.5;
C, filtration are also dried described volcanized rock powder, namely get the volcanized rock sorbent material.
4. use modification volcanized rock according to claim 3 is processed the method for lower concentration mercury-containing waste water, it is characterized in that: adopt the method for volcanized rock sorbent treatment mercury-containing waste water to be described in step (2): regulating waste water ph is 10.5～11.5, the addition of described volcanized rock sorbent material is 1.0～4.0g/500mL, oscillation treatment 30-60min, standing 15min.
5. use modification volcanized rock according to claim 4 is processed the method for lower concentration mercury-containing waste water, and it is characterized in that: described traditional sorbent material is hydrochloric acid, sulfuric acid, sodium hydroxide or iron trichloride.
6. use modification volcanized rock according to claim 5 is processed the method for lower concentration mercury-containing waste water, and it is characterized in that: described traditional sorbent material is iron trichloride, and the concentration of solution is 1～1.5mol/L.
7. use modification volcanized rock according to claim 6 is processed the method for lower concentration mercury-containing waste water, and it is characterized in that: described strippant is HCl solution, and concentration is 1mol/L.
8. use modification volcanized rock according to claim 3 is processed the method for lower concentration mercury-containing waste water, and it is characterized in that: the bake out temperature in described step (4) and step C is 100～105 ℃.
9. the method for processing the lower concentration mercury-containing waste water with the modification volcanized rock according to claim 4, is characterized in that: the pulverizing of described volcanized rock employing electric mill; Oscillation treatment adopts shaking table to carry out.
10. use modification volcanized rock according to claim 2 is processed the method for lower concentration mercury-containing waste water, and it is characterized in that: it is more than 10 times that described volcanized rock sorbent circulation is utilized number of times.
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| CN103962092A (en) * | 2014-05-16 | 2014-08-06 | 宁波工程学院 | Modified vesuvianite adsorbent and electroplating wastewater treatment method |
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| CN107224974A (en) * | 2017-07-14 | 2017-10-03 | 河北科技大学 | α‑Fe2O3The preparation method and applications of/volcanic rock catalyst |
| CN110548476A (en) * | 2019-09-30 | 2019-12-10 | 长春工业大学 | Preparation method and application of modified volcanic cinders filter material |
| CN110921811A (en) * | 2019-11-29 | 2020-03-27 | 南京华创环境技术研究院有限公司 | Modified volcanic rock filler and preparation method and application thereof |
| CN117362128A (en) * | 2023-11-15 | 2024-01-09 | 湖北茂盛生物有限公司 | Preparation process of synergistic fertilizer containing volcanic mineral substances |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103962092A (en) * | 2014-05-16 | 2014-08-06 | 宁波工程学院 | Modified vesuvianite adsorbent and electroplating wastewater treatment method |
| CN103962092B (en) * | 2014-05-16 | 2015-10-21 | 宁波工程学院 | A kind of modification pelelith adsorbent and electroplating effluent treatment method |
| CN104624630A (en) * | 2015-01-14 | 2015-05-20 | 中节能六合天融环保科技有限公司 | Passivant for in-situ remediation of polluted farmland and application method of passivant |
| CN107224974A (en) * | 2017-07-14 | 2017-10-03 | 河北科技大学 | α‑Fe2O3The preparation method and applications of/volcanic rock catalyst |
| CN107224974B (en) * | 2017-07-14 | 2019-10-29 | 河北科技大学 | α-Fe2O3The preparation method and applications of/volcanic rock catalyst |
| CN110548476A (en) * | 2019-09-30 | 2019-12-10 | 长春工业大学 | Preparation method and application of modified volcanic cinders filter material |
| CN110921811A (en) * | 2019-11-29 | 2020-03-27 | 南京华创环境技术研究院有限公司 | Modified volcanic rock filler and preparation method and application thereof |
| CN117362128A (en) * | 2023-11-15 | 2024-01-09 | 湖北茂盛生物有限公司 | Preparation process of synergistic fertilizer containing volcanic mineral substances |
| CN117362128B (en) * | 2023-11-15 | 2024-10-18 | 湖北茂盛生物有限公司 | Preparation process of synergistic fertilizer containing volcanic mineral substances |
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Application publication date: 20130529 |