CN102285746B - Method for controlling odor of polluted bottom sediment - Google Patents
Method for controlling odor of polluted bottom sediment Download PDFInfo
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- CN102285746B CN102285746B CN 201110154297 CN201110154297A CN102285746B CN 102285746 B CN102285746 B CN 102285746B CN 201110154297 CN201110154297 CN 201110154297 CN 201110154297 A CN201110154297 A CN 201110154297A CN 102285746 B CN102285746 B CN 102285746B
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Abstract
The embodiment of the invention discloses a method for controlling the odor of polluted bottom sediment, which comprises a step of adding a ferric iron (Fe(III))-containing chemical medicine into the polluted bottom sediment. The method for controlling the odor of the bottom sediment, which is provided by the embodiment of the invention, can improve the polluted bottom sediment, inhibit the generation and release of odor and enhance the quality of the surrounding environment.
Description
Technical field
The present invention relates to environment protection and improvement field, relate in particular to a kind of method of controlling contaminated bed mud stink.
Background technology
Along with the development of society, deposit in receiving water body from the particulate pollutant of industry, municipal effluent, agricultural irrigation water and rainwash etc., form contaminated bed mud.Many experiments are verified, and contaminated bed mud has a strong impact on the water-quality guideline of upper strata water body, contaminated bed mud human health and environment structure threat.
And at present the most direct to environmental threat be that the bed mud that do not covered by water body the some parts time is (as exposed beach under in tidal action, or the riverbed expose etc. that descends because of water level), these contaminated bed muds tend to distribute unpleasant stink, influence the surrounding environment quality.And the source of these stinks is the vitriol generation reduction reaction under the anaerobion effect that comes from the bed mud mostly:
This reaction is with the hydrogen sulfide (H that produces
2S) gas, the hydrogen sulfide with rotten egg smell is distributed in the atmosphere, and environment (particularly air) is on every side caused negative impact.
Summary of the invention
Embodiment of the invention technical problem to be solved is, a kind of method of controlling contaminated bed mud stink is provided, and can improve contaminated bed mud, suppresses generation and the release of odorous gas, the environmental quality around improving.
In order to solve the problems of the technologies described above, the embodiment of the invention provides a kind of method of controlling contaminated bed mud stink, take to shed to contaminated bed mud top layer and/or add with shallow-layer bed mud hybrid mode and contain ferric chemical agent, it is wherein, described that to contain ferric chemical agent be in iron alkali compound, the iron alkali nitre nitrogen compound one or more; In the described iron alkali compound, molysite comprises a kind of of iron(ic) chloride, ferric sulfate; Alkali makes a living/in the white lime, caustic alkali, soda one or more; In the described iron alkali nitre nitrogen compound, molysite comprises a kind of in iron(ic) chloride, the iron nitrate; Alkali makes a living/in the white lime, caustic alkali, soda one or more; Nitrate is one or more in SODIUMNITRATE, the iron nitrate;
Wherein, the weight ratio of molysite and unslaked lime is 1: 1.5; The weight ratio of molysite and soda is 1: 2.84.
Wherein, described containing also contained alkali in the ferric compound, and its effect is that the pH value of compound is increased.
Wherein, contaminated bed mud refers to that part-time is covered by water body, can distribute the bed mud of hydrogen sulfide and other odorous gas.
Implement the method for the contaminated bed mud stink of control that the embodiment of the invention provides, the chemical agent that is added in the contaminated bed mud contains ferric iron, this ferric iron can with hydrogen sulfide generation redox reaction, hydrogen sulfide is oxidized to stablizes harmless elemental sulfur.
Further, the ferrous iron that produces after the above-mentioned redox reaction can continue with contaminated bed mud in hydrogen sulfide reaction, generate the Iron sulfuret precipitation.And the Iron sulfuret precipitation is generated ferric iron and stablizes harmless elemental sulfur by after the dissolved oxygen oxidation on bed mud surface.
Further, because the continuous in-situ regeneration of ferric iron, so can play longer deodorization.
Further, when containing nitrate (being nitre nitrogen) in the chemical agent that adds, because the microorganism in the bed mud tends to oxygenant---the nitrate (nitrate＞vitriol) that utilizes oxidation capacity stronger, this reaction will replace sulfate reduction, thereby suppress the generation of hydrogen sulfide in the bed mud.Simultaneously, it is organic that this reaction also can consume a large amount of easily degradeds, is conducive to improve contaminated bed mud.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, to do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below, apparently, accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the method first embodiment schematic flow sheet of the contaminated bed mud stink of control provided by the invention;
Fig. 2 is the method second embodiment schematic flow sheet of the contaminated bed mud stink of control provided by the invention.
Embodiment
The method of the contaminated bed mud stink of the control that the embodiment of the invention provides can be improved contaminated bed mud, suppresses generation and the release of hydrogen sulfide and other odorous gas, the environmental quality around improving.
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
Referring to Fig. 1, be the method first embodiment schematic flow sheet of the contaminated bed mud stink of control provided by the invention, as shown in Figure 1:
The first step adds in the contaminated bed mud and contains ferric chemical agent.More specifically, the mode that adds chemical agent in the contaminated bed mud comprises: shed to contaminated bed mud top layer, chemical agent is mixed with the shallow-layer bed mud or above dual mode is combined.The purpose that shed on the bed mud top layer is to form oxide protective layer, is applicable to emergent deodorizing in a short time; Repair for longer bed mud is biochemical and the shallow-layer bed mud is mixed more suitable.
In the present embodiment, it is described that to contain ferric chemical agent be iron alkali compound, trivalent iron salt can be one or more in iron(ic) chloride, ferric sulfate, the iron nitrate etc. in the chemical agent, and alkali can be one or more in life/white lime, caustic alkali, the soda etc.The effect of alkali is that the pH value of chemical agent is increased.
In second step, the hydrogen sulfide reaction in the ferric iron in the chemical agent and the contaminated bed mud generates ferrous iron and stablizes harmless elemental sulfur, and this reaction formula is as follows:
2Fe(III)+H
2S→2Fe
2++S
0+2H
+
This shows, the ferric iron in the chemical agent can with contaminated bed mud in hydrogen sulfide reaction, generate ferrous iron and stablize harmless elemental sulfur, thereby prevent that hydrogen sulfide from overflowing from bed mud, improve the environment around the contaminated bed mud.
The 3rd step, the ferrous iron (Fe that in the previous step reaction, generates
2+) continue with contaminated bed mud in hydrogen sulfide generation precipitin reaction, generate the Iron sulfuret precipitation, the hydrogen sulfide in the contaminated bed mud is further consumed, this reaction formula is as follows:
Fe
2++H
2S→FeS↓+2H
+
In the 4th step, the Iron sulfuret precipitation that reaction generates in the 3rd step is oxidized, generates active ferric oxide (Fe (III)) and stablizes harmless elemental sulfur (S
0).More specifically, because bed mud is exposed in the air at part-time at least, therefore contain dissolved oxygen on the surface of bed mud at least, and dissolved oxygen can precipitate Iron sulfuret oxidation, generate Fe (III) and stablize harmless elemental sulfur, its reaction formula is as follows:
4FeS+3O
2+6H
2O→4Fe(III)↓+4S
0+12OH
In whole process, the continuous in-situ regeneration of ferric iron can not overflowed from contaminated bed mud with other odorous gas so can suppress hydrogen sulfide in a long time by completely consumed in reaction process, plays long deodorization.
Preferably, also contain alkali in the compound of the embodiment of the invention, its effect is that the pH value of compound is increased.
The optimum proportion of trivalent iron salt and alkali can obtain according to stoichiometric equation.Certainly trivalent iron salt and alkali can not be optimum proportions.Be example with iron calcification medicament, its reaction formula is as follows:
2Fe
3++3CaO+3H
2O→2Fe(III)↓+3Ca
2++6OH
Whenever add a gram molysite (in iron), need add the unslaked lime of 1.5 grams during optimum proportion simultaneously.
Be example with iron soda chemical agent, its reaction formula is as follows:
2Fe
3++3Na
2CO
3+H
2O→2FeOOH↓+3CO
2↑+6Na
+
Whenever add a gram molysite (in iron), need add the soda of 2.84 grams during optimum proportion simultaneously.
The method of the contaminated bed mud stink of control that the enforcement embodiment of the invention provides, the chemical agent that is added in the contaminated bed mud contains ferric iron, this ferric iron will play the effect of catalyzer, the dissolved oxygen of hydrogen sulfide in the contaminated bed mud is oxidized to stablize harmless elemental sulfur.And in this process, ferric iron is not by completely consumed, so can play longer deodorization.
Referring to Fig. 2, the method second embodiment schematic flow sheet for the contaminated bed mud stink of control provided by the invention, the difference of the method that the method for the contaminated bed mud stink of the control that present embodiment provides and a last embodiment provide is, in the method for the contaminated bed mud stink of the control that present embodiment provides, the chemical agent that adopts not only contains ferric iron and alkali, also contains nitrate.This method of controlling contaminated bed mud stink is as shown in Figure 2:
The first step adds the chemical agent that contains ferric iron, alkali and nitrate in contaminated bed mud.More specifically, the mode that adds chemical agent in the contaminated bed mud can be equally: shed to contaminated bed mud top layer, chemical agent is mixed with the shallow-layer bed mud or above dual mode is combined.
In the present embodiment, it is described that to contain ferric chemical agent be iron alkali nitre nitrogen compound, trivalent iron salt can be one or more in iron(ic) chloride, ferric sulfate, the iron nitrate etc. in the chemical agent, and alkali can be one or more in life/white lime, caustic alkali, the soda etc.The effect of alkali is that the pH value of compound is increased.The contained nitrate of compound can be in any medicament that contains nitrate radical such as nitrocalcite, SODIUMNITRATE, the iron nitrate one or more.
Need to prove, be directly to be added on the contaminated bed mud or in the shallow-layer bed mud at chemical agent provided by the invention, avoids chemical agent is spread marine, because the nitrate of chemical agent may make the eutrophication of seawater, causes red tide.
In second step, ferric iron is as catalyzer, the dissolved oxygen of hydrogen sulfide in the contaminated bed mud is oxidized to stablizes harmless elemental sulfur.This process is consistent with the process in second step to the 4th step among the last embodiment, repeats no more herein.
In the 3rd step, anti-nitration reaction takes place in the nitrate in the chemical agent in contaminated bed mud under action of microorganisms, as follows
C wherein
H2O represents the organic matter of easily degrading in the bed mud.Because microorganism tends to the oxygenant (nitrate＞vitriol) that utilizes oxidation capacity stronger, this reaction will replace sulfate reduction, thus the generation of inhibition hydrogen sulfide.This reaction is organic matter and mass consumption is easily degraded, and is conducive to improve contaminated bed mud.The chemical reaction in the 3rd step and second step are synchronously.
The method of the contaminated bed mud stink of control that the enforcement embodiment of the invention provides, the chemical agent that is added in the contaminated bed mud contains ferric iron, this ferric iron will play the effect of catalyzer, the dissolved oxygen of hydrogen sulfide in the contaminated bed mud is oxidized to stablize harmless elemental sulfur.And in this process, the continuous in-situ regeneration of ferric iron is not therefore by completely consumed, so can play longer deodorization.
Further, contain nitrate (being nitre nitrogen) in the chemical agent that adds, can replace sulfate reduction, thereby suppress the generation of hydrogen sulfide in the bed mud.Simultaneously, a large amount of easily degradeds of this reaction consumes are organic, are conducive to improve contaminated bed mud.
Effect embodiment
One, carrying out stink control experiment, result data and statistical study with the bed mud that exposes after the ebb of gulf, Shenzhen is example, and reliability and the high efficiency of the Method for odor control of contaminated bed mud provided by the invention is described.
(1) experiment flow
1, takes a sample according to bank distance off sea order from the near to the remote, respectively called after No. 1, No. 2 and No. 3 zones (seeing Table 1).Offshore is more far away, and bed mud is more black, and stink is more heavy.The pH value of contaminated bed mud is about 8, and is identical with the pH value of gulf, Shenzhen seawater.Correspondingly, the chemical oxygen demand (COD) of bed mud (COD) increases (from 23.7 to 103.9 milligrams/gram dry bottom mud) with the increase of offshore distance, and this explanation offshore bed mud at a distance is fresher bed mud, and is less by the microbiological deterioration in the bed mud.Bed mud sampling to No. 2 moderate zones of contaminated degree detects and finds that the ratio that volatile solid (VSS) accounts in the total solids (SS) in the bed mud is higher, is about 7.6%, illustrates and contain great number of organic matters in the bed mud that this measurement result with COD is consistent.But the culturing bacterium number is about 1.5 * 10 in the bed mud
8Individual/gram, quantity is more, illustrates that the ecosystem of former bed mud is comparatively intact.
Solvablely in the bed mud tap a blast furnace, the concentration of calcium and magnesium is respectively 2.2,11.5 and 0.17 milligrams/gram.Concentration of iron higher in the bed mud is conducive to H
2The elimination of S (referring to the Method for odor control embodiment part of contaminated bed mud).Leachable H in the bed mud
2The concentration of S is respectively 0.060,0.074 and 0.080 milligram/gram dry bottom mud from the near to the remote according to sampling point, illustrates that the iron level in the former bed mud still is not enough to eliminate H
2The release of S.The concentration of acid volatile sulfur compounds (AVS) is according to the different significant differences in the position of sampling point.The concentration of No. 1 bed mud AVS that offshore is nearer is about 0.336 milligram/gram dry bottom mud, and the concentration of No. 3 AVS farthest up to 3.998 milligrams/gram (be about No. 1 10 times).This and No. 3 bed mud organic content height, the aerobic environment difference is relevant.
Leachable vitriol and sampling point are in close relations.Two nearer sampling spot sulfate concentrations of offshore are about 0.9 milligram/gram dry bottom mud, illustrate that the additional speed of vitriol greater than wear rate, is not H
2The limiting factor that S produces; And offshore No. 3 bed mud sulfate concentrations far away are 0, illustrate that the vitriol wear rate is very fast, H
2S produces the speed height, and this and bed mud contain a large amount of organic matters and match.
2, add compound (the iron nitrate 3.5kg/m that contains iron nitrate, lime and nitrocalcite to No. 2 zones
2, lime 0.25kg/m
2, and nitrocalcite 1.25kg/m
2), and mix in the degree of depth of bed mud top layer 30cm, got the bed mud sample in second day and analyze.
(2) experimental result and analysis
Table 1
| Location parameter | No. 1 | No. 2 | No. 3 | After handling for No. 2 |
| The pH value | 7.95 | 7.93 | 8.3 | 9.45 |
| COD(mg/g) | 23.7 | 59.5 | 103.9 | 39.5 |
| VSS/SS | ? | 0.076 | ? | ? |
| Can cultivate total bacterial count (#/g) | ? | 1.5×10 8 | ? | 1.8×10 8 |
| Solvable tapping a blast furnace (mg/g) | ? | 2.196 | ? | 6.58 |
| Leachable calcium (mg/g) | ? | 11.5 | ? | 19.1 |
| Leachable magnesium (mg/g) | ? | 0.167 | ? | 0.25 |
| Leachable vitriol (mg/g) | 0.86 | 0.956 | 0 | 1.384 |
| Leachable H 2S(mg/g) | 0.06 | 0.074 | 0.08 | 0 |
| AVS(mg/g) | 0.336 | 0.837 | 3.998 | 0.248 |
Table 1 is former bed mud and controls each location parameter of handling the back bed mud through stink and tabulate.After advancing stink control processing, bed mud top layer and shallow-layer present khaki color, and free from extraneous odour produces.The bed mud ecosystem after stink control is handled still remains intact, and Crustaceans such as crab freely creep and come in and go out.
The pH value that the back bed mud is handled in stink control is 9.45, still belongs to the weakly alkaline scope.Bed mud water ratio after stink control is handled is about 54.4%, ill effects such as bed mud hardens do not occur.Compare with No. 2 former bed muds in zone, stink control is handled the chemical oxygen demand (COD) of back bed mud and is down to 39.5 milligrams/gram dry bottom mud (consumption is about 34%), and this promotes that with the molysite biochemical oxidation agent that adds the denitrification process of bed mud is closely related.The culturing bacterium sum is in the same order of magnitude with No. 2 bed muds in the bed mud of back but repair, and further specifies stink control treatment process provided by the invention and does not destroy the good ecosystem of former bed mud.Great changes will take place for the leachable magnesium salts of bed mud and vitriol after stink control was handled, but the then greatly raising of leachable molysite, the medicament that this and we add matches.
The most significant performance was that the concentration of leachable hydrogen sulfide is down to 0 after stink control was handled, and the release of this explanation hydrogen sulfide has obtained control fully.The concentration of acid volatile sulfur compounds (AVS) also is down to 0.248 milligram/gram dry bottom mud by original 0.837.After stink control was handled, the redox potential of bed mud was improved, and has changed original pure anaerobic environment, is conducive to the elimination gradually of AVS.
To sum up, the relative prior art of the present invention has following advantage: utilize the molysite (ferric iron) in the chemical agent, the dissolved oxygen of hydrogen sulfide in the contaminated bed mud is oxidized to stablizes harmless elemental sulfur.Utilize the nitrate in the chemical agent, consume easily degraded organic matter, suppress the generation of hydrogen sulfide in the bed mud.This method green non-pollution, the speed of controlling contaminated bed mud stink is fast, and is easy to operate, and expense is low, has very high practicality.
Claims (3)
1. the method for the contaminated bed mud stink of control is characterized in that, take to shed to contaminated bed mud top layer and/or add with shallow-layer bed mud hybrid mode to contain ferric chemical agent,
It is wherein, described that to contain ferric chemical agent be in iron alkali compound, the iron alkali nitre nitrogen compound one or more; In the described iron alkali compound, molysite comprises a kind of of iron(ic) chloride, ferric sulfate; Alkali makes a living/in the white lime, caustic alkali, soda one or more; In the described iron alkali nitre nitrogen compound, molysite comprises a kind of in iron(ic) chloride, the iron nitrate; Alkali makes a living/in the white lime, caustic alkali, soda one or more; Nitrate is one or more in SODIUMNITRATE, the iron nitrate;
Wherein, the weight ratio of molysite and unslaked lime is 1: 1.5; The weight ratio of molysite and soda is 1: 2.84.
2. the method for the contaminated bed mud stink of control as claimed in claim 1 is characterized in that, described containing also contained alkali in the ferric compound, and its effect is that the pH value of compound is increased.
3. the method for the contaminated bed mud stink of control as claimed in claim 2 is characterized in that, described contaminated bed mud refers to that part-time is covered by water body, can distribute the bed mud of hydrogen sulfide and other odorous gas.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209868A (en) * | 2007-12-21 | 2008-07-02 | 中国科学院广州地球化学研究所 | Method for inhibiting offensive odor of riverway water body and bottom mud |
| CN101786720A (en) * | 2010-03-31 | 2010-07-28 | 广州市污水治理有限责任公司 | Treatment method of river polluted bed mud |
| CN101811811A (en) * | 2010-05-10 | 2010-08-25 | 南京师范大学 | Method for inhibiting release of substrate sludge nutritive salt of eutrophic water body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209868A (en) * | 2007-12-21 | 2008-07-02 | 中国科学院广州地球化学研究所 | Method for inhibiting offensive odor of riverway water body and bottom mud |
| CN101786720A (en) * | 2010-03-31 | 2010-07-28 | 广州市污水治理有限责任公司 | Treatment method of river polluted bed mud |
| CN101811811A (en) * | 2010-05-10 | 2010-08-25 | 南京师范大学 | Method for inhibiting release of substrate sludge nutritive salt of eutrophic water body |
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