CN114369625A - Method for producing sulfur by artificially enhancing elemental sulfur biological disproportionation and method for biologically removing heavy metal in wastewater by using same - Google Patents
Method for producing sulfur by artificially enhancing elemental sulfur biological disproportionation and method for biologically removing heavy metal in wastewater by using same Download PDFInfo
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- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 90
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 69
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- 229910052799 carbon Inorganic materials 0.000 claims description 11
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- 241000203069 Archaea Species 0.000 claims description 2
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- 230000009467 reduction Effects 0.000 abstract description 13
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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Abstract
The invention discloses a method for producing sulfur by artificially reinforcing biological disproportionation of elemental sulfur, which comprises the following steps: in an anoxic or anaerobic environment, sulfur disproportionation bacteria and sulfur filler are planted, and the temperature and alkalinity of the water environment in the elemental sulfur disproportionation pool are controlled to promote the stable growth of the sulfur disproportionation bacteria and continuously generate soluble sulfides. The invention also discloses a method for biologically removing heavy metals in wastewater, which comprises the following steps: the sulfide obtained by the sulfur production method is mixed with heavy metal wastewater in a reaction tank, the sulfide is combined with heavy metal ions to form metal sulfide, or high valence state metal is reduced to low valence state metal and forms metal oxide to further precipitate, and finally the heavy metal in the wastewater is removed. According to the invention, sulfur disproportionation bacteria is introduced into the field of heavy metal wastewater treatment for the first time, and sulfide is stably and sustainably produced by utilizing the disproportionation of elemental sulfur rather than dissimilatory reduction, so that an artificially-regulated and completely-autotrophic sulfide production mode is realized, and further, the effective removal of heavy metals is realized, and the method has application potential.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a method for producing sulfur by artificially reinforcing elemental sulfur biological disproportionation and a method for biologically removing heavy metals in wastewater by using the same.
Background
The metal wastewater is mainly from mine mining, smelting and tailing drainage, and wastewater discharged by industrial enterprises such As electrolysis, electroplating, medicine, paint, pigment and the like, and generally contains various metal ions such As Cu, Cd, Cr, Pb, Sb, Hg, Ag, As and the like. The types, the contents and the existing forms of the heavy metals in the wastewater vary greatly with different production enterprises.
Heavy metals cannot be biodegraded and are easily adsorbed by various organic and inorganic colloids and particulate matters in water and deposited at the bottom of the water body, so that the harm duration is long. Related researches show that the heavy metal has the effects of causing distortion, carcinogenesis and mutation, and after entering a water body, the heavy metal is subjected to biological enrichment, biological accumulation and biological amplification through a food chain and finally enters a human body, so that the life health and safety of human beings are harmed.
At present, the method for treating heavy metals in wastewater mainly comprises the following steps: physical, chemical, biological methods. Common physical processes include ion exchange, adsorption, membrane filtration, flocculation, flotation, and electrochemical processes. Physical methods have high requirements for wastewater pretreatment, involve relatively large capital investment, and thus have limited applications.
The chemical method is to add chemical reagent into the sewage to increase the pH value of the wastewater and generate hydroxide or other precipitates with low solubility, thereby achieving the purpose of removing heavy metal ions, and comprises an alkali neutralization precipitation method and a sulfide precipitation method. The chemical method has the advantages of simple operation, low operation cost and the like, and is widely applied.
For chemical precipitation to remove heavy metals, sulfide formation can make the heavy metals remaining in solution much smaller than in alkaline neutralization because the solubility product constant of metal sulfides is smaller. And the sulfide is produced by using organismsHas the advantages of low cost, high energy efficiency and the like. Therefore, the biological sulfidation treatment method is considered as a promising technology for removing toxic metal ions from industrial wastewater, and common methods include a sulfate reduction method and an elemental sulfur reduction method. Wherein the Sulfate reduction method is to utilize Sulfate-reducing bacteria (SRB) to reduce SO4 2-Reducing the heavy metal into sulfide to precipitate heavy metal, releasing alkalinity and improving the pH value of the wastewater, wherein the reaction equation is as follows: CH (CH)3COO-+SO4 2-→2HCO3 -+HS-，HS-+Me2+→MeS+H+(ii) a The method has the advantages of thorough treatment, stable process and capability of removing various metal ions; also has the disadvantages of large consumption of external carbon source, high cost, long hydraulic retention time and the like.
Elemental sulfur in an intermediate valence state widely exists in nature, has oxidizing property and reducing property, and can be used as an electron acceptor or an electron donor to participate in biological treatment of sewage, underground water and surface water. The elemental Sulfur reduction method for treating heavy metal wastewater refers to the reduction of elemental Sulfur (S) in an anaerobic or anoxic environment0RB) reducing elemental sulfur to sulfide with a carbon source for heavy metal removal, the electron donor consumption of the reaction being only 1/4, S of the sulfate reduction reaction0+2e-+2H+→H2S、SO4 2-+8e-+10H+→H2S+4H2And O, the adding amount of the carbon source can be greatly reduced, and the cost is saved. Although the elemental sulfur reduction treatment can reduce the investment of carbon source compared with the sulfate reduction treatment, the addition amount is difficult to be accurately controlled, and the problem of secondary pollution generated in the heterotrophic reduction process is easily caused.
Compared with the dissimilatory reduction of the former two, the disproportionation of elemental Sulfur is Sulfur-disproportionating bacteria (S) with intermediate valence of elemental Sulfur0DB) is a completely autotrophic process, and the reaction equation is as follows: s0+H2O→1/4SO4 2-+3/4HS-+5/4H+. Adding elemental sulfurWhen the disproportionation process is applied to heavy metal wastewater treatment, an additional organic electron donor is not needed to be supplemented, the secondary environmental problem caused by adding a carbon source is avoided, the cost is further reduced theoretically, and the economy is improved. In recent years, elemental sulfur disproportionation has proven to be an important metabolic mode in aquatic systems, and microorganisms capable of such metabolism are abundant in species and number. However, elemental sulfur disproportionation is an inert process under standard conditions and the process is limited to low sulfide concentrations for thermodynamic reasons. Even though elemental sulfur disproportionation exists widely in nature, no engineering report is available so far, and the key control method is unknown.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for artificially enhancing the biological disproportionation of elemental sulfur to produce sulfur. Artificially strengthening the activity of sulfur disproportionation bacteria under the anaerobic or anoxic condition, promoting the stable growth of sulfur disproportionation bacteria, enhancing the driving force of simple substance sulfur disproportionation reaction, promoting the biological disproportionation of simple substance sulfur under the condition of no addition of organic matters, and further stably and continuously producing soluble sulfide (HS)-、S2-And undissociated H2S) to realize a fully autotrophic sulfide production mode capable of being manually regulated.
The invention also aims to provide a method for removing heavy metals in wastewater by utilizing the artificially enhanced elemental sulfur biological disproportionation to produce sulfides. The sulfide is combined with metal ions or the sulfide reduces high valence state metal into low valence state metal, so that the metal is precipitated and removed in the form of sulfide or oxide, and the purposes of heavy metal removal and sewage purification are achieved.
The purpose of the invention is realized by the following technical scheme:
a method for artificially enhancing elemental sulfur biological disproportionation to produce sulfur comprises the following steps:
in an anoxic or anaerobic environment, sulfur disproportionation bacteria and sulfur filler are planted, the temperature and the alkalinity of the water environment in the elemental sulfur disproportionation pool are controlled, the sulfur disproportionation bacteria are promoted to stably grow, and soluble sulfides are continuously generated; said dissolved sulfurThe compound comprises S2-、HS-And H2And S, three forms.
Preferably, the water temperature is 25-35 ℃; the alkalinity is 0.11-3 g/L.
Preferably, the alkalinity is derived from NaHCO3、CaCO3Or Na2CO3And (4) generating.
Preferably, the concentration D of oxygen in said environmentO＝0～0.5mg/L。
Preferably, the sulfur filler is elemental sulfur or a composite filler mainly containing elemental sulfur.
Preferably, the sulfur-disproportionating bacteria are bacteria or archaea which can survive in various environments by taking elemental sulfur as an electron donor and an acceptor to perform sulfur disproportionating reaction and taking inorganic carbon as a carbon source, and belong to the genera Dissulfuricrobium, Desulfobulbus, Desulfofustics, Desulfurella, Desulfurivibrio and Dissulfuribacter.
Preferably, the elemental sulfur disproportionation pool is a sulfur packed bed reactor.
Preferably, the sulfur-colonizing disproportionated bacteria specifically comprise: inoculating sulfur disproportionation bacteria pure bacteria or sludge, bottom mud and mixed liquid containing the sulfur disproportionation bacteria in the elemental sulfur disproportionation pool.
The method for biologically removing heavy metals in wastewater based on the artificially enhanced elemental sulfur biological disproportionation sulfur production method comprises the following steps:
(1) in the elemental sulfur disproportionation pool, the method for producing sulfur based on artificial enhanced elemental sulfur biological disproportionation is adopted to obtain soluble sulfide;
(2) mixing the soluble sulfide obtained in the step (1) with heavy metal wastewater in a reaction tank, and combining the sulfide with heavy metal to form metal sulfide or reducing high-valence metal into low-valence metal to form metal oxide;
(3) further precipitating the sewage treated in the step (2) in a precipitation tank; and part of the supernatant in the sedimentation tank flows back to the elemental sulfur disproportionation tank, and the other part of the supernatant enters a next-stage sewage purification system as effluent to realize the removal of heavy metals in the sewage.
Preferably, the heavy metal comprises one or more of Cu, Cd, Cr, Pb, Sb, Hg, Ag and As.
The principle of the invention is as follows:
in an anaerobic or anoxic environment, the water environment temperature and alkalinity in the elemental sulfur disproportionation reaction are artificially strengthened, so that sulfur disproportionation bacteria can stably grow, dissolved sulfides are continuously and spontaneously generated, and the effective removal of heavy metal ions in industrial sewage is realized through the combined precipitation reaction of the soluble sulfides and the heavy metal ions. In the present invention, thiobacillus species undergoes the following reaction: s0+H2O→1/4SO4 2-+3/4HS-+5/4H+Elemental sulphur undergoes redox by itself in the absence of an organic carbon source to form sulphides and sulphates. The combined precipitation reaction of soluble sulfide and heavy metal ions is a non-biological process, and the reaction equation is as follows: HS-+Me2+→MeS+H+。
The invention establishes a sulfur disproportionation reactor filled with sulfur filler, inoculates sulfur disproportionation bacteria, and provides the conditions of environmental temperature, alkalinity and the like which are favorable for the growth and metabolism of sulfur disproportionation bacteria, thereby leading the sulfur disproportionation bacteria to be capable of stably growing and proliferating, driving the simple substance sulfur disproportionation reaction to be stably and continuously carried out, and continuously generating soluble sulfide. Mixing the effluent of sulfur disproportionation reactor containing soluble sulfide with heavy metal-containing waste water in reaction tank to promote the combination of metal and sulfide to form precipitate or reduce high-valence metal into low-valence metal, and precipitating in the form of metal sulfide or metal oxide in precipitation tank. The effluent of the sedimentation tank can be directly discharged or enter a next-stage sewage purification system, and finally the heavy metals in the sewage are removed.
The influence mechanism of the environmental temperature and alkalinity in the biological sulfur production process is as follows:
temperature: temperature is one of the most important factors affecting the activity of microorganisms, particularly in terms of affecting the enzymatic reaction rate, the fluidity of cell membranes, and the solubility of substances.
Alkalinity: disproportionation of elemental sulfur to produce H+Process, from NaHCO3、CaCO3The generated alkalinity can absorb waterThe protons in the sulfur-containing material maintain the pH value of the water environment, which is beneficial to the growth and metabolism of sulfur-disproportionating bacteria and the formation of polysulfide in the disproportionation process of elemental sulfur.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method for producing sulfur by artificially enhancing the biological disproportionation of elemental sulfur artificially enhances the activity of sulfur disproportionation bacteria and enhances the driving force of the disproportionation reaction of elemental sulfur by controlling the temperature and the alkalinity of the disproportionation reaction of elemental sulfur, thereby realizing the biological disproportionation of elemental sulfur to produce soluble sulfide (HS) without adding organic matters-、S2-And undissociated H2S) to realize a fully autotrophic sulfide production mode capable of being manually regulated.
(2) The invention introduces sulfur disproportionation bacteria into the field of heavy metal wastewater treatment for the first time, and utilizes the disproportionation of elemental sulfur rather than dissimilatory reduction to generate sulfide, thereby realizing the removal of heavy metals. The traditional heavy metal wastewater treatment technology based on a biological sulfur production method is to utilize sulfate reducing bacteria or elemental sulfur reducing bacteria to dissimilatorily reduce high-valence sulfur such as elemental sulfur and sulfate to generate soluble sulfide (HS)-、S2-And undissociated H2S), and then the heavy metal ions are combined and precipitated and removed. However, this conventional technique requires a large consumption of electron donors (usually organic compounds) in the dissimilatory reduction of high-valence sulfur to produce sulfide, which leads to excessive costs. Compared with an elemental sulfur reduction method and a sulfate reduction method which are driven by taking organic matters as electron donors, the method disclosed by the invention does not need to add an organic carbon source, and also avoids the problem caused by insufficient or excessive addition of the organic matters in the heterotrophic reduction process. The disproportionation reaction of the elemental sulfur can continuously produce sulfur with low cost, has high removal rate of heavy metals, and has application potential.
(3) The method for biologically removing the heavy metal in the wastewater can enlarge the treatment capacity of a plurality of groups of reactors which are connected in parallel, and can be used for treating high-concentration heavy metal wastewater discharged by enterprises such as drainage in mine pits, tailing drainage of concentrating mills, electrolysis, electroplating, medicines, paints, pigments and the like.
Drawings
FIG. 1 is a graph showing the variation of sulfide concentration according to different basicities in example 1 of the present invention.
FIG. 2(a) is a graph showing the change in the sulfide concentration of the effluent of the reactor with time in example 2 of the present invention.
FIG. 2(b) is a graph showing the change of pH values of the inlet and outlet water of the reactor with time in example 2 of the present invention.
FIG. 2(c) is a schematic view of an apparatus of an upflow packed reactor in example 2 of the present invention, wherein: 1. a water inlet pool; 2. a sulfur packed bed reactor; 3. and (4) a water outlet pool.
FIG. 3 shows the results of colony analysis of sludge in the reactor in example 2 of the present invention.
FIG. 4 is a graph of the sulfide concentration in the reaction, the sulfate concentration, and the mole ratio of sulfide to sulfate in the reaction for the anaerobic bottle in example 3 of the present invention.
FIG. 5 is a schematic view of the steps of a wastewater treatment method for removing heavy metals in example 4 of the present invention.
FIG. 6 is a graph showing the total chromium concentration in the influent water and the total chromium concentration in the effluent water of the sedimentation tank in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A part of sludge obtained from estuary bottom sludge (containing sulfur-disproportioning bacteria) for anaerobic culture is divided into equal parts and distributed into anaerobic bottles, and the anaerobic bottles are washed with deoxidized water for three times to completely remove residual soluble sulfides. The elemental sulfur is added in a form of being wetted by deionized water, and the content is 1 g/L. NaHCO is added into the bottle in different concentrations3(0.1, 0.5, 1 and 2g/L) to preliminarily study the influence of different alkalinity contents on the disproportionation reaction of the elemental sulfur. The results show (fig. 1): when NaHCO is added into the reaction system3When the content is small (0.1g/L), the yield of soluble sulfides is low and unstable; as the basicity increases, the rate of sulfide production increases. The increase of the alkalinity is beneficial to the disproportionation reaction of the elemental sulfur.
Example 2
The method for producing sulfur by artificially enhancing the biological disproportionation of elemental sulfur comprises the following steps: in an anoxic or anaerobic (Do is 0-0.5 mg/L) environment, sulfur disproportionation bacteria and sulfur filler are planted, the water environment temperature and alkalinity of the elemental sulfur disproportionation pool are controlled, and the sulfur disproportionation bacteria can be promoted to stably grow and continuously generate soluble sulfides; the soluble sulfide includes S2-、HS-And H2And S, three forms.
In this example, an upflow sulfur packed bed reactor was used with elemental sulfur (99.99% purity) as the biological carrier for the inoculated sludge. Stage one, maintaining the disproportionation reaction temperature of elemental sulfur at 30 +/-2 ℃, and feeding water NaHCO3The concentration was 1 g/L. In the second stage, the disproportionation reaction temperature of the elemental sulfur is maintained at 33 +/-2 ℃, and NaHCO is fed into water3The concentration was 2 g/L. Stage three, maintaining the disproportionation reaction temperature of the elemental sulfur at 33 +/-2 ℃, and feeding NaHCO water3The concentration was 3 g/L. The hydraulic retention time of the three-stage reactor was 10 h. And (3) regularly detecting the sulfide concentration of the outlet water of the elemental sulfur disproportionation reactor.
In this example, the sludge enriched with the thiobacillus is taken from bottom sludge of a river mouth in China.
In this example, the alkalinity of the feed water was controlled by varying the concentration of sodium bicarbonate in the feed water to the reactor.
In this embodiment, the concentration of sulfide in the effluent is controlled by the ambient temperature of the reactor and the alkali content in the influent.
The reactor was run continuously for 150 days. The reactor achieved long term sulfur production with an average production of 102.3mg S/L sulfide, an influent pH of about 8.5 and an effluent pH of about 7.0 (FIGS. 2(a) -2 (b)).
FIG. 2(c) is a schematic view of the apparatus of the upflow packed reactor of this example, which comprises an inlet tank 1, a sulfur packed bed reactor 2 and an outlet tank 3.
Community analysis of the sludge in the reactor revealed that the relative abundance of microorganisms with capacity for disproportionation of elemental sulfur was about 9.1% at the genus level (fig. 3).
Example 3
From the sulphur packed bed reactor in example 2Some sludge samples were cultured anaerobically. The sludge taken out was placed in an anaerobic flask and washed three times with deoxygenated water to completely remove the remaining soluble sulfides. Setting NaHCO3The concentration is 1g/L, the pH of inlet water is 8.5, the concentration of elemental sulfur is 1g/L, and the temperature is 25 +/-2 ℃. The results of the experiment are shown in FIG. 4: the molar ratio of sulfide to sulfate in the reaction process is close to 3: 1, in accordance with the ratio of both of the chemical reaction formulae (see elemental sulfur disproportionation equation). The method shows that in an engineering system, the directional, stable and sustainable regulation and control of the elemental sulfur disproportionation reaction can be realized.
Example 4
The concentration of hexavalent chromium in the production wastewater of a certain electroplating plant is about 13.5mg/L, and the chromium-containing wastewater is artificially synthesized according to the national standard (HJ 757-. After enhancing the stability of elemental sulfur disproportionation reaction by increasing alkalinity and continuously producing sulfides, according to the steps of the sewage treatment method (figure 5) for realizing heavy metal removal, a chromium removal experiment is carried out for 15 days, and the method specifically comprises the following steps:
(1) in an elemental sulfur disproportionation reactor, the method for producing sulfur based on artificially enhanced elemental sulfur biological disproportionation of the embodiment 2 of the invention is adopted to obtain soluble sulfide;
(2) mixing the soluble sulfide obtained in the step (1) with the production wastewater of a synthetic electroplating plant in a reaction tank to promote hexavalent chromium to be reduced into low-valence metal, and precipitating the hexavalent chromium in a precipitation tank in the form of metal oxide;
(3) further precipitating the sewage treated in the step (2) in a precipitation tank; and returning part of the supernatant of the sedimentation tank to the elemental sulfur disproportionation reactor, and taking the other part of the supernatant as effluent to enter a next-stage sewage purification system to remove heavy metal chromium in the sewage.
The total chromium concentration of the reactor inlet water and the sedimentation tank outlet water was periodically measured during the experiment (fig. 6), and the results showed that: the total chromium concentration of the inlet water is 12.6-13.6mg/L, and the chromium removal rate of the chromium-containing wastewater can reach 96.91% -99.91%. The experiment shows that the sulfide generated by the disproportionation reaction of the elemental sulfur can completely remove the metal chromium in the production wastewater of the electroplating plant, and the manual control of the elemental sulfur disproportionation has a good effect of removing heavy metals.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, for example, the heavy metal may be Cu, Cd, Pb, Sb, Hg, Ag, As, or other metal ions that can chemically precipitate or undergo redox reaction with sulfide; the sludge enriched by the sulfur-disproportioning bacteria can be more than one of the sludge, such as activated sludge of an urban sewage treatment plant, ocean bottom sludge, bottom sludge of a saline-alkali lake, soil of an ore district or hot spring sediment; other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A method for artificially enhancing elemental sulfur biological disproportionation to produce sulfur is characterized by comprising the following steps:
in an anoxic or anaerobic environment, sulfur disproportionation bacteria and sulfur filler are planted, the temperature and the alkalinity of the water environment in the elemental sulfur disproportionation pool are controlled, the sulfur disproportionation bacteria are promoted to stably grow, and soluble sulfides are continuously generated; the soluble sulfide includes S2-、HS-And H2And S, three forms.
2. The method for artificially enhancing the biological disproportionation of elemental sulfur to produce sulfur according to claim 1, wherein the water temperature is 25-35 ℃; the alkalinity is 0.11-3 g/L.
3. The method for artificially enhancing the biological disproportionation of elemental sulfur to produce sulfur according to claim 1 or 2, wherein the alkalinity is determined by NaHCO3、CaCO3Or Na2CO3And (4) generating.
4. The method of artificially enhanced biological disproportionation of elemental sulfur to produce sulfur as claimed in claim 1, wherein the concentration of oxygen D in the environmentO＝0～0.5mg/L。
5. The method for artificially enhancing the biological disproportionation of elemental sulfur to produce sulfur according to claim 1, wherein the sulfur filler is elemental sulfur or a composite filler mainly containing elemental sulfur.
6. The method for artificially enhancing the biological disproportionation of elemental sulfur to produce sulfur according to claim 1, wherein the sulfur-disproportionating bacteria refers to bacteria or archaea which can survive in various environments and take sulfur disproportionation reaction with elemental sulfur as an electron donor and acceptor and take life activities with inorganic carbon as a carbon source, and belongs to the genera Dissulfurifurbium, Desulfobulbus, Desulfofustics, Desulfurella, Desulfurivibrio and Dissulfurobacteriaceter.
7. The method for artificially enhancing the biological disproportionation of elemental sulfur to produce sulfur according to claim 1, wherein the elemental sulfur disproportionation pool is a sulfur packed bed reactor.
8. The method for artificially enhancing the biological disproportionation of elemental sulfur to generate sulfur according to claim 1, wherein the sulfur-colonizing disproportionation bacteria specifically are: inoculating sulfur disproportionation bacteria pure bacteria or sludge, bottom mud and mixed liquid containing the sulfur disproportionation bacteria in the elemental sulfur disproportionation pool.
9. The method for biologically removing heavy metals in wastewater based on the artificial enhanced elemental sulfur biological disproportionation sulfur production method of any one of claims 1-8, characterized by comprising the following steps:
(1) obtaining soluble sulfide in an elemental sulfur disproportionation pool by adopting the artificial enhanced elemental sulfur biological disproportionation-based sulfur production method of any one of claims 1-8;
(2) mixing the soluble sulfide obtained in the step (1) with heavy metal wastewater in a reaction tank, and combining the sulfide with heavy metal to form metal sulfide or reducing high-valence metal into low-valence metal to form metal oxide;
(3) further precipitating the sewage treated in the step (2) in a precipitation tank; and part of the supernatant in the sedimentation tank flows back to the elemental sulfur disproportionation tank, and the other part of the supernatant enters a next-stage sewage purification system as effluent to realize the removal of heavy metals in the sewage.
10. The method for biologically removing heavy metals from wastewater according to claim 9, wherein the heavy metals include one or more of Cu, Cd, Cr, Pb, Sb, Hg, Ag, As.
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