Preparation method of pyrite microorganism combined permeable reaction wall
Technical Field
The invention relates to a preparation method of a pyrite microorganism combined permeable reaction wall, belonging to the technical field of environmental protection.
Background
The Permeable Reactive Barrier (PRB) technology is a kind of emerging soil and underground water in-situ remediation technology in recent years, has become a main technology for remediating foreign heavy metal pollution at present, and gradually becomes a research focus in the field of remediating soil and underground water in China. The reaction medium is the key of the repair effect of the PRB technology. Mainly comprises redox reaction medium, adsorption reaction medium, precipitation reaction medium and mixed reaction medium.
The zero-valent iron has become one of the most effective reaction media in the in-situ remediation of the water body due to the advantages of high reaction speed, high reduction potential, low price, easy obtainment and the like, is also one of the most common media in the PRB technology, and can effectively reduce and remediate the water body polluted by various organic matters and heavy metals.
A large amount of experiment and field operation data show that the removal capability of zero-valent iron-PRB is reduced along with the lapse of time, and the repair effect is deteriorated. Mainly because the zero-valent iron is oxidized into Fe (III) and Fe (II) in the process of reducing pollutants and hydroxide is generated to cover the surface, and the active sites on the surface of the zero-valent iron are reduced. Meanwhile, the precipitated product is easy to block the pore channels of the wall material, and the permeability of PRB is reduced.
In addition to zero-valent iron, Fe (II) also has reducing properties. Methods for removing organic and heavy metals from water using fe (ii) minerals such as pyrite, hematite, siderite are becoming increasingly important.
Pyrite is a sulfide mineral with the widest distribution in the earth crust, and the main component is ferrous disulfide (FeS)2) Containing Fe having reducibility2+Ions and polysulfides (S)2 2-). Heavy metals and organic matter can be reduced. However, Fe (II) has a reduction potential lower than that of zero-valent iron and is therefore more easily consumed, and if used as a PRB material, has a short service life.
In the beginning of the 20 th century, microbial dissimilarity of Fe (III) reduction has been recognized. The dissimilatory iron reducing microorganisms can oxidize organic matters by taking Fe (III) as an exogenous electron acceptor in the metabolic process, and reduce Fe (III) into Fe (II) in the process. PRB repair is mostly in an anaerobic environment, and if Fe (III) on the surface of the pyrite can be reduced by using dissimilatory iron reducing bacteria to generate Fe (II) with reducibility, the problem of reduction of PRB long-term treatment capacity caused by consumption of Fe (II) in the pyrite can be effectively solved.
However, the specific surface area of the iron ore is not large, so that the growth of microorganisms is not facilitated, and an iron ore-microorganism removing system is difficult to construct.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a pyrite microorganism combined permeable reaction wall. The pollutants in the groundwater and the soil are treated by utilizing the synergistic effect of the pyrite and the dissimilatory iron reducing bacteria. The problem of traditional PRB filler is easily passivated, and the service life is low is solved.
A pyrite-microorganism combined permeable reaction wall is composed of pyrite, slow-release nutrient fertilizer and biochar immobilized microorganism.
Crushing the pyrite by a ball mill to obtain the particle size of 20-40 meshes.
The nutrient fertilizer is a commercial slow-release fertilizer Haokadou.
Burning coconut shell of 2-3cm at 300 deg.C under oxygen deficiency for 2 hr, soaking in 0.1mol/L hydrochloric acid for 12 hr to remove ash, washing with deionized water until pH is constant, and oven drying at 105 deg.C. Grinding to particle size of 20-40 mesh.
The microorganism is Shewanella Decolorationis (MCCC 1A11454), purchased from China center for culture Collection of marine microorganisms, activated and stored on LB slant.
The biochar immobilized microorganism is prepared by the following steps: preparing 10L of sterile culture medium, adding 500g of coconut shell biochar sterilized at 120 ℃ for 20min, inoculating 100mL of S.decoloniones bacterial suspension, standing and culturing for 48h, filtering the coconut shell biochar under the sterile condition, transferring the coconut shell biochar to 10L of fresh sterile culture medium, inoculating 100mL of S.decoloniones bacterial suspension, and standing and culturing for 48 h. And finishing the film formation after ten times of circulation.
The culture medium for preparing the bacterial suspension consists of the following components: 10g/L of glucose; NH (NH)4Cl 1g/L;KH2PO40.5 g/L; 5g/L of yeast powder.
PRB is formed by completely and uniformly mixing pyrite, slow-release nutrient fertilizer, nutrient elements and biochar immobilized microorganisms according to a ratio of 4:1: 4.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method selects pyrite with rich natural content as the reducing filler of PRB, and is cheaper and more easily obtained than zero-valent iron.
(2) The method adopts a pyrite-dissimilatory iron reducing bacteria synergistic system, utilizes the advantage of rapid reaction by a chemical method, simultaneously continuously breeds microorganisms, reduces the generated Fe (III) into Fe (II), ensures that the reaction is continuously carried out, and prolongs the service life of PRB.
(3) The method enriches microorganisms in the biochar through an immobilization technology and then mixes the biochar with the pyrite powder, solves the problems of small specific surface area and difficult film formation of the pyrite, and successfully constructs a pyrite-microorganism reaction system.
(4) The activated carbon is fired by using agricultural waste coconut shells as a raw material, a carbon source is provided for microbial growth, and a nitrogen source and a phosphorus source are provided by using common fertilizers in agriculture. Low cost and environmental protection.
(5) The permeable reactive barrier material disclosed by the invention can be used for treating heavy metals and organic matters, and has a wide application prospect.
Drawings
FIG. 1 is a permeable reaction wall experimental set-up.
FIG. 2 is a graph of the removal rate of the permeable reactive barrier of the present invention within 30 days of treatment at 100mg/LCr (VI).
FIG. 3 shows the removal rate of 3,3 ', 4, 4' -tetrachlorobiphenyl of 10mg/L in 30 days after the treatment of the permeable reaction wall of the present invention.
A permeable reaction wall experimental device 10 and a water inlet area 11; a coarse sand packing region 12; permeable reaction walls 13.
Detailed Description
The permeable reactive barrier experimental device 10 is composed of a water inlet area 11, a coarse sand filling area 12 and a permeable reactive barrier 13. The invention is further described below with reference to the accompanying drawings.
Example 1: preparation of the permeable reactive barrier 13 filler:
purchasing commercial pyrite, crushing and sieving the pyrite by a ball mill, sieving the pyrite by a 20-mesh sieve, sieving the pyrite by a 40-mesh sieve again, and taking the pyrite on the pyrite by a 40-mesh sieve.
Cutting coconut shell to 2-3cm with a cutting machine, placing in a muffle furnace, performing anoxic ignition at 300 deg.C for 2h, soaking to 0.1mol/L hydrochloric acid for 12h, washing with deionized water to remove ash, washing until pH value is constant, and oven drying at 105 deg.C. Grinding, sieving with 20 mesh sieve, sieving with 40 mesh sieve to obtain the oversize product, i.e. charcoal.
LB medium 100mL was prepared, S.deconiorationis stored on a slant was inoculated, and the mixture was cultured for 24 hours.
Weighing 500g of coconut shell biochar, and sterilizing at 121 ℃ for 20 min.
10L of the strain suspension culture medium is prepared. The formula is as follows: 10g/L of glucose; NH (NH)4Cl 1g/L;KH2PO40.5 g/L; 5g/L of yeast powder. Sterilizing at 121 deg.C for 20 min. 500g of sterilized coconut shell charcoal was added and 100mL [0031 ] of the resulting mixture was inoculated]The s.decoloration seed solution obtained in (1). And standing and culturing for 48 hours.
Filtering out coconut shell biochar under aseptic conditions. Transfer to 10L fresh sterile medium, inoculate 100mL fresh S.decoloresoniis bacterial suspension, and culture for 48 h.
Repeating the steps for ten times to obtain the biochar with successful biofilm formation.
The pyrite and the purchased slow release fertilizer are well-mixed, and the biochar immobilized microorganisms are completely and uniformly mixed according to the ratio of 4:1: 4. The permeable reaction wall 13 shown in fig. 1 is installed.
Example 2: the prepared permeable reactive barrier 13 treats wastewater containing Cr (VI).
In recent years, chromium and compounds thereof are widely applied to industries such as metal processing, metallurgy, electroplating, leather making, coating, paint, fertilizer, printing and dyeing and the like, and chromium-containing waste water and waste residues can be generated in the industrial production process. According to incomplete statistics, the chromium slag is discharged by about 60 ten thousand tons every year in China, wherein the discharge or the comprehensive utilization rate after treatment is less than 17 percent. Chromium in water exists mainly in two forms of Cr (VI) and Cr (III). Cr (III) is stable in property, is easy to generate hydroxide precipitate, is an important micronutrient element of a human body, but Cr (VI) has strong mobility and toxicity, can induce cancer, has potential teratogenic and mutagenic effects, and has 100 times higher toxicity to the human body than Cr (III). The water-soluble Cr (VI) is listed as one of 8 chemical substances with the greatest harm to human bodies and is also one of 3 internationally recognized carcinogenic metal substances. Therefore, how to reduce and remove chromium pollution in the environment, especially the very water-soluble cr (vi), becomes a difficult problem and a hotspot in the environmental field.
Preparing raw water containing 100mg/LCr (VI). The concentration of Cr (VI) in the water was measured by spectrophotometry with a peristaltic pump at 10rpm for 30d (FIG. 1) every 24 h. The removal rate was calculated and the measurement results are shown in FIG. 2.
The pyrite microorganism combined permeable reaction wall 13 has a better removal rate to Cr (VI), and the removal rate is always kept above 95% within 30 days of the experiment.
Example 3: the permeable reactive barrier 13 thus produced treats polychlorinated biphenyl.
Polychlorinated biphenyls (PCBs) are artificially synthesized organic compounds, and are chlorides formed by substituting chlorine for hydrogen atoms on a biphenyl ring. Due to its persistence, bioaccumulation, long-range migration and biotoxicity. The first list of controlled pollutants, which may be enriched by the food chain and pose a significant threat to biological and human health, has been listed in the stockholm convention on persistent organic pollutants. The wide industrial use of polychlorinated biphenyls has caused a problem of global environmental pollution.
Preparing raw water containing 10mg/L of 3,3 ', 4, 4' -tetrachlorobiphenyl. Feeding water at a speed of 10rpm for 30d (figure 1) by using a peristaltic pump, sampling every 24h, extracting by using n-hexane, and measuring the concentration of residual tetrachlorobiphenyl in the water by using a high performance liquid chromatography. The removal rate of the PRB to tetrachlorobiphenyl is calculated, and the result is shown in figure 3.
The removal rate of the pyrite microorganism combined permeable reaction wall 13 to tetrachlorobiphenyl is maintained to be about 82% at the initial stage of operation, the effect of microorganisms at the later stage is more and more important, and the removal rate reaches 97% in 30 days.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.