CN112624330A - Method for promoting anaerobic degradation of phenolic wastewater by adding biochar - Google Patents
Method for promoting anaerobic degradation of phenolic wastewater by adding biochar Download PDFInfo
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- CN112624330A CN112624330A CN202011630410.6A CN202011630410A CN112624330A CN 112624330 A CN112624330 A CN 112624330A CN 202011630410 A CN202011630410 A CN 202011630410A CN 112624330 A CN112624330 A CN 112624330A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2866—Particular arrangements for anaerobic reactors
- C02F3/2893—Particular arrangements for anaerobic reactors with biogas recycling
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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Abstract
The invention discloses a method for promoting anaerobic degradation of phenol-containing wastewater by adding biochar. Moreover, the conductivity of the biochar based on the redox activity can excite the direct transfer of electrons among species, thereby promoting the anaerobic degradation of the phenolic wastewater, and the promotion effect is continuous. The advantages of the invention are mainly reflected in that: firstly, the biochar can be prepared by utilizing solid wastes, the optimal preparation condition of the biochar can be determined through batch experiments, and the biochar can be recycled; secondly, the biological carbon relieves the biological toxicity of the phenol wastewater through the adsorption effect, and is beneficial to the quick start of a phenol anaerobic degradation system; the biochar has obvious promotion effect on anaerobic degradation of phenol wastewater with different concentrations, and the promotion effect is continuous.
Description
Technical Field
The invention relates to the technical field of environmental engineering, in particular to a method for promoting anaerobic degradation of phenolic wastewater by adding biochar.
Background
Phenol, an important organic chemical raw material, widely exists in industrial wastewater of coal chemical industry and textile industry, and attracts wide attention due to carcinogenicity and intractable. Anaerobic biological treatment of wastewater is to utilize anaerobic microorganisms to degrade organic pollutants and simultaneously produce methane under anaerobic conditions. The anaerobic biological treatment technology has the remarkable advantages of low energy consumption, less generated residual sludge and small carbon emission, and is widely used for treating wastewater and waste. By adopting the anaerobic digestion technology, the organic matters which are difficult to degrade can be effectively removed, and clean biological energy can be obtained.
However, the biological toxicity and thermodynamic barrier of phenol limit the efficiency of anaerobic degradation, and the rate of methane production is low, so a method for enhancing the anaerobic degradation of phenol needs to be searched.
In view of this, the method for promoting anaerobic degradation of phenol-containing wastewater by adding biochar is provided, which is very beneficial to widely using anaerobic technology to treat phenol-containing wastewater.
Disclosure of Invention
In order to overcome the problems of slow starting and low phenol degradation efficiency of the process, the invention provides a method for promoting anaerobic degradation of phenol-containing wastewater by adding biochar, the biotoxicity of phenol is relieved by means of the huge specific surface area and the porous structure of the biochar, so that the quick starting of the anaerobic biological treatment process is accelerated, and oxygen-containing functional groups on the surface of the biochar enable the biochar to have redox activity, so that direct transmission of electrons between species of interoperable methanogens can be stimulated, the methanogenic efficiency is promoted, and the method has a continuous promotion effect on the methanogenic process. The optimal preparation condition of the biochar is determined through experiments, and the anaerobic degradation effect of the biochar on the phenol-containing wastewater is verified.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for promoting anaerobic degradation of phenolic wastewater by adding biochar comprises the following steps:
step one, preparing wood chip biochar;
step two, preparing a serum bottle, and adding a certain amount of anaerobic sludge, nutrient solution and phenol into the bottle to form a phenol-containing wastewater anaerobic biological treatment system;
step three, the wood chip biochar obtained in the step one is added into a phenolic wastewater anaerobic biological treatment system;
and step four, after the substrate is consumed, when the digestive juice is removed, the biochar in the digestive juice can be recovered.
The temperature of the anaerobic biological treatment system in the second step is 35 +/-1 ℃.
In the step one, the wood chip biochar is prepared by using solid waste, and the solid waste is wood chips, coconut shells or excess sludge.
The concentration of phenol in the anaerobic biological treatment system in the second step is 500-1700 mg/L.
The wood chip biochar in the step one is prepared by pyrolysis: respectively controlling the temperature rise amplitude to be 10-15 ℃/min at the temperature of 300, 500 and 700 ℃, and maintaining for 2h after the temperature reaches 300, 500 and 700 ℃; cooling to room temperature after complete carbonization, taking out from a muffle furnace to obtain sawdust biochar, uniformly mixing and grinding the biochar, sieving with 16-60 mesh sieves, separating to obtain 0.25-1mm sawdust biochar, preserving in a dryer for later use under the protection of nitrogen, adding the sawdust biochar into deionized water, repeatedly cleaning for several times, drying at 105 ℃, and then putting into the dryer for later use.
The adding amount of the wood chip biochar is 15g/L, and the biochar is added once.
And in the fourth step, after the phenol anaerobic degradation reaction is finished, the wood chip biochar is filtered and then recovered.
And in the second step, the nutrient solution of the anaerobic biological treatment system comprises 0.24g/L of monopotassium phosphate, 1.12g/L of dipotassium phosphate, 0.5g/L of ammonium bicarbonate, 0.05g/L of calcium chloride, 0.1g/L of magnesium chloride, 1ml of mixed solution of trace elements and the pH value of an acclimation culture medium of 7.5.
The mixed solution of the trace elements comprises: 20.89g/L of ferrous chloride tetrahydrate, 1.41g/L of boric acid, 0.98g/L of copper sulfate pentahydrate, 1.09g/L of manganese chloride, 0.18g/L of potassium iodide, 0.53g/L of sodium molybdate, 1.11g/L of zinc sulfate heptahydrate, 2.01g/L of cobalt dichloride hexahydrate, 2.02g/L of nickel dichloride hexahydrate, 0.55g/L of sodium selenite and 0.42g/L of sodium tungstate.
The results show that the wood chip biochar prepared at 500 ℃ has the best treatment effect on the whole anaerobic biological treatment system, and an optimal biochar preparation method is provided. And the addition of the biochar is found to promote the anaerobic treatment even when the phenol concentration is higher (the phenol content is far higher than the biochar adsorption capacity) along with the increase of the phenol concentration, so that an anaerobic biological treatment system can operate efficiently and stably. This shows that in actual work, when the concentration of phenol is higher, biochar can be added to ensure the normal operation of the system, and simultaneously, the stability of the system is improved, and that the added biochar has an additional promoting effect besides the effect of degrading biotoxicity through adsorption.
The invention has the beneficial effects that:
the self-made wood chip biochar is added into a phenol wastewater anaerobic degradation system, the biotoxicity of the phenol wastewater can be obviously reduced through the adsorption effect of the biochar, so that the adaptation of anaerobic microorganisms to the environment is accelerated, the system is favorable for quick start, phenolic substances are further degraded, oxygen-containing functional groups on the surface of the biochar can stimulate electrons among intervarietal bacterial groups to be directly transferred, and the phenol anaerobic degradation efficiency is improved.
The biochar can be prepared by utilizing solid waste, so that the solid waste can be recycled, and experiments show that the biochar has a continuous promoting effect on an anaerobic degradation system of the phenolic wastewater, and can be recycled;
the biological carbon relieves the biological toxicity of the phenol wastewater through the adsorption effect, and is beneficial to the quick start of a phenol anaerobic degradation system;
the biochar has obvious promotion effect on anaerobic degradation of phenol wastewater (500-1700mg/L) with different concentrations, and the promotion effect is continuous.
Drawings
FIG. 1 is a graph showing the cumulative methane production and phenol degradation curves for the first cycle of the experiment.
FIG. 2 is a graph showing cumulative methane production and phenol degradation curves for the second period of the experiment.
FIG. 3 is a graph showing the cumulative amount of methane produced and the degradation of phenol in experiment two.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The invention relates to a method for promoting anaerobic degradation of phenolic wastewater by adding biochar, which is further explained by combining specific examples in order to make the implementation method of the invention clearer and easier to understand.
The invention is applied to an anaerobic biological treatment system, and has good effect, and the specific implementation mode is as follows: and in the initial stage of anaerobic degradation, adding biochar into the phenol anaerobic biological treatment system, and periodically detecting the gas production rate, gas components and phenol concentration. Two batches of experiments were set up for the study of phenol anaerobic digestion experiments, while a parallel control group without additives was set up, as follows.
(1) Preparing wood chip biochar: 50-100g of sawdust is put in a crucible and covered. Controlling the temperature rise amplitude to be 10-15 ℃/min at the temperature of 300, 500 and 700 ℃, and maintaining for 2h after the temperature reaches 300, 500 and 700 ℃ respectively; cooling to room temperature after complete carbonization, taking out from a muffle furnace to obtain wood chip biochar, uniformly mixing and grinding the biochar, sieving with 16-60 mesh sieves, controlling the particle size of the biochar to be 0.25-1mm, and placing in a dry environment for later use. Adding the sawdust carbon into deionized water under the protection of nitrogen, repeatedly cleaning for several times, drying at 105 ℃, and then putting into a dryer for later use.
(2) Preparing anaerobic seed sludge: anaerobic seed sludge is obtained from a UASB (upflow anaerobic sludge blanket) mesophilic digestion reactor of a local beer wastewater plant, and related parameters of the seed sludge are shown in a table 1.
TABLE 1 mud related parameters
(3) Batch experiment 1:
preparing 11 120mL ultrasonically cleaned serum bottles, respectively adding 50mL seed sludge, adding a phenol solution, controlling the phenol concentration to be 1g/L, numbering CTA (non-added material group), CTB (non-added material control group), SD3A (300 ℃ firing wood chip biochar), SD3B (300 ℃ firing wood chip biochar control group), SD5A (500 ℃ firing wood chip biochar), SD5B (500 ℃ firing wood chip biochar control group), SD7A (700 ℃ firing wood chip biochar), SD7B (700 ℃ firing biochar control group), BLANK (BLANK group without added wood chip and phenol). Adding materials into SDA and SDB bottles respectively according to the concentration of 15g/L, finally fixing the volume to 90ml by using nutrient solution, ensuring that the state of each group of seed sludge is the same, then blowing off for 2min by N2, removing headspace oxygen, sealing by using an aluminum cover gland, placing in a 35 ℃ water bath shaking table, exhausting by using a needle after ten minutes, wherein the frequency of the shaking table is 120-130 r/min. Phenol concentration, gas production and gas panels were monitored continuously and the first cycle was 40d incubation.
After the first period is finished, the biochar is screened by 0.25mm, the screened sludge mixed liquor is uniformly mixed and equally divided to control the same sludge activity and is respectively added into two 120mL serum bottles, the screened biochar is added into one of the bottles again to ensure that the biochar concentration is 15g/L, a phenol solution with the initial concentration of 1g/L is added, and the volume is constant to 90mL by using a culture medium solution, wherein the biochar is numbered SD3-CT (no screened biochar is added), SD3, SD5-CT (no screened biochar is added), SD5, SD7-CT (no screened biochar is added), and SD 7. And starting a new cycle again, continuously monitoring the phenol concentration, the gas production and the gas group, and carrying out 20d culture in the second cycle.
Batch experiment 2:
preparing 11 120mL ultrasonic-cleaned serum bottles, respectively adding 20mL acclimated seed sludge, adding a phenol solution, controlling the phenol concentration to be respectively 500, 800, 1200, 1500 and 1700mg/L, then adding 15g/L of wood chip biochar prepared at 500 ℃ into each bottle, and adding no biochar into a control group. The blank group was not dosed with phenol and biochar. And finally, fixing the volume to 90ml by using nutrient solution, ensuring that the state of each group of seed sludge is the same, blowing off for 2min by using N2, removing headspace oxygen, sealing by using an aluminum cover gland, placing in a 35 ℃ water bath shaking table, exhausting by using a needle after ten minutes, wherein the frequency of the shaking table is 120-130 r/min. The phenol concentration, gas production and gas composition were monitored continuously and the culture was carried out for 70 days.
(4) Quantitatively measuring the gas production rate by using a glass injector, wherein when the internal pressure and the external pressure of the fermentation bottle are the same, the gas in the glass injector does not rise any more; the gas was sampled at a 500uL sample injection needle and the gas composition and phenol concentration were determined by gas chromatography. The methane production consists of two parts: the gas in the headspace of the fermentation bottle and the gas in the needle tube are respectively used. Cumulative methane production was observed as a function of cumulative time.
(5) Using the mathematical model Gommpertz formula:
and (3) fitting the kinetic parameters P0, Rmax and t0, and calculating the methanogenesis potential, the maximum methanogenesis rate and the lag phase, wherein the fitting result is shown in a table II.
TABLE two batch experiment first second period methane production process kinetic parameters
Therefore, the methane production rate and the domestication period of the experimental group of adding the biochar and the blank group of not adding the biochar are compared, the optimal biochar preparation condition can be selected through comparing the experimental results, and the promotion effect of the biochar when the concentration of the phenol is higher is verified, so that a method is provided for keeping the actual phenol wastewater anaerobic treatment system stable.
From FIG. 1, it is observed that phenol was completely degraded in 10-15 days in the experimental group to which biochar was added, while phenol was not completely degraded in 38 days in the experimental group to which biochar was not added. It is therefore possible to conclude that: the experimental group added with the biochar can enable microorganisms in an anaerobic system to adapt to the environment and domesticate more quickly through the adsorption effect and other effects of the biochar, promote the anaerobic degradation of phenol wastewater to start quickly, and improve the methane production rate. From fig. 2, it can be observed that the sludge acclimated by the biochar can rapidly start anaerobic degradation of phenol wastewater, and the methane production efficiency of the experimental group added with the biochar is obviously higher than that of the experimental group not added with the biochar. And through data (table II) obtained by mathematical simulation, the lag phase of the domesticated sludge experimental group added with the biochar is obviously lower than that of the experimental group without the biochar, and the methane production rate of the experimental group added with the biochar is obviously improved. We can therefore conclude that: the biochar has a continuous promoting effect on an anaerobic biological treatment system.
From fig. 3, it can be observed that the added biochar has an obvious promoting effect on the degradation of phenol wastewater with different concentrations (500-1700mg/L), when the phenol concentration exceeds the biochar adsorption capacity, the adsorption of the biochar cannot relieve the biotoxicity of the high-concentration phenol, and the biochar still has an obvious promoting effect on the phenol degradation, which may be that the biochar excites interspecies electrons to be directly transferred, so as to promote the methane production process, further explaining that the biochar has a continuous promoting effect on the anaerobic degradation of the phenol.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The above-described embodiments of the invention are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims, and not by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A method for promoting anaerobic degradation of phenolic wastewater by adding biochar is characterized by comprising the following steps:
step one, preparing wood chip biochar;
step two, preparing a serum bottle, and adding a certain amount of anaerobic sludge, nutrient solution and phenol into the bottle to form a phenol-containing wastewater anaerobic biological treatment system;
step three, the wood chip biochar obtained in the step one is added into a phenolic wastewater anaerobic biological treatment system;
and step four, after the substrate is consumed, when the digestive juice is removed, the biochar in the digestive juice can be recovered.
2. The method for promoting anaerobic degradation of phenolic wastewater by adding biochar as claimed in claim 1, wherein in the first step, the wood chip biochar is prepared by using solid waste, and the solid waste is wood chips, coconut shells or excess sludge.
3. The method for promoting anaerobic degradation of phenolic wastewater by adding biochar as claimed in claim 1, wherein the wood chip biochar is prepared by pyrolysis in the first step: respectively controlling the temperature rise amplitude to be 10-15 ℃/min at the temperature of 300, 500 and 700 ℃, and maintaining for 2h after the temperature reaches 300, 500 and 700 ℃; cooling to room temperature after complete carbonization, taking out from a muffle furnace to obtain sawdust biochar, uniformly mixing and grinding the biochar, sieving with 16-60 mesh sieves, separating to obtain 0.25-1mm sawdust biochar, preserving in a dryer for later use under the protection of nitrogen, adding the sawdust biochar into deionized water, repeatedly cleaning for several times, drying at 105 ℃, and then putting into the dryer for later use.
4. The method for promoting anaerobic degradation of phenol-containing wastewater by adding biochar according to claim 1, wherein the adding amount of the wood chip biochar is 15g/L, and the adding manner of the biochar is one-time adding.
5. The method for promoting anaerobic degradation of phenolic wastewater by adding biochar according to claim 1, wherein the temperature of the anaerobic biological treatment system in the second step is 35 +/-1 ℃.
6. The method for promoting anaerobic degradation of phenol-containing wastewater by adding biochar as claimed in claim 1, wherein the phenol concentration in the anaerobic biological treatment system in the second step is 500-1700 mg/L.
7. The method for promoting anaerobic degradation of phenol-containing wastewater by adding biochar as claimed in claim 1, wherein in the fourth step, the wood chip biochar is filtered after the phenol anaerobic degradation reaction is finished and then is recovered.
8. The method for promoting anaerobic degradation of phenolic wastewater by adding biochar according to claim 1, wherein the nutrient solution of the anaerobic biological treatment system in the second step comprises 0.24g/L of monopotassium phosphate, 1.12g/L of dipotassium phosphate, 0.5g/L of ammonium bicarbonate, 0.05g/L of calcium chloride, 0.1g/L of magnesium chloride, 1ml of trace element mixed solution, and the pH value of the domestication culture medium is 7.5.
9. The method for promoting anaerobic degradation of phenolic wastewater by adding biochar according to claim 8, wherein the trace element mixed solution comprises: 20.89g/L of ferrous chloride tetrahydrate, 1.41g/L of boric acid, 0.98g/L of copper sulfate pentahydrate, 1.09g/L of manganese chloride, 0.18g/L of potassium iodide, 0.53g/L of sodium molybdate, 1.11g/L of zinc sulfate heptahydrate, 2.01g/L of cobalt dichloride hexahydrate, 2.02g/L of nickel dichloride hexahydrate, 0.55g/L of sodium selenite and 0.42g/L of sodium tungstate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114772721A (en) * | 2022-04-11 | 2022-07-22 | 中国农业大学 | Method for promoting anaerobic degradation of polycyclic aromatic hydrocarbon in wastewater by using biochar |
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