CN108503025A - A method of promoting high-carbon N ratio wastewater advanced treating effect - Google Patents
A method of promoting high-carbon N ratio wastewater advanced treating effect Download PDFInfo
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- CN108503025A CN108503025A CN201810325453.XA CN201810325453A CN108503025A CN 108503025 A CN108503025 A CN 108503025A CN 201810325453 A CN201810325453 A CN 201810325453A CN 108503025 A CN108503025 A CN 108503025A
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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
- C02F3/2813—Anaerobic digestion processes using anaerobic contact processes
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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
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Abstract
The invention discloses a kind of methods promoting high-carbon N ratio wastewater advanced treating effect, belong to technical field of waste water processing.The present invention provides a kind of methods promoting high-carbon N ratio wastewater advanced treating effect to overcome the low problem of high-carbon N ratio wastewater anaerobic organism advanced treating gas producing efficiency by adding metallic element in high-carbon N ratio wastewater.The present invention may make high-carbon N ratio wastewater accumulation factor of created gase to reach 174.8mL/gCOD;So that β glucuroides, proteolytic enzyme and the coenzyme F of anaerobic processes42030820.0U/gVSS, 850.0U/gVSS and 1.00U/gVSS is respectively increased in activity;So that polysaccharide is respectively increased with protein degradation rate to 75.3% and 61.2% in high carbon-nitrogen ratio production biogas system.
Description
Technical field
The present invention relates to a kind of methods promoting high-carbon N ratio wastewater advanced treating effect, belong to wastewater processing technology neck
Domain.
Background technology
It is reported that China generates the sewage disposal plant excess sludge of ten thousand tons of about 3000-4000 every year, it is mostly simple to stack
Afterwards, be periodically transported to refuse landfill landfill or natural air drying dehydration after burn heat supply, these processing disposal options costs compared with
Height, and easily lead to the secondary pollution of soil and atmospheric environment.
Excess sludge contains abundant using organic matter, can be used for extracting protein.Wastewater treatment in China factory is remaining dirty
Crude protein content is about 28.7-40.9% in mud, after zymolysis technique hydrolysed residual sludge, can effectively recycle sludge protein
Matter, gained protein crude product contain seven kinds of essential amino acids, and content of beary metal also meets China's feed relevant criterion;Using heat
After basic hydrolysis excess sludge, sludge protein, the crude protein of gained protein product and required are recycled using isoelectric point precipitation
Amino acid content is higher, respectively 49.5% and 12.37%, compared with former excess sludge, heavy metal reduction rate 90% with
On, heavy metal pollution risk is not present in gained protein crude product.
Through the raffinate after Protein Extraction still contain it is abundant using organic matter, if directly carry out discharge be not only one
The waste of kind resource, can also damage environment, this partial organic substances can be further processed, for producing natural pond
Gas.
However, the separation and Extraction of sludge protein causes gained extraction raffinate nitrogen missing, carbon-nitrogen ratio to be increased to 50-120,
And the optimum carbon nitrogen ratio of anaerobic methane production gas is 20-25, high carbon-nitrogen ratio causes the gas producing efficiency of anaerobic organism advanced treating low.By
Raffinate after Protein Extraction can not directly carry out anaerobic bio-treated, can not arbitrarily discharge, and cause a large amount of available
The wasting of resources.
Therefore, search out it is a kind of promote high-carbon N ratio wastewater advanced treating production biogas method can be excess sludge resource
Change provides a strong guarantee.
Invention content
To solve the above problems, the present invention provides a kind of method promoting high-carbon N ratio wastewater advanced treating effect,
By adding metallic element in high-carbon N ratio wastewater, high-carbon N ratio wastewater anaerobic organism advanced treating methane phase efficiency is overcome
Low problem.
Technical scheme is as follows:
The present invention provides a kind of methods promoting high-carbon N ratio wastewater advanced treating effect, are thrown in high-carbon N ratio wastewater
Add metallic element, strengthens methanogen anaerobic fermentation, and then intensified high-carbon N ratio wastewater produces biogas;The metallic element is iron.
In one embodiment of the invention, the carbon-nitrogen ratio of the waste water is 50-120.
In one embodiment of the invention, the metallic element is Zero-valent Iron.
In one embodiment of the invention, dosage of the metallic element in waste water is 10-40mg/L.
In one embodiment of the invention, dosage of the metallic element in waste water is 30-40 μm of ol/L.
In one embodiment of the invention, dosage of the metallic element in waste water is 40 μm of ol/L.
The present invention provides above-mentioned promotion high-carbon N ratio wastewater advanced treatings to produce the method for biogas at production biogas, sewage
Application in terms of reason.
The present invention provides a kind of high-carbon N ratio wastewater inorganic agent, contain metallic element in this waste water treating agent;The gold
Category element is iron;The iron is Zero-valent Iron.
In one embodiment of the invention, the content of metallic element is not less than 5% in the waste water treating agent.
In one embodiment of the invention, the content of metallic element is not less than 8% in the waste water treating agent.
The present invention provides application of the above-mentioned high-carbon N ratio wastewater inorganic agent in terms of production biogas, sewage disposal.
The present invention provides the application methods of above-mentioned high-carbon N ratio wastewater inorganic agent, and high-carbon N ratio wastewater is added in waste water
Inorganic agent so that content of the metallic element in waste water in high-carbon N ratio wastewater inorganic agent is 10-40 μm of ol/L.
In one embodiment of the invention, high-carbon N ratio wastewater inorganic agent is added in waste water so that high carbon-nitrogen ratio
Content of the metallic element in waste water in waste water treating agent is 30-40 μm of ol/L.
In one embodiment of the invention, high-carbon N ratio wastewater inorganic agent is added in waste water so that high carbon-nitrogen ratio
Content of the metallic element in waste water in waste water treating agent is 40 μm of ol/L.
Advantageous effect:
(1) present invention is improved high by adding metallic element, promoting hydrolysis acidification and producing the activity of process of methane key enzyme
Degradation effect of organic compound and aerogenesis effect in carbon-nitrogen ratio waste water.
(2) present invention may make high-carbon N ratio wastewater accumulation factor of created gase to be up to 174.8mL/gCOD, than not using the present invention
The factor of created gase of method improves 99.5%.
(3) present invention may make the beta-glucosidase, proteolytic enzyme and coenzyme F of anaerobic processes420Activity is respectively increased
To 30820.0U/gVSS, 850.0U/gVSS and 1.00U/gVSS, than being improved without using the enzyme activity of the method for the present invention
243.2%, 50.0% and 400.0%.
(4) present invention may make that polysaccharide is respectively increased with protein degradation rate to 75.3% in high carbon-nitrogen ratio production biogas system
With 61.2%, compared with without using the method for the present invention, 71.1% and 53.0% has been respectively increased.
Specific implementation mode
Following embodiment facilitates a better understanding of the present invention, but is not covered by and is exhausted all realities that inventor is done
It tests, purpose is only in that the intuitive and accuracy that the present invention is illustrated with those data.
The detection method of the present invention is as follows:
Activity of beta-glucosidase detection method:Mud mixed liquid is centrifuged into 10min in 8000g, collects supernatant;It takes
100 μ L of clear liquid, 200 μ Lp-NPG are added, and (5mmol/L is dissolved in pH5.0 citrate-phosphate disodium hydrogen buffer solutions, P-C bufferings
Liquid) mixing, 50 DEG C are reacted 30min, and 2mL1mol/LNa is added immediately2CO3It terminates and reacts and develop the color, extinction is measured under 400nm
Value, enzyme activity is calculated by following formula:
In formula:U is enzyme activity unit, U/mL;C is the concentration of p-nitrophenol;V is the volume of reaction system;N is dilution
Multiple;T is the reaction time;0.1 for taken supernatant or cell liquid volume.
β-glucosidase activity unit of force is defined as, and under the above-described reaction conditions, substrate is released 1 μm of ol in 1min
The required enzyme amount of p-NP.
Hydrolase of proteolysis detection method:It is measured using GB/T23527-2009 standard methods, that is, utilizes protease point
The chromogenic reaction that casein (substrate) generates amino acid containing phenolic group and Folin-Phenol reagent is solved, the vigor of indirect determination protease is carried out.
Coenzyme F420Activity test method:It takes 5 grams of wet muds to add water to 15mL, 15min is centrifuged under conditions of 4000r/m,
Liquid is discarded supernatant, precipitation adds water to 15mL, repeats the above steps twice;Precipitation plus physiological saline impregnate 30min to 15mL, then
It is centrifuged with the same terms, obtained supernatant adds water to heating water bath (95~100 DEG C, 30min) after 15mL, and glass bar constantly stirs
It mixes, 4000r/m centrifuges 15min again after cooling, obtains glassy yellow extracting solution;With ethyl alcohol:Extracting solution is 2:1 ratio adds second
Alcohol is stirred, and precipitates 2h, then 10000r/m centrifuges 15min, the absorbance of supernatant is measured at wavelength 420nm, under
Formula calculates coenzyme F420Activity:
In formula:C --- the coenzyme F in sludge420Concentration, mmol/L;A1--- absorbance value of the sample at 420nm;
A2--- absorbance value of the reference at 420nm;The extension rate of f --- sample;The thickness of l --- cuvette, cm;
ε --- coenzyme F420MM extinction coefficient, l/cmmmol.When pH=13.5, ε=54.3.
Polysaccharide degradation rate detection method:Solution 2.0mL to be measured is taken, 5% phenol liquid 1.0mL is added, mixing is added dropwise rapidly dense
Sulfuric acid 7.5mL, shakes up, and is placed at room temperature for 15min, then sets cooling 30min in cold water, absorbance is measured at 490nm wavelength, is obtained
The content for obtaining polysaccharide in prepare liquid, its degradation rate is calculated according to the difference of polyoses content before and after degradation.
Protein degradation rate detection method:Prepare liquid 0.1mL is drawn, is put into tool plug scale test tube, 5mL coomassies are added
Brilliant blue G-250 protein reagents, are sufficiently mixed, and use 1cm cuvettes colorimetric at 595nm after placing 2min, record optical density
OD595Nm obtains the content of protein in prepare liquid, its degradation rate is calculated according to the difference of protein content before and after degradation.
Accumulate factor of created gase detection method:Lye measures gas volume after absorbing.
Embodiment 1
Control inlet COD concentration is 6300mg/L, and carbon-nitrogen ratio 120, the inoculum density for having tamed anaerobic activated sludge is
30mg/L adds 40mg/L Zero-valent Irons, 40mg/L cobalts, 40mg/L nickel, 40mg/L ferrous ions, 40mg/L ferric ions,
After mixing, with rubber stopper seal, it is placed in anaerobic methane production gas in 35 ± 1 DEG C of thermostatic chambers, during which, daily oscillating reactions bottle is primary.Gold
It is as shown in table 1 to the influence for producing biogas effect to belong to type.
It is control not add any metallic element, when operation is to 16d, the facilitation effect of Zero-valent Iron is the most apparent,
Beta-glucosidase, proteolytic enzyme, coenzyme F420Activity is respectively 30820.0U/gVSS, 850.0U/gVSS, 1.00U/
GVSS, polysaccharide and protein degradation rate are respectively 65.3% and 57.2% in system.Meanwhile it accumulating factor of created gase and reaching 165.8mL/
GCOD improves 89.3% compared with control experiment.(specific testing result such as table 1)
Influence of 1 metal species of table to production biogas effect
Embodiment 2
Control inlet COD concentration is 6500mg/L, and carbon-nitrogen ratio 110, the inoculum density for having tamed anaerobic activated sludge is
30mg/L, add 10mg/L Zero-valent Irons, 20mg/L Zero-valent Irons, 30mg/L Zero-valent Irons, 40mg/L Zero-valent Irons, 50mg/L Zero-valent Irons,
60mg/L Zero-valent Irons, after mixing, with rubber stopper seal, it is placed in anaerobic methane production gas in 35 ± 1 DEG C of thermostatic chambers, during which, is vibrated daily
Reaction bulb is primary, is control not add Zero-valent Iron, the results are shown in Table 2.When adding 10-40mg/L iron, factor of created gase is accumulated
Up to 132.2-174.8mL/gCOD, compared with control experiment, 50.9-99.5% is improved.When adding 40mg/L Zero-valent Irons, β-
Glucuroide, proteolytic enzyme and coenzyme F42028750.0U/gVSS, 845.6U/gVSS and 0.90U/ is respectively increased in activity
GVSS, polysaccharide is respectively increased with protein degradation rate to 75.3% and 60.2% in system;Meanwhile it accumulating factor of created gase and reaching
174.8mL/gCOD improves 99.5% compared with control experiment.(specific testing result such as table 2)
Influence of the 2 Zero-valent Iron dosage of table to production biogas effect
Embodiment 3
Inlet COD concentration is 5180mg/L, and carbon-nitrogen ratio 50, the inoculum density for having tamed anaerobic activated sludge is 30mg/
L, adds 10mg/L Zero-valent Irons, after mixing, with rubber stopper seal, is placed in anaerobic methane production gas in 35 ± 1 DEG C of thermostatic chambers, during which, often
Its oscillating reactions bottle is primary, is control not add Zero-valent Iron.When operation is to 16d, beta-glucosidase, proteolysis
Enzyme, coenzyme F420Activity is respectively 28456.1.0U/gVSS, 845.3U/gVSS, 0.80U/gVSS, polysaccharide and protein in system
Degradation rate is respectively 70.5% and 61.2%.Meanwhile accumulating factor of created gase and reaching 154.3mL/gCOD, compared with control experiment, improve
76.1%.
Embodiment 4
Inlet COD concentration is 5890mg/L, and carbon-nitrogen ratio 80, the inoculum density for having tamed anaerobic activated sludge is 30mg/
L, adds 20mg/L Zero-valent Irons, after mixing, with rubber stopper seal, is placed in anaerobic methane production gas in 35 ± 1 DEG C of thermostatic chambers, during which, often
Its oscillating reactions bottle is primary, is control not add Zero-valent Iron.When operation is to 16d, beta-glucosidase, proteolysis
Enzyme, coenzyme F420Activity is respectively 28045.2U/gVSS, 810.4U/gVSS, 0.70U/gVSS, and polysaccharide is dropped with protein in system
Solution rate is respectively 60.6% and 53.7%.Meanwhile it accumulating factor of created gase and being improved compared with control experiment up to 157.7mL/gCOD
80.0%.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not limited to the present invention, any to be familiar with this skill
The people of art can do various change and modification, therefore the protection model of the present invention without departing from the spirit and scope of the present invention
Enclosing be subject to what claims were defined.
Claims (10)
1. a kind of method promoting high-carbon N ratio wastewater advanced treating effect, which is characterized in that the method is in high carbon-nitrogen ratio
Metallic element is added in waste water, strengthens methanogen anaerobic fermentation, and then intensified high-carbon N ratio wastewater produces biogas;The metal member
Element is iron.
2. a kind of method promoting high-carbon N ratio wastewater advanced treating effect as described in claim 1, which is characterized in that described
The carbon-nitrogen ratio of waste water is 50-120.
3. a kind of method promoting high-carbon N ratio wastewater advanced treating effect as claimed in claim 1 or 2, which is characterized in that
The iron is Zero-valent Iron.
4. a kind of method promoting high-carbon N ratio wastewater advanced treating effect as described in any one of claims 1-3, feature exist
In dosage of the metallic element in waste water is 10-40mg/L.
5. a kind of method of promotion high-carbon N ratio wastewater advanced treating effect as described in claim 1-4 is any, feature exist
In dosage of the metallic element in waste water is 30-40 μm of ol/L.
6. a kind of method promoting high-carbon N ratio wastewater advanced treating effect according to any one of claims 1 to 5, feature exist
In dosage of the metallic element in waste water is 40 μm of ol/L.
7. a kind of method of any promotion high-carbon N ratio wastewater advanced treating effects of claim 1-6 production biogas,
Application in terms of sewage disposal.
8. a kind of high-carbon N ratio wastewater inorganic agent, which is characterized in that contain metallic element in the waste water treating agent;The metal
Element is iron;The iron is Zero-valent Iron.
9. a kind of application of the high-carbon N ratio wastewater inorganic agent according to any one of claims 8 in terms of production biogas, sewage disposal.
10. a kind of application method of high-carbon N ratio wastewater inorganic agent according to any one of claims 8, which is characterized in that add in waste water
Enter high-carbon N ratio wastewater inorganic agent so that content of the metallic element in waste water in high-carbon N ratio wastewater inorganic agent is 10-40 μ
mol/L。
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Citations (2)
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CN105036320A (en) * | 2015-07-02 | 2015-11-11 | 中国环境科学研究院 | Method utilizing magnetic field enhanced iron powder to improve organic waste and wastewater anaerobic biogas production efficiency |
JP2016055216A (en) * | 2014-09-05 | 2016-04-21 | 栗田工業株式会社 | Method and apparatus for anaerobically digesting sewage treatment sludge |
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JP2016055216A (en) * | 2014-09-05 | 2016-04-21 | 栗田工業株式会社 | Method and apparatus for anaerobically digesting sewage treatment sludge |
CN105036320A (en) * | 2015-07-02 | 2015-11-11 | 中国环境科学研究院 | Method utilizing magnetic field enhanced iron powder to improve organic waste and wastewater anaerobic biogas production efficiency |
Non-Patent Citations (1)
Title |
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徐浩等: "零价铁强化上流式厌氧污泥床反应器处理煤化工费托合成废水研究", 《环境污染与防治》 * |
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