CN107522375A - A kind of method that Zero-valent Iron and activated carbon strengthen excess sludge anaerobic digestion methane phase - Google Patents
A kind of method that Zero-valent Iron and activated carbon strengthen excess sludge anaerobic digestion methane phase Download PDFInfo
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- CN107522375A CN107522375A CN201710724209.6A CN201710724209A CN107522375A CN 107522375 A CN107522375 A CN 107522375A CN 201710724209 A CN201710724209 A CN 201710724209A CN 107522375 A CN107522375 A CN 107522375A
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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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
- C02F11/04—Anaerobic treatment; Production of methane by such 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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/006—Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention belongs to Treatment of Sludge and resource technology field, discloses a kind of Zero-valent Iron and activated carbon strengthens the method for excess sludge anaerobic digestion methane phase.Methods described：(1) by excess sludge, seed sludge and water mix, regulation pH be 6~7.5, and cause mixture solid content be 8~12%, obtain mixing sludge；(2) mixing sludge, activated carbon and Zero-valent Iron are added into anaerobic digestion device, then anaerobic digestion；(3) caused gas in anaerobic digestion process is collected.Add activated carbon and Zero-valent Iron has more preferable facilitation effect to anaerobic digestion to the present invention simultaneously；The inventive method is simple, and reaction condition is gentle, and aerogenesis effect is better than conventional method, realizes the recycling of sewage disposal plant excess sludge, innoxious and minimizing, has good economic and social benefit.
Description
Technical field
The invention belongs to Treatment of Sludge and resource technology field, is related to one kind while adds Zero-valent Iron and activated carbon reinforcing
The method of excess sludge anaerobic digestion methane phase.
Background technology
Due to the increasing number of town sewage plant, sewage load increases, surplus sludge volume caused by activated sludge process
Also more and more, the dewatered sludge total value of European Union member countries has reached annual more than 10,000,000 tons.In China, 11,200,000 are had more than every year
The dewatered sludge of ton is produced, and nearly 80% stabilization that do not obtain is handled, and annual growth is more than 10%.In caused excess sludge
Containing substantial amounts of organic matter such as protein, polysaccharide etc., directly discharge can not only cause the secondary pollution of environment, also create a large amount of
Energy waste.
Anaerobic sludge digestion is the processing mode of a kind of not only effective but also economic sustainability, is not only had very to excess sludge
Good reduction, and methane gas can be produced, methane is a kind of alternative energy source of fossil fuel, is contributed at reduction
The cost of reason.The anaerobic sludge digestion admittedly that contains high at this stage is study hotspot, and its advantage can effectively reduce anaeroic digestor
Reaction volume, improves the concentration of organic matter, but there is also many problems, and such as ammonia inhibition, degradation effect of organic compound is low, methane phase
The shortcomings such as efficiency is low, so as to limit the promotion and application of the technology.
Anaerobic sludge digestion process includes hydrolysis acidification stage and methane phase stage.The hydrolysis acidification stage refers to that macromolecular has
Machine compound, such as protein, carbohydrate, fat are converted into amino acid, monose, aliphatic acid, glycerine etc. in the presence of hydrolytic bacteria
Small molecular organic compounds, it by organic matter degradations such as carbohydrate is organic acid to be then acidified bacterium, mainly acetic acid, butyric acid and
The process of propionic acid etc., hydrolysis and acidification reaction carry out relatively fast, are generally more difficult to separate them.The methane phase stage refers to produce
Methane backeria utilizes H2、CO2, acetic acid, the compound such as methanol be matrix, convert it into methane, research shows, in anaerobic digestion system
About 70% CH in system4Acetic acid is originated from, supervenes substantial amounts of CO2, so as to reduce CH in biogas4Concentration.
The content of the invention
In order to overcome shortcoming and defect of the prior art, the suppression of ammonia nitrogen is reduced, improves the yield of methane, improves anaerobism
The effect of digestion, Zero-valent Iron (ZVI) and activated carbon (AC) reinforcing residue are added simultaneously object of the present invention is to provide a kind of
The method of anaerobic sludge digestion methane phase.
Activated carbon (AC) has bigger specific surface area in this method, and the place of apposition growth is provided for microorganism, increase
Substrate and the contact area of microorganism, strengthen contact of the microorganism with substrate, and it has good suction-operated to ammonia nitrogen, can
Effectively to limit the concentration of ammonia nitrogen.In addition, the Zero-valent Iron (ZVI) of addition can be used as electron donor to provide electronics, oxidation is reduced also
Former current potential, accelerate the electron transmission in organic matter degradation and methane generating process, suitable growing environment is provided for methanogen.
Again while galvanic cell can be formed in reaction system by adding activated carbon and Zero-valent Iron, caused ferrous ion and oxidisability are strong
[H] larger molecular organicses of difficult degradation can be promoted to decompose, the hydrolysis of reinforced anaerobic digestion process, acidifying efficiency；It is caused
Ferrous ion is that microorganism grows the important substance needed, and the important substance of constitutive enzyme.The present invention is using regulation activated carbon
And the dosage of Zero-valent Iron (ZVI) and ratio reinforced anaerobic digestion process, (AC) reach overall and improve anaerobic digestion effect, increase
The purpose of energy recovery.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method for adding Zero-valent Iron (ZVI) and activated carbon (AC) reinforcing excess sludge anaerobic digestion methane phase simultaneously,
Comprise the following steps：
(1) excess sludge, seed sludge and water are mixed, regulation pH is 6~7.5, and causes the solid content of mixture
For 8~12%, mixing sludge is obtained；
(2) mixing sludge, activated carbon and Zero-valent Iron are added into anaerobic digestion device, then anaerobic digestion；
(3) caused gas in anaerobic digestion process is collected.
Seed sludge described in step (1) is anaerobically digested sludge；The excess sludge is dirty for the residue of town sewage plant
Mud.The Zero-valent Iron is iron powder, 60~100 mesh；Activated carbon is powdered activated carbon, 100~200 mesh.
Activated carbon described in step (1) and the mass ratio of Zero-valent Iron are 1：(2~20)；The activated carbon and mixing sludge
Mass ratio is 1：(300~350).
It is 13~15% that excess sludge described in step (1), which adopts water use regulation solid content, and it is dirty to adjust the residue after solid content
The volume ratio of mud and seed sludge is (2~4)：1；The solid content of the excess sludge is 75~85%.
Anaerobic digestion described in step (2) is that anaerobic digestion device is positioned in constant temperature oscillator to carry out anaerobic digestion,
The condition of anaerobic digestion is that reaction temperature is 35~37 DEG C, and rotating speed is 120~150rpm, and the time of anaerobic digestion is 20~28
My god.
In step (2) before anaerobic digestion, nitrogen is passed through into anaerobic digestion device and make it that no oxygen is present in device.
To when caused gas is collected in anaerobic digestion process, caused gas uses gas phase described in step (3)
The concentration of methane in chromatography determination gas phase, by measuring the volume of gas and the concentration of methane in gas, calculate methane
Volume.
The seed sludge is ripe anaerobically digested sludge.It is dirt to cultivate the kind mud being inoculated with ripe anaerobically digested sludge
The anaerobic sludge of water factory.
The Zero-valent Iron added in the present invention is a kind of strong reductant, can provide substantial amounts of electronics, in addition caused ferrous iron
The growth of ion pair microorganism has good facilitation, there are some researches show Zero-valent Iron can accelerate the degraded of larger molecular organicses,
Oxidation-reduction potential is reduced, promotes hydrolysis acidification and methane phase process.Ammonia can be produced in the degradation process of some itrogenous organic substances
Nitrogen adversely affects to methane phase process, and such as protein caused amino acid in degradation process can discharge ammonia nitrogen.And
Methanogen is very sensitive to ammonia nitrogen, and after ammonia nitrogen concentration exceedes finite concentration, methane phase process can be suppressed.It is living in the present invention
Property charcoal be a kind of larger material of specific area, have good suction-operated to pollutants such as ammonia nitrogens, also can be to strengthen micro- life in addition
Contact of the thing with substrate.The present invention adds activated carbon and Zero-valent Iron in anaerobic digester system simultaneously, and both in systems can shape
Into galvanic cell, electron exchange can not only be accelerated, promote organic matter degradation, and caused ferrous ion is microorganism growth needs
Important substance, have good facilitation effect to Hydrolysis Acidification and methane phase process.
The present invention compared with the existing technology, has the advantage that and beneficial effect:
The activated carbon and Zero-valent Iron that the present invention adds can be provided suitably due to the suction-operated of itself for microorganism
Place is grown, strengthens contact of the microorganism with substrate, promotes the decomposition of larger molecular organicses, while adsorb the unfavorable dirt such as ammonia nitrogen
Contaminate thing.Other Zero-valent Iron is a kind of stronger reducing agent of reproducibility, and the progress of reaction can be accelerated as electron donor, and
Zero-valent Iron can increase the activity of hydrolysis acidification bacterium, accelerate larger molecular organicses and change into small organic molecule.Zero-valent Iron can be with
It is used to reduce carbon dioxide methane phase directly as electron donor.
Activated carbon and Zero-valent Iron are added simultaneously, the Zero-valent Iron of low potential and high potential in the substrate for there are a large amount of electrolyte
Activated carbon produces potential difference, the galvanic cell of formation, and [H] of its caused electronics, ferrous ion and strong oxidizing property etc. disappears to anaerobism
Change has facilitation.Under slant acidity environment, iron powder can consume H+, system pH is increased, under neutral and slight alkali environment,
Galvanic cell can consume the remaining oxygen in system, reduce the ORP of anaerobic digester system, be provided suitably for methanogen
Growing environment.
Compared with individually addition activated carbon, in addition to electron donor is provided for anaerobic System, Zero-valent Iron and activated carbon shape
Into the reaction that occurs due to it under different pH environment of galvanic cell, the pH in course of reaction can be adjusted so that in reactor
PH maintain always in suitable scope, provide suitable growing environment for methanogen；In addition in galvanic interaction
The ferrous ion of release is the important component that the important substance that microorganism growth needs is also biology enzyme, strong caused by reaction
[H] of oxidisability can also promote degraded of the hydrolysis acidification bacterium to larger molecular organicses, and the substrate of abundance is provided for methane phase process.
Methane production has obtained significantly being lifted after digestion, by 1:10 ratios add activated carbon and Zero-valent Iron cumulative methane gas production is relative
In blank and individually add activated carbon 37.6% and 32.5% has been respectively increased.
Brief description of the drawings
Fig. 1 is the anaerobic digestion device schematic diagram of the present invention；1- Zero-valent Irons, 2- activated carbons, 3- tongses, 4- collection airbags,
5- breather pipes (i.e. stainless steel tube), 6- reaction bulbs (digest bottle), 7- bottle caps；
Fig. 2 is the curve of the average daily gas production of methane and time change under different Zero-valent Irons in embodiment and activated carbon addition
Figure；
Fig. 3 is methane cumulative gas production and time changing curve under different Zero-valent Irons in embodiment and activated carbon addition
Figure.
Embodiment
The present invention is described in further detail with reference to specific embodiment and accompanying drawing, but embodiments of the present invention
Not limited to this.
The schematic diagram of the anaerobic digestion device of the present invention is as shown in figure 1, including reaction bulb 6, cover the bottle of reaction bulb bottleneck
Lid 7, breather pipe 5, collection airbag 4, the bottle cap 7 are provided with through hole, and breather pipe 5 passes through through hole, and one end of breather pipe 5 is deeply reacted
In bottle 6, the other end is connected with collection airbag 4；The breather pipe is the breather pipe of stainless steel, and the anaerobic digestion device also includes rubber
Rubber cushion, the rubber blanket are arranged on the bottleneck of reaction bulb 6 with the contact surface of bottle cap 7, ensureing good air-tightness；It is described collection airbag 4 be
Aluminium foil collection airbag；The anaerobic digestion device also includes conduit, and conduit is provided with tongs 3 through the through hole on bottle cap, conduit
And entrainment, sealed after emptying.Mixing sludge, Zero-valent Iron 1 and activated carbon 2 are housed in the reaction bulb.
Embodiment
A kind of method for adding Zero-valent Iron (ZVI) and activated carbon (AC) reinforcing excess sludge anaerobic digestion methane phase simultaneously,
Comprise the following steps：
(1) zeroth order iron powder analyzes pure zeroth order iron powder (manufacturer is Tianjin good fortune morning chemical reagent factory), zeroth order to be commercially available
The size of iron powder is 60-100 mesh；Activated carbon is commercially available powdered activated carbon (without phosphorus) (Zhengzhou Newt agricultural technology Co., Ltd),
Size is 100-200 mesh；It is 75-85% excess sludge (sewage plants that solid content after being dehydrated is obtained from Guangzhou LiKau sewage treatment plants
Between dehydration be dehydrated after excess sludge), with distilled water adjust to solid content be 14%, it is adjusted after excess sludge；It will adjust
Excess sludge after section and seed sludge by volume 2:1 ratio mixes, and it is 6.5 to measure pH, does not adjust pH and then using distillation
Solid content reaches 12% after water causes mixing, obtains mixing sludge；The solid content of mixing sludge, volatile solid content and solvable
Property COD is respectively 12.3%, 46.3% and 6401.34mg/L；The seed sludge comes from the maturation of culture a couple of days
Anaerobically digested sludge (the kind mud of digested sludge inoculation is the sludge that Guangzhou drips Kau secondary sedimentation tank of sewage treatment work)；Seed sludge contains
Gu rate is 3.4%；
(2) 350g mixing sludges are added in anaerobic digestion device in reaction bulb, be separately added into different amounts of Zero-valent Iron and
Activated carbon, bottle cap is covered tightly, inject nitrogen 5min discharge oxygen into reaction bulb by conduit, it is close then to seal conduit with tongs
Envelope, breather pipe are connected with aluminium foil collection airbag；The addition of Zero-valent Iron+activated carbon is divided into following several ways：0g+0g (blank),
0g+1g(1gAC)、2g+1g(1gAC+2gZVI)、6g+1g(1gAC+6gZVI)、10g+1g(1gAC+10gZVI)；
(4) reaction bulb is placed in water-bath constant temperature oscillator, design temperature is 35 DEG C, rotating speed 130rpm, carries out anaerobism
Digestion reaction 28 days, biogas caused by daily aluminium foil collection airbag collection are simultaneously determined volume, determined using gas chromatography in gas phase
The concentration of methane, so as to by the way that methane volumetric is calculated.
Gas-chromatography selects TCD detectors, TCD detector operational factors:Injector temperature is 100 DEG C, and detector temperature is
200 DEG C, post case temperature is 300 DEG C.
Methane yield is determined using 100ml with a scale syringe.Pass through the total biogas volume and gas phase color measured
Obtained methane concentration is composed, methane volumetric is calculated.
Test result is as shown in Figures 2 and 3.Fig. 2 is methane day under different Zero-valent Irons in the present embodiment and activated carbon addition
The curve map of equal gas production and time change；Fig. 3 is methane accumulation production under different Zero-valent Irons in embodiment and activated carbon addition
Tolerance and time changing curve figure.
Intensive treatment is carried out to sludge with activated carbon and Zero-valent Iron, both can strengthen contact of the microorganism with substrate,
Zero-valent Iron is good electron donor as strong reductant, and galvanic cell is formed with activated carbon in reaction system, can be in system
Middle generation galvanic interaction, accelerate electron exchange, provide electronics for anaerobe, reduce oxidation-reduction potential, adjust pH, be
Methanogen provides suitable growth conditions.
From Fig. 2,3, when activated carbon and Zero-valent Iron dosage are 1g and 10g, methane cumulative production reaches maximum
2256.5ml, compared to blank and individually add activated carbon and add 37.6% and 32.5% respectively.The average daily gas production of methane exists
Reach peak within 9th day, shift to an earlier date 6 days compared to blank group.
Claims (8)
1. method that is a kind of while adding Zero-valent Iron and activated carbon reinforcing excess sludge anaerobic digestion methane phase, it is characterised in that：
(1) excess sludge, seed sludge and water are mixed, regulation pH is 6~7.5, and cause the solid content of mixture for 8~
12%, obtain mixing sludge；
(2) mixing sludge, activated carbon and Zero-valent Iron are added into anaerobic digestion device, then anaerobic digestion；
(3) caused gas in anaerobic digestion process is collected.
2. add Zero-valent Iron simultaneously according to claim 1 and activated carbon strengthens the side of excess sludge anaerobic digestion methane phase
Method, it is characterised in that：
Seed sludge described in step (1) is anaerobically digested sludge；The excess sludge is the excess sludge of town sewage plant.
3. add Zero-valent Iron simultaneously according to claim 1 and activated carbon strengthens the side of excess sludge anaerobic digestion methane phase
Method, it is characterised in that：Activated carbon described in step (1) and the mass ratio of Zero-valent Iron are 1：(2~20)；The activated carbon is with mixing
The mass ratio of sludge is 1：(300~350).
4. add Zero-valent Iron simultaneously according to claim 1 and activated carbon strengthens the side of excess sludge anaerobic digestion methane phase
Method, it is characterised in that：It is 13~15% that excess sludge described in step (1), which adopts water use regulation solid content, after adjusting solid content
The volume ratio of excess sludge and seed sludge is (2~4)：1；The solid content of the excess sludge is 75~85%.
5. add Zero-valent Iron simultaneously according to claim 1 and activated carbon strengthens the side of excess sludge anaerobic digestion methane phase
Method, it is characterised in that：Anaerobic digestion described in step (2) is that anaerobic digestion device is positioned in constant temperature oscillator to carry out anaerobism
Digestion, the condition of anaerobic digestion is that reaction temperature is 35~37 DEG C, and rotating speed is 120~150rpm, and the time of anaerobic digestion is 20
~28 days.
6. add Zero-valent Iron simultaneously according to claim 1 and activated carbon strengthens the side of excess sludge anaerobic digestion methane phase
Method, it is characterised in that：To when caused gas is collected in anaerobic digestion process, caused gas is adopted described in step (3)
The concentration of methane in gas phase is determined with gas chromatography, by measuring the volume of gas and the concentration of methane in gas, is calculated
The volume of methane.
7. add Zero-valent Iron simultaneously according to claim 1 and activated carbon strengthens the side of excess sludge anaerobic digestion methane phase
Method, it is characterised in that：In step (2) before anaerobic digestion, nitrogen is passed through into anaerobic digestion device and causes no oxygen in device
In the presence of.
8. add Zero-valent Iron simultaneously according to claim 1 and activated carbon strengthens the side of excess sludge anaerobic digestion methane phase
Method, it is characterised in that：The Zero-valent Iron is iron powder, 60~100 mesh；Activated carbon is powdered activated carbon, 100~200 mesh.
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Cited By (19)
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| CN108249725A (en) * | 2018-01-24 | 2018-07-06 | 上海交通大学 | A kind of method that pre fermentation strengthens excess sludge anaerobic digestion methane phase |
| CN108913541A (en) * | 2018-08-08 | 2018-11-30 | 农业部沼气科学研究所 | High ammonia nitrogen organic waste dry-type biogas fermentation device and its fermentation process |
| CN109161564A (en) * | 2018-09-03 | 2019-01-08 | 北京高能时代环境技术股份有限公司 | A kind of matrix liner and its preparation method and application for organic waste anaerobic dry fermentation |
| CN109207527A (en) * | 2018-08-08 | 2019-01-15 | 太原理工大学 | A kind of method that Zero-valent Iron inhibits kitchen garbage peracid phenomenon in high-load anaerobic digestion process |
| CN109626567A (en) * | 2019-02-27 | 2019-04-16 | 中国科学院过程工程研究所 | A kind of method of organic wastewater with difficult degradation thereby Anaerobic Treatment |
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| CN110759616A (en) * | 2019-11-15 | 2020-02-07 | 重庆大学 | Method for promoting anaerobic digestion of sludge by using α type ferric oxide modified bentonite |
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| CN108249725A (en) * | 2018-01-24 | 2018-07-06 | 上海交通大学 | A kind of method that pre fermentation strengthens excess sludge anaerobic digestion methane phase |
| CN108913541A (en) * | 2018-08-08 | 2018-11-30 | 农业部沼气科学研究所 | High ammonia nitrogen organic waste dry-type biogas fermentation device and its fermentation process |
| CN109207527A (en) * | 2018-08-08 | 2019-01-15 | 太原理工大学 | A kind of method that Zero-valent Iron inhibits kitchen garbage peracid phenomenon in high-load anaerobic digestion process |
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