CN107117789A - It is a kind of to improve anaerobic sludge digestion process methane production and strengthen the method for heavy metal stabilization process - Google Patents

It is a kind of to improve anaerobic sludge digestion process methane production and strengthen the method for heavy metal stabilization process Download PDF

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CN107117789A
CN107117789A CN201710420772.4A CN201710420772A CN107117789A CN 107117789 A CN107117789 A CN 107117789A CN 201710420772 A CN201710420772 A CN 201710420772A CN 107117789 A CN107117789 A CN 107117789A
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sludge
anaerobic
heavy metal
mno
heavy
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杨长明
张敏
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Tongji University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
    • 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
    • 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 present invention relates to a kind of method of methane yield and enhancing heavy metal stabilization process during raising urban mud anaerobic digestion.Using maize straw as raw material, under nitrogen protection, straw-stem active charcoal is prepared under 550 DEG C of pyrolysis temperatures.Using straw-stem active charcoal as carrier, by with KMnO4Solution reaction, the final active carbon functional material that load nanometer MnO is made.Acid phase is produced in anaerobic sludge digestion, the active carbon functional material for loading nanometer MnO is added in anaerobic reaction device in proportion, the cumulative gas production of methane during anaerobic sludge digestion can be significantly improved, the free state heavy metal for effectively adsorbing, being complexed in sludge simultaneously, the biological effectiveness and migration of heavy metal are reduced, strengthens the stabilization procedures of heavy metal.The present invention can be used in urban wastewater treatment firm excess sludge anaerobic digestion, effectively improve methane cumulative gas production, reduce the biological effectiveness of anaerobic sludge digestion heavy metals in process, strengthen the stabilization procedures of heavy metal.

Description

One kind improves anaerobic sludge digestion process methane production and enhancing heavy metal stabilization mistake The method of journey
Technical field
The invention belongs to Environmental Technology protection field, a kind of work(of activated carbon supported nanometer MnO particles is specifically related to synthesized Energy material, and this material is added to during sludge mesophilic anaerobic digestion, sludge anaerobic is disappeared after research addition functional material Change the influence of heavy metals in process form and aerogenesis.
Background technology
With the increase of domestic city wastewater discharge, produce substantial amounts of excess sludge and be discharged into natural environment By in September, 2010, China is completed sewage treatment plant 2630, day sewage treatment capacity reach 1.2 × 108 m3, production daily Go out about 11.2 × 107T dewatered sludge, and sludge quantity is produced it is expected that increasing with annual 10% speed.Therefore how the processing of science Disposing sludge is one of environmental area urgent problem.The utilization of resources of mud decrement-stabilisation-sludge turns at sludge Put the Main Trends of The Development of technology, statistics China there are about 80% sludge without stabilization processes, cause serious environment dirty Dye.The stabilization treatment mode of sludge mainly has aerobic compost, anaerobic digestion, anhydration and incineration etc..Contain substantial amounts of battalion in sludge Trace element necessary to organic matter and plant growth, such as N, P, K are supported, therefore anaerobic sludge digestion+land use turns into dirt The major way that mud stabilization processes are recycled with recycling.
Heavy metal and easy absorption migration are into sludge and with potential ecological risk in sewage disposal process.Study this hair Existing harm of the heavy metal to environment is not only relevant with its total amount, to a greater extent depending on its chemical form and biological effectiveness, The same metal that i.e. total amount is identical but form is different can be to triggering different environmental risks.Sludge cumulative volume subtracts after anaerobic digestion Less and energy gas methane is produced, therefore anaerobic digestion develops into the major way of specific resistance to filtration.But it is organic in sludge Matter content is limited and carbon-nitrogen rate（C/N）It is relatively low, cause volatile fatty acid in anaerobic digestion process（VFA）It is a large amount of with ammonia nitrogen amount Accumulation, reduces the activity of methane backeria, influences the efficiency of anaerobic sludge digestion.In order to further reduce a huge sum of money after anaerobic sludge digestion The biological effectiveness of category and the yield for improving energy gas methane, in addition it is also necessary to further adopt an effective measure.
By adding high carbon containing matter（Such as charcoal synthetic material）The C/N ratios of conditioning of mud, i.e. sludge and height is carbon containing Material carries out joint anaerobism and digested altogether, can improve first with active balance organic matter ratio and increase microorganism degradable biological amount Alkane gas production.Charcoal（Biochar）Be biomass under anoxic or anoxic condition, the class produced after being carbonized through high temperature pyrolysis Height aromatization, slightly solubility solid matter.Charcoal is made up of the stable aromatic compound of property, therefore with higher life Thing and chemical stability.Charcoal not only contains substantial amounts of charcoal, also containing more rich K（Kalium）、P（Phosphrous）、 The elements such as Mg (Magnesium)；Charcoal has in larger specific surface area, surface texture containing a large amount of exposed alkaline officials Can group（- OH, COOH- ,-O- ,-COO-）Deng；Charcoal may contain the material to microorganism catalysis or suppression, such as it discharges Ethene can be used as microbial inhibitor.Therefore charcoal can be used as soil conditioner, height containing charcoal source, can also be used as metal Complexing agent, fertilizer slow release carrier etc., good environmental effect is had been shown to have, soil remediation, water pollution is widely used in and controls Reason, solid charcoal emission reduction etc., by good reputation of the scientific circles titled with " black gold ".Mn oxide MnO has strong oxidizing property, can pass through oxidation The modes such as decomposition, oxidative coupling and heavy metal react.And research finds the Mn oxide and iron oxygen of identical specific surface area Compound, can form more stable metal complex key between Mn oxide and heavy metal.Therefore Mn oxide is widely used in In terms of water body purification, heavy metal adsorption and soil improvement.The present invention is raw after high temperature anaerobic is cracked using stalk as raw material Into straw-stem active charcoal, chemical modification, the activated carbon of synthesis load MnO nano particles are further carried out to straw-stem active charcoal（BC- MnO）Functional material.Based on the respective self character of activated carbon and Mn oxide, and combine anaerobic digestion microbial activity feature and Heavy metal stabilization process, is added to active carbon functional material during anaerobic sludge digestion, can effectively improve sludge and detest The methane yield of oxygen process, and modified active carbon functional material, can accelerate Heavy Metals in Sludge with complexing heavy metal Stabilization procedures, reduction Bioavailability of Metals and land use risk.
The content of the invention
It is an object of the invention to provide weight in methane yield, reduction sludge during one kind raising anaerobic sludge digestion The method of the biological effectiveness of metal.
A kind of anaerobic sludge digestion process methane yield that improves proposed by the present invention strengthens heavy metal stabilization mistake simultaneously The method of journey, is comprised the following steps that：
（1）Using maize straw as raw material, under nitrogen protection, 3.5h is pyrolyzed at a temperature of 550 DEG C~600 DEG C, corn stalk is made Stalk activated carbon（BC）, using corn stalk active carbon as carrier, by being reacted with liquor potassic permanganate, obtain load MnO nanometers The active carbon functional material (BC-MnO) of grain；Repeatedly washed through distilled water, air-dry after grind and cross 100 mesh sieves, obtain sludge weight Metal-stabilized reinforcing agent；For the high sludge of content of beary metal,（BC-MnO）Amount can be properly added, but no more than 3%, Otherwise it is unfavorable for anaerobic sludge digestion process；
（2）Acid phase is produced in urban mud anaerobic digestion, by step（1）Obtained sludge heavy-metal stabilizes reinforcing agent and is added to In anaerobic digestion device, anaerobic fermentation altogether is carried out with anaerobically digested sludge；Wherein：With quality dry weight ratio, sludge heavy-metal is steady Surely changing the dosage of reinforcing agent must control within 3%；In anaerobic digestion process, sludge heavy-metal stabilizes reinforcing agent using work Property the abundant functional group in the loose structure of charcoal itself, surface and MnO nano particles strong reducing property, with anaerobically digested sludge middle reaches Absorption, complexing and redox reaction occur for the heavy metal of amorph, change the heavy metal existing forms in anaerobically digested sludge, drop The biological effectiveness of low heavy metal, and then the stabilization procedures of Heavy Metals in Sludge are realized, it is the soil money of anaerobically digested sludge Sourceization utilizes and provides theoretical foundation；Meanwhile, the active carbon functional material of addition（BC-MnO）Methanogen can effectively be strengthened Activity, increases methane production；When methane aerogenesis is tapered off, represent that reaction terminates.
In the present invention, step（1）The mass ratio of middle corn stalk active carbon and potassium permanganate is 1:15.
In the present invention, step（2）Middle anaerobically digested sludge is necessary for municipal sludge, its heavy metal and other every pollutants Concentration is below agricultural sludge standard（GB4284-1984）.
In the present invention, step（1）Middle active carbon functional material（BC-MnO）Must be through being fully ground, and 100 mesh sieves are crossed, make Its particle diameter is less than 0.15mm;.
In the present invention, test of many times conclusion shows, function nano material（BC-MnO）The addition time be preferably that anaerobism disappears 3d~5d after change, now anaerobic System tend to balance, anaerobic sludge digestion is in production acid phase, the weight in sludge The content that metal is in free state is high, it is easy to is adsorbed and captures by functional material, increases the stability of Heavy Metals in Sludge.
In the present invention, the stalk content of organic matter for making biological carbon materials is high, is so conducive to having in conditioning of mud Machine matter content and C/N ratios, the activity of catalytic methane bacterium improve volatile fatty acid（VFA）Conversion ratio, increase methane aerogenesis Amount.
In the present invention, the sludge heavy-metal stabilization material used is using stalk as raw material, in Muffle furnace N2Under protection, The straw biological charcoal that Pintsch process is made, the charcoal has the cavernous structure of good rule, and is evenly distributed, and is follow-up The load of Mn oxide provides good condition.
By adopting the above-described technical solution, the present invention has advantages below：
1st, a kind of new activated carbon supported nano oxidized sub- manganese is synthesized in the present invention（BC-MnO）Functional material, activated carbon Straw under high temperature anaerobic cracking after handling is synthesized, and materials are extensive, pollution-free, realize recycling.
2nd, because function nano material is using straw biological charcoal as substrate, poisonous and harmful substance is less, is split by high temperature anaerobic Xie Hou, its a small amount of heavy metal included leaching experiments that are cured show, it is undetected that it extracts liquid heavy metal, what it contained The detection level of polycyclic arene compound is less than detection line.The Mn contents of its synthetic material are 5% or so, the addition of material Control itself is 3%（Quality dry weight ratio）Within, test result indicates that Mn content is not resulted within control line in material Secondary pollution.
3rd, active sludge carbon relies on its stable chemical property, high-specific surface area, superior absorption property, material source The advantages such as environmental protection are widely used as adsorbent, catalyst, catalyst carrier etc.；Surname is further changed to charcoal, in its structure MnO in load, MnO have strong oxidizing property, and stable metal complex key can be formed between heavy metal.（BC-MnO）Have work concurrently The advantageous characteristic of property both charcoal and MnO.
4th, due to addition functional material（BC-MnO）Afterwards, the content of organic matter in sludge is added, C/N ratios, methane backeria is balanced Increased activity, increases the conversion efficiency of volatile fatty acid, improves methane yield；Activated carbon has well in itself simultaneously Containing-COOH in absorption property, surface texture, MnO has strong oxidizing property and catalysis in the functional group, and material such as-OH ,-O- Property, the methane yield in anaerobic sludge digestion journey can be increased, and the biological effectiveness of Heavy Metals in Sludge is reduced, realize dirty Mud resource land use.
5th, the anaerobic sludge digestion process addition functional material that the present invention is taken（BC-MnO）, can effectively capture life The conversion of microbial activity and organic matter in thing validity and the stronger free state heavy metal of toxicity, enhancing system, lifts methane Gas production, and shorten the anaerobic digestion cycle.
6th, in addition, after sludge is granted in soil after stabilizing, the charcoal added has to the physicochemical property of soil Obvious improvement result；Manganese element is to add appropriate manganese element in nutrient necessary to microorganism and plant growth, soil Soil Microorganism activity is effectively increased, promotes plant growth.
Brief description of the drawings
Fig. 1 is the XRD of straw-stem active charcoal after load manganese monoxide nano particle.
Fig. 2 is SEM electron-microscope scanning figures.Note：A is straw-stem active charcoal SEM scanning figures after pretreatment；B is MnO nanometers of load Particle（BC-MnO）SEM figure.
Fig. 3 is accumulation methane production in R1, R2, R3, R4 and R5 slaking apparatus.Note：R1 be without（BC-MnO）Sky White control group； R2：150g sludge+0.75g（BC-MnO）Active carbon nano material； R3：The g of 150g sludge+1.5（BC- MnO）Active carbon nano material；R4：150 g sludge+3g（BC-MnO）Active carbon nano material；R5：150g sludge+4.5g （BC-MnO）Active carbon nano material.
Fig. 4 is the relative amount of heavy metal in sludge aqueous phase after R1, R2, R3, R4 and R5 anaerobic digestion.
Fig. 5 is distributed for Heavy Metals in sludge solid phase after R1, R2, R3, R4 and R5 anaerobic digestion.Note：F1 is water-soluble state Metal；F2 is exchangeable species metal；F3 is carbonate combine state metal；F4 is iron and manganese oxides reference state metal；F5 is to have Machine sulfide reference state metal；F6 is residual form metal.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1：The present embodiment is comprised the following steps that：
Activated Carbon Pretreatment:Stalk is immersed in ZnCl2Activated in solution（Stalk and ZnCl2Mass ratio is 1:2）, magnetic force stirs Mix and centrifuged after 7h（4000r ·min-1）, oven for drying.Sample is carbonized using OTF-1200x types vacuum tube furnace after drying 180min.It is 550 DEG C, N to set carbonization temperature2Make protection gas, heating rate is 20 DEG C of min-1.Obtained crude samples are spent Ionized water cyclic washing, low temperature drying to constant weight.
Load the activated carbon of MnO nano materials（BC-MnO）Preparation：Pretreated milled 100 mesh sieve of activated carbon, 6g activated carbons are taken to be immersed in KMnO4In solution, make BC and KMnO4Mass ratio be 1：15.Under suspension normal temperature ultrasound 3h after 650 DEG C of calcination 1h in tube furnace, deionized water cyclic washing, vacuum freeze drying are transferred to after drying in oven, drying.Grinding, 100 mesh mesh screens are crossed, are finally given（BC-MnO）Heavy metal stabilizer.
Table 1 is element composition, specific surface area and the aperture parameters of activated carbon after corn stalk active carbon and load.Activated carbon Specific surface area be 59.8 m2/ g,（BC-MnO）Specific surface area be 9.32 m2/ g, it can be seen that with activated carbon phase after load Than the specific surface area after load MnO nano particles greatly reduces, and this is due to be passed through again after activated carbon soaks through liquor potassic permanganate High temperature anaerobic is cracked, and itself is destructurized（KMnO4With strong oxidizing property）, the MnO nano particles of formation are present in activity In the duct and hole of charcoal（See that SEM schemes）, cause the pore structure of activated carbon to change, show that MnO nano particles are successfully loaded On the activated carbon.
Samples C (%) H (%) N (%) S (%) Mn (%) SBET (m2/g) Pore width (nm)
BC 83.2 1.25 0.82 2.26 -- 59.8 21.3
BC-MnO 75.6 0.37 0.75 1.98
The element of table 1 composition, specific surface area and aperture
BC-MnO nano material XRD analysis：
Fig. 1 is the XRD of activated carbon after load manganese monoxide nano particle.2 θ be 26.6 ° at be activated carbon（BC）Feature spread out Penetrate peak；It is the characteristic diffraction peak for loading MnO nano particles at 35.0 °, 40.6 °, 58.8 °, 70.2 ° and 73.96 ° that 2 θ, which are,. XRD Most strong diffraction maximum is in 2 θ=40.6 ° in figure, and the Average Particle Diameters for calculating MnO nano particles by Scherrer formula are 9.86nm.
SEM is analyzed：
Fig. 2 (a),（b）It is straw-stem active charcoal, the SEM figures of load MnO nano particles (BC-MnO) after pretreatment respectively.As schemed Shown, many nano level fine particles are dispersed in activated carbon surface and pore structure.Figure（a）It is shown, straw-stem active charcoal table Face gloss is consistent, and surface is discontinuously scattered here and there to adsorbing the pore structure played a major role.Figure（b）It is shown, nano particle MnO It is irregular to be supported in activated carbon surface and pore structure, and larger gap is there is between particle, be conducive to a huge sum of money in sludge The absorption solidification of category.
The implementation case employs height containing solid sludge mesophilic anaerobic digestion technique, and anaerobically digested sludge is derived from the sewage of Hefei Manage the dewatered sludge of factory, main shale index：TS 11.3%, TS 57.6%, pH 7.3, C/N 4.6%, Heavy Metals Content (mg/Kg)：Cr (226.9), Ni (163.1), Cd (62.9) Cu (186.9), Zn (2011.5), experiment With kind mud of the seed sludge from the operation 3 months of laboratory ferment tank.Before experiment, N is used2The purging experiment min of shaking flask 15, To exclude oxygen, it is ensured that anaerobic or anaerobic environment, digestion temperature is（35±1）℃.R1 is set：150 g sludge are without activity Carbon nano material（Control）； R2：150g sludge+0.75g (BC-MnO) activity carbon nano materials（0.5 %）； R3：150g The g of sludge+1.5 (BC-MnO) activity carbon nano materials（ 1%）；R4：150 g sludge+3g (BC-MnO) activated carbons nanometer material Material（2%）；R5：150g sludge+4.5g (BC-MnO) activity carbon nano materials (3%).In anaerobic digestion running, often Day entry gas production, surveys gases methane content in every three days.Meanwhile, 3d, 6d, 9d, 12d, the 15d of plant running, 18d, 23d, 28d, 33d mud extraction sample about 50mL, determine wherein total metalses and fractions distribution, while determining mud sample PH, VS, TS, VFA, basicity and ammonia-nitrogen content.After anaerobic digestion terminates, morphological analysis is carried out to the heavy metal in body refuse.Experiment As a result Fig. 3 is seen.Total methane production R1, R2, R3, R4, R5 are 85.21,99.02,108.29,66.79 respectively 、 40.76 L Kg -1VS .R3 methane contents are most（Than blank R1 increases by 27.09）, R5 methane contents are minimum（Subtract than blank R1 Few 52.16%）.Test result indicates that, appropriate addition BC-MnO can promote methane to produce, excessive to suppress methane production.Addition In material BC-MnO structures, activated carbon is in itself containing abundant nutrition organic matter, and it, which decomposes intermediate product humus, to promote The work of methanogen；Next, under normal circumstances itself alkalescence is presented in activated carbon, can alleviate a large amount of the having of hydrolysis acid-producing bacteria generation The sour suppression that machine acid is caused, promotes the conversion of volatile fatty acid, increases methane factor of created gase.Meanwhile, contain in added material Some manganese elements are the necessary nutrients of microorganism growth institute, and appropriate addition can strengthen the activity of microorganism, improve hydrolysis and produce The conversion ratio of the nutrition organic matter of sour bacterium and methanogen.If on the contrary, being excessively added, excessive manganese element is contained in system, Beyond the tolerance range of microbial bacteria, trigger the Ecotoxicologies such as methane backeria, hydrolysis acid-producing bacteria, anaerobic System is destroyed, Gas production, which is reduced, even stops aerogenesis.
It is equal into aqueous liquid content of beary metal by Fig. 4 it will be evident that after anaerobic digestion added material (BC-MnO) It is fewer than R1, and addition is more, the heavy metal amount into water-soluble state is fewer.Test result indicates that activated carbon functional material adds Plus the heavy metal in fixed sludge can be effectively adsorbed, the toxicity of Heavy Metals in Sludge is reduced, metal dissolving amount is reduced.
R1, R2, R3, R4, R5 system solid phase Heavy Metals distribution map after anaerobic sludge digestion shown in Fig. 5.Detest Oxygen digestion addition activated carbon functional material（R2 、 R3 、 R4 、 R5）Middle metal water-soluble state and ion-exchange state content are reduced； Heavy metal Fe-Mn oxidizables content increase in R2, R3 contrast R1, organic sulfur compound reference state content is reduced；R4 and R5 Organically combine state and the increase of carbonate combine state content in R2 and R3 are contrasted, Fe-Mn reference states are reduced.In R2 and R3 systems Methane production is higher than R1, shows anaerobic digestion production acid phase volatile fatty acid conversion ratio increase, and this stage is conducive to heavy metal Converted from organically combine state to Fe-Mn reference states；On the contrary, in R4 and R5 systems, methane production is less than blank R1, shows micro- life Thing methane backeria activity inhibited, the conversion ratio reduction of volatile fatty acid, heavy metal is more to be existed with organically combine state.
Table 2 show the transport coefficient of heavy metal before and after anaerobic sludge digestion（MF）Value, MF values are F1, F2 and F3 content The ratio of sum and all form sums of heavy metal.Test result indicates that, after addition activated carbon functional material, can substantially it change The fractions distribution of Heavy Metals in Sludge, turns from labile state to Fe-Mn reference states and organically combine state with higher stability Change, reduce the biological effectiveness of heavy metal, obvious the tending towards stability of Heavy Metals in Sludge.
Heavy metal transformation coefficient before and after the anaerobic sludge digestion of table 2
The invention discloses a kind of anaerobic sludge digestion heavy metals in process stabilisation function material, add in anaerobic System Enter the material, microbial activity can be improved, increase the cumulative gas production of methane, and make the heavy metal in sludge by labile state Converted to stable state, the biological effectiveness and migration of Heavy Metals in Sludge are reduced, beneficial to the recycling of sludge.

Claims (5)

1. a kind of anaerobic sludge digestion process methane yield that improves strengthens the method for heavy metal stabilization process, its feature simultaneously It is to comprise the following steps that：
（1）Using maize straw as raw material, under nitrogen protection, 3.5h is pyrolyzed at a temperature of 550 DEG C~600 DEG C, corn stalk is made Stalk activated carbon（BC）, using corn stalk active carbon as carrier, by being reacted with liquor potassic permanganate, obtain load MnO nanometers The active carbon functional material (BC-MnO) of grain；Repeatedly washed through distilled water, air-dry after grind and cross 100 mesh sieves, obtain sludge weight Metal-stabilized reinforcing agent；
（2）Acid phase is produced in urban mud anaerobic digestion, by step（1）Obtained sludge heavy-metal stabilizes reinforcing agent and is added to In anaerobic digestion device, anaerobic fermentation altogether is carried out with sludge；Wherein：With quality dry weight ratio, sludge heavy-metal stabilizes enhancing The dosage of agent must be controlled within 3%；In anaerobic digestion process, sludge heavy-metal stabilizes reinforcing agent and utilizes activated carbon itself Loose structure, the strong reducing property of the abundant functional group in surface and MnO nano particles, the weight with free state in anaerobically digested sludge Absorption, complexing and redox reaction occur for metal, change the heavy metal existing forms in anaerobically digested sludge, reduce heavy metal Biological effectiveness, and then realize the stabilization procedures of Heavy Metals in Sludge, be that the land resourceization of anaerobically digested sludge is utilized Theoretical foundation is provided；Meanwhile, the active carbon functional material of addition（BC-MnO）The activity of methanogen can effectively be strengthened, increased Methane production；Methane yield is tapered off behind after anaerobic digestion starts the 33rd day, represents that anaerobic digestion process reaction terminates.
2. the method according to claim 1, it is characterised in that step（1）Middle corn stalk active carbon and potassium permanganate Mass ratio is 1:15.
3. the method according to claim 1, it is characterised in that step（2）Middle anaerobically digested sludge is necessary for municipal sludge, Its heavy metal and other every pollutant concentrations are below agricultural sludge standard（GB4284-1984）.
4. the method according to claim 1, it is characterised in that step（1）Middle active carbon functional material（BC-MnO）It is necessary Through being fully ground, and 100 mesh sieves are crossed, its particle diameter is less than 0.15mm.
5. the method according to claim 1, it is characterised in that sludge heavy-metal stabilizes the addition time of reinforcing agent to detest Postdigestive 3d~the 5d of oxygen, now anaerobic System tend to balance, anaerobic sludge digestion is in production acid phase, in sludge Heavy metal be in free state content it is high, it is easy to adsorbed and capture by functional material, increase the stability of Heavy Metals in Sludge.
CN201710420772.4A 2017-06-07 2017-06-07 It is a kind of to improve anaerobic sludge digestion process methane production and strengthen the method for heavy metal stabilization process Pending CN107117789A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
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CN109368986A (en) * 2018-12-06 2019-02-22 齐鲁工业大学 It is a kind of to promote excess sludge digestion production H using charcoal2The method of yield
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CN112142284A (en) * 2020-08-26 2020-12-29 同济大学 Method for improving methane yield of anaerobic digestion of sludge and simultaneously reducing heavy metal ecotoxicity
CN114749150A (en) * 2022-04-28 2022-07-15 南开大学 Biochar loaded manganese oxide composite material and preparation method and application thereof
CN114849646A (en) * 2022-05-07 2022-08-05 南京信息工程大学 Modified gasification ash activated carbon adsorption material
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CN108273496A (en) * 2018-03-16 2018-07-13 西南大学 A kind of preparation method and applications of the bionic enzyme based on bacteria cellulose
CN108927107A (en) * 2018-07-25 2018-12-04 中央民族大学 A kind of straw base heavy-metal adsorption material and preparation method thereof
CN109399882A (en) * 2018-10-18 2019-03-01 山东省科学院能源研究所 A method of nano zine oxide is reduced to excess sludge anaerobic fermentation toxicity
CN109368986A (en) * 2018-12-06 2019-02-22 齐鲁工业大学 It is a kind of to promote excess sludge digestion production H using charcoal2The method of yield
CN111876173A (en) * 2020-07-14 2020-11-03 大连理工大学 Preparation method of iron-containing sludge-based biochar material and application of iron-containing sludge-based biochar material in anaerobic digestion
CN112142284A (en) * 2020-08-26 2020-12-29 同济大学 Method for improving methane yield of anaerobic digestion of sludge and simultaneously reducing heavy metal ecotoxicity
CN112142284B (en) * 2020-08-26 2021-11-02 同济大学 Method for improving methane yield of anaerobic digestion of sludge and simultaneously reducing heavy metal ecotoxicity
NL2031154B1 (en) * 2022-03-03 2023-09-08 Univ Hohai Modified straw biochar and preparation method and application thereof
CN114749150A (en) * 2022-04-28 2022-07-15 南开大学 Biochar loaded manganese oxide composite material and preparation method and application thereof
CN114849646A (en) * 2022-05-07 2022-08-05 南京信息工程大学 Modified gasification ash activated carbon adsorption material

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