CN107010722A - A kind of method that two-stage anaerobic digestion handles molasses alcohol waste water - Google Patents

A kind of method that two-stage anaerobic digestion handles molasses alcohol waste water Download PDF

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Publication number
CN107010722A
CN107010722A CN201710190042.XA CN201710190042A CN107010722A CN 107010722 A CN107010722 A CN 107010722A CN 201710190042 A CN201710190042 A CN 201710190042A CN 107010722 A CN107010722 A CN 107010722A
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uasb
waste water
level
reactor
anaerobic
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CN107010722B (en
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赵明星
陈阳
阮文权
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Jiangsu Masheng Biotechnology Co ltd
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Jiangnan 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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
    • 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
    • C02F3/286—Anaerobic digestion processes including two or more steps
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • C02F2103/325—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from processes relating to the production of wine products
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

The invention discloses a kind of method that two-stage anaerobic digestion handles molasses alcohol waste water, belong to waste water dis posal, environmental purification processing technology field.The present invention carries out anaerobic bio-treated by two stage UASB reactor to molasses alcohol waste water, has not only effectively disposed molasses alcohol waste water, and realize the innoxious and recycling of molasses alcohol waste water.

Description

A kind of method that two-stage anaerobic digestion handles molasses alcohol waste water
Technical field
The present invention relates to a kind of method that two-stage anaerobic digestion handles molasses alcohol waste water, belong to waste water dis posal, environmental protection only Change processing technology field.
Background technology
Molasses alcohol waste water organic concentration and sulfate concentration are high, and colourity is larger, and its COD (COD) is 8~120,000 mg/L, sulfate concentration reaches 6000~10000mg/L.Often production 1t alcohol discharges about 15t waste liquids.At present, it is domestic Have studied a variety of molasses alcohol water process or the technique and technology of recycling outside, such as anaerobic process, aerobic method, agriculture fill method and Fodder making method etc., wherein anaerobic biological process have processing load height, and floor space is small, low power consumption and other advantages, in anaerobic waste water It is widely used in processing.
UASB reactors are a kind of efficient anaerobic devices, strong with capacity of resisting impact load, stable, manager Just, the low advantage of operating cost, is widely used in the processing of molasses alcohol waste water.But in anaerobic bio-treated process In, the sulfate of molasses alcohol waste water middle and high concentration can have a negative impact to Anaerobic Digestion effect, one side sulfate radical The larger sulfide of generation toxicity can be reduced by sulfate reducing bacteria (SRB) so that methanogen (MPB) and SRB in sludge Activity is suppressed, and another aspect SRB utilizes substrate during sulfate radical is reduced, so as to produce Competition with MPB.Sulphur The reduzate sulfide of acid group can combine the H in waste water+Generate H2S, this can cause methane quantity to decline to a great extent, or even can make to detest Oxygen processing procedure fails.And in single-stage anaerobic reactor, because there is primary suppression and secondary inhibitory action to MPB in SRB, Reactor operation is had a negative impact and even result in operation failure.
In view of the above-mentioned problems, mainly being pre-processed to waste water for current solution, such as active by adding Charcoal carries out absorption sulfate radical in waste water or addition chemical agent such as barium salt, Ca (OH)2Precipitate, directly reach Deng being generated with sulfate radical Reduce the purpose of sulfate radical in waste water；But the investment of this physical method is larger, be not suitable for extensive processing molasses alcohol Water, and active carbon adsorption also can CO absorption D etc., influence producing methane through anaerobic fermentation.Also two-phase anaerobic technology, will Produce hydrogen production acid phase and the methane phase stage is separated, carried out respectively in two anaerobic reactors.Diphasic anaerobic technique is needed to anti- Answer condition to be controlled, such as the pH of the sour phase of reduction production hydrogen production, prevent methanogen from carrying out metabolic activity, to ensure two reactions Dominant microflora in device is respectively acid-producing bacteria group and methanogen floras.
The content of the invention
Technical problem solved by the invention is to provide a kind of method that two stage UASB handles molasses alcohol waste water.The present invention Technical scheme be by molasses alcohol waste water by two stage UASB reactor carry out Anaerobic Digestion, reach reduction waste water in have The effect of organic pollutants concentration.
Two stage UASB reactor of the present invention be two series connection UASB reactors, be respectively one-level UASB reactors and Two grades of UASB reactors；The one-level anaerobic UASB reactor dischargeable capacity is 12L, and wherein reaction zone volume is 7.7L, precipitation Area's volume is 4.3L, and secondary anaerobic UASB reactors dischargeable capacity is 10L, and wherein reaction zone volume is 6.6L, settling zone volume For 3.4L.
A certain amount of anaerobic grain sludge is inoculated with to one-level UASB reactors and two grades of UASB reactors, allowing need to be to be processed Molasses alcohol waste water successively flows through two stage UASB reactor, carries out producing methane through anaerobic fermentation；The temperature of two stage UASB reactor is 35 DEG C, the initial pH into the waste water of one-level UASB reactors with sodium carbonate liquor is adjusted to 7.20~7.50, useless by changing The extension rate adjustment inlet COD loading of water is respectively 2,4,6,8,16,22,24 and 28kg/ (m3D), highest COD loads bar Under part, molasses alcohol waste water has still provided for dilution.One-level UASB reactor seed sludges amount is 4L, two grades of UASB reactors inoculations Sludge quantity is 3L, is intake as one-level UASB reactor water outlets；Hydraulic detention time (HRT) is 24h and keeps constant, and waste water is equal Reactor is entered by the water distribution system of the reacted device bottom of feed pump.
The present invention uses two stage UASB anaerobic treatment process, it is not necessary to separate production hydrogen production acid phase and methane phase stage, The reaction in two stages is carried out in one-level UASB reactors and two grades of UASB reactors, by one-level UASB reactor for treatment Waste water afterwards carries out anaerobic fermentation again by two grades of UASB reactors.After two stage UASB reactor for treatment, the COD of waste water and Sulfate radical total removal rate is stablized 65% and 88% or so respectively, one-level Anaerobic Treatment to the removal contribution of COD and sulfate radical compared with Greatly, clearance is respectively 45% and 70% or so, and aerogenesis effect is also preferable, and daily output tolerance reaches 35L or so, methane content 70% Left and right.Secondary anaerobic processing is 30% or so to COD clearance, and 63% or so is maintained to the clearance of sulfate radical.Work as COD Load reaches 28kg/ (m3When d), one-level anaerobism inlet COD concentration is 28000mg/L, sulfate concentration about 2600mg/L, warp It is 14000mg/L or so to cross COD concentration in two-stage anaerobic digestion processing, one-level anaerobic effluent, and sulfate concentration is less than 788mg/ L, COD concentration is 9000mg/L or so in secondary anaerobic water outlet, and sulfate concentration is less than 300mg/L.One-level anaerobic effluent and two Level anaerobic effluent sulfide concentration is respectively 568.8mg/L and 720mg/L.
The technique of the present invention is simple, it is easy to operates, and improves biogas yield and the biomass energy rate of recovery, improves molasses The Anaerobic Treatment effect of alcohol waste water.The present invention has good research application prospect.
Brief description of the drawings
Fig. 1 experimental provision sketches
Fig. 2 anaerobic effluents pH change
The situation of change of Fig. 3 Inlet and outlet water COD concentration and COD clearances
The change of Fig. 4 one-level anaerobic digestion methane production amounts and methane content
Average factor of created gase situation of change under Fig. 5 difference inlet COD loadings
The situation of change of Fig. 6 Inlet and outlet waters sulfate concentration and sulfate radical clearance
The change of Fig. 7 anaerobic effluent sulfide concentrations
The situation of change of electron current distribution in Fig. 8 one-level anaerobic digestion process
Embodiment
The experimental provision sketch of embodiment 1
The temperature of reaction system of two stage UASB reactor for treatment molasses alcohol waste water is 35 DEG C, initial pH sodium carbonate of intaking Solution is adjusted to 7.20~7.50.The biogas of generation is measured after water-sealed drainage bottle desulfurization by wet gas flow meter, then uses gas collection Bag, which is collected, determines gas componant and content.Before and after anaerobic digestion reaction, to the pH of waste water, COD concentration, sulfate concentration and vulcanization Thing concentration is measured；After reaction terminates, biogas volume and methane content are measured, assay method is using country's mark Quasi- method is analyzed (table 1).
The analysis project of table 1 and method
Experimental design is that one-level anaerobic UASB reactor dischargeable capacity is 12L, and wherein reaction zone volume is 7.7L, settling zone Volume is 4.3L, and secondary anaerobic UASB reactors dischargeable capacity is 10L, and wherein reaction zone volume is 6.6L, and settling zone volume is 3.4L.One-level UASB reactor seed sludges amount is 4L, is respectively by the extension rate adjustment inlet COD loading for changing waste water 0~6d 2kg/ (m3D), 7~12d4kg/ (m3D), 13~18d 6kg/ (m3D), 19~26d 8kg/ (m3·d)、27 ~34d 16kg/ (m3D), 35~42d 22kg/ (m3D), 43~50d 24kg/ (m3D) with 51~60d 28kg/ (m3·d).The use of sodium carbonate and sodium acid carbonate regulation inlet flow-patterm is 7.20~7.50；Two grades of UASB reactor seed sludge amounts are 3L, intakes as one-level UASB reactor water outlets；Waste water enters reactor, water by the water distribution system of the reacted device bottom of feed pump The power residence time, (HRT) was 24h.
The anaerobic effluent pH of embodiment 2 change
The pH of two-stage anaerobic reactor water outlet is above the pH into water as shown in Figure 2, and is presented with the lifting of load The trend of liter, one-level anaerobic effluent pH is up to 8.40, and secondary anaerobic water outlet is up to 9.03.The reason for water outlet pH value is raised can Can be that organic acid concentration is higher into water, in anaerobic digestion process, MPB and SRB are directly carried out using the organic acid in waste water The metabolic activity such as methane phase and sulfate radical reduction, acid-producing bacteria is in weak position, and metabolic activity is suppressed, organic acid in waste water Concentration is reduced.
The situation of change of the Inlet and outlet water COD concentration of embodiment 3 and COD clearances
The degraded situation of waste water COD is as shown in Figure 3.From Fig. 3-a, with the raising of inlet COD concentration, one-level anaerobism COD removal takes the lead in reducing and gradually stablizing 45% or so after raising in digestion process.Reactor initial operating stage one-level anaerobism Process COD clearances are relatively low, this be probably in sludge microorganism do not adapt to molasses alcohol waste water also；Reactor is run to 9d When, one-level COD clearances rise to 58.3%, illustrate that microorganism adapts to waste water substantially, can effectively utilize in waste water Organic matter carries out metabolic activity；When reactor is run to 18d, one-level COD clearances, which reach, is 71% to the maximum.Water inlet sulfate radical Concentration increases with the lifting of load, and the sulfide concentration that SRB reduction sulfate radicals are produced becomes big, and the microorganism in system is lived Property produce suppression, this cause COD one-levels clearance reduction；And COD clearances finally keep stable, show one-level anaerobic digestion system System is not because sulfide concentration is raised and collapses, and anaerobe can still provide for metabolic activity.
Fig. 3-b show that bis- grades of clearances of COD and total removal rate in trend stable after falling before, are finally stablized respectively 30% and 65% or so.As one-level anaerobism inlet COD concentration about 28000mg/L, one-level anaerobic effluent COD concentration is about 14000mg/L, secondary anaerobic effluent COD concentration is 9000mg/L or so.
The change of the one-level anaerobic digestion methane production amount of embodiment 4 and methane content
Situation of change such as Fig. 4 of the daily gas production of one-level anaerobic digestion process and methane content of bilogas.Produce daily tolerance with The lifting of load and increase, when reactor load brings up to 28kg/ (m3When d), daily output tolerance reaches 35L or so.Biogas The variation tendency that middle methane content is stablized afterwards with the lifting of load in first rising, reactor initial operating stage, load is 2kg/ (m3D), methane content is about 55%, when load brings up to 16kg/ (m3D) after, methane content of bilogas is about 70% and protected It is fixed to keep steady.
The biogas of secondary anaerobic digestion process generation is not collected into experiment, analysis reason is probably one-level anaerobic effluent pH It is higher, the water inlet that pH digests directly as secondary anaerobic is not adjusted, can produce inhibitory action to the MPB activity in sludge, and When load is relatively low, to organic matter removal effect in waste water preferably, this is also resulted in can be micro- in water outlet for one-level anaerobic digestion process The content of organics of biological utilisation is less, with the lifting of one-level anaerobic digestion process load, and water inlet sulfate concentration is also improved, Sulfide content increases in one-level anaerobic effluent, and the sulfide of high concentration can also be produced to MPB poisons and inhibitory action so that production Methane activity is weaker or even stops.
Average factor of created gase situation of change under the different inlet COD loadings of embodiment 5
Factor of created gase can reflect the gas generation property of reactor, and factor of created gase such as Fig. 5 of one-level anaerobic digestion process is produced as seen from the figure Gas rate tends towards stability again as Load lifting first reduces to raise afterwards.Load is 2kg/ (m3When d), factor of created gase is 265.6mL/ GCOD, because the MPB biomass in initial operating stage sludge is very big, is in the ascendance in substrate competition.Load is 8kg/(m3When d), the minimum 122.5mL/gCOD of factor of created gase illustrates that inlet COD concentration is relatively low, microorganism is available organic When object amount is not enough, SRB activity is higher, dominant when competing substrate with MPB, reactor initial operating stage SRB multiplication rates faster, More organic matters are utilized by SRB, cause reactor gas producing efficiency step-down.With the further lifting of load, factor of created gase is improved To 220mL/gCOD, and do not occur larger fluctuation, illustrate when substrate is sufficient, SRB Competitive assays MPB is influenceed compared with It is small.
The situation of change of the Inlet and outlet water sulfate concentration of embodiment 6 and sulfate radical clearance
The situation of change of sulfate radical in waste water concentration such as Fig. 6, the concentration of sulfate radical in waste water is lifted with inlet COD loading Become larger, initial concentration is about 200mg/L, COD Load liftings to 28kg/ (m3When d), sulfate concentration about 2600mg/ L, is handled by two-stage anaerobic digestion, and sulfate concentration is less than 300mg/L in secondary anaerobic water outlet.Reactor is understood by Fig. 6-b The preceding 30d of operation, sulfate radical total removal rate is reduced with the increase of water inlet sulfate concentration, afterwards, sulfate radical total removal rate Stabilization is 88% or so.
Fig. 6-a show that the sulfate radical in waste water is mainly degraded in one-level anaerobic digestion process, in one-level anaerobic effluent Sulfate concentration is not less than 800mg/L, Load lifting to 28kg/ (m3D) after, sulfate concentration is 2592mg/L to the maximum, goes out Water concentration is 788mg/L, and one-level clearance tends towards stability afterwards as Load lifting is first reduced, and is eventually held in 70% or so.By Fig. 6-b understand bis- grades of clearances of preceding 44d of reactor operation as Load lifting is in elevated trend, minimum removal after first reducing Rate is 42.1%, appears in 25d；Clearance is relatively stable after 44d, is maintained at 63% or so.
Observe that one-level UASB reactors have preferable removal effect to COD and sulfate radical in this experiment, this explanation exists In one-level anaerobic digestion process, SRB and MPB activity do not produce large effect because of the competition to substrate.Analyze reason, It is probably COD concentration height in the water inlet of one-level UASB reactors, the available organic matter of microorganism is sufficient, and SRB and MPB is carrying out sulphur Hydrochlorate is reduced will not produce keen competition effect with during methane phase because substrate deficiency.
The change of the anaerobic effluent sulfide concentration of embodiment 7
The situation of change of water outlet sulfide concentration such as Fig. 7.As seen from the figure water outlet sulfide concentration with water inlet sulfate concentration It is proportionate, the sulfide concentration of secondary anaerobic water outlet is higher than one-level anaerobic effluent, this degraded situation phase with sulfate radical in Fig. 6 Symbol.One-level anaerobic effluent sulfide concentration is 568.8mg/L to the maximum, and secondary anaerobic water outlet sulfide concentration is 720mg/L to the maximum.
The situation of change of electron current distribution in the one-level anaerobic digestion process of embodiment 8
Electron current distribution in one-level anaerobic digestion process as shown in figure 8, MPB percent electron flow general morphologictrend be with The lifting of load and become big, phenomenon is reduced by a small margin twice when load is relatively low.This variation tendency with factor of created gase It is more consistent.
Reactor operation starting stage SRB percent electron flow it is higher, be 33.8% to the maximum, illustrate organic concentration compared with When low, SRB is compared fierce with MPB to the competition of substrate, and SRB occupies some superiority in competition, but due to water inlet sulfuric acid Root concentration is relatively low, and removal contributions of the MPB to COD is bigger, and electron stream allocation result also demonstrates this conclusion, illustrates to run one-level MPB remains in that of a relatively high bioactivity in anaerobic UASB reactor for treatment molasses alcohol waste water initial stage, sludge.In water inlet Load is 6kg/ (m3D) with 8kg/ (m3D) in runtime, SRB percent electron flows have been raised, and are increased to by 20.6% 28.6%, this is probably the anaerobic digester system sulfide concentration rise because water inlet sulfate concentration becomes big, MPB activity by Of short duration suppression, but as reactor is continued to run with, MPB is adapted to and is recovered higher bioactivity quickly, MPB percent electron flows Become larger again.
Although the present invention is disclosed as above with preferred embodiment, it is not limited to the present invention, any to be familiar with this skill The people of art, without departing from the spirit and scope of the present invention, can do various changes and modification, therefore the protection model of the present invention Enclose being defined of being defined by claims.

Claims (7)

1. a kind of method that two stage UASB handles molasses alcohol waste water, it is characterised in that molasses alcohol waste water is passed through into two-stage UASB reactors carry out Anaerobic Digestion, and the two stage UASB reactor is the UASB reactors of two series connection.
2. a kind of method according to claim 1, it is characterised in that the two stage UASB reactor is the one-level of series connection UASB reactors and two grades of UASB reactors；The water inlet of two grades of UASB reactors is one-level UASB reactor water outlets；Waste water by The water distribution system of the reacted device bottom of feed pump enters reactor；Effective appearance of one-level UASB reactors and two grades of UASB reactors Product is than being 6：5, reaction zone volumetric ratio is 7：6.
3. a kind of method according to claim 1 or 2, it is characterised in that anti-to one-level UASB reactors and two grades of UASB Device is answered to be inoculated with a certain amount of anaerobic grain sludge, allowing needs molasses alcohol waste water to be processed successively to flow through two stage UASB reactor, Carry out producing methane through anaerobic fermentation.
4. according to any a kind of described method of claims 1 to 3, it is characterised in that the temperature of two stage UASB reactor is 35 ℃。
5. according to any a kind of described method of Claims 1 to 4, it is characterised in that enter the waste water of one-level UASB reactors Initial pH be adjusted to 7.20~7.50 with sodium carbonate liquor, by the time interval of 6~10 days, gradually adjust the dilution times of waste water Number, raising inlet COD loading are respectively 2,4,6,8,16,22,24 and 28kg/ (m3D), hydraulic detention time is 24h.
6. according to any a kind of described method of Claims 1 to 5, it is characterised in that one-level UASB reactor seed sludge amounts For 4L；Two grades of UASB reactor seed sludges amounts are 3L.
7. according to any a kind of described method of claim 1~6, it is characterised in that the one-level anaerobic UASB reactor has Effect volume is 12L, and wherein reaction zone volume is 7.7L, and settling zone volume is 4.3L, secondary anaerobic UASB reactor dischargeable capacitys For 10L, wherein reaction zone volume is 6.6L, and settling zone volume is 3.4L.
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Cited By (1)

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