CN108821429A - A kind of apparatus system and its processing method of sulfate wastewater treatment - Google Patents
A kind of apparatus system and its processing method of sulfate wastewater treatment Download PDFInfo
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- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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Abstract
The present invention provides a kind of apparatus system of sulfate wastewater treatment and its processing methods.The processing system includes anaerobic reaction unit, stripping unit, absorptive unit, biological desulphurization unit and gas storage element.The processing method provided by the present invention includes 1) carrying out anaerobism desulfurization to sulfate wastewater, obtains the biogas containing hydrogen sulfide and anaerobic reaction liquid；2) stripping is carried out to anaerobic reaction liquid, obtains hydrogen sulfide containing stripping gas and stripping waste water；3) biogas containing hydrogen sulfide and hydrogen sulfide containing stripping gas are absorbed, obtains sulfide absorbing liquid and purified gas；4) biological sulphur oxidation is carried out under aeration condition to sulfide absorbing liquid, obtains elemental sulfur and clear liquid；5) purified gas is stored, and is recycled back to stripping step as stripping gas.System and method provided by the invention realize efficient, the green innoxious and recycling treatment of acid high sulfate-containing wastewater, and significantly improve the economy of process.
Description
Technical field
The invention belongs to field of environment engineering, are related to the apparatus system and its processing method of a kind of sulfate wastewater treatment.
Background technique
Sulfuric acid and sulfurous acid are a kind of important industrial chemicals, with the continuous development of industry, chemical industry, monosodium glutamate, pharmacy, sugar
The fields such as mulse essence, process hides, papermaking give off the largely salt (SO containing high-concentration sulfuric acid in process of production4 2-) organic wastewater.
Wherein paper industry pollutant discharge amount is only second to chemical industry, and wastewater discharge is 31.8 hundred million tons, accounts for national industrial wastewater row
(Chemical Oxygen Demand, i.e. COD, the index are also used as organic matter is opposite to contain to 16.1%, COD high-volume
One of overall target of amount) 148.8 ten thousand tons of discharge amount, account for the 33% of national COD discharge amount.It is useless with acid sulphite process slurrying
For water, pH value is that 1.2~2.0, COD is 500~2000mg/L, SO4 2-And SO3 2-Total concentration is up to 1000~3000mg/L.And
Typical antibiotic waste water, for sulphates content generally in 2000mg/L or more, some is even as high as 15000mg/L.Sulfuric acid
Although salt itself is harmless, it, which encounters anaerobic environment, to generate hydrogen sulfide (H under sulfate reducing bacteria (SRB) effect2S),
H2S energy heavy corrosion treatment facility and drainage pipeline, in addition, H2S breath malodor, concentration reach a timing and can cause in people's nerve
Poison, and can react with ozone in atmosphere and generate sulfuric acid, this is one of origin cause of formation of acid rain.Sulfate wastewater is discharged into water body
Receiving water body can be made to be acidified, pH value reduces, and endangers aquatile, and soil texture can be destroyed by being discharged into farmland, makes soil hardening, reduces
Crop yield and reduction quality of agricultural product.Since most of sulfuric acid salt solubilities are very big, property is stablized in nature, so
It is difficult to remove by self cleaning.Therefore, a kind of not only stability and high efficiency is searched out, but also economical and practical sulfate-containing wastewater
Processing method, it has also become the hot spot of various countries' research.Currently, bioanalysis anaerobic digestion process is processing organic wastewater main method.
Compared with physico-chemical process, bioanalysis anaerobic digestion process has high treating effect, attended operation at low cost, without secondary pollution
The features such as.By anaerobic digestion, COD is converted into clean energy resource biogas, and the sludge of generation is high-quality organic fertilizer.
When handling high-concentration sulfuric acid salt organic waste water using anaerobic process, due to the intervention of sulfate reduction, make anaerobism
Degradation process is suppressed or even system crash, the main reason is that existing simultaneously methanogen (MPB) and sulfate in system
The problems such as substrate competition and sulfate reduction product (sulfide) of reducing bacteria (SRB) generate toxicity inhibition to MPB and SRB.
Wherein, the reduzate HS of sulfate-, S2-It is the inhibitor of bacterial growth, the microorganism especially pole MPB with metal sulfide etc.
Vulnerable to the inhibiting effect of these reduzates, MPB is resistant to S2-Concentration is 25mg/L, and the toxicity of sulfide reduce with pH value and
Enhancing.The H to dissociate in these inhibitor2The toxic action of S is maximum, and reason may be H2S is in electroneutral, only electroneutral
Electronegative somatic cells film can be passed through, its protein is destroyed.Research finds that the toxicity of sulfide is far longer than other compound states
Sulphur, and insoluble sulfide acts on the general unrestraint of anaerobic processes.It is mainly molten to the inhibiting effect of microorganism in sulfide
Solution property H2S.During SRB growth metabolism, sulfate is indispensable as electron acceptor.Different types of SRB it
Between there is also the competition to sulfate, this point is especially prominent when sulfate concentration is lower.It intakes in a certain range
SO4 2-S in concentration and water outlet2-Concentration there are some linear, so SO in water inlet4 2-Can concentration normal for reactor
Operation is played the role of vital.S2-Accumulation can also generate inhibition to acid-producing bacteria and sulfate reducing bacteria, influence sulfate
Removal effect.
Sulphur is a kind of important industrial chemicals, and global crude sulfur yield is seldom, China almost without crude sulfur mine,
Sulphur is recycled in the sulfide that most sulfur sources generate in oil and natural gas process, Recovered sulphur yield has accounted for
96% or more world's sulphur yield.Biological desulphurization refers to utilizes sulfur oxidizing bacterium by the Oxidation of Hydrogen Sulfide in biogas at normal temperatures and pressures
For elemental sulfur, and the process removed from system, it is a kind of desulfurization technology of the development nineties in last century.With conventional physical, change
Method is compared, and biological desulfurizing technology has many advantages, such as that mild condition, without secondary pollution, equipment is simple.In addition, the biology generated
The particle of sulphur is nanoscale, has good biological compatibility and hydrophily, is medicine and the optimal raw material of pesticide producing.The world
Have in range and covered commercialized Shell-Paques bio-desulfurization device more 100, has been more than 14 applied to natural gas field
Set.With the continuous improvement of development and people to environmental requirement of human society gradually, bacterial desulfurization is as a kind of new
H in processing natural gas, biogas2S method, it will be apparent that advantage will make it have wide development space and application prospect in future.Mesh
The sulfur oxidizing bacterium of preceding use is mainly Thiobacillus, and optimal pH is 8.0 or so, and tolerance salinity is only 0.5-2.5%.
Thermophilic salt basophilic bacterium is a kind of Situation of Microorganism Under Extremity Environment, they can be normal in the solution of high salt concentration and high pH
Growth, and when salinity or pH too low, this growth will be suppressed, therefore be a kind of double factor extreme microorganism.It is extremely micro-
Biology is survived in various extreme environments for a long time, the unique physiological mechanism of formation.In general, there are Na for halophile+/
H+The respiratory chain of antiport system, cell secrets out of H+, make intracellular to be in alkaline state, cell is under the action of the system by Na+
It excretes, while making H+Into intracellular, ensure that acid-base balance intracellular, enable various vital movements intracellular normally into
Row.Traditional gas biological desulfurization process absorbing liquid basicity is low, the problem that internal circulating load is big, energy consumption is high.
CN102351381A discloses the processing unit and method of a kind of sulfate wastewater, and this approach includes the following steps：
Level-one Anaerobic Treatment：Waste water to be processed is subjected to level-one anaerobism by anaerobic expanded bed by addition ethyl alcohol.Sulfate reduction
Reaction and methane fermentation are substantially to complete in level-one anaerobic reactor.Secondary anaerobic processing：Sulfide stripping, anaerobism are dirty
Mud precipitating and secondary anaerobic are further processed and complete in combined type settling vessel.The program needs sulfate wastewater to be used to need
Sucrose and ethyl alcohol are added, and also comprising the process just tamed to sludge, it is cumbersome, it is with high costs, it is unfavorable for promoting.
CN205500936U discloses a kind of high-sulfate waste water multi-reflow processing unit, and described device includes at waste water
Pond is managed, the purification tank for liquid waste rear portion is connected with No.1 sedimentation basin and No. two sedimentation basins in turn, and No. two sedimentation basin rear portions connect
It is connected to reflux pump one end, the reflux pump other end connects purification tank for liquid waste.The purification tank for liquid waste, No.1 sedimentation basin, No. two
The side wall of sedimentation basin is provided with discharge outlet, is provided with liquidometer and automatic valve in the discharge outlet.The waste water of the program
Treatment effect is general, and is unable to get elemental sulfur, affects its economic benefit.
Therefore, develop a kind of low in cost, good economy performance, the apparatus system of the high sulfate wastewater treatment of recovery efficiency and
Processing method has this field important meaning.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of sulfate wastewater treatments
Apparatus system and its processing method.The apparatus system and processing method of sulfate wastewater treatment provided by the invention can handle highly concentrated
Sulfate wastewater is spent, treatment effeciency is high, and low energy consumption, and operating cost is low, and added value of product is high, is easy to carry out industrialization promotion.
In the present invention, the system is referred to as device, equipment or process units and its combination etc..
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of apparatus system of sulfate wastewater treatment, the system comprises：Anaerobic reaction
Unit, stripping unit, absorptive unit, biological desulphurization unit and gas storage element；
Anaerobic reaction unit, with sulfate wastewater feeding pipe, stripping unit liquid outlet, the import of stripping unit liquid and
Absorptive unit gas feed is respectively connected with；
Stripping unit, with the liquid-inlet of anaerobic reaction unit, the liquid outlet of anaerobic reaction unit, absorptive unit gas
Import and the outlet of gas storage element are respectively connected with；
Absorptive unit, with the gas vent of anaerobic reaction unit, the gas vent of stripping unit, biological desulphurization unit liquid
Body outlet, the gas feed of the liquid-inlet of biological desulphurization unit and gas storage element are respectively connected with；
Biological desulphurization unit, with the liquid-inlet of absorptive unit, the liquid outlet of absorptive unit and air input passageway point
Xiang Lian not；
Gas storage element, the gas feed with the gas vent and stripping unit of absorptive unit are respectively connected with.
In the apparatus system of sulfate wastewater treatment provided by the invention, anaerobic reaction unit will under the action of microorganism
SO in high concentration sulfate wastewater4 2-It is transformed into hydrogen sulfide containing biogas with COD；Anaerobic reaction is obtained and is detested by stripping unit
Hydrogen sulfide in oxygen reaction solution is stripped out, and is mixed into stripping gas, into next stage processing unit；Absorptive unit will contain vulcanization
Hydrogen sulfide in the gas of hydrogen is changed into sulfur compound absorbing liquid with liquid absorption；Biological desulphurization unit is by the absorption of sulfur compound
Sulphur in liquid is changed into the elemental sulfur of high added value under the action of microorganism；Gas storage element stores gas, makes stripping mistake
Cheng Wending is carried out, while can provide gas for downstream process.Each unit cooperates, the common height for realizing sulfate wastewater
The innoxious and recycling treatment of effect, green, and significantly improve the economy of process.
In system provided by the invention, closed liquid circulation is formed between anaerobic reaction unit and stripping unit, is absorbed
Closed liquid circulation is formed between unit and biological desulphurization unit, between stripping unit, absorptive unit and gas storage element
Form closed gas circulation.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the anaerobic reaction unit includes anaerobic reactor and conditioning tank, described
The liquid outlet of anaerobic reactor is connected with the liquid-inlet of the import of conditioning tank and stripping unit respectively, the anaerobic reactor
Liquid-inlet be connected with the liquid outlet of stripping unit, the gas of the gas vent of the anaerobic reactor and absorptive unit into
Mouth is connected, and the import of the conditioning tank and the liquid outlet of anaerobic reactor and sulfate wastewater feeding pipe are respectively connected with, institute
The outlet for stating conditioning tank is connected with the liquid-inlet of stripping unit.
Preferably, the anaerobic reactor further includes the liquid outlet connecting with downstream section.
Preferably, the pipeline between the liquid outlet of stripping unit and the liquid-inlet of anaerobic reactor is equipped with power transmission
Device.
Preferably, the pipeline between the liquid outlet of anaerobic reactor and the liquid-inlet of stripping unit is equipped with power transmission
Device.
Preferably, the pipeline between the outlet of conditioning tank and the liquid-inlet of stripping unit is equipped with power conveying device.
Preferably, the power conveying device is water pump.
It preferably, include methanogenesis activity sludge in the anaerobic reactor.
It preferably, include sulfate reducing bacteria and methanogen in the methanogenesis activity sludge.The sulfate reduction
Bacterium and methanogen are this field Conventional bacteria, and specific type those skilled in the art according to circumstances can voluntarily choose.
As currently preferred technical solution, the stripping unit includes stripping tower, the overhead liquid charging of stripping tower
Mouth is connected with the outlet of conditioning tank, and the tower central liquid feed inlet of stripping tower is connected with the liquid outlet of anaerobic reactor, stripping
The gas vent of tower is connected with absorptive unit gas feed, and the gas feed of stripping tower is connected with the outlet of gas storage element.
Preferably, the stripping tower is two-stage series connection packed tower, and the overhead liquid feed inlet of stripping tower is located at upper layer filler
The top of layer, the tower central liquid feed inlet of stripping tower is between two-stage packing layer.
As currently preferred technical solution, the absorptive unit includes the first absorption tower and second absorption tower, described
The gas feed on the first absorption tower is connected with the gas vent of stripping tower, the gas vent and gas storage element on the first absorption tower
Gas feed be connected, the liquid-inlet on the first absorption tower is connected with the liquid outlet of biological desulphurization unit, the first absorption tower
Liquid outlet is connected with the liquid-inlet of biological desulphurization unit, and the gas feed of second absorption tower and the gas of anaerobic reactor go out
Mouth is connected, and the gas vent of second absorption tower is connected with the gas feed of gas storage element, the liquid-inlet of second absorption tower
It is connected with the liquid outlet of biological desulphurization unit, the liquid-inlet phase of the liquid outlet and biological desulphurization unit of second absorption tower
Even.
In the present invention, " first " and " second " in first absorption tower and second absorption tower only carries out area to name
Point, it is not to limit the quantity on absorption tower.
Preferably, power transmission is equipped between the liquid outlet of biological desulphurization unit and the liquid-inlet of absorptive unit to fill
It sets.
Preferably, the power conveying device is water pump.
As currently preferred technical solution, the biological desulphurization unit includes biological desulphurization reactor and subsider,
The liquid outlet of the liquid-inlet of the biological desulphurization reactor and the liquid outlet on the first absorption tower and second absorption tower difference
It is connected, the liquid outlet of biological desulphurization reactor is connected with the liquid-inlet of subsider, the gas feed of biological desulphurization reactor
It is connected with air input passageway, the liquid-inlet of subsider is connected with the liquid outlet of biological desulphurization reactor, the liquid of subsider
Body outlet is connected with the liquid-inlet on the first absorption tower.
Preferably, tail gas outlet is additionally provided on the biological desulphurization reactor.
Preferably, air inlet duct road is equipped with power conveying device.
Preferably, the power conveying device is air pump.
Preferably, the sedimentation trench bottom is additionally provided with elemental sulfur outlet.
It preferably, include sulfur oxidizing bacterium in the biological desulphurization reactor.The sulfur oxidizing bacterium is this field Conventional bacteria,
Its specific type those skilled in the art according to circumstances can voluntarily choose.
Preferably, the sulfur oxidizing bacterium is multipotency sulphur alkali vibrios D301 (Thioalkalivibrio versutus
D301).The multipotency sulphur alkali vibrios D301 (Thioalkalivibrio versutus D301) be the prior art (referring to
The 0004th section-the 0005 section and the 0013rd section of CN105483110A specification), those skilled in the art can foundation
Related record of CN105483110A obtains such bacterium.
As currently preferred technical solution, the gas storage element includes gas holder, the gas feed of the gas holder
It is respectively connected with the gas vent on the first absorption tower and the gas vent of second absorption tower, the gas vent of gas holder and stripping tower
Gas feed is connected.
Preferably, the gas vent being connected with boiler is additionally provided on the gas holder.
Preferably, the pipeline between the gas feed of the gas vent and stripping tower of gas holder is equipped with power conveying device.
Preferably, the power conveying device is booster fan.
Second aspect, the present invention provide a kind of processing of the apparatus system of sulfate wastewater treatment as described in relation to the first aspect
Method the described method comprises the following steps：
(1) anaerobism desulfurization is carried out to sulfate wastewater, obtains the biogas containing hydrogen sulfide and anaerobic reaction liquid；
(2) stripping is carried out to step (1) the anaerobic reaction liquid, obtains hydrogen sulfide containing stripping gas and stripping waste water；
(3) the hydrogen sulfide containing stripping gas of the biogas containing hydrogen sulfide and step (2) described in step (1) is inhaled
It receives, obtains sulfide absorbing liquid and purified gas；
(4) biological sulphur oxidation is carried out under aeration condition to step (3) the sulfide absorbing liquid, obtains elemental sulfur and clear
Liquid；
(5) step (3) described purified gas is stored, and is recycled back to stripping step as stripping gas.
Treatment effeciency is high, and low energy consumption, and operating cost is low, and added value of product is high, is easy to carry out industrialization promotion.
As currently preferred technical solution, the sulfate concentration in step (1) described sulfate wastewater is >
1500mg/L, for example, 1510mg/L, 1800mg/L, 2000mg/L, 2500mg/L, 3000mg/L, 3500mg/L, 4000mg/L or
4500mg/L etc..In the present invention, the sulfate concentration is the concentration calculation with sulfate radical.
Preferably, step (1) sulfate wastewater is acid waste water.
Preferably, the anaerobism desulfurization carries out under the action of microorganism.
Preferably, the microorganism includes sulfate reducing bacteria and methanogen.The sulfate reducing bacteria and methane phase
Bacterium is this field Conventional bacteria, and specific type those skilled in the art according to circumstances can voluntarily choose.Sulfate reducing bacteria and
Methanogen handles sulfate and COD in high-concentration waste water respectively.
Preferably, in step (1), the pH of the anaerobism desulfurization is 6.0~8.0, such as 6.0,6.5,7.0,7.5 or 8.0
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, in step (1), obtained anaerobic reaction liquid is divided into two parts, and a part carries out stripping, another part into
Enter downstream section.
Preferably, in step (2) described stripping, stripping gas and anaerobic reaction liquid counter current contacting.
Preferably, in step (2) described stripping, the adding manner of anaerobic reaction liquid is spray.
Preferably, in step (2), the anaerobic reaction liquid for carrying out stripping is divided into two parts, and first part directly carries out stripping,
Second part carries out stripping after mixing with sulfate wastewater again.The sulfate wastewater refers to that untreated sulfate wastewater is former
Liquid.The pH of second part waste water is lower than first part waste water, is conducive to stripping and goes out more hydrogen sulfide.
Preferably, in step (2), the stripping carries out in two-stage series connection packed tower, carries out the anaerobic reaction liquid of stripping
It is divided into two parts, first part directly enters two-stage series connection packed tower from middle part, stripping only is carried out by second level packing area, the
Two parts enter two-stage series connection packed tower from top again after mixing with sulfate wastewater, carry out by the first order and second level filler
Two-stage stripping.This mode can be such that the hydrogen sulfide in waste water is come out by abundant stripping.
Preferably, in step (2) described stripping, stripping gas is purified biogas.
Waste water to stripping often contains the CH of dissolution4, therefore, after stripping, the CH that is dissolved in waste water4Gone out by stripping
Come, CH in the gas after improving stripping4Concentration, to improve the calorific value of biogas.
As currently preferred technical solution, step (3) absorbing liquid used that absorbs is lye.
Preferably, the lye is Na2CO3And NaHCO3The buffer of composition.
Preferably, the pH of the lye is 8.5~10.5, such as 8.5,9,9.5 or 10.5 etc., it is not limited to listed
The numerical value of act, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (4) the biological sulphur oxidation carries out under the action of sulfur oxidizing bacterium.
Preferably, the sulfur oxidizing bacterium is multipotency sulphur alkali vibrios D301 (Thioalkalivibrio versutus
D301).The multipotency sulphur alkali vibrios D301 (Thioalkalivibrio versutus D301) is the strain (ginseng of the prior art
See the 0004th section, the 0005th section and the 0013rd section of CN105483110A specification), those skilled in the art can foundation
Related record of CN105483110A obtains such bacterium.Such sulfur oxidizing bacterium has the property of thermophilic salt basophilic.Under the conditions of high pH,
Sulfide is mostly with HS-Form exist, HS-It not can enter cell membrane, therefore the toxicity generated to cell is smaller, thermophilic salt basophilic
Microorganism has relatively high tolerance to flowers of sulfur object.HS-It will form polysulfide with simple substance reaction of Salmon-Saxl, this substance is in high pH
Under the conditions of it is highly stable.Thermophilic salt halophile can be 9.5-11.0 in pH, and salinity reaches efficient oxidation sulphur in the case of 10-15%
Change hydrogen, significantly reduces energy consumption.The biological sulphur of generation is with S8Form exists, and good dispersion, not will form blocking in water.Together
When, biological sulphur in 30 seconds can rapid subsidence, convenient for recycling.
Preferably, in step (4), the thio-oxidizing oxidation-reduction potential of biology is -400~-300mV, such as -
400mV, -380mV, -360mV, -340mV, -320mV or -300mV etc., it is not limited to cited numerical value, the numerical value model
Other unlisted numerical value are equally applicable in enclosing.In the present invention, using oxidation-reduction potential (Oxidation-Reduction
Potential, ORP) response control aeration quantity.
Preferably, in step (4), elemental sulfur and clear liquid that biological sulphur aoxidizes are separated by settling.
Preferably, in step (4), the clear liquid is back in step (3) described absorption process as absorbing liquid.
Preferably, in step (4), the elemental sulfur enters downstream sulfur recovery system and carries out Recovery Purifying.
Preferably, in step (5), the purified gas stored is also used in addition to being recycled back to stripping step as stripping gas
Downstream energy supply.
Preferably, in step (5), purified gas is stored in gas holder.
Preferably, the pressure remained steady of the gas holder.
In the present invention, the biogas of purified anaerobic processes is initial source and the subsequent process gas source of gas holder gas,
The gas of stripping is initially a part of purified anaerobic processes biogas, after by stripping and absorbing, is turned again in gas holder.
As the further preferred technical solution of processing method of the present invention, the described method comprises the following steps：
(1) under the action of sulfate reducing bacteria and methanogen, control pH is 6.0~8.0, is carried out to sulfate wastewater
Anaerobism desulfurization obtains the biogas containing hydrogen sulfide and anaerobic reaction liquid, and the anaerobic reaction liquid is divided into two parts, and a part carries out
Stripping, another part enter downstream section；
(2) in two-stage series connection packed tower, stripping is carried out to step (1) the anaerobic reaction liquid, carries out the anaerobism of stripping
Reaction solution is divided into two parts, and a part directly enters two-stage series connection packed tower from middle part and sprayed, only by second level filler
Area carries out stripping, and another part enters two-stage series connection packed tower from top again after mixing with sulfate wastewater and sprayed, and passes through
The first order and second level filler carry out two-stage stripping, obtain hydrogen sulfide containing stripping gas and stripping waste water；
Wherein, the stripping gas of stripping process and anaerobic reaction liquid counter current contacting, stripping gas are purified biogas；
(3) it is with pH to the hydrogen sulfide containing stripping gas of the biogas containing hydrogen sulfide and step (2) described in step (1)
8.5~10.5 lye is absorbed, and sulfide absorbing liquid and purified gas are obtained；
Wherein, the lye is Na2CO3And NaHCO3The buffer of composition；
(4) under the action of sulfur oxidizing bacterium, biological sulphur is carried out under aeration condition to step (3) the sulfide absorbing liquid
Oxidation, the thio-oxidizing oxidation-reduction potential of control biology is -400~-300mV, and sedimentation separation obtains elemental sulfur and clear liquid, institute
It states elemental sulfur and enters downstream sulfur recovery system progress Recovery Purifying, the clear liquid is back to step (3) described suction as absorbing liquid
During receipts；
(5) step (3) described purified gas is stored in gas holder, the purified gas stored is removed to be recycled back to as stripping gas
Outside stripping step, it is also used to downstream energy supply.
Above-mentioned further preferred technical solution provided by the invention carries out anaerobic methane production fermentation using methanogen, main
Wanting product is methane, methane is blown into anaerobic System, the S of generation2-With H2S-shaped formula is blown out, S in reduction system2-It is dense
Degree not only removes the sulfide in water body in time, alleviates the inhibition of reactor, greatly improve the processing capacity of reactor,
And avoid S2-Accumulation inhibition is generated to acid-producing bacteria and sulfate reducing bacteria.Use purified biogas as stripping gas, energy
Stripping goes out the methane gas dissolved in waste water, to improve the concentration of methane in gas, increases the calorific value of biogas.
Since the effect of gas stripping is influenced by system pH, pH value is higher, S2-It is converted into H2S is more difficult, gas stripping
Effect it is poorer；If waste water fermentation to be carried out to certain acidification, it can effectively strengthen H2The stripping of S, will to a greater extent
Reduce H2Inhibition of the S to anaerobic processes, and anaerobic reactor is discharged pH generally 7.0 or more.Therefore, above-mentioned further preferred
Technical solution will be discharged and be sufficiently mixed with waste water to be processed, make the pH of mixed liquor close to flow condition, simultaneously as mixed liquor
It is reduced when pH is relative to water outlet, is more advantageous to the progress of stripping, makes more S2-It is converted into H2The form of S enters in gas phase,
After stripping, the pH of liquid rises, and also reaches the condition of Anaerobic Treatment.The effective deactivation system of the increase of stripping effect is due to S2-'s
The inhibition for accumulating and generating, greatly improves the waste water treatment efficiency of system.Further, since the process passes through inflow and outflow
Mixing, to greatly reduce the dependence to alkali, effectively reduces process cost to adjust pH.Further, since during stripping,
The methane of liquid strain dissolution is easy to be come out by stripping, and into gas phase, therefore, above-mentioned further preferred technical solution passes through biogas
Stripping is carried out, the calorific value of biogas can be effectively increased.
In addition, making S using inertia purified gas stripping waste water fermentation2-With H2The form of S is stripped, into gas phase, then it is right
Containing H2S gas carries out desulfurization, not only can achieve the purpose of thorough pollution administration, moreover it is possible to realize the recycling of sulphur resource.
Compared with the prior art, the present invention has the advantages that：
(1) the apparatus system each unit of sulfate wastewater treatment provided by the invention cooperates, and is realized jointly to acid
Efficient, the green innoxious and recycling treatment of property high sulfate content waste water, and significantly improve the economy of process；
(2) the processing method provided by the present invention reduces S by stripping process2-Concentration suppression that anaerobic reaction is generated
System, and the methane in waste water can further be extracted, furthermore make anaerobic reaction process not need that pH adjusting is added
Agent；The product that the processing method provided by the present invention obtains is elemental sulfur, and economy is more preferable；The processing method provided by the present invention SO4 2-
Removal rate is up to 80%, COD removal rate up to 65%.
Detailed description of the invention
Fig. 1 is the apparatus system schematic diagram of the sulfate wastewater treatment of the embodiment of the present invention 1；
Wherein, 1- anaerobic reactor, 2- conditioning tank, 3- stripping tower, the first absorption tower 41-, 42- second absorption tower, 5- are raw
Object desulfurization reactor, 6- subsider, 7- gas holder, solid line with the arrow indicates liquid flow direction in figure, and dotted line with the arrow indicates gas
Body flow direction；
Fig. 2 is SO in the embodiment of the present invention 14 2-Pass in and out water concentration and S2-The variation of concentration；
Fig. 3 is SO after system stripping in the embodiment of the present invention 14 2-With the variation of COD removal rate；
Fig. 4 is SO in the embodiment of the present invention 24 2-Pass in and out water concentration and S2-The variation of concentration；
Fig. 5 is SO after system stripping in the embodiment of the present invention 24 2-With the variation of COD removal rate.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
The following are typical but non-limiting embodiments of the invention：
Embodiment 1
The apparatus system of the sulfate wastewater treatment of the present embodiment as shown in Figure 1, the system comprises：Anaerobic reaction list
Member, stripping unit, absorptive unit, biological desulphurization unit and gas storage element；
The anaerobic reaction unit includes anaerobic reactor 1 and conditioning tank 2, the liquid outlet point of the anaerobic reactor 1
It is not connected with the liquid-inlet of the import of conditioning tank 2 and stripping unit, the liquid-inlet and stripping unit of the anaerobic reactor 1
Liquid outlet be connected, the gas vent of the anaerobic reactor 1 is connected with the gas feed of absorptive unit, the conditioning tank 2
Import and the liquid outlet and sulfate wastewater feeding pipe of anaerobic reactor 1 be respectively connected with, the outlet of the conditioning tank 2 with
The liquid-inlet of stripping unit is connected；The anaerobic reactor 1 further includes the liquid outlet connecting with downstream section；Stripping
Pipeline between the liquid outlet of unit and the liquid-inlet of anaerobic reactor 1 is equipped with water pump, the liquid outlet of anaerobic reactor 1
Pipeline between the liquid-inlet of stripping unit is equipped with water pump, between the outlet of conditioning tank 2 and the liquid-inlet of stripping unit
Pipeline is equipped with water pump, includes methanogenesis activity sludge in the anaerobic reactor 1, contains sulfate reduction in the activated sludge
Bacterium and methanogen；
The stripping unit includes stripping tower 3, and the overhead liquid feed inlet of stripping tower 3 is connected with the outlet of conditioning tank 2, blows
The tower central liquid feed inlet of de- tower 3 is connected with the liquid outlet of anaerobic reactor 1, and the gas vent of stripping tower 3 and absorption are single
First gas feed is connected, and the gas feed of stripping tower 3 is connected with the outlet of gas storage element；The stripping tower 3 is two-stage string
Join packed tower, the overhead liquid feed inlet of stripping tower 3 is located at the top of upper layer packing layer, the tower central liquid charging of stripping tower 3
Mouth is between two-stage packing layer；
The absorptive unit includes the first absorption tower 41 and second absorption tower 42, the gas feed on first absorption tower 41
It is connected with the gas vent of stripping tower 3, the gas vent on the first absorption tower 41 is connected with the gas feed of gas storage element, the
The liquid-inlet on one absorption tower 41 is connected with the liquid outlet of biological desulphurization unit, the liquid outlet and biology on the first absorption tower 41
The liquid-inlet of desulfurization unit is connected, and the gas feed of second absorption tower 42 is connected with the gas vent of anaerobic reactor 1, and second
The gas vent on absorption tower 42 is connected with the gas feed of gas storage element, and the liquid-inlet and biology of second absorption tower 42 are de-
The liquid outlet of sulphur unit is connected, and the liquid outlet of second absorption tower 42 is connected with the liquid-inlet of biological desulphurization unit；Biology
Water pump is equipped between the liquid outlet of desulfurization unit and the liquid-inlet of absorptive unit；
The biological desulphurization unit includes biological desulphurization reactor 5 and subsider 6, the liquid of the biological desulphurization reactor 5
Body import is respectively connected with the liquid outlet on the first absorption tower 41 and the liquid outlet of second absorption tower 42, biological desulphurization reactor
5 liquid outlet is connected with the liquid-inlet of subsider 6, gas feed and the air input passageway phase of biological desulphurization reactor 5
Even, the liquid-inlet of subsider 6 is connected with the liquid outlet of biological desulphurization reactor 5, and the liquid outlet of subsider 6 and first is inhaled
The liquid-inlet for receiving tower 41 is connected；Tail gas outlet is additionally provided on the biological desulphurization reactor 5；Air inlet duct road is equipped with
Air pump；6 bottom of subsider is additionally provided with elemental sulfur outlet；It include multipotency sulphur alkali arc in the biological desulphurization reactor 5
Bacterium D301 (Thioalkalivibrio versutus D301)；
The gas storage element includes gas holder 7, the gas vent of the gas feed of the gas holder 7 and the first absorption tower 41
It is respectively connected with the gas vent of second absorption tower 42, the gas vent of gas holder 7 is connected with the gas feed of stripping tower (3)；Institute
State the gas vent for being additionally provided on gas holder 7 and being connected with boiler；Between the gas feed of the gas vent and stripping tower 3 of gas holder 7
Pipeline is equipped with booster fan.
The sulfate wastewater of the present embodiment processing is simulated wastewater.Simulated wastewater group becomes (in 1L waste water)：1.0g
NH4Cl,2g KH2PO4, 0.05g MgCl2、0.01g FeCl3、0.01g MnSO4, 0.5g yeast powder, 98% concentrated sulfuric acid 1mL.
Carbon source is used glucose as, and sodium sulphate is added to make SO in liquid4 2-Maximum concentration be 2000mg/L, COD/SO4 2-For
2.0.Adjust pH to 5.0.
The sulfate wastewater treatment method of the present embodiment is：
Maintain water conservancy residence time (HRT) for 24 hours.Simulated wastewater pH is first adjusted to 6.0, then by conditioning tank anaerobism into
Enter system, starts anaerobic processes, obtain the biogas containing hydrogen sulfide and anaerobic reaction liquid.What anaerobic reactor 1 generated contains sulphur
The biogas for changing hydrogen, which imports in second absorption tower, carries out absorption cleaning, and purified gas is stored in gas holder, and absorbing liquid is exposing
Biological sulphur oxidation is carried out by biological desulphurization reactor 5 under the conditions of gas, generates sulphur.
After anaerobic processes are stablized, opens blow-removing system and carry out stripping.A part of left side water outlet is introduced directly into stripping tower 3
Middle part carries out stripping, and another part enters conditioning tank 2 and mixes with waste water to be processed, is then introduced into 3 progress strippings of stripping tower top.
The maintenance system water conservancy residence time is constant, and the cyclic process between reinforced anaerobic reactor 1 and stripping tower 2.Adjust waste water with
It is discharged conditioning tank mixed proportion again, the flow of each branch is adjusted, anaerobic reactor inlet flow-patterm is made to reach 6.0 or more.
The first stage is tested, the liquid circulation between anaerobic reactor 1 and stripping tower 3 is closed, without waste water blowoff.It is useless
Water is directly entered anaerobic reactor 1 from conditioning tank 2, is gradually increased into water SO4 2-Concentration, until being increased to maximum concentration 2000mg/
L。
The present embodiment SO4 2-Pass in and out water concentration and S2-The variation of concentration is as shown in Fig. 2, with SO4 2-The raising of concentration, S2-
Concentration gradually accumulates.But SO4 2-Removal efficiency maintains always lower level.As water inlet SO4 2-When concentration is 2000mg/L,
Highest removal efficiency is only 60% or so.
Second stage opens the waste water circulatory system and blow-removing system, carries out stripping to anaerobic reaction liquid, obtains sulfide hydrogen
Stripping gas and stripping waste water, the biogas containing hydrogen sulfide and hydrogen sulfide containing stripping gas are absorbed, obtain sulfide suction
Liquid and purified gas are received, sulfide absorbing liquid carries out biological sulphur oxidation under aeration condition, obtains elemental sulfur and clear liquid, purified gas storage
It stores away, and is recycled back to stripping step as stripping gas, system enters stable state.
SO after the present embodiment system stripping4 2-Variation with COD removal rate is as shown in figure 3, continue to run 25 days, SO4 2-It is de-
Except the removal rate that rate rises to 80%, COD from 49% also rises to 60% from 40%.Stripping gas enters at biological sulphur oxidative system
Reason, obtains elemental sulfur.
After system stripping, the yield of the elemental sulfur of the present embodiment is 2.1g/L/ days.
Embodiment 2
The apparatus system of the sulfate wastewater treatment of the present embodiment is same as Example 1.
The sulfate wastewater of the present embodiment processing is true pharmacy waste water, wastewater parameter SO4 2-Concentration 3000-3500mg/
L, COD concentration 8000-10000mg/L.
The specific steps reference implementation example 1 of the sulfate wastewater treatment method of the present embodiment, wherein：
Maintain water conservancy residence time (HRT) for 24 hours.Waste water enters carry out Anaerobic Treatment from anaerobic reactor bottom.
First stage handles high concentration medical wastewater using anaerobic reactor, and system continuous and steady operation 20 days, mistake herein
Cheng Zhong closes waste water blowoff system.
Second stage opens waste water blowoff system and carries out stripping, while running biological sulphur oxidative system and obtaining elemental sulfur, locates
Manage stripping gas.
SO in the present embodiment4 2-Pass in and out water concentration and S2-The variation of concentration is as shown in figure 4, at first 20 days, SO4 2-Removal rate
About 50%, it is discharged S2-Concentration is about 500mg/L, after starting stripping, SO4 2-Removal rate be promoted to 85% effect, in water outlet
SO4 2-Content less than 600mg/L, however the S in being discharged2-Do not obviously increase.This is because the sulfide generated is gone out by stripping
To enter in gas phase.
SO after system stripping in the present embodiment4 2-After variation with COD removal rate is as shown in figure 5, stripping opens, system COD
Removal rate rises to about 65% from 40%, illustrates that stripping effect is beneficial to the inhibition of deactivation system.Stripping gas is aoxidized through biological sulphur
System processing, the yield of elemental sulfur can reach 3.5g/L/ days.
After system stripping, the SO of the present embodiment4 2-Removal rate is 81%.
Embodiment 3
The apparatus system of the sulfate wastewater treatment of the present embodiment is same as Example 1.
The sulfate wastewater of the present embodiment processing is true pharmacy waste water, wastewater parameter SO4 2-Concentration 3000-3500mg/
L, COD concentration 8000-10000mg/L.
The sulfate wastewater treatment method of the present embodiment is：
(1) water conservancy residence time (HRT) is maintained for 24 hours, under the action of sulfate reducing bacteria and methanogen, control pH is
6.0, anaerobism desulfurization is carried out to sulfate wastewater, obtains the biogas containing hydrogen sulfide and anaerobic reaction liquid, the anaerobic reaction liquid
It is divided into two parts, a part carries out stripping, and another part enters downstream section；
(2) in two-stage series connection packed tower, stripping is carried out to step (1) the anaerobic reaction liquid, carries out the anaerobism of stripping
Reaction solution is divided into two parts, and a part directly enters two-stage series connection packed tower from middle part and sprayed, only by second level filler
Area carries out stripping, and another part enters two-stage series connection packed tower from top again after mixing with sulfate wastewater and sprayed, and passes through
The first order and second level filler carry out two-stage stripping, obtain hydrogen sulfide containing stripping gas and stripping waste water；
Wherein, the stripping gas of stripping process and anaerobic reaction liquid counter current contacting, stripping gas are purified biogas；
(3) it is with pH to the hydrogen sulfide containing stripping gas of the biogas containing hydrogen sulfide and step (2) described in step (1)
8.5 lye is absorbed, and sulfide absorbing liquid and purified gas are obtained；
Wherein, the lye is Na2CO3And NaHCO3The buffer of composition；
(4) under the action of sulfur oxidizing bacterium, biological sulphur is carried out under aeration condition to step (3) the sulfide absorbing liquid
Oxidation, the thio-oxidizing oxidation-reduction potential of control biology is -400mV, and sedimentation separation obtains elemental sulfur and clear liquid, the simple substance
Sulphur enters downstream sulfur recovery system and carries out Recovery Purifying, and the clear liquid is back to step (3) described absorption process as absorbing liquid
In；
(5) step (3) described purified gas is stored in gas holder, the purified gas stored is removed to be recycled back to as stripping gas
Outside stripping step, it is also used to downstream energy supply.
In the present embodiment, SO4 2-Removal rate is that 79%, COD removal rate is 62%, and the yield of elemental sulfur is 3.0g/L/ days.
Embodiment 4
The apparatus system of the sulfate wastewater treatment of the present embodiment is same as Example 1.
The sulfate wastewater of the present embodiment processing is true pharmacy waste water, wastewater parameter SO4 2-Concentration 3000-3500mg/
L, COD concentration 8000-10000mg/L.
The sulfate wastewater treatment method of the present embodiment is：
(1) water conservancy residence time (HRT) is maintained for 24 hours, under the action of sulfate reducing bacteria and methanogen, control pH is
8.0, anaerobism desulfurization is carried out to sulfate wastewater, obtains the biogas containing hydrogen sulfide and anaerobic reaction liquid, the anaerobic reaction liquid
It is divided into two parts, a part carries out stripping, and another part enters downstream section；
(2) in two-stage series connection packed tower, stripping is carried out to step (1) the anaerobic reaction liquid, carries out the anaerobism of stripping
Reaction solution is divided into two parts, and a part directly enters two-stage series connection packed tower from middle part and sprayed, only by second level filler
Area carries out stripping, and another part enters two-stage series connection packed tower from top again after mixing with sulfate wastewater and sprayed, and passes through
The first order and second level filler carry out two-stage stripping, obtain hydrogen sulfide containing stripping gas and stripping waste water；
Wherein, the stripping gas of stripping process and anaerobic reaction liquid counter current contacting, stripping gas are purified biogas；
(3) it is with pH to the hydrogen sulfide containing stripping gas of the biogas containing hydrogen sulfide and step (2) described in step (1)
10.5 lye is absorbed, and sulfide absorbing liquid and purified gas are obtained；
Wherein, the lye is Na2CO3And NaHCO3The buffer of composition；
(4) under the action of sulfur oxidizing bacterium, biological sulphur is carried out under aeration condition to step (3) the sulfide absorbing liquid
Oxidation, the thio-oxidizing oxidation-reduction potential of control biology is -300mV, and sedimentation separation obtains elemental sulfur and clear liquid, the simple substance
Sulphur enters downstream sulfur recovery system and carries out Recovery Purifying, and the clear liquid is back to step (3) described absorption process as absorbing liquid
In；
(5) step (3) described purified gas is stored in gas holder, the purified gas stored is removed to be recycled back to as stripping gas
Outside stripping step, it is also used to downstream energy supply.
In the present embodiment, the pH of step (1) is relatively high, so that sulfate wastewater treatment effect is declined, this implementation
The SO of example4 2-Removal rate is that 60%, COD removal rate is 55%, and the yield of elemental sulfur is 2.2g/L/ days.
Embodiment 5
The apparatus system of the sulfate wastewater treatment of the present embodiment is same as Example 1.
The sulfate wastewater of the present embodiment processing is true pharmacy waste water, wastewater parameter SO4 2-Concentration 3000-3500mg/
L, COD concentration 8000-10000mg/L.
The sulfate wastewater treatment method of the present embodiment is：
(1) water conservancy residence time (HRT) is maintained for 24 hours, under the action of sulfate reducing bacteria and methanogen, control pH is
7.0, anaerobism desulfurization is carried out to sulfate wastewater, obtains the biogas containing hydrogen sulfide and anaerobic reaction liquid, the anaerobic reaction liquid
It is divided into two parts, a part carries out stripping, and another part enters downstream section；
(2) in two-stage series connection packed tower, stripping is carried out to step (1) the anaerobic reaction liquid, carries out the anaerobism of stripping
Reaction solution is divided into two parts, and a part directly enters two-stage series connection packed tower from middle part and sprayed, only by second level filler
Area carries out stripping, and another part enters two-stage series connection packed tower from top again after mixing with sulfate wastewater and sprayed, and passes through
The first order and second level filler carry out two-stage stripping, obtain hydrogen sulfide containing stripping gas and stripping waste water；
Wherein, the stripping gas of stripping process and anaerobic reaction liquid counter current contacting, stripping gas are purified biogas；
(3) it is with pH to the hydrogen sulfide containing stripping gas of the biogas containing hydrogen sulfide and step (2) described in step (1)
9.5 lye is absorbed, and sulfide absorbing liquid and purified gas are obtained；
Wherein, the lye is Na2CO3And NaHCO3The buffer of composition；
(4) under the action of sulfur oxidizing bacterium, biological sulphur is carried out under aeration condition to step (3) the sulfide absorbing liquid
Oxidation, the thio-oxidizing oxidation-reduction potential of control biology is -350mV, and sedimentation separation obtains elemental sulfur and clear liquid, the simple substance
Sulphur enters downstream sulfur recovery system and carries out Recovery Purifying, and the clear liquid is back to step (3) described absorption process as absorbing liquid
In；
(5) step (3) described purified gas is stored in gas holder, the purified gas stored is removed to be recycled back to as stripping gas
Outside stripping step, it is also used to downstream energy supply.
In the present embodiment, SO4 2-Removal rate is that 78%, COD removal rate is 61%, and the yield of elemental sulfur is 3.4g/L/ days.
Based on the above embodiments it is found that the apparatus system of sulfate wastewater treatment provided by the invention and its processing method are real
Show efficient, the green innoxious and recycling treatment of acid high sulfate-containing wastewater, and significantly improves the economy of process
Property.Stripping process especially therein plays the role of the good water treatment effect of present invention acquirement very important.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of apparatus system of sulfate wastewater treatment, which is characterized in that the system comprises：Anaerobic reaction unit, stripping
Unit, absorptive unit, biological desulphurization unit and gas storage element；
Anaerobic reaction unit, with sulfate wastewater feeding pipe, the outlet of stripping unit liquid, the import of stripping unit liquid and absorption
Unitary gas import is respectively connected with；
Stripping unit, with the liquid-inlet of anaerobic reaction unit, the liquid outlet of anaerobic reaction unit, absorptive unit gas feed
Outlet with gas storage element is respectively connected with；
Absorptive unit, with the gas vent of anaerobic reaction unit, the gas vent of stripping unit, biological desulphurization unit liquid discharge
The gas feed of mouth, the liquid-inlet of biological desulphurization unit and gas storage element is respectively connected with；
Biological desulphurization unit distinguishes phase with the liquid-inlet of absorptive unit, the liquid outlet of absorptive unit and air input passageway
Even；
Gas storage element, the gas feed with the gas vent and stripping unit of absorptive unit are respectively connected with.
2. the apparatus system of sulfate wastewater treatment according to claim 1, which is characterized in that the anaerobic reaction unit
Including anaerobic reactor (1) and conditioning tank (2), the import with conditioning tank (2) respectively of the liquid outlet of the anaerobic reactor (1)
It is connected with the liquid-inlet of stripping unit, the liquid-inlet of the anaerobic reactor (1) is connected with the liquid outlet of stripping unit,
The gas vent of the anaerobic reactor (1) is connected with the gas feed of absorptive unit, the import and anaerobism of the conditioning tank (2)
The liquid outlet and sulfate wastewater feeding pipe of reactor (1) are respectively connected with, the outlet of the conditioning tank (2) and stripping unit
Liquid-inlet be connected；
Preferably, the anaerobic reactor (1) further includes the liquid outlet connecting with downstream section；
Preferably, the pipeline between the liquid outlet of stripping unit and the liquid-inlet of anaerobic reactor (1) is equipped with power transmission
Device；
Preferably, the pipeline between the liquid outlet of anaerobic reactor (1) and the liquid-inlet of stripping unit is equipped with power transmission
Device；
Preferably, the pipeline between the outlet of conditioning tank (2) and the liquid-inlet of stripping unit is equipped with power conveying device；
Preferably, the power conveying device is water pump；
It preferably, include methanogenesis activity sludge in the anaerobic reactor (1)；
It preferably, include sulfate reducing bacteria and methanogen in the methanogenesis activity sludge.
3. the apparatus system of sulfate wastewater treatment according to claim 1 or 2, which is characterized in that the stripping unit
Including stripping tower (3), the overhead liquid feed inlet of stripping tower (3) is connected with the outlet of conditioning tank (2), in the tower of stripping tower (3)
Portion's liquid inlet opening is connected with the liquid outlet of anaerobic reactor (1), the gas vent of stripping tower (3) and absorptive unit gas into
Mouth is connected, and the gas feed of stripping tower (3) is connected with the outlet of gas storage element；
Preferably, the stripping tower (3) is two-stage series connection packed tower, and the overhead liquid feed inlet of stripping tower (3) is filled out positioned at upper layer
The top of the bed of material, the tower central liquid feed inlet of stripping tower (3) is between two-stage packing layer.
4. the apparatus system of sulfate wastewater treatment according to claim 1-3, which is characterized in that the absorption
Unit includes the first absorption tower (41) and second absorption tower (42), the gas feed of first absorption tower (41) and stripping tower
(3) gas vent is connected, and the gas vent of the first absorption tower (41) is connected with the gas feed of gas storage element, and first inhales
The liquid-inlet for receiving tower (41) is connected with the liquid outlet of biological desulphurization unit, the liquid outlet and biology of the first absorption tower (41)
The liquid-inlet of desulfurization unit is connected, and the gas feed of second absorption tower (42) is connected with the gas vent of anaerobic reactor (1),
The gas vent of second absorption tower (42) is connected with the gas feed of gas storage element, the liquid-inlet of second absorption tower (42)
It is connected with the liquid outlet of biological desulphurization unit, the liquid outlet of second absorption tower (42) and the liquid-inlet of biological desulphurization unit
It is connected；
Preferably, power conveying device is equipped between the liquid outlet of biological desulphurization unit and the liquid-inlet of absorptive unit；
Preferably, the power conveying device is water pump.
5. the apparatus system of sulfate wastewater treatment according to claim 1-4, which is characterized in that the biology
Desulfurization unit includes biological desulphurization reactor (5) and subsider (6), the liquid-inlet of the biological desulphurization reactor (5) and
The liquid outlet on one absorption tower (41) and the liquid outlet of second absorption tower (42) are respectively connected with, biological desulphurization reactor (5)
Liquid outlet is connected with the liquid-inlet of subsider (6), gas feed and the air input passageway phase of biological desulphurization reactor (5)
Even, the liquid-inlet of subsider (6) is connected with the liquid outlet of biological desulphurization reactor (5), the liquid outlet of subsider (6) and
The liquid-inlet on the first absorption tower (41) is connected；
Preferably, tail gas outlet is additionally provided on the biological desulphurization reactor (5)；
Preferably, air inlet duct road is equipped with power conveying device；
Preferably, the power conveying device is air pump；
Preferably, subsider (6) bottom is additionally provided with elemental sulfur outlet；
It preferably, include sulfur oxidizing bacterium in the biological desulphurization reactor (5)；
Preferably, the sulfur oxidizing bacterium is multipotency sulphur alkali vibrios D301.
6. the apparatus system of sulfate wastewater treatment according to claim 1-5, which is characterized in that the gas
Storage element includes gas holder (7), and the gas feed of the gas holder (7) and the gas vent of the first absorption tower (41) and second absorb
The gas vent of tower (42) is respectively connected with, and the gas vent of gas holder (7) is connected with the gas feed of stripping tower (3)；
Preferably, the gas vent being connected with boiler is additionally provided on the gas holder (7)；
Preferably, the pipeline between the gas vent of gas holder (7) and the gas feed of stripping tower (3) is filled equipped with power transmission
It sets；
Preferably, the power conveying device is booster fan.
7. a kind of processing method of the apparatus system of sulfate wastewater treatment as claimed in any one of claims 1 to 6, feature
It is, the described method comprises the following steps：
(1) anaerobism desulfurization is carried out to sulfate wastewater, obtains the biogas containing hydrogen sulfide and anaerobic reaction liquid；
(2) stripping is carried out to step (1) the anaerobic reaction liquid, obtains hydrogen sulfide containing stripping gas and stripping waste water；
(3) the hydrogen sulfide containing stripping gas of the biogas containing hydrogen sulfide and step (2) described in step (1) is absorbed, is obtained
To sulfide absorbing liquid and purified gas；
(4) biological sulphur oxidation is carried out under aeration condition to step (3) the sulfide absorbing liquid, obtains elemental sulfur and clear liquid；
(5) step (3) described purified gas is stored, and is recycled back to stripping step as stripping gas.
8. processing method according to claim 7, which is characterized in that the sulfate in step (1) described sulfate wastewater
Concentration > 1500mg/L；
Preferably, step (1) sulfate wastewater is acid waste water；
Preferably, the anaerobism desulfurization carries out under the action of microorganism；
Preferably, the microorganism includes sulfate reducing bacteria and methanogen；
Preferably, in step (1), the pH of the anaerobism desulfurization is 6.0~8.0；
Preferably, in step (1), obtained anaerobic reaction liquid is divided into two parts, and a part carries out stripping, under another part enters
Swim workshop section；
Preferably, in step (2) described stripping, stripping gas and anaerobic reaction liquid counter current contacting；
Preferably, in step (2) described stripping, the adding manner of anaerobic reaction liquid is spray；
Preferably, in step (2), the anaerobic reaction liquid for carrying out stripping is divided into two parts, and first part directly carries out stripping, and second
Part carries out stripping after mixing with sulfate wastewater again；
Preferably, in step (2), the stripping carries out in two-stage series connection packed tower, and the anaerobic reaction liquid for carrying out stripping is divided into
Two parts, first part directly enter two-stage series connection packed tower from middle part, only by second level packing area carry out stripping, second
Divide after being mixed with sulfate wastewater and enter two-stage series connection packed tower from top again, carries out two-stage by the first order and second level filler
Stripping；
Preferably, in step (2) described stripping, stripping gas is purified biogas.
9. processing method according to claim 7 or 8, which is characterized in that step (3) absorbing liquid that uses of absorbing is
Lye；
Preferably, the lye is Na2CO3And NaHCO3The buffer of composition；
Preferably, the pH of the lye is 8.5~10.5；
Preferably, step (4) the biological sulphur oxidation carries out under the action of sulfur oxidizing bacterium；
Preferably, the sulfur oxidizing bacterium is multipotency sulphur alkali vibrios D301；
Preferably, in step (4), the thio-oxidizing oxidation-reduction potential of biology is -400~-300mV；
Preferably, in step (4), elemental sulfur and clear liquid that biological sulphur aoxidizes are separated by settling；
Preferably, in step (4), the clear liquid is back in step (3) described absorption process as absorbing liquid；
Preferably, in step (4), the elemental sulfur enters downstream sulfur recovery system and carries out Recovery Purifying；
Preferably, in step (5), the purified gas stored is also used to downstream in addition to being recycled back to stripping step as stripping gas
Energy supply；
Preferably, in step (5), purified gas is stored in gas holder；
Preferably, the pressure remained steady of the gas holder.
10. according to the described in any item processing methods of claim 7-9, which is characterized in that the described method comprises the following steps：
(1) under the action of sulfate reducing bacteria and methanogen, control pH is 6.0~8.0, carries out anaerobism to sulfate wastewater
Desulfurization obtains the biogas containing hydrogen sulfide and anaerobic reaction liquid, and the anaerobic reaction liquid is divided into two parts, and a part is blown
De-, another part enters downstream section；
(2) in two-stage series connection packed tower, stripping is carried out to step (1) the anaerobic reaction liquid, carries out the anaerobic reaction of stripping
Liquid is divided into two parts, and a part directly enters two-stage series connection packed tower from middle part and sprayed, only by second level packing area into
Row stripping, another part enters two-stage series connection packed tower from top again after mixing with sulfate wastewater and is sprayed, by first
Grade and second level filler carry out two-stage stripping, obtain hydrogen sulfide containing stripping gas and stripping waste water；
Wherein, the stripping gas of stripping process and anaerobic reaction liquid counter current contacting, stripping gas are purified biogas；
(3) hydrogen sulfide containing stripping gas pH described to the biogas containing hydrogen sulfide and step (2) described in step (1) be 8.5~
10.5 lye is absorbed, and sulfide absorbing liquid and purified gas are obtained；
Wherein, the lye is Na2CO3And NaHCO3The buffer of composition；
(4) under the action of sulfur oxidizing bacterium, biological sulphur oxygen is carried out under aeration condition to step (3) the sulfide absorbing liquid
Change, the thio-oxidizing oxidation-reduction potential of control biology is -400~-300mV, and sedimentation separation obtains elemental sulfur and clear liquid, described
Elemental sulfur enters downstream sulfur recovery system and carries out Recovery Purifying, and the clear liquid is back to step (3) described absorption as absorbing liquid
In the process；
(5) step (3) described purified gas is stored in gas holder, the purified gas stored, which is removed, is recycled back to stripping as stripping gas
Outside step, it is also used to downstream energy supply.
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| CN110862144A (en) * | 2019-11-29 | 2020-03-06 | 山东环发科技开发有限公司 | Anaerobic biological treatment desulfurization method |
| CN111635002A (en) * | 2020-06-19 | 2020-09-08 | 中国电力工程顾问集团华北电力设计院有限公司 | Power plant desulfurization wastewater-based elemental sulfur preparation system and method |
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