CN102351381A - Device and method for treating sulfate wastewater - Google Patents
Device and method for treating sulfate wastewater Download PDFInfo
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- CN102351381A CN102351381A CN2011102337571A CN201110233757A CN102351381A CN 102351381 A CN102351381 A CN 102351381A CN 2011102337571 A CN2011102337571 A CN 2011102337571A CN 201110233757 A CN201110233757 A CN 201110233757A CN 102351381 A CN102351381 A CN 102351381A
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Abstract
The invention belongs to the technical field of wastewater treatment, in particular to a method and a device for treating sulfate wastewater. The treatment method comprises the following steps of: performing first-stage anaerobic treatment, namely adding ethanol into wastewater to be treated, and performing first-stage anaerobic treatment by using an anaerobic expanded bed, wherein a sulfate reduction reaction and methane fermentation are basically finished in a first-stage anaerobic reactor; and performing second-stage anaerobic treatment, namely finishing sulfate blow-off, anaerobic sludge precipitation and further second-stage anaerobic treatment in a combined precipitator. The sulfate reduction amount is extremely low in the second-stage anaerobic treatment process, but 30 to 70 percent of organic matters can be removed; and chemical oxygen demand (COD) removal efficiency rises along with the reduction in first-stage anaerobic amount so as to ensure that the whole set of system has a higher level of organic matter removal efficiency. The treatment device comprises an anaerobic expanded bed reactor, the combined precipitator, a water inlet pump, a backflow pump and the like. The device and the method have good treatment effects on high-concentration sulfate wastewater; and by the device and the method, the organic matter removal efficiency and methane fermentation efficiency can be improved.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to a kind of treatment unit and method of sulfate wastewater.
Background technology
In recent years; The pollution of sulfate wastewater is on the rise; A lot of production fields emerge a large amount of trade effluents that contains high concentration sulfate; Like chemical industry, pharmacy, process hides, papermaking, fermentation, food-processing and mining etc.; And sulfate wastewater has contaminated area big; Latency period is long, the characteristics that are difficult to administer.In well-known Basin of Huaihe River water pollution problems, the gourmet powder waste water that is rich in vitriol is second largest source of pollution.The underground water in a lot of cities of China has been subjected to sulfate contamination in various degree in addition.Therefore seeking effective sulfate wastewater treatment process has become environmental engineering circle question of common concern.
The pollution of acidic mine waste water is a global problem.Since the forties, the origin cause of formation of acidic mine waste water has been carried out a large amount of research with control abroad.Since the seventies, China also active adoption the whole bag of tricks administers acid wastewater in mine.At present both at home and abroad the method that adopts is mainly handled with neutralisation and wetland method that Wingdale or lime are made neutralizing agent.But the flood tide solid waste-calcium sulfate that neutralisation produces is difficult to dispose, and causes serious secondary pollution.Wetland method same for treating acidic mine wastewater has less investment, and working cost is low, is easy to advantages such as management; But wetland method floor space is big, handle affected by environment very big, and also not thorough to the processing of sulphur, remaining H
2S overflows from soil and gets into atmosphere, contaminate environment, and the natural condition that the wetland method also need be certain, and therefore, the wetland method has received certain limitation on using.Microbial method is handled the acid mine wastewater of sulfur acid salt, and to have a cost low, and suitability is strong, and non-secondary pollution, and advantage such as recyclable elemental sulfur receive home and abroad environment worker's extensive concern at present.
Mainly adopt destructive biotechnology for the organic waste water that is rich in vitriol, just utilize action of microorganisms that organism is transformed and decompose.Because it is higher to be rich in the organic waste water organic concentration of vitriol; The general Anaerobic Microbiological Treatment Technology that adopts is handled, and existing anaerobic biological treatment technology has: upflow anaerobic sludge blanket process, anaerobic filter, single-phase anaerobic technique such as anaerobic fluidized bed and diphasic anaerobic technique and the process integration that some grow up on the diphasic anaerobic basis.
With regard to biologic treating technique, existing technology is primarily aimed at the organic waste water that is rich in high concentration sulfate, and its emphasis is that this type of waste water is considered as high concentrated organic wastewater, produces the methane processing and it is carried out anaerobic digestion.
Both at home and abroad diphasic anaerobic techniques that adopt separate to avoid the inhibition of substrate competition property the bacterial classification metabolism more
[1,2], the result is illustrated in and reduces pH and COD/SO in the acid mutually
4 2-[3,4], use high temperature (55 ℃)
[5,6], and utilize H
2/ CO
2, contain H
2Gas (coal gas) or H
2Precursor (methyl alcohol, ethanol, lactic acid etc.) as electron donor
[7 ~ 8]Can improve the competitive edge of SRB, promote SO substrate
4 2-Reduction reduces SO
4 2-Influence to the methane phase.Because aerogenesis is seldom controlled H in the acid mutually
2The toxicity of S suppresses also need use rare gas element (N
2Deng) or little air stripping reduction sulfide concentration
[9,10]
Summary of the invention
The objective of the invention is to the deficiency that exists in the prior art, a kind of device and method to the high treatment of high concentration sulfate wastewater of vitriol and organic matter removal efficient is provided.
The device of treatment of high concentration sulfate wastewater provided by the invention adopts two-stage anaerobic and circulation gas to carry stripping process, and device comprises: anaerobic expanded bed bioreactor 1, built-up type settling vessel 2; Intake pump 5, reflux pump 6, alkali lye absorption bottle, air pump 8; Under meter 9, gas collection capsule 10, heat tracing system.Wherein, anaerobic expanded bed bioreactor 1 is a cylindrical body, and the bottom is a cone, and its bottom links to each other with intake pump 5 through pipeline; Anaerobic expanded bed bioreactor 1 side is provided with thief hole, and top is the gas-liquid separation part, and gas gets into the alkali lye absorption bottle through connecting tube and collects, and liquid portion gets into built-up type settling vessel 2 through connecting tube; Anaerobic expanded bed bioreactor 1 periphery is provided with the heat tracing system; Built-up type settling vessel 2 also is a cylindrical body, and the bottom is a cone, and its bottom links to each other with reflux pump 6 through pipeline; The top of built-up type settling vessel 2 is provided with the gas output tube pipeline joint that connects another alkali lye absorption bottle; And the water-in of the inlet channel that is connected with anaerobic expanded bed bioreactor 1; Upper side is provided with water outlet; The centre of built-up type settling vessel 2 is that stream chamber 3 falls in the center; This center falls in the upstream room that flows 3 inboards, chamber and is provided with floating stuffing floor 4, and all the other are the settling region; Built-up type settling vessel 2 adopts the jacketed type heating in water bath; The center falls 3 interior bottoms, stream chamber and is provided with the air-blowing device, by pneumatic tube connection traffic meter 9 and gas collection capsule 10; There is soft-filler at the interval that stream chamber 3 falls in built-up type settling vessel 2 walls and center, and built-up type settling vessel 2 peripheries also are provided with the heat tracing system; The gas that connects the alkali lye absorption bottle collection of anaerobic expanded bed bioreactor 1 and built-up type settling vessel 2 is collected in the gas collection capsule 10 through air pump 8.
In this device; The one-level anaerobic processing device that anaerobic expanded bed bioreactor 1 is a sulfate wastewater; Vast scale outer circulation through water outlet is to reduce the influence to anaerobic sludge of water inlet middle and high concentration vitriol and organism; And the method that adopts gas to carry stripping is removed the hydrogen sulfide in the recirculated water; Reduce the sulphur content in the recirculated water, reduce its toxic action.
In this device; Built-up type settling vessel 2 is anaerobic reaction districts, the second stage of sulfate wastewater; It has replaced the solid-liquid separation effect of triphase separator; And fall the indoor employing rare gas element of stream (like biogas after the desulfurization or nitrogen etc.) at the center of settling vessel and recirculated water is carried out gas carry stripping and good mud-water separation condition is provided; In the combination settling vessel, add floating stuffing floor (not stopping up) and form anaerobic reaction district, the second stage; Not only can effectively tackle and be difficult to sedimentary mud on a small quantity; And can strengthen the treatment effect of reactor, improve effluent characteristics.
The effect of gas collection capsule 10 is the collections to biogas, and connects gas meter and the stream chamber is fallen in the center carry out stripping.
It is following that apparatus of the present invention are carried out the sulfate wastewater processed steps:
At first, anaerobic expanded bed bioreactor 1 and built-up type settling vessel 2 are carried out the seed sludge domestication, the sulfate wastewater that adopts the low discharge lower concentration between domestication is as water inlet, and wherein water inlet is interpolation sucrose and alcoholic acid sulfate wastewater, and adjustment ethanol/SO
4 2-Within the specific limits.Keep temperature of reactor and recurrence rate within the specific limits in the domestication process; Take the mode of water inlet continuously that various microorganisms such as sulphate reducing bacteria (SRB), acid-producing bacteria (AB) and methanogen MPB are tamed; When reactor reaches certain flow and water inlet requirement; When sludge concentration was relatively stable, domestication finished.(carrying out wastewater treatment) begins normally to intake.
Then; Carry out normal wastewater treatment; Begin to transfer big sulfate wastewater flooding quantity; And raising sulfate wastewater concentration; Waste water gets into anaerobic expanded bed bioreactor 1 through intake pump 5; At sulphate reducing bacteria (SRB); Carry out the one-level anaerobism under the various action of microorganisms such as acid-producing bacteria (AB) and methanogen MPB; Through first order reaction; Most of material is degraded, and its aerogenesis focuses in the gas collection capsule 10 via the alkali lye absorption bottle, and stream chamber 3 falls in the center that its water outlet (mud mixture) flows into built-up type settling vessel 2; Carry out stripping; Deposition, stripping gas are the biogas that anaerobism produces, and through the alkali lye absorption bottle biogas are carried out purifying and collect; Muddy water through post precipitation is back to anaerobic expanded bed bioreactor 1 through reflux pump 6, to dilute former water-bed substrate concentration and to keep biomass and upflow velocity; The clear liquid of post precipitation is degraded water outlet then once more through floating stuffing layer (secondary anaerobic) mud.
Among the present invention, the mud of anaerobic expanded bed bioreactor 1 inoculation adopts the granule sludge of handling sulfate wastewater, and the TSS of inoculation back mud is 30 ~ 37 gL
-1, VSS is 28 ~ 34gL
-1Water inlet between domestication is through adding sucrose and ethanol control COD/SO
4 2-, generally be adjusted into 7:1 ~ 15:1, ethanol/SO
4 2-Be 1:1 ~ 3:1, COD concentration is 1500 ~ 3000mgL
-1, SO
4 2-Concentration is 150 ~ 300mgL
-1, pH is adjusted into 6.5 ~ 7.5, and HRT is 0.5 ~ 1.5d, and setting temperature of reactor is 30 ~ 40 ℃; Through domestication after a while, form a high density, highly active sludge blanket in the bottom of anaerobic expanded bed bioreactor, most organism forms CH here
4And CO
2The COD clearance of reactor reaches more than 88%, and the clearance of vitriol reaches more than 10%, the domestication end of processing.
Among the present invention, when carrying out normal wastewater treatment, flooding velocity is adjusted into 18 ~ 25 Ld
-1, water inlet COD/SO
4 2-Still remain unchanged, water inlet COD concentration is 5500 ~ 6200 mgL
-1, SO
4 2-Concentration is 500 ~ 650 mgL
-1, ethanol/SO
4 2-Be 2:1 ~ 3:1, the water temperature in the reactor is at 30 ~ 40 ℃, and the pH value fluctuates in 6.5 ~ 7.5 scope.
Among the present invention, wherein built-up type settling vessel 2 adopts 5 ~ 10 times recurrence rate, and by reflux pump 6 controls, the temperature of reactor is controlled at 30 ~ 40 ℃.
Alcoholic acid is added with to be beneficial to and improves organic matter removal and methane fermentation efficient, regulates ethanol/SO
4 2-Be 1:1 ~ 3:1, take biogas that sulfide is carried out stripping, can reduce the toxicity restraining effect between various bacterium, anaerobic expanded bed bioreactor one-level anaerobic COD clearance is 78% ~ 80%, and the COD clearance of system is 90% ~ 95%; The sulfate reduction rate 83% ~ 89% of system, one-level anaerobic sulfate reduction rate is 82% ~ 88%, ethanol is fairly obvious to the effect that improves sulfate reduction.
Beneficial effect of the present invention:
To the unfavorable factor (competitive inhibition between each bacterial classification and the SO that occur in the sulfur acid salt organic waste water anaerobic biological treatment process
4 2-Reduction produces H
2The toxicity restraining effect of S),, adopt two-stage anaerobic and circulation gas to carry stripping process, through adding ethanol control ethanol/SO according to the niche characteristics of sulphate reducing bacteria (SRB), acid-producing bacteria (AB) and methanogen (MPB)
4 2-When the two ratio and recurrence rate within the specific limits under the situation; The sulfate reduction rate of system can reach 83% ~ 89%; One-level anaerobic sulfate reduction rate is promoted to 82% ~ 88%; Ethanol is fairly obvious to the effect that improves sulfate reduction; The COD clearance of system can reach 90% ~ 95%, and final sulfate wastewater has obtained handling effectively.
Description of drawings
Fig. 1 carries the stripping process front elevation for two-stage anaerobic of the present invention and circulation gas.
Label among the figure: 1. anaerobic expanded bed bioreactor, 2. built-up type settling vessel, 3. the stream chamber falls in the center, 4. floating stuffing layer, 5. intake pump, 6. reflux pump, 7. alkali lye absorption bottle, 8. air pump, 9. under meter, 10. air bag, 11. heat tracing systems.
Embodiment
Below in conjunction with accompanying drawing and concrete instance the present invention is further specified.
The present invention is the sulfate wastewater treatment unit, as shown in Figure 1, mainly comprises anaerobic expanded bed bioreactor and built-up type settling vessel two parts.Wherein anaerobic expanded bed bioreactor manufacturing materials can be that synthetic glass or pvc pipe are processed, and total height is 1400 mm, diameter 150 mm, and useful volume is 20 L.Sulfate wastewater gets into bed body bottom through pump, the passing through of upward flow formula, and the water pump of employing is common topping-up pump or peristaltic pump.The expanded bed side is provided with 4 thief hatchs, and its spacing is 20cm.The expanded bed water outlet gets into the CD chamber through connecting water pipe, and it is 310 mm that stream chamber height falls in the center, diameter 100 mm, and useful volume is 2.1 L, is up and down pyramidal structure, manufacturing materials is synthetic glass or pvc pipe.Built-up type settling vessel total height is 700 mm, diameter 200 mm, and useful volume is 17.3 L; Adopt suspension material to fill between itself and the CD pond; Suspension material is for hanging film effect flexible material preferably, and its body bottom, pond is a pyramidal structure, is convenient to the discharge of excess sludge.The high floating stuffing layer of 200 mm is set in the upstream room, and useful volume is 4.7 L; All the other are the settling region.Reactor adopts the jacketed type heating in water bath, adopts the well heater heat supply of certain production of buying, and keeping the inside reactor temperature is 35 ℃.Used alkali lye absorption bottle for the band fill in vial, can connect two pipe connectings, volume is 4L.The pipe connecting that reactor adopts can be silicone tube or conventional hoses.The gas collection capsule is a kind of soft rubber capsule.
The present invention utilizes two-stage anaerobic and circulation gas to put forward the treatment process that stripping process carries out sulfate wastewater, its processing step:
The sludge seeding domestication stage: adopt the granule sludge of handling sulfate wastewater, the TSS of inoculation back mud is 30 ~ 37 gL
-1, VSS is 28 ~ 34 gL
-1Water inlet between domestication is through adding sucrose and ethanol control COD/SO
4 2-, generally be adjusted into 7:1 ~ 15:1, ethanol/SO
4 2-Be 1:1 ~ 3:1, COD concentration is 1500 ~ 3000mgL
-1, SO
4 2-Concentration is 150 ~ 300mgL
-1, pH is adjusted into 6.5 ~ 7.5, and HRT is 0.5 ~ 1.5d, and setting temperature of reactor is 30 ~ 40 ℃; Through domestication after a while, form a high density, highly active sludge blanket in the bottom of anaerobic expanded bed bioreactor, most organism forms CH here
4And CO
2
The one-level anaerobic treatment: the adjustment flooding velocity is 18 ~ 25 Ld
-1, the backflow ratio is 5 ~ 10 times, water inlet COD/SO
4 2-Still be 7:1 ~ 15:1, water inlet COD concentration is 5500 ~ 6200 mgL
-1, SO
4 2-Concentration is 500 ~ 650 mgL
-1, ethanol/SO
4 2-Be 1:1 ~ 3:1, the water temperature in the reactor is fluctuation in 30 ~ 40 ℃, the scope of pH value 6.5 ~ 7.5.Through the one-level anaerobism, the COD clearance of system is 90% ~ 95%, the sulfate reduction rate 83% ~ 89% of system.Wherein the alcoholic acid effect also is mainly reflected in this stage, and content is very low.Sulfate reduction is accomplished in the one-level anaerobic reactor basically.
Secondary anaerobic is handled: the adjustment recurrence rate is 5 ~ 10.Sulfide stripping, anaerobic sludge deposition and secondary anaerobic are further handled and in the built-up type settling vessel, are accomplished.Secondary anaerobic is very little to the sulfate reduction amount, but can remove 30% ~ 70% organism, and the COD clearance reduces with the one-level anaerobism and raise, and the organic matter removal efficient that has guaranteed whole system is in higher level.
Reference
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et?al.?Optimisation?of?sulphate?reduction?in?a?methanol-fed?thermophilic?bioreactor?[J].?Water?Res,?2002,?36:?1825-1833.
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Claims (5)
1. the device that sulfate wastewater is handled is characterized in that comprising: anaerobic expanded bed bioreactor (1), built-up type settling vessel (2), intake pump (5); Reflux pump (6), alkali lye absorption bottle, air pump (8); Under meter (9), gas collection capsule (10), heat tracing system; Wherein, anaerobic expanded bed bioreactor (1) is a cylindrical body, and the bottom is a cone, and its bottom links to each other with intake pump (5) through pipeline; Anaerobic expanded bed bioreactor (1) side is provided with thief hole, and top is the gas-liquid separation part, and gas gets into the alkali lye absorption bottle through connecting tube and collects, and liquid portion gets into built-up type settling vessel (2) through connecting tube; Anaerobic expanded bed bioreactor (1) periphery is provided with the heat tracing system; Built-up type settling vessel (2) also is a cylindrical body, and the bottom is a cone, and its bottom links to each other with reflux pump (6) through pipeline; The top of built-up type settling vessel (2) is provided with the gas output tube pipeline joint that connects another alkali lye absorption bottle; And the water-in of the inlet channel that is connected with anaerobic expanded bed bioreactor (1); Upper side is provided with water outlet; The centre of built-up type settling vessel (2) is that stream chamber (3) falls in the center; This center falls in the inboard upstream room in stream chamber (3) and is provided with floating stuffing floor (4), and all the other are the settling region; Built-up type settling vessel (2) adopts the jacketed type heating in water bath; The center falls stream middle and lower part, chamber (3) and is provided with the air-blowing device, by pneumatic tube connection traffic meter (9) and gas collection capsule (10); There is soft-filler at the interval that stream chamber (3) falls in built-up type settling vessel (2) wall and center, and built-up type settling vessel (2) periphery also is provided with the heat tracing system; Connecting the gas that the alkali lye absorption bottle of anaerobic expanded bed bioreactor (1) and built-up type settling vessel (2) absorbs is collected in the gas collection capsule (10) through air pump (8).
A utilization according to claim 1 device carry out the method that sulfate wastewater is handled, it is characterized in that concrete steps are:
At first, anaerobic expanded bed bioreactor (1) and built-up type settling vessel 2 are carried out the seed sludge domestication, the sulfate wastewater that adopts the low discharge lower concentration between domestication is as water inlet, and wherein water inlet is interpolation sucrose and alcoholic acid sulfate wastewater, and adjustment ethanol/SO
4 2-Within the specific limits; Keep temperature of reactor and recurrence rate within the specific limits in the domestication process; Take the mode of water inlet continuously that the various microorganisms of sulphate reducing bacteria, acid-producing bacteria and methanogen are tamed; When reactor reaches certain flow and water inlet requirement, when sludge concentration is relatively stable, tames and finish;
Then; Carry out normal wastewater treatment; Begin to transfer big sulfate wastewater flooding quantity; And raising sulfate wastewater concentration; Waste water gets into anaerobic expanded bed bioreactor (1) through intake pump (5); At sulphate reducing bacteria; Carry out the one-level anaerobism under the various action of microorganisms of acid-producing bacteria and methanogen; Through first order reaction; Most of material is degraded, and its aerogenesis focuses in the gas collection capsule (10) via the alkali lye absorption bottle, and stream chamber (3) falls in the center that its water outlet flows into built-up type settling vessel (2); Carry out stripping; Deposition, stripping gas are the biogas that anaerobism produces, and through the alkali lye absorption bottle biogas are carried out purifying and collect; Muddy water through post precipitation is back to anaerobic expanded bed bioreactor (1) through reflux pump (6), to dilute former water-bed substrate concentration and to keep biomass and upflow velocity; The clear liquid of post precipitation is degraded water outlet then once more through floating stuffing layer mud.
3. the method that sulfate wastewater according to claim 2 is handled is characterized in that the mud of anaerobic expanded bed bioreactor (1) inoculation adopts the granule sludge of handling sulfate wastewater, and the TSS of inoculation back mud is 30 ~ 37 gL
-1, VSS is 28 ~ 34gL
-1Water inlet between domestication is through adding sucrose and ethanol control COD/SO
4 2-, adjustment COD/SO
4 2-Be 7:1 ~ 15:1, ethanol/SO
4 2-Be 1:1 ~ 3:1, COD concentration is 1500 ~ 3000mgL
-1, SO
4 2-Concentration is 150 ~ 300mgL
-1, adjustment pH is 6.5 ~ 7.5, and HRT is 0.5 ~ 1.5d, and temperature of reactor is 30 ~ 40 ℃; Through domestication after a while, form a high density, highly active sludge blanket in the bottom of anaerobic expanded bed bioreactor, most organism forms CH here
4And CO
2The COD clearance reaches more than 88%, and the clearance of vitriol reaches more than 10%, the domestication end of processing.
4. the method that sulfate wastewater according to claim 3 is handled is characterized in that when carrying out normal wastewater treatment, flooding velocity is adjusted into 18 ~ 25 Ld
-1, water inlet COD/SO
4 2-Still remain unchanged, water inlet COD concentration is 5500 ~ 6200 mgL
-1, SO
4 2-Concentration is 500 ~ 650 mgL
-1, ethanol/SO
4 2-Be 2:1 ~ 3:1, the water temperature in the reactor is at 30 ~ 40 ℃, and the pH value fluctuates in 6.5 ~ 7.5 scope.
5. the method for handling according to claim 2,3 or 4 described sulfate wastewaters is characterized in that wherein built-up type settling vessel (2) adopts 5 ~ 10 times recurrence rate, is controlled by reflux pump (6).
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| CN113526661A (en) * | 2021-07-30 | 2021-10-22 | 皖创环保股份有限公司 | UASB reactor system with self-heating function |
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| CN104944575A (en) * | 2015-05-29 | 2015-09-30 | 江汉大学 | Biological treatment method of acidic sulfate wastewater containing Fe<3+> and Cu<2+> |
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| CN105950534A (en) * | 2016-05-30 | 2016-09-21 | 青岛理工大学 | Method for preparing efficient ecological restoration flora for Pb-polluted site by utilizing sludge |
| CN109231443A (en) * | 2018-09-25 | 2019-01-18 | 大连理工大学 | A kind of industrial wastewater anaerobism desulfurizer and technique based on magnetic iron ore reinforcing |
| CN109319928A (en) * | 2018-12-13 | 2019-02-12 | 北京舞鹤环境工程设计有限公司 | High Fat wastewater treatment device and technique |
| CN109319928B (en) * | 2018-12-13 | 2021-09-17 | 北京舞鹤环境工程设计有限公司 | High-grease wastewater treatment device and process |
| CN113526661A (en) * | 2021-07-30 | 2021-10-22 | 皖创环保股份有限公司 | UASB reactor system with self-heating function |
| CN113526661B (en) * | 2021-07-30 | 2022-04-08 | 皖创环保股份有限公司 | UASB reactor system with self-heating function |
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