CN103102012A - Anaerobic biochemistry treatment method for cellulose ethanol wastewater - Google Patents
Anaerobic biochemistry treatment method for cellulose ethanol wastewater Download PDFInfo
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Abstract
The present invention relates to an anaerobic biochemistry treatment method for cellulose ethanol wastewater, wherein a treatment is performed on cellulose ethanol wastewater under anaerobic biochemistry treatment conditions, an iron filler is arranged in an anaerobic biochemistry treatment reactor, and the anaerobic biochemistry treatment conditions of the cellulose ethanol wastewater comprise that: an influent SO4<2-> concentration is 1000-5000 mg/L, a COD concentration is 10000-40000 mg/L, a COD/SO4<2-> ratio is 4-10, a reflux ratio is 1:1-3:1, a temperature in the reactor is controlled to 30-40 DEG C, a pH value range is 6.5-7.5, and an oxidation-reduction potential ORP is -380 to -420 mV. Compared to the method in the prior art, the method of the present invention has the following advantages that: sulfate can be effectively removed while no adverse influence on the cellulose ethanol wastewater anaerobic biochemistry treatment process can be generated.
Description
Technical field
The invention belongs to water-treatment technology field, relate to a kind of biochemical processing method and anaerobic biological treatment reactor of high-sulfate cellulose ethanol production wastewater.
Background technology
When adopting anaerobic process to process the high-concentration sulfuric acid salt organic waste water, due to the intervention of sulfate reduction, its product H
2S, HS
-And S
2-Deng can produce the severe inhibition effect to anaerobic methanogens, make the gas production rate even system crash that descends.Cellulose ethanol production wastewater belongs to a kind of acid organic waste water that contains high concentration sulfate, high solid suspended substance, generally adopts anaerobic-aerobic joint technology to carry out biochemical treatment.Therefore, the Coal Gas Washing Cycling Water sulfate radical can be removed and the whether normally key of operation of anaerobic technique will be become.
At present, the technological method that removes sulfate radical mainly contains BaC1
2Method, CaC1
2Method and cold method.BaC1
2Method is the industrial application method of chemical sulfate radical the most widely, and its technological operation is simple, removal effect good, but BaC1
2Have the shortcomings such as stronger toxicity, the storage requirement requirement is high, use cost is high.CaC1
2Method is because the solubility product of calcium sulfate is larger, and the effect when removing sulfate radical is poor than barium chloride method, and remaining a large amount of calcium ion has restraining effect to the little biochemical reaction of anaerobism, and the calcium dirt of generation very easily blocks pipeline.The energy consumption that cold method removes sulfate radical is very high, and industrial application is extremely rare at present.In recent years, people had developed ion exchange method, membrane separation process and absorption method etc., but these methods are multiplex in the removing of chlor-alkali sulfate radical in waste water, and were few at the applied research report of cellulose ethanol field of waste water treatment.
For above problem, carried out a large amount of research both at home and abroad.Many researchs are many with the front-end process of coagulation process as the biochemical treatment of cellulose ethanol anaerobic waste water, although the biodegradability of processed waste water improves, but coagulation can't be removed deliquescent sulfate radical in waste water, and the coagulating agent that adds such as aluminium salt, molysite, its negatively charged ion also can increase the murder by poisoning to anaerobion.
The CN1089579A proposition is a kind of can overcome the method that high concentration sulphate is poisoned biogas fermentation, and the pond of filling the iron plane flower is set before biogas fermentation device, by controlling the flow of waste water, first makes iron plane spend ingress of air, and oxidation generates Fe
2+, then will be dissolved in waste water, satisfy the needs of biogas fermentation.Although the method is simple in structure, the iron plane flower contacts with air, and the iron rust that produces fast causes adhesion, the obstruction between iron filings, makes the short stream of sewage, reduces sewage treating efficiency.In addition, need frequent regulating pondage to control Fe in operating process
2+Concentration, operational management is comparatively loaded down with trivial details.Generate Fe
2+Process in, need introducing air, follow-up anaerobic fermentation process is had obvious disadvantageous effect.
Summary of the invention
In order to overcome problems of the prior art, the invention provides a kind for the treatment of process that efficiently removes the cellulose ethanol production wastewater of sulfate radical, in the effective elimination sulfate radical, cellulose ethanol anaerobic biological treating processes is not had a negative impact.
The anaerobic biological treatment process of cellulose ethanol waste water of the present invention comprises following process: under the anaerobic biological treatment condition, cellulose ethanol waste water is processed, in the anaerobic biological treatment reactor, iron filler is set.
In the inventive method, cellulose ethanol waste water is the waste water that produces take the Mierocrystalline cellulose in various sources as raw material production cellulose ethanol process.The condition of cellulose ethanol anaerobic waste water biochemical treatment is generally: water inlet SO
4 2-Concentration is 1 000 ~ 5 000 mg/L, and COD concentration is 10 000 ~ 40 000 mg/L, COD/SO
4 2-Ratio is 4 ~ 10, and reflux ratio is 1:1 ~ 3:1, works as COD/SO
4 2-＜2 o'clock, the sulfate radical clearance obviously descended.Control reactor temperature and be (35 ± 5) ℃, the scope of pH between 6.5 ~ 7.5, redox potential ORP-380mV～-420mV between.
In the inventive method, the iron filler that arranges in the anaerobic biological treatment reactor is made with fe, and shape is any, is preferably the ring-like iron filler of θ, and the external diameter of the ring-like iron filler of θ is generally 4 ~ 8 mm.Iron filler generally can be loaded 1%～20% of biochemical reactor volume, is preferably 5%～10%.The ring-like iron filler of θ forms by cutting and rolling, and has larger specific surface area and voidage, is easy to fluidisation under the effect of current, also can mix with other fillers interpolation.
In the inventive method, the anaerobic biological treatment reactor can adopt structure of reactor conventional in this area.In a kind of concrete anaerobic biological treatment reactor, at anaerobic biological treatment reactor inner bottom part, water distributor is set, waste water and recirculated water enter the anaerobic biological treatment reactor from water distributor; Recirculated water draws from the middle and upper part of anaerobic biological treatment reactor, and the introducing of recirculated water is conducive to iron filler and is in fluidized state; Anaerobic biological treatment reactor top arranges the gas phase escape route; Outlet pipeline after the set handling of anaerobic biological treatment reactor top; Anaerobic biological treatment reactor internal upper part arranges triphase separator, and triphase separator can adopt this area conventional structure.Triphase separator is comprised of settling region, gas skirt and sealing gland, enters gas skirt after gas is separated, and the solid-liquid mixed solution carries out solid-liquid separation in the settling region, and the solid of sinking returns to reaction zone by gravity by the seam that refluxes, thereby reaches the effect of three phase separation.
In the inventive method, the accessory constituent of anaerobic biological treatment reactor comprises return of waste water system and on-line monitoring system.The return of waste water system is back to equalizing tank with the water outlet of reactor middle and upper part through peristaltic pump, mixes by water distributor entering reaction zone with water inlet, its objective is the water speed of crossing that improves by iron filler, thereby strengthens molten Fe
2+Effect.Simultaneously, go up the expansion effect that Flow Velocity can improve reactor lower part mud district faster, raising waste water contacts with mud and filler.On-line monitoring system comprises well heater, pH/ORP metrical instrument and wet flow indicator etc., can show accurately that temperature, pH, redox potential and the gas production rate of anaerobic reactor are whether within normal range.
This area it is generally acknowledged, therefore the anaerobic biological treating processes can't complete the reaction process that fe generates iron ion due to anaerobic in system.But find through research, although cellulose ethanol anaerobically fermenting system is in anaerobic environment, fe can be converted into the FeS precipitation in reaction system, thereby avoided the hydrogen sulfide of anaerobic fermentation process generation on the impact of biochemical treatment.The present invention utilizes this discovery, has designed the anaerobic biological treatment process of cellulose ethanol waste water, effective elimination sulfate radical, simultaneously anaerobic fermentation process is not had a negative impact, obtained good treatment effect.The present invention is easy to operate, and running cost is low, and the sulfate radical removal effect is good.
Description of drawings
Fig. 1 is a kind of experimental installation structural representation that efficiently takes off the anaerobic biological treatment reactor of sulfate radical in waste water.
Wherein: 1, pH/ORP survey meter, 2, anaerobic reactor, 3, hot water jacket, 4, heating rod, 5, well heater, 6, hot water circulating pump, 7, support, 8, iron filler, 9, water distributor, 10, circulation intake pump, 11, equalizing tank, 12, intake pump, 13, triphase separator, 14, thief hole, 15, sealing gland, 16, wet flow indicator; A, water inlet, b, gas, c, water outlet, d, recirculated water, e, settling region, f, reaction zone.
Embodiment
Fig. 1 has shown a kind of structural representation that efficiently takes off the anaerobic biological experimental reactor of sulfate radical in waste water.This device mainly comprises a columnar closed reactor 2, arrange successively from the bottom to top a water distributor 9 in anaerobic biological treatment reactor 2, iron filler 8 and a triphase separator 13, the inner chamber of anaerobic reactor 2 is divided into the reaction zone f of bottom and the settling region e on top, and the intersection of reaction zone f and settling region e is the recirculated water extraction location.The housing of anaerobic reactor adopts synthetic glass or glass reinforced plastic to make, and its internal diameter is 550 mm, and external diameter is 600 mm, and height is 2 000 mm, and useful volume is 0.4 m
3Water inlet a enters equalizing tank 11 by intake pump 12, mixes by circulation intake pump 10 entering reactor bottom at equalizing tank 11 with recirculated water d, fully mixes at reaction zone f with iron filler 8 by water distributor 9.The a large amount of gases that upwards flow and generate of water inlet a and recirculated water d have played good natural stirring action to filler and the mud of reaction zone f, impel mud and filler in reaction zone f internal recycling.The mud of the subsidiary bubble of a part flows into settling region e with waste water, and this zone does not have the effect of recirculated water d, and flow velocity is less, and bubble separates with mud with waste water after clashing into, through passing through wet flow indicator 16 metered volume after air seal set 15 again.Mud after the release bubble is deposited to the surface of sludge blanket due to action of gravitation, return to reaction zone f.Water outlet c is through the overflow weir outflow reactor.Be provided with hot water jacket 3 between the inside and outside wall of anaerobic biological treatment reactor 2, well heater 5 is heated by heating rod 4, and insulation water is connected by the upper and lower of pipeline with hot water jacket 3 through hot water circulating pump 6, and the water temperature that control is incubated water is (35 ± 5) ℃.The top of anaerobic biological treatment reactor 2 is provided with pH/ORP on-line measurement instrument 1, controls the scope of pH in reactor between 6.5 ~ 7.5, the scope of redox potential ORP-380mV～-420mV between.If in actually operating, redox potential is higher than this scope, can suitably turn down into water pH, accelerate molten Fe
2+Speed.Mud can regularly discharge by thief hole 14.
The working process of above-mentioned anaerobic biological treatment reactor is as follows: waste water enters from the bottom of reactor, fully contacts in reaction zone with active sludge with iron filler, and the anaerobic biological process is constantly dissolved fe and generated Fe
2+, due to isolated with air, the corrosive nature of iron is slow, can evenly discharge Fe
2+, the reductive action of iron can reduce the anaerobic oxidation reduction potential, is conducive to the growth of sulfate radical reducing bacteria.Simultaneously, Fe
2+S with the generation of sulfate radical reducing bacteria
2-Form the FeS precipitation, this precipitation can be considered good biochemical carrier, and anaerobion can be precipitated as kernel and constantly breed with FeS, finally develops into the granule sludge with greater particle size.Mix with water inlet to equalizing tank in the water outlet of the middle and upper part of reactor backflow part, reflux ratio is 1:1 ~ 3:1(quantity of circulating water and processing wastewater flow rate volume ratio).The gas of waste water and sludge creation enters gas gathering system after triphase separator, water outlet is discharged from the top of reactor, and mud can discharge by thief hole.
Embodiment: certain cellulose ethanol waste water adopts this device to process, and its biochemical treatment condition is: reactor temperature is (35 ± 1) ℃, and pH is 6.5, and ORP is-400 mV; The iron filler packing ratio is 6%; Reflux ratio is 2:1.Device continuous operation 6 months, water inlet SO
4 2-Drop to 300 mg/L from 4 000 mg/L, clearance is 92.5%; COD drops to 11 000 mg/L from 20 000 mg/L, and clearance is 45%; Water outlet S
2-Lower than 20 mg/L, Fe
2+Lower than 10 mg/L, illustrate that this anaerobic biological treatment reactor can realize efficiently removing the purpose of sulfate radical.
Claims (10)
1. the anaerobic biological treatment process of a cellulose ethanol waste water, process cellulose ethanol waste water under the anaerobic biological treatment condition, it is characterized in that: in the anaerobic biological treatment reactor, iron filler is set.
2. method according to claim 1 is characterized in that: cellulose ethanol waste water is the waste water that produces take Mierocrystalline cellulose as raw material production cellulose ethanol process.
3. method according to claim 1 and 2, it is characterized in that: the condition of cellulose ethanol anaerobic waste water biochemical treatment is: water inlet SO
4 2-Concentration is 1 000 ~ 5 000 mg/L, and COD concentration is 10 000 ~ 40 000 mg/L, COD/SO
4 2-Ratio is 4 ~ 10, and reflux ratio is 1:1 ~ 3:1; Controlling reactor temperature is 35 ± 5 ℃, the scope of pH between 6.5 ~ 7.5, redox potential ORP-380mV～-420mV between.
4. method according to claim 1, it is characterized in that: the iron filler that arranges in the anaerobic biological treatment reactor is made with fe, adopts the ring-like iron filler of θ.
5. method according to claim 4, it is characterized in that: the external diameter of the ring-like iron filler of θ is 4～8 mm.
6. according to claim 1 or 4 described methods, is characterized in that: 1%～20% of iron filler filling biochemical reactor volume.
7. according to claim 1 or 4 described methods, is characterized in that: 5%～10% of iron filler filling biochemical reactor volume.
8. method according to claim 1, it is characterized in that: anaerobic biological treatment reactor inner bottom part arranges water distributor, and waste water and recirculated water enter the anaerobic biological treatment reactor from water distributor.
9. method according to claim 1, it is characterized in that: anaerobic biological treatment reactor internal upper part arranges triphase separator.
10. an anaerobic biological treatment reactor, is characterized in that in the anaerobic biological treatment reactor, iron filler being set.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698655A (en) * | 2015-11-18 | 2017-05-24 | 中国石油化工股份有限公司 | Wastewater denitrification nitrogen removal treatment device and method |
| CN106698643A (en) * | 2015-11-18 | 2017-05-24 | 中国石油化工股份有限公司 | Wastewater treatment device and wastewater treatment method thereof |
| CN106755125A (en) * | 2016-12-28 | 2017-05-31 | 华中农业大学 | A kind of cellulose ethanol draff liquid and the processing method of agricultural wastes mixed fermentation |
| CN108002522A (en) * | 2016-11-01 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of dual-purpose wastewater treatment biological fluidized bed device and process of aerobic-anoxic |
| CN108017158A (en) * | 2016-11-01 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of dual-purpose wastewater treatment Biological expanded bed device and process of aerobic-anoxic |
| CN111439885A (en) * | 2019-07-16 | 2020-07-24 | 邓燕军 | Paper making wastewater pretreatment process of dosing type CSTR (continuous stirred tank reactor) and coagulation air flotation |
| CN114315045A (en) * | 2021-12-13 | 2022-04-12 | 苏沃特环境(江苏)有限公司 | Treatment system and treatment method for sulfate wastewater |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698655A (en) * | 2015-11-18 | 2017-05-24 | 中国石油化工股份有限公司 | Wastewater denitrification nitrogen removal treatment device and method |
| CN106698643A (en) * | 2015-11-18 | 2017-05-24 | 中国石油化工股份有限公司 | Wastewater treatment device and wastewater treatment method thereof |
| CN108002522A (en) * | 2016-11-01 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of dual-purpose wastewater treatment biological fluidized bed device and process of aerobic-anoxic |
| CN108017158A (en) * | 2016-11-01 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of dual-purpose wastewater treatment Biological expanded bed device and process of aerobic-anoxic |
| CN106755125A (en) * | 2016-12-28 | 2017-05-31 | 华中农业大学 | A kind of cellulose ethanol draff liquid and the processing method of agricultural wastes mixed fermentation |
| CN106755125B (en) * | 2016-12-28 | 2020-04-24 | 华中农业大学 | Treatment method for mixed fermentation of cellulosic ethanol waste liquid and agricultural wastes |
| CN111439885A (en) * | 2019-07-16 | 2020-07-24 | 邓燕军 | Paper making wastewater pretreatment process of dosing type CSTR (continuous stirred tank reactor) and coagulation air flotation |
| CN114315045A (en) * | 2021-12-13 | 2022-04-12 | 苏沃特环境(江苏)有限公司 | Treatment system and treatment method for sulfate wastewater |
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