CN108911364A - A kind of processing method of cellulosic ethanol waste water - Google Patents
A kind of processing method of cellulosic ethanol waste water Download PDFInfo
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- CN108911364A CN108911364A CN201810646782.4A CN201810646782A CN108911364A CN 108911364 A CN108911364 A CN 108911364A CN 201810646782 A CN201810646782 A CN 201810646782A CN 108911364 A CN108911364 A CN 108911364A
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- cellulosic ethanol
- ethanol waste
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4611—Fluid flow
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4618—Supplying or removing reactants or electrolyte
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
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- Life Sciences & Earth Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a kind of processing methods of cellulosic ethanol waste water.The processing method of the cellulosic ethanol waste water includes the following steps：Cellulosic ethanol waste water pretreatment, the aerobic integrated treatment of diphasic anaerobic-and electrochemical oxidation advanced treating.The present invention provides a kind of processing method of cellulosic ethanol waste water, COD value, ammonia-nitrogen content and the sulfate radical content of cellulosic ethanol waste water can be substantially reduced, make the side reaction products such as furan nucleus class, furfural, formic acid and the levulic acid in cellulosic ethanol waste water simultaneously, the content of the solid contents such as cellulose, lignin, hemicellulose and inorganic salts is reduced to the degree for not influencing the longtime running of the biochemical treatment of wastewater and smoothly implementing, and operating cost is low, ingenious in design, easy to maintain.
Description
Technical field
The present invention relates to technical field of waste water processing, specifically, being related to a kind of processing method of cellulosic ethanol waste water.
Background technique
In recent years, countries in the world put into substantial contribution, to the biochemistry for producing alcohol fuel using lignocellulosic as raw material
Technique is studied, and remarkable result is achieved in each process procedure, but its waste water generated is (referred to as fine below
Tie up plain alcohol wastewater) processing and recycling the problem of it is also more and more prominent.
The lignocellulosic material used when producing cellulosic ethanol is varied, different lignocellulosic pretreatments
The composition for the cellulosic ethanol waste water that method causes is also rather complicated.Especially destroyed in lignocellulosic pretreatment
The natural structure of lignocellulosic inevitably has occurred many side reactions, produces some such as furan nucleus classes, chaff
The side reaction products such as aldehyde, formic acid and levulic acid.These side reaction products, which remove, generates strongly cellulase and fermentative microorganism
Inhibiting effect, influence outside the conversion and final alcohol getting rate of lignocellulosic, these side reaction products without exception into
Enter into cellulosic ethanol waste water, and these side reaction products are generally difficult to be completed in a short time biodegrade, so that fiber
The biodegradability of plain alcohol wastewater reduces, and determines and the attainable COD removal rate of biochemical treatment institute is used to will be far below with starch
The alcohol wastewater that matter is produced by raw material can achieve the effect that.And COD value, ammonia-nitrogen content and the sulfuric acid of cellulosic ethanol waste water
The content of root is very high, significantly increases waste water load, and sulfate radical is easy to be reduced into hydrogen sulfide under anaerobic, vulcanization
Hydrogen has certain murder by poisoning to microorganism, anaerobic methanogens can be caused directly to be poisoned to death, to keep the efficiency of Anaerobic Treatment aobvious
Decline is write, the burden of subsequent Aerobic Process for Treatment and advanced treating is further increased.Meanwhile containing part in cellulosic ethanol waste water
Solid content is high in the recalcitrant substances such as cellulose, lignin, hemicellulose, mash, and is not easy to be layered, and separation is tired
Difficulty, the content of inorganic salts also greatly exceed the range of routine biochemistry processing, also substantially increase cellulosic ethanol waste water
Processing difficulty.
Summary of the invention
In order to solve the intractable technical problem of above-mentioned cellulosic ethanol waste water, it is useless that the present invention provides a kind of cellulosic ethanol
The processing method of water, using enzymatic hydrolysis+diphasic anaerobic-it is aerobic+electrochemical oxidation advanced treating to cellulosic ethanol waste water at
Reason, can substantially reduce COD value, ammonia-nitrogen content and the sulfate radical content of cellulosic ethanol waste water, while making cellulosic ethanol
The side reaction products such as furan nucleus class, furfural, formic acid and levulic acid in waste water, the solids such as cellulose, lignin, hemicellulose
The content of object and inorganic salts is reduced to the degree for not influencing the longtime running of the biochemical treatment of wastewater and smoothly implementing, fortune
Row is at low cost, easy to maintain.
The present invention provides a kind of processing methods of cellulosic ethanol waste water, include the following steps：
Step 1: cellulosic ethanol waste water pre-processes：Mixed enzyme is added into cellulosic ethanol waste water, is stirred after mixing anti-
It answers 20~24 hours；
Step 2: the aerobic integrated treatment of diphasic anaerobic-：Pretreated cellulosic ethanol waste water is passed sequentially through and is continuously stirred
It mixes groove type reactor, Expanded Granular Sludge Bed Reactor and sequencing batch reactor and carries out biological treatment；
Step 3: electrochemical oxidation advanced treating：By the cellulosic ethanol waste water after biological treatment into electrochemistry oxygen
Change advanced treating.
In a kind of preferred embodiment of the processing method of cellulosic ethanol waste water provided by the invention, the step 1
In, the additional amount of the mixed enzyme is 2~4g/L, and stirring rate is 100~120rpm；The mixed enzyme is by laccase, acid fibre
Tie up plain enzyme and hemicellulase in mass ratio 1:1.2~1.5:1.2~1.5 are mixed.
In a kind of preferred embodiment of the processing method of cellulosic ethanol waste water provided by the invention, the enzyme of the laccase
Vigor is 10000u/g, and the enzyme activity of the acidic cellulase is 20000u/g, and the enzyme activity of the hemicellulase is
100000u/g。
In a kind of preferred embodiment of the processing method of cellulosic ethanol waste water provided by the invention, the step 2
In, the volumetric loading of the continuous stirred tank reactor is 32kg COD/ (m3D), the continuous stirred tank reactor
Hydraulic detention time be 10 hours, the hydraulic detention time of the Expanded Granular Sludge Bed Reactor is 26 hours, the sequence
Batch reactor uses intermittent water inflow, Limited Aeration, and aeration rate is 0.8~1L/min, the aeration reaction time 8 hours, precipitates
Time 4 hours；The continuous stirred tank reactor and the seed sludge of the Expanded Granular Sludge Bed Reactor are derived from ethyl alcohol
Factory handles the inner circulation reactor of fermentation waste water, and the seed sludge of the sequencing batch reactor is derived from the work of sewage treatment plant
Property sludge.
It is described to continuously stir in a kind of preferred embodiment of the processing method of cellulosic ethanol waste water provided by the invention
Stripping tower is equipped between groove type reactor and the Expanded Granular Sludge Bed Reactor, and in the continuous stirred tank reactor
Before, between the stripping tower and the Expanded Granular Sludge Bed Reactor, the Expanded Granular Sludge Bed Reactor and the sequence
Between batch reactor and the sequencing batch reactor after be respectively equipped with conditioning tank, for match each unit processing water and
Adjust the pH of cellulosic ethanol waste water.
In a kind of preferred embodiment of the processing method of cellulosic ethanol waste water provided by the invention, the step 3
In, the current density of the electrochemical oxidation advanced treating is 20mA/cm2, reaction time 40min, using 0.1M NaCl conduct
Support electrolyte.
Compared to the prior art, the processing method of cellulosic ethanol waste water provided by the invention has the advantages that：
The present invention using enzymatic hydrolysis+diphasic anaerobic-it is aerobic+electrochemical oxidation advanced treating handles cellulosic ethanol waste water, can
COD value, ammonia-nitrogen content and the sulfate radical content of cellulosic ethanol waste water are substantially reduced, while being made in cellulosic ethanol waste water
The side reaction products such as furan nucleus class, furfural, formic acid and levulic acid, the solid contents such as cellulose, lignin, hemicellulose and nothing
The content of machine salt is reduced to the longtime running for not influencing the biochemical treatment of wastewater and the degree smoothly implemented, operating cost
It is low, easy to maintain.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The processing method of the cellulosic ethanol waste water includes the following steps：
(1) cellulosic ethanol waste water pre-processes：Mixed enzyme is added into cellulosic ethanol waste water, is stirred to react 20 after mixing
~24 hours；
The additional amount of the mixed enzyme is 2~4g/L, and stirring rate is 100~120rpm；The mixed enzyme is by laccase, acid
Property cellulase and hemicellulase in mass ratio 1:1.2~1.5:1.2~1.5 are mixed；
The enzyme activity of the laccase is 10000u/g, and the enzyme activity of the acidic cellulase is 20000u/g, described half
The enzyme activity of cellulase is 100000u/g；
(2) the aerobic integrated treatment of diphasic anaerobic-：Pretreated cellulosic ethanol waste water is passed sequentially through and continuously stirs slot
Formula reactor, Expanded Granular Sludge Bed Reactor and sequencing batch reactor carry out biological treatment；
The volumetric loading of the continuous stirred tank reactor is 32kg COD/ (m3It is d), described that continuously stir slot type anti-
The hydraulic detention time for answering device is 10 hours, and the hydraulic detention time of the Expanded Granular Sludge Bed Reactor is 26 hours, institute
Sequencing batch reactor is stated using intermittent water inflow, Limited Aeration, aeration rate is 0.8~1L/min, the aeration reaction time 8 hours,
Sedimentation time 4 hours；The continuous stirred tank reactor and the seed sludge of the Expanded Granular Sludge Bed Reactor are derived from
Ethanol production plant handles the inner circulation reactor of fermentation waste water, and the seed sludge of the sequencing batch reactor is derived from sewage treatment plant
Activated sludge；
Stripping tower is equipped between the continuous stirred tank reactor and the Expanded Granular Sludge Bed Reactor, and in institute
Before stating continuous stirred tank reactor, between the stripping tower and the Expanded Granular Sludge Bed Reactor, the expanded granular
Between sludge bed reactor and the sequencing batch reactor and the sequencing batch reactor after be respectively equipped with conditioning tank, for
The pH of processing water and adjusting cellulosic ethanol waste water with each unit；
Before handling cellulosic ethanol waste water, need to carry out acclimation；Cellulosic ethanol after taking enzymatic hydrolysis is useless
Water is diluted to 20%, 40%, 60% and the 80% of original content respectively, negative in the volume for guaranteeing the continuous stirred tank reactor
In the case that lotus is constant, is first passed through and is diluted to the cellulosic ethanol waste water of original content 20% and is handled, to each unit operation compared with
It is passed through again after stabilization and is diluted to the cellulosic ethanol waste water of original content 40% and is handled, until after being passed through undiluted enzymatic hydrolysis
Cellulosic ethanol waste water is handled, and acclimation terminates；
(3) electrochemical oxidation advanced treating：Cellulosic ethanol waste water after biological treatment is deep into electrochemical oxidation
Degree processing；
The current density of the electrochemical oxidation advanced treating is 20mA/cm2, reaction time 40min, using 0.1M
NaCl is as support electrolyte.
The processing method of cellulosic ethanol waste water provided by the invention has the advantages that：Present invention use enzymatic hydrolysis+
Diphasic anaerobic-is aerobic+and electrochemical oxidation advanced treating handles cellulosic ethanol waste water, cellulose second can be substantially reduced
COD value, ammonia-nitrogen content and the sulfate radical content of alcohol waste water, while making furan nucleus class, furfural, first in cellulosic ethanol waste water
The content of the side reaction products such as acid and levulic acid, the solid contents such as cellulose, lignin, hemicellulose and inorganic salts is reduced to
The degree for not influencing the longtime running of the biochemical treatment of wastewater and smoothly implementing, operating cost are low, easy to maintain.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (6)
1. a kind of processing method of cellulosic ethanol waste water, which is characterized in that include the following steps：
Step 1: cellulosic ethanol waste water pre-processes：Mixed enzyme is added into cellulosic ethanol waste water, is stirred to react 20 after mixing
~24 hours；
Step 2: the aerobic integrated treatment of diphasic anaerobic-：Pretreated cellulosic ethanol waste water is passed sequentially through and continuously stirs slot
Formula reactor, Expanded Granular Sludge Bed Reactor and sequencing batch reactor carry out biological treatment；
Step 3: electrochemical oxidation advanced treating：Cellulosic ethanol waste water after biological treatment is deep into electrochemical oxidation
Degree processing.
2. the processing method of cellulosic ethanol waste water according to claim 1, which is characterized in that in the step 1, institute
The additional amount for stating mixed enzyme is 2~4g/L, and stirring rate is 100~120rpm；The mixed enzyme is by laccase, acidic cellulase
And hemicellulase in mass ratio 1:1.2~1.5:1.2~1.5 are mixed.
3. the processing method of cellulosic ethanol waste water according to claim 2, which is characterized in that the enzyme activity of the laccase
Enzyme activity for 10000u/g, the acidic cellulase is 20000u/g, and the enzyme activity of the hemicellulase is
100000u/g。
4. the processing method of cellulosic ethanol waste water according to claim 1, which is characterized in that in the step 2, institute
The volumetric loading for stating continuous stirred tank reactor is 32kg COD/ (m3D), the waterpower of the continuous stirred tank reactor
Residence time is 10 hours, and the hydraulic detention time of the Expanded Granular Sludge Bed Reactor is 26 hours, and the batch-type is anti-
Answer device using intermittent water inflow, Limited Aeration, aeration rate is 0.8~1L/min, and the aeration reaction time 8 hours, the sedimentation time 4 was small
When；The continuous stirred tank reactor and the seed sludge of the Expanded Granular Sludge Bed Reactor are derived from ethanol production plant
The inner circulation reactor of fermentation waste water is managed, the seed sludge of the sequencing batch reactor is derived from the activated sludge of sewage treatment plant.
5. the processing method of cellulosic ethanol waste water according to claim 4, which is characterized in that described to continuously stir slot type
Stripping tower is equipped between reactor and the Expanded Granular Sludge Bed Reactor, and before the continuous stirred tank reactor,
Between the stripping tower and the Expanded Granular Sludge Bed Reactor, the Expanded Granular Sludge Bed Reactor and the batch-type
It is respectively equipped with conditioning tank between reactor and after the sequencing batch reactor, for matching the processing water and adjusting of each unit
The pH of cellulosic ethanol waste water.
6. the processing method of cellulosic ethanol waste water according to claim 1, which is characterized in that in the step 3, institute
The current density for stating electrochemical oxidation advanced treating is 20mA/cm2, reaction time 40min, using 0.1M NaCl as support
Electrolyte.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004108609A1 (en) * | 2003-06-06 | 2004-12-16 | Forskningscenter Risø | Fermentation media comprising wastewater and use hereof |
| CN102718369A (en) * | 2012-07-12 | 2012-10-10 | 哈尔滨工业大学 | Method for recycling wastewater obtained from cellulosic ethanol production |
| CN103102036A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Cellulose ethanol production wastewater treatment method |
| CN106145507A (en) * | 2015-04-03 | 2016-11-23 | 中粮集团有限公司 | The biochemical processing method of a kind of cellulosic ethanol waste water and the method process the waste water and application obtained |
-
2018
- 2018-06-21 CN CN201810646782.4A patent/CN108911364A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004108609A1 (en) * | 2003-06-06 | 2004-12-16 | Forskningscenter Risø | Fermentation media comprising wastewater and use hereof |
| CN103102036A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Cellulose ethanol production wastewater treatment method |
| CN102718369A (en) * | 2012-07-12 | 2012-10-10 | 哈尔滨工业大学 | Method for recycling wastewater obtained from cellulosic ethanol production |
| CN106145507A (en) * | 2015-04-03 | 2016-11-23 | 中粮集团有限公司 | The biochemical processing method of a kind of cellulosic ethanol waste water and the method process the waste water and application obtained |
Non-Patent Citations (3)
| Title |
|---|
| 单莉莉: ""CSTR-EGSB-SBR与电化学氧化联合处理纤维素乙醇废水的效能与机制"", 《中国博士学位论文全文数据库工程科技I辑》 * |
| 李佳谣等: ""东北土著白腐真菌处理玉米秸秆纤维素乙醇废水的可行性探讨"", 《环境科学研究》 * |
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Application publication date: 20181130 |