CN104986855A - Treatment method for cellulose fuel ethanol waste water - Google Patents
Treatment method for cellulose fuel ethanol waste water Download PDFInfo
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- CN104986855A CN104986855A CN201510442801.8A CN201510442801A CN104986855A CN 104986855 A CN104986855 A CN 104986855A CN 201510442801 A CN201510442801 A CN 201510442801A CN 104986855 A CN104986855 A CN 104986855A
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Abstract
The invention discloses a treatment method for cellulose fuel ethanol waste water, and relates to a treatment method for fuel ethanol waste water. The problems that sulfate and ammonia nitrogen in waste water produced in a current cellulose fuel ethanol production process are high in concentration and cannot be effectively treated are solved. The treatment method comprises: I, carrying out anaerobic reduction reaction in an anaerobic CSTR (continuous stirred-tank reactor) reactor; II, carrying out anaerobic methanation reaction in an anaerobic IC (internal circulation) reactor; and III, treating in an SBR (styrene butadiene rubber) reactor. The method disclosed by the invention is adopted to treat cellulose fuel ethanol waste water, so that a sulfate radical removal rate in the waste water is higher than 65%, and an ammonia removal rate in the waste water is higher than 90%, and therefore, the outlet water meets the national emission standards.
Description
Technical field
The present invention relates to a kind of fuel ethanol wastewater treatment process.
Background technology
In order to alleviate the environmental pollution and energy dilemma that use fossil oil to cause for a long time, biofuel ethanol is extensively promoted, and realizes industrialization gradually.The raw materials for production of early stage biofuel are the food crop such as soybean and corn, and in order to avoid there is the crisis of " strive grain with people, strive ground with grain ", biofuel is produced and used the Mierocrystalline cellulose such as stalk, straw instead is raw material.
Along with the expansion of cellulose fuel ethanol industry size, the waste water total amount produced in its production process also constantly increases; According to the literature, often 1 ton of cellulose fuel ethanol is produced, by generation about 25 ~ 35t trade effluent.Cellulose fuel ethanol factory effluent has the feature of high-sulfate and high ammonia nitrogen.
In the raw materials pretreatment stage that cellulose fuel ethanol is produced, ammonia fiber blasting procedure or dilute acid pretreatment method usually can be adopted to carry out pre-treatment to raw material, adopt sulfuric acid to be the engineering selection scheme relatively commonly used; Therefore sulfate radical in waste water concentration is high, and generally all at more than 3000mg/L, high even reaches 10000mg/L.The content that different cellulosic material produces the sulfate radical in waste water that ethanol produces is not identical, such as, in the alcohol wastewater produced for raw material with cassava and corn, the content difference of sulfate radical is very large, and the content of the former sulfate radical in waste water is about 10 ~ 12 times of the latter.Because sulfate radical is under anaerobic easily reduced into hydrogen sulfide by sulphate reducing bacteria; And hydrogen sulfide (HS in aqueous phase
-) existence, can suppress the growth of anaerobic methanogens, severe patient also can cause directly being poisoned to death, and organic removal efficiency is obviously declined, and causes follow-up aerobic and advanced treatment burden, running cost strengthen, water outlet cannot be up to standard.
The raw materials pretreatment rank that cellulose fuel ethanol is produced also can increase the content of nitrogen in waste water, in the waste water produced for raw material production ethanol with Mierocrystalline cellulose, the content of ammonia nitrogen is higher more than 100 times than the waste water produced for raw material production ethanol with starch, and exists mainly with the form of inorganic ammonium salt.
The wastewater discharge that cellulose fuel ethanol produces is large, and Organic substance in water, vitriol, ammonia nitrogen concentration are high, so very serious to the pollution of environment, this constrains the development of cellulose fuel ethanol industry greatly.
Summary of the invention
The present invention is to solve vitriol in the waste water that produces in current cellulose fuel ethanol production process and ammonia nitrogen concentration is high, the problem that can not effectively process, and a kind of cellulose fuel ethanol waste water treatment process provided.
Cellulose fuel ethanol waste water processes according to the following steps:
One, the cellulose fuel ethanol waste water of dilution 5 ~ 6 times is passed in anaerobism CSTR reactor carry out anaerobic hydrolysis reaction, containing the anaerobic sludge through domestication in anaerobism CSTR reactor;
Two, the water outlet of step one anaerobism CSTR reactor passes into anaerobism IC reactor and carries out anaerobic methane production reaction, containing the anaerobic grain sludge through domestication in anaerobism IC reactor;
Three, after the water outlet of step 2 anaerobism IC reactor passes into the process of sbr reactor device, cellulose fuel ethanol waste water process is namely completed;
In step one, in anaerobism CSTR reactor, hydraulic detention time is 54h;
In step 2, in anaerobism IC reactor, hydraulic detention time is 20h;
Step 3 carries out water treatment in the following order in sbr reactor device: first aeration 3h, stop aeration again, add sodium acetate and stir 1h and carry out denitrification, then continue aeration 3h, then stop aeration, add sodium acetate and stir 2 ~ 3h, leave standstill 2h afterwards, namely complete the process of sbr reactor device to water body; Wherein, aeration adopts micro-oxygen aeration.
The inventive method step one, in anaerobism CSTR reactor, utilizes sulphate reducing bacteria to be under anaerobic sulfide by sulfate conversion, through twice anaerobic reaction of step one and step 2, and SO in the water outlet of anaerobism IC reactor
4 2-concentration at below 60mg/L, reduce by more than 90%.Sulfate concentration significantly reduces, and in water body, basicity rolls up simultaneously.
Through step one of the present invention and two two-stage anaerobic process, the basicity of waste water significantly improves.Cellulose fuel ethanol waste water influent alkalinity is very low, and a small amount of basicity mainly comes from the basicity of hydrocarbonate.Through step one of the present invention and two two-stage anaerobic process, anaerobism IC reactor goes out alkalinity of water and is increased to more than 10000mg/L; And the basicity mainly bicarbonate alkalinity of anaerobism IC reactor water outlet, to solution acid-basicity, there is very strong surge capability.Through step one of the present invention and two two-stage anaerobic process, the vitriol in water body is significantly removed, and simultaneously in water outlet, basicity is increased dramatically, and is conducive to the carrying out of follow-up SBR short distance nitration reaction.
Step 3 reaction needed of the present invention consumes a large amount of basicity in water body, after the inventive method process in water outlet total alkalinity still at more than 2500mg/L, illustrate that the inventive method utilizes cellulose fuel ethanol waste water can meet the needs of nitrifying process to basicity completely, without the need to additionally adding alkaline matter, save cost.
The inventive method process cellulose fuel ethanol waste water, waste water is through its COD clearance average out to more than 80% of process of step one and step 2.
Step one of the present invention and two anaerobic reactions make use of cellulose fuel ethanol waste water and produce a large amount of basicity, for the reaction of follow-up SBR short distance nitration provides sufficient basicity; Step 3 adopts the mode of micro-oxygen aeration afterwards, while realizing short distance nitration denitrogenation, avoids reduced sulfur to the transformation of vitriol, ensure that the up to standard of water outlet.
The inventive method adopts biologic treating technique process cellulose fuel ethanol waste water completely, and sulfate radical in waste water clearance reaches more than 65%, and in waste water, ammonia clearance reaches more than 90%, and water outlet meets discharging standards.
Accompanying drawing explanation
Fig. 1 is the COD concentration that embodiment 1 dilutes rear cellulose fuel ethanol waste water inlet COD concentration and the water outlet of anaerobism CSTR reactor, the water outlet of anaerobism IC reactor, and after step 2 process water body COD clearance graphic representation.
Fig. 2 is the change curve of water body pH in step 3 reaction process of the present invention.
Fig. 3 is three nitrogen concentration column diagrams in embodiment 1 step 3 reaction process.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment cellulose fuel ethanol waste water processes according to the following steps:
One, the cellulose fuel ethanol waste water of dilution 5 ~ 6 times is passed in anaerobism CSTR reactor carry out anaerobic hydrolysis reaction, containing the anaerobic sludge through domestication in anaerobism CSTR reactor;
Two, the water outlet of step one anaerobism CSTR reactor passes into anaerobism IC reactor and carries out anaerobic methane production reaction, containing the anaerobic grain sludge through domestication in anaerobism IC reactor;
Three, after the water outlet of step 2 anaerobism IC reactor passes into the process of sbr reactor device, cellulose fuel ethanol waste water process is namely completed;
In step one, in anaerobism CSTR reactor, hydraulic detention time is 54h;
In step 2, in anaerobism IC reactor, hydraulic detention time is 20h;
Step 3 carries out water treatment in the following order in sbr reactor device: first aeration 3h, stop aeration again, add sodium acetate and stir 1h and carry out denitrification, then continue aeration 3h, then stop aeration, add sodium acetate and stir 2 ~ 3h, leave standstill 2h afterwards, namely complete the process of sbr reactor device to water body; Wherein, aeration adopts micro-oxygen aeration.
The volumetric loading rate of present embodiment step one anaerobism CSTR reactor reaches 6.5kg/ (m
3d), the volumetric loading of step 2 anaerobism IC reactor reaches 4.0kg/ (m
3d), system cloud gray model is more stable.
In present embodiment, in CSTR reactor, anaerobic digestion has successively been carried out producing acid and producing alkali (methane phase) two processes, and the basicity entered when producing acid phase in water body can reduce, and then can raise when entering methane phase stage water body basicity subsequently.Along with step one and two anaerobic reaction, the reduction of sulfate radical in waste water (often reduces the SO of 0.5mol
4 2-the basicity of 1mol will be produced), the fermentation of amino acid and protein, degraded (the equal NH of product of itrogenous organic substance
3, free NH
3alkaline material) all can produce basicity.
In present embodiment step 3 sbr reactor device, aeration carries out nitration reaction, stops aeration, stirs and carry out anti-nitration reaction.In present embodiment step 3 reaction process, pH value curve presents the change of rising-decline-rising, the rising of the pH value of initial reaction stage, is that aeration causes the CO in water caused by gas stripping and nitration reaction
2by stripping out, CO
2the speed ratio nitration reaction speed of overflowing is fast, causes pH to rise (change curve of pH as shown in Figure 2); But along with the carrying out of nitration reaction, the basicity in system is consumed, pH value starts to decline.In step 3 reaction process, pH value is stabilized between 7.8 ~ 8.4, this pH scope is the most suitable growth scope of short distance nitration bacterium, therefore the activity of short distance nitration bacterium is high, and within the scope of this pH, the activity of nitrobacteria can be suppressed, thus the short distance nitration process in sbr reactor device is carried out smoothly.
Because step 3 aeration adopts micro-oxygen aeration, therefore in reaction process, nitrate concentration rangeability is little, after nitrated, denitrification in water outlet ammonia-nitrogen content probably at about 30mg/L, nitrite and nitrate content are all at below 5mg/L, the change of three nitrogen is corresponding with the change of pH and basicity, and nitrated and anti-nitration reaction terminates all to there will be corresponding " flex point ".Therefore, what the change of pH and basicity well indicated reaction carries out degree, determines aeration time (nitration reaction carries out aeration), can avoid the energy dissipation that excess aeration causes by the change curve of pH.
The present embodiment aeration nitration reaction nitrated stage strictly controls dissolved oxygen and remains on lower concentration (below 1mg/L), thus avoid a large amount of aeration and cause the reduced sulfur in water body to be converted into vitriol in a large number, the generation causing sulfate concentration in water outlet significantly to raise, makes SO in water outlet
4 2-content remained on lower level, reach the wastewater discharge standard of national requirements.
Use anaerobic grain sludge to add respectively in anaerobism CSTR reactor and anaerobism IC reactor as kind of mud, utilize cellulose fuel ethanol waste water to carry out domestication and cultivate.
Embodiment two: the difference of present embodiment and embodiment one is: step 3 adds denitrifying carbon source after each aeration in water body.Other step and parameter identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment two is: the denitrifying carbon source that step 3 adds is sodium acetate.Other step and parameter identical with embodiment two.
Embodiment four: the difference of present embodiment and embodiment two is: add sodium acetate according to Nitrite content in step 3, the mass values of sodium acetate amount and Nitrite is 1.0 ~ 1.2:1.Other step and parameter identical with embodiment two.
Embodiment five: the difference of one of present embodiment and embodiment one to four is: step one cellulose fuel ethanol waste water is introduced into equalizing tank, then pass into anaerobism CSTR reactor by equalizing tank.Other step and parameter identical with embodiment one to four.
Embodiment six: the difference of one of present embodiment and embodiment one to five is: in step 3 aeration control be in sbr reactor device dissolved oxygen concentration at 0.5 ~ 1.0mg/L.Other step and parameter identical with embodiment one to five.
Embodiment 1
Cellulose fuel ethanol waste water processes according to the following steps:
One, the cellulose fuel ethanol waste water of dilution 5 ~ 6 times is passed in anaerobism CSTR reactor carry out anaerobic hydrolysis reaction, containing the anaerobic sludge through domestication in anaerobism CSTR reactor;
Two, the water outlet of step one anaerobism CSTR reactor passes into anaerobism IC reactor and carries out anaerobic methane production reaction, containing the anaerobic grain sludge through domestication in anaerobism IC reactor;
Three, after the water outlet of step 2 anaerobism IC reactor passes into the process of sbr reactor device, cellulose fuel ethanol waste water process is namely completed;
In step one, in anaerobism CSTR reactor, hydraulic detention time is 54h;
In step 2, in anaerobism IC reactor, hydraulic detention time is 20h;
Step 3 carries out water treatment in the following order in sbr reactor device: first aeration 3h, then stops aeration, adds sodium acetate and stir 1h and carry out denitrification, then continues aeration 3h, stop aeration again, add sodium acetate stirring 2h, leave standstill 2h afterwards, namely complete the process of sbr reactor device to water body, water outlet; Wherein, aeration adopts micro-oxygen aeration, and aeration adopts micro-oxygen aeration, controls as dissolved oxygen concentration in sbr reactor device is at 0.5 ~ 1.0mg/L; The mass values of sodium acetate amount and Nitrite is 1.0 ~ 1.2:1.
In the present embodiment, the COD concentration of cellulose fuel ethanol waste water inlet COD concentration and the water outlet of anaerobism CSTR reactor after dilution, the water outlet of anaerobism IC reactor, and water body COD clearance is as shown in Figure 1 after step 2 process.
The inventive method has satisfactory stability and high clearance to cellulose fuel ethanol waste water COD fluctuation, influent COD is at 10000 ~ 12000mg/L, after anaerobic treatment, anaerobism IC reactor effluent COD concentration maintains about 2000mg/L substantially, has processed rear water outlet COD and has been down to 1500mg/L.After dilution, cellulose fuel ethanol waste water water inlet sulfate concentration is 500 ~ 600mg/L, after step one and step 2 process, water outlet sulfate concentration is down to 60mg/L, after step 3 process, water outlet sulfate concentration still remains on below 250mg/L, reaches the wastewater discharge standard of Standard.Influent ammonium concentration is at 250 ~ 350mg/L, and after the inventive method process, water outlet ammonia nitrogen concentration is 30mg/L.
The present embodiment through step one and two anaerobic reaction abundant process, the changing conditions of waste water basicity is as shown in table 1.
Table 1
| Wastewater source | PH value | Basicity is (with CaCO 3Meter, mg/L) |
| Cellulose fuel ethanol waste water is intake | 6.89 | 980 |
| The water outlet of anaerobism IC reactor | 7.81 | 10032 |
Two-stage anaerobic process through step one of the present invention and two is described, the basicity of waste water water body significantly improves.
The present embodiment step 3 adopts intermittent type short-cut denitrification, makes SO in water body
4 2-concentration increasing degree is little, ensure that water outlet SO
4 2-remain on below 250mg/L to concentration stabilize.
The present embodiment step 3 significantly reduces through the concentration of nitrifying process ammonia nitrogen, and corresponding nitrite content increases, and after adding carbon source (sodium acetate), proceeds denitrification, and water outlet nitrite reduces, and ammonia nitrogen concentration slightly rises.Step 3 nitrifying process makes the organonitrogen in waste water decompose and produces ammonia nitrogen, thus cause ammonia nitrogen concentration to increase, in the whole process of step 3, nitrate concentration rangeability is little, after nitrated, denitrification, in water outlet, ammonia-nitrogen content is about about 30mg/L, and nitrite and nitrate content are all at below 5mg/L.In the present embodiment step 3 reaction process, change in concentration as shown in Figure 3 for three nitrogen (ammonia nitrogen, nitric acid Asia, nitrite).
The present embodiment step 3 denitrification can complete within 2 hours, and water outlet nitrite content is at below 10mg/L, and nitrite clearance can reach 97%.
Claims (4)
1. a cellulose fuel ethanol waste water treatment process, is characterized in that cellulose fuel ethanol waste water processes according to the following steps:
One, the cellulose fuel ethanol waste water of dilution 5 ~ 6 times is passed in anaerobism CSTR reactor carry out anaerobic hydrolysis reaction, containing the anaerobic sludge through domestication in anaerobism CSTR reactor;
Two, the water outlet of step one anaerobism CSTR reactor passes into anaerobism IC reactor and carries out anaerobic methane production reaction, containing the anaerobic grain sludge through domestication in anaerobism IC reactor;
Three, after the water outlet of step 2 anaerobism IC reactor passes into the process of sbr reactor device, cellulose fuel ethanol waste water process is namely completed;
In step one, in anaerobism CSTR reactor, hydraulic detention time is 54h;
In step 2, in anaerobism IC reactor, hydraulic detention time is 20h;
Step 3 carries out water treatment in the following order in sbr reactor device: first aeration 3h, stop aeration again, add sodium acetate and stir 1h and carry out denitrification, then continue aeration 3h, then stop aeration, add sodium acetate and stir 2 ~ 3h, leave standstill 2h afterwards, namely complete the process of sbr reactor device to water body; Wherein, aeration adopts micro-oxygen aeration.
2. a kind of cellulose fuel ethanol waste water treatment process according to claim 1, is characterized in that adding sodium acetate according to Nitrite content in step 3, and the mass values of sodium acetate amount and Nitrite is 1.0 ~ 1.2:1.
3. a kind of cellulose fuel ethanol waste water treatment process according to claim 1, is characterized in that step one cellulose fuel ethanol waste water is introduced into equalizing tank, then passes into anaerobism CSTR reactor by equalizing tank.
4. a kind of cellulose fuel ethanol waste water treatment process according to claim 1, to it is characterized in that in step 3 aeration control be in sbr reactor device dissolved oxygen concentration at 0.5 ~ 1.0mg/L.
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| CN106892502A (en) * | 2015-12-18 | 2017-06-27 | 中粮集团有限公司 | A kind of processing method of cellulosic ethanol waste water |
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| CN101767907A (en) * | 2009-12-30 | 2010-07-07 | 天津大学 | Coupling treatment device and coupling treatment method for sweet sorghum fuel ethanol wastewater circumfluence bioreactor |
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| CN106892502A (en) * | 2015-12-18 | 2017-06-27 | 中粮集团有限公司 | A kind of processing method of cellulosic ethanol waste water |
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Effective date of registration: 20210810 Address after: 1 Exhibition Road, Xicheng District, Beijing Patentee after: Beijing University of Civil Engineering and Architecture Address before: 150001 No. 92 West straight street, Nangang District, Heilongjiang, Harbin Patentee before: HARBIN INSTITUTE OF TECHNOLOGY |