CN109468344B - Straw and method for preparing ethanol by fermenting pretreated wastewater and sludge thereof - Google Patents
Straw and method for preparing ethanol by fermenting pretreated wastewater and sludge thereof Download PDFInfo
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
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- C02F3/28—Anaerobic digestion processes
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- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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Abstract
The invention relates to a method for preparing ethanol, in particular to a method for preparing ethanol by fermenting straw, pretreated wastewater of the straw and excess sludge of an urban sewage treatment plant. The method for preparing the ethanol comprises the following specific steps: using straws with different COD, pH and ORP to pretreat the wastewater and the excess sludge of the urban sewage treatment plant, and starting domesticating the ethanol type fermentation sludge to prepare ethanol at the same time; and synchronously saccharifying and fermenting the obtained ethanol type fermentation sludge and NaOH pretreated straws to prepare ethanol. The invention not only saves the production cost of ethanol, but also can solve the problem of treatment and disposal of the pretreatment wastewater in the process of preparing the ethanol from the sludge of the urban sewage treatment plant and the straws, realizes the reclamation of the pretreatment wastewater of the straws and the sludge generated in the treatment process in the process of preparing the ethanol from the straws, and can be popularized in the process of preparing the ethanol from other crop straws.
Description
Technical Field
The invention relates to the technical field of ethanol preparation, in particular to a method for preparing ethanol by fermenting straw, pretreated straw wastewater and excess sludge of an urban sewage treatment plant.
Background
With the increasing energy crisis and environmental problems, the development and utilization of renewable clean energy sources is urgent. Biomass energy is an excellent alternative to traditional energy sources due to its renewable nature and cleanliness. Ethanol is one of the most potential alternative energy sources as a high-efficiency, clean and renewable energy source. Ethanol is taken as an oxygen-containing additive and is added into gasoline (diesel oil) in a certain proportion to prepare clean and environment-friendly ethanol gasoline (ethanol diesel oil) for vehicles, which receives high attention from all countries in the world.
China is a big agricultural country, rice is one of main crops in China, a large amount of straws can be generated along with the harvest of the rice every year, and environmental pollution can be caused if the rice is not properly treated. The main components of the straw are cellulose, hemicellulose and lignin, and the cellulose in the straw can be converted into reducing sugar by adopting a proper technology, and the ethanol can be generated by further fermentation. Because the complicated structure of hemicellulose and lignin in the straws and cellulose and the high crystallization property of cellulose molecules limit the conversion of the straws into reducing sugar and ethanol, proper pretreatment is needed, the crystallinity of the cellulose is reduced, the porosity of the cellulose is increased, the protection effect of the lignin is removed, the ineffective combination of enzyme is reduced, the contact site and the contact area of the enzyme and a substrate are increased, and the enzymolysis efficiency is improved.
However, a large amount of waste water is generated in the straw pretreatment process, the main components are polysaccharide, monosaccharide, a small amount of cellulose and hemicellulose, and the components can be utilized by microorganisms to prepare ethanol. The straw pretreated wastewater has extremely high COD content, low transparency, extremely high chroma and pungent smell. If the waste water is directly discharged into a natural water body, not only can serious pollution be caused to a large-area water area, but also resource waste can be caused.
Along with the expansion of urbanization and population concentration, the discharge amount of industrial wastewater and domestic sewage is increasing day by day, and the output of sludge is also rapidly increased through an urban sewage treatment system. The accumulation of the sludge not only occupies a large amount of land, but also contains a large amount of organic substances (mainly carbohydrates, proteins and the like), toxic and harmful heavy metals, pathogenic microorganisms, parasitic ova, salts, radionuclides and other refractory substances. How to reasonably and scientifically treat the sludge is a global widely concerned problem, and the current consensus is how to use the sludge as an effectively utilized resource and change waste into valuable in pollution treatment. The sludge is fully utilized, so that the environmental pollution caused by the sludge is reduced, and better economic benefit and social benefit can be obtained.
Because the sludge contains a large amount of mixed flora and nitrogenous organic matters, and the straws contain a large amount of cellulose and hemicellulose, if the straws and the sludge are used for preparing the ethanol by synchronous saccharification and fermentation, the straws and the sludge are fully utilized, the adverse phenomenon of the straws and the sludge on the environment is solved, and the better development of the 'two-type' society in China is facilitated.
In the anaerobic treatment of sewage, the fermentation is generally divided into: two fermentation types, butyric and propionic. In recent years, many scholars have conducted extensive studies on ethanol-type fermentation of wastewater. Chenchen de peak and nanqi (harbin)Doctrine of university of industry 2006) found an ethanol-type fermentation when operating a biological hydrogen production reactor at low pH, organic wastewater containing higher carbohydrates was fermented to produce liquid end products, mainly ethanol, acetic acid and small amounts of butyric acid, and larger amounts of H2And CO2。
Liuguanrui et al (environmental engineering report, 2016, 10 (2): 729-. The results show that when the volume load of the inlet water is respectively 9 kgCOD/(m)3·d)、48kgCOD/(m3D), the concentration of acetic acid and ethanol respectively reaches a maximum.
Malachi et al (proceedings of Harbin university of Industrial science 2011, 43 (4): 37-41) add potassium dihydrogen phosphate, sucrose, sodium sulfide, ammonium chloride, sodium acetate and other substances into water to simulate wastewater, inoculate anaerobic granular sludge into the simulated wastewater, investigate the fermentation condition in the reaction system, investigate the operation condition of the system by controlling variables such as alkalinity, starting volume load and the like, and observing pH, ORP, liquid phase end products and the like in the reaction system, thereby completing the rapid start of the ethanol type fermentation.
Liu Xiao Ye et al (environmental science, 2014, 35 (6): 2434-.
Royal east yang (doctrine of doctorals of the university of harbin industry, 2011) uses molasses wastewater as an organic carbon source, studies the difference between butyric acid type fermentation and ethanol type fermentation, and realizes the quick start of the ethanol type fermentation by controlling the organic load of the wastewater and adjusting the pH value.
However, the above-mentioned starting ethanol type fermentation has the following disadvantages:
1. the method mainly simulates real wastewater in a laboratory to start the ethanol type fermentation, such as Liuguanrui and the like (environmental engineering bulletin, 2016, 10 (2): 729-;
2. the method is mainly characterized in that single-component wastewater or simulated wastewater is used for starting ethanol type fermentation to prepare hydrogen, and reports of starting ethanol type fermentation to prepare ethanol by using sewage or wastewater are not shown;
3. there is no report of using ethanol-type fermentation sludge and crop straws (such as rice straws) to prepare ethanol after the completion of starting ethanol-type fermentation by using sewage or simulated wastewater.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a method for preparing ethanol by fermenting straw, pretreated straw wastewater and excess sludge of an urban sewage treatment plant. The method not only saves the production cost of the ethanol, but also can solve the problem of treatment and disposal of the pretreated wastewater in the process of preparing the ethanol by the sludge of a sewage treatment plant and the straws, realize the reclamation of the pretreated wastewater of the straws in the process of preparing the ethanol by the straws and the sludge generated in the treatment process, and can be popularized in the process of preparing the ethanol by utilizing other crop straws.
The technical scheme of the invention is as follows:
a method for preparing ethanol by fermenting straw, pretreated wastewater and sludge thereof comprises the following steps:
(1) pretreating straw powder by using a NaOH solution, and filtering to obtain a filtrate, namely a straw pretreatment wastewater stock solution; the obtained filter cake is the pretreated rice straw and is dried for standby;
(2) diluting the straw pretreatment wastewater stock solution, and adding KH with different mass2PO4And urea, the mass ratio of COD to N to P is 1000 to 5 to 1, and then the mixture is mixed with the residual sludge obtained after the dehydration of a sewage treatment plant; vacuumizing, placing in a constant-temperature shaking table at 37 deg.C, changing liquid every 2 days, acclimating for 6 days, centrifuging, and collecting supernatantPreparing the obtained ethanol solution; the solid matter obtained after centrifugation is ethanol type fermentation sludge;
(3) taking straw pretreated wastewater and excess sludge, starting acclimatization to obtain ethanol type fermented sludge, carrying out synchronous diastatic fermentation on the ethanol type fermented sludge, the dried NaOH pretreated straw and water under the conditions of initial pH value of 5 and temperature of 37 ℃ to prepare ethanol, and centrifuging after the synchronous diastatic fermentation is finished, wherein the supernatant is the prepared ethanol solution.
The COD, the chroma and the SS of the straw pretreated wastewater stock solution in the step (1) are respectively 14.9g/L, 50000 and 420 mg/L.
Preferably, the mass concentration of the NaOH solution in the step (1) is 3.5%; the dosage of the NaOH solution is controlled to be 1:20 (g: mL) of solid-to-liquid ratio; the pretreatment method is to keep at 100 ℃ for 35 minutes.
Preferably, the straw powder in step (1) is that the straw is crushed and then passes through a 40-mesh sieve, but cannot pass through a 60-mesh sieve.
Preferably, the filter cake in the step (1) is washed to be neutral by distilled water; the drying in the step (1) is drying at 65 ℃.
Preferably, the dilution in the step (2) is to dilute the straw pretreatment wastewater stock solution into COD 4750-7308 mg/L, pH 6.2-7.8 and ORP-115-29 mV.
Preferably, the mass ratio of the volume of the diluted straw pretreatment wastewater in the step (2) to the excess sludge in the sewage treatment plant is 30 to (0.5-1.5) (mL to g).
Preferably, the centrifugation method in the step (2) is 6000r/min for 5 min.
Preferably, the mass ratio of the mass of the ethanol type fermentation sludge obtained after the straw pretreatment wastewater and the excess sludge in the step (3) are acclimated for 6 days to the mass of the dried NaOH pretreatment straw to the volume of water is 5:1:100 (g: mL).
Preferably, the centrifugation method in the step (3) is 6000r/min for 5 min.
The beneficial technical effects of the invention are as follows:
the method utilizes the straw NaOH to pretreat the waste water and the excess sludge of the urban sewage treatment plant, starts domestication of the ethanol type fermentation sludge to prepare the ethanol at the same time, and then utilizes the ethanol type fermentation sludge obtained after domestication as an inoculation flora to degrade the NaOH to pretreat the straw to prepare the ethanol. The reaction principle is as follows: in the process of starting acclimatization of ethanol type fermented sludge by using straw NaOH pretreated wastewater and excess sludge of an urban sewage treatment plant, monosaccharide and polysaccharide are fermented into ethanol by microorganisms in the sludge, and the excess sludge is gradually formed into the ethanol type fermented sludge; and degrading cellulose and hemicellulose in the straws by using degradable cellulose and hemicellulose floras in the domesticated ethanol type fermented sludge to form monosaccharides such as glucose, xylose and the like, and fermenting the glucose and the xylose into ethanol by using yeast floras in the ethanol type fermented sludge.
Compared with the prior art, the invention has the advantages that: (1) the bottleneck of starting domestication of ethanol type fermentation by using single-component wastewater or simulated wastewater and sludge in the prior art is broken through, ethanol is prepared by successfully starting domestication of ethanol type fermentation sludge by using actual wastewater (straw pretreatment wastewater) and excess sludge of an urban sewage treatment plant, and part of COD (chemical oxygen demand) of the straw pretreatment wastewater is removed, so that the subsequent treatment pressure of the straw pretreatment wastewater is reduced, and the resource utilization of the straw pretreatment wastewater is realized; (2) the method realizes the synchronous saccharification and fermentation of the acclimated ethanol-type fermented sludge and the straws to prepare the ethanol, obtains higher ethanol yield, and provides a new idea for the treatment of the straws and the sludge generated in the wastewater pretreatment process of the straws.
The best technical parameters of the invention are as follows: diluting the straw pretreatment wastewater stock solution into: the COD is 6281mg/L, pH, the value is 6.7, the ORP is-42 mV, excess sludge of a sewage treatment plant is inoculated into the diluted straw pretreatment wastewater, domestication of ethanol fermentation sludge is started to prepare ethanol, when the volume ratio of the mass of the excess sludge to the volume of the diluted straw pretreatment wastewater is 1: 30 (g: mL), and the domestication time is 6 days, the sludge with the highest ethanol type fermentation degree can be obtained, and the ethanol concentration is 8.34 g/L. After the straw pretreated wastewater and the excess sludge are domesticated for 6 days, the COD removal rate of the wastewater is 54.83%, the pH value is 5.6, and the ORP is-99.5 mV; and (2) synchronously saccharifying and fermenting the ethanol type fermentation sludge of the domestication system and the NaOH pretreated straws to prepare ethanol, and synchronously saccharifying and fermenting for 36 hours under the conditions that the mass of the ethanol type fermentation sludge, the mass of the dried NaOH pretreated straws and the volume ratio of water are 5:1:100 (g: mL), the initial pH value is 5 and the temperature is 37 ℃, so that the concentration of the ethanol is 3.75 g/L.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Treating straw powder (40 mesh sieve but not 60 mesh sieve) with 3.5% NaOH solution at solid-to-liquid ratio of 1:20 (g: mL), and placing in 100 deg.C water bath for 35 min. And filtering by using filter paper, and collecting filtrate, wherein the obtained filtrate is the straw pretreatment wastewater stock solution, and the COD, the chroma and the SS of the straw pretreatment wastewater stock solution are 14.9g/L, 50000 and 420mg/L respectively. Diluting the straw pretreatment wastewater stock solution into: after a COD of 4750mg/L, pH value of 7.5 and an ORP of-69 mV, different masses of KH were added2PO4And urea, the mass ratio of COD to N to P is 1000 to 5 to 1, then excess sludge of a sewage treatment plant is inoculated into the straw pretreatment wastewater to start domestication of the ethanol type fermentation sludge and prepare ethanol at the same time, and the volume ratio of the mass of the excess sludge to the diluted straw pretreatment wastewater is 0.5 to 30 (g: mL). Vacuumizing, placing in a constant-temperature shaking table at 37 ℃, changing the solution once every 2 days, starting acclimatization of the straw pretreated wastewater and the residual sludge for 6 days, and centrifuging, wherein the ethanol concentration in the supernatant is 6.01g/L, and the COD removal rate of the straw pretreated wastewater is 13.82%, the pH value is 5.6 and the ORP is-90.5 mV.
Example 2
Treating straw powder (40 mesh sieve but not 60 mesh sieve) with 3.5% NaOH solution at solid-to-liquid ratio of 1:20 (g: mL), and placing in 100 deg.C water bath for 35 min. And filtering by using filter paper, and collecting filtrate, wherein the obtained filtrate is the straw pretreatment wastewater stock solution, and the COD, the chroma and the SS of the straw pretreatment wastewater stock solution are 14.9g/L, 50000 and 420mg/L respectively. And washing the filter cake to be neutral by distilled water, and drying the filter cake in a 65 ℃ drying oven for later use. Diluting the straw pretreatment wastewater stock solution into: after a COD of 6281mg/L, pH of 6.7 and an ORP of-42 mV, KH of different masses was added2PO4Mixing with urea at a mass ratio of COD to N to P of 1000:5:1, and adding rice strawThe excess sludge of a sewage treatment plant is inoculated into the pretreated wastewater to start domestication of ethanol type fermentation sludge and simultaneously prepare ethanol, and the ratio of the mass of the excess sludge to the volume of the diluted straw pretreated wastewater is 1: 30 (g: mL). Vacuumizing, placing in a constant-temperature shaking table at 37 ℃, changing liquid every 2 days, starting acclimation of straw pretreatment wastewater and excess sludge for 6 days to obtain sludge with the highest ethanol fermentation degree, centrifuging, and obtaining supernatant with ethanol concentration of 8.34g/L, wherein the COD removal rate of the straw pretreatment wastewater is 54.83%, the pH value is 5.6 and the ORP is-99.5 mV.
Example 3
Treating straw powder (40 mesh sieve but not 60 mesh sieve) with 3.5% NaOH solution at solid-to-liquid ratio of 1:20 (g: mL), and placing in 100 deg.C water bath for 35 min. And filtering by using filter paper, and collecting filtrate, wherein the obtained filtrate is the straw pretreatment wastewater stock solution, and the COD, the chroma and the SS of the straw pretreatment wastewater stock solution are 14.9g/L, 50000 and 420mg/L respectively. Diluting the straw pretreatment wastewater stock solution into: after a COD of 7308mg/L, pH value of 7.5 and an ORP of-62 mV, different masses of KH were added2PO4And urea, the mass ratio of COD to N to P is 1000 to 5 to 1, then excess sludge of a sewage treatment plant is inoculated into the straw pretreatment wastewater to start domestication of the ethanol type fermentation sludge and prepare ethanol at the same time, and the volume ratio of the mass of the excess sludge to the diluted straw pretreatment wastewater is 1.5 to 30 (g: mL). Vacuumizing, placing in a constant-temperature shaking table at 37 ℃, changing the solution every 2 days, starting acclimatization of the straw pretreatment wastewater and the residual sludge for 6 days, and centrifuging, wherein the ethanol concentration in the supernatant is 4.05g/L, and the COD removal rate of the straw pretreatment wastewater is 26.18%, the pH value is 5.9 and the ORP is-76.5 mV.
Example 4
The ethanol-type fermented sludge obtained in example 2, the dried NaOH-pretreated straw, and water were simultaneously saccharified and fermented at an initial pH of 5 and a temperature of 37 ℃ for 36 hours at a ratio of 5:1:100 (g: mL) and then centrifuged, and the ethanol concentration in the supernatant was 3.75 g/L.
Claims (4)
1. A method for preparing ethanol by fermenting straw, pretreated wastewater and sludge thereof is characterized by comprising the following steps:
(1) pretreating straw powder by using a NaOH solution, and filtering to obtain a filtrate, namely a straw pretreatment wastewater stock solution; the obtained filter cake is the pretreated rice straw and is dried for standby;
(2) diluting the straw pretreatment wastewater stock solution, and adding KH with different mass2PO4And urea, wherein the mass ratio of COD to N to P is 1000:5:1, and then the mixture is mixed with the residual sludge obtained after the dehydration of a sewage treatment plant; vacuumizing, placing in a constant-temperature shaking table at 37 ℃, changing the solution every 2 days, domesticating for 6 days, and centrifuging to obtain supernatant, namely the prepared ethanol solution; the solid matter obtained after centrifugation is ethanol type fermentation sludge;
(3) taking straw pretreated wastewater and excess sludge, starting acclimatization to obtain ethanol type fermented sludge, carrying out synchronous diastatic fermentation on the ethanol type fermented sludge, the dried NaOH pretreated straw and water under the conditions that the initial pH value is 5 and the temperature is 37 ℃ to prepare ethanol, and centrifuging after the synchronous diastatic fermentation is finished, wherein the supernatant is the prepared ethanol solution;
the COD, the chroma and the SS of the straw pretreated wastewater stock solution in the step (1) are respectively 14.9g/L, 50000 and 420 mg/L;
the dilution in the step (2) is to dilute the straw pretreatment wastewater stock solution into COD 4750-7308 mg/L, pH 6.2.2-7.8 and ORP-115-29 mV;
the mass ratio of the volume of the diluted straw pretreatment wastewater in the step (2) to the mass of the excess sludge in the sewage treatment plant is 30 (0.5-1.5), and the unit is as follows: mL is g;
the mass ratio of the ethanol type fermentation sludge obtained after the straw pretreatment wastewater and the excess sludge are acclimated for 6 days to the mass of the dried NaOH pretreatment straw to the water volume is 5:1:100, and the unit is as follows: g is mL;
the mass concentration of the NaOH solution in the step (1) is 3.5%; the dosage of the NaOH solution is controlled in a solid-liquid ratio of 1:20, and the unit is as follows: g is mL; the pretreatment method is to keep the temperature at 100 ℃ for 35 minutes;
washing the filter cake obtained in the step (1) to be neutral by using distilled water; the drying in the step (1) is drying at 65 ℃.
2. The method of claim 1, wherein the straw powder in step (1) is obtained by pulverizing straw and sieving with a 40-mesh sieve, but not with a 60-mesh sieve.
3. The method according to claim 1, wherein the centrifugation method in step (2) is 6000r/min for 5 min.
4. The method according to claim 1, wherein the centrifugation method in step (3) is 6000r/min for 5 min.
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| CN108178427A (en) * | 2017-12-20 | 2018-06-19 | 佛山科学技术学院 | A kind of red bayberry is pickled biochemical procss for treating waste water |
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| Title |
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| Pretreatment of Lignocellulosic Wastes to Improve Ethanol and Biogas Production A Review;Mohammad J. Taherzadeh等;《Int. J. Mol. Sci.》;20081231;第9卷;第1621-1651页 * |
| 半同步和同步糖化发酵稻草转化乙醇的研究;黄书鑫 等;《湖北理工大学学报》;20171231;第33卷(第6期);第22-26页 * |
| 稻草和污泥同步糖化发酵转化乙醇研究;吕继良 等;《湖北理工学院学报》;20151231;第31卷(第6期);第22-25页 * |
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