CN104789603A - Method for treating starch wastewater and simultaneously generating renewable energy source - Google Patents
Method for treating starch wastewater and simultaneously generating renewable energy source Download PDFInfo
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Abstract
The invention discloses a method for treating starch wastewater and simultaneously generating renewable energy source and relates to a method for treating starch wastewater and simultaneously generating renewable energy source. The invention solves the problems that the current starch wastewater treatment method is high in cost and the environment pollution can be caused. The method comprises the following steps: 1, processing a hydrogen production inoculum to obtain a hydrogen production flora; 2, taking the starch wastewater, adjusting the pH value and inoculating the hydrogen production flora to obtain the hydrogen and organic acid fermented solution; and 3, removing the hydrogen production flora in the fermented solution, adjusting the pH value, inoculating a microalgae, culturing and harvesting the microalgae, and extracting the grease in the microalgae. The hydrogen production volume is 755.5-883.3 mL H2/L working volume, the oil production volume is 0.31-0.41g/L working volume and the COD removing rate is 79-84%. The method can be applied to the biological energy source and the wastewater treatment fields.
Description
Technical field
The present invention relates to and a kind ofly process the method that starch wastewater generates renewable energy source simultaneously.
Background technology
Starch wastewater is the high concentrated organic wastewater produced in the starch course of processing, containing materials such as a large amount of solvability starch and a small amount of protein, its chemical oxygen demand (COD) (COD) is very high, is about 2000-40000mg/L, therefore could discharge after having to pass through process.But the intractability of starch wastewater is large, the cost that puts into operation is very high, if waste water is directly drained into environment water, can cause body eutrophication, the problem of environmental pollution such as putrid and deteriorated, and effectively cannot utilize the organic matter in waste water, cause the serious waste of resource.
Application number: 201310533944.0, the denomination of invention method of production capacity " a kind of hydrogen-producing bacteria be coupled with oil-containing micro-algae step " discloses a kind of coupling and produces the method for hydrogen and produce oil, utilize pure substrate as raw material, and do not provide the utilization power of raw material, pure substrate expensive, is difficult to large-scale production; This invention adopts pure bacterial strain to carry out product hydrogen, easily contaminated aborning, utilizes the ability of complicated raw material (as starch wastewater), is difficult to adapt to long-continued suitability for industrialized production; In addition, adopt high pressure steam sterilization process fermented liquid in this invention, energy consumption is very high, greatly can improve production cost, be unfavorable for practical application.
Summary of the invention
The present invention be to solve the method cost of existing process starch wastewater high, be not easy to suitability for industrialized production and cause the problem of environmental pollution, provide and a kind ofly process the method that starch wastewater generates renewable energy source simultaneously.
The present invention is a kind of processes the method that starch wastewater generates renewable energy source simultaneously, comprises the steps: one, processes product hydrogen inoculum, obtain mixture A; Two, get starch wastewater, regulate pH to 5 ~ 10, then by account for starch wastewater cumulative volume 5 ~ 10% inoculum size, inoculated mixture A, then cultivate, obtains hydrogen and organic acid fermentation liquid; Three, remove the solid phase in fermented liquid, then regulate pH to 5 ~ 10 of liquid phase, then press total liquid volume 5 ~ 10% inoculum size, inoculate micro-algae and cultivate, cultivate microalgae afterwards, extract the grease in micro-algae, namely complete;
Product hydrogen inoculum wherein described in step one is that one or more in excess sludge, digested sludge, anaerobic grain sludge and sewage sludge are by arbitrarily than the mixture formed;
Micro-algae described in step 3 is that one or more in grid algae, chlorella, diatom, Crypthecodinium cohnii, flat algae, Dunaliella salina, spirulina and chrysophyceae are by arbitrarily than the mixture formed.Produce in hydrogen inoculum and often there is hydrogen-consuming bacteria, the hydrogen produced by hydrogenogens can be consumed, cause hydrogen output to decline.But hydrogen-consuming bacteria is more responsive to high temperature, soda acid or chemical agent, activity can be suppressed after treatment, because hydrogenogens can form the gemma can resisting severe environment, therefore can survive after treatment and keep active, product hydrogen inoculum is processed, effectively can suppress the hydrogen-consuming bacteria in inoculum, reach the object improving fermentation and hydrogen production usefulness.Therefore the disposal methods using the present invention to enumerate produces hydrogen inoculum, can suppress hydrogen-consuming bacteria, reaches the object improving fermentation and hydrogen production usefulness.Hydrogen output of the present invention is 755.5-883.3mL H
2/ L working volume, oil offtake is 0.31-0.41g/L working volume, and COD clearance is 79-84%.Hydrogenogens group is first inoculated in starch wastewater to produce hydrogen by the present invention, then cultivates micro-algae with the fermented liquid removing hydrogen-producing bacteria and produces grease.The present invention is by dark ferment for hydrogen production and micro-algae produce oil coupling processing starch wastewater, the COD quantity discharged of waste water can be reduced, improve water surrounding, reduce the detrimentally affect that starch wastewater causes environment, reclaimed renewable energy source simultaneously, reduce bioenergy production cost, achieve the recycling treatment of starch wastewater, the industrialization paces accelerating biofuel and bio-hydrogen production technology are also had great importance.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention 1 process flow diagram;
Fig. 2 is test 1 and test 2 hydrogen output figure; Wherein
for hydrogen output,
for hydrogen-producing speed;
Fig. 3 is test 1 and tests grease concentration figure in 2; Wherein
for grease concentration,
for produce oil speed;
Fig. 4 is the COD clearance figure of test 1 and test 2; Wherein
for control group,
for test group.
Embodiment
Embodiment one: present embodiment is a kind of processes the method that starch wastewater generates renewable energy source simultaneously, comprises the steps: one, processes product hydrogen inoculum, obtain mixture A; Two, get starch wastewater, regulate pH to 5 ~ 10, then by account for starch wastewater cumulative volume 5 ~ 10% inoculum size, inoculated mixture A, then cultivate, obtains hydrogen and organic acid fermentation liquid; Three, remove the solid phase in fermented liquid, then regulate pH to 5 ~ 10 of liquid phase, then press total liquid volume 5 ~ 10% inoculum size, inoculate micro-algae and cultivate, cultivate microalgae afterwards, extract the grease in micro-algae, namely complete;
Product hydrogen inoculum wherein described in step one is that one or more in excess sludge, digested sludge, anaerobic grain sludge and sewage sludge are by arbitrarily than the mixture formed;
Micro-algae described in step 3 is that one or more in grid algae, chlorella, diatom, Crypthecodinium cohnii, flat algae, Dunaliella salina, spirulina and chrysophyceae are by arbitrarily than the mixture formed.Wherein mixture A contains hydrogen-producing bacteria flora, and wherein hydrogen-producing bacteria flora is the flora based on fusobacterium.
In present embodiment, excess sludge, digested sludge and anaerobic grain sludge are from the sewage work of Border in Harbin Area; Sewage sludge is from Border in Harbin Area water drain.
In present embodiment, chlorella, diatom, Crypthecodinium cohnii, flat algae, Dunaliella salina, spirulina and chrysophyceae are purchase and obtain.Grid algae (Scenedesmus sp.) adopts the method screening disclosed in Chinese invention patent " a kind of high-throughput screening method of oil-rich microalgae " (application number: CN201310096030.2) to obtain.
The process flow diagram of present embodiment as shown in Figure 1.
Produce in hydrogen inoculum and often there is hydrogen-consuming bacteria, the hydrogen produced by hydrogenogens can be consumed, cause hydrogen output to decline.But hydrogen-consuming bacteria is more responsive to high temperature, soda acid or chemical agent, activity can be suppressed after treatment, because hydrogenogens can form the gemma can resisting severe environment, therefore can survive after treatment and keep active, product hydrogen inoculum is processed, effectively can suppress the hydrogen-consuming bacteria in inoculum, reach the object improving fermentation and hydrogen production usefulness.Therefore the disposal methods using present embodiment to enumerate produces hydrogen inoculum, can suppress hydrogen-consuming bacteria, reaches the object improving fermentation and hydrogen production usefulness.Hydrogen output of the present invention is 755.5-883.3mL H
2/ L working volume, oil offtake is 0.31-0.41g/L working volume, and COD clearance is 79-84%.Hydrogenogens group is first inoculated in starch wastewater to produce hydrogen by the present invention, then cultivates micro-algae with the fermented liquid removing hydrogen-producing bacteria and produces grease.Present embodiment is by dark ferment for hydrogen production and micro-algae produce oil coupling processing starch wastewater, the COD quantity discharged of waste water can be reduced, improve water surrounding, reduce the detrimentally affect that starch wastewater causes environment, reclaimed renewable energy source simultaneously, reduce bioenergy production cost, achieve the recycling treatment of starch wastewater, the industrialization paces accelerating biofuel and bio-hydrogen production technology are also had great importance.
Embodiment two: present embodiment and embodiment one unlike: the treatment process described in step one is thermal treatment, and concrete grammar for process 30min at 100 DEG C.Other steps are identical with embodiment one with parameter.
Embodiment three: present embodiment and embodiment one or two unlike: the treatment process described in step one is the one or more combination in acid treatment, alkaline purification, hydrogen peroxide treatment, ultrasonication, microwave treatment, methane inhibitor process, chloroform process, the process of ethylene dibromide sodium sulfonate, radiation treatment, Air Exposure and impact load process.Other steps are identical with embodiment one or two with parameter.
Embodiment four: present embodiment and one of embodiment one to three can be one or more in corn starch wastewater, potato starch wastewater, green starch waste water, wheat kind of starch waste water, cassava starch wastewater, water caltrop starch waste water, Rhizoma Nelumbinis starch waste water and Sweet Potato Starch Processing Waste Water by arbitrarily than the mixture formed unlike the starch wastewater described in step 2.Other steps are identical with one of embodiment one to three with parameter.
Embodiment five: one of present embodiment and embodiment one to four are undertaken regulating by the NaOH solution of concentration to be the HCl solution of 1mol/L or concentration be 1mol/L unlike the adjustment pH described in: step 2 and step 3.Other steps are identical with one of embodiment one to four with parameter.
Embodiment six: one of present embodiment and embodiment one to five unlike: the culture condition described in step 2 is temperature 30 ~ 40 DEG C, isolated air jet flow, shaking speed 50 ~ 200rpm, incubation time 20 ~ 120h.Other steps are identical with one of embodiment one to five with parameter.
Embodiment seven: one of present embodiment and embodiment one to six unlike: in the removal fermented liquid described in step 3 the method for solid phase be centrifuging and filtration method one or both combination.Other steps are identical with one of embodiment one to six with parameter.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the microdisk electrode condition described in step 3 is temperature 15 ~ 40 DEG C, shaking speed 50 ~ 200rpm, incubation time 120 ~ 192h.Other steps are identical with one of embodiment one to seven with parameter.
Embodiment nine: one of present embodiment and embodiment one to eight are one or both combinations of centrifuging and filtration method unlike: the microalgae recovery method described in step 3.Other steps are identical with one of embodiment one to eight with parameter.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: the Microalgae grease extraction method described in step 3 is chloroform-methanol method, soxhlet extraction methods, normal hexane-isopropanol method, normal hexane-Ethanol Method or ether-petroleum ether method.Other steps are identical with one of embodiment one to nine with parameter.
By following verification experimental verification beneficial effect of the present invention:
Test 1, this test test group process starch wastewater generate the method for renewable energy source simultaneously, comprise the steps: one, excess sludge carries out process 30min under 100 DEG C of conditions, obtains mixture A; Two, extracting corn starch waste water, regulating pH to 7 with the HCl that concentration is 1mol/L, is then 10% inoculated mixture A of corn starch wastewater cumulative volume by inoculum size, again temperature 35 DEG C, shaking speed 130rpm, cultivates 48h under isolated air conditions, obtains hydrogen and organic acid fermentation liquid; Three, the method adopting centrifuging and filtration method to combine removes the solid formation in fermented liquid, then liquid phase pH to 7 is regulated with the NaOH that concentration is 1mol/L, press the inoculum size inoculation grid algae of 10% of total liquid volume again, then temperature 25 DEG C, 144h is cultivated under the condition of shaking speed 130rpm, centrifugal microalgae after cultivating, employing chloroform-methanol method extracts the grease in micro-algae, namely completes.Mixture A is fusobacterium is main flora.
Control group is the corn starch wastewater adopting the method process of dark ferment for hydrogen production identical with test 1.
Test 2, this test test group process starch wastewater generate the method for renewable energy source simultaneously, comprise the steps: one, excess sludge carries out process 30min under 100 DEG C of conditions, obtains mixture A; Two, get potato starch wastewater, regulating pH to 7 with the HCl that concentration is 1mol/L, is then 10% inoculated mixture A of potato starch wastewater cumulative volume by inoculum size, again temperature 35 DEG C, shaking speed 130rpm, cultivates 48h under isolated air conditions, obtains hydrogen and organic acid fermentation liquid; Three, the method adopting centrifuging and filtration method to combine removes the solid formation in fermented liquid, then liquid phase pH to 7 is regulated with the NaOH that concentration is 1mol/L, press the inoculum size inoculation grid algae of 10% of total liquid volume again, then temperature 25 DEG C, 144h is cultivated under the condition of shaking speed 130rpm, centrifugal microalgae after cultivating, employing chloroform-methanol method extracts the grease in micro-algae, namely completes.Mixture A is fusobacterium is main flora.
Control group is the potato starch wastewater adopting the method process of dark ferment for hydrogen production identical with test 1.
The grid algae (Scenedesmus sp.) wherein tested in 1 and 2 adopts the method screening disclosed in Chinese invention patent " a kind of high-throughput screening method of oil-rich microalgae " (application number: CN201310096030.2) to obtain; Excess sludge is from the secondary sedimentation basins of Harbin sewage work.
Test the hydrogen output of test 1 test group and test 2 test group, as shown in Figure 2, as shown in Figure 2, when adopting corn starch wastewater to be raw material, the hydrogen output testing 1 test group is 883.3mL H to result
2/ L working volume, hydrogen-producing speed is 18.4mL H
2/ L/h; When adopting potato starch wastewater to be raw material, the hydrogen output testing 2 test group is 755.5mLH
2/ L working volume, hydrogen-producing speed is 15.7mL H
2/ L/h.
Test the grease concentration of test 1 test group and test 2 test group, as shown in Figure 3, as shown in Figure 3, when adopting corn starch wastewater to be raw material, grease concentration is 0.41g/L working volume to result, and produce oil speed is 68.3mg/L/d; When adopting potato starch wastewater to be raw material, lipid concentration is 0.31g/L working volume, and produce oil speed is 51.7mg/L/d.
The test group of test 1, control group and the test group of test 2, the COD clearance of control group are tested, result as shown in Figure 4, as shown in Figure 4, adopts corn starch wastewater when being raw material, the COD clearance of control group is 24.2%, and the COD clearance testing 1 test group is 84%; When adopting potato starch wastewater to be raw material, the COD clearance of control group is 20.8%, and the COD clearance testing 2 test group is 79%.
The hydrogen output of test 1 and test 2 is 755.5-883.3mL H
2/ L working volume, oil offtake is 0.31-0.41g/L working volume, and COD clearance is 79-84%.Often there is hydrogen-consuming bacteria in excess sludge, the hydrogen produced by hydrogenogens can be consumed, cause hydrogen output to decline.But hydrogen-consuming bacteria is more responsive to high temperature, after heat treatment activity can be suppressed, because hydrogenogens can form the gemma can resisting severe environment, therefore can survive after heat treatment and keep active, therefore this test is heat-treated excess sludge, effectively can suppress the hydrogen-consuming bacteria in inoculum, reach the object improving fermentation and hydrogen production usefulness.This test is by dark ferment for hydrogen production and micro-algae produce oil coupling processing starch wastewater, the COD quantity discharged of waste water can be reduced, improve water surrounding, reduce the detrimentally affect that starch wastewater causes environment, reclaimed renewable energy source simultaneously, reduce bioenergy production cost, achieve the recycling treatment of starch wastewater, the industrialization paces accelerating biofuel and bio-hydrogen production technology are also had great importance.
Claims (10)
1. process the method that starch wastewater generates renewable energy source simultaneously, it is characterized in that the method comprises the steps: one, processes product hydrogen inoculum, obtain mixture A; Two, get starch wastewater, regulate pH to 5 ~ 10, then by account for starch wastewater cumulative volume 5 ~ 10% inoculum size, inoculated mixture A, then cultivate, obtains hydrogen and organic acid fermentation liquid; Three, remove the solid phase in fermented liquid, then regulate pH to 5 ~ 10 of liquid phase, then press total liquid volume 5 ~ 10% inoculum size, inoculate micro-algae and cultivate, cultivate microalgae afterwards, extract the grease in micro-algae, namely complete;
Product hydrogen inoculum wherein described in step one is that one or more in excess sludge, digested sludge, anaerobic grain sludge and sewage sludge are by arbitrarily than the mixture formed;
Micro-algae described in step 3 is that one or more in grid algae, chlorella, diatom, Crypthecodinium cohnii, flat algae, Dunaliella salina, spirulina and chrysophyceae are by arbitrarily than the mixture formed.
2. according to claim 1ly a kind ofly process the method that starch wastewater generates renewable energy source simultaneously, it is characterized in that the treatment process described in step one is thermal treatment, concrete grammar for process 30min at 100 DEG C.
3. according to claim 1ly a kind ofly process the method that starch wastewater generates renewable energy source simultaneously, it is characterized in that the treatment process described in step one is the one or more combination in acid treatment, alkaline purification, hydrogen peroxide treatment, ultrasonication, microwave treatment, methane inhibitor process, chloroform process, the process of ethylene dibromide sodium sulfonate, radiation treatment, Air Exposure and impact load process.
4. according to claim 1ly a kind ofly process the method that starch wastewater generates renewable energy source simultaneously, it is characterized in that the starch wastewater described in step 2 can be one or more in corn starch wastewater, potato starch wastewater, green starch waste water, wheat kind of starch waste water, cassava starch wastewater, water caltrop starch waste water, Rhizoma Nelumbinis starch waste water and Sweet Potato Starch Processing Waste Water by arbitrarily than the mixture formed.
5. according to claim 1ly a kind ofly process the method that starch wastewater generates renewable energy source simultaneously, the adjustment pH that it is characterized in that described in step 2 and step 3 is undertaken regulating by the NaOH solution of concentration to be the HCl solution of 1mol/L or concentration be 1mol/L.
6. according to claim 1ly a kind ofly process the method that starch wastewater generates renewable energy source simultaneously, it is characterized in that the culture condition described in step 2 is temperature 30 ~ 40 DEG C, isolated air jet flow, shaking speed 50 ~ 200rpm, incubation time 20 ~ 120h.
7. according to claim 1ly a kind ofly process the method that starch wastewater generates renewable energy source simultaneously, it is characterized in that the method for solid phase in the removal fermented liquid described in step 3 is one or both combinations of centrifuging and filtration method.
8. according to claim 1ly a kind ofly process the method that starch wastewater generates renewable energy source simultaneously, the microdisk electrode condition described in step 3 that it is characterized in that is temperature 15 ~ 40 DEG C, shaking speed 50 ~ 200rpm, incubation time 120 ~ 192h.
9. according to claim 1ly a kind ofly process the method that starch wastewater generates renewable energy source simultaneously, it is characterized in that the microalgae recovery method described in step 3 is one or both combinations of centrifuging and filtration method.
10. according to claim 1ly a kind ofly process the method that starch wastewater generates renewable energy source simultaneously, it is characterized in that the Microalgae grease extraction method described in step 3 is chloroform-methanol method, soxhlet extraction methods, normal hexane-isopropanol method, normal hexane-Ethanol Method or ether-petroleum ether method.
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Cited By (7)
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| CN105174476A (en) * | 2015-09-28 | 2015-12-23 | 中国科学院城市环境研究所 | Activated sludge and microalgae coupled granular system for waste water treatment and establishment and operation method thereof |
| CN108660162A (en) * | 2018-05-30 | 2018-10-16 | 江南大学 | A method of inhibiting hydrogen consumption during kitchen garbage dry fermentation production hydrogen |
| CN110484571A (en) * | 2019-09-29 | 2019-11-22 | 哈尔滨工业大学 | Utilize the method for corn stover semi-successive cultivation hydrogen and grease |
| CN110894467A (en) * | 2019-11-12 | 2020-03-20 | 湖南工业大学 | Method for culturing chlorella by using starch processing wastewater anaerobic fermentation liquid |
| CN111763694A (en) * | 2019-04-18 | 2020-10-13 | 哈尔滨工业大学 | Method for producing energy by coupling high-temperature hydrogen production and microalgae oil production |
| CN113293103A (en) * | 2021-06-04 | 2021-08-24 | 江南大学 | Method for improving biomass of chlorella based on corn starch processing wastewater |
| WO2024087097A1 (en) * | 2022-10-27 | 2024-05-02 | 哈尔滨工业大学 | Method for simultaneously treating wastewater and producing clean energy by means of sludge fermentation and microalgal culture |
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Cited By (10)
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| CN105174476A (en) * | 2015-09-28 | 2015-12-23 | 中国科学院城市环境研究所 | Activated sludge and microalgae coupled granular system for waste water treatment and establishment and operation method thereof |
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| CN108660162B (en) * | 2018-05-30 | 2021-06-25 | 江南大学 | Method for inhibiting hydrogen consumption in dry-type fermentation hydrogen production process of kitchen waste |
| CN111763694A (en) * | 2019-04-18 | 2020-10-13 | 哈尔滨工业大学 | Method for producing energy by coupling high-temperature hydrogen production and microalgae oil production |
| CN110484571A (en) * | 2019-09-29 | 2019-11-22 | 哈尔滨工业大学 | Utilize the method for corn stover semi-successive cultivation hydrogen and grease |
| CN110484571B (en) * | 2019-09-29 | 2023-04-25 | 哈尔滨工业大学 | Method for semi-continuously producing hydrogen and grease by using corn straw |
| CN110894467A (en) * | 2019-11-12 | 2020-03-20 | 湖南工业大学 | Method for culturing chlorella by using starch processing wastewater anaerobic fermentation liquid |
| CN113293103A (en) * | 2021-06-04 | 2021-08-24 | 江南大学 | Method for improving biomass of chlorella based on corn starch processing wastewater |
| WO2024087097A1 (en) * | 2022-10-27 | 2024-05-02 | 哈尔滨工业大学 | Method for simultaneously treating wastewater and producing clean energy by means of sludge fermentation and microalgal culture |
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Application publication date: 20150722 |
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