CN111518843A - Anaerobic fermentation hydrogen production method and additive using excess sludge as raw material - Google Patents
Anaerobic fermentation hydrogen production method and additive using excess sludge as raw material Download PDFInfo
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Abstract
The invention relates to an anaerobic fermentation hydrogen production method and an additive by taking excess sludge as a raw material, wherein the hydrogen production method comprises the following steps of S1: taking residual activated sludge generated by a sewage treatment plant as a raw material, settling, and removing supernatant of the residual activated sludge to obtain an anaerobic fermentation raw material; s2: adding anaerobic fermentation raw materials into a fermentation reactor, adding ferrate, uniformly stirring, and keeping the anaerobic environment in the fermentation reactor; s3: controlling the temperature, continuously carrying out the fermentation reaction, and continuously or intermittently outputting the generated hydrogen. Compared with the prior art, the ferrate added in the invention can not only destroy the structure of the excess sludge and promote the release of a large amount of biodegradable organic matters in the sludge, but also obviously inhibit and reduce the activity and abundance of hydrogen consuming microorganisms such as methanogens and the like, thereby obviously promoting the amount of hydrogen produced by the fermentation of the excess sludge; the operation is simple, and the long-term operation management is convenient; can obviously increase the hydrogen yield of the excess sludge resource.
Description
Technical Field
The invention relates to the technical field of environmental protection and sludge treatment recycling, in particular to an anaerobic fermentation hydrogen production method and an additive by taking excess sludge as a raw material.
Background
The activated sludge process has been widely used in municipal sewage treatment. Although this process is effective in treating wastewater, it also produces a large amount of process by-product, i.e., excess activated sludge. Estimated that the residual sludge yield of China is estimated to reach 6000 million metric tons (the water content is 80%) in 2020. The excess sludge is concentrated with a large amount of toxic and harmful substances, such as pathogens, heavy metals, persistent organic pollutants, etc. Without effective disposal, the contained contaminants pose a significant threat to human health and the ecological environment. At present, the cost of sludge treatment and disposal is high, accounting for 60% of the total operation cost of sewage treatment plants, which poses a great challenge to the long-term operation of sewage treatment plants. Meanwhile, the excess sludge is rich in organic substances such as proteins, polysaccharides, lipids and polyhydroxyalkanoates, which generally account for 50-70% of the sludge cells. With the annual increase in global resource demand, the society's awareness of sludge has also shifted from "pollutants" to "resource pools".
At present, the global warming problem is getting more and more serious due to the large amount of greenhouse gas emission, so the development and utilization of clean energy are widely regarded. The anaerobic fermentation of the sludge is a common method for recycling the sludge at present, and can realize sludge reduction and resource recovery (such as volatile fatty acid and hydrogen). Hydrogen is an ideal fuel that is non-polluting, renewable and has a high calorific value, and has received increasing attention worldwide. The method for producing hydrogen by anaerobic fermentation of excess sludge not only realizes effective treatment of sludge, but also produces valuable clean energy, and has important environmental significance. However, in the prior art, the hydrogen amount and the hydrogen rate generated by anaerobic fermentation of sludge are low, and large-scale application is difficult to realize.
CN109593791A discloses a method for improving the yield of hydrogen produced by anaerobic fermentation of excess sludge by using low-temperature thermal pretreatment in combination with free ammonia treatment, which comprises the following steps: step one, taking sludge of a sewage treatment plant as a raw material, and carrying out low-temperature pyrohydrolysis pretreatment; performing FA treatment on the sludge subjected to thermal pretreatment; and step three, performing anaerobic fermentation on the sludge serving as a substrate and the inoculated sludge to produce hydrogen. The technical scheme adopts a mode of combining low-temperature thermal pretreatment with free ammonia treatment to promote hydrogen production, which is equivalent to additionally increasing a low-temperature pretreatment process, so that the whole process flow is complex and the energy consumption is increased.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the method for producing hydrogen by anaerobic fermentation with excess sludge as the raw material and the additive, so that the reduction of sludge is realized, the environmental pollution is effectively reduced, the produced hydrogen is clean and sustainable energy with high calorific value, the situation of energy shortage and global warming can be effectively relieved, and the method conforms to the concept of sustainable development.
The purpose of the invention can be realized by the following technical scheme:
the invention discloses an anaerobic fermentation hydrogen production method by taking excess sludge as a raw material, which is characterized by comprising the following steps:
s1: taking residual activated sludge generated by a sewage treatment plant as a raw material, settling, and removing supernatant of the residual activated sludge to obtain an anaerobic fermentation raw material;
s2: adding anaerobic fermentation raw materials into a fermentation reactor, adding ferrate, uniformly stirring, and keeping the anaerobic environment in the fermentation reactor;
s3: controlling the temperature, continuously carrying out the fermentation reaction, and continuously or intermittently outputting the generated hydrogen.
Further, in step S1, the sedimentation is natural sedimentation.
Further, in step S1, the environmental temperature in the process of sedimentation is 3-5 ℃, and the sedimentation time is 24-48 h.
Further, in step S2, the dosage of ferrate is 0.03-0.15 g/g TSS. The adding amount in the range can realize better effect of promoting hydrogen production, the activity of various active bacteria can be gradually inhibited when the adding amount is too high, and the promoting effect is not obvious when the adding amount is too low.
Further, in step S2, the dosage of ferrate is 0.06-0.09 g/g TSS.
Further, in step S2, the anaerobic environment of the fermentation reactor is maintained by introducing nitrogen.
Further, in step S2, the ferrate includes potassium ferrate and sodium ferrate.
Further, the stirring speed during the reaction is 120 to 180 rpm/min. The stirring speed of more than 120 can realize repeated stirring dispersion effect, and when the stirring speed exceeds 180rpm/min, the hydrogen production promoting effect is reduced because the hydrogen production process of the active bacteria is influenced.
Further, in the step S3, the fermentation reaction temperature is 18-42 ℃, and under the condition, the hydrogen-producing microorganism has strong activity; in order to obtain the maximum hydrogen yield, the fermentation reaction time is 3-10 days.
Further, in step S3, the fermentation reaction temperature is 25-37 ℃.
The invention relates to an additive for promoting anaerobic fermentation of excess sludge of a sewage treatment plant to produce hydrogen, which comprises one or two of potassium ferrate and sodium ferrate.
In the anaerobic fermentation process of sludge, under the combined action of microorganisms, the anaerobic degradation process of organic matters can be divided into six stages: a dissolution stage, a hydrolysis stage, an acidification stage, an acetoxylation stage, a homoacetoxylation stage and a methanation stage. The organic matter in the sludge consists of extracellular polymer and intracellular organic matter. Before they can be used for fermentative hydrogen production, they need to be converted from solid phase to liquid phase by a sludge solubilization stage. However, the rate of sludge solubilization is generally at a low level due to the protective action of the cell wall/membrane and extracellular polymers, and the solubilization phase is considered to be the rate-limiting step in the production of hydrogen by anaerobic fermentation. In the technical scheme, the target product hydrogen is an intermediate product in the anaerobic fermentation process of the sludge, is generated in the acidification and acetoxylation stages, and is consumed by hydrogenconsuming microorganisms such as methanotrophic bacteria and the like in the homoacetogenesis stage and the methanation stage. Therefore, the ferrate used in the invention promotes the activity and abundance of the hydrogen-producing microorganisms and reduces the activity and abundance of the hydrogen-consuming microorganisms, which is the key for improving the anaerobic fermentation hydrogen production of the sludge.
In the technical scheme, the ferrate used is a strong oxidant which is green and environment-friendly, and can destroy the structure of sludge cells to release a large amount of solid-phase organic matters into a liquid phase, so that the solid-phase organic matters are converted and utilized by microorganisms.
In addition, the ferrate not only can obviously inhibit the activity of hydrogen consuming microorganisms, but also can reduce the abundance of the hydrogen consuming microorganisms, thereby obviously improving the yield of hydrogen produced by anaerobic fermentation of sludge.
Compared with the prior art, the invention has the following advantages:
1) the invention utilizes the byproduct, namely the excess sludge, generated by the urban sewage treatment plant to produce the hydrogen, thereby not only realizing the reduction of the sludge and effectively reducing the environmental pollution, but also producing the hydrogen which is clean and sustainable energy with high calorific value, effectively relieving the situation of energy shortage and global warming and conforming to the concept of sustainable development.
2) In the prior art, the amount and the speed of hydrogen generated by anaerobic fermentation of sludge are low, ferrate used in the invention can remarkably promote the cracking of sludge cells and release a large amount of biodegradable organic matters such as protein, sugar and the like in the sludge, thereby providing more available substrates for hydrogen-producing microorganisms, improving the speed and the yield of hydrogen production, having simple overall process, realizing the promotion effect only by adding additives and being beneficial to realizing large-scale popularization and application.
3) The ferrate used in the invention can inhibit the activity of hydrogen consuming microorganisms and can obviously reduce the relative abundance of the hydrogen consuming microorganisms, thereby greatly reducing the consumption of hydrogen and promoting the accumulation of hydrogen.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
(1) In an organic glass reactor with a working volume of 1L, excess sludge produced by a municipal sewage treatment plant is placed at 3 ℃ for natural sedimentation for 24h, and a fermented raw material (i.e., an excess sludge sample, the same as in the following example) is obtained after discharging supernatant.
(2) Adding 0.05g/g TSS ferrate into the reactor, charging nitrogen into the reactor, keeping for 10min to remove oxygen, sealing the reactor, and placing in a shaking table for anaerobic fermentation. The organic matters in the sludge are converted into hydrogen through the combined action of the microorganisms in the sludge and the ferrate. Wherein the fermentation temperature of the reactor is controlled to be 25 +/-1 ℃, the stirring speed of the shaking table is 120rpm/min, the retention time of sludge in the reactor is 3d, and the yield of the produced hydrogen is 4.03mL/g VSS.
Example 2
(1) In an organic glass reactor with a working volume of 1L, excess sludge produced by a municipal sewage treatment plant is placed at 5 ℃ for natural sedimentation for 48h, and a fermented raw material (i.e., an excess sludge sample, the same as in the following example) is obtained after discharging supernatant.
(2) Adding 0.07g/g TSS ferrate into the reactor, charging nitrogen into the reactor, keeping for 10min to remove oxygen, sealing the reactor, and placing into a shaking table for anaerobic fermentation. The organic matters in the sludge are converted into hydrogen through the combined action of the microorganisms in the sludge and the ferrate. Wherein the fermentation temperature of the reactor is controlled to be 37 +/-1 ℃, the stirring speed of the shaking table is 180rpm/min, the retention time of sludge in the reactor is 3d, and the yield of the produced hydrogen is 5.82mL/g VSS.
Example 3
(1) In an organic glass reactor with a working volume of 1L, excess sludge produced by a municipal sewage treatment plant is placed at 4 ℃ for natural sedimentation for 24h, and a fermented raw material (i.e., an excess sludge sample, the same as in the following example) is obtained after supernatant liquid is drained.
(2) Adding 0.03g/g TSS ferrate into the reactor, charging nitrogen into the reactor, keeping for 10min to remove oxygen, sealing the reactor, and placing in a shaking table for anaerobic fermentation. The organic matters in the sludge are converted into hydrogen through the combined action of the microorganisms in the sludge and the ferrate. Wherein the fermentation temperature of the reactor is controlled to be 30 +/-1 ℃, the stirring speed of the shaking table is 150rpm/min, the retention time of sludge in the reactor is 3d, and the yield of the produced hydrogen is 2.67mL/g VSS.
Example 4
(1) In an organic glass reactor with the working volume of 1L, the excess sludge produced by the municipal sewage treatment plant is placed at 4 ℃ for natural sedimentation for 24h, and the fermented raw material is obtained after the supernatant is discharged.
(2) Adding 0.03g/g TSS ferrate into the reactor, charging nitrogen into the reactor, keeping for 10min to remove oxygen, sealing the reactor, and placing in a shaking table for anaerobic fermentation. The organic matters in the sludge are converted into hydrogen through the combined action of the microorganisms in the sludge and the ferrate. Wherein the fermentation temperature of the reactor is controlled to be 30 +/-1 ℃, the stirring speed of the shaking table is 150rpm/min, the retention time of sludge in the reactor is 10d, and the yield of the produced hydrogen is 3.10mL/g VSS.
Example 5
(1) In an organic glass reactor with the working volume of 1L, the excess sludge produced by the municipal sewage treatment plant is placed at 4 ℃ for natural sedimentation for 24h, and the fermented raw material is obtained after the supernatant is discharged.
(2) Adding 0.06g/g TSS ferrate into the reactor, charging nitrogen into the reactor, keeping for 10min to remove oxygen, sealing the reactor, and placing in a shaking table for anaerobic fermentation. The organic matters in the sludge are converted into hydrogen through the combined action of the microorganisms in the sludge and the ferrate. Wherein the fermentation temperature of the reactor is controlled to be 30 +/-1 ℃, the stirring speed of the shaking table is 150rpm/min, the retention time of sludge in the reactor is 10d, and the yield of the produced hydrogen is 4.90mL/g VSS.
Example 6
(1) In an organic glass reactor with the working volume of 1L, the excess sludge produced by the municipal sewage treatment plant is placed at 4 ℃ for natural sedimentation for 24h, and the fermented raw material is obtained after the supernatant is discharged.
(2) Adding 0.09g/g TSS ferrate into the reactor, charging nitrogen into the reactor, keeping for 10min to remove oxygen, sealing the reactor, and placing in a shaking table for anaerobic fermentation. The organic matters in the sludge are converted into hydrogen through the combined action of the microorganisms in the sludge and the ferrate. Wherein the fermentation temperature of the reactor is controlled to be 30 +/-1 ℃, the stirring speed of the shaking table is 150rpm/min, the retention time of sludge in the reactor is 5d, and the yield of the produced hydrogen is 8.30mL/g VSS.
Comparative example 1
(1) In an organic glass reactor with the working volume of 1L, the excess sludge produced by the municipal sewage treatment plant is placed at 4 ℃ for natural sedimentation for 24h, and the fermented raw material is obtained after the supernatant is discharged. And (3) filling nitrogen into the reactor without adding ferrate for 10min to remove oxygen, sealing the reactor, and putting the reactor into a shaking table for anaerobic fermentation. The organic matters in the sludge are converted into hydrogen under the action of microorganisms contained in the sludge. Wherein the fermentation temperature of the reactor is controlled to be 30 +/-1 ℃, the stirring speed of the shaking table is 150rpm/min, the retention time of sludge in the reactor is 10d, and the yield of the produced hydrogen is 1.47mL/g VSS.
The hydrogen yields of the examples and comparative examples are shown in table 1:
as can be seen from the table, the hydrogen production yields of examples 1 to 4 were significantly improved as compared with that of comparative example 1, and in particular, the hydrogen production yield of example 4 under optimum conditions was most significantly improved as compared with that of comparative example 1.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many modifications to the invention as possible, or modify equivalent embodiments with equivalent variations, without departing from the spirit and scope of the invention. Therefore, any simple improvements and modifications without departing from the scope of the present invention should be within the protection scope of the present invention.
Claims (10)
1. The method for producing hydrogen by using excess sludge as a raw material through anaerobic fermentation is characterized by comprising the following steps of:
s1: taking residual activated sludge generated by a sewage treatment plant as a raw material, settling, and removing supernatant of the residual activated sludge to obtain an anaerobic fermentation raw material;
s2: adding anaerobic fermentation raw materials into a fermentation reactor, adding ferrate, uniformly stirring, and keeping the anaerobic environment in the fermentation reactor;
s3: controlling the temperature, continuously carrying out the fermentation reaction, and continuously or intermittently outputting the generated hydrogen.
2. The method for producing hydrogen by anaerobic fermentation using excess sludge as raw material according to claim 1, wherein the sedimentation is natural sedimentation in step S1.
3. The method for producing hydrogen by anaerobic fermentation with excess sludge as raw material according to claim 1, wherein in step S1, the environmental temperature in the sedimentation process is 3-5 ℃ and the sedimentation time is 24-48 h.
4. The method for producing hydrogen by anaerobic fermentation using excess sludge as raw material according to claim 1, wherein in step S2, the addition amount of ferrate is 0.03-0.15 g/g TSS.
5. The method for producing hydrogen by anaerobic fermentation using excess sludge as raw material according to claim 4, wherein in step S2, the addition amount of ferrate is 0.06-0.010 g/g TSS.
6. The method for producing hydrogen by anaerobic fermentation using excess sludge as raw material according to claim 1, wherein in step S2, the anaerobic environment of the fermentation reactor is maintained by introducing nitrogen gas.
7. The method for producing hydrogen by anaerobic fermentation using excess sludge as claimed in claim 1, wherein in step S2, said ferrate comprises potassium ferrate and sodium ferrate.
8. The method for producing hydrogen by anaerobic fermentation using excess sludge as raw material according to claim 1, wherein in step S3, the fermentation reaction temperature is 18-42 ℃ and the fermentation reaction time is 3-10 days.
9. The method for producing hydrogen by anaerobic fermentation using excess sludge as raw material according to claim 8, wherein the fermentation reaction temperature in step S3 is 25-37 ℃.
10. An additive for promoting anaerobic fermentation of excess sludge of a sewage treatment plant to produce hydrogen is characterized by comprising one or two of potassium ferrate and sodium ferrate.
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Cited By (4)
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| CN113697949A (en) * | 2021-08-20 | 2021-11-26 | 中钢集团鞍山热能研究院有限公司 | Short-flow anaerobic reactor device and high-concentration organic wastewater pretreatment method |
| CN113930781A (en) * | 2021-10-14 | 2022-01-14 | 太原理工大学 | Method for synchronously producing hydrogen and vivianite through iron anode mediated residual sludge electric fermentation |
| CN114394724A (en) * | 2022-01-17 | 2022-04-26 | 同济大学 | Method for improving sludge anaerobic fermentation hydrogen yield by using calcium hypochlorite |
| CN114558417A (en) * | 2022-02-18 | 2022-05-31 | 湖南农业大学 | Method for reducing emission of greenhouse gas in rice field |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113697949A (en) * | 2021-08-20 | 2021-11-26 | 中钢集团鞍山热能研究院有限公司 | Short-flow anaerobic reactor device and high-concentration organic wastewater pretreatment method |
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| CN113930781A (en) * | 2021-10-14 | 2022-01-14 | 太原理工大学 | Method for synchronously producing hydrogen and vivianite through iron anode mediated residual sludge electric fermentation |
| CN113930781B (en) * | 2021-10-14 | 2023-12-01 | 太原理工大学 | Method for synchronously producing hydrogen and wustite through electric fermentation of excess sludge mediated by iron anode |
| CN114394724A (en) * | 2022-01-17 | 2022-04-26 | 同济大学 | Method for improving sludge anaerobic fermentation hydrogen yield by using calcium hypochlorite |
| CN114558417A (en) * | 2022-02-18 | 2022-05-31 | 湖南农业大学 | Method for reducing emission of greenhouse gas in rice field |
| CN114558417B (en) * | 2022-02-18 | 2024-06-07 | 湖南农业大学 | Emission reduction method for greenhouse gases in rice field |
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Application publication date: 20200811 |