CN106830308A - A Method for Accelerated Anaerobic Propionic and Butyric Acid Decomposition Using Ethanol and Biochar - Google Patents
A Method for Accelerated Anaerobic Propionic and Butyric Acid Decomposition Using Ethanol and Biochar Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 title claims abstract description 88
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 title claims abstract description 73
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 title abstract description 14
- 230000029087 digestion Effects 0.000 claims abstract description 82
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002351 wastewater Substances 0.000 claims abstract description 39
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 238000012544 monitoring process Methods 0.000 claims abstract description 4
- 239000010802 sludge Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 5
- 239000000463 material Substances 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000020477 pH reduction Effects 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 description 17
- 230000027756 respiratory electron transport chain Effects 0.000 description 15
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 9
- 241001135750 Geobacter Species 0.000 description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 5
- 244000005700 microbiome Species 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 230000000789 acetogenic effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000037361 pathway Effects 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 229940095602 acidifiers Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003501 co-culture Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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Abstract
一种利用乙醇和生物炭加快厌氧丙酸和丁酸分解的方法包括以下步骤：采用乙醇按照化学需氧量的比例为4:1‑1:1添加进含丙酸或丁酸的废水，运行厌氧消化装置。控制该装置的水力停留时间，该装置内的pH值和温度。将生物炭投加到该装置内生物炭填充层，密封该装置。运行该装置后逐步减少乙醇的添加量，直到废水中不含乙醇，同时监测该装置出水中丙酸或丁酸的浓度和该装置的甲烷产量。本发明的技术方案，可达到如下技术效果：加快厌氧丙酸或丁酸的分解速率，维持产甲烷酸性平衡，提高甲烷产量。该技术的投资成本少，操作简单，提高效果明显。可用于恢复处于酸化或甲烷化受到抑制的厌氧消化装置，也可用于厌氧消化装置为抵抗高进水负荷冲击的升级改造。
A method for accelerating the decomposition of anaerobic propionic acid and butyric acid by using ethanol and biochar comprises the following steps: adding ethanol to wastewater containing propionic acid or butyric acid according to a chemical oxygen demand ratio of 4:1-1:1, and operating an anaerobic digestion device. Controlling the hydraulic retention time of the device, the pH value and the temperature in the device. Adding biochar to the biochar filling layer in the device, and sealing the device. After running the device, gradually reducing the amount of ethanol added until the wastewater does not contain ethanol, while monitoring the concentration of propionic acid or butyric acid in the effluent of the device and the methane production of the device. The technical scheme of the present invention can achieve the following technical effects: accelerating the decomposition rate of anaerobic propionic acid or butyric acid, maintaining the acidic balance of methanogenicity, and increasing the methane production. The technology has low investment cost, simple operation, and obvious improvement effect. It can be used to restore anaerobic digestion devices that are in acidification or methanogenicity is inhibited, and can also be used for upgrading and transforming anaerobic digestion devices to resist high water inlet load shocks.
Description
技术领域technical field
本发明涉及环境保护领域。The invention relates to the field of environmental protection.
背景技术Background technique
厌氧甲烷化技术是目前实现污染物能源化最现实、最有效的方法之一。厌氧的产酸与产甲烷在微生物的生态、代谢速度等方面的差异较大，容易导致甲烷化失衡而停顿。在厌氧甲烷化故障时，经常表现为厌氧消化装置内丙酸和丁酸浓度的升高，破坏厌氧甲烷化的酸性平衡，进而抑制产甲烷。Anaerobic methanation technology is currently one of the most realistic and effective methods to realize the energy conversion of pollutants. Anaerobic acid production and methanogenesis are quite different in terms of microbial ecology and metabolic speed, which can easily lead to an imbalance of methanation and stop. When anaerobic methanation fails, it often manifests as an increase in the concentration of propionic acid and butyric acid in the anaerobic digestion unit, which destroys the acid balance of anaerobic methanation, thereby inhibiting methane production.
半个世纪以来，厌氧丙酸和丁酸的代谢一直被认为是酸化菌与产甲烷菌交换氢电子的过程，即种间氢气传递——酸化菌分解丙酸或丁酸为乙酸并释放H2，耗氢产甲烷菌利用H2还原CO2为CH4。然而，酸化菌和产甲烷菌之间的这种电子链接受到产氢底物、氢扩散速度、耗氢甲烷菌活性等影响，一些微小的波动可能使种间氢气传递受阻，H2分压升高，使丙酸和丁酸积累，产甲烷停顿。For half a century, the metabolism of anaerobic propionate and butyrate has been considered as a process in which acidifying bacteria exchange hydrogen electrons with methanogens, that is, interspecies hydrogen transfer—acidifying bacteria decompose propionate or butyrate to acetate and release H 2. Hydrogen-consuming methanogens use H 2 to reduce CO 2 to CH 4 . However, the electronic link between acidifying bacteria and methanogens is affected by the hydrogen-producing substrate, hydrogen diffusion rate, and activity of hydrogen-consuming methane bacteria, and some small fluctuations may hinder the interspecies hydrogen transfer, and the partial pressure of H2 will increase. High, so that propionic acid and butyric acid accumulate, methane production stops.
最近的研究表明，厌氧丙酸和丁酸的分解能够在纯菌共培养体系中通过某些酸化菌，比如地杆菌等与耗乙酸产甲烷菌直接交换电子来实现，即直接种间电子传递——酸化菌分解丙酸或丁酸并释放电子和H+，耗乙酸产甲烷菌直接接受电子和H+还原CO2为CH4。由于耗乙酸产甲烷菌在常规厌氧消化装置内占优势地位，这种直接种间电子传递机制也被寄予厚望来缓解厌氧消化装置内丙酸或丁酸的积累。然而，受电子传递速率的影响，这种通过直接种间电子传递来分解丙酸和丁酸的机制在常规的厌氧消化装置内并不普遍。一些研究尝试将导体碳材料，比如颗粒活性炭，石墨棒和碳布等投加到厌氧消化装置，提高直接种间电子传递速率，以达到加快丙酸和丁酸分解的目的。但是，收到的效果却不明显。原因被归结为能够分解丙酸和丁酸，并将产生的电子直接传递给耗乙酸产甲烷菌的酸化菌，比如地杆菌，在常规厌氧消化装置内的丰度较低。因此，在常规厌氧消化装置内富集具备直接种间电子传递能力的酸化菌，同时提高直接种间电子传递速率，是加快厌氧丙酸和丁酸分解的关键。Recent studies have shown that the decomposition of anaerobic propionic acid and butyric acid can be achieved by direct exchange of electrons between some acidifying bacteria, such as Geobacter, and acetate-consuming methanogens in a pure bacterial co-culture system, that is, direct interspecies electron transfer. ——Acidifying bacteria decompose propionic acid or butyric acid and release electrons and H + , and acetogenic methanogens directly accept electrons and H + to reduce CO 2 to CH 4 . Due to the dominance of acetophilic methanogens in conventional anaerobic digesters, this direct interspecies electron transfer mechanism is also expected to alleviate the accumulation of propionate or butyrate in anaerobic digesters. However, this mechanism for breaking down propionate and butyrate through direct interspecies electron transfer is not prevalent in conventional anaerobic digestion units due to the electron transfer rate. Some studies have tried to add conductive carbon materials, such as granular activated carbon, graphite rods and carbon cloth, to the anaerobic digestion device to increase the direct interspecies electron transfer rate, so as to accelerate the decomposition of propionic acid and butyric acid. However, the effect received is not obvious. The reason has been put down to the fact that acidifying bacteria, such as Geobacter, which break down propionate and butyrate and transfer the resulting electrons directly to acetate-consuming methanogens, are low in abundance in conventional anaerobic digestion units. Therefore, enriching acidifying bacteria capable of direct interspecies electron transfer in a conventional anaerobic digestion unit and increasing the rate of direct interspecies electron transfer are the key to accelerating the decomposition of anaerobic propionate and butyrate.
发明内容Contents of the invention
为解决厌氧消化装置内丙酸和丁酸的积累，导致酸性失衡，进而抑制甲烷化的问题，本发明提出以下技术方案：设有外保温层的筒体内自下向上依次设有布水器、污泥层、生物炭填充层与悬浮污泥层，筒体内上方为三相分离区，三相分离器固定于所述筒体的上盖。进水阀门一端连接布水器而另一端连接进水管道经进水泵插入进水池。三相分离器的上端设有排气管道而筒体的上方侧面设有出水管道。In order to solve the problem that the accumulation of propionic acid and butyric acid in the anaerobic digestion device leads to acid imbalance and then inhibits methanation, the present invention proposes the following technical proposal: the cylinder with the outer insulation layer is provided with water distributors in sequence from bottom to top , a sludge layer, a biochar filling layer and a suspended sludge layer, the upper part of the cylinder is a three-phase separation area, and the three-phase separator is fixed on the upper cover of the cylinder. One end of the water inlet valve is connected to the water distributor and the other end is connected to the water inlet pipe and inserted into the water inlet pool through the water inlet pump. The upper end of the three-phase separator is provided with an exhaust pipe and the upper side of the cylinder is provided with a water outlet pipe.
一种使用上述的上流式厌氧消化装置利用乙醇和生物炭加快厌氧丙酸和丁酸分解的方法，其特征在于包括下述工序：A method using the above-mentioned upflow anaerobic digestion device to utilize ethanol and biochar to accelerate the decomposition of anaerobic propionic acid and butyric acid is characterized in that it comprises the following steps:
采用浓度≥99.7％的分析纯乙醇，按照化学需氧量(COD)的比例为4:1-1:1添加到含丙酸或丁酸的废水。Analytical pure ethanol with a concentration ≥ 99.7% is used to add to the wastewater containing propionic acid or butyric acid according to the chemical oxygen demand (COD) ratio of 4:1-1:1.
选用生物炭通过作物秸秆或树枝落叶在450-550℃的厌氧条件下烧制6-8个小时。选用的生物炭为片状或颗粒状，粒径控制在10-30mm。The biochar is selected to burn through crop stalks or branches and fallen leaves under anaerobic conditions of 450-550° C. for 6-8 hours. The selected biochar is flake or granular, and the particle size is controlled at 10-30mm.
采用工序1)所述废水，运行上流式厌氧消化装置10-20天，同时监测该装置出水中丙酸或丁酸的浓度和该装置的甲烷产量。Using the wastewater described in step 1), run the upflow anaerobic digestion device for 10-20 days, and simultaneously monitor the concentration of propionic acid or butyric acid in the effluent of the device and the methane output of the device.
厌氧消化装置的水力停留时间控制在6-12小时。厌氧消化装置内pH控制在6.5-7.5之间。厌氧消化装置内温度控制在30-37℃。The hydraulic retention time of the anaerobic digestion unit is controlled at 6-12 hours. The pH in the anaerobic digestion unit is controlled between 6.5-7.5. The temperature in the anaerobic digestion unit is controlled at 30-37°C.
采用工序3)中所述条件，运行厌氧消化装置10-20天之后，称取工序中2)生物炭中5-20g投加到厌氧消化装置内生物碳填充层(3)。Using the conditions described in step 3), after running the anaerobic digestion device for 10-20 days, weigh 5-20 g of the biochar in step 2) and add it to the biochar filling layer (3) in the anaerobic digestion device.
密封厌氧消化装置，并运行该装置10-20天，同时监测该装置出水中丙酸或丁酸的浓度和该装置的甲烷产量。Seal the anaerobic digestion unit and run the unit for 10-20 days while monitoring the concentration of propionic acid or butyric acid in the effluent of the unit and the methane production of the unit.
逐步减少废水中乙醇的添加量，按照乙醇与废水的COD比例从4:1-1:1逐步减少至废水中不含乙醇。Gradually reduce the amount of ethanol added in the wastewater, and gradually reduce the COD ratio of ethanol to wastewater from 4:1-1:1 until the wastewater does not contain ethanol.
在每个乙醇添加比例下，依次运行厌氧消化装置10-20天，同时监测该装置出水中丙酸或丁酸的浓度和该装置的甲烷产量。Under each ethanol addition ratio, the anaerobic digestion unit was operated sequentially for 10-20 days, and at the same time, the concentration of propionic acid or butyric acid in the effluent water of the unit and the methane production of the unit were monitored.
这种利用乙醇和生物炭加快厌氧丙酸和丁酸分解的方法，其特点是：采用乙醇按照化学需氧量(COD)的比例为4:1-1:1添加进含丙酸或丁酸废水。厌氧消化装置内可以逐步地富集出能够分解丙酸或丁酸，并将产生的电子直接传递给耗乙酸产甲烷菌的酸化菌，比如地杆菌。该酸化菌，比如地杆菌的丰度在厌氧消化装置内明显提高。投加生物碳至厌氧消化装置内生物碳填充层，加快直接种间电子传递速率。生物碳表面的多孔结构有效地截留微生物，降低其受外界环境扰动的影响。将这两种技术方案同时应用到厌氧消化装置内，所富集的酸化菌，比如地杆菌，和耗乙酸产甲烷菌有效地截留在生物炭的表面或孔隙内，通过直接种间电子传递途径而不是传统的种间氢气传递途径来分解丙酸和丁酸。因此，丙酸和丁酸的分解速率得以加快，甲烷产量得到提高。This method of using ethanol and biochar to accelerate the decomposition of anaerobic propionic acid and butyric acid is characterized in that ethanol is added to the chemical oxygen demand (COD) containing propionic acid or butyric acid at a ratio of 4:1-1:1. acid waste water. Acidifying bacteria, such as Geobacter, which can decompose propionic acid or butyric acid and directly transfer the generated electrons to acetogenic methanogens can be gradually enriched in the anaerobic digestion unit. The abundance of the acidifying bacteria, such as Geobacter, is significantly increased in the anaerobic digestion unit. Add biochar to the biochar filling layer in the anaerobic digestion unit to accelerate the rate of direct interspecies electron transfer. The porous structure on the surface of biochar effectively traps microorganisms and reduces their influence from external environmental disturbances. When these two technical solutions are applied to the anaerobic digestion unit at the same time, the enriched acidifying bacteria, such as Geobacter, and acetogenic methanogens are effectively trapped on the surface or pores of the biochar, and through direct interspecies electron transfer pathway rather than the traditional interspecies hydrogen transfer pathway to decompose propionate and butyrate. As a result, the decomposition rates of propionic and butyric acids are accelerated and methane production is enhanced.
采用上述这种利用乙醇和生物炭加快厌氧丙酸和丁酸分解的方法的技术方案，达到如下技术效果：加快厌氧丙酸和丁酸的分解速率，缓解由于丙酸和丁酸的积累导致的厌氧甲烷化停滞或抑制，维持厌氧消化装置内酸性平衡，提高厌氧消化装置的甲烷产量。该技术的投资成本少，操作简单，提高效果明显。乙醇只需初次投加，无需反复。该技术方案可以应用于恢复正处于酸化或甲烷化受到抑制的厌氧消化装置，以及用于厌氧消化装置为抵抗高进水负荷冲击的升级改造。Adopting the above-mentioned technical scheme of using ethanol and biochar to accelerate the decomposition of anaerobic propionic acid and butyric acid achieves the following technical effects: accelerate the decomposition rate of anaerobic propionic acid and butyric acid, and alleviate the accumulation of propionic acid and butyric acid The resulting stagnation or inhibition of anaerobic methanation maintains the acid balance in the anaerobic digestion unit and increases the methane output of the anaerobic digestion unit. The investment cost of this technology is low, the operation is simple, and the improvement effect is obvious. Ethanol only needs to be added for the first time, without repetition. This technical solution can be applied to restore the anaerobic digestion unit that is undergoing acidification or suppressed methanation, and can be used for the upgrading of the anaerobic digestion unit to resist the impact of high influent load.
附图说明：Description of drawings:
图1是上流式厌氧消化装置工作原理图Figure 1 is a working principle diagram of an upflow anaerobic digestion device
图2为图1的M-M剖面放大图Figure 2 is an enlarged view of the M-M section in Figure 1
图中：1、布水器，2、污泥层，3、生物炭填充层，4、悬浮污泥层，5、三相分离区，6、三相分离器，7、保温层，8、进水池，9、进水管道，10、进水泵，11、出水管道，12、排气管道，13、进水阀门14、筒体。In the figure: 1. Water distributor, 2. Sludge layer, 3. Biochar filling layer, 4. Suspended sludge layer, 5. Three-phase separation zone, 6. Three-phase separator, 7. Insulation layer, 8. Water inlet pool, 9, water inlet pipe, 10, water inlet pump, 11, water outlet pipe, 12, exhaust pipe, 13, water inlet valve 14, cylinder body.
具体实施方式detailed description
本发明的应用机理是：Application mechanism of the present invention is:
1、乙醇是具备直接种间电子传递能力的酸化菌，比如地杆菌，比较喜欢利用的底物之一。采用乙醇按照COD比例为4:1-1:1添加进含丙酸或丁酸的废水，可以在厌氧消化装置内逐渐地富集这种不仅能够分解丙酸或丁酸，并将产生的电子直接传递给耗乙酸产甲烷菌的酸化菌。提高该酸化菌在厌氧消化装置内的丰度。1. Ethanol is one of the substrates that acidifying bacteria with direct interspecies electron transfer capabilities, such as Geobacter, prefer to use. Adding ethanol to the wastewater containing propionic acid or butyric acid according to the COD ratio of 4:1-1:1 can gradually enrich in the anaerobic digestion device, which can not only decompose propionic acid or butyric acid, but also produce Electrons are delivered directly to the acidifiers of the acetophilic methanogens. Increase the abundance of the acidifying bacteria in the anaerobic digestion unit.
2、投加生物碳至厌氧消化装置内生物碳填充层，加快直接种间电子传递速率。所富集的酸化菌，比如地杆菌，和耗乙酸产甲烷菌附着在生物炭的表面，依靠生物炭高电导性，进行直接种间电子交换。所富集的酸化菌，比如地杆菌，和耗乙酸产甲烷菌依托生物碳进行电子传递，无需生长导电的细胞菌丝和色素进行直接种间电子传递，降低所富集的酸化菌和耗乙酸产甲烷菌细胞的能量消耗。此外，生物碳的多孔结构可以有效地截留微生物，降低其受外界环境扰动的影响。2. Add biochar to the biochar filling layer in the anaerobic digestion unit to speed up the direct interspecies electron transfer rate. The enriched acidifying bacteria, such as Geobacter, and acetate-consuming methanogens attach to the surface of biochar, relying on the high electrical conductivity of biochar for direct interspecies electron exchange. The enriched acidifying bacteria, such as Geobacter, and acetic acid-consuming methanogens rely on biochar for electron transfer, and do not need to grow conductive cell hyphae and pigments for direct interspecies electron transfer, reducing the enriched acidifying bacteria and acetic acid consumption Energy expenditure of methanogen cells. In addition, the porous structure of biochar can effectively trap microorganisms and reduce their influence from external environmental disturbances.
3、将上述两种技术方案同时应用到厌氧消化装置内，所富集的酸化菌，比如地杆菌，和耗乙酸产甲烷菌可以有效地截留在生物炭的表面和孔隙内，通过直接种间电子传递途径分解丙酸和丁酸。生物碳提高直接种间电子传递效率。生物碳表面和孔隙内进行的丙酸或丁酸分解是不受生物碳表面和孔隙内以外的微生物种间氢气传递受阻而影响。因此，乙醇只需初次投加，无需反复。3. Applying the above two technical solutions to the anaerobic digestion device at the same time, the enriched acidifying bacteria, such as Geobacter, and acetic acid-consuming methanogens can be effectively trapped on the surface and pores of the biochar, through direct planting Electron transfer pathway breaks down propionate and butyrate. Biochar improves direct interspecies electron transfer efficiency. Propionate or butyrate decomposition on the biochar surface and within the pores was unaffected by the impeded interspecies hydrogen transfer of microorganisms beyond the surface and within the pores of the biochar. Therefore, ethanol only needs to be added for the first time, without repetition.
这种利用乙醇和生物碳加快厌氧丙酸和丁酸分解的方法使用上流式厌氧消化装置，设有外保温层7的筒体14内自下向上依次设有布水器1、污泥层2、生物炭填充层3与悬浮污泥层4。筒体14内上方为三相分离区5。三相分离器6固定于筒体14的上盖。进水阀门13一端连接布水器1而另一端连接进水管道9经进水泵10插入进水池8。三相分离器6的上端设有排气管道12而筒体14的上方侧面设有出水管道11。采用取自污泥处理厂的厌氧消化污泥回流液来驯化厌氧消化装置，使该装置内的悬浮固体浓度(MLSS)达到10-20g/L。This method of utilizing ethanol and biochar to accelerate the decomposition of anaerobic propionic acid and butyric acid uses an upflow anaerobic digestion device, and the cylinder body 14 provided with an outer insulation layer 7 is sequentially provided with a water distributor 1 and a sludge tank from bottom to top. Layer 2, biochar filling layer 3 and suspended sludge layer 4. The upper part of the cylinder body 14 is a three-phase separation zone 5 . The three-phase separator 6 is fixed on the upper cover of the cylinder body 14 . One end of the water inlet valve 13 is connected to the water distributor 1 and the other end is connected to the water inlet pipe 9 and inserted into the water inlet pool 8 through the water inlet pump 10 . The upper end of the three-phase separator 6 is provided with an exhaust pipe 12 and the upper side of the cylinder 14 is provided with a water outlet pipe 11 . Use the anaerobic digestion sludge reflux liquid from the sludge treatment plant to domesticate the anaerobic digestion unit, so that the concentration of suspended solids (MLSS) in the unit reaches 10-20g/L.
使用上述装置利用乙醇和生物炭加快厌氧丙酸和丁酸分解的方法，其特点在于包括下述具体操作工序：Use above-mentioned device to utilize ethanol and biochar to accelerate the method for anaerobic propionic acid and butyric acid decomposition, it is characterized in that comprising following specific operating procedures:
采用浓度≥99.7％的分析纯乙醇，按照化学需氧量(COD)比例为4:1-1:1添加到含丙酸或丁酸的废水。作为优选，添加的乙醇与废水COD的最佳比例为4:1。进水中应包含微生物所必需的微量元素和矿物质。Analytical pure ethanol with a concentration ≥ 99.7% is added to the wastewater containing propionic acid or butyric acid according to the chemical oxygen demand (COD) ratio of 4:1-1:1. As a preference, the optimal ratio of added ethanol to wastewater COD is 4:1. Influent water should contain trace elements and minerals necessary for microorganisms.
选用生物炭通过农林废弃物在450-550℃的厌氧条件下烧制6-8个小时。作为优选，农林废弃物应选用作物秸秆或树枝落叶。选用的生物炭为片状或颗粒状，粒径应该控制在10-30mm。为了增加处理效果，选用的生物炭需在5mol/L的盐酸溶液中浸泡3-5小时，在用清水淋洗0.5-1小时，以达到去除表面灰分和杂质的目的。Biochar is selected to burn agricultural and forestry wastes under anaerobic conditions at 450-550°C for 6-8 hours. Preferably, agricultural and forestry wastes should be crop stalks or fallen leaves. The selected biochar is flake or granular, and the particle size should be controlled at 10-30mm. In order to increase the treatment effect, the selected biochar needs to be soaked in 5mol/L hydrochloric acid solution for 3-5 hours, and rinsed with water for 0.5-1 hour to achieve the purpose of removing surface ash and impurities.
采用上述添加乙醇的废水，运行厌氧消化装置10-20天。最佳时间为15天。同时监测厌氧消化装置出水中丙酸或丁酸的浓度和该装置的甲烷产量。Using the above-mentioned wastewater added with ethanol, run the anaerobic digestion unit for 10-20 days. The optimal time is 15 days. Simultaneously monitor the concentration of propionic acid or butyric acid in the effluent of the anaerobic digestion unit and the methane production of the unit.
厌氧消化装置的水力停留时间控制在6-12小时，最佳水力停留时间为10小时。The hydraulic retention time of the anaerobic digestion unit is controlled at 6-12 hours, and the optimal hydraulic retention time is 10 hours.
厌氧消化装置内pH控制在6.5-7.5之间，最佳pH为7.2。The pH in the anaerobic digestion unit is controlled between 6.5-7.5, and the optimum pH is 7.2.
厌氧消化装置内温度控制在30-37℃，最佳温度为37℃。The temperature in the anaerobic digestion unit is controlled at 30-37°C, and the optimum temperature is 37°C.
称取上述生物炭5-20g投加到厌氧消化装置内生物碳填充层。作为优选，选用生物碳为片状，粒径为20mm。生物炭的最佳投加量为20g。Weigh 5-20g of the above-mentioned biochar and add it to the biochar filling layer in the anaerobic digestion device. Preferably, the biochar is in the form of flakes with a particle size of 20 mm. The optimal dosage of biochar is 20g.
密封厌氧消化装置，运行该装置10-20天，最佳时间为15天，同时监测厌氧消化装置出水丙酸或丁酸的浓度和该装置的甲烷产量。Seal the anaerobic digestion unit, run the unit for 10-20 days, the best time is 15 days, and monitor the concentration of propionic acid or butyric acid in the effluent of the anaerobic digestion unit and the methane production of the unit.
逐步减少废水中乙醇的添加量，按照乙醇与废水的COD比例从4:1-1:1减少至废水中不含乙醇。Gradually reduce the amount of ethanol added in wastewater, and reduce the COD ratio of ethanol to wastewater from 4:1-1:1 to no ethanol in wastewater.
每个乙醇添加比例下，依次运行厌氧消化装置10-20天。最佳时间为15天。同时监测该装置出水中丙酸或丁酸的浓度和该装置的甲烷产量。Under each ethanol addition ratio, run the anaerobic digestion unit for 10-20 days in sequence. The optimal time is 15 days. Simultaneously monitor the concentration of propionic acid or butyric acid in the effluent water of the device and the methane production of the device.
下面通过实施例对本发明做进一步说明：Below by embodiment the present invention will be further described:
实施例1：Example 1:
有效容积为1L的上流式厌氧消化装置，接种厌氧污泥400mL，污泥浓度(MLSS)为13g/L。废水中丙酸的浓度为5137.5mgCOD/L。采用浓度≥99.7％的分析纯乙醇，按照COD比例为4:1添加至该废水，运行厌氧消化装置15天。厌氧消化装置内pH控制为7.2，温度控制为37℃。厌氧消化装置的水力停留时间控制为12小时。称取5g生物碳(片状，粒径20-30mm)投加到厌氧消化装置内生物碳填充层，密封厌氧消化装置，并运行厌氧消化装置15天。逐步减少废水中乙醇的添加量，按照乙醇与废水的COD比例为4:1依次减少至3:2、2:3、1:4，直到废水中不含乙醇。每个乙醇添加比例条件下，依次运行厌氧消化装置15天。丙酸的去除率提高17％，产甲烷速率提高16％。An upflow anaerobic digestion unit with an effective volume of 1L is inoculated with 400mL of anaerobic sludge, and the sludge concentration (MLSS) is 13g/L. The concentration of propionic acid in wastewater is 5137.5mgCOD/L. Analytical pure ethanol with a concentration ≥ 99.7% was added to the wastewater according to the COD ratio of 4:1, and the anaerobic digestion device was operated for 15 days. The pH in the anaerobic digestion unit is controlled at 7.2, and the temperature is controlled at 37°C. The hydraulic retention time of the anaerobic digestion unit is controlled at 12 hours. Weigh 5g of biochar (flaky, particle size 20-30mm) and add it to the biochar filling layer in the anaerobic digestion device, seal the anaerobic digestion device, and run the anaerobic digestion device for 15 days. Gradually reduce the amount of ethanol added in the wastewater, according to the COD ratio of ethanol and wastewater from 4:1 to 3:2, 2:3, 1:4, until the wastewater does not contain ethanol. Under the conditions of each ethanol addition ratio, the anaerobic digestion unit was operated for 15 days in sequence. The removal rate of propionic acid increased by 17%, and the rate of methane production increased by 16%.
实施例2：Example 2:
有效容积为1L的上流式厌氧消化装置，接种厌氧污泥400mL，污泥浓度为13g/L。废水中丁酸的浓度为5137.5mgCOD/L。采用浓度≥99.7％的分析纯乙醇，按照COD比例为4:1添加至该废水，运行厌氧消化装置15天。厌氧消化装置内pH控制为7.2，温度控制为37℃。厌氧消化装置的水力停留时间控制为12小时。取5g粒径为20-30mm的片状生物碳投加到厌氧消化装置内生物炭填充层，密封厌氧消化装置，并运行厌氧消化装置15天。逐步减少废水中乙醇的添加量，按照乙醇与废水的COD比例为4:1减少至3:2、2:3、1:4，直到废水中不含乙醇。每个乙醇添加比例条件下，依次运行厌氧消化装置15天。丁酸的去除率提高23％，甲烷产量提高25％。An upflow anaerobic digestion unit with an effective volume of 1L is inoculated with 400mL of anaerobic sludge, and the sludge concentration is 13g/L. The concentration of butyric acid in wastewater is 5137.5mgCOD/L. Analytical pure ethanol with a concentration ≥ 99.7% was added to the wastewater according to the COD ratio of 4:1, and the anaerobic digestion device was operated for 15 days. The pH in the anaerobic digestion unit is controlled at 7.2, and the temperature is controlled at 37°C. The hydraulic retention time of the anaerobic digestion unit is controlled at 12 hours. Take 5g of flake biochar with a particle size of 20-30mm and add it to the biochar filling layer in the anaerobic digestion device, seal the anaerobic digestion device, and run the anaerobic digestion device for 15 days. Gradually reduce the amount of ethanol added in the wastewater, and reduce the COD ratio of ethanol to wastewater from 4:1 to 3:2, 2:3, and 1:4 until there is no ethanol in the wastewater. Under the conditions of each ethanol addition ratio, the anaerobic digestion unit was operated for 15 days in sequence. Butyric acid removal was increased by 23% and methane production was increased by 25%.
实施例3：Example 3:
有效容积为1L的上流式厌氧消化装置，接种厌氧污泥350mL，污泥浓度为17g/L。废水中丙酸浓度为5031mgCOD/L。采用浓度≥99.7％的分析纯乙醇，按照COD比例为4:1添加进该废水中，运行厌氧消化装置10天。厌氧消化装置内pH控制为7.2，温度控制为37℃。厌氧消化装置水力停留时间控制为6.7小时。取10g生物碳(片状，粒径20-25mm)投加到该厌氧消化装置内生物碳填充层，密封厌氧消化装置，并运行厌氧消化装置10天。逐步减少废水中乙醇的添加量，按照乙醇与废水的COD比例为4:1至3:1、2:1，直到废水中不含乙醇。每个乙醇添加比例条件下，依次运行厌氧消化装置10天。厌氧丙酸去除率提高23％，甲烷产量提高40％。An upflow anaerobic digestion unit with an effective volume of 1L is inoculated with 350mL of anaerobic sludge, and the sludge concentration is 17g/L. The concentration of propionic acid in wastewater is 5031mgCOD/L. Analytical pure ethanol with a concentration ≥ 99.7% was added to the wastewater according to the COD ratio of 4:1, and the anaerobic digestion device was operated for 10 days. The pH in the anaerobic digestion unit is controlled at 7.2, and the temperature is controlled at 37°C. The hydraulic retention time of the anaerobic digestion unit is controlled at 6.7 hours. Take 10g of biochar (flaky, particle size 20-25mm) and add it to the biochar filling layer in the anaerobic digestion device, seal the anaerobic digestion device, and run the anaerobic digestion device for 10 days. Gradually reduce the amount of ethanol added in the wastewater, according to the COD ratio of ethanol to wastewater from 4:1 to 3:1, 2:1, until the wastewater does not contain ethanol. Under the conditions of each ethanol addition ratio, the anaerobic digestion unit was operated for 10 days in sequence. Anaerobic propionic acid removal increased by 23% and methane production increased by 40%.
实施例4：Example 4:
有效容积为1L的上流式厌氧消化装置，接种厌氧污泥350mL，污泥浓度为17g/L。废水中丁酸浓度为5031mgCOD/L。采用浓度≥99.7％的分析纯乙醇，按照COD的比例为3:2添加至该废水，运行厌氧消化装置10天。厌氧消化装置内pH控制为7.2，温度控制为37℃。厌氧消化装置水力停留时间控制为6.7小时。取10g粒径为15-20mm的片状生物碳投加到厌氧消化装置内生物碳填充层，密封厌氧消化装置，并运行厌氧消化装置10天。逐步降低废水中乙醇的添加量，按照乙醇与废水的COD比例从3:2至2:3、1:4，直到废水中不含乙醇。每个乙醇添加比例条件下，依次运行厌氧消化装置10天。厌氧丁酸去除率提高20％，甲烷产量提高1倍。An upflow anaerobic digestion unit with an effective volume of 1L is inoculated with 350mL of anaerobic sludge, and the sludge concentration is 17g/L. Butyric acid concentration in wastewater is 5031mgCOD/L. Analytical pure ethanol with a concentration ≥ 99.7% was added to the wastewater according to the COD ratio of 3:2, and the anaerobic digestion device was operated for 10 days. The pH in the anaerobic digestion unit is controlled at 7.2, and the temperature is controlled at 37°C. The hydraulic retention time of the anaerobic digestion unit is controlled at 6.7 hours. Take 10g of flake biochar with a particle size of 15-20mm and add it to the biochar filling layer in the anaerobic digestion device, seal the anaerobic digestion device, and run the anaerobic digestion device for 10 days. Gradually reduce the amount of ethanol added in the wastewater, according to the COD ratio of ethanol to wastewater from 3:2 to 2:3, 1:4, until the wastewater does not contain ethanol. Under the conditions of each ethanol addition ratio, the anaerobic digestion unit was operated for 10 days in sequence. Anaerobic butyric acid removal rate increased by 20%, and methane production doubled.
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