CN110697889A - A method for promoting anaerobic mineralization of phenol-containing wastewater - Google Patents
A method for promoting anaerobic mineralization of phenol-containing wastewater Download PDFInfo
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002351 wastewater Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000033558 biomineral tissue development Effects 0.000 title claims abstract description 10
- 230000001737 promoting effect Effects 0.000 title claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 121
- 229910052742 iron Inorganic materials 0.000 claims abstract description 65
- -1 iron ions Chemical class 0.000 claims description 10
- 239000010802 sludge Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims 2
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 36
- 239000002131 composite material Substances 0.000 abstract description 32
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000000855 fermentation Methods 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000001186 cumulative effect Effects 0.000 description 5
- 150000004698 iron complex Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 238000011197 physicochemical method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000193403 Clostridium Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
本发明公开了一种促进含酚废水厌氧矿化的方法，是向厌氧生物处理系统中投加铁基复合剂，所述铁基复合剂主要由四氧化三铁和单价铁组成。本发明铁基复合剂一方面通过强化含酚废水厌氧生物处理过程中的苯酚及其中间产物的水解，解除其对微生物的毒害作用，另一方面可提高含酚废水厌氧发酵系统的产甲烷的效率和甲烷产量，使含酚废水最终完全矿化。
The invention discloses a method for promoting anaerobic mineralization of phenol-containing wastewater, which is to add an iron-based composite agent to an anaerobic biological treatment system, and the iron-based composite agent is mainly composed of ferric tetroxide and monovalent iron. On the one hand, the iron-based composite agent of the invention relieves the toxic effect on microorganisms by strengthening the hydrolysis of phenol and its intermediate products in the anaerobic biological treatment of phenol-containing wastewater, and on the other hand, it can improve the production rate of the phenol-containing wastewater anaerobic fermentation system. Methane efficiency and methane production, resulting in the final complete mineralization of phenolic wastewater.
Description
技术领域technical field
本发明涉及一种促进含酚废水厌氧矿化的方法，属于工业废水生物处理领域。The invention relates to a method for promoting anaerobic mineralization of phenol-containing wastewater, belonging to the field of biological treatment of industrial wastewater.
背景技术Background technique
苯酚是一种重要的有机化工原料，广泛应用于塑料、合成橡胶、医药、农药、香料、染料、涂料、炼油等工业。含酚废水正是生产各类产品过程中产生的工业废水，由于苯酚应用广泛，每年都有上千吨的含酚废水产生。含酚废水属于二类污染物，需在生产企业排出口检测到标后，方可排放。Phenol is an important organic chemical raw material, widely used in plastics, synthetic rubber, medicine, pesticides, spices, dyes, coatings, oil refining and other industries. Phenol-containing wastewater is the industrial wastewater produced in the production of various products. Due to the wide application of phenol, thousands of tons of phenol-containing wastewater are produced every year. Phenol-containing wastewater belongs to the second category of pollutants, and can only be discharged after the standard is detected at the discharge outlet of the production enterprise.
目前，含酚废水常规的处理方法主要是物化法和生物法。物化法包括如萃取法、蒸汽吹脱法等，该法处理含酚废水的优点是可回收苯酚，但其处理成本太高，一般只适用于高浓度含酚废水处理。相对于物化法，生物处理含酚废水的成本会降低很多，特别是厌氧生物处理法，其占地少，能耗低，无产生剩余污泥，并且能回收生物能(甲烷)，是处理含酚废水的理想工艺。然而，厌氧生物处理含酚废水也存在短板，即苯酚及其中间产物对厌氧产甲烷菌的活性有抑制毒害作用，从而限制了苯酚厌氧生物处理的应用。At present, the conventional treatment methods of phenol-containing wastewater are mainly physicochemical methods and biological methods. The physicochemical method includes extraction method, steam stripping method, etc. The advantage of this method in treating phenol-containing wastewater is that phenol can be recovered, but its treatment cost is too high, and it is generally only suitable for high-concentration phenol-containing wastewater treatment. Compared with the physicochemical method, the cost of biological treatment of phenol-containing wastewater will be much lower, especially the anaerobic biological treatment method, which occupies less land, has low energy consumption, does not produce excess sludge, and can recover biological energy (methane), which is a good treatment method. Ideal process for phenolic wastewater. However, anaerobic biological treatment of phenol-containing wastewater also has shortcomings, that is, phenol and its intermediates have inhibitory and toxic effects on the activity of anaerobic methanogens, thus limiting the application of phenol anaerobic biological treatment.
发明内容SUMMARY OF THE INVENTION
本发明旨在提供一种促进含酚废水厌氧矿化的方法，能有效提高含酚废水中苯酚、苯甲酸等有毒有害物质的降解速率，同时能促进苯酚矿化产甲烷，以达到回收生物能的目的。The invention aims to provide a method for promoting the anaerobic mineralization of phenol-containing wastewater, which can effectively improve the degradation rate of toxic and harmful substances such as phenol and benzoic acid in the phenol-containing wastewater, and simultaneously promote the mineralization of phenol to produce methane, so as to achieve recovery of biological able purpose.
本发明促进含酚废水厌氧矿化的方法，是向厌氧生物处理系统中投加铁基复合剂。The method for promoting the anaerobic mineralization of phenol-containing wastewater in the present invention is to add iron-based composite agent into the anaerobic biological treatment system.
所述铁基复合剂包括单价铁和四氧化三铁，其中单价铁占铁基复合剂的质量百分比为20％-80％，四氧化三铁占铁基复合剂的质量百分比为20％-80％。The iron-based composite agent includes monovalent iron and iron tetroxide, wherein the mass percentage of monovalent iron in the iron-based composite agent is 20%-80%, and the mass percentage of triiron tetroxide in the iron-based composite agent is 20%-80%. %.
所述铁基复合剂的投加量与待处理的含酚废水的化学需氧量(COD)浓度以及厌氧生物处理系统中的污泥浓度相关，铁基复合剂的质量投加量为0.1-10倍COD或0.1-5倍完全混合液挥发性悬浮物浓度(MLVSS)。The dosage of the iron-based composite agent is related to the chemical oxygen demand (COD) concentration of the phenol-containing wastewater to be treated and the sludge concentration in the anaerobic biological treatment system, and the mass dosage of the iron-based composite agent is 0.1 -10 times COD or 0.1-5 times complete mixed liquid volatile suspended solids concentration (MLVSS).
所述铁基复合剂的投加方式可根据出水铁离子浓度确定，在厌氧生物处理系统的出水处设置在线铁离子监测仪，当铁离子浓度低于1％-20％的MLVSS浓度(质量比)，即可打开自动加药系统，向污泥循环系统投加铁基复合剂。The dosing method of the iron-based composite agent can be determined according to the iron ion concentration in the effluent. An online iron ion monitor is set at the effluent of the anaerobic biological treatment system. When the iron ion concentration is lower than the MLVSS concentration of 1%-20% (mass) ratio), the automatic dosing system can be turned on, and the iron-based compound agent can be added to the sludge circulation system.
向厌氧生物处理系统中添加导电材料，可提高厌氧生物系统的稳定性和甲烷产量。导电材料中如单价铁、四氧化三铁，在厌氧系统中充当电子穿梭体，促进厌氧系统中发酵细菌和产甲烷细菌之间的种间电子传递作用。本发明铁剂复合剂中的四氧化三铁能强化苯酚及其中间产物的水解，同时铁基复合剂中的单价铁对厌氧产甲烷有显著的促进作用，二者强强联合，既提高了苯酚的水解效率，又提高厌氧系统的生物能回收。通过实验验证本发明的铁基复合剂的作用机制为铁基复合剂中的四氧化三铁可提高乙酸氧化细菌Clostridium的丰度，从而加快了苯酚厌氧消化系统中中间产物乙酸向氢气和二氧化碳方向转移，而铁基复合剂中的单价铁大大促进了嗜氢产甲烷菌的生长，从而使得含酚废水的厌氧发酵系统的末端产甲烷过程的效率大大提高。因此该复合剂不仅有效提高含酚废水中酚类化合物及其中间产物的降解速率，而且能快速促进含酚废水矿化产甲烷的速率和甲烷产量。Adding conductive materials to anaerobic biological treatment systems can improve the stability and methane production of anaerobic biological systems. Conductive materials such as monovalent iron and ferric tetroxide act as electron shuttles in anaerobic systems, promoting the interspecies electron transfer between fermentation bacteria and methanogens in anaerobic systems. The ferric oxide in the iron-based composite agent of the invention can strengthen the hydrolysis of phenol and its intermediate products, and at the same time, the monovalent iron in the iron-based composite agent has a significant promoting effect on anaerobic methane production. The hydrolysis efficiency of phenol is improved, and the bioenergy recovery of anaerobic system is improved. It is verified through experiments that the action mechanism of the iron-based composite agent of the present invention is that the ferric oxide in the iron-based composite agent can increase the abundance of the acetic acid-oxidizing bacteria Clostridium, thereby accelerating the conversion of the intermediate product acetic acid to hydrogen and carbon dioxide in the phenol anaerobic digestion system While the monovalent iron in the iron-based composite agent greatly promotes the growth of hydrophilic methanogens, the efficiency of the terminal methanogenesis process of the anaerobic fermentation system of phenol-containing wastewater is greatly improved. Therefore, the composite agent not only effectively improves the degradation rate of phenolic compounds and their intermediates in the phenol-containing wastewater, but also can rapidly promote the mineralization rate and methane yield of the phenol-containing wastewater.
本发明投加的铁基复合剂，原材料广泛易得，价格低廉，对厌氧系统的处理成本增加甚微。The iron-based composite agent added in the present invention has wide and readily available raw materials, low price, and little increase in the treatment cost of the anaerobic system.
本发明方法能提高苯酚降解速率14.1％-42.8％，提高甲烷产量13.7％-32.9％。The method of the invention can increase the degradation rate of phenol by 14.1%-42.8%, and increase the methane output by 13.7%-32.9%.
本发明投加的铁基复合剂可采用智能在线投加，可实现全自动控制，方便管理。The iron-based composite agent dosed in the present invention can be dosed intelligently online, which can realize automatic control and facilitate management.
附图说明Description of drawings
图1是不同浓度的苯酚厌氧降解速率对比。从图1中可以看出，相对于未投加铁剂复合剂的厌氧生物处理系统，向厌氧生物系统投机不同投加比的铁基复合剂，其苯酚降解速率提高了14.1％-42.8％。Figure 1 is a comparison of anaerobic degradation rates of phenol at different concentrations. As can be seen from Figure 1, compared with the anaerobic biological treatment system without the addition of iron-based composite agent, the phenol degradation rate increased by 14.1%-42.8% when different dosage ratios of iron-based composite agents were added to the anaerobic biological system. %.
图2是不同浓度苯酚的厌氧甲烷累积总产量对比。从图2中可以看出，相对于未投加铁剂复合剂的厌氧生物处理系统，添加了铁剂复合剂的厌氧生物系统的甲烷累积总产量提高了13.7％-32.9％。Figure 2 is a comparison of the cumulative total production of anaerobic methane with different concentrations of phenol. It can be seen from Figure 2 that, compared with the anaerobic biological treatment system without the addition of the iron complex agent, the cumulative total production of methane in the anaerobic biological system with the iron complex agent increased by 13.7%-32.9%.
图3是不同浓度苯酚的厌氧产甲烷速率对比。从图3中可以看出，相对于未投加铁剂复合剂的厌氧生物处理系统，添加了铁剂复合剂的厌氧生物系统的产甲烷速率提高了1.1-1.4倍。Figure 3 is a comparison of the anaerobic methanogenesis rates of different concentrations of phenol. It can be seen from Figure 3 that, compared with the anaerobic biological treatment system without the addition of the iron complex agent, the methane production rate of the anaerobic biological system with the iron complex agent was increased by 1.1-1.4 times.
具体实施方式Detailed ways
本发明促进含酚废水厌氧矿化的方法，是向厌氧生物处理系统中投加铁基复合剂。The method for promoting the anaerobic mineralization of phenol-containing wastewater in the present invention is to add iron-based composite agent into the anaerobic biological treatment system.
所述铁基复合剂包括单价铁和四氧化三铁，其中单价铁占铁基复合剂的质量百分比为20％-80％，四氧化三铁占铁基复合剂的质量百分比为20％-80％。The iron-based composite agent includes monovalent iron and iron tetroxide, wherein the mass percentage of monovalent iron in the iron-based composite agent is 20%-80%, and the mass percentage of triiron tetroxide in the iron-based composite agent is 20%-80%. %.
所述铁基复合剂的投加量与待处理的含酚废水的COD浓度以及厌氧生物处理系统中的种泥浓度相关，铁基复合剂的投加量为10％-10COD(质量比)或10％-5MLVSS(质量比)。The dosage of the iron-based composite agent is related to the COD concentration of the phenol-containing wastewater to be treated and the concentration of seed sludge in the anaerobic biological treatment system, and the dosage of the iron-based composite agent is 10%-10COD (mass ratio) Or 10%-5MLVSS (mass ratio).
所述铁基复合剂的投加方式可根据出水铁离子浓度确定，在厌氧生物处理系统的污泥床内设置在线铁离子监测仪，当铁离子浓度低于10％的MLVSS浓度(质量比)，即可打开自动加药系统，向污泥循环系统投加铁基复合剂。The dosing method of the iron-based composite agent can be determined according to the iron ion concentration in the effluent. An online iron ion monitor is set in the sludge bed of the anaerobic biological treatment system. When the iron ion concentration is lower than 10% of the MLVSS concentration (mass ratio) ), the automatic dosing system can be turned on, and the iron-based compound agent can be added to the sludge circulation system.
以苯酚为例，向二者的厌氧生物体系中投加铁基复合剂，铁基复合剂的剂量为5g/L，其中四氧化三铁：单价铁＝50％:50％(质量比)，处理的含酚废水中，其苯酚的初始浓度为200mg/L、接种的初始污泥浓度为3gMLVSS/L，在相同的环境条件下，对比投加铁基复合剂对苯酚的降解速率、产甲烷速率和甲烷总量。通过图1所示，在厌氧生物处理系统中，苯酚浓度从200mg/L提高至到800mg/L(即COD浓度从500mg/L提高至1900mg/L)，铁基复合剂的投加比分别为从10倍COD、7倍COD、4.2倍COD和2.6倍COD，相对于空白对照组铁基复合剂，添加了各种剂量铁基复合剂的厌氧生物系统的苯酚降解速率均得到了提高，其中铁基复合剂的投加比为4.2倍COD的苯酚降解速率提高了42.8％。图2和图3所示，相对于空白对照组，添加了各种剂量铁基复合剂的厌氧生物系统的甲烷累积总产量和产甲烷速率均得到了提高，其中甲烷累积总产量均得到提高了，其中铁基复合剂的投加比为2.6倍COD的甲烷累积产量和产甲烷速率提高的最多，分别提高了32.9％和1.4倍。Taking phenol as an example, add iron-based composite agent to the anaerobic biological system of the two, and the dosage of iron-based composite agent is 5g/L, in which ferric oxide: monovalent iron = 50%: 50% (mass ratio) , in the treated phenol-containing wastewater, the initial concentration of phenol was 200 mg/L, and the initial sludge concentration of inoculation was 3 gMLVSS/L. Methane rate and total methane. As shown in Figure 1, in the anaerobic biological treatment system, the concentration of phenol was increased from 200mg/L to 800mg/L (ie, the concentration of COD was increased from 500mg/L to 1900mg/L). In order to change from 10 times COD, 7 times COD, 4.2 times COD and 2.6 times COD, the phenol degradation rate of the anaerobic biological system added with various doses of iron-based complex agent was improved compared to the iron-based complex in the blank control group. , the phenol degradation rate increased by 42.8% when the dosage ratio of iron-based composite agent was 4.2 times of COD. As shown in Figures 2 and 3, compared with the blank control group, the total methane cumulative production and methane production rate of the anaerobic biological system added with various doses of iron-based composite agents were improved, and the cumulative total production of methane was improved. Among them, the addition ratio of iron-based composite agent was 2.6 times the COD, the cumulative methane production and methane production rate increased the most, which were increased by 32.9% and 1.4 times, respectively.
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