The method that advanced oxidation processes and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen
阅读说明：本技术 高级氧化法和生物电化学法联用促进剩余污泥产氢的方法 (The method that advanced oxidation processes and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen ) 是由 丁豪 胡凯 孙杏 许航 陈卫 于 2019-08-21 设计创作，主要内容包括：本发明公开了一种高级氧化法和生物电化学法联用促进剩余污泥产氢的方法,包括启动微生物电解池,以污水处理厂剩余污泥为接种物,运行单室微生物电解池,富集阳极产电菌；使用碱溶液调理剩余污泥24h后,利用高级氧化技术处理调理污泥,得到预处理污泥；在常温环境下,以预处理污泥为底物,运行单室微生物电解池,实现产氢等步骤。本发明利用新型高级氧化技术(PM/BS技术),通过高锰酸钾与亚硫酸氢钠在水中反应生成具有强氧化性的Mn(III)离子,调理剩余污泥,将污泥大分子有机物转化为易于生物利用的可溶性小分子有机物,以提高剩余污泥的可生化性,促进微生物电解产氢效率。(The invention discloses a kind of methods that advanced oxidation processes and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, including starting microorganism electrolysis cell, using sewage treatment plant excess sludge as inoculum, run single-chamber microbial electrolytic cell, enrichment anode produces electricity bacterium；After improving excess sludge for 24 hours using aqueous slkali, conditioning sludge is handled using high-level oxidation technology, obtains pretreating sludge；Under normal temperature environment, using pretreating sludge as substrate, operation single-chamber microbial electrolytic cell, realization production hydrogen and etc..The present invention utilizes advanced oxidation technology (PM/BS technology), Mn (III) ion for generating and there is strong oxidizing property is reacted in water with sodium hydrogensulfite by potassium permanganate, improve excess sludge, convert sludge larger molecular organics to the soluble small organic molecule for being easy to biological utilisation, to improve the biodegradability of excess sludge, promote microorganism electrolytic hydrogen production efficiency.)
1. the method that advanced oxidation processes and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, which is characterized in that including following Step:
(1), start microorganism electrolysis cell, using sewage treatment plant excess sludge as inoculum, run single-chamber microbial electrolytic cell, it is rich Collect anode and produces electricity bacterium；
(2), after improving excess sludge for 24 hours using aqueous slkali, conditioning sludge is handled using high-level oxidation technology, it is dirty to obtain pretreatment Mud；
(3), under normal temperature environment, using pretreating sludge as substrate, single-chamber microbial electrolytic cell is run, realizes and produces hydrogen.
2. the method that advanced oxidation processes according to claim 1 and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, It is characterized in that, producing electricity bacterium using single-chamber microbial electrolytic cell enrichment anode in the step (1), comprising the following steps:
Step 1: sewage treatment plant excess sludge and solution A are mixed in a certain ratio obtained mixed liquid B；
Step 2: single-chamber microbial electrolytic cell is added in above-mentioned mixed liquid B；
Step 3: starting single-chamber microbial electrolytic cell, when single-chamber microbial electrolytic cell voltage value no longer increases, more under room temperature Change solution B；
Step 4: repeat the above steps one to three, when single-chamber microbial electrolytic cell maximum voltage value reappears 2 periods, reaction Device completes the enrichment of anode electricity production bacterium.
3. the method that advanced oxidation processes according to claim 1 and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, It is characterized by: aqueous slkali is NaOH solution in the step (2), NaOH solution is added to excess sludge in concentration 4mol/L PH value is 11, and alkaline hydrolysis is for 24 hours with this condition.
4. the method that advanced oxidation processes according to claim 1 and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, It is characterized by: potassium permanganate/sodium hydrogensulfite technology of high-level oxidation technology is employed as in the step (2), operation step Suddenly are as follows: first add solution of sodium bisulfite into alkaline hydrolysis sludge, then add liquor potassic permanganate.
5. the method that advanced oxidation processes according to claim 4 and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, It is characterized by: the liquor potassic permanganate concentration used in potassium permanganate/sodium hydrogensulfite technology is 0.5mol/L, bisulfite Sodium solution concentration is 2.5mol/L, and potassium permanganate and sodium bisulfite liquor volume ratio are 1: 1, and dosage is every liter of excess sludge 20mL potassium permanganate and solution of sodium bisulfite are added, 10min is reacted under room temperature, obtains pretreating sludge.
6. the side that a kind of advanced oxidation processes according to claim 1 and the combination of bioelectrochemistry method promote excess sludge production hydrogen Method, it is characterised in that: realize that excess sludge produces hydrogen in the step (3), comprising the following steps: taking appropriate pretreating sludge is bottom 2.41gKH is added in object2PO4、7.35g KH2PO4·3H2O、0.31g NH4Cl, 0.13g KCl, 12.5mL mixed liquor C and 5mL Mixed liquor D, is settled to 1L, obtains mixed liquor E；Mixed liquor E investment step (1) is completed to the single-chamber microbial of anode electricity production bacterium enrichment In electrolytic cell；In two interpolars, the 10 Ω resistance of series connection of single-chamber microbial electrolytic cell, applied voltage 0.5V runs 7-12d, completes to produce Hydrogen.
7. the method that advanced oxidation processes according to claim 1 and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, It is characterized by: used single-chamber microbial electrolytic cell anode material is graphite fibre brush electrode, cathode material is carbon cloth electricity Pole, graphite fibre brush electrode and carbon cloth electrode are successively cleaned by ultrasonic 10min in acetone, ethyl alcohol and pure water before the use, it The high-temperature heat treatment 30min at 450 DEG C afterwards.
8. the method that advanced oxidation processes according to claim 5 and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, It is characterized by: the volume ratio of sewage treatment plant excess sludge and solution A is 1: 2 in the step 1.
9. the method that advanced oxidation processes according to claim 2 and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, It is characterized by: the ingredient of the solution A be every liter of deionized water in include: 1.5g NaAc, 2.4145g KH2PO4、 7.3539g KH2PO4·3H2O、0.31g NH4Cl and 0.13g KCl.
10. the method that advanced oxidation processes according to claim 6 and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, It is characterized by: the ingredient of mixed liquor C be every liter of solution in include: 1.5g triacetic acid, 3.0g MgSO4·7H2O、0.5g MnSO4·2H2O、1.0g NaCl、0.1g FeSO4·7H2O、0.1g CoCl2、0.1g CoCl2·2H2O、0.1g ZnSO4、 0.01g CuSO4·5H2O、0.01g AlK(SO4)2、0.01g H3BO3、0.025g Na2MoO4With 0.024g NiCl6H2O；
The ingredient of mixed liquor D is in every liter of solution: 2mg biotin, 2mg folic acid, 10mg vitamin B6, 5mg vitamin B1、 5mg vitamin B2, 5mg niacin, 5mg calcium pantothenate, 0.1mg vitamin B12, 5mg 4-aminobenzoic acid and 5mg lipoic acid.
Technical field
The present invention relates to Disposal Technology of Residual Sludge fields, and in particular to a kind of advanced oxidation processes and bioelectrochemistry method connection With the method for promoting excess sludge to produce hydrogen.
Background technique
As China's water environment treatment and water prevention and cure of pollution put more effort, urban wastewater treatment amount increasingly increases, as dirt The surplus sludge volume of water process by-product is more and more.Excess sludge moisture content is high (99% or so), includes silt particle, fiber, glue Body, organic matter, microorganism and metallic element etc..Untreated excess sludge causes secondary pollution to environment, becomes environment guarantor The hot issue of shield.
Anaerobic digestion is existing Disposal Technology of Residual Sludge, and technical principle is that anaerobic bacteria has under anaerobic environment using sludge Machine matter generates the gases such as methane and hydrogen.The process efficiency of anaerobic digestion is by factors such as mud organic substance composition and contents It influences, it is inefficient.Microorganism electrolysis cell (microbial electrolysis cell, MEC) is a novel bioelectricity Chemical technology, using electricity-producing microorganism degradation of organic substances, applying small voltage can be realized production hydrogen.
Mud organic substance quilt wadding surrounds, and the hydrolysis rate of excess sludge is very slow under normal temperature condition, it is difficult to by microorganism electricity The electricity production bacterium of Xie Chizhong utilizes.To improve the performance and raising gas producing efficiency that microorganism electrolysis cell handles sludge, need to improve dirt Mud shale discharges organic matter intracellular, improves biodegradable concentration of substrate by cracking, aoxidizing excess sludge.
High-level oxidation technology generates the living radical with strong oxidizing property, oxidation of organic compounds by chemical reaction.Gao Meng Sour potassium reacts in water with sodium hydrogensulfite generates Mn (III) ion, has preferable oxidation to the organic matter for being difficult to aoxidize Effect.
Summary of the invention
Present invention aim to address deficiency existing for existing hydrogen production by biological technology, a kind of advanced oxidation processes and life are provided The method that the combination of object electrochemical process promotes excess sludge to produce hydrogen, by improving excess sludge biodegradability, enhancing electricity production bacterium to having The utilization rate of machine object, and then improve the yield of hydrogen.
In order to solve the above-mentioned technical problem, the invention is realized by the following technical scheme:
The method that advanced oxidation processes and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, comprising the following steps:
(1), start microorganism electrolysis cell, using sewage treatment plant excess sludge as inoculum, operation single-chamber microbial electrolysis Pond, enrichment anode produce electricity bacterium；
(2), after improving excess sludge for 24 hours using aqueous slkali, conditioning sludge is handled using high-level oxidation technology, obtains pre- place Manage sludge；
(3), under normal temperature environment, using pretreating sludge as substrate, single-chamber microbial electrolytic cell is run, realizes and produces hydrogen.
Further, bacterium, including following step are produced electricity using single-chamber microbial electrolytic cell enrichment anode in the step (1) It is rapid:
Step 1: sewage treatment plant excess sludge and solution A are mixed in a certain ratio obtained mixed liquid B；
Step 2: single-chamber microbial electrolytic cell is added in above-mentioned mixed liquid B；
Step 3: starting single-chamber microbial electrolytic cell, when single-chamber microbial electrolytic cell voltage value no longer increases under room temperature When, replace solution B；
Step 4: repeat the above steps one to three, when single-chamber microbial electrolytic cell maximum voltage value reappears 2 periods, Reactor completes the enrichment of anode electricity production bacterium.
Further, aqueous slkali is Na0H solution in the step (2), concentration 4mol/L, and Na0H solution is added to surplus Remaining sludge pH is 11, and alkaline hydrolysis is for 24 hours with this condition.
Preferably, it is employed as potassium permanganate/sodium hydrogensulfite technology of high-level oxidation technology in the step (2), grasps Make step are as follows: first add solution of sodium bisulfite into alkaline hydrolysis sludge, then add liquor potassic permanganate.
Specifically, the liquor potassic permanganate concentration used in potassium permanganate/sodium hydrogensulfite technology is 0.5mol/L, sulfurous Sour hydrogen sodium solution concentration is 2.5mol/L, and potassium permanganate and sodium bisulfite liquor volume ratio are 1: 1, and dosage is every liter of residue Sludge adds 20mL potassium permanganate and solution of sodium bisulfite, reacts 10min under room temperature, obtains pretreating sludge.
Further, realize that excess sludge produces hydrogen in the step (3), comprising the following steps: take appropriate pretreating sludge For substrate, 2.41gKH is added2PO4、7.35g KH2PO4·3H2O、0.31g NH4Cl, 0.13g KCl, 12.5mL mixed liquor C and 5mL mixed liquor D, is settled to 1L, obtains mixed liquor E；The single chamber that mixed liquor E investment step (1) is completed anode electricity production bacterium enrichment is micro- In biological electrolytic cell；In two interpolars, the 10 Ω resistance of series connection of single-chamber microbial electrolytic cell, applied voltage 0.5V runs 7-12d, complete At production hydrogen.
Preferably, used single-chamber microbial electrolytic cell anode material is graphite fibre brush electrode, and cathode material is carbon Cloth electrode, graphite fibre brush electrode and carbon cloth electrode are successively cleaned by ultrasonic in acetone, ethyl alcohol and pure water before the use 10min, later the high-temperature heat treatment 30min at 450 DEG C.
Preferably, the volume ratio of sewage treatment plant excess sludge and solution A is 1: 2 in the step 1.
Preferably, the ingredient of the solution A be every liter of deionized water in include: 1.5gNaAc, 2.4145g KH2PO4、 7.3539g KH2PO4·3H2O、0.31gNH4Cl and 0.13g KCl.
Preferably, the ingredient of mixed liquor C be every liter of solution in include: 1.5g triacetic acid, 3.0g MgSO4·7H2O、0.5g MnSO4·2H2O、1.0g NaCl、0.1g FeSO4·7H2O、0.1g CoCl2、0.1g CoCl2·2H2O、0.1g ZnSO4、 0.01g CuSO4·5H2O、0.01g AlK(SO4)2、0.01g H3BO3、0.025g Na2MoO4With 0.024g NiCl6H2O；
The ingredient of mixed liquor D is in every liter of solution: 2mg biotin, 2mg folic acid, 10mg vitamin B6, 5mg dimension life Plain B1, 5mg vitamin B2, 5mg niacin, 5mg calcium pantothenate, 0.1mg vitamin B12, 5mg 4-aminobenzoic acid and 5mg lipoic acid.
Compared with prior art, the beneficial effects of the present invention are:
Compared with conventional oxidation technology, the present invention utilizes advanced oxidation technology (PM/BS technology), passes through potassium permanganate It reacts Mn (III) ion for generating and there is strong oxidizing property in water with sodium hydrogensulfite, excess sludge is improved, by sludge macromolecular Organic matter is converted into the soluble small organic molecule for being easy to biological utilisation, to improve the biodegradability of excess sludge, promotes micro- Biology electrolysis hydrogen generation efficiency.
The present invention cracks excess sludge by lye, and release sludge is intracellular, extracellular biological organic matter, and improving sludge liquid phase has Machine object concentration promotes subsequent electricity-producing microorganism to the degradation of organic matter and produces hydrogen.
The present invention is directly initiated using single-chamber microbial electrolytic cell, i.e., the starting of microorganism electrolysis cell is with operation same It is carried out in a microorganism electrolysis cell reactor, it is easy to operate.
PM/BS oxidation technology is used in combination with alkaline hydrolysis, promotes excess sludge larger molecular organics and is converted into small molecule and waves It turns sour；Compared with former mud (sewage treatment plant excess sludge), pretreating sludge (i.e. microorganism electrolysis cell into mud) liquid phase acetic acid is dense Degree increases by 39.47%, propionate concentration and increases by 71.29%.The present invention realizes the stabilisation of excess sludge, innoxious and resource Change.Sludge liquid phase Uv254Index removal rate is 74.10%, extracellular biological organic matter UV254Index removal rate is 49.50%, remaining The aromatic compound of Humus larger molecular organics and double bond containing C=C and C=0 double bond is effectively degraded in sludge. Compared with the independent microorganism electrolysis tech of sludge, this technology increases to excess sludge acetic acid removal rate from 20.18% 60.45%, propionic acid removal rate increases to 85.77% from 15.05%；The biodegradability of sludge is improved, microorganism electrolysis cell Hydrogen generation efficiency gets a promotion, hydrogen yield 0.033-0.050m3H2/(m3D), the resource of sewage plant excess sludge is realized Change.
Specific embodiment
The method that advanced oxidation processes and the combination of bioelectrochemistry method promote excess sludge to produce hydrogen, comprising the following steps:
(1), start microorganism electrolysis cell, using sewage treatment plant excess sludge as inoculum, operation single-chamber microbial electrolysis Pond, enrichment anode produce electricity bacterium；
Bacterium is produced electricity using single-chamber microbial electrolytic cell enrichment anode, comprising the following steps:
Step 1: being by volume to be mixed to prepare mixed liquid B at 1: 2 by sewage treatment plant excess sludge and solution A；
The ingredient of the solution A is in every liter of deionized water: 1.5g NaAc, 2.4145g KH2PO4、7.3539g KH2PO4·3H2O、0.31gNH4C1 and 0.13g KCl.
Step 2: single-chamber microbial electrolytic cell is added in above-mentioned mixed liquid B；
Step 3: starting single-chamber microbial electrolytic cell, when single-chamber microbial electrolytic cell voltage value no longer increases under room temperature When, replace solution B；
Step 4: repeat the above steps one to three, when single-chamber microbial electrolytic cell maximum voltage value reappears 2 periods, Reactor completes the enrichment of anode electricity production bacterium.
Single-chamber microbial electrolytic cell anode material is graphite fibre brush electrode, and cathode material is carbon cloth electrode, graphite fibre Brush electrode and carbon cloth electrode are successively cleaned by ultrasonic 10min in acetone, ethyl alcohol and pure water before the use, later at 450 DEG C High-temperature heat treatment 30min.
(2), excess sludge is added using the NaOH solution that concentration is 4mol/L, until excess sludge pH value is 11, at this Alkaline hydrolysis for 24 hours, improves sludge using potassium permanganate/sodium hydrogensulfite technical treatment, obtains pretreating sludge under part；Specifically: high Liquor potassic permanganate concentration in potassium manganate/sodium hydrogensulfite technology is 0.5mol/L, and solution of sodium bisulfite concentration is 2.5mol/L, potassium permanganate and sodium bisulfite liquor volume ratio are 1: 1, and when operation first adds bisulfite into alkaline hydrolysis sludge Sodium solution, then liquor potassic permanganate is added, dosage is that every liter of excess sludge adds 20mL potassium permanganate and sodium hydrogensulfite is molten Liquid reacts 10min under room temperature, obtains pretreating sludge.
(3), under normal temperature environment, using pretreating sludge as substrate, single-chamber microbial electrolytic cell is run, realizes and produces hydrogen.
Realize that excess sludge produces hydrogen, comprising the following steps: taking appropriate pretreating sludge is substrate, and 2.4145g is added KH2PO4、7.3539g KH2PO4·3H2O、0.31gNH4Cl and 0.13g KCl, 12.5mL mixed liquor C and 5mL mixed liquor D, it is fixed Hold to 1L, obtains mixed liquor E；In the single-chamber microbial electrolytic cell that mixed liquor E investment step (1) is completed to anode electricity production bacterium enrichment； In two interpolars, the 10 Ω resistance of series connection of single-chamber microbial electrolytic cell, applied voltage 0.5V runs 7-12d, completes to produce hydrogen.
The ingredient of mixed liquor C is in every liter of solution: 1.5g triacetic acid, 3.0g MgSO4·7H2O、0.5g MnSO4· 2H2O、1.0g NaCl、0.1g FeSO4·7H2O、0.1g CoCl2、0.1g CoCl2·2H2O、0.1g ZnSO4、0.01g CuSO4·5H2O、0.01gAlK(SO4)2、0.01gH3BO3、0.025g Na2MoO4With 0.024g NiCl6H2O；
The ingredient of mixed liquor D is in every liter of solution: 2mg biotin, 2mg folic acid, 10mg vitamin B6, 5mg dimension life Plain B1, 5mg vitamin B2, 5mg niacin, 5mg calcium pantothenate, 0.1mg vitamin B12, 5mg 4-aminobenzoic acid and 5mg lipoic acid.
Compared with former mud, after PM/BS technology and alkali co-conditioning, the liquid phase acetic acid concentration of pretreating sludge increases 39.47%, propionate concentration increases by 71.29%.Compared with directly handling excess sludge using microorganism electrolysis cell, mud extraction acetic acid is gone 85.77% is increased to from 15.05% except rate increases to 60.45%, propionic acid removal rate from 20.18%；Hydrogen yield is 0.033- 0.050m3H2/(m3D), single-chamber microbial electrolytic cell is for excess sludge liquid phase UV254Index removal rate is 74.10%, extracellular Biological organic matter UV254Index removal rate is 49.50%.
Undeclared part involved in the present invention is same as the prior art or is realized using the prior art.