CN110550735B - Preparation method of coated slow-release carbon source and product thereof - Google Patents
Preparation method of coated slow-release carbon source and product thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920002472 Starch Polymers 0.000 claims abstract description 23
- 239000008107 starch Substances 0.000 claims abstract description 23
- 235000019698 starch Nutrition 0.000 claims abstract description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 14
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 7
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 7
- 230000008014 freezing Effects 0.000 claims abstract description 4
- 238000007710 freezing Methods 0.000 claims abstract description 4
- 238000010257 thawing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002351 wastewater Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 244000005700 microbiome Species 0.000 abstract description 4
- 238000005728 strengthening Methods 0.000 abstract description 4
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000010406 interfacial reaction Methods 0.000 abstract 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 17
- 239000010865 sewage Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- LECSHJWIACEDPZ-UHFFFAOYSA-N ethane-1,2-diamine naphthalene hydrochloride Chemical compound C(CN)N.C1=CC=CC2=CC=CC=C12.Cl LECSHJWIACEDPZ-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
本发明提供了一种包膜缓释碳源的制备方法及其产品。所述包膜缓释碳源由聚乙烯醇和淀粉获得缓释碳源芯包裹间苯二胺和均苯三甲酰氯通过界面反应获得的膜组成。本发明的采用冷冻解冻循环法制备的碳源芯,该过程操作简单、易控制、制备的碳源结构更加稳定。采用界面聚合制备包膜法,在其外部包裹一层有机多孔膜,形成包膜缓释碳源,能够长期缓慢稳定的释放碳源,且释放的碳源能够被微生物利用,有效的强化了脱氮过程。采用淀粉为碳源,PVA为骨架,其来源广泛,界面聚合层本身无毒,属于环境友好型,生物相容性好。本发明的包膜缓释碳源属于可回收材料,避免了使用过程中造成二次污染的问题,节能环保,经济和社会价值巨大。
The invention provides a method for preparing a coated slow-release carbon source and a product thereof. The coated slow-release carbon source is composed of polyvinyl alcohol and starch to obtain a slow-release carbon source core wrapped with m-phenylenediamine and trimesoyl chloride to form a film obtained by interfacial reaction. The carbon source core prepared by the freezing and thawing cycle method of the present invention is simple to operate and easy to control, and the prepared carbon source structure is more stable. The coating method is prepared by interfacial polymerization, and a layer of organic porous membrane is wrapped on the outside to form a coating slow-release carbon source, which can release carbon source slowly and stably for a long time, and the released carbon source can be used by microorganisms, effectively strengthening the removal process. nitrogen process. Starch is used as the carbon source and PVA is used as the skeleton, which has a wide range of sources, and the interfacial polymer layer itself is non-toxic, environmentally friendly, and has good biocompatibility. The coated slow-release carbon source of the present invention belongs to recyclable materials, avoids the problem of secondary pollution during use, is energy-saving and environment-friendly, and has great economic and social value.
Description
技术领域technical field
本发明属于污水处理领域,涉及一种强化生物反硝化脱氮的控释碳源复合材料及其制备方法。The invention belongs to the field of sewage treatment, and relates to a controlled-release carbon source composite material for strengthening biological denitrification and denitrification and a preparation method thereof.
背景技术Background technique
我国水质特点之一为碳氮比低,约为3.3-8.5。低碳氮比的城市污水经生物处理后TN的去除率很低,很难达到国家“一级A”排放标准,因此,碳源成为脱氮工艺的限制性因素。而二级处理出水由于TN达不到一级A标准,常常需要进行深度处理,而水中的碳源不足以进行反硝化作用,因此需要外加碳源。另有研究表明,在反硝化过程中,如果碳源不足,就会导致中间产物亚硝酸盐的积累,若碳源过量,又会反过来抑制反硝化的进行,出水的有机物过多,出水不达标。正因如此,针对低碳氮比污水寻求高效经济的缓释碳源具有重要意义。One of the characteristics of my country's water quality is the low carbon-nitrogen ratio, about 3.3-8.5. The removal rate of TN in urban sewage with low carbon-to-nitrogen ratio is very low after biological treatment, and it is difficult to meet the national "Class A" discharge standard. Therefore, the carbon source becomes the limiting factor of the denitrification process. However, because the TN of the secondary treatment effluent does not meet the standard of the first grade A, advanced treatment is often required, and the carbon source in the water is not enough for denitrification, so an additional carbon source is required. Another study shows that in the process of denitrification, if the carbon source is insufficient, the intermediate product nitrite will accumulate. If the carbon source is excessive, it will in turn inhibit the progress of denitrification. There will be too much organic matter in the effluent, and the effluent will not Up to standard. For this reason, it is of great significance to seek efficient and economical slow-release carbon sources for low carbon-to-nitrogen ratio sewage.
诸多学者通过投加甲醇、乙酸、葡萄糖等液态碳源对反硝化过程进行探索,发现投加这些液体碳源易造成碳源投加不足或过量、活性污泥驯化时间过长、微生物沉降性能变差、系统运行复杂。基于这种弊端,国内外很多研究者尝试采用各种新方法来为反硝化过程提供电子供体,以期开发出一种较为完善高效的脱氮工艺。工艺的技术关键在于电子供体的供给量能够自适应地满足反硝化的需求量,对处理水质水量具有一定的抗波动性。该种技术的研究,对于推进污水资源化进程,提高再生水品质具有切实的重要意义。Many scholars have explored the denitrification process by adding liquid carbon sources such as methanol, acetic acid, and glucose, and found that adding these liquid carbon sources can easily lead to insufficient or excessive carbon source addition, excessively long domestication time of activated sludge, and deterioration of microbial settlement performance. Poor, complex system operation. Based on this disadvantage, many researchers at home and abroad try to use various new methods to provide electron donors for the denitrification process, in order to develop a more complete and efficient denitrification process. The technical key of the process is that the supply of electron donors can self-adaptively meet the demand of denitrification, and has a certain degree of anti-fluctuation for the quality and quantity of treated water. The research of this kind of technology is of great significance for promoting the process of recycling sewage and improving the quality of reclaimed water.
近年来,许多研究者通过多种途径寻找可以代替传统碳源的高效、无副产物的新型碳源。新型碳源主要以一些低廉、易得的天然固体有机物为主。固体碳源在充当碳源的同时还可以作为生物载体,不仅可以解决传统碳源投加量的问题,还可以为反硝化菌群提供一个安全、稳定的生存环境。上述几项研究均处于实验室初步探索阶段,未见实际应用报道。因此开发安全、持续、稳定、高效的人工制备固相有机碳源载体并探究其在受硝酸盐污染地下水中的作用机制是地下水生物脱氮技术需进一步解决的核心问题。In recent years, many researchers have searched for new carbon sources with high efficiency and no by-products that can replace traditional carbon sources through various methods. The new carbon sources are mainly some cheap and easy-to-obtain natural solid organic matter. The solid carbon source can also be used as a biological carrier while serving as a carbon source, which can not only solve the problem of traditional carbon source dosage, but also provide a safe and stable living environment for denitrifying bacteria. The above-mentioned studies are all in the preliminary stage of laboratory exploration, and no practical application reports have been seen. Therefore, developing a safe, continuous, stable and efficient artificially prepared solid-phase organic carbon source carrier and exploring its mechanism of action in nitrate-contaminated groundwater are the core issues that need to be further solved in groundwater biological denitrification technology.
发明内容Contents of the invention
针对目前强化生物反硝化脱氮中有机碳源缓释效果差的问题,本发明提供一种强化生物反硝化脱氮的包膜缓释碳源复合材料,碳源控释效果好,强化脱氮中不会造成二次污染。Aiming at the problem of poor slow-release effect of organic carbon source in the current enhanced biological denitrification denitrification, the present invention provides a coated slow-release carbon source composite material for enhanced biological denitrification denitrification, which has good carbon source controlled release effect and enhanced denitrification No secondary pollution will be caused.
本发明的另一目的是提供一种上述包膜缓释碳源的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned coated slow-release carbon source.
为实现上述目的,本发明采用如下技术方案。In order to achieve the above object, the present invention adopts the following technical solutions.
一种强化生物反硝化脱氮的包膜缓释碳源的制备方法,包括以下步骤:A method for preparing a coated slow-release carbon source for strengthening biological denitrification and denitrification, comprising the following steps:
(1)按将聚乙烯醇(PVA)和淀粉加入水混匀,加热溶解后放置室温;(1) Add polyvinyl alcohol (PVA) and starch to water and mix well, heat to dissolve and place at room temperature;
(2)将步骤(1)的配料倒入模具,冷冻成型,室温下解冻,烘干后获得缓释碳源芯;(2) Pour the ingredients in step (1) into the mold, freeze and form, thaw at room temperature, and obtain slow-release carbon source cores after drying;
(3)将步骤(2)制备的缓释碳源芯浸入2wt%间苯二胺(MPD)水溶液,晾干;然后再浸入0.1%w/v均苯三甲酰氯(TMC)的正己烷溶液,烘干。(3) Immerse the slow-release carbon source core prepared in step (2) into a 2wt% m-phenylenediamine (MPD) aqueous solution and dry it; then immerse it in a n-hexane solution of 0.1% w/v trimesoyl chloride (TMC), drying.
步骤(1)中,聚乙烯醇和淀粉的质量比为1:1-1:3。所述聚乙烯醇的醇解度≥99%。In step (1), the mass ratio of polyvinyl alcohol to starch is 1:1-1:3. The alcoholysis degree of the polyvinyl alcohol is more than or equal to 99%.
步骤(1)中,聚乙烯醇和淀粉总质量与水的质量比为1:3-10。In step (1), the mass ratio of the total mass of polyvinyl alcohol and starch to water is 1:3-10.
步骤(1)中,加热温度为95-99℃,加热时间为1-2h。In step (1), the heating temperature is 95-99°C, and the heating time is 1-2h.
步骤(2)中,所述冷冻温度为-20℃。优选的,冷冻成型-室温下解冻过程重复2-3次。In step (2), the freezing temperature is -20°C. Preferably, the freeze forming-thawing process at room temperature is repeated 2-3 times.
步骤(2)中,模具为立方体;优选的,模具边长为1-1.5cm。In step (2), the mold is a cube; preferably, the side length of the mold is 1-1.5cm.
步骤(3)中,浸渍时间为1-4min。In step (3), the soaking time is 1-4min.
一种上述制备方法获得的包膜缓释碳源。由淀粉和聚乙烯醇构成的碳源芯外层包裹有机多孔膜构成。A coated slow-release carbon source obtained by the above-mentioned preparation method. The outer layer of the carbon source core composed of starch and polyvinyl alcohol is wrapped with an organic porous membrane.
一种上述包膜缓释碳源在污水强化生物反硝化脱氮中的应用。An application of the above-mentioned coated slow-release carbon source in enhanced biological denitrification of sewage.
所述包膜缓释碳源的用量为3-5g/L。The dosage of the coated slow-release carbon source is 3-5g/L.
本发明具有以下优点:The present invention has the following advantages:
本发明的制备方法采用冷冻解冻循环法制备的碳源,该过程操作简单、易控制、制备的碳源结构更加稳定。采用界面聚合制备包膜法,在其外部包裹一层有机多孔膜,形成包膜缓释碳源,能够长期缓慢稳定的释放碳源,且释放的碳源能够被微生物利用,有效的强化了脱氮过程。采用淀粉为碳源,PVA为骨架,其来源广泛,界面聚合层本身无毒,属于环境友好型,生物相容性好。本发明的包膜缓释碳源属于可回收材料,避免了使用过程中造成二次污染的问题,节能环保,经济和社会价值巨大。The preparation method of the present invention adopts the carbon source prepared by the freeze-thaw cycle method, the process is simple to operate and easy to control, and the prepared carbon source structure is more stable. The coating method is prepared by interfacial polymerization, and a layer of organic porous membrane is wrapped on the outside to form a coating slow-release carbon source, which can release carbon source slowly and stably for a long time, and the released carbon source can be used by microorganisms, effectively strengthening the removal process. nitrogen process. Starch is used as the carbon source and PVA is used as the skeleton, which has a wide range of sources, and the interfacial polymer layer itself is non-toxic, environmentally friendly, and has good biocompatibility. The coated slow-release carbon source of the present invention belongs to recyclable materials, avoids the problem of secondary pollution during use, is energy-saving and environment-friendly, and has great economic and social value.
附图说明Description of drawings
图1是包膜缓释碳源结构示意图;Fig. 1 is a schematic diagram of the structure of the coated slow-release carbon source;
图2是样品3、12的COD和硝态氮去除率;Fig. 2 is the COD and nitrate nitrogen removal rate of
图3是样品4、13的COD和硝态氮去除率;Fig. 3 is the COD and nitrate nitrogen removal rate of
图4是样品5、14的COD和硝态氮去除率;Fig. 4 is the COD and nitrate nitrogen removal rate of
图5是样品1、2、3的COD和硝态氮去除率;Fig. 5 is the COD and nitrate nitrogen removal rate of
图6是样品3、4、5的COD和硝态氮去除率;Fig. 6 is the COD and nitrate nitrogen removal rate of
图7是样品3、6、9的COD和硝态氮去除率;Fig. 7 is the COD and nitrate nitrogen removal rate of
图8是样品4、7、10的COD和硝态氮去除率;Fig. 8 is the COD and nitrate nitrogen removal rate of
图9是样品5、8、11的COD和硝态氮去除率。Figure 9 shows the COD and nitrate nitrogen removal rates of
具体实施方式Detailed ways
下面结合实施例和附图对本发明做进一步说明,但本发明不受下述实施例的限制。The present invention will be further described below in conjunction with the embodiments and accompanying drawings, but the present invention is not limited by the following embodiments.
实施例1 缓释碳源的制备Example 1 Preparation of slow-release carbon source
按照表1中不同的原料质量和参数控制制备不同的缓释碳源或包膜缓释碳源:Prepare different slow-release carbon sources or coated slow-release carbon sources according to different raw material quality and parameter control in Table 1:
表1 缓释碳源的原料配比和参数控制Table 1 Raw material ratio and parameter control of slow-release carbon source
样品1-11的制备方法如下:Samples 1-11 were prepared as follows:
(1)称取淀粉和PVA加入去离子水,使其完全混匀,之后放入水浴加热,使得水温从室温到95℃逐渐升温,然后在95℃水浴中搅拌1h,制得共混物;(1) Weigh starch and PVA and add deionized water to make it completely mixed, then put it into a water bath to heat, so that the water temperature gradually rises from room temperature to 95°C, and then stir in a 95°C water bath for 1 hour to prepare a blend;
(2)将共混物倒入边长为1.3cm的立方体磨具中,放入-20℃的冰箱内冷冻20h,室温下解冻4h,冷冻解冻循环3次,脱模后使其在60℃下烘干24h,隔氧保存待用;(2) Pour the blend into a cube mold with a side length of 1.3cm, freeze in a -20°C refrigerator for 20 hours, thaw at room temperature for 4 hours, freeze and thaw cycle 3 times, and let it cool at 60°C after demoulding Dry it under the oven for 24 hours, and store it in an oxygen barrier for later use;
(3)将2g间苯二胺溶于98g水中,配置成2wt%的MPD溶液;将0.1g均苯三甲酰氯溶于100mL正己烷中,配置成质量浓度为0.1%w/v的TMC溶液;将步骤(2)的缓释碳源芯放入MPD溶液中,充分浸泡后放入烘箱内,在60℃下烘干5min;再将上述烘干的缓释碳源放入TMC溶液中,充分浸泡后放入烘箱内,在60℃下烘干5min,制得包膜缓释碳源,隔氧保存待用。(3) Dissolve 2g of m-phenylenediamine in 98g of water to prepare a 2wt% MPD solution; dissolve 0.1g of trimesoyl chloride in 100mL of n-hexane to prepare a TMC solution with a mass concentration of 0.1%w/v; Put the slow-release carbon source core in step (2) into the MPD solution, soak it fully, put it in an oven, and dry it at 60°C for 5 minutes; then put the dried slow-release carbon source into the TMC solution, fully After soaking, put it in an oven, and dry it at 60°C for 5 minutes to prepare a coated slow-release carbon source, which is stored in an oxygen barrier until use.
样品12-14通过上述步骤(1)-(2)制备获得。Samples 12-14 were prepared through the above steps (1)-(2).
实施例2 添加不同碳源后对硝态氮的去除效果Example 2 The removal effect of nitrate nitrogen after adding different carbon sources
检测实施例1制备的不同样品对废水的硝态氮去除率:Detect the different samples prepared by Example 1 to the nitrate nitrogen removal rate of waste water:
(1)配制模拟废水:将放置一天的自来水,加入硝酸钾、磷酸二氢钾和盐酸,使NO3--N浓度为50 mg/L,TP为1mg/L,pH为7.5;(1) Prepare simulated wastewater: add potassium nitrate, potassium dihydrogen phosphate and hydrochloric acid to tap water that has been left for one day, so that the concentration of NO 3- -N is 50 mg/L, TP is 1 mg/L, and pH is 7.5;
(2)分别称取5.0g不同样品和100mL接种污泥,加入400mL模拟废水,最终获得500mL的生物反硝化脱氮体系;(2) Weigh 5.0g of different samples and 100mL of inoculated sludge, add 400mL of simulated wastewater, and finally obtain a 500mL biological denitrification system;
(3)将生物反硝化脱氮体系于25±1℃下振荡培养,每天更换新的模拟废水(进水),将处理后废水(出水)经0.45μm滤膜过滤后测NO3 --N、NO2 --N、CODcr;(3) The biological denitrification and denitrification system was shaken and cultivated at 25±1°C, and new simulated wastewater (influent) was replaced every day, and the treated wastewater (effluent) was filtered through a 0.45μm filter membrane to measure NO 3 - -N , NO 2 - -N, COD cr ;
参照《水和废水监测分析方法》(国家环境保护总局《水和废水监测分析方法》编委会. 水和废水监测分析方法[M]. 4版. 北京:中国环境科学出版社, 2002),用紫外分光光度计(Shimadzu UV-3100)在220nm和275nm处测定NO3 --N,用盐酸萘乙二胺分光光度法和重铬酸钾法测定NO2 --N和CODcr。各不同样品第1-15天的出水COD(mg/L)和硝态氮去除率(%)如图2-9所示。Refer to "Water and Wastewater Monitoring and Analysis Methods" (Editorial Committee of "Water and Wastewater Monitoring and Analysis Methods" of the State Environmental Protection Administration. Water and Wastewater Monitoring and Analysis Methods [M]. 4th Edition. Beijing: China Environmental Science Press, 2002), NO 3 - -N was measured at 220nm and 275nm by UV spectrophotometer (Shimadzu UV-3100), NO 2 - -N and CODcr were determined by naphthalene ethylenediamine hydrochloride spectrophotometry and potassium dichromate method. The effluent COD (mg/L) and nitrate nitrogen removal rate (%) of different samples on the 1st to 15th day are shown in Figure 2-9.
图2-4中,相同时间点,包膜碳源所释放的COD比不包膜碳源低了近一倍,出水硝酸盐氮几乎没太大区别,大多数稳定在5mg/L以下。初始阶段,两者的COD释放量均较高,第6天左右,COD的释放量趋于稳定。这是由于高温下淀粉和PVA共混的时候,产生了一些易降解的小分子物质,容易释放进入水中,同时,共混后的碳源表层的淀粉分子更容易被微生物释放的水解酶分解。待表层淀粉分子分解掉,淀粉PVA材料内部形成微晶区作为物理交联点,两者之间通过氢键和交联作用,由此得到的三维网络结构可将淀粉分子包裹缠绕,使得共混的碳源固化性很好,在水中不易解体,从而控制淀粉的释放。可见包膜碳源所释放的碳源能够被微生物利用,同时又避免了碳源的过量释放的问题。In Figure 2-4, at the same time point, the COD released by the coated carbon source is nearly twice as low as that of the uncoated carbon source, and the nitrate nitrogen in the effluent is almost the same, most of which are stable below 5mg/L. At the initial stage, the release of COD in both plants was high, and the release of COD tended to be stable around the 6th day. This is because when starch and PVA are blended at high temperature, some easily degradable small molecular substances are produced, which are easily released into the water. At the same time, the starch molecules on the surface of the carbon source after blending are more likely to be decomposed by the hydrolytic enzymes released by microorganisms. After the starch molecules on the surface are decomposed, microcrystalline regions are formed inside the starch PVA material as physical cross-linking points, and hydrogen bonds and cross-linking are formed between the two. The resulting three-dimensional network structure can wrap and entangle the starch molecules, making blending The carbon source has good solidification and is not easy to disintegrate in water, thereby controlling the release of starch. It can be seen that the carbon source released by the coated carbon source can be utilized by microorganisms, while avoiding the problem of excessive release of carbon source.
由图5可知:淀粉和PVA质量比为30:30包膜2min时,随着含水量的增加,碳源释放COD越多;加水量为200mL时,COD基本维持在30mg/L左右,但去除率较低;加水量为400mL和600mL对应的COD基本都超过50mg/L,去除率基本在95%以上。It can be seen from Figure 5 that when the mass ratio of starch and PVA is 30:30 for 2 minutes, as the water content increases, the carbon source releases more COD; The rate is low; the COD corresponding to the water addition of 400mL and 600mL is basically more than 50mg/L, and the removal rate is basically above 95%.
包膜时间为2min、加水量为200mL,不同淀粉和PVA配比的碳源处理后出水COD和硝态氮去除率如图6所示:55:5的出水COD较高,30:30和45:15的出水COD大多维持在50mg/L以下,三者的硝态氮去除率均较高。The coating time is 2min, and the water addition is 200mL. The COD and nitrate nitrogen removal rates of the effluent after treatment with different starch and PVA ratios are shown in Figure 6: the effluent COD of 55:5 is higher, and the effluent COD of 30:30 and 45 The effluent COD of :15 is mostly maintained below 50mg/L, and the removal rates of nitrate nitrogen among the three are relatively high.
图7-9反映了不同淀粉和PVA比例下不同包膜时间对COD和硝态氮去除率的影响:在淀粉和PVA比为30:30下,包膜2min和4min,出水COD差别较小;在包膜1min下,相较于2min和4min,其出水COD较高,大多在50mg/L左右,包膜1min的去除率最好,基本在80%左右,包膜2min和4min的去除率呈现下降趋势。淀粉和PVA比为45:15,不同包膜时间的硝态氮去除率都在80%以上;包膜2min和4min的,出水COD差别较小;包膜1min的出水COD超过50mg/L。淀粉和PVA比为55:5,包膜时间1-4min获得的碳源的硝态氮去除率都在90%以上,但是由于碳源内部解体所致,包膜材料本身机械性能偏差,碳源内部解体导致薄膜材料断裂,使得三者出水COD均较高。Figure 7-9 reflects the influence of different coating times on the removal rate of COD and nitrate nitrogen under different starch and PVA ratios: when the ratio of starch and PVA is 30:30, the difference in effluent COD is small; Under the coating for 1 minute, compared with 2 minutes and 4 minutes, the COD of the effluent is higher, mostly around 50mg/L, the removal rate of the coating for 1 minute is the best, basically about 80%, and the removal rate of the coating for 2 minutes and 4 minutes shows downward trend. The ratio of starch and PVA is 45:15, and the removal rate of nitrate nitrogen at different coating times is above 80%; the COD of the effluent is small when the coating is 2 minutes and 4 minutes; the COD of the effluent after the coating is 1 minute exceeds 50mg/L. The ratio of starch to PVA is 55:5, and the nitrate nitrogen removal rate of the carbon source obtained by coating time of 1-4min is above 90%. However, due to the internal disintegration of the carbon source, the mechanical properties of the coating material itself deviate, and the carbon source The internal disintegration leads to the rupture of the membrane material, which makes the COD of the three effluents all higher.
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