WO2018133378A1 - 一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法 - Google Patents

一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法 Download PDF

Info

Publication number
WO2018133378A1
WO2018133378A1 PCT/CN2017/095851 CN2017095851W WO2018133378A1 WO 2018133378 A1 WO2018133378 A1 WO 2018133378A1 CN 2017095851 W CN2017095851 W CN 2017095851W WO 2018133378 A1 WO2018133378 A1 WO 2018133378A1
Authority
WO
WIPO (PCT)
Prior art keywords
tdn
dialysis
concentration
sewage
dissolved organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/095851
Other languages
English (en)
French (fr)
Inventor
任洪强
胡海冬
耿金菊
丁丽丽
黄辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University
Nanjing Tech University
Original Assignee
Nanjing University
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing University, Nanjing Tech University filed Critical Nanjing University
Publication of WO2018133378A1 publication Critical patent/WO2018133378A1/zh
Priority to US16/274,213 priority Critical patent/US20190178803A1/en
Anticipated expiration legal-status Critical
Priority to US16/902,213 priority patent/US11014835B2/en
Ceased legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/24—Dialysis ; Membrane extraction
    • B01D61/243—Dialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/24—Dialysis ; Membrane extraction
    • B01D61/32—Controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/089—Modules where the membrane is in the form of a bag, membrane cushion or pad
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • B01D69/061—Membrane bags or membrane cushions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/34—Purifying; Cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B01D2325/02834—Pore size more than 0.1 and up to 1 µm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/24—Dialysis ; Membrane extraction
    • B01D61/28—Apparatus therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/775—Indicator and selective membrane

Definitions

  • the invention belongs to the technical field of municipal sewage treatment, and more particularly to a method for detecting dissolved organic nitrogen concentration in municipal sewage based on dialysis pretreatment.
  • Sewage dissolved total nitrogen includes inorganic nitrogen (DIN, including ammonia nitrogen, nitrate nitrogen and nitrite nitrogen) and dissolved organic nitrogen (DON).
  • DIN inorganic nitrogen
  • DON dissolved organic nitrogen
  • Many municipal wastewater treatment plants have a nitrogen removal process, and most of the inorganic nitrogen is successfully removed by nitrification-denitrification.
  • DON is difficult to remove during the nitrification-denitrification process, and the final efwater DON can account for the water TDN 80. %the above.
  • Sewage DON has a certain amount of bioavailable portion that can be a nutrient for the growth of microorganisms and algae in rivers.
  • DON is an important precursor of nitrogen-containing disinfection by-products of high mutagenicity and high carcinogenicity. Therefore, the discharge of municipal sewage treatment plant DON will affect the water quality safety and eutrophication of the receiving water.
  • the present invention provides a method for detecting DON concentration of municipal sewage based on dialysis pretreatment, according to the measured (NH 4 + +NO 3 - ) /TDN ratio and NO 3 - /NH 4 + ratio, choose different measurement schemes, have the advantages of low energy consumption and easy operation.
  • a method for detecting dissolved organic nitrogen concentration in municipal sewage based on dialysis pretreatment the steps of which are:
  • TDN dissolved total nitrogen
  • NH 4 + ammonia nitrogen
  • NO 3 - nitrate nitrogen
  • the pore diameter of the filter is 0.45 ⁇ m.
  • the measurement scheme I when (C NH4 + (I) + C NO3 - (I) ) / C TDN (I) ⁇ 0.7, the measurement scheme I is used, that is, the direct measurement is not performed without pretreatment.
  • the concentration of nitrite nitrogen (NO 2 - ) in wastewater is recorded as C NO2 - (I) .
  • the sewage is placed in the suspension dialysis bag for dialysis pretreatment, the dialysis time is 22-26h; after the dialysis, the TDN, NH 4 + , NO 3 - and NO 2 - in the sewage are determined respectively.
  • Concentrations are denoted as C TDN (II) , C NH4 + (II) , C NO3 - (II) and C NO2 - (II), respectively .
  • step (3) when (C NH4 + (I) + C NO3 - (I) ) / C TDN (I) ⁇ 0.7 and C NO3 - (I) / C NH4 + (I) ⁇ 1, using the measurement scheme III, the sewage is put into the suspension dialysis bag for dialysis pretreatment, the dialysis time is 34-38h; after the dialysis is finished, the TDN, NH 4 + , NO 3 - and NO 2 - in the sewage are determined respectively. Concentrations are denoted as C TDN (III) , C NH4 + (III) , C NO3 - (III) and C NO2 - (III), respectively . at this time,
  • suspension dialysis bag is a cellulose ester film, hydrophilic, cutting molecular weight is 100-500 Da; dialysate hydraulic retention time is 4 h.
  • concentrations of TDN, NH 4 + , NO 3 - and NO 2 - are respectively determined by potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite photometry, ion chromatography and N-(1- Spectrophotometric determination of naphthyl)-ethylenediamine.
  • the invention utilizes the difference concentration inside and outside the dialysis membrane to realize the separation of DON and DIN, and does not need to apply nitrogen to control the transmembrane pressure, and the energy consumption is low;
  • the pretreatment method provided by the invention can effectively reduce the concentration of inorganic nitrogen in the municipal sewage while retaining the content of DON, thereby greatly reducing the deviation caused by the difference method to calculate the DON concentration, and ensuring the accuracy and accuracy of the test;
  • the invention has simple operation, no pre-experiment, low analysis cost, and can be widely applied to the determination of DON concentration of municipal sewage.
  • FIG. 1 is a schematic flow chart of detecting DON concentration in municipal sewage according to the present invention
  • Figure 2 is a comparison diagram of the determination of DON concentration in sewage according to the present invention.
  • TDN concentration of TDN, NH 4 + and NO 3 - in the sewage treated by step 1 were determined by potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite photometry and ion chromatography, respectively, and recorded as C. TDN(I) , C NH4 + (I) and C NO3 - (I) .
  • TDN and NH 4 Determination of TDN and NH 4 in wastewater by potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite photometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry after dialysis
  • concentrations of + , NO 3 - and NO 2 - are denoted as C TDN (II) , C NH4 + (II) , C NO3 - (II) and C NO2 - (II), respectively .
  • the DON concentration of Sample 1 was 0.80 mg/L.
  • the present embodiment repeatedly measured the average of three times, and the results are shown in Fig. 2.
  • TDN concentration of TDN, NH 4 + and NO 3 - in the sewage treated by step 1 were determined by potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite photometry and ion chromatography, respectively, and recorded as C. TDN(I) , C NH4+(I) and C NO3-(I) .
  • TDN and NH 4 Determination of TDN and NH 4 in wastewater by potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite photometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry after dialysis
  • concentrations of + , NO 3 - and NO 2 - are denoted as C TDN (III) , C NH4 + (III) , C NO3 - (III) and C NO2 - (III), respectively .
  • TDN and NH 4 Determination of TDN and NH 4 in wastewater by potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite photometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry after dialysis
  • concentrations of + , NO 3 - and NO 2 - are denoted as C TDN (II) , C NH4 + (II) , C NO3 - (II) and C NO2 - (II), respectively .
  • the DON concentration of Sample 3 was 1.89 mg/L.
  • the present embodiment repeatedly measured the average of three times, and the results are shown in Fig. 2.
  • sample 4 Take 100mL of water from a municipal sewage treatment plant in Wuxi (recorded as sample 4). The sewage sample was filtered through a filter having a pore size of 0.45 ⁇ m.
  • TDN concentration of TDN, NH 4 + and NO 3 - in the sewage treated by step 1 were determined by potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite photometry and ion chromatography, respectively, and recorded as C. TDN(I) , C NH4 + (I) and C NO3 - (I) .
  • TDN and NH 4 Determination of TDN and NH 4 in wastewater by potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite photometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry after dialysis
  • concentrations of + , NO 3 - and NO 2 - are denoted as C TDN (II) , C NH4 + (II) , C NO3 - (II) and C NO2 - (II), respectively .
  • the DON concentration of Sample 4 was 0.51 mg/L.
  • the present embodiment repeated three times of averaging, and the results are shown in Fig. 2.
  • TDN and NH 4 Determination of TDN and NH 4 in wastewater by potassium persulfate oxidation-ion chromatography, salicylic acid-hypochlorite photometry, ion chromatography and N-(1-naphthyl)-ethylenediamine spectrophotometry after dialysis
  • concentrations of + , NO 3 - and NO 2 - are denoted as C TDN (II) , C NH4 + (II) , C NO3 - (II) and C NO2 - (II), respectively .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Molecular Biology (AREA)
  • Biomedical Technology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Plasma & Fusion (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
  • External Artificial Organs (AREA)

Abstract

一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，属于市政污水处理技术领域，包括如下步骤：1)污水样品过滤；2)分别测定经步骤1)处理的污水的溶解性总氮(TDN)、氨氮(NH4 +)和硝态氮(NO3 -)浓度，分别记为C TDN( Ⅰ)、CNH4 + ( Ⅰ)　和C NO3 - ( Ⅰ)；3)根据(C NH4 + ( Ⅰ)+C NO3 - ( Ⅰ))/C TDN( Ⅰ)比值和C NO3 - ( Ⅰ)/C NH4 + ( Ⅰ)比值，选择不同的测定方案测定污水中含氮基团的浓度；4)根据步骤3)中选择的测定方案得到的数值，计算污水溶解性有机氮浓度。提供的污水中溶解性有机氮浓度检测方法无需预实验、操作简便、成本低，可广泛应用于市政污水溶解性有机氮浓度测定。

Description

一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法 技术领域
本发明属于市政污水处理技术领域，更具体地说，涉及一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法。
背景技术
污水溶解性总氮(TDN)包括无机氮(DIN，包含氨氮、硝态氮和亚硝态氮)和溶解性有机氮(DON)。许多市政污水处理厂具有脱氮工艺，大部分无机氮通过硝化-反硝化作用被成功去除，相比之下，DON在硝化-反硝化过程中很难被去除，最终出水DON可占出水TDN 80％以上。污水DON具有一定量的可生物利用部分，其可以成为河流中微生物和藻类生长的营养物质。另外，DON是高致突变性和高致癌性的含氮消毒副产物的重要前体物。因此，市政污水处理厂DON的排放会影响受纳水体的水质安全性和富营养化。
尽管人们已经意识到污水DON对环境的危害，但目前尚无直接测定DON浓度的方法，主要通过以计算TDN和DIN(包含氨氮、硝态氮和亚硝态氮)的差值来实现。由于每个无机氮指标在检测时都会产生测量误差，在减差过程中造成误差累积，从而放大DON测量误差，影响DON测量的准确性。为了解决这一问题，许多学者提出把DIN与DON分离后再测定TDN和DIN，从而提高DON浓度测定的准确性。目前国内外学者主要采用两种方法进行DIN和DON的分离：纳滤法和透析法。中国专利申请号CN201010022653.1公开了一种应用纳滤膜分离技术来实现DON浓度测量的方法，在预处理过程中，采用截留分子量为150-500Da的选择性纳滤膜进行死端或错流方式过滤。该方法虽然能对水样中DON进行浓缩，实现DON和DIN的分离。但是，该方法需要使用外加氮气控制跨膜压力，能耗大且对测试水样的需求量较大。有美国学者提出采用一定分子量的透析膜，利用透析膜内外DIN浓度差来去除污水中的DIN，从而实现DON和DIN的分离，该方法已有效应用于地表水DON分析。对于污水样品，由于DIN/TDN比例高，氮存在形态的不确定性，实验人员往往需要多次预实验来确定最终透析参数，操作步骤繁琐且对操作人员要求高，难于大面积推广应用。对于市政污水处理厂污水DON的日常监测，需要一种耗能低且操作简便的测定方法。
发明内容
1.要解决的问题
针对现有的市政污水中DON的测定方法存在误差大、能耗大以及不确定因素多等问题，本发明提供一种基于透析预处理的市政污水DON浓度检测方法，根据测定的(NH4 ++NO3 -) /TDN比值和NO3 -/NH4 +比值，选择不同的测定方案，具有能耗低，操作简便等优点。
2.技术方案
为了解决上述问题，本发明所采用的技术方案如下：
一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其步骤为：
(1)用滤膜过滤污水样品；
(2)分别测定经步骤(1)处理的污水的溶解性总氮(TDN)、氨氮(NH4 +)和硝态氮(NO3 -)浓度，分别记为CTDN(Ⅰ)、CNH4 + (Ⅰ)和CNO3 - (Ⅰ)；
(3)根据(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)比值和CNO3 - (Ⅰ)/CNH4 + (Ⅰ)比值，选择不同的测定方案测定污水中含氮基团的浓度；
(4)根据步骤(3)中选择的测定方案得到的数值，计算市政污水DON浓度。
更进一步地，所述步骤(1)中滤膜孔径为0.45μm。
更进一步地，所述步骤(3)中，当(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)<0.7时，采用测定方案I，即不进行预处理直接测定污水中亚硝态氮(NO2 -)浓度，记为CNO2 - (Ⅰ)。此时，DON浓度计算公式为：DON＝CTDN(Ⅰ)－CNH4 + (Ⅰ)－CNO3 - (Ⅰ)－CNO2 - (Ⅰ)。
更进一步地，所述步骤(3)中，当(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)≥0.7且CNO3 - (Ⅰ)/CNH4 + (Ⅰ)≥1时，采用测定方案II，即将污水放入悬浮透析袋中进行透析预处理，透析时间为22-26h；透析结束后分别测定污水中TDN、NH4 +、NO3 -和NO2 -的浓度，分别记为CTDN(Ⅱ)、CNH4 + (Ⅱ)、CNO3 - (Ⅱ)和CNO2 - (Ⅱ)。此时，DON浓度计算公式为：DON＝CTDN(Ⅱ)－CNH4 + (Ⅱ)－CNO3 - (Ⅱ)－CNO2-(Ⅱ)。
更进一步地，所述步骤(3)中，当(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)≥0.7且CNO3 - (Ⅰ)/CNH4 + (Ⅰ)<1时，采用测定方案III，即将污水放入悬浮透析袋中进行透析预处理，透析时间为34-38h；透析结束后分别测定污水中TDN、NH4 +、NO3 -和NO2 -的浓度，分别记为CTDN(Ⅲ)、CNH4 + (Ⅲ)、CNO3 - (Ⅲ)和CNO2 - (Ⅲ)。此时，
DON浓度计算公式为：DON＝CTDN(Ⅲ)－CNH4 + (Ⅲ)－CNO3 - (Ⅲ)－CNO2 - (Ⅲ)。
更进一步地，所述的悬浮透析袋为纤维素酯膜，亲水性，切割分子量为100-500Da；透析液水力停留时间为4h。
更进一步地，TDN、NH4 +、NO3 -和NO2 -的浓度分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法、离子色谱法和N-(1-萘基)-乙二胺光度法测定。
3.有益效果
相比于现有技术，本发明的有益效果为：
(1)本发明提供的市政污水中DON浓度检测方法对水样的需求量少；
(2)本发明利用透析膜内外浓度差实现DON和DIN的分离，无需外加氮气控制跨膜压力，耗能低；
(3)通过本发明提供的预处理方法可有效减少市政污水中无机氮浓度，同时保留DON的含量，从而大大降低差量法计算DON浓度带来的偏差，保证测试的准确性和精确性；
(4)本发明操作简单、无需预实验、分析成本低，可广泛应用于市政污水DON浓度测定。
附图说明
图1为本发明检测市政污水中DON浓度的流程示意图；
图2为本发明对污水中DON浓度测定对比图。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。
实施例1
1.取100mL南京某市政污水处理厂出水(记为样品1)，用孔径为0.45μm的滤膜过滤污水样品。
2.分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法和离子色谱法测定经步骤1处理的污水的TDN、NH4 +和NO3 -浓度，分别记为CTDN(Ⅰ)、CNH4 + (Ⅰ)和CNO3 - (Ⅰ)。
3.(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)＝0.92>0.7，CNO3 - (Ⅰ)/CNH4 + (Ⅰ)>1，采用测定方案II。将污水放入悬浮透析袋中进行透析预处理，透析时间为24h。悬浮透析袋为纤维素酯膜，亲水性，切割分子量为100Da。透析液水力停留时间为4h。透析结束后分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法、离子色谱法和N-(1-萘基)-乙二胺光度法测定污水中TDN、NH4 +、NO3 -和NO2 -的浓度，分别记为CTDN(Ⅱ)、CNH4 + (Ⅱ)、CNO3 - (Ⅱ)和CNO2 - (Ⅱ)。
4.DON浓度由公式DON＝CTDN(Ⅱ)－CNH4 + (Ⅱ)－CNO3 - (Ⅱ)－CNO2 - (Ⅱ)计算而得。样品1的DON浓度为0.80mg/L。为了提高测定的准确性和可靠性，本实施例重复测定了三次取平均值，结果如附图2所示。
实施例2
1.取100mL南京某市政污水处理厂厌氧段污水(记为样品2)。用孔径为0.45μm的滤膜过滤污水样品。
2.分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法和离子色谱法测定经步骤1处理的污水的TDN、NH4 +和NO3 -浓度，分别记为CTDN(Ⅰ)、CNH4+(Ⅰ)和CNO3-(Ⅰ)。
3.(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)＝0.73>0.7，CNO3 - (Ⅰ)/CNH4 + (Ⅰ)<1，采用测定方案III。将污水放入悬浮透析袋中进行透析预处理，透析时间为34h。悬浮透析袋为纤维素酯膜，亲水性，切割分 子量为100Da。透析液水力停留时间为4h。透析结束后分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法、离子色谱法和N-(1-萘基)-乙二胺光度法测定污水中TDN、NH4 +、NO3 -和NO2 -的浓度，分别记为CTDN(Ⅲ)、CNH4 + (Ⅲ)、CNO3 - (Ⅲ)和CNO2 - (Ⅲ)。
4.DON浓度由公式DON＝CTDN(Ⅲ)－CNH4 + (Ⅲ)－CNO3 - (Ⅲ)－CNO2 - (Ⅲ)计算而得。样品2的DON浓度为2.43mg/L。为了提高测定的准确性和可靠性，本实施例重复测定了三次取平均值，结果如附图2所示。
实施例3
1.取100mL南京某市政污水处理厂好氧段污水(记为样品3)。用孔径为0.45μm的滤膜过滤污水样品。
2.分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法和离子色谱法测定经步骤1处理的污水的TDN、NH4 +和NO3 -浓度，分别记为CTDN(Ⅰ)、CNH4 + (Ⅰ)和CNO3 - (Ⅰ)。
3.(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)＝0.75>0.7，CNO3 - (Ⅰ)/CNH4 + (Ⅰ)>1，采用测定方案II。将污水放入悬浮透析袋中进行透析预处理，透析时间为24h。悬浮透析袋为纤维素酯膜，亲水性，切割分子量为100Da。透析液水力停留时间为4h。透析结束后分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法、离子色谱法和N-(1-萘基)-乙二胺光度法测定污水中TDN、NH4 +、NO3 -和NO2 -的浓度，分别记为CTDN(Ⅱ)、CNH4 + (Ⅱ)、CNO3 - (Ⅱ)和CNO2 - (Ⅱ)。
4.DON浓度由公式DON＝CTDN(Ⅱ)－CNH4 + (Ⅱ)－CNO3 - (Ⅱ)－CNO2 - (Ⅱ)计算而得。样品3的DON浓度为1.89mg/L。为了提高测定的准确性和可靠性，本实施例重复测定了三次取平均值，结果如附图2所示。
实施例4
1.取100mL无锡某市政污水处理厂出水(记为样品4)。用孔径为0.45μm的滤膜过滤污水样品。
2.分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法和离子色谱法测定经步骤1处理的污水的TDN、NH4 +和NO3 -浓度，分别记为CTDN(Ⅰ)、CNH4 + (Ⅰ)和CNO3 - (Ⅰ)。
3.(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)＝0.95>0.7，CNO3 - (Ⅰ)/CNH4 + (Ⅰ)>1，采用测定方案II。将污水放入悬浮透析袋中进行透析预处理，透析时间为25h。悬浮透析袋为纤维素酯膜，亲水性，切割分子量为100Da。透析液水力停留时间为4h。透析结束后分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法、离子色谱法和N-(1-萘基)-乙二胺光度法测定污水中TDN、NH4 +、NO3 -和NO2 -的浓度，分别记为CTDN(Ⅱ)、CNH4 + (Ⅱ)、CNO3 - (Ⅱ)和CNO2 - (Ⅱ)。
4.DON浓度由公式DON＝CTDN(Ⅱ)－CNH4 + (Ⅱ)－CNO3 - (Ⅱ)－CNO2 - (Ⅱ)计算而得。样品4的DON浓度为0.51mg/L。为了提高测定的准确性和可靠性，本实施例重复测定了三次取平均值，结 果如附图2所示。
实施例5
1.取100mL 0.99mg/L谷氨酸标准溶液，加入10mL 40.09mg/L硝酸钾溶液，混合后用孔径为0.45μm的滤膜过滤(记为样品5)。
2.分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法和离子色谱法测定经步骤1处理的水样的TDN、NH4 +和NO3 -浓度，分别记为CTDN(Ⅰ)、CNH4 + (Ⅰ)和CNO3 - (Ⅰ)。
3.(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)＝0.81>0.7，CNO3 - (Ⅰ)/CNH4 + (Ⅰ)>1，采用测定方案II。将水样放入悬浮透析袋中进行透析预处理，透析时间为24h。悬浮透析袋为纤维素酯膜，亲水性，切割分子量为100Da。透析液水力停留时间为4h。透析结束后分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法、离子色谱法和N-(1-萘基)-乙二胺光度法测定污水中TDN、NH4 +、NO3 -和NO2 -的浓度，分别记为CTDN(Ⅱ)、CNH4 + (Ⅱ)、CNO3 - (Ⅱ)和CNO2 - (Ⅱ)。
4.DON浓度由公式DON＝CTDN(Ⅱ)－CNH4 + (Ⅱ)－CNO3 - (Ⅱ)－CNO2 - (Ⅱ)计算而得。样品5的DON浓度为1.05mg/L。为了提高测定的准确性和可靠性，本实施例重复测定了三次取平均值，结果如附图2所示。
从图2可以看出，污水样品1-4在未进行本发明提供的预处理时，数据的标准偏差均较大，无法得到污水中DON的浓度，甚至测量得到负值。经过本发明提供的预处理后样品5的DON测定值为1.03±0.03mg/L，与真值(0.99mg/L)之间的标准误差为4.04％。而样品5在未进行本发明提供的预处理时测定的DON值与真值之间的标准误差为33.33％。因此，采用本预处理方法测定市政污水DON浓度时，具有良好的测量结果，重复试验标准偏差在10％范围内，有效提高了污水DON测量的准确性和精确性。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (11)

  1. 一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其步骤为：
    (1)用滤膜过滤污水样品；
    (2)分别测定经步骤(1)处理的污水的溶解性总氮(TDN)、氨氮(NH4 +)和硝态氮(NO3 -)浓度，分别记为CTDN(Ⅰ)、CNH4 + (Ⅰ)和CNO3 - (Ⅰ)；
    (3)根据(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)比值和CNO3 - (Ⅰ)/CNH4 + (Ⅰ)比值，选择不同的测定方案测定污水中含氮基团的浓度；
    (4)根据步骤(3)中选择的测定方案得到的数值，计算污水溶解性有机氮(DON)浓度。
  2. 根据权利要求1中所述的一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其特征在于：所述步骤(1)中滤膜孔径为0.45μm。
  3. 根据权利要求1中所述的一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其特征在于：所述步骤(3)中，当(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)<0.7时，采用测定方案I，即不进行预处理直接测定污水中亚硝态氮(NO2 -)浓度，记为CNO2 - (Ⅰ)；DON浓度计算公式为：DON＝CTDN(Ⅰ)－CNH4 + (Ⅰ)－CNO3 - (Ⅰ)－CNO2 - (Ⅰ)。
  4. 根据权利要求1中所述的一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其特征在于：所述步骤(3)中，当(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)≥0.7且CNO3 - (Ⅰ)/CNH4 + (Ⅰ)≥1时，采用测定方案II，即将污水放入悬浮透析袋中进行透析预处理，透析时间为22-26h；透析结束后分别测定污水中TDN、NH4 +、NO3 -和NO2 -的浓度，分别记为CTDN(Ⅱ)、CNH4 + (Ⅱ)、CNO3 - (Ⅱ)和CNO2 - (Ⅱ)；DON浓度计算公式为：DON＝CTDN(Ⅱ)－CNH4 + (Ⅱ)－CNO3 - (Ⅱ)－CNO2-(Ⅱ)。
  5. 根据权利要求1中所述的一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其特征在于：所述步骤(3)中，当(CNH4 + (Ⅰ)+CNO3 - (Ⅰ))/CTDN(Ⅰ)≥0.7且CNO3 - (Ⅰ)/CNH4 + (Ⅰ)<1时，采用测定方案III，即将污水放入悬浮透析袋中进行透析预处理，透析时间为34-38h；透析结束后分别测定污水中TDN、NH4 +、NO3 -和NO2 -的浓度，分别记为CTDN(Ⅲ)、CNH4 + (Ⅲ)、CNO3 - (Ⅲ)和CNO2 - (Ⅲ)；DON浓度计算公式为：DON＝CTDN(Ⅲ)－CNH4 + (Ⅲ)－CNO3 - (Ⅲ)－CNO2 - (Ⅲ)。
  6. 根据权利要求4中所述的一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其特征在于：所述的悬浮透析袋为纤维素酯膜，亲水性，切割分子量为100-500Da；透析液水力停留时间为4h。
  7. 根据权利要求5中所述的一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其特征在于：所述的悬浮透析袋为纤维素酯膜，亲水性，切割分子量为100-500Da；透 析液水力停留时间为4h。
  8. 根据权利要求1中的一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其特征在于：TDN、NH4 +、NO3 -和NO2 -的浓度分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法、离子色谱法和N-(1-萘基)-乙二胺光度法测定。
  9. 根据权利要求3中的一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其特征在于：TDN、NH4 +、NO3 -和NO2 -的浓度分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法、离子色谱法和N-(1-萘基)-乙二胺光度法测定。
  10. 根据权利要求4中的一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其特征在于：TDN、NH4 +、NO3 -和NO2 -的浓度分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法、离子色谱法和N-(1-萘基)-乙二胺光度法测定。
  11. 根据权利要求5中的一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法，其特征在于：TDN、NH4 +、NO3 -和NO2 -的浓度分别采用过硫酸钾氧化-离子色谱法、水杨酸-次氯酸盐光度法、离子色谱法和N-(1-萘基)-乙二胺光度法测定。
PCT/CN2017/095851 2017-01-20 2017-08-03 一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法 Ceased WO2018133378A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US16/274,213 US20190178803A1 (en) 2017-01-20 2019-02-12 Method of measuring concentration of dissolved organic nitrogen in sewage
US16/902,213 US11014835B2 (en) 2017-01-20 2020-06-15 Method of measuring concentration of dissolved organic nitrogen in sewage

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710048270.3A CN106769946B (zh) 2017-01-20 2017-01-20 一种基于透析预处理的污水中溶解性有机氮浓度检测方法
CN201710048270.3 2017-01-20

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/274,213 Continuation-In-Part US20190178803A1 (en) 2017-01-20 2019-02-12 Method of measuring concentration of dissolved organic nitrogen in sewage

Publications (1)

Publication Number Publication Date
WO2018133378A1 true WO2018133378A1 (zh) 2018-07-26

Family

ID=58941662

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/095851 Ceased WO2018133378A1 (zh) 2017-01-20 2017-08-03 一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法

Country Status (3)

Country Link
US (1) US20190178803A1 (zh)
CN (1) CN106769946B (zh)
WO (1) WO2018133378A1 (zh)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106769946B (zh) * 2017-01-20 2020-08-07 南京大学 一种基于透析预处理的污水中溶解性有机氮浓度检测方法
CN108414645B (zh) * 2018-04-19 2023-05-23 南京大学 一种体积排阻色谱联用型氮检测器及应用方法
CN110412220A (zh) * 2019-07-25 2019-11-05 叶建锋 一种建成区排水管道高有机含量通沟底泥精准定位的方法与系统
CN110672485B (zh) * 2019-09-06 2020-07-28 浙江大学 一种吸附染料精确测定活性污泥表面疏水性的方法
CN111781198A (zh) * 2020-07-15 2020-10-16 南通大学 一种针对水体、土壤或沉积物中氨氮含量的二维测定方法
CN114112614B (zh) * 2021-12-01 2024-11-26 浙江大学 利用水质氨氮快速检测试剂盒测定土壤中氨氮的方法
CN115140847B (zh) * 2022-07-05 2023-11-03 南京大学 一种介体强化的废水深度生物脱氮方法
CN116712866B (zh) * 2023-05-06 2025-09-02 中国环境科学研究院 一种优化反渗透前处理效果的运行方案确定方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0526863A (ja) * 1991-07-18 1993-02-02 Babcock Hitachi Kk 有機窒素化合物の濃度測定方法および装置
CN101782566A (zh) * 2010-01-12 2010-07-21 同济大学 一种测定水中低浓度溶解性有机氮浓度的方法
CN103969411A (zh) * 2014-04-09 2014-08-06 陈白杨 一种基于电渗析预处理方式直接测量水体中溶解性有机氮浓度的方法
CN104297189A (zh) * 2014-10-31 2015-01-21 南京大学 一种测定二级出水中溶解性有机氮浓度的方法
CN106769946A (zh) * 2017-01-20 2017-05-31 南京大学 一种基于透析预处理的污水中溶解性有机氮浓度检测方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0526863A (ja) * 1991-07-18 1993-02-02 Babcock Hitachi Kk 有機窒素化合物の濃度測定方法および装置
CN101782566A (zh) * 2010-01-12 2010-07-21 同济大学 一种测定水中低浓度溶解性有机氮浓度的方法
CN103969411A (zh) * 2014-04-09 2014-08-06 陈白杨 一种基于电渗析预处理方式直接测量水体中溶解性有机氮浓度的方法
CN104297189A (zh) * 2014-10-31 2015-01-21 南京大学 一种测定二级出水中溶解性有机氮浓度的方法
CN106769946A (zh) * 2017-01-20 2017-05-31 南京大学 一种基于透析预处理的污水中溶解性有机氮浓度检测方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LEE, W. ET AL.: "Dissolved Organic Nitrogen Measurement Using Dialysis Pretreatment", ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 29, no. 3, 16 December 2014 (2014-12-16), pages 879 - 884, XP055504693 *

Also Published As

Publication number Publication date
CN106769946B (zh) 2020-08-07
US20190178803A1 (en) 2019-06-13
CN106769946A (zh) 2017-05-31

Similar Documents

Publication Publication Date Title
WO2018133378A1 (zh) 一种基于透析预处理的市政污水中溶解性有机氮浓度检测方法
CN101782566B (zh) 一种测定水中低浓度溶解性有机氮浓度的方法
CN105289314B (zh) 一种废旧平板膜性能的综合评价方法
CN103969411B (zh) 一种基于电渗析预处理方式直接测量水体中溶解性有机氮浓度的方法
CN107655842B (zh) 一种基于静态培养的污水生物可降解溶解性有机氮测定方法
Yi et al. A novel forward osmosis reactor assisted with microfiltration for deep thickening waste activated sludge: performance and implication
Wang et al. Transition of fouling characteristics after development of membrane wetting in membrane-aerated biofilm reactors (MABRs)
AU2015230864B2 (en) Method for measuring concentration of dissolved organic nitrogen of secondary effluent
CN115639333A (zh) 一种利用硝化生物反应检测氨氮含量的方法
CN107515287B (zh) 一种基于动态培养的污水生物可降解溶解性有机氮测定方法
CN101187637A (zh) 海水中酚类化合物的自动分析方法
Lameloise et al. Combining reverse osmosis and ion-exchange allows beet distillery condensates to be recycled as fermentable dilution water
CN110568058A (zh) 一种基于icp-ms快速测定厌氧氨氧化污泥活性的方法
TWI409448B (zh) 測定水中低濃度溶解性有機氮濃度的方法
CN108614059B (zh) 疏水性低共熔溶剂涡旋辅助分散液液微萃取-高效液相色谱法检测亚硝酸根的方法
CN210119465U (zh) 一种水质氨氮在线检测分析系统
CN107219102A (zh) 一种基于渗析叠加电场预处理方式直接测量水体中溶解性有机氮浓度的方法
US20220187270A1 (en) Method for Evaluating Carbon Source Quality of Water Body, Apparatus, Device and Readable Storage Medium
CN109133433B (zh) 一种反渗透膜的有机污堵控制方法
CN110498543A (zh) 一种半导体废水的处理方法
US20200308027A1 (en) Method of measuring concentration of dissolved organic nitrogen in sewage
JPS585198A (ja) クレアチニン検定のための自動連続流れ法
JP3033280B2 (ja) 微生物中のａｔｐの測定方法
JP2026013821A (ja) 濃縮システム
CN117110401A (zh) 用于电极法检测Cr3+的核孔膜及其制备方法与用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17892331

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17892331

Country of ref document: EP

Kind code of ref document: A1