CN107324529B - Automatic device and method for separating soluble organic matter components in water - Google Patents

Automatic device and method for separating soluble organic matter components in water Download PDF

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CN107324529B
CN107324529B CN201710470552.2A CN201710470552A CN107324529B CN 107324529 B CN107324529 B CN 107324529B CN 201710470552 A CN201710470552 A CN 201710470552A CN 107324529 B CN107324529 B CN 107324529B
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exchange resin
substance
chromatographic column
eluent
storage bottle
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CN107324529A (en
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胡洪营
孙丽娟
巫寅虎
陈卓
孙艳
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Tsinghua University
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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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • 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
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/005—Processes using a programmable logic controller [PLC]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/21—Dissolved organic carbon [DOC]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The invention discloses an automatic device and a method for separating soluble organic matter components in water, namely, macroporous adsorption resin DAX-8, cation exchange resin MSC-H and anion exchange resin AIIIS are utilized to separate the soluble organic matter in the water into six components, namely hydrophobic acidic substance (HOA), hydrophobic basic substance (HOB), hydrophobic neutral substance (HON), hydrophilic acidic substance (HIA), hydrophilic basic substance (HIB) and hydrophilic neutral substance (HIN), so that the characterization of the soluble organic matter in the water is more refined, and the pollution characteristic is more definite. The device comprises a hydrophobic substance separation part and a hydrophilic substance separation part, can realize automatic, continuous and convenient separation of hydrophilic and hydrophobic substances of soluble organic matters in water, and has less maintenance and high efficiency.

Description

Automatic device and method for separating soluble organic matter components in water
Technical Field
The invention belongs to the technical field of water treatment and utilization, and relates to a method for separating hydrophilic and hydrophobic substances of soluble organic matters in water, in particular to an automatic device and method for separating components of the soluble organic matters in water.
Background
Water shortage is becoming a serious problem, and in some places, reclaimed water has become an important second largest water source. At present, secondary effluent of a sewage plant is generally used as a water source in a reclaimed water plant, and a MF (UF) and RO double-membrane process is adopted to produce reclaimed water. However, the membrane fouling and cleaning problems prevalent in membrane processes make their operation costly. Therefore, there is a need for an efficient method for analyzing pollutants in water, which can distinguish organic matters with different properties in secondary effluent to perform quantitative and qualitative determination, so as to facilitate selection of a proper pretreatment process before membrane and reduce the problem of membrane pollution.
The secondary effluent contains more soluble organic matters, such as humic substances such as humic acid and fulvic acid, and macromolecular organic matters such as polysaccharide and protein, and organic matters with different properties need to be removed by different treatment processes. Humic substances such as humic acid and fulvic acid are widely present in nature and generally belong to hydrophobic substances, while polysaccharides and proteins generally belong to microorganisms and metabolites thereof and are hydrophilic substances in secondary effluent. The device for separating hydrophilic and hydrophobic substances of soluble organic matters in water divides organic pollutants into six components of hydrophobic acidity, hydrophobic alkalinity, hydrophobic neutrality and hydrophilic acidity, hydrophilic alkalinity and hydrophilic neutrality by means of DAX adsorption resin, cation exchange resin MSC-H and anion exchange resin AIIIS, and can quantitatively determine the content of the organic pollutants.
Disclosure of Invention
The invention aims to make up the defects of the prior art, provides an automatic device and a method for separating soluble organic matter components in water based on macroporous adsorption resin and anion-cation exchange resin, and can realize automation, continuity and convenience.
In order to achieve the purpose, the technical scheme of the invention is as follows: a method for separating water-soluble organic components based on macroporous adsorption resin and anion-cation exchange resin comprises the steps of utilizing macroporous adsorption resin DAX-8 to divide organic matters in a water sample to be analyzed into four components of hydrophobic acidic substance HOA, hydrophobic alkaline substance HOB, hydrophobic neutral substance HON and hydrophilic substance HIS, and then dividing the HIS components into three components of hydrophilic acidic substance HIA, hydrophilic alkaline substance HIB and hydrophilic substance HIN through cation exchange resin MSC-H and anion exchange resin AIIIS.
Further, when the liquid to be separated is 200ml, the loading of the macroporous adsorption resin DAX-8 is 3ml, the loading of the cation exchange resin MSC-H is 6ml, and the loading of the anion exchange resin AIIIS is 12 ml; the amount of liquid to be separated and the loading of resin can be adjusted in the above ratio.
The invention also provides an automatic device for separating the components of the soluble organic matters in water based on the macroporous adsorption resin and the anion-cation exchange resin, which comprises a hydrophobic substance separation part and a hydrophilic substance separation part. The hydrophobic substance separation part comprises a first PLC man-machine control system S1, a first peristaltic pump S2, an electronic balance S3, a chromatography column (filled with DAX-8 adsorption resin) S4 with the diameter of 10mm multiplied by 100mm, a chromatography column upper end port S5 with the diameter of 10mm multiplied by 100mm, a chromatography column lower end port S6 with the diameter of 10mm multiplied by 100mm, first liquid inlet storage bottles S7, S8, S9, S10 and S11, and first eluent storage bottles S12, S13, S14 and S15. The first peristaltic pump S2 is connected with a first feed liquid storage bottle S7 (or S11) and an upper end port S5 of a chromatographic column S4 with the diameter of phi 10mm multiplied by 100mm, a lower end port S6 of the chromatographic column S4 with the diameter of phi 10mm multiplied by 100mm is connected with a first eluent storage bottle S12 (or S14) arranged on an electronic balance, the electronic balance S3 is connected with a first PLC man-machine control system S1, a weight value of needed eluent is set on an interface of the first PLC man-machine control system S1, an interface start button is clicked, the positive elution process is started, and the eluent is obtained by the first eluent storage bottle S12 (or S14); the first liquid inlet storage bottles S7, S8, S9 and S10 are respectively filled with liquid to be separated, 0.1MHCl, 0.1MNaOH and UPW; the first eluent storage bottles S12, S13 and S15 are respectively used for containing the eluent of the liquid to be separated in the first liquid inlet storage bottles S7, S8 and S9 after passing through the adsorption resin, and the first eluent storage bottle S14 is used for containing the eluent after the eluent in the S12 is acidified and is adsorbed by the DAX resin again.
The hydrophilic substance separation part comprises a second PLC (programmable logic controller) man-machine control system Q1, a second peristaltic pump Q2, a first 12-direction switching valve Q3, a second 12-direction switching valve Q4, a third 12-direction switching valve Q5, a chromatography column (filled with cation exchange resin) Q6 with phi 15mm multiplied by 150mm, a chromatography column (filled with cation exchange resin) Q7 with phi 15mm multiplied by 150mm, a first electromagnetic valve Q8, a second electromagnetic valve Q9, a third electromagnetic valve Q10, a fourth electromagnetic valve Q11, a fifth electromagnetic valve Q12, a sixth electromagnetic valve Q13, a first three-way pipe Q13, a second three-way pipe Q13, a third three-way pipe Q13, a fourth three-way pipe Q13, a second eluent storage bottle Q13, a second eluent storage bottle Q13, a Q13 and a Q13.
Furthermore, the liquid inlet and outlet pipelines of the upper and lower end ports S5 and S6 of the chromatographic column S4 can be manually switched at any time.
Furthermore, the resin filled in the chromatographic column leaves a space of 3-5mm above the resin so as to facilitate air exhaust.
Hydrophobic substance separation system connection
The first peristaltic pump S2 is connected with a first feed liquid storage bottle S7 (or S11) and an upper end port S5 of a chromatographic column S4 with the diameter of phi 10mm multiplied by 100mm, a lower end port S6 of the chromatographic column S4 with the diameter of phi 10mm multiplied by 100mm is connected with a first eluent storage bottle S12 (or S14) arranged on an electronic balance, the electronic balance S3 is connected with a first PLC man-machine control system S1, a weight value of needed eluent is set on an interface of the first PLC man-machine control system S1, an interface start button is clicked, the positive leaching process is started, and the eluent is obtained from the first eluent storage bottle S12 (or S14);
connecting a first peristaltic pump S2 with a first feed liquid storage bottle S8 (or S9, S10) and a lower end port S6 of a chromatographic column S4, connecting an upper end port S5 of the chromatographic column S4 with the first eluent storage bottle S13 (or S15), setting a weight value of required eluent on an interface of a first PLC man-machine control system S1, clicking an interface 'start' button, namely starting a reverse elution process, and obtaining the eluent from the first eluent storage bottle S13 (or S15);
hydrophilic substance separation system connection
The inlet ports of the first 12-way selector valve Q3 are automatically switchable between 12 ports numbered A, B, C and 1-9, as shown in the FIG. 312 schematic diagram of the ports of the automatic selector valve. The 9th, a, B, C, and 1th ports of the first 12-way switching valve Q3 are connected to second feed liquid storage bottles Q18, Q19, Q20, Q21, and a first eluent storage bottle S14, respectively, the second peristaltic pump Q2 is connected to the IN port of the first 12-way switching valve Q3 and the COM port of the first solenoid valve Q8, the NC port of the first solenoid valve Q8 is connected to the NC port of the second solenoid valve Q9, the NO port of the first solenoid valve Q8 is connected to the COM port of the third solenoid valve Q10, the first three-way Q14 is connected to the upper port of the cation exchange resin Q6, the NO port of the third solenoid valve Q10, and the NC port of the fourth solenoid valve Q11, the second three-way Q15 is connected to the NC port of the third solenoid valve Q10, the NO port of the fourth solenoid valve Q11, and the lower port of the cation exchange resin Q6, the COM port of the fourth solenoid valve Q11 is connected to the IN port of the second switching valve Q4, the second eluent storage bottle Q22, and the second eluent storage bottle Q22, Q23, Q24, and Q25, wherein a C port of the second 12-way switching valve Q4 is connected to a NO port of the second electromagnetic valve Q9, a COM port of the second electromagnetic valve Q9 is connected to a COM port of the fifth electromagnetic valve Q12, a third three-way valve Q16 is connected to an upper port of the anion exchange resin Q7, a NO port of the fifth electromagnetic valve Q12, and an NC port of the sixth electromagnetic valve Q13, respectively, a fourth three-way valve Q17 is connected to a lower port of the anion exchange resin, an NC port of the fifth electromagnetic valve Q12, and a NO port of the sixth electromagnetic valve Q13, a COM port of the sixth electromagnetic valve is connected to an IN port of the third 12-way switching valve Q5, and 9th, a, C, and 1th ports of the third 12-way switching valve Q5 are connected to the second eluent reservoir bottles Q26, Q27, Q28, and Q29, respectively.
The process of separating the soluble organic components in the water by using the device comprises the following steps:
hydrophobic substance separation process:
filtering the liquid to be separated by using a 0.45 micron filter membrane, placing the liquid into a first liquid inlet storage bottle S7, and measuring the DOC value of the liquid to be separated to obtain DOC 1;
the first liquid inlet storage bottles S7, S8 and S9 are respectively filled with liquid to be separated, leacheate 0.1MHCl and leacheate 0.1MNaOH, and the S10 is filled with UPW;
a first peristaltic pump S2 is connected with a first feed liquid storage bottle S7 and the upper end port S5 of a chromatographic column S4, and the lower end port S6 of the chromatographic column S4 is connected with a first eluent storage bottle S12 arranged on an electronic balance;
the electronic balance S3 is connected with the first PLC man-machine control system S1 through a data line to realize automatic control of an analysis process, a weight value of required eluent is set on an interface of the first PLC man-machine control system S1, the flow rate of the first peristaltic pump S2 is set to be 0.8ml/min, a start button of the interface is clicked, a positive leaching process is started, the electronic balance S3 transmits the weight data to the first PLC control system S1 in real time, the leaching process is automatically terminated when the set weight value is reached, and the eluent is obtained by a first eluent storage bottle S12;
connecting a first peristaltic pump S2 with a lower end port S6 of a first liquid inlet storage bottle S8 and a chromatographic column S4, connecting an upper end port S5 of the chromatographic column S4 with a first eluent storage bottle S13, setting a weight value of a required eluent on an interface of a first PLC (programmable logic controller) man-machine control system S1, setting the flow rate of the first peristaltic pump S2 to be 0.3ml/min, clicking an interface 'start' button, starting a reverse leaching process, obtaining the eluent from a first eluent storage bottle S13, and measuring a DOC value DOC2, namely an HOB component;
adjusting the pH value of liquid in a first eluent storage bottle S12 to 2.0-2.5, placing the liquid in a first liquid inlet storage bottle S11, connecting a first peristaltic pump S2 with the first liquid inlet storage bottle S11 and an upper end port S5 of a chromatographic column S4, connecting a lower end port S6 of the chromatographic column S4 with the first eluent storage bottle S14, setting the flow rate of the first peristaltic pump S2 to be 0.8ml/min, setting the weight value of required eluent on an interface of a first PLC man-machine control system S1, clicking an interface 'start' button to start a positive leaching process, obtaining the eluent from the first eluent storage bottle S14, and measuring the DOC value to be DOC4, namely an HIS component;
the first peristaltic pump S2 is connected with a first feed liquid storage bottle S9 and a lower end port S6 of a chromatographic column S4, an upper end port S5 of the chromatographic column S4 is connected with a first eluent storage bottle S15, the weight value of the needed eluent is set on an interface of a first PLC (programmable logic controller) man-machine control system S1, the flow rate of the first peristaltic pump S2 is set to be 0.3ml/min, a start button of the interface is clicked, the reverse elution process is started, the eluent is obtained by the first eluent storage bottle S15, and the DOC value of the eluent is measured to be DOC3, namely the HOA component.
Performing Soxhlet extraction on DAX-8 resin in a chromatographic column S4 for 24h with chromatographic grade anhydrous methanol, concentrating and evaporating to dryness to 20ml with a rotary evaporator, blow-drying methanol with a nitrogen blower, dissolving the residual solid component (HON component) in a certain amount of UPW, and measuring DOC value to be DOC 5.
And (3) hydrophilic substance separation process:
connecting an HIS component (namely DOC4) liquid storage bottle S14 obtained in the hydrophobic substance separation process with a port 1 of a first 12-direction switching valve Q3, connecting a port 1 of a third 12-direction switching valve Q5 with a second eluent storage bottle Q29, setting the flow rate of a second peristaltic pump Q2 to be 0.8ml/min, setting the stabilization time on a second PLC control system interface Q1 to be 60min, starting the stabilization process of the second PLC control system interface Q1, wherein at the moment, the first electromagnetic valve Q8, the second electromagnetic valve Q9, the third electromagnetic valve Q10, the fourth electromagnetic valve Q11, the fifth electromagnetic valve Q12 and the sixth electromagnetic valve Q13 are not powered, the HIS component sequentially flows through cation exchange resin and anion exchange resin, and the stabilization process aims to replace liquid in the ion exchange resin into liquid to be separated;
after the stabilization process is finished, setting the collection time of the effluent of the anion exchange resin for 35min, starting the separation process of an interface Q1 of a second PLC control system, and obtaining liquid, namely a HIN component (namely DOC6), in a second eluent storage bottle Q29;
after the separation process is finished, the substance adsorbed on the cation exchange resin is the HIB component, the substance adsorbed on the anion exchange resin is the HIA component, the substance needs to be eluted by 0.1MNaOH respectively, the elution time of the cation exchange resin Q6 is set to 80min, the elution time of the anion exchange resin Q7 is set to 80min, the flow rate of the second peristaltic pump Q2 is set to 0.3ml/min, three ports A, B, C of a first 12-direction switching valve Q3 are connected with a second liquid inlet storage bottle Q19, Q20 and Q21 which are filled with UPW, 0.1MNaOH and 0.1MNaOH respectively, a port B of a second 12-direction switching valve Q4 is connected with a second eluent storage bottle Q24, a port C of a third 12-direction switching valve Q5 is connected with a second liquid storage bottle Q28, the elution process of an interface of a second PLC control system Q1 is started, at the moment, the substance obtained in the Q24 is the HIB component, the measured DOC7 value of the DOC 28 is the HIB component, measuring the DOC value of the product to be DOC 8;
if a plurality of samples exist, only 2-8 ports of the first 12-direction switching valve Q3 are needed to correspond to different samples, and the stabilizing process, the separating process and the eluting process are carried out according to the steps.
The operation flow of the component separation is detailed in Table 1.
TABLE 1 separation of soluble organic components in water
Figure BDA0001326967420000061
Compared with the reported method for separating the components of the organic matters soluble in water, the method has the following advantages:
the component separation device and the method only divide soluble organic matters in water into four components of HOA, HOB, HON and HIS, and the invention further separates the HIS component into the HIA, HIB and HIN components besides separating and extracting hydrophobic substances of HOA, HOB and HON, so that the characterization of the soluble organic matters in water is more refined, and the pollution characteristic is more definite.
The invention makes clear regulation on the relation between the water sample amount to be separated and the resin filling amount, overcomes the deviation caused by different separation results due to different proportions of the water sample amount to be separated and the resin filling amount, and ensures that the analysis result is more comparable.
The invention utilizes the electronic balance to carry out accurate quantification, and overcomes the error caused by manual sampling.
The invention adopts the PLC control system to carry out automatic continuous operation, has high automation degree, can simultaneously carry out component separation of a plurality of water samples, and is more efficient and convenient.
Drawings
FIG. 1 is a schematic view of a separation part of a hydrophobic substance according to the present invention.
FIG. 2 is a schematic view of a portion of the present invention for separating hydrophilic substances.
FIG. 3 is a schematic diagram of the port distribution of the apparatus 12 directional switch valve of the present invention
FIG. 4 is a diagram showing the results of the secondary water component analysis in different water plants
Detailed Description
The invention is described in further detail below with reference to the following figures and specific embodiments.
Sample pretreatment:
200ml of the sample to be separated is filtered by a 0.45 micron filter membrane, placed in a first feed liquid storage bottle S7, and the DOC is measured, namely DOC 1.
Filling of resin:
1. packing of hydrophobic separation part resin
Filling 3ml of DAX-8 macroporous adsorption resin into a chromatographic column S4 with the diameter of phi 10mm multiplied by 100mm, and reserving a space of 3-5mm above the resin so as to facilitate air exhaust;
2. loading of hydrophilic separation part resin
Respectively filling 6ml of MSC-H cation exchange resin and 12ml of AIIIS anion exchange resin in chromatographic columns Q6 and Q7 with the diameter of phi 15mm multiplied by 150mm, and reserving a space of 3-5mm above the resin so as to facilitate air exhaust;
3. separation process of sample hydrophobic substances:
(1) obtaining of blank value of DAX-8 resin
Setting a target weight value of an electronic balance S3 to be 20g on an S1 interface of a first PLC man-machine control system, connecting a first peristaltic pump S2 with a first liquid inlet storage bottle S9(0.1MNaOH) and a lower end port S6 of a chromatographic column S4, connecting an upper end port S5 of the chromatographic column with a TOC bottle arranged on the electronic balance S3, adjusting the flow rate of the first peristaltic pump S2 to be 0.3ml/min, clicking an interface start option, taking a water sample from the TOC bottle, adjusting the obtained sample to be neutral by using 35% HCl, and determining DOC (NPOC), wherein the DOC _ BN is a 0.1MNaOH alkali elution blank value DAX _ BN of DAX-9;
a first peristaltic pump S2 is connected with a first liquid inlet storage bottle S10(UPW), and the resin is washed by pure water at the flow rate of 0.8ml/min until the effluent is neutral;
setting a target weight value of an electronic balance S3 to be 20g on an S1 interface of a first PLC man-machine control system, connecting a first peristaltic pump S2 with a liquid inlet storage bottle S8(0.1MHCl) and a lower end port S6 of a chromatographic column S4, connecting an upper end port S5 of the chromatographic column with a TOC bottle arranged on the electronic balance S3, adjusting the flow rate of the first peristaltic pump S2 to be 0.3ml/min, clicking an interface start option, taking a water sample by using the TOC bottle, and measuring a DOC of the obtained sample, wherein the DOC is a 0.1MHCl acid elution blank value DAX _ BH of DAX-8;
a first peristaltic pump S2 is connected with a first liquid inlet storage bottle S10(UPW), and the resin is washed by pure water at the flow rate of 0.8ml/min until the effluent is neutral;
setting an electronic balance S3 target weight value to be 20g on an S1 interface of a first PLC man-machine control system, connecting a port S5 at the upper end of a chromatographic column with a TOC bottle arranged on the electronic balance S3, clicking an interface start option, adjusting the flow rate of a first peristaltic pump S2 to be 0.8ml/min, taking a water sample by using the TOC bottle, and measuring a DOC (Doc) of the obtained sample, wherein the DOC is a water elution blank value DAX _ BW of DAX-8;
(2) separation process of sample hydrophobic substance
Setting an electronic balance S3 target weight value to be 200g (or adjusting according to the sample demand) on an S1 interface of a first PLC man-machine control system, connecting a first peristaltic pump S2 with a first liquid inlet storage bottle S7 and an upper end port S5 of a chromatographic column S4, connecting a lower end port S6 of the chromatographic column with a first eluent storage bottle S12 arranged on the electronic balance S3, adjusting the flow rate of the first peristaltic pump S2 to be 0.8ml/min, clicking an interface start option, namely starting a positive leaching process, obtaining eluent by using the first eluent storage bottle S12, sealing the obtained eluent by using tin foil and placing the obtained eluent in an environment below 25 ℃ to be protected from light for storage;
setting a target weight value of an electronic balance S3 to be 20g (the weight value can also be adjusted according to needs) on an S1 interface of a first PLC man-machine control system, connecting a first peristaltic pump S2 with a first liquid inlet storage bottle S8(0.1MHCl) and a lower end port S6 of a chromatographic column S4, connecting an upper end port S5 of the chromatographic column with a first eluent storage bottle S13 arranged on the electronic balance S3, adjusting the flow rate of the first peristaltic pump S2 to be 0.3ml/min, clicking an interface start option, namely starting a reverse leaching process, obtaining eluent by using a first eluent storage bottle S13, and measuring the DOC value of the eluent to be DOC2, namely an HOB component;
adjusting the pH value of liquid in a first eluent storage bottle S12 to 2.0-2.5, placing the liquid in a first liquid inlet storage bottle S11, connecting a first peristaltic pump S2 with the first liquid inlet storage bottle S11 and an upper end port S5 of a chromatographic column S4, connecting a lower end port S6 of the chromatographic column S4 with the first eluent storage bottle S14, setting the weight value of required eluent to be 200g (or adjusting the weight value according to requirements) on an interface of a first PLC (programmable logic controller) man-machine control system S1, adjusting the flow rate of the first peristaltic pump S2 to be 0.8ml/min, clicking an interface start button to start the positive leaching process again, obtaining the eluent from the first eluent storage bottle S14, and measuring the DOC value to be DOC4, namely an HIS component;
setting a target weight value of an electronic balance S3 to be 20g (the weight value can also be adjusted according to needs) on an S1 interface of a first PLC man-machine control system, connecting a first peristaltic pump S2 with a first liquid inlet storage bottle S9(0.1MNaOH) and a lower end port S6 of a chromatographic column S4, connecting an upper end port S5 of the chromatographic column with a first eluent storage bottle S15 arranged on the electronic balance S3, adjusting the flow rate of the first peristaltic pump S2 to be 0.3ml/min, clicking an interface start option, namely starting a reverse leaching process, obtaining eluent by using a first eluent storage bottle S15, and measuring the DOC value of the eluent to be DOC3, namely an HOA component;
performing Soxhlet extraction on DAX-8 resin in a chromatographic column S4 for 24h with chromatographic grade anhydrous methanol, concentrating and evaporating to dryness to 20ml with a rotary evaporator, blow-drying methanol with a nitrogen blower, dissolving the residual solid, namely HON component, with quantitative UPW, and determining DOC value to be DOC 5.
4. Separation process of sample hydrophilic substance
(1) Determination of blank value of anion-cation resin
The second liquid inlet storage bottles Q18, Q19, Q20 and Q21 are respectively filled with 0.1MNaOH, UPW, 0.1MNaOH and 0.1 MNaOH;
a port "9" of the first 12-direction switching valve Q3 is connected with the second liquid inlet storage bottle Q18, a port "a" of the first 12-direction switching valve Q3 is connected with the second liquid inlet storage bottle Q19, a port "9" of the second 12-direction switching valve Q4 is connected with the second eluent storage bottle Q22, a port "9" of the third 12-direction switching valve Q5 is connected with the second eluent storage bottle Q26, a port "a" of the third 12-direction switching valve Q5 is connected with the second eluent storage bottle Q27, the flow rate of the second peristaltic pump Q6 is set to 0.8ml/min, the stabilization time is set to 60min, the cation blank sampling time is set to 35min, the anion and cation tandem system blank sampling time is set to 35min, the cleaning time is set to 60min, the start button is clicked, and after the operation is finished, measuring DOC values in Q22, Q26 and Q27, which are respectively 0.1MNaOH alkali elution blank CB of cation exchange resin, 0.1MNaOH alkali elution blank NB of anion exchange resin and water washing blank SB of anion-cation series system;
(2) separation process of sample hydrophilic substance
A port 1 of the first 12-direction switching valve Q3 is connected with a first eluent storage bottle S14 (namely DOC4 and HIS components) in the hydrophobic separation process, a port 1 of the third 12-direction switching valve Q5 is connected with a second eluent storage bottle Q29, the flow rates of the second peristaltic pump Q2 are all 0.8ml/min, the stabilization time is set to 60min on a Q1 interface of the second PLC man-machine control system, the sampling time of anion resin is set to 35min, the separation process of the Q1 interface of the second PLC man-machine control system is started after the stabilization process is finished, at the moment, the liquid obtained from the Q29 is the HIN component, and the DOC value is measured to be DOC 6;
two ports 'B' and 'C' of a first 12-direction switching valve Q3 are respectively connected with a second liquid inlet storage bottle Q20 and a second liquid inlet storage bottle Q21, a port 'B' of a second 12-direction switching valve Q4 is connected with a second eluent storage bottle Q24, a port 'C' of a third 12-direction switching valve Q5 is connected with a second eluent storage bottle Q28, the elution time of cation exchange resin is set to be 80min, the elution time of anion exchange resin is set to be 80min, the flow rate of a second peristaltic pump Q2 is 0.3ml/min, the elution process of an interface of a second PLC control system Q1 is started, at the moment, a substance obtained from Q24 is a HIB component, the DOC value is measured to be DOC7, the component obtained from Q28 is measured to be a HIA component, and the DOC value is measured to be DOC 8;
if a plurality of samples exist, only 2-8 ports of the first 12-direction switching valve Q3 are needed to correspond to different samples, and the stabilizing process, the separating process and the eluting process are carried out according to the steps.
5. Calculation of the content of each component
The content of each component of the soluble organic matter in the sample can be calculated according to the following formula:
HOB (DOC2-DAX _ BH) × amount of eluent/sample injection
HOA (DOC3-DAX _ BN). times.elution liquid amount/sample amount
HON (DOC5-DAX _ BW) Xthe amount of eluent/sample
(DOC7-CB) times amount of eluent/sample injection
(DOC 8-NB). times.eluent/sample size
HIN＝DOC6-SB
Example 1: separation result of two-stage effluent components of different water plants
The second grade effluent from different water plants was obtained, filtered through 0.45 micron filtration membranes and tested repeatedly using the apparatus and method set up in this patent, and the results of the component separations are shown in table 2.
TABLE 2 separation results of hydrophilic and hydrophobic organic substances in secondary effluent of different waterworks
Figure BDA0001326967420000101
As can be seen from Table 2, the automatic device and the method for separating the components of the soluble organic matters in the water, which are established by the patent, have better repeatability and more reliable results; the proportions of the components of the secondary water of different water plants are different, so that the pre-membrane pretreatment process of the regenerated water plant can be specifically removed by selecting different treatment methods according to the analysis result of the components of the secondary water of each water plant.
The separation results of the soluble organic components in the second-level water of different water plants are shown in the attached figure 4.
The above embodiments describe the technical solutions of the present invention in detail. It will be clear that the invention is not limited to the described embodiments. Based on the embodiments of the present invention, those skilled in the art can make various changes, but any changes equivalent or similar to the present invention are within the protection scope of the present invention.

Claims (3)

1. A method for separating water soluble organic components based on macroporous adsorption resin and anion-cation exchange resin is characterized in that: separating organic matters in a water sample to be analyzed into four components of a hydrophobic acidic substance HOA, a hydrophobic alkaline substance HOB, a hydrophobic neutral substance HON and a hydrophilic substance HIS by using macroporous adsorption resin DAX-8, and then separating the HIS component into three components of the hydrophilic acidic substance HIA, the hydrophilic alkaline substance HIB and the hydrophilic substance HIN by using cation exchange resin MSC-H and anion exchange resin AIIIS; when the macroporous adsorption resin is filled, a space of 3-5mm is reserved above the resin so as to facilitate air exhaust;
the method uses an automated apparatus for separating water-soluble organic components based on macroporous adsorbent resins and anion-cation exchange resins, the apparatus comprising: the separation device comprises a hydrophobic substance separation part and a hydrophilic substance separation part, wherein the hydrophobic substance separation part comprises a first PLC (programmable logic controller) man-machine control system, a first peristaltic pump, an electronic balance, a phi 10mm multiplied by 10mm chromatographic column, a plurality of first feed liquid storage bottles and a plurality of first eluent storage bottles, wherein the chromatographic column is used for filling DAX-8 adsorption resin; the first peristaltic pump is respectively connected with a first liquid inlet storage bottle and an upper end port of the phi 10mm multiplied by 10mm chromatographic column, a lower end port of the phi 10mm multiplied by 10mm chromatographic column is connected with a first eluent storage bottle arranged on the electronic balance, and the electronic balance is connected with a first PLC man-machine control system; the first liquid inlet storage bottle is respectively used for containing liquid to be separated, 0.1MHCl, 0.1MNaOH and UPW; the first eluent storage bottles are respectively used for containing the eluent of the liquid to be separated in the first liquid inlet storage bottles after passing through the adsorption resin; the hydrophilic substance separation part comprises a second PLC man-machine control system, a second peristaltic pump, a 12-direction switching valve, an electromagnetic valve, a phi 15mm multiplied by 15mm chromatographic column for filling cation exchange resin, a phi 15mm multiplied by 15mm chromatographic column for filling anion exchange resin, a plurality of second liquid inlet storage bottles and a plurality of second eluent storage bottles; the second peristaltic pump is respectively connected with the 12-direction switching valve and the electromagnetic valve, and further connected with a phi 15mm multiplied by 15mm chromatographic column used for filling cation exchange resin and a phi 15mm multiplied by 15mm chromatographic column used for filling anion exchange resin, the 12-direction switching valve is also respectively connected with a second liquid inlet storage bottle and a second eluent storage bottle, and the second liquid inlet storage bottle is respectively used for containing 0.1MNaOH, UPW, 0.1MNaOH and 0.1 MNaOH;
the hydrophilic substance separation part comprises a second PLC man-machine control system (Q1), a second peristaltic pump (Q2), a first 12-direction switching valve (Q3), a second 12-direction switching valve (Q4), a third 12-direction switching valve (Q5), a phi 15mm multiplied by 15mm chromatographic column (Q6) filled with cation exchange resin, a phi 15mm multiplied by 15mm chromatographic column (Q7) filled with anion exchange resin, a first electromagnetic valve (Q8), a second electromagnetic valve (Q9), a third electromagnetic valve (Q10), a fourth electromagnetic valve (Q11), a fifth electromagnetic valve (Q12), a sixth electromagnetic valve (Q13), a first three-way pipe (Q13), a second three-way pipe (Q13), a third three-way pipe (Q13), a fourth three-way pipe (Q13), a second liquid inlet bottle (Q13, Q13 and Q13).
2. The method of claim 1, further comprising: when the volume of the liquid to be separated is 200ml, the loading of the macroporous adsorption resin DAX-8 is 3ml, the loading of the cation exchange resin MSC-H is 6ml, and the loading of the anion exchange resin AIIIS is 12 ml.
3. The method as claimed in claim 1, wherein the inlet and outlet pipes of the upper and lower ports of the chromatography column can be manually switched at any time.
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