CN111103216A - Film diffusion gradient DGT (differential global temperature sensor) collecting device for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radical in environment and production method thereof - Google Patents
Film diffusion gradient DGT (differential global temperature sensor) collecting device for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radical in environment and production method thereof Download PDFInfo
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 37
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 32
- 239000010452 phosphate Substances 0.000 title claims abstract description 22
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 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 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002033 PVDF binder Substances 0.000 claims abstract description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
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- 230000001360 synchronised effect Effects 0.000 claims abstract description 5
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- 239000003463 adsorbent Substances 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
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- 230000008569 process Effects 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
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- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
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- 238000009835 boiling Methods 0.000 claims description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
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- QALQXPDXOWOWLD-UHFFFAOYSA-N [N][N+]([O-])=O Chemical compound [N][N+]([O-])=O QALQXPDXOWOWLD-UHFFFAOYSA-N 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 13
- 239000011574 phosphorus Substances 0.000 abstract description 13
- 238000004458 analytical method Methods 0.000 abstract description 10
- 238000000605 extraction Methods 0.000 abstract description 9
- 235000015097 nutrients Nutrition 0.000 abstract description 8
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- 238000006722 reduction reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 14
- 239000010409 thin film Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D71/06—Organic material
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- 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
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- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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Abstract
The invention discloses a method for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radical in environmentThe film Diffusion Gradient (DGT) device comprises a PVDF filter membrane, a diffusion membrane and an adsorption fixed membrane which are sequentially arranged from outside to inside, wherein the adsorption fixed membrane takes agarose as a carrier and is loaded with NO3-N adsorbing material, NH4-an N adsorbing material and a phosphate adsorbing material, the thickness and pore size of the PVDF filter membrane being 100 ± 20 μm and 0.45 ± 0.1 μm, respectively. The device realizes synchronous acquisition and analysis of nitrogen and phosphorus in water, sediments and soil, and the accuracy of acquisition, extraction, reduction and analysis of nitrogen and phosphorus can reach 95.6 percent respectively; the invention has high DGT capacity of nitrogen and phosphorus and has higher nutrient substance adsorption upper limit; meanwhile, the invention has extremely high fixed adsorption rate and extraction rate for ammonium nitrogen and nitrate nitrogen.
Description
Technical Field
The invention belongs to the technical field of enrichment, collection and analysis of nutrient elements in an environmental medium, and particularly relates to collection of nitrogen and phosphorus elements in water, sediments and soil.
Background
Currently, active phosphorus and nitrogen in the environment are generally determined in an active mode, that is, a collected sample is sent back to a laboratory for analysis. Because the sample can be changed in form in the processes of collection, transmission and treatment, the currently developed passive sampling analysis mode thin film diffusion gradient technology DGT can be used for carrying out in-situ enrichment on a fixed gel thin film capable of absorbing elements such as phosphorus, nitrogen, sulfur, heavy metals and the like in an environment, and analyzing the fixed gel thin film after the fixed gel thin film is taken out, thereby indirectly obtaining the information of the elements such as active nitrogen, phosphorus, sulfur, heavy metals and the like in the environment. However, the existing fixed gel film can only selectively adsorb single elements, so that the efficiency of analysis and determination is low, and in-situ synchronous enrichment detection cannot be realized. In addition, NO is mainly present due to nitrogen in the natural environment3-N and NH4The adsorption rate of the existing direct adsorption gel is too consistent and poor, and the adsorption rate is not enough.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the existing problems and defects, the invention aims to provide a film diffusion gradient DGT acquisition device for synchronously acquiring ammonia nitrogen, nitrate nitrogen and phosphate radical in the environment and a production and preparation method thereof, the device realizes synchronous acquisition and analysis of nitrogen and phosphorus in water, sediments and soil, and the acquisition, extraction, reduction and analysis accuracy of nitrogen and phosphorus can reach 95.6 percent respectively; the invention has high DGT capacity to nitrogen and phosphorus and higher nutrient substance adsorption upper limit; meanwhile, the invention has extremely high fixed adsorption rate and extraction rate for ammonium nitrogen and nitrate nitrogen.
The technical scheme is as follows: in order to realize the purpose, the invention adopts the following technical scheme: a film diffusion gradient DGT (differential global temperature coefficient) acquisition device for synchronously acquiring ammonia nitrogen, nitrate nitrogen and phosphate radicals in an environment comprises a PVDF (polyvinylidene fluoride) filter membrane, a diffusion membrane and a composite membrane of an adsorption fixed membrane which are sequentially arranged from outside to inside, wherein the adsorption fixed membrane takes agarose as a carrier and is loaded with NH (hydrogen sulfide)4-N adsorbent material, NO3-an N adsorbing material and a phosphate adsorbing material, the thickness and pore size of the PVDF filter membrane being 100 ± 20 μm and 0.45 ± 0.1 μm, respectively; the NH4the-N adsorption material is NH with a macroporous structure matrix loaded with sulfonic acid active groups4-an N adsorbent material; said NO3the-N adsorbing material adopts palygorskite loaded with an active substance of polyammonium methacrylate.
Furthermore, the composite membrane device also comprises a base and an annular upper cover buckled on the base, wherein the base is provided with a boss for containing the composite membrane, and the inner side of the annular upper cover is composed of fin feet arranged at intervals.
Further, the thickness of the adsorption and fixation film is 0.4 mm.
Further, the diffusion membrane is an agarose diffusion membrane.
The invention also provides a production and preparation method of the device, which is characterized by comprising the following steps:
(1) the NH4-preparation of N-adsorption material: grinding and sieving a macroporous structure substrate, adding 4-vinylbenzenesulfonic acid with the mass ratio of 1 (1.2-2.5), performing high-speed dispersion in a high-speed dispersion instrument, and drying at 30-60 ℃ for 12-24 hours for later use; said NO3-preparation of N-adsorption material: grinding and sieving palygorskite, adding ammonium polymethacrylate in the mass ratio of 1 (1.2-2.5)And after high-speed dispersion is carried out in a high-speed dispersion instrument, drying for 12-24h at the temperature of 30-60 ℃ for later use;
(2) reacting NH4-N adsorbent material and NO3-N adsorbing materials are soaked in sodium chloride solution for at least 24 hours respectively and then are repeatedly soaked and washed by deionized water; NH after soaking and rinsing4-N adsorbent material and NO3Drying the N adsorbing material to be semi-dry at the temperature of 30-60 ℃;
(3) adding NO3-N sorbent material was ground to 70 ± 5 μm by mortar; reacting NH4-grinding the N-adsorbing material to a particle size of 5 ± 1 μm by means of a ball mill;
(4) mixing agarose and water according to the mass volume ratio of 3%, heating and boiling the mixture, keeping the temperature of the mixture within the range of 80-90 ℃, adding 2mM NaCl, stirring and dissolving the mixture to form a uniform solution, and sequentially adding NO which is ground in the step (2) and has the total mass volume ratio of 30-60%3-N adsorbent material and NH4-an N adsorbent material;
(5) then, adding 10-25% of Zr-oxide powder at the temperature of 80-90 ℃ under the stirring condition, and stirring and dispersing uniformly;
(6) injecting the mixed solution obtained in the step (4) into a preheated glass mold in a vacuum-pumping environment, and naturally cooling at room temperature to obtain an adsorption fixed film; and finally, stacking the adsorption fixed membrane, the diffusion membrane and the PVDF filter membrane on a boss of the base in sequence, and tightly buckling the adsorption fixed membrane, the diffusion membrane and the PVDF filter membrane by using an annular upper cover to finish the process.
Further, the macroporous structure matrix material is one of zeolite, palygorskite, attapulgite, medical stone, diatomite and bentonite.
Further, NH in the agarose solution is added in the step (3)4-N adsorbent material and NO3The mass ratio of the N adsorbing material to the N adsorbing material is 1 (0.7-1.0).
Further, in the agarose solution in step (3), NH4-N adsorbent material and NO3Adding NH into the-N adsorbing material at a mass ratio of 1:14-N adsorbent material and NO3The N adsorbing material accounts for 35% of the total mass volume of the agarose solution; the mass volume ratio of the added Zr-oxide powder is 15%.
Has the advantages that: compared with the prior art, the invention has the following advantages: the device realizes synchronous acquisition and analysis of nitrogen and phosphorus in water, sediments and soil, and the acquisition-extraction-reduction analysis accuracy of the nutrient elements of nitrogen and phosphorus can reach 95.6 percent respectively; the invention has high DGT capacity to nitrogen and phosphorus and higher nutrient substance adsorption upper limit; meanwhile, the invention has extremely high fixed adsorption rate and extraction rate for ammonium nitrogen and nitrate nitrogen.
Drawings
FIG. 1 is a schematic structural diagram of a thin film diffusion gradient DGT collection Device (DGT) for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radicals in the environment of the invention;
FIG. 2 shows the NO pair of a film diffusion gradient DGT collecting Device (DGT) for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radical in the environment of the invention3-N、NH4-N and PO4-graph of adsorption capacity versus P;
FIG. 3 is a comparison graph of the influence of lake water pH on a thin film diffusion gradient DGT collection Device (DGT) for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radicals in the environment of the present invention;
FIG. 4 shows the determination of NO by a thin film diffusion gradient DGT collection Device (DGT) for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radical in the environment of the invention3-N、NH4-N and PO4Respectively receive Na when-P is+Effect of concentration versus plot;
film diffusion gradient DGT (differential global DGT) acquisition device for synchronously acquiring ammonia nitrogen, nitrate nitrogen and phosphate radical in environment
Wherein, the base 1, the boss 2, the adsorption fixed membrane 3, the diffusion membrane 4, the PVDF filter membrane 5, the annular upper cover 6.
Detailed Description
The present invention is further illustrated by the following figures and specific examples, which are to be understood as illustrative only and not as limiting the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
As shown in figure 1, the thin film diffusion gradient DGT collecting device for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radical in the environment comprises a core component composite film, a PVDF filter membrane, a diffusion membrane and an adsorption fixed membrane which are sequentially arranged from outside to inside, wherein the adsorption fixed membrane takes agarose as a carrier and is loaded with NH4-N adsorbent material, NO3-an N adsorbing material and a phosphate adsorbing material, the thickness and pore size of the PVDF filter membrane being 100 ± 20 μm and 0.45 ± 0.1 μm, respectively; the thickness of the adsorption and fixation film is 0.4 mm; the diffusion membrane also uses agarose as the diffusion membrane material. The preparation method of the adsorption and fixation membrane comprises the following specific steps:
firstly, respectively weighing attapulgite and 4-vinyl benzene sulfonic acid according to the mass ratio of 1:1.5, grinding in a grinding machine, sieving by a 50-mesh sieve, mixing, uniformly dispersing in a high-speed dispersion instrument, and finally drying at 40-50 ℃ to obtain NH4-N adsorbent material, ready for use; NO3The N adsorbing material is prepared by mixing and dispersing palygorskite and ammonium polymethacrylate in a mass ratio of 1:2 at a high speed, and drying at about 40 ℃ for 12-24h, wherein the pore channels of the palygorskite are sufficiently covered with water for nitryl nitrogen to permeate and be adsorbed.
To reduce NO3-N adsorbent material and NH4A blank of an N adsorbing material, wherein the adsorbing material needs to be soaked in 1M NaCl solution for 24 hours and then repeatedly soaked and washed by deionized water; in order to keep the activity of the adsorbing material and avoid damaging functional groups on the adsorbing material in the process of drying the adsorbing material to be completely dry at high temperature, the adsorbing material is dried to be semi-dry at 50 ℃, and no water is required to be dropped.
Due to NO3-N adsorbent material and NH4Under the condition that the particle size of the N adsorbing material is the same, the N adsorbing material is easy to agglomerate when mixed in a solution. Thus, the present invention was ground to different particle sizes with a ball mill and a mortar, respectively, due to NH4The density of the N adsorbent material is high, and NH is used to keep the mass of the two adsorbent materials the same4The N-adsorbing material is milled with a ball mill to a smaller particle size: semi-dry NH4Grinding the N-adsorbing material with a ball mill at a rotation speed of 500r/min for 6 hours to obtain NH4Grinding the grain diameter of the-N adsorbing material to 5 +/-2 mum; semi-dried NO3The N-adsorbing material was ground to 74. + -. 5 μm with a mortar.
To avoid NO3-N adsorbent material and NH4The N-adsorbing material was coagulated in an agarose solution, and 2mM NaCl was added at the time of preparing a 2.5% (m/v) hot agarose solution (80 ℃ C.). Boiling 2.5% (m/v) agarose, maintaining at 80 deg.C, adding 2mM NaCl, and accurately weighing 1.0g NH with particle size of 5 μm4Adding the N adsorbing material powder into 5mL of the hot agarose solution, and uniformly stirring at 80 ℃; then 0.8g of NO with a particle size of 74 μm was accurately weighed3Adding N adsorbing material powder into the hot mixed solution, and uniformly stirring at 80 ℃; finally, 0.5g of Zr-oxide powder having a water content of 47% was accurately weighed and stirred at 80 ℃. NH destruction due to prolonged high temperature conditions4Activity of N adsorbent material, therefore, NO addition first3-N adsorbent material, plus NH4-N adsorbing material, and finally adding Zr-oxide powder.
And finally, injecting the mixed solution into a preheated glass mold in a vacuum-pumping environment, naturally cooling at room temperature to obtain an adsorption and fixation membrane, taking out the adsorption and fixation membrane, soaking in deionized water, changing water every 3 hours, and soaking to remove NaCl on the membrane. And finally, stacking the adsorption fixed membrane, the diffusion membrane and the PVDF filter membrane on a boss of the base in sequence, and tightly buckling the adsorption fixed membrane, the diffusion membrane and the PVDF filter membrane by using an annular upper cover to finish the process. The performance test of the film diffusion gradient DGT acquisition device for synchronously acquiring ammonia nitrogen, nitrate nitrogen and phosphate radical in the environment is carried out as follows:
(1) adsorption and extraction rates of the adsorption film
Soaking the adsorption membrane in a solution containing 2 mg/L NO3-N、2 mg/L NH4-N and 1 mg/L PO4A mixed solution of P and 0.001M NaCl, and soaked at 25 ℃ for 24 hours (pH 5.5). The adsorption rate of the membrane to the three nutrients can be calculated by measuring the concentration of the solution before and after 24 hours of membrane release. Then the adsorption membrane is taken out of the solution and immersed in 20 ml of 1.0M NaCl for 24 hours to extract NO3-N and NH4N, then the adsorption membrane is immersed in 20 ml of 1.0M NaOH for 24 hours to extract PO4-P。And calculating the extraction rate. The results are as follows: adsorption film pair NO3-N, NH4-N and PO4The adsorption rates of-P were 91.6. + -. 0.6%, 93.0. + -. 0.8% and 95.6. + -. 0.3%, respectively. 1.0M NaCl to NO3-N and NH4The extraction rates of-N were 100.5. + -. 1.6% and 84.3. + -. 1.5%, respectively. 1.0M NaOH on PO4The extraction rate of-P was 95.5. + -. 0.7%.
（4）NO3-N, NH4-N and PO4DGT Capacity of-P
The large DGT capacity ensures that the accumulation amount does not approach the adsorption upper limit of the adsorption film during long-term use of the device. The DGT capacities of the three nutrients were investigated by immersing the DGT device in a high concentration mixed solution containing the three nutrients. NO3-N, NH4-N and PO4The accumulated amount of-P stabilizes at 8, 5 and 7 hours, respectively. The results shown in fig. 2 indicate that: NO3-N, NH4-N and PO4The DGT capacities of P were 659.4, 446.8 and 127.8. mu.g/device, respectively.
(5) Determination of NO by pH and ionic Strength versus DGT3-N, NH4-N and PO4Influence of-P
If DGT is calculated concentration (C DGT) And actual concentration of solution: (C Sol) Ratio of (C DGT/C Sol) Between 0.9 and 1.1, it can be shown that the determination of DGT is reliable. The experimental results shown in fig. 3 show that: in the pH value range of 3.2-8.7,C DGT/C Solthe values are all between 0.9 and 1.1, indicating that the DGT is on NO in the pH range 3.2-8.73-N, NH4-N and PO4The measurement of-P is not affected.
In addition, the applicant also tested Na+The effect on the DGT assay, as shown in figure 4, is shown by the experimental results: for NO3-N、NH4-N and PO4Maximum Na unaffected by P determination+The concentrations were 10, 5 and 750 mM, respectively.
Finally, applying the DGT device of the present invention in an aqueous environment, the target in the water undergoes a transition from advection to diffusion in a so-called Diffusion Boundary Layer (DBL). This studyThe calculated DBL thicknesses were basalt lake (0.24 cm), pearl river (0.18 cm), respectively. When the DGT of the device of the invention calculates the concentration (C DGT) And actual concentration of solution: (C Sol) Ratio of (C DGT/C Sol) Between 0.9 and 1.1, it can be shown that the determination of DGT is reliable. The device is put into the water, takes out every 3 days and washes once to avoid the surface to adhere to the biomembrane, blockked target substance and adsorbed by the adsorption film, discover through the comparative result: the device for washing the water-containing biological material,C DGT/C Solvalues between 0.9 and 1.1 illustrate the reliability stability of the DGT device of the present invention.
Claims (9)
1. The utility model provides a film diffusion gradient DGT collection system of synchronous collection ammonia nitrogen, nitro-nitrogen and phosphate radical in environment which characterized in that: the composite membrane comprises a PVDF filter membrane, a diffusion membrane and an adsorption fixed membrane which are sequentially arranged from outside to inside, wherein the adsorption fixed membrane takes agarose as a carrier and is loaded with NH4-N adsorbent material, NO3-an N adsorbing material and a phosphate adsorbing material, the thickness and pore size of the PVDF filter membrane being 100 ± 20 μm and 0.45 ± 0.1 μm, respectively; the NH4the-N adsorption material is NH with a macroporous structure matrix loaded with sulfonic acid active groups4-an N adsorbent material; said NO3the-N adsorbing material adopts palygorskite loaded with an active substance of polyammonium methacrylate.
2. The film diffusion gradient DGT collecting device for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radical in the environment as claimed in claim 1, wherein: the composite membrane packaging machine is characterized by further comprising a base and an annular upper cover buckled on the base, wherein the base is provided with a boss for containing a composite membrane, and the inner side of the annular upper cover is composed of fin feet arranged at intervals.
3. The film diffusion gradient DGT collecting device for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radical in the environment as claimed in claim 1, wherein: the thickness of the adsorption and fixation film is 0.4 mm.
4. The film diffusion gradient DGT collecting device for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radical in the environment as claimed in claim 1, wherein: the diffusion membrane is an agarose diffusion membrane.
5. The film diffusion gradient DGT collecting device for synchronously collecting ammonia nitrogen, nitrate nitrogen and phosphate radical in the environment as claimed in claim 1, wherein: the phosphate radical adsorption material adopts Zr-oxide powder.
6. A method for manufacturing a device according to any one of claims 1 to 5, characterized in that it comprises the following steps:
(1) the NH4-preparation of N-adsorption material: grinding and sieving a macroporous structure substrate, adding 4-vinylbenzenesulfonic acid with the mass ratio of 1 (1.2-2.5), performing high-speed dispersion in a high-speed dispersion instrument, and drying at 30-60 ℃ for 12-24 hours for later use; said NO3-preparation of N-adsorption material: grinding and sieving palygorskite, adding ammonium polymethacrylate with the mass ratio of 1 (1.2-2.5), performing high-speed dispersion in a high-speed dispersion instrument, and drying at 30-60 ℃ for 12-24h for later use;
(2) reacting NH4-N adsorbent material and NO3-N adsorbing materials are soaked in sodium chloride solution for at least 24 hours respectively and then are repeatedly soaked and washed by deionized water; NH after soaking and rinsing4Drying the-N adsorbing material and the NO3-N adsorbing material to be semi-dry at the temperature of 30-60 ℃;
(3) adding NO3-N sorbent material was ground to 70 ± 5 μm by mortar; reacting NH4-grinding the N-adsorbing material to a particle size of 5 ± 1 μm by means of a ball mill;
(4) mixing agarose and water according to the mass volume ratio of 3%, heating and boiling, keeping the mixture at the temperature of 80-90 ℃, adding 2mM NaCl, stirring and dissolving to form a uniform solution, and sequentially adding the NO3-N adsorbing material and the NH4-N adsorbing material which are ground in the step (2) and have the total mass volume ratio of 30-60%;
(5) then, adding 10-25% of Zr-oxide powder at the temperature of 80-90 ℃ under the stirring condition, and stirring and dispersing uniformly;
(6) injecting the mixed solution obtained in the step (4) into a preheated glass mold in a vacuum-pumping environment, and naturally cooling at room temperature to obtain an adsorption fixed film; and finally, stacking the adsorption fixed membrane, the diffusion membrane and the PVDF filter membrane on a boss of the base in sequence, and tightly buckling the adsorption fixed membrane, the diffusion membrane and the PVDF filter membrane by using an annular upper cover to finish the process.
7. Method for the production of a device according to claim 6, characterized in that: the macroporous structure matrix material is one of zeolite, palygorskite, attapulgite, medical stone, diatomite and bentonite.
8. Method for the production of a device according to claim 6, characterized in that: adding NH in the agarose solution in the step (3)4-N adsorbent material and NO3The mass ratio of the N adsorbing material to the N adsorbing material is 1 (0.7-1.0).
9. Method for the production of a device according to claim 6, characterized in that: NH in the agarose solution in step (3)4-N adsorbent material and NO3Adding NH into the-N adsorbing material at a mass ratio of 1:14-N adsorbent material and NO3The N adsorbing material accounts for 35% of the total mass volume of the agarose solution; the mass volume ratio of the added Zr-oxide powder is 15%.
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