CN109900673B - Method for improving the detection sensitivity of heavy metal elements in biomass tar - Google Patents
Method for improving the detection sensitivity of heavy metal elements in biomass tar Download PDFInfo
- Publication number
- CN109900673B CN109900673B CN201910316929.8A CN201910316929A CN109900673B CN 109900673 B CN109900673 B CN 109900673B CN 201910316929 A CN201910316929 A CN 201910316929A CN 109900673 B CN109900673 B CN 109900673B
- Authority
- CN
- China
- Prior art keywords
- solution
- heavy metal
- tar
- detection
- detected
- 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.)
- Active
Links
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 51
- 238000001514 detection method Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002028 Biomass Substances 0.000 title claims abstract description 21
- 230000035945 sensitivity Effects 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008139 complexing agent Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000002189 fluorescence spectrum Methods 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 claims description 6
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 27
- 239000011269 tar Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 24
- 239000000523 sample Substances 0.000 description 15
- 235000013824 polyphenols Nutrition 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CFPFMAGBHTVLCZ-UHFFFAOYSA-N (4-chlorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(Cl)C=C1 CFPFMAGBHTVLCZ-UHFFFAOYSA-N 0.000 description 2
- CXVOIIMJZFREMM-UHFFFAOYSA-N 1-(2-nitrophenoxy)octane Chemical compound CCCCCCCCOC1=CC=CC=C1[N+]([O-])=O CXVOIIMJZFREMM-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000005375 photometry Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- QKAOOWJWWKWWOZ-UHFFFAOYSA-N 1-isothiocyanato-2-methoxybenzene Chemical compound COC1=CC=CC=C1N=C=S QKAOOWJWWKWWOZ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical compound Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- DEGAKNSWVGKMLS-UHFFFAOYSA-N calcein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(CN(CC(O)=O)CC(O)=O)=C(O)C=C1OC1=C2C=C(CN(CC(O)=O)CC(=O)O)C(O)=C1 DEGAKNSWVGKMLS-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000012629 conventional elemental analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000009585 enzyme analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002536 laser-induced breakdown spectroscopy Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229960002378 oftasceine Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Images
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention provides a method for improving detection sensitivity of heavy metal elements in biomass tar, which comprises the following steps: (1) dissolving a quantitative tar sample in a quantitative methanol solution; (2) adding a complexing agent solution into the solution prepared in the step (1) to obtain a solution to be detected; (3) placing the solution to be detected in a detection pool, and detecting the fluorescence spectrum performance of the solution to be detected; and (4) comparing the fluorescence spectrum performance of the solution to be detected with the fluorescence spectrum performance of the standard substance, and calculating the content of heavy metal elements in the tar. The method has high detection sensitivity and selectivity for heavy metal ions.
Description
Technical Field
The invention belongs to the technical field of detection, and particularly relates to a method for improving detection sensitivity of heavy metal elements in biomass tar.
Background
Compared with common oil products such as fuel oil and edible oil, the biomass tar has very complex components, contains various condensed ring compounds, phenolic compounds and the like, and also contains heavy metal ions, alkali metals, acids, gases, alkaline gases and the like. Measurement techniques for these contaminants enable the determination of tar cleanliness levels and assessment of quality for subsequent applications such as engine use. The nickel and vanadium elements in the biomass tar can cause the poisoning of a catalyst used in the subsequent deep processing of the coal tar, so that the catalyst loses activity and loses effectiveness, and on the other hand, the coal tar can generate corrosive products in the combustion process to cause equipment corrosion, so that the accurate determination of the nickel, iron and vanadium contents in the coal tar is particularly important. The commonly used test methods are spectrophotometry and atomic absorption, the two measurement methods are complicated to operate, various metal elements interfere with each other, and corresponding reagents are required to be added to eliminate the interference so as to measure the corresponding elements.
CN105466982B discloses a method for detecting heavy metals in water, which comprises the following steps: (A1) sending the liquid with the volume of V0 and containing the heavy metal ions to be detected to a detection pool to obtain the peak current value P01 for dissolving out the heavy metal ions to be detected; (A2) sending a water sample with the volume of V1 to the detection pool, and mixing the water sample with liquid in the detection pool to obtain a peak current value Ps for dissolving out the heavy metal ions to be detected; (A3) discharging the mixed liquid in the detection pool, and cleaning the detection pool; (A4) sending the liquid with the volume of V0 and containing the heavy metal ions to be detected to a detection pool to obtain the peak current value P02 for dissolving out the heavy metal ions to be detected; (A5) and (3) sending the heavy metal ion correction liquid to be detected with the volume of V1 to the detection pool, and mixing the heavy metal ion correction liquid with the liquid in the detection pool to obtain the peak current value Pb dissolved out by the heavy metal ions to be detected.
CN108051426A discloses a heavy metal detection method, which comprises the following steps: step 1, adopting electrode enrichment reaction to provide different voltage values, selecting a pure aluminum sheet with the length of 5cm and the width of 1cm as a cathode of a power supply, using a platinum wire electrode as an anode, and adding a reference electrode; in the electrode enrichment process, an electrochemical workstation provides electrons for a cathode, heavy metal cations in a solution can gather to the cathode under the action of an electric field to obtain electrons, and the cations are converted into simple substances from an ionic state and are attached to the surface of a cathode material; with the progress of the reaction process, a layer of uniform heavy metal attached film which is an object of LIBS laser ablation is formed on the surface of an aluminum sheet in the solution, and a sample is obtained after the aluminum sheet is dried for 5 min; and 2, performing laser ablation on the surface of the sample by adopting laser with enough power emitted by a laser, instantly gasifying surface substances and generating plasma signals, emitting characteristic spectra of elements by the plasma in the evolution process, and correspondingly obtaining the element composition and the content of the sample by analyzing information such as the wavelength, the intensity and the like of spectral lines.
CN108827890A discloses a method for detecting heavy metals in wastewater, which comprises the following steps: (1) collecting a water sample in wastewater, filtering impurities after collection, storing at normal temperature, adding 5mL of concentrated nitric acid into a test tube filled with the wastewater, shaking up, putting the test tube on an electric hot plate, heating and digesting the test tube to about 85mL, taking out the test tube, adding 5mL of concentrated nitric acid and 2mL of hydrogen peroxide, continuously putting the test tube on the electric hot plate, heating the test tube to about 75mL, taking out the test tube, cooling to the room temperature, adding 10mL of hydrochloric acid and 2mL of 10% of ammonium chloride, and transferring the test tube to a 100mL colorimetric tube; (2) putting the pretreated sample into a beaker, adding aminoacetic acid-HCl buffer solution to adjust the pH value of the solution to 3.0-4.0, putting the solution into a conical flask, and titrating with EDTA standard solution; (3) taking the solution, analyzing the overlapping problem of two absorption spectra by using a least square method by using a multivariate calibration-ultraviolet visible light photometry method and using the difference between the absorption spectra of the Cr (III) complex and the Cr (VI) per se, and simultaneously measuring the Cr (III) and the Cr (VI).
CN108325508A discloses an adsorption film for heavy metal active states, wherein the active ingredient of the adsorption film is sodium alginate-polyglutamic acid SA-PGA gel, and the SA-PGA gel is prepared by the following steps: and placing SA-PGA resin powder into an acrylamide gel solution, uniformly stirring, adding an ammonium persulfate solution and tetramethylethylenediamine, injecting into a glass mold, culturing at a certain temperature, placing the glass mold in distilled water for a certain time, taking out gel formed in the glass mold, and hydrating with distilled water to obtain the SA-PGA gel.
The research of the heavy metal detection method, such as the creep culture and the like, the agriculture science of Anhui, 20 2013, comparatively analyzes the traditional method (such as an atomic absorption spectrometry, an atomic fluorescence photometry, a high performance liquid chromatography and the like) and the rapid detection method (an enzyme analysis method, an immunoassay technology and the like) of the heavy metal detection, and discusses the problems of the existing heavy metal detection technology and the development direction of the future detection technology.
For the detection of heavy metal ions in aqueous solutions, there are established measurement techniques. However, for the detection of heavy metal elements, especially heavy metal ions, in tar, there is no perfect measurement technique in the related art, and the conventional detection technique of heavy metal ions in aqueous solution is still used. However, when the conventional technology for detecting heavy metal ions in an aqueous solution is adopted, there is a case where a detection error is conspicuous due to insufficient detection sensitivity, which causes a great limitation in the detection of heavy metal ions in tar. In the prior art, reports on how to carry out high-sensitivity detection on heavy metal ions in biomass tar are not found.
Disclosure of Invention
The inventor carries out deep research and a large number of experiments aiming at the factors restricting the detection sensitivity of the heavy metal elements in the biomass tar through cooperative development on the basis of system research, and can effectively solve the problem of the detection sensitivity of the heavy metal ions in the biomass tar.
In one aspect of the invention, a method for improving the detection sensitivity of heavy metal elements in biomass tar is provided, and the method comprises the following steps: (1) dissolving a quantitative tar sample in a quantitative methanol solution; (2) adding a complexing agent solution into the solution prepared in the step (1) to obtain a solution to be detected; (3) placing the solution to be detected in a detection pool, and detecting the fluorescence spectrum performance of the solution to be detected; and (4) comparing the fluorescence spectrum performance of the solution to be detected with the fluorescence spectrum performance of the standard substance, and calculating the content of heavy metal elements in the tar.
Preferably, the pH of the solution to be tested is adjusted to 8-10, preferably 9, using a buffer in step (2).
As understood by those skilled in the art, the quantification is the basis of the final calculation, and those skilled in the art can select an appropriate quantification according to the actual detection needs, such as detection equipment and the like.
Preferably, prior to step (1), the tar is filtered.
Preferably, the filtration is performed using an organic membrane.
Preferably, the organic film is a polymer film.
Preferably, the filtration is capable of removing phenolics from the tar sample.
More preferably, the filtration is capable of removing 50 to 90 wt% of the phenolics in the tar sample.
More preferably, the phenolic substance comprises one or more of ethylphenol, m-cresol, phenol, methoxyphenol.
The inventor of the invention finds that, in the biomass tar, according to the biomass source, there may be contained ethyl phenol, m-cresol, phenol, methoxyphenol and other phenolic substances, and these phenolic substances have certain interference effect on the subsequent fluorescence detection. For example, the phenolic substance may affect the complexation of heavy metal ions by the complexing agent, and the phenolic substance may easily interact with the complexing agent, including hydrogen bonds, to deteriorate the fluorescence effect of the complexing agent. Thus, in the present application, it is preferred to remove or reduce the phenolic content of the biomass tar sample prior to detection.
Of course, as will be appreciated by those skilled in the art, for the detection of heavy metal elements in certain types of biomass tar, such filtration to remove phenolics is unnecessary or unnecessary.
The present inventors have found that a particularly effective and simple way of handling is to filter a tar sample using a filter membrane of a specific material. This filtration is carried out at normal temperature. Compared with the common distillation method, the method is simpler. In addition, if distillation separation is performed, on one hand, the separated substance is easy to form an azeotropic mixture with other substances and is difficult to remove by distillation, and on the other hand, other substances in the tar, such as a fused ring compound, can be decomposed due to heating, and the decomposition product can complex heavy metal ions and has certain fluorescence, so that the accuracy of subsequent fluorescence detection is influenced.
Particularly preferably, the material of the filter membrane is a material prepared by the following steps: dissolving 1-5 parts by weight of cyclodextrin, 20-50 parts by weight of PVC powder, 50-70 parts by weight of 2-nitrophenyl-octyl ether polar plasticizer and 50-70 parts by weight of potassium tetrakis (4-chlorophenyl) borate lipophilic ionic additive in THF, uniformly mixing, and evaporating THF.
More particularly preferably, 1g of dextrin, 30g of PVC powder, 66g of 2-nitrophenyl-octyl ether polar plasticizer, 120g of potassium tetrakis (4-chlorophenyl) borate lipophilic ionic additive are dissolved in 2000mL of THF, mixed until homogeneous, and the THF is evaporated off.
In the preparation of the membrane, the material can be dissolved in THF, then spread on a vessel, and the solvent is removed to obtain the filter membrane. Preferably, the solution is placed in a polytetrafluoroethylene vessel with the diameter of 20mm, and is slowly dried to obtain the filter membrane.
The filter membrane has a preferred adsorption function for biomass tar and is capable of removing 50 to 90 wt% of phenolic substances, preferably 60 to 90 wt% of phenolic substances, and more preferably 80 to 90 wt% of phenolic substances in a tar sample. The preparation method of the membrane is simple and has low cost.
In a preferred embodiment of the present invention, the methanol in step (1) contains MeCN and water, each independently in a volume of 5 to 20% of the total volume of methanol. That is, the volume percentages of MeCN and water are based on the total volume of methanol, MeCN and water.
Preferably, the complexing agent is a multidentate complex.
Particularly preferably, the complex is a complex represented by the following formula (1):
the complexing agent has particularly good complexing fluorescence property on heavy metal ions in tar. In particular in mixed aqueous-organic media, with heavy metal ions (e.g. Cr)3+、Pb2+、Ni2+) When combined, the fluorescent probe can show a fluorescence emission signal at 488nm and a fluorescence excitation signal at 388nm, and has a considerable fluorescence response in a visible light region, so that the fluorescent probe can be used as a heavy metal ion selective detection sensing platform.
The complexing agent of formula (I) may be prepared by the following method: the substituted aroylhydrazide (e.g. 4g, 2.32mmol) was dissolved in THF (60mL) and an equimolar amount of o-methoxyphenyl isothiocyanate (2.32mmol) was dissolved in 50mL of THF respectively, the two solutions were mixed slowly and stirred at room temperature for 20 h, the degree of reaction progress was monitored by thin layer chromatography, and at the end, THF was evaporated off to give the complexing agent of formula (I).
The compound is characterized as follows: mp 131-; rf 0.31 (n-hexane: ethyl acetate, 8: 2); FT-IR (v/cm)-1) 3331,3211(NH),1658, (C ═ O),1551,1536,1498(C ═ C),1254 (C ═ S); 1H NMR (400MHz, DMSO-d6) Δ 9.95(s,1H, NH),8.65(bs,1H, NH), 8.09(bs,1H, NH), 7.43-7.40 (s,1H, Ar-H), 7.39-7.23 (m,4H, Ar-H), 7.19-7.12 (m,3H, Ar-H),3.56(s,3H, OCH 3); 13C NMR (100MHz, DMSO-d6) delta 178.6, 162.4,159.3,158.7,135.6,131.5,130.5,129.8,125.4,119.7,118.2,114.24,114.1, 56.3; elemental analysis C15H14FN3O2S C56.41, H4.42, N13.16; the results were C55.32, H4.40, N13.21%.
The aroylhydrazide is commercially available and has a structural formula shown in the following formula (2):
the complex is found to form a fluorescent complex with heavy metal ions in the biomass tar. Formula (3) is represented by Ni2+The fluorescent complex structure is shown for example:
when the complex is used, heavy metal ions of the order of μmol/L can be detected, that is, the detection limit can be up to 1.0 μmol/L, for example, heavy metal ions of 5.0 μmol/L or less, preferably 2.0 μmol/L or less in biomass tar can be detected.
In another aspect of the invention, an application of a complexing agent in detecting heavy metal elements in biomass tar is provided, which is used for improving the detection sensitivity of the heavy metal elements in the biomass tar.
Preferably, the complexing agent and its method of use are as described above.
Preferably, the method for detecting the heavy metal elements in the biomass tar adopts fluorescence spectroscopy, wherein the excitation is carried out at 388nm, and the emission maximum is 488 nm.
The complexing agent shown in formula (1) of the present application alone does not show any significant fluorescence signal at 488nm under excitation at 388nm in the fluorescence emission spectrum, and does not show any significant fluorescence signal at 388nm in the same fluorescence excitation spectrum when the 488nm emission is fixed in the absence of nickel ions, whereas it has a very significant signal with an emission maximum of 488nm and an excitation maximum of 388nm after the addition of nickel ions is detected. This provides the possibility of detection of heavy metal ions such as nickel ions.
Description of the drawings:
FIG. 1 shows the complexation of different equivalents of Ni by the complex according to the invention2+Fluorescence spectrum of (5.0) μ M ligand, Ni 2+1 to 6 equivalents thereof;
FIG. 2 shows the fluorescence intensity at 488nm with and without the complexing agent of formula (1) according to the invention.
Detailed description of the preferred embodiments
The present invention will be described in further detail below with reference to the following examples and corresponding comparative examples, but the embodiments of the present invention are not limited thereto.
Example 1
2.0ml of tar sample standard (obtained from the laboratory of the institute of energy and Power engineering, university of Nanjing, containing 5.0. mu.M Ni)2+) Dissolving in 20ml of methanol solution containing 10 v% MeCN and 10 v% water, adding 2.0ml of a solution of a complexing agent represented by the formula (1) in methanol, wherein the concentration of the complexing agent in methanol is 5.0 μ M, to obtain a solution to be measured, adjusting the pH of the solution to be measured to 9.0 with a PBS buffer solution, placing the solution to be measured in a detection cell, detecting the fluorescence spectrum performance of the solution to be measured with an RF-5301PC type fluorescence spectrometer (RF-5301PC type fluorescence spectrometer), and subjecting the solution to be measured toFluorescence spectrum performance of (2) and calibrated Ni-containing2+Comparing the fluorescence spectrum performance of the standard substance, calculating the content of heavy metal elements in the tar, and measuring the Ni in the tar sample2+The content was 4.68. mu.M.
Comparative example 1
Detection by conventional flame atomic absorption spectrometry (Thermo Scientific M series-iCE 3000) failed to detect Ni distinctively2+。
Comparative example 2
The same preparation as in example 1 was followed, except that calcein (available from Amresco, USA) was selected as the fluorescent complexing agent, and Ni was detected2+The content was 0.84. mu.M.
As is clear from the above examples and comparative examples, when conventional elemental analysis is employed, Ni ions are not detected selectively well, which is an inherent disadvantage of flame atomic absorption spectrometry, which cannot simultaneously analyze multiple elements, is unsatisfactory in the sensitivity of measurement of a sparingly soluble element, and requires enrichment and separation for the measurement of trace amounts, particularly ultra trace amount components, due to the low sensitivity of flame atomic absorption.
In addition, as can be seen from comparative example 2, when the conventional fluorescent complexing agent was used, the detection result error was large because the fluorescence property of the formed complex was weak, and thus the detection sensitivity was also significantly low as compared with example 1.
This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. All citations referred to herein are incorporated herein by reference to the extent that no inconsistency is made.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910316929.8A CN109900673B (en) | 2019-04-19 | 2019-04-19 | Method for improving the detection sensitivity of heavy metal elements in biomass tar |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910316929.8A CN109900673B (en) | 2019-04-19 | 2019-04-19 | Method for improving the detection sensitivity of heavy metal elements in biomass tar |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109900673A CN109900673A (en) | 2019-06-18 |
| CN109900673B true CN109900673B (en) | 2021-07-30 |
Family
ID=66956080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910316929.8A Active CN109900673B (en) | 2019-04-19 | 2019-04-19 | Method for improving the detection sensitivity of heavy metal elements in biomass tar |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109900673B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113945444A (en) * | 2021-10-28 | 2022-01-18 | 科正检测(苏州)有限公司 | A solvent extraction method for hydrocarbons in trace rock samples |
| CN117470890B (en) * | 2023-10-16 | 2025-02-11 | 湖州久岳新材料有限公司 | A method for detecting the content of palladium in a noble metal palladium compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7939335B1 (en) * | 2004-09-16 | 2011-05-10 | Marathon Ashland Petroleum Llc | Detection and classification of heavy hydrocarbon contamination in refinery process streams via spectrofluorometry |
| CN102565111A (en) * | 2011-12-30 | 2012-07-11 | 上海出入境检验检疫局机电产品检测技术中心 | Method for simultaneous enrichment and analysis of heavy metal lead, cadmium and mercury ions |
| CN105758850A (en) * | 2016-02-22 | 2016-07-13 | 天津大学 | Preparation method and application of bistriazole bridged fluorescent cyclodextrin molecule with AIE (Aggreagation-Induced Emission) effect |
| CN109438638A (en) * | 2017-12-30 | 2019-03-08 | 黄河科技学院 | The strong modification imprinting polymer and preparation method thereof of adsorption capacity |
-
2019
- 2019-04-19 CN CN201910316929.8A patent/CN109900673B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7939335B1 (en) * | 2004-09-16 | 2011-05-10 | Marathon Ashland Petroleum Llc | Detection and classification of heavy hydrocarbon contamination in refinery process streams via spectrofluorometry |
| CN102565111A (en) * | 2011-12-30 | 2012-07-11 | 上海出入境检验检疫局机电产品检测技术中心 | Method for simultaneous enrichment and analysis of heavy metal lead, cadmium and mercury ions |
| CN105758850A (en) * | 2016-02-22 | 2016-07-13 | 天津大学 | Preparation method and application of bistriazole bridged fluorescent cyclodextrin molecule with AIE (Aggreagation-Induced Emission) effect |
| CN109438638A (en) * | 2017-12-30 | 2019-03-08 | 黄河科技学院 | The strong modification imprinting polymer and preparation method thereof of adsorption capacity |
Non-Patent Citations (3)
| Title |
|---|
| 《基于吲哚多齿荧光试剂的合成及对重金属离子的识别》;刘慧;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20170315(第03期);第4-39页 * |
| 《煤焦油酸性及碱性组分分离方法分析》;蔡颖等人;《内蒙古石油化工》;20081231(第23期);第21-22页 * |
| 刘慧.《基于吲哚多齿荧光试剂的合成及对重金属离子的识别》.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2017,(第03期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109900673A (en) | 2019-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ensafi et al. | A novel sensitive DNA–biosensor for detection of a carcinogen, Sudan II, using electrochemically treated pencil graphite electrode by voltammetric methods | |
| Chen et al. | Fluorescence and electrochemical assay for bimodal detection of lead ions based on Metal–Organic framework nanosheets | |
| CN104109126B (en) | A kind of for Ratiometric fluorescent probe detecting hydrazine and preparation method thereof | |
| US20140147926A1 (en) | Method of analyzing aldehyde compound in metal plating solution | |
| CN108329904B (en) | A cysteamine-modified copper nanocluster solution fluorescent probe and its preparation and application | |
| CN110297025B (en) | A nanoscale Ni-Fe Prussian blue analog material and its preparation method and application of electrochemical detection of o-nitrophenol | |
| CN113788788B (en) | Fluorescent ionic liquid and synthesis method and application thereof | |
| CN105241854A (en) | Method for detecting ferric ions by using fluorescent carbon quantum dots | |
| CN109900673B (en) | Method for improving the detection sensitivity of heavy metal elements in biomass tar | |
| CN109777412A (en) | A kind of double emission fluorescent carbon dot and its preparation method and application | |
| Zuo et al. | Ratiometric fluorescence sensing of formaldehyde in food samples based on bifunctional MOF | |
| CN108178766A (en) | A kind of fluorescent probe molecule of recognizable iron ion and dihydrogen phosphate ions and its preparation method and application | |
| CN106083645A (en) | A kind of iron-ion fluorescent probe compound and its preparation method and application | |
| Kazemzadeh et al. | Determination of Hg2+ by diphenylcarbazone compound in polymer film | |
| Jiao et al. | Voltammetric detection of the DNA interaction with toluidine blue | |
| CN106248609B (en) | A kind of method that ultraviolet specrophotometer measures hexafluorophosphoric acid lithium content in lithium-ion battery electrolytes | |
| CN102288568B (en) | Nano-gold Catalysis-Silver Nitrate Reduction Spectrophotometry for Rapid Determination of UO22+ in Water | |
| CN107044963A (en) | A kind of new arsenic aptamers nucleotide sequence and the application for detecting arsenic ion | |
| CN103048374A (en) | Electrochemical method for detecting anthracene of polycyclic aromatic hydrocarbon | |
| Ivoilova et al. | Study of Different Carbonaceous Materials as Modifiers of Screen‐printed Carbon Electrodes for the Triazid as Potential Antiviral Drug | |
| CN113024468A (en) | Fluorescent molecular probe for detecting picric acid and preparation method and application thereof | |
| CN109580564B (en) | Method for detecting mercury ions in water | |
| CN108303388B (en) | Method for in-situ quantitative characterization of complex organic matter and metal ion complexing process | |
| Samanta et al. | Engineering a bromophenol derivative for rapid detection of Hg 2+/CH 3 Hg+ in both environmental and biological samples through a unique activation process | |
| CN115479926A (en) | Method for detecting permanganate in water samples using ginger carbon quantum dots |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |