CN109900673A - The method for improving biomass coke tar heavy metal element detection sensitivity - Google Patents
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Abstract
The present invention provides a kind of methods for improving biomass coke tar heavy metal element detection sensitivity, method includes the following steps: quantitative tar sample is dissolved in quantitative methanol solution by (1)；(2) enveloping agent solution is added in the solution prepared to step (1), obtains solution to be measured；(3) solution to be measured is placed in detection cell, detects the fluorescence spectrum performance of the solution to be measured；(4) the fluorescence spectrum performance of the solution to be measured is compared with the fluorescence spectrum performance of standard items, calculates the contents of heavy metal elements in tar.This method is to heavy metal ion detection sensitivity with higher and selectivity.
Description
Technical field
Detection technique field of the present invention, and in particular to the method for improving biomass coke tar heavy metal element detection sensitivity.
Background technique
Significantly different with general oil product such as fuel oil and edible oil, the ingredient of biomass coke tar is extremely complex, containing various thick
Cycle compound, phenolic compound etc. also contain heavy metal ion, alkali metal, acid, gas and alkaline gas etc..These pollutions
The measuring technique of object permits a determination that tar clean-up performance, and assesses the quality used in subsequent applications such as engine.It is raw
Nickel, vanadium can cause catalyst poisoning used in the subsequent deep processing of coal tar in substance tar, and catalyst is made to lose activity
And fail, another aspect coal tar produces corrosion products in combustion and equipment is caused to be corroded, so Accurate Determining
Nickel, iron, content of vanadium are particularly important in coal tar.Common test method is spectrophotometry and atomic absorption method, both surveys
Determine that method is cumbersome, interferes with each other between various metallic elements, needs plus corresponding reagent eliminates these interference to measure
Corresponding element.
CN105466982B discloses heavy metal detection method in water, and heavy metal detection method includes following step in the water
Rapid: (A1) send the liquid containing heavy metal ion to be measured that volume is V0 to detection cell, obtains heavy metal ion dissolution to be measured
Peak point current P01；(A2) water sample that volume is V1 is sent to the detection cell, mixes, obtains with the liquid in the detection cell
Obtain the peak point current Ps of heavy metal ion dissolution to be measured；(A3) mixed liquor in the detection cell is discharged, cleans the detection
Pond；(A4) liquid containing heavy metal ion to be measured that volume is V0 is sent to detection cell, obtains heavy metal ion dissolution to be measured
Peak point current P02；(A5) the heavy metal ion correcting fluid to be measured that volume is V1 is sent to the detection cell, with the detection cell
Interior liquid mixing obtains the peak point current Pb of heavy metal ion dissolution to be measured.
CN108051426A discloses a kind of heavy metal detection method, comprising the following steps: step 1 is enriched with using electrode
Reaction provides different voltage value, selects long 5cm, cathode of the fine aluminium piece of wide 1cm as power supply, platinum electrode as anode,
And it joined reference electrode；In electrode enrichment process, electrochemical workstation provides electronics for cathode, molten due to the effect of electric field
Electronics can be gathered to cathode and be obtained to heavy metal cation in liquid, and cation is converted into " simple substance " from " ionic state " and is attached to yin
Pole material surface；With the progress of reaction process, the aluminum flake surface in solution will form one layer of uniform heavy metal coherent film i.e.
It is sample after 5min dries for the object of LIBS laser ablation；Step 2 swashs using laser sending power is sufficiently large
Light carries out laser ablation to sample surfaces, and surface mass moment is gasified and produces plasma signal, and plasma is at it
Emit the characteristic spectrum of element during evolution, the wavelength of analysis spectral line corresponding can obtain the member of sample to information such as intensity
Element composition and its content.
CN108827890A discloses a kind of detection method of heavy metal in waste water comprising following steps: (1) acquiring
Water sample in waste water, impurity screening after acquisition, is stored at room temperature, and the concentrated nitric acid that 5mL is added into the test tube equipped with waste water shakes up, so
The hydrogen peroxide that concentrated nitric acid and 2mL that 5mL is added are taken out when heating resolution is placed on electric hot plate afterwards to about 85mL, continues to be placed on
Taking-up when being heated approximately at 75mL on electric hot plate, is cooled to room temperature, and the hydrochloric acid of 10mL and the ammonium chloride of 2mL10% is added,
It is transferred to the colorimetric cylinder of 100mL；(2) take pretreated sample in a beaker, ammonification guanidine-acetic acid-HCl buffer solution is adjusted
Solution PH=3.0-4.0 takes above-mentioned solution in a conical flask, is titrated with EDTA standard solution；(3) above-mentioned solution is taken to utilize more
First correction-ultraviolet-visible photometry, using the difference between Cr (III) complex compound and Cr (VI) extinction spectrum itself, by most
Small square law parses two kinds of extinctions and composes overlap problem, while measuring Cr (III) and Cr (VI).
CN108325508A discloses a heavy metal species available state adsorbed film, and the effective component of the adsorbed film is alginic acid
Sodium-polyglutamic acid SA-PGA gel, by the following method prepared by step for the SA-PGA gel: SA-PGA toner being taken to be placed in
It is stirred evenly in acrylamide gel solution, adds ammonium persulfate solution and tetramethylethylenediamine, in implantation glass mold, one
Determine to cultivate under the conditions of temperature, glass mold placed to the gel for taking out formed in glass mold after a certain period of time in distilled water,
Distilled water is hydrated to get the SA-PGA gel.
" research of heavy metal detection method ", Xu Peipei etc., Agriculture of Anhui science, 20 phases in 2013, comparative analysis weight
The conventional method (such as atomic absorption spectrography (AAS), Atomic fluorophotometry, high performance liquid chromatography) of metal detection and quickly inspection
Survey method (enzyme assay, immunoassay technology etc.), and discuss existing heavy metal analysis technology there are the problem of and the following inspection
The developing direction of survey technology.
There is mature measuring technique in the detection for heavy metal ion in aqueous solution.However, for heavy metal in tar
The detection of element, particularly heavy metal ion does not have perfect measuring technique in correlative technology field, usually still continues to use tradition
Aqueous solution in heavy metal ion detection technique.However, when using detection of heavy metal ion technology in traditional aqueous solution,
There are detection sensitivity it is not high enough caused by obvious detection error the case where generation, this makes heavy metal ion in tar
Detection is very limited.In the prior art there is not yet how to carry out high sensitivity for the heavy metal ion in biomass coke tar
The report of detection.
Summary of the invention
The present inventor is on the basis of system research, by cooperative development, for restriction biomass coke tar heavy metal element
The factor of detection sensitivity, has made intensive studies and many experiments, can effectively solve the problem that heavy metal ion in biomass coke tar
The sensitivity problem of detection.
In one aspect of the invention, a kind of method for improving biomass coke tar heavy metal element detection sensitivity is provided,
Method includes the following steps: quantitative tar sample is dissolved in quantitative methanol solution by (1)；(2) it is prepared to step (1)
Enveloping agent solution is added in solution, obtains solution to be measured；(3) solution to be measured is placed in detection cell, detects the solution to be measured
Fluorescence spectrum performance；(4) the fluorescence spectrum performance of the solution to be measured is compared with the fluorescence spectrum performance of standard items, is counted
Calculate the contents of heavy metal elements in tar.
Preferably, the pH of solution to be measured is adjusted to 8-10, preferably 9 using buffer in step (2).
As understood by those skilled in the art, described is quantitatively the basis finally calculated, and those skilled in the art can be with
It is suitably quantitative according to actually detected needs selection such as detection device.
Preferably, before step (1), the tar is filtered.
Preferably, the filtering is filtered using organic film.
Preferably, the organic film is polymer film.
Preferably, the filtering can remove the phenolic substances in tar sample.
It is highly preferred that the filtering can remove the phenolic substances of 50-90wt% in tar sample.
It is highly preferred that the phenolic substances includes one of ethyl -phenol, metacresol, phenol, metoxyphenol or more
Kind.
The present inventor it has been investigated that, in biomass coke tar, according to biomass source, may containing ethyl -phenol,
Cresols, phenol, metoxyphenol etc. divide substance, these phenolic substancess have certain interference effect to subsequent fluorescence detection.
For example, the phenolic substances will affect complexing of the complexing agent to heavy metal ion, in addition the phenolic substances is easy and complexing agent
The interaction including hydrogen bond occurs, deterioration is generated to the fluorescent effect of complexing agent.Therefore, in this application, preferably exist
The aldehydes matter content in biomass char oil samples is removed or reduced before detection.
Certainly, as understood by those skilled in the art, for the inspection of heavy metal element in some kinds of biomass coke tar
It surveys, it is nonessential or non-essential which, which removes phenolic substances,.
The present inventor is the study found that an especially effective and easy processing mode is focused using the filter membrane of specific materials
Oil samples are filtered.This filtering can carry out at normal temperature.Compared with general distillating method, more simply.In addition, such as
Fruit carries out distillation separation, and one side separate substance is easy to form azeotropic mixture with other materials, it is difficult to be distilled off, another party
Face may be such that the other materials such as fused ring compound in tar decomposes, decomposition product may be to a huge sum of money due to heating
Belong to ion be complexed and itself also have certain fluorescence, to influence the accuracy of subsequent fluorescence detection.
It is particularly preferred that the material of the filter membrane be the material as made from following steps: by 1-5 parts by weight of cyclodextrin,
20-50 parts by weight PVC powder, 50-70 parts by weight 2- nitrobenzophenone-Octyl Ether polarity plasticizer, (the 4- chlorine of 50-70 parts by weight four
Phenyl) potassium borate lipophilicity ionic additive is dissolved in THF, is uniformly mixed, and THF is removed in evaporation.
Most particularly preferably, by 1g dextrin, 30g PVC powder, 66g 2- nitrobenzophenone-Octyl Ether polarity plasticizer,
120g tetra- (4- chlorphenyl) potassium borate lipophilicity ionic additive is dissolved in 2000mL THF, is uniformly mixed, and THF is removed in evaporation.
In the preparation of film, which can be dissolved in THF, then spread on vessel, remove solvent to get filter
Film.Preferably, which is placed in the polytetrafluoroethylene (PTFE) vessel that diameter is 20mm, is slowly dried to get filter membrane.
The filter membrane has preferred adsorption function to biomass coke tar, can remove 50-90 wt% in tar sample
Phenolic substances, the preferably phenolic substances of 60-90wt%, the phenolic substances of more preferable 80-90wt%.The preparation method of the film is simple
And cost is relatively low.
In a preferred embodiment of the present invention, the methanol in step (1) contains MeCN and water, MeCN and water
Volume is each independently the 5-20% of methanol total volume.That is, the percentage by volume of MeCN and water is based on methanol, MeCN and water
Total volume meter.
Preferably, the complexing agent is multiple tooth complex compound.
It is particularly preferred that the complex compound is complexing shown in following formula (1):
The complexing agent has particularly good complexing fluorescence property to the heavy metal ion in tar.Especially mixing
Water-organic media in, the complexing agent and heavy metal ion (such as Cr3+、Pb2+、Ni2+) combine when can express in 488nm
The fluorescent emission signals at place and the fluorescence excitation signal at 388nm have sizable fluorescence response in visible light region, make
It must can be used as heavy metal ion selective enumeration method sensing platform.
Complexing agent shown in formula (I) can be prepared by following method: by substituted fragrant hydrazides (such as 4g,
It 2.32mmol) is dissolved in THF (60mL), and respectively by the o-methoxyphenyl isothiocyanates (2.32mmol) of equimolar amounts
It is dissolved in the THF of 50mL, both solution are slowly mixed together and are stirred at room temperature 20 hours, monitored by thin-layer chromatography anti-
Degree should be carried out, at the end, evaporation removes THF up to complexing agent shown in formula (I).
The characterization of compound is as follows: 131-133 DEG C of mp；Rf:0.31 (n-hexane: ethyl acetate, 8:2)； FT-IR(ν/
cm-1): 3331,3211 (NH), 1658, (C=O), 1551,1536,1498 (C=C), 1254 (C=S)；1H NMR
(400MHz,DMSO-d6)δ9.95(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,OCH3)；13C NMR
(100MHz,DMSO-d6)δ178.6, 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:C 56.41, H 4.42, N 13.16；Knot
Fruit: C 55.32, H 4.40, N 13.21%.
The virtue hydrazides is commercially available, shown in structural formula such as following formula (2):
The study found that the complex compound can form fluorescent complex with the heavy metal ion in biomass coke tar.Following formula
(3) with Ni2+For show fluorescent complex structure:
When using the complex compound, it is able to detect a μm heavy metal ion for ol/L rank, i.e., its detection limit can achieve 1.0
5.0 μm of ol/L are hereinafter, it is preferred that 2.0 μm of ol/L heavy metal ion below in μm ol/L, such as detectable biomass coke tar.
In another aspect of this invention, the application of heavy metal element of the complexing agent in detection biomass coke tar is provided,
It is used to improve biomass coke tar heavy metal element detection sensitivity.
Preferably, the complexing agent and its application method are as described above.
Preferably, the heavy metal element in detection biomass coke tar of the present invention uses fluorescent spectrometry, wherein
388nm is excited, and emission maximum is 488nm.
Complexing agent shown in the formula (1) of simple the application does not have at 488nm under 388nm excitation in fluorescence emission spectrum
There is any apparent fluorescence signal of display, and in the case where no nickel ion, in same fluorescence when fixed 488nm emits
Without showing any apparent fluorescence signal at 388nm in excitation spectrum, and after detecting addition nickel ion, there is transmitting most
Big value is 488nm, and excitation maximum is the signal of the highly significant of 388nm.This is mentioned for the detection of heavy metal ion such as nickel ion
Having supplied may.
Detailed description of the invention:
Fig. 1 is complex compound according to the present invention in the Ni that different equivalents are complexed2+When fluorescence spectra, wherein ligand be
5.0 μM, Ni2+For its 1-6 equivalent；
Fig. 2 is shown with complexing agent shown in formula (1) and without complexing agent situation shown in formula (1)
Under fluorescence intensity at 488nm.
Specific embodiment
Below with reference to following embodiment and corresponding comparative example, the present invention is described in further detail, but of the invention
Embodiment is without being limited thereto.
Embodiment 1
2.0ml tar sample standard items (are derived from Institutes Of Technology Of Nanjing's energy and power engireering institute laboratory, contained
5.0 μM of Ni2+) be dissolved in MeCN and 10v% that 20ml contains 10v% water methanol solution in, into the mixed solution plus
Enter the solution of complexing agent in methyl alcohol shown in 2.0ml formula (1), the concentration of complexing agent in methyl alcohol is 5.0 μM, is obtained to be measured molten
Liquid, adjusting pH value of solution to be measured using PBS buffer solution is 9.0, and solution to be measured is placed in detection cell, RF-5301PC type is used
The fluorescence spectrum performance that Fluorescence Spectrometer (RF-5301PC type Fluorescence Spectrometer) detects the solution to be measured, by the solution to be measured
Fluorescence spectrum performance contains Ni with calibration2+The fluorescence spectrum performance of standard items is compared, and calculates the heavy metal member in tar
Cellulose content measures the Ni in tar sample2+Content is 4.68 μM.
Comparative example 1
It is examined using conventional flame atomic absorption spectrometry (Thermo Scientific M series-iCE 3000)
It surveys, fails discriminatively to detect Ni2+。
Comparative example 2
According to preparation method similarly to Example 1, difference is only that fluorexone selection calcein (purchased from beauty
Amresco company, state), through detecting Ni2+Content is 0.84 μM.
It, can not be very by above-described embodiment and comparative example it can be clearly seen that when using conventional elemental microanalysis method
Selective enumeration method goes out Ni ion well, this is also the inherent defect of flame atomic absorption spectrometry, it cannot be to multielement simultaneously
Analysis, it is also unsatisfactory to the measurement sensitivity of refractory element, and since the sensitivity of Flame Atomic Absorption Spectrometry is lower, for
The measurement of trace especially ultra trace component, need to carry out enrichment and separation.
In addition, testing result error is larger it can be seen from comparative example 2 when using conventional fluorescent complexing agent, this be by
It is weaker in the fluorescence property of the complex compound of formation, therefore compared with Example 1, detection sensitivity is also obvious relatively low.
This written description discloses the present invention, including optimal mode using example, and also enables those skilled in the art
The manufacture and use present invention.It is of the invention can patentable scope be defined by the claims, and may include this field skill
Other examples that art personnel expect.If this other examples have not different from the structural elements of the literal language of claims
Element, or if this other examples include the equivalent structure element with the literal language of claims without substantial differences,
Then this other examples are intended within the scope of claims.In the case where not will cause inconsistent degree, by reference to
It will be incorporated herein in place of all references referred to herein.
Claims (10)
1. a kind of method for improving biomass coke tar heavy metal element detection sensitivity, method includes the following steps:
(1) quantitative tar sample is dissolved in quantitative methanol solution；
(2) enveloping agent solution is added in the solution prepared to step (1), obtains solution to be measured；
(3) solution to be measured is placed in detection cell, detects the fluorescence spectrum performance of the solution to be measured；With
(4) the fluorescence spectrum performance of the solution to be measured is compared with the fluorescence spectrum performance of standard items, is calculated in tar
Contents of heavy metal elements.
2. the method according to claim 1, wherein before step (1), the tar is filtered.
3. according to the method described in claim 2, wherein, the filtering is filtered using organic film.
4. according to the method described in claim 3, wherein, the organic film is polymer film.
5. according to the described in any item methods of claim 2-5, wherein the filtering can remove the phenolic material in tar sample
Matter.
6. according to the method described in claim 5, wherein, the filtering can remove the phenols of 50-90wt% in tar sample
Substance.
7. method according to claim 5 or 6, wherein the phenolic substances includes ethyl -phenol, metacresol, phenol, first
One of oxygroup phenol is a variety of.
8. method according to any of the preceding claims, wherein the methanol in step (1) contains MeCN and water,
The volume of MeCN and water is each independently the 5-20% of methanol total volume.
9. method according to any of the preceding claims, wherein the complexing agent is multiple tooth complex compound.
10. the application of heavy metal element of the complexing agent in detection biomass coke tar, is used to improve biomass coke tar heavy metal
Element detection sensitivity.
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| CN113945444A (en) * | 2021-10-28 | 2022-01-18 | 科正检测(苏州)有限公司 | Solvent extraction method for hydrocarbon substances in trace rock sample |
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