CN113866339B - Method for detecting total phosphorus content in biodiesel by accelerated oxidation-ion chromatography - Google Patents
Method for detecting total phosphorus content in biodiesel by accelerated oxidation-ion chromatography Download PDFInfo
- Publication number
- CN113866339B CN113866339B CN202111066986.9A CN202111066986A CN113866339B CN 113866339 B CN113866339 B CN 113866339B CN 202111066986 A CN202111066986 A CN 202111066986A CN 113866339 B CN113866339 B CN 113866339B
- Authority
- CN
- China
- Prior art keywords
- biodiesel
- phosphorus content
- oxidation
- ion chromatography
- detecting
- 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
- 239000003225 biodiesel Substances 0.000 title claims abstract description 66
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 50
- 239000011574 phosphorus Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004255 ion exchange chromatography Methods 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000001514 detection method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004458 analytical method Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000004677 Nylon Substances 0.000 claims abstract description 5
- 229920001778 nylon Polymers 0.000 claims abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 4
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- 239000012488 sample solution Substances 0.000 claims description 16
- 239000000523 sample Substances 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 8
- 239000012086 standard solution Substances 0.000 claims description 7
- 238000009423 ventilation Methods 0.000 claims description 4
- 239000003755 preservative agent Substances 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 description 7
- 241001048891 Jatropha curcas Species 0.000 description 5
- 238000004380 ashing Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for detecting total phosphorus content in biodiesel by accelerated oxidation-ion chromatography, which comprises the steps of adopting phosphoric acid solution with known concentration to carry out ion chromatography analysis to obtain a standard curve, adopting Rannimat oxidation method to carry out rapid oxidation on the biodiesel, adopting water bath-liquid separation mode to carry out pretreatment on the oxidized biodiesel, adopting C18 reverse phase column and 0.22 mu m nylon filter head to treat an oil sample, and finally adopting ion chromatograph to detect and combine the standard curve to obtain phosphorus content; the method has the advantages of good linear correlation, low detection limit and reasonable repeatability, is independent of a large instrument, is simple and quick to operate, can meet the requirement of batch sample injection detection in precision, and has more practical significance for detecting the phosphorus content in biodiesel.
Description
Technical Field
The invention relates to a method for detecting the phosphorus content in biodiesel, in particular to an ion chromatography quantitative detection analysis method for the phosphorus content in biodiesel under accelerated oxidation treatment.
Technical Field
The biodiesel is used as a typical green energy source and is used as fuel oil, and has very important strategic significance on the aspects of assisting 'carbon peak, carbon neutralization' target, pushing fossil energy to replace, relieving environmental pressure and the like. And different animal and vegetable oils and waste food and beverage oils can be used for producing biodiesel, and the low-quality oils contain a certain amount of phospholipids besides triglyceride and free fatty acid. An important parameter for evaluating the quality of biodiesel is the phosphorus content, which can form oxide particles at high temperature to be adsorbed on the surface of the catalyst, so that the catalyst cannot be contacted with exhaust gas to cause the phenomenon of catalyst poisoning. In addition, the presence of phosphorus can increase the sulphated ash in biodiesel automotive exhaust particulates and biodiesel, which has a great relationship to the formation of carbon deposits in automotive engines. British Standard EN14214 sets the maximum limit of total phosphorus in biodiesel to 4 mg.kg -1 American test and Material society ASTMD6751 and China GB 25199 set the maximum limit of total phosphorus in biodiesel to 10mgkg -1 . The above standards all specify that the inductively coupled plasma emission spectrometry (ICP-OES) is adopted to detect the total phosphorus in the biodiesel, the method is efficient and sensitive, but organic solvents with high toxicity such as n-propanol, xylene, cyclohexane, petroleum ether and the like are needed in the dilution process of the sample, and meanwhile, the high-power dilution of the sample can reduce the detection limit and the quantitative limit of measurement, thereby influencing the analysis result. Therefore, some scholars have proposed alternative methods such as spectrophotometry, capillary electrophoresis-capacitive coupling non-contact conductivity detection, colorimetry, and graphite oven atomic absorption spectrometry. Wherein, lira (Fuel, 2011,90 (11): 3254-3258) uses spectrophotometric detection (FIA-SD) flow injection analysis method to determine phosphorus in biodiesel; nogueira, T (Microchemical Journal,2011,99 (2): 267-272) detected and analyzed phosphate in biodiesel by capacitive coupling non-contact conductivity detection; de Campos (Spectrochimica Acta Part B Atomic Spectroscopy,2011,66 (9-10): 733-739) directly measured phosphorus in biodiesel using high resolution continuous source graphite furnace atomic absorption spectrometry. These analytical methods each have advantages, but also limitations such as complex sample pretreatment processes and difficult control precision.
Disclosure of Invention
The invention provides a method for detecting the phosphorus content in biodiesel, which is independent of a large instrument, is simple and convenient to operate and can meet the requirement of batch sampling detection. The invention firstly adopts Rannimat oxidation method to oxidize biodiesel rapidly, and the oxidized biodiesel is pretreated in a water bath-liquid separation mode, then adopts C18 reverse phase column and 0.22 mu m nylon filter head to treat oil sample, and finally detects phosphorus content by ion chromatograph with on-line matrix elimination function.
The technical scheme adopted for achieving the purposes of the invention is as follows:
a method for quantitatively detecting total phosphorus content in biodiesel based on accelerated oxidation-Ion Chromatography (IC) comprises the following specific steps: (1) drawing a standard curve:
the concentration of phosphoric acid is 0.5, 1.0, 2.0, 4.0 and 8.0 mg.L -1 PO of (2) 4 3- Standard solution, PO with different concentrations is obtained by detection and analysis of an ion chromatograph 4 3- The standard curve of the phosphorus concentration and the chromatographic peak height is drawn, and the standard curve formula is obtained:
H＝5.6943×10 -3 +2.6461×10 -3 Q
wherein Q is the concentration of phosphorus in the solution, mg.L -1 The method comprises the steps of carrying out a first treatment on the surface of the H is chromatographic peak height, mu s cm -1 ；
(2) Preparation and testing of sample solutions:
1) Accurately weighing 3-5 g biodiesel in a 50mL test tube by adopting an electronic balance with the accuracy of 0.0001;
2) The method comprises the steps of (1) rapidly oxidizing biodiesel in a test tube by adopting a Rannimat 873 biodiesel oxidation stability tester;
3) After the oxidation reaction is finished, transferring the oxidized biodiesel into a 100mL beaker, adding 30mL of extracting agent, sealing the mouth of the beaker by using a preservative film, and then placing the beaker into a water bath kettle for constant-temperature water bath;
4) Transferring the mixture into a 250mL separating funnel after the water bath is finished, fully vibrating the separating funnel for 1-2 min, standing for layering, placing the lower clear liquid into a 200mL volumetric flask after layering is finished, repeating the water bath-liquid separation for 3-5 times, and using ultrapure water to fix the volume to the scale mark of the volumetric flask;
5) Extracting a proper amount of sample solution in a 200mL volumetric flask by adopting a 10mL injector, sequentially treating the sample solution into a sample injection tube through a C18 reverse phase column and a 0.22 mu m nylon filter head, detecting the chromatographic peak height H of the sample solution by adopting an ion chromatography, bringing the H into a standard curve formula to obtain the phosphorus concentration in the sample solution corresponding to the chromatographic peak height, and calculating the phosphorus content in biodiesel by adopting the following formula:
wherein X: phosphorus content in biodiesel, mg.kg -1 The method comprises the steps of carrying out a first treatment on the surface of the Q: phosphorus concentration in solution, mg.L -1 The method comprises the steps of carrying out a first treatment on the surface of the V: constant volume body of oxidized sample extractProduct, mL; m: mass of biodiesel, g.
The conditions of the rapid oxidation are: the temperature is 110-115 ℃ and the ventilation amount is 10-12 L.h -1 The oxidation time is 22-24 h.
The extractant is ultrapure water.
The water bath temperature is 83-85 ℃ and the water bath time is 30-35 min.
Compared with the prior art, the method has the beneficial effects that:
the biodiesel can be converted into inorganic phosphate by adopting a rapid oxidation mode, and potential safety hazards caused by splashing and burning of samples in the carbonization and ashing processes of the biodiesel can be avoided, meanwhile, the pH value does not need to be adjusted, and complicated operation is avoided.
The method established by the invention has better linear correlation (r=0.9997) and lower detection limit (C) min ＝0.0048mg·L -1 ) Reasonable Reproducibility (RSD)<1.5 percent) and the recovery rate is between 74.35 and 108.14 percent.
The method provided by the invention does not depend on a large instrument, is simple and quick to operate, can meet the requirements of batch sample injection detection in precision, and has more practical significance for detecting the phosphorus content in biodiesel.
Drawings
Fig. 1 is a standard graph of example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples. According to common knowledge, the phosphorus content in the present invention is referred to as phosphate ion content.
When the invention adopts ion chromatography to detect the phosphorus content, PO 4 3- The detection of (1) needs to adopt chemical inhibition conductance detection, and the related parameters comprise the following contents:
(1) Ion chromatography column: the method adopts a Metrosep A support 5-150/4.0 separation column for measurement and analysis, the length is 150mm, the inner diameter is 4mm, and the separation principle is an ion exchange chromatography principle.
(2) Mobile phase composition: 3.2 mmol.L of standard leacheate is adopted -1 Na 2 CO 3 And 1.0 mmol.L -1 NaHCO 3 Prepared in 1000mL volumetric flask, and used as mobile phase with ultrapure water of 18.2M omega resistance to scale mark.
(3) The inhibition phase composition: 5mL of concentrated sulfuric acid was dissolved in 1000mL of ultra pure water to prepare H with a volume concentration of 5% 2 SO 4 Solution, as inhibitor.
Example 1
Drawing a standard curve:
phosphoric acid is adopted to prepare the concentration of 0.5, 1.0, 2.0, 4.0 and 8.0 mg.L respectively -1 PO of (2) 4 3- Standard solution, PO with different concentrations is obtained by detection and analysis of an ion chromatograph 4 3- The chromatographic peak height of the standard solution is drawn, and a standard curve of the phosphorus concentration and the chromatographic peak height is drawn, as shown in fig. 1, and the standard curve is obtained as follows:
H＝5.6943×10 -3 +2.6461×10 -3 Q (1)
the correlation coefficient r= 0.99975 of the standard curve has good linear correlation, and Q is the concentration of phosphorus in the sample solution, mg.L -1 The method comprises the steps of carrying out a first treatment on the surface of the H is chromatographic peak height, mu s cm -1 。
Example 2
A method for quantitatively detecting the phosphorus content in biodiesel based on an accelerated oxidation-ion chromatography method comprises the following specific steps:
(1) Accurately weighing 5g biodiesel in a 50mL test tube by adopting an electronic balance with the accuracy of 0.0001;
(2) The method comprises the steps of rapidly oxidizing biodiesel by adopting a Rannimat 873 biodiesel oxidation stability tester, controlling the temperature at 110 ℃ and controlling the ventilation amount to be 12 L.h -1 Performing rapid oxidation for 24 hours;
(3) After the oxidation reaction is finished, transferring the oxidized biodiesel into a 100mL beaker, adding 30mL of extracting agent (18.2M omega ultrapure water), sealing the mouth of the beaker by using a preservative film, and then placing the beaker in a water bath kettle at 85 ℃ for 30min in a constant-temperature water bath;
(4) Transferring the mixture into a 250mL separating funnel after the water bath is finished, sufficiently vibrating the separating funnel for 1min, standing for layering, placing the lower clear liquid into a 200mL volumetric flask after layering is finished, repeating the water bath-liquid separation in the step (3) and the step (4) for 5 times, and using ultrapure water to fix the volume of the 200mL volumetric flask to a scale mark;
(5) Extracting 10mL of sample solution from a 200mL volumetric flask by using a 10mL syringe, sequentially passing through a C18 reverse phase column (needing to be activated by ultrapure water for at least 10 min) and a 0.22 mu m nylon filter head for filtration treatment to obtain a sample feeding tube, detecting the chromatographic peak height H of the sample solution by using an IC method, bringing H into a standard curve formula (1) of the embodiment 1 to obtain the concentration of the sample solution corresponding to the chromatographic peak height, and calculating the phosphorus content in the biodiesel by using the following formula (3):
wherein X: phosphorus content in biodiesel, mg.kg -1 The method comprises the steps of carrying out a first treatment on the surface of the Q: phosphorus concentration in sample solution, mg.L -1 The method comprises the steps of carrying out a first treatment on the surface of the V: the volume of the oxidized sample extract is fixed, and mL is measured; m: mass of biodiesel, g.
In the embodiment, the biodiesel weighed in the step (1) is 3-5 g, the oxidation temperature in the step (2) is controlled between 110 and 115 ℃ and the ventilation rate is 10-12 L.h -1 The oxidation time is 22-24 hours; the water bath temperature of the step (3) is 83-85 ℃, and the water bath is constant-temperature for 30-35 min; and (4) oscillating the separating funnel for 1-2 min, and carrying out water bath-liquid separation for 3-5 times, wherein the fluctuation can be achieved within the range.
Limit of detection of method:
preparing concentration 0.2 mg.L -1 H of (2) 3 PO 4 The standard solution was repeatedly assayed 3 times using an ion chromatograph by recording PO 4 3- The peak height of the chromatogram and the peak value of the baseline noise are calculated according to the formula (2) to obtain PO 4 3- Is the lowest detected concentration of (2):
wherein H is N : baseline noise peak-to-peak value (μs.cm) -1 )，C min : concentration of standard solution (mg.L) -1 ) V: volume of sample loop (μl), H: height of peak of substance (μs.cm) -1 )。
The results are shown in Table 1.
TABLE 1
| Anions (v-v) | H N (μs·cm -1 ) | C(mg·L -1 ) | H(μs·cm -1 ) | V(μL) | C min (mg·L -1 ) |
| PO 4 3- | 0.001 | 0.2 | 0.049 | 20 | 0.0048 |
As can be seen from Table 1, PO 4 3- The baseline noise peak of (2) was 0.001. Mu.s.cm -1 Less than 0.02 mu s cm -1 Meets the requirement of ion chromatography detection standard GB/T36240-2018 on the baseline noise of the conductivity detector; PO (Positive oxide) 4 3- The lowest detected concentration of (C) is 0.0048mg.L -1 Less than 0.005 mg.L -1 Satisfies the ion colorThe spectrum detection standard GB/T36240-2018 requires a minimum detection concentration for the conductivity detector.
Precision of the method:
preparing concentration 0.2 mg.L -1 H of (2) 3 PO 4 The standard solution is continuously and repeatedly measured for 6 times by adopting an ion chromatograph, and PO is detected each time 4 3- Chromatographic peak height and retention time of (2), and calculate PO 4 3- The Relative Standard Deviation (RSD) was further calculated and the results are shown in table 2.
TABLE 2
| Anions (v-v) | Average peak height (mu s cm) -1 ) | RSD Peak height (％) | Average retention time (min) | RSD Retention time (％) |
| PO 4 3- | 0.331 | 0.400 | 14.18 | 0.05 |
As can be seen from Table 2, PO 4 3- The relative standard deviation of the average chromatographic peak height and average retention time is less than 1.5%, which indicates that the ion chromatographic system is used for detecting inorganic PO 4 3- The stability of the system is better, and meanwhile, the requirements of the ion chromatography detection standard GB/T36240-2018 on the quantitative and qualitative repeatability of the whole machine performance are met.
Example 3
The phosphorus content in the five biodiesel samples was detected and analyzed for the labeled recovery by the method of example 2, and the labeled recovery was calculated according to equation (4):
the results of the five biodiesel tests are shown in table 3.
TABLE 3 Table 3
As shown in Table 3, the range of the standard recovery rate of the five biodiesel samples is 74.35-108.14%, and the range of the acceptable standard recovery rate of the biodiesel samples is 70-120%, which indicates that the method is effective for detecting the phosphorus content in the biodiesel.
Example 4
PO before and after biodiesel oxidation treatment 4 3- Comparison of the content of untreated Jatropha Curcas biodiesel and Jatropha Curcas biodiesel oxidized by Rannimat oxidation method in step (2) of example 2, PO in the two biodiesel was detected by steps (3) - (5) of example 2, respectively 4 3- The content and the results are shown in Table 4.
TABLE 4 Table 4
As can be seen from Table 4, after 24 hours of Jatropha curcas biodiesel treatment by Rannimat oxidation, PO thereof 4 3- The content of PO in untreated Jatropha curcas biodiesel 4 3- 2.3 times of the content, and the phosphorus content is far more than that of the mixture10 mg/kg prescribed by American Society of Testing and Materials (ASTM) D6751 and national biodiesel Standard (GB 25199-2017) -1 It also shows that the phosphorus-containing organic matters in the biodiesel can undergo oxidation-reduction reaction under the condition of accelerating oxidation to generate inorganic phosphate, thereby leading PO to 4 3- The content is increased.
Example 5
The Rannimat oxidation process of step (2) in example 2 was replaced with the "charring-ashing" process of the prior art (heating rate 10 ℃ C. Min -1 Ashing at 680 ℃ for 2 hours), and detecting the phosphorus content in the Jatropha curcas biodiesel respectively without changing other steps, wherein the obtained results are shown in table 5.
TABLE 5
As is clear from Table 5, PO treated by Rannimat oxidation in example 2 4 3- Content and PO under the common carbonization-ashing treatment mode 4 3- The content is close to that of the phosphorus, and the phosphorus content after the Rannimat oxidation treatment is slightly higher, because the Rannimat oxidation treatment has no problems of phosphorus overflow caused by splashing or combustion of samples in a common carbonization-ashing treatment mode, and the accuracy is higher.
Claims (4)
1. A method for detecting total phosphorus content in biodiesel by accelerated oxidation-ion chromatography is characterized by comprising the following specific steps:
(1) Drawing a standard curve:
the concentration of phosphoric acid is 0.5, 1.0, 2.0, 4.0 and 8.0 mg.L -1 PO of (2) 4 3- Standard solution, PO with different concentrations is obtained by detection and analysis of an ion chromatograph 4 3- The standard curve of the phosphorus concentration and the chromatographic peak height is drawn, and the standard curve formula is obtained:
H＝5.6943×10 -3 +2.6461×10 -3 Q
wherein Q is a solutionConcentration of phosphorus in mg.L -1 The method comprises the steps of carrying out a first treatment on the surface of the H is chromatographic peak height, mu s cm -1 ；
(2) Preparation and testing of sample solutions:
1) Carrying out rapid oxidation on biodiesel by adopting a Rannimat oxidation method;
2) Adding an extractant into the oxidized biodiesel, sealing the biodiesel by using a preservative film, and carrying out constant-temperature water bath;
3) After the water bath is finished, standing and layering, separating liquid, placing the supernatant liquid in a volumetric flask, repeating the water bath-liquid separation for 3-5 times, and using ultrapure water to fix the volumetric flask;
4) Extracting a sample solution in a volumetric flask by using an injector, sequentially treating the sample solution to a sample injection tube through a C18 reverse phase column and a 0.22 mu m nylon filter head, detecting the chromatographic peak height H of the sample solution by using an ion chromatography, bringing the H into a standard curve formula to obtain the phosphorus concentration in the sample solution corresponding to the chromatographic peak height, and calculating the phosphorus content in biodiesel by using the following formula:
wherein X: phosphorus content in biodiesel, mg.kg -1 The method comprises the steps of carrying out a first treatment on the surface of the Q: phosphorus concentration in sample solution, mg.L -1 The method comprises the steps of carrying out a first treatment on the surface of the V: the volume of the sample extract is fixed, and mL is measured; m: mass of biodiesel, g.
2. The method for detecting the total phosphorus content in biodiesel by accelerated oxidation-ion chromatography according to claim 1, wherein the conditions of rapid oxidation are: the temperature is 110-115 ℃ and the ventilation amount is 10-12 L.h -1 The oxidation time is 22-24 h.
3. The method for detecting the total phosphorus content in biodiesel by accelerated oxidation-ion chromatography according to claim 1, wherein the extractant is 18.2mΩ ultrapure water.
4. The method for detecting the total phosphorus content in the biodiesel by the accelerated oxidation-ion chromatography according to claim 1, wherein the water bath temperature is 83-85 ℃ and the water bath time is 30-35 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111066986.9A CN113866339B (en) | 2021-09-13 | 2021-09-13 | Method for detecting total phosphorus content in biodiesel by accelerated oxidation-ion chromatography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111066986.9A CN113866339B (en) | 2021-09-13 | 2021-09-13 | Method for detecting total phosphorus content in biodiesel by accelerated oxidation-ion chromatography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113866339A CN113866339A (en) | 2021-12-31 |
| CN113866339B true CN113866339B (en) | 2023-11-24 |
Family
ID=78995392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111066986.9A Active CN113866339B (en) | 2021-09-13 | 2021-09-13 | Method for detecting total phosphorus content in biodiesel by accelerated oxidation-ion chromatography |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113866339B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100096907A (en) * | 2009-02-25 | 2010-09-02 | 한국전기연구원 | Qualitative and quantitative analyses method of materials in high voltage cathode materials in lithium ion secondary batteries |
| CN106769941A (en) * | 2017-01-09 | 2017-05-31 | 西北大学 | The detection method of phosphorus content in a kind of biodiesel |
| CN107966521A (en) * | 2017-12-27 | 2018-04-27 | 黄河三角洲京博化工研究院有限公司 | The quantitative approach of dimethylamine in a kind of detection nicosulfuron recycling waste water using suppressed ion chromatography |
| CN111239275A (en) * | 2020-01-22 | 2020-06-05 | 广西大学 | Method for measuring total phosphorus content of soil or sludge |
| CN112505190A (en) * | 2020-12-16 | 2021-03-16 | 中煤浙江检测技术有限公司 | Method for detecting acrylic acid in soil |
-
2021
- 2021-09-13 CN CN202111066986.9A patent/CN113866339B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100096907A (en) * | 2009-02-25 | 2010-09-02 | 한국전기연구원 | Qualitative and quantitative analyses method of materials in high voltage cathode materials in lithium ion secondary batteries |
| CN106769941A (en) * | 2017-01-09 | 2017-05-31 | 西北大学 | The detection method of phosphorus content in a kind of biodiesel |
| CN107966521A (en) * | 2017-12-27 | 2018-04-27 | 黄河三角洲京博化工研究院有限公司 | The quantitative approach of dimethylamine in a kind of detection nicosulfuron recycling waste water using suppressed ion chromatography |
| CN111239275A (en) * | 2020-01-22 | 2020-06-05 | 广西大学 | Method for measuring total phosphorus content of soil or sludge |
| CN112505190A (en) * | 2020-12-16 | 2021-03-16 | 中煤浙江检测技术有限公司 | Method for detecting acrylic acid in soil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113866339A (en) | 2021-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liang et al. | Dispersive liquid–liquid microextraction preconcentration of palladium in water samples and determination by graphite furnace atomic absorption spectrometry | |
| CN108120790B (en) | Low-pressure anion exchange chromatography-photometric turbidimetry for simultaneously analyzing trace sulfur ions and chloride ions in water sample on line | |
| Orozco et al. | Analysis of metals and phosphorus in biodiesel B100 from different feedstock using a Flow Blurring® multinebulizer in inductively coupled plasma-optical emission spectrometry | |
| de Souza et al. | Determination of trace elements in crude oil by ICP-OES using ultrasound-assisted acid extraction | |
| Soares et al. | A flow-based procedure exploiting the lab-in-syringe approach for the determination of ester content in biodiesel and diesel/biodiesel blends | |
| Duan et al. | Direct determination of arsenic in soil samples by fast pyrolysis–chemical vapor generation using sodium formate as a reductant followed by nondispersive atomic fluorescence spectrometry | |
| CN113866339B (en) | Method for detecting total phosphorus content in biodiesel by accelerated oxidation-ion chromatography | |
| CN108593606B (en) | Method for testing germanium content in coal by utilizing atomic fluorescence spectroscopy | |
| CN1769872A (en) | Method and apparatus for measuring chromium by chemical vapor generation-atomic fluorescence spectrometry | |
| Zhou et al. | Determination of total phosphorus in biodiesel by ion chromatography | |
| CN101324520B (en) | Method for rapidly detecting micro trace quantity lead in ship hull steel with graphite oven atomic absorption | |
| Zhang et al. | Determination of inorganic arsenic speciation in municipal solid waste incineration fly ash by high performance liquid chromatography-hydride generation-atomic fluorescence spectroscopy with phosphoric acid as extracting agent | |
| CN115326914B (en) | Method for simultaneously and rapidly measuring chlorine, bromine and iodine by high-temperature hydrolysis combined ICP-MS | |
| CN103234957B (en) | Method for determining concentration of cyanides in environment | |
| CN111855866A (en) | Method for rapidly determining formaldehyde in tobacco additive | |
| CN109632933B (en) | Analysis method of fat emulsion injection | |
| CN111562303A (en) | Method for quantitatively detecting concentration of bismuth in serum by inductively coupled plasma mass spectrometry | |
| CN114324657B (en) | Method for detecting myrcene in soil by combining purging and trapping with GC-MS (gas chromatography-mass spectrometer) | |
| CN104713954B (en) | Method for detecting content of haloacetonitrile substances in water sample through dispersive liquid-liquid microextraction programmed temperature gas chromatography-mass spectrometry | |
| CN111443056B (en) | Method for measuring mercury content in copper concentrate | |
| Carballo-Paradelo et al. | Pressurized liquid extraction to determine Mg, Al, Ti, Cu, Sn and Pb in lubricating oils by inductively coupled plasma mass spectrometry | |
| Chen et al. | Determination of Hg and Pb in fuels by inductively coupled plasma mass spectrometry using flow injection chemical vapor generation | |
| CN111024858B (en) | Method for detecting alkane in drinking water | |
| CN108931516B (en) | System parameter optimization method capable of saving sample introduction amount and serum element quantitative analysis method | |
| CN112557576A (en) | Method for measuring content of calcium and magnesium ions in industrial circulating water |
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 |