CN101281181B - Method for measuring organic acid and ester of centrifuge waste water in cis-anhydride production process with liquid phase chromatography - Google Patents
Method for measuring organic acid and ester of centrifuge waste water in cis-anhydride production process with liquid phase chromatography Download PDFInfo
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Abstract
The invention relates to a detecting method for the organic acid and ester in centrifugal waste water in the cis-butenedioic anhydride production process through liquid chromatography, the method uses Agilent C18 chromatographic column as the analytical column, water, methanol, and acetidin are mixed in a certain proportion as mobile phase, the flow velocity is 1.0ml/min, the column temperature is 40 DEG C, the operating time is 25min, the sample volume is 20mul, an external standard method quantificationally analyzes the organic acid and ester in the cis-butenedioic anhydride waste water through liquid chromatography, the linearly dependent coefficient is more than 0.9969. The invention carries out the effective quantitative analysis for the organic acid and ester in centrifugal waste water in the cis-butenedioic anhydride production process, the detecting method is simple and has good reproducibility; the detecting result is accuracy, the sensitivity is high, which acts a positive pushing effect for enhancing the product quality and lowing product cost of the cis-butenedioic anhydride.
Description
Technical field
The invention belongs to chemical analysis field, relating to a kind of is the analytical approach of maleic acid, fumaric acid, phthalic acid and dibutyl phthalate in the centrifuge waste water in the raw material production maleic acid anhydride process with the butane.
Background technology
Maleic anhydride is called for short cis-butenedioic anhydride; Be a kind of important Organic Chemicals and fine chemical product; Be mainly used in and produce unsaturated polyester resin, alkyd resin; Fields such as coating, printing ink, oil dope, agricultural chemicals, paper sizing agent, the agent of textile permanent finiss, surfactant in addition, are that raw material can also be produced a series of important fine chemical products such as tetrahydrofuran, maleic acid, the calculation of rich horse and tetrahydrochysene acid anhydrides with the cis-butenedioic anhydride.
Cis-butenedioic anhydride is to be that raw material generates through catalytic oxidation with the butane; Maleic acid, fumaric acid, phthalic acid and dibutyl phthalate (hereinafter to be referred as organic acid and ester) are main organic compositions in the centrifuge waste water in the cis-anhydride production process, and the height of its content directly affects the quality and the production cost of cis-butenedioic anhydride product.Therefore, for carrying out smoothly of adapting device production, set up one fast, accurately the analytical approach of organic acid and ester is necessary in the easy cis-butenedioic anhydride centrifuge waste water.
At present, domestic to maleic acid, fumaric mensuration employing gas chromatography analysis method in the centrifuge waste water in the cis-anhydride production process, the spectrophotometric analysis method of phthalic acid, repefral.But owing to maleic acid, fumaric acid are isomerss, difficulty is bigger in chromatographic resolution; In addition, in the ordinary course of things, maleic acid, fumaric acid, the phthalic acid solubleness in water is little, and is accurately quantitatively comparatively difficult.And because gas chromatography analysis method is different fully with the sample background of spectrophotometric analysis method, therefore, maleic acid, fumaric acid, phthalic acid and dibutyl phthalate can not be with measuring simultaneously with a kind of analytical approach.
Summary of the invention
The objective of the invention is to set up a liquid phase chromatography analytical method with maleic acid, fumaric acid, phthalic acid and dibutyl phthalate content in the centrifuge waste water in the external standard method quantitative test simultaneously cis-anhydride production process.
The present invention adopts in the liquid chromatogram measuring cis-anhydride production process in the centrifuge waste water method of maleic acid, fumaric acid, phthalic acid and dibutyl phthalate following:
(1) preparation of standard model solution
Accurately take by weighing maleic acid, fumaric acid, phthalic acid and dibutyl phthalate standard substance 0.01 gram (accurately to ± 0.0001 gram) respectively, be mixed with the standard solution of 4～5 variable concentrations respectively, subsequent use.For guaranteeing detection signal in the optimal response value scope of instrument (full-scale 20% one 80%), the concentration range of this sample standard solution is 0.05～5mg/ml.
(2) standard working curve is drawn
With Agilent C18 chromatographic column is analytical column, and water, methyl alcohol, ethyl acetate are by mixing than row as moving phase (initial than being listed as: water/methanol/ethyl acetate=10/20/70, carry out gradient elution for each component can fully be separated); Flow velocity 1.0mL/min, 40 ℃ of column temperatures, working time 25min; Sample size 20 μ L, external standard method is quantitatively carried out liquid-phase chromatographic analysis to the standard solution that step (1) is prepared, and records the peak area at each peak; Use peak area to be ordinate; Concentration is horizontal ordinate drawing standard curve, obtains linear equation and property shape related coefficient, and calculates the absolute correction factor of each standard substance.
(3) actual sample determination and analysis
Earlier cis-butenedioic anhydride centrifuge waste water sample is shaken up, take by weighing 2 grams (accurately to ± 0.0001 gram) then rapidly and place 50ml volumetric flask, water dissolving and constant volume; Shake up the back with this solution of pipette, extract 1ml in the 10ml volumetric flask, be diluted with water to scale, shake up; Process sample solution, subsequent use.
With Agilent C18 chromatographic column is analytical column; Water, methyl alcohol, ethyl acetate mix as moving phase in proportion, flow velocity 1.0mL/min, 40 ℃ of column temperatures; Working time, 25min was a condition; Sample solution to preparation carries out liquid-phase chromatographic analysis, records the peak area of each component, directly checks in each component concentration from above-mentioned typical curve according to peak area; Or pass through following formula and calculate each component concentration:
Computing formula: Wi%=fiAi
In the formula: Ai---the peak area of component to be measured
The absolute correction factor of fi---standard substance
Wi---desire is surveyed components contents.
For each component is fully separated, the initial proportion of moving phase is: gradient elution is adopted in water/methanol/ethyl acetate=10/20/70.
The present invention has carried out effective quantitative test simultaneously to the organic acid and the ester (maleic acid, fumaric acid, phthalic acid and dibutyl phthalate) of centrifuge waste water in the cis-anhydride production process, and its assay method is simple, favorable reproducibility; It is accurate, highly sensitive to measure the result, has played positive impetus to improving the cis-butenedioic anhydride product quality with reducing cost.
Description of drawings
The canonical plotting of Fig. 1 maleic acid
The fumaric canonical plotting of Fig. 2
The canonical plotting of Fig. 3 phthalic acid
The canonical plotting of Fig. 4 dibutyl phthalate
Each component chromatogram separating effect figure of Fig. 5
Embodiment
(1) preparation of standard model solution
Take by weighing maleic acid, fumaric acid, phthalic acid and dibutyl phthalate standard substance 0.01 gram (accurately to ± 0.0001 gram) respectively, be mixed with the standard solution of 4～5 variable concentrations respectively, subsequent use.For guaranteeing detection signal in the optimal response value scope (full-scale 20%～80%) of instrument, the concentration range of the standard model solution of this experiment is 0.05～5mg/ml.
(2) chromatographiccondition
Instrument and chromatographic column: Agilent HP1090 or Tianjin, island SCL-10AVP liquid chromatograph, matching used with it PDAD and data handling system, Agilent C18 chromatographic column.
Moving phase: water/methanol/ethyl acetate adopts gradient elution with 10/20/70 initial mass mixed.
Raw material: methyl alcohol (chromatographically pure), ethyl acetate (chromatographically pure), pure water (resistivity >=18.23 Ω).
Flow velocity: 1.0ml/min.
Column temperature: 40 ℃.
Working time: 25min.
Sample size: 20 μ l.
Quantivative approach: external standard method.
(3) range of linearity and related coefficient are measured
By above-mentioned chromatographic condition; After treating instrument stabilizer, each the standard model solution sample introduction to step (1) is prepared carries out liquid-phase chromatographic analysis; Record the peak area of component to be measured; Draw the typical curve of peak area, and record the range of linearity of curve, linear related coefficient, calculate the absolute correction factor of each component concentration.
Mensuration result is following:
Maleic acid: typical curve is: y=1696.2x+65.251, and the range of linearity is 10～3720ppm, and linearly dependent coefficient is 0.9969, and absolute correction factor is 4.83 * 10
-7
Fumaric acid: typical curve is: y=2848.2x+510.46, and the range of linearity is 10～2760ppm10～3720ppm, and linearly dependent coefficient is 0.9973, and absolute correction factor is 3.04 * 10
-7
Phthalic acid: typical curve is: y=1790.9x+225.1, and the range of linearity is 10～4280ppm, and linearly dependent coefficient is 0.9989, and absolute correction factor is 4.11 * 10
-7
Dibutyl phthalate: typical curve is: y=1190.8x+173.2, and the range of linearity is 10～2840ppm, and linearly dependent coefficient is 0.9999, and absolute correction factor is 6.02 * 10
-7
Record standard model solution maleic acid, fumaric acid, phthalic acid and dibutyl phthalate typical curve and separate colors spectrogram such as Fig. 1～5.Among Fig. 5,1---maleic acid, 2---fumaric acid, 3---phthalic acid, 4---dibutyl phthalate.
(4) actual sample determination and analysis
Earlier cis-butenedioic anhydride centrifuge waste water sample is shaken up, take by weighing 2 grams (accurately to ± 0.0001 gram) then rapidly and place 50ml volumetric flask, water dissolving and constant volume; Shake up the back with this solution of pipette, extract 1ml in the 10ml volumetric flask, be diluted with water to scale, shake up; Process testing sample solution, subsequent use.
Press the chromatographic condition of standard specimen, treat instrument stabilizer after, sample introduction 20 μ l carry out liquid-phase chromatographic analysis, record the peak area of each component, directly check in each component concentration from typical curve according to peak area.Also can calculate each component concentration through following formula:
Computing formula: Wi%=fiAi
In the formula: Ai---desire is surveyed the peak area of component
The absolute correction factor of fi---standard substance
Wi---desire is surveyed components contents
Measure the result: each components contents is seen table 1 in the cis-butenedioic anhydride centrifuge waste water.
The mensuration result of each component in the table 1 part cis-butenedioic anhydride centrifuge waste water actual sample
| Batch | Maleic acid (%) | Fumaric acid (%) | Phthalic acid (%) | Ditridecyl phthalate (%) |
| 07-6-11 | 0.73 | 0.39 | 0.35 | 0.02 |
| 07-6-12 | 4.80 | 0.57 | 10.61 | 1.25 |
| 07-6-13 | 0.03 | 0.12 | 0.17 | 0.03 |
| 07-6-14 | 2.10 | 0.74 | 14.32 | 0.24 |
| 07-6-15 | 1.98 | 0.75 | 14.90 | 0.70 |
Claims (1)
1. the method for organic acid and ester in the centrifuge waste water in the liquid chromatogram measuring cis-anhydride production process may further comprise the steps:
(1) preparation of standard model solution
Take by weighing maleic acid, fumaric acid, phthalic acid and dibutyl phthalate standard substance 0.01 gram respectively, be mixed with the standard solution of several variable concentrations respectively, subsequent use; The concentration range of standard solution is 0.05～5mg/ml;
(2) standard working curve is drawn
With Agilent C18 chromatographic column is analytical column, and water, methyl alcohol, ethyl acetate mix as moving phase flow velocity 1.0mL/min by 10: 20: 70 mass ratio; 40 ℃ of column temperatures, working time 25min, sample size 20 μ L; External standard method is quantitatively carried out liquid-phase chromatographic analysis to the above-mentioned standard solution of preparing; Record the peak area at each peak, use peak area to be ordinate, concentration is horizontal ordinate drawing standard curve; Obtain linear equation and linearly dependent coefficient, and calculate the absolute correction factor of each standard substance;
(3) actual sample determination and analysis
Earlier cis-butenedioic anhydride centrifuge waste water sample is shaken up, accurately takes by weighing 2g then rapidly and place the 50ml volumetric flask, water dissolving and constant volume, shake up the back with this solution of pipette, extract 1ml in the 10ml volumetric flask, be diluted with water to scale, shake up, process sample solution, subsequent use;
With Agilent C18 chromatographic column is analytical column, and water, methyl alcohol, ethyl acetate mix as moving phase flow velocity 1.0mL/min by 10: 20: 70 mass ratio; Sample size 20 μ L; 40 ℃ of column temperatures, working time, 25min was a chromatographic condition, and the sample solution for preparing is carried out liquid-phase chromatographic analysis; Record the peak area of each component, directly check in each component concentration from above-mentioned typical curve according to peak area; Or pass through following formula and calculate each component concentration:
Computing formula: Wi%=fiAi
In the formula: Ai---the peak area of component to be measured
The absolute correction factor of fi---standard substance
Wi---desire is surveyed components contents.
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Citations (3)
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|---|---|---|---|---|
| US20010029302A1 (en) * | 2000-04-10 | 2001-10-11 | Soon-Haeng Cho | Preparation of gamma-butyrolactone by catalytic hydrogenation of maleic anhydride |
| CN1916620A (en) * | 2005-08-18 | 2007-02-21 | 宝山钢铁股份有限公司 | Method for determining picric acid in desulfurization solution |
| CN101046467A (en) * | 2006-03-30 | 2007-10-03 | 国药控股深圳中药有限公司 | Process of measuring matrine content in Qingbai cleaning lotion |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010029302A1 (en) * | 2000-04-10 | 2001-10-11 | Soon-Haeng Cho | Preparation of gamma-butyrolactone by catalytic hydrogenation of maleic anhydride |
| CN1916620A (en) * | 2005-08-18 | 2007-02-21 | 宝山钢铁股份有限公司 | Method for determining picric acid in desulfurization solution |
| CN101046467A (en) * | 2006-03-30 | 2007-10-03 | 国药控股深圳中药有限公司 | Process of measuring matrine content in Qingbai cleaning lotion |
Non-Patent Citations (4)
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| 周秋华等.高效液相色谱-质谱法测定废水中微量氯苯酚和硝基苯酚.《淮阴师范学院学报（自然科学版）》.2005,第4卷(第1期),全文. * |
| 张晓峰.反相高效液相色谱法测定废水中的邻苯二甲酸酯类化合物.《石化技术》.2001,第8卷(第4期),225-228. * |
| 李金昶等.用反相高效液相色谱法分离和测定丁烯二酸的顺反异构体.《分析测试学报》.2000,第19卷(第2期),72-74. * |
| 王远等.代森锰锌废水中乙撑硫脲的高效液相色谱分析.《农药》.2007,第46卷(第2期),全文. * |
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