CN104749271A - Determination method for content of methanol in water of methanol cracking device - Google Patents
Determination method for content of methanol in water of methanol cracking device Download PDFInfo
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- CN104749271A CN104749271A CN201510099184.6A CN201510099184A CN104749271A CN 104749271 A CN104749271 A CN 104749271A CN 201510099184 A CN201510099184 A CN 201510099184A CN 104749271 A CN104749271 A CN 104749271A
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Abstract
The invention provides a determination method for content of methanol in water of a methanol cracking device and aims at solving the problem in the prior art that the methanol in the water cannot be determined. wherein a hydrogen flame ionization detector is used for detecting the content of the methanol in a water sample and an external standard method is utilized to calculate; and the method is simple and rapid to operate. The invention provides the accurate and efficient detection method. With the adoption of the scheme, an injector can be used for conveniently feeding the sample under a selected working condition, and the hydrogen flame ionization detector is used for detecting; and the method has the characteristics of low detection limit, accurate analysis result, simplicity and convenience for operation and rapidness.
Description
Technical field
The present invention relates to a kind of assay method technical field of chemical analysis, the assay method of methanol content in the methanol cracking device water of particularly a kind of analysis and test method.Be applicable to the mensuration of methanol content in methanol cracking device fresh water (FW) and recycle-water.
Background technology
Methyl alcohol is one of basic organic.Mainly for the manufacture of multiple organic products such as formaldehyde, acetic acid, chloromethanes, methylamine and dimethyl suflfates.Can be used as the solvent of coating, varnish, shellac, ink, adhesive, dyestuff, alkaloid, cellulose acetate, cellulose nitrate, ethyl cellulose, polyvinyl butyral etc., can be used as that analytical reagent is clear, motor vehicle antifreeze fluid, metal surface cleaning agent and alcotate, for organic synthesis etc.Methyl alcohol is important fuel, can mix gasoline and do alternative fuel use.Methyl alcohol uses as the fuel additive of F1 racing car, is also widely used in methanol fuel cell.Manufacture agricultural chemicals, medicine, plastics, synthon and Organic chemical products as the raw material of formaldehyde, methylamine, chloromethanes, dimethyl suflfate etc.It is one of important industrial chemicals.In recent years, along with the development of C1 chemical industry, methyl alcohol has become the important source material manufacturing ethene and propylene.
Methanol decomposition alkene alkene commercial production adopts fixed bed reactors to produce, and relative to traditional methanol-to-olefins fluidized-bed process, less at industrial amplification process risk, cost is lower, and its reactive system is more ripe simple, possesses the condition of industrial applications.The principal ingredient of methanol decomposition is alkene and water, simultaneously the product such as by-product BTX aromatics, liquefied gas.
Methyl alcohol has hypotoxicity to microorganism in water, and mass concentration is that the methyl alcohol of 790mg/l can make organic discomposing effect in biological filter weaken, and mass concentration is the digestion that the methyl alcohol of 5000mg/l can suppress mud in digester.If the fresh water (FW) containing methyl alcohol is directly entered water body, serious pollution and destruction can be caused to environment.
Along with developing rapidly of China's economy, methanol consumption amount with average annual 15.11% speed increase, in addition, the expansion of methanol production scale and the change of production work technique cause the methanol waste water water yield to increase, and water quality is complicated.Therefore, when selecting methanol waste water treatment process, following problem is considered in suggestion: (1) due to the water yield of methanol waste water, water quality, fluctuating temperature comparatively large, advise the cooling regulating reservoir that certain scale is set before methanol waste water disposal system; (2) adopt new technology, secondary product (as biogas etc.) that methanol waste water disposal system produces by new equipment recycles, reduce methanol waste water processing cost, avoid producing secondary pollution.(3) because methanol waste water Middle nutrition material is single, can consider suitably to introduce other waste water with supplementary nitrogen, phosphorus source, thus reduce the addition of medicament; (4) each treatment process is optimized combination, to ensure the stable of methyl alcohol treatment effect, standard water discharge is discharged.
This just needs analytical control accurately, measures methanol content in water outlet, according to methanol content in water, takes effective measures the methyl alcohol in recovery process water, and the methyl alcohol in waste water is reclaimed in process, makes discharged wastewater met the national standard.Separate in this methanol cracking device work alcohol fresh water (FW), thus reach the object of Methanol Recovery.
Summary of the invention
The object of the invention is the assay method that methanol content in a kind of methanol cracking device water is provided by external standard method utilizing analytical test.Because methyl alcohol is a kind of important poisonous industrial chemicals, be widely used in production, and the method can detect the content of methyl alcohol in water fast, so that formulate the monitoring standard method of methyl alcohol in water and waste water.
The technical solution adopted in the present invention is:
This method is vapor-phase chromatography, and sample, after capillary chromatographic column is separated, is identified with flame ionization ditector and records the methyl alcohol peak obtained, dividing methanol content in bleed with quantified by external standard method;
An assay method for methanol content in methanol cracking device water, is characterized in that through following each step:
A. chromatograph condition of work is regulated:
Chromatographic column: restek Stadilwax 30m × 0.53mm × 1 μm capillary chromatograph;
Detecting device: flame ionization ditector;
Injector temperature: 180 ~ 220 DEG C;
Post case temperature: 110 ~ 140 DEG C;
Split ratio: 40 ~ 50: 1;
Bypass flow: 120 ~ 150ml/min;
Detected temperatures: 300 DEG C;
Carrier gas: N2, flow 25ml/min;
Hydrogen flowing quantity: 40ml/min;
Air mass flow: 450ml/min;
Sample size: 0.5 ~ 2 μ l;
B. according to the actual needs that methanol cracking device is produced, first select the concentration be close with methanol content in production technology water and recycle-water as standard point configuration standard solution, the methanol concentration of this standard solution is the standard mixed solution of 0.005 ~ 5%, and the solute of this standard mixed solution is methyl alcohol (content (CH
3oH)>=99.9%, density 0.791 ~ 0.793), solvent is distilled water;
C., after chromatograph is stable, draw in standard solution 0.5 ~ 2 μ l inject gas chromatograph with micro syringe and measure, obtain the spectrogram of the standard solution of corresponding above-mentioned B methanol concentration, in table of corrections, input methanol concentration accurately;
D. be horizontal ordinate with time, to output signal size for ordinate, drawing standard curve, and calculate peak area according to the typical curve drawn, obtain standard spectrogram, A ~ D sets up and completes outer calibration method;
E. after chromatograph is stable, according to the step of above-mentioned A ~ D, testing sample solution 0.5 ~ 2 μ l is drawn with micro syringe
Measure in injecting chromatograph, obtain the peak area of testing sample, according to the retention time of methyl alcohol, on step D spectrogram, methanol content in testing sample can be drawn according to the peak area of testing sample.
The chromatograph condition of work of optimization of the present invention is:
Chromatographic column: restek Stadilwax 30m × 0.53mm × 1 μm capillary chromatograph;
Detecting device: flame ionization ditector;
Injector temperature: 190 ~ 210 DEG C;
Post case temperature: 120 ~ 130 DEG C;
Split ratio: 45 ~ 50: 1;
Bypass flow: 120 ~ 130ml/min;
Detected temperatures: 300 DEG C;
Carrier gas: N2, flow 25ml/min;
Hydrogen flowing quantity: 40ml/min;
Air mass flow: 450ml/min;
Sample size: 1 μ l.
Gas chromatographic column of the present invention is strong polar column restek Stadilwax, methyl alcohol is strong polarity thing, in stratographic analysis, strong polarity thing adopts strong polar column restek Stadilwax to be separated, good separating effect can be obtained, use flame ionization ditector the material of more low content can be detected;
Due to the concentration such as 0.005% that configuration is too low, the sample size of weighing is too little, and weighing error is large; Configuration higher concentration such as 5%, can consume more methanol reagent, and according to the principle that economical rationality is suitable for, it is the standard solution of 1.5% that the present invention have selected configuration methanol content.
In above-mentioned after chromatograph is stable, draw in standard solution 1 μ l sample introduction to gas chromatograph with micro syringe and measure, obtain the spectrogram of the standard solution of 1.5% methanol concentration configured, methanol concentration is accurately inputted in table of corrections, this routine methyl alcohol actual concentrations is 1.4917%, as accompanying drawing 1.Because 0.5 μ l sample size is too little, affect by external condition comparatively large, analyze inaccurate.2 μ l sample sizes more greatly, owing to being nearly all water in sample, affect the serviceable life of chromatographic column.1 μ l sample size can ensure the accuracy analyzed, less on chromatographic column impact again, is best sample size.
The advantage that the present invention has and positive technique effect are: the assay method that the invention provides methanol content in a kind of water, by vapor-phase chromatography, the peak area of first bioassay standard sample, drawing standard curve, and with bioassay standard sample the same terms under measure the peak area of testing sample, according to gained testing sample peak area, methanol quality mark in water can be obtained in typical curve.The present invention restek Stadilwax capillary column is separated sample, makes methyl alcohol and other magazins' layout, Trace Methanol content in energy Accurate Determining water, and easy to operate, quick, applied widely, is conducive to the advantages such as analyst's health and environmental protection.
The present invention is that the mensuration of methanol content in water provides one detection method accurately and effectively, adopt such scheme, can easily under selected condition of work, utilize syringe sampling, detect with flame ionization ditector, the method detection limit is low, and analysis result is accurate, easy and simple to handle, feature efficiently.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described.
Fig. 1 is that the inventive method measures methanol content standard colour chart simplified schematic diagram in water;
Fig. 2 is that the inventive method measures methanol content in water and to purify waste water chromatogram simplified schematic diagram;
Fig. 3 is that the inventive method measures methanol content fresh water (FW) chromatogram simplified schematic diagram in water;
Fig. 4 is that the inventive method measures methanol content technique cold water chromatogram simplified schematic diagram in water.
The present invention to be described in further detail by example below in conjunction with accompanying drawing; but following example is only the present invention's example wherein; do not represent the rights protection scope that the present invention limits, the scope of the present invention is as the criterion with claims.
Embodiment
The present invention is achieved through the following technical solutions: the assay method of methanol content in a kind of water, it is characterized in that through following each step:
Example 1:
1 instrument, reagent and material
1) instrument
Gas chromatograph: the gas chromatograph 6890N being furnished with flame ionization ditector.
Chromatographic column: restek Stadilwax 30m × 0.53mm × 1 μm capillary chromatograph
2) reagent and material
Carrier gas: nitrogen, purity is greater than 99.99% (V/V)
Combustion gas: hydrogen, purity is greater than 99.99% (V/V)
Combustion-supporting gas: air, through silica gel and 5A molecular sieve drying, purification.
Micro syringe: 10 μ l.
2 chromatographic condition settings:
3 experimental procedures
3.1 regulate chromatograph condition of work by above-mentioned requirements;
3.2 prepare the standard mixed solution that methanol concentration is 1.5%, and the solute of this standard mixed solution is methyl alcohol, and solvent is distilled water; 3.3 after chromatograph is stable, draw in standard solution 1 μ l sample introduction to gas chromatograph with micro syringe and measure, obtaining methanol concentration in water is the spectrogram of the standard solution of 1.5%, methanol concentration is accurately inputted in table of corrections, in this routine water, methyl alcohol actual concentrations is 1.4917%, as accompanying drawing 1.
Apply this kind of analytical approach to measure the methanol content in methanol cracking device recycle-water sample, carry out quantitatively by external standard method to methanol content in water, surveying middle methanol content of purifying waste water is 0.0108%, in fresh water (FW) water, methanol content is 0.0453%, in technique cold water water, methanol content is 0.6837%, the result obtained as accompanying drawing 2,3,4.These data are that the chromatographic work station directly configured by gas chromatograph calculates automatically, are the solution of the normal concentration using the methyl alcohol of >=99.9% and distilled water accurately to configure for quantitative criterion sample.
Example 2
Changing injector temperature is 220 DEG C, and other condition, with example 1, the results are shown in " the sample result table of comparisons ".
Example 3
Changing split ratio is 40: 1, and other condition, with example 1, the results are shown in " the sample result table of comparisons ".
Example 4
Changing post case temperature is 140 DEG C, and other condition, with example 1, the results are shown in " the sample result table of comparisons ".
The sample result table of comparisons
From above result, the absolute deviation of example 1 is minimum, and relative deviation is equally also minimum, therefore the operating conditions in prioritizing selection example 1.
Claims (2)
1. the assay method of methanol content in methanol cracking device water, is characterized in that through following each step:
A. chromatograph condition of work is regulated:
Chromatographic column: restek Stadilwax 30m × 0.53mm × 1 μm capillary chromatograph;
Detecting device: flame ionization ditector;
Injector temperature: 180 ~ 220 DEG C;
Post case temperature: 110 ~ 140 DEG C;
Split ratio: 40 ~ 50: 1;
Bypass flow: 120 ~ 150ml/min;
Detected temperatures: 300 DEG C;
Carrier gas: N2, flow 25ml/min;
Hydrogen flowing quantity: 40ml/min;
Air mass flow: 450ml/min;
Sample size: 0.5 ~ 2 μ l;
B. according to the actual needs that methanol cracking device is produced, first select the concentration be close with methanol content in production technology water and recycle-water as standard point configuration standard solution, the methanol concentration of this standard solution is the standard mixed solution of 0.005 ~ 5%, and the solute of this standard mixed solution is methyl alcohol (content (CH
3oH)>=99.9%, density 0.791 ~ 0.793), solvent is distilled water;
C., after chromatograph is stable, draw in standard solution 0.5 ~ 2 μ l inject gas chromatograph with micro syringe and measure, obtain the spectrogram of the standard solution of corresponding above-mentioned B methanol concentration, in table of corrections, input methanol concentration accurately;
D. be horizontal ordinate with time, to output signal size for ordinate, drawing standard curve, and calculate peak area according to the typical curve drawn, obtain standard spectrogram, A ~ D sets up and completes outer calibration method;
E. after chromatograph is stable, according to the step of above-mentioned A ~ D, draw in testing sample solution 0.5 ~ 2 μ l injecting chromatograph with micro syringe and measure, obtain the peak area of testing sample, according to the retention time of methyl alcohol, on step D spectrogram, methanol content in testing sample can be drawn according to the peak area of testing sample.
2. the assay method of methanol content in methanol cracking device water according to right 1, is characterized in that:
The chromatograph condition of work optimized:
Chromatographic column: restek Stadilwax 30m × 0.53mm × 1 μm capillary chromatograph;
Detecting device: flame ionization ditector;
Injector temperature: 190 ~ 210 DEG C;
Post case temperature: 120 ~ 130 DEG C;
Split ratio: 45 ~ 50: 1;
Bypass flow: 120 ~ 130ml/min;
Detected temperatures: 300 DEG C;
Carrier gas: N2, flow 25ml/min;
Hydrogen flowing quantity: 40ml/min;
Air mass flow: 450ml/min;
Sample size: 1 μ l.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105588895A (en) * | 2015-12-16 | 2016-05-18 | 湖北兴瑞化工有限公司 | Detecting method for methyl alcohol content in acid |
| CN108896672A (en) * | 2018-06-21 | 2018-11-27 | 北京城市排水集团有限责任公司 | A kind of measuring method for methanol in sewage |
| CN113198637A (en) * | 2021-04-07 | 2021-08-03 | 太原理工大学 | Spraying device and method for detecting multi-carbon alcohol in methanol gasoline |
Citations (1)
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| EP2111763A1 (en) * | 2008-04-21 | 2009-10-28 | Unilever N.V. | Process of making hoodia plant extract with improved flavor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2111763A1 (en) * | 2008-04-21 | 2009-10-28 | Unilever N.V. | Process of making hoodia plant extract with improved flavor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105588895A (en) * | 2015-12-16 | 2016-05-18 | 湖北兴瑞化工有限公司 | Detecting method for methyl alcohol content in acid |
| CN108896672A (en) * | 2018-06-21 | 2018-11-27 | 北京城市排水集团有限责任公司 | A kind of measuring method for methanol in sewage |
| CN113198637A (en) * | 2021-04-07 | 2021-08-03 | 太原理工大学 | Spraying device and method for detecting multi-carbon alcohol in methanol gasoline |
| CN113198637B (en) * | 2021-04-07 | 2022-03-15 | 太原理工大学 | Spraying device and method for detecting multi-carbon alcohol in methanol gasoline |
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Application publication date: 20150701 |