CN107345944A - A kind of method of acetaldehyde in measure liquid phase mixture - Google Patents
A kind of method of acetaldehyde in measure liquid phase mixture Download PDFInfo
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Abstract
The present invention relates to a kind of method for determining acetaldehyde in liquid phase mixture, methacrylaldehyde, acrylic acid, acetic acid are mainly contained in liquid phase mixture, using butanone as internal standard compound, the content of acetaldehyde in inner mark method ration analysis prepare liquid.The assay method cost of the present invention is low, and easy to operate, method is simple and quick, and measurement result is accurate, reproducible.
Description
Technical field
The present invention relates to a kind of method for determining acetaldehyde in liquid phase mixture, particularly relates to the measure that acrolein oxidation prepares acetaldehyde in acrylic acid reaction liquid product.
Background technology
At present, legal system acrylic acid, i.e. generally use fixed bed reactors are mainly industrially aoxidized with propylene two-step, for propylene initial oxidation into methacrylaldehyde (one section of reaction), methacrylaldehyde is reoxidised into acrylic acid (second-stage reaction).
Using propylene as waste methacrylaldehyde (ACR), acrylic acid (AA) catalyst research in, the distribution to reaction product is needed accurately to be detected with content, to the reliable data of the offer such as life-span, the optimised process operating condition of selecting catalyst screened catalyst formulation, investigate catalyst.It is mainly methacrylaldehyde, also acrylic acid, acetic acid, acetaldehyde etc. in one section of liquid product.It is mainly acrylic acid, also methacrylaldehyde, acetic acid, acetaldehyde etc. in two sections of liquid products.Gas phase mainly determines CO, CO in reaction end gas2、C3 =(propylene), O2、N2Content, the content (acetic acid, acetaldehyde) of methacrylaldehyde, acrylic acid and its major impurity is determined in liquid phase.At present, acrylic acid (AA) industry is also without the acrylic acid production analysis professional standard of more holonomic system, there is enterprise to continuously enter several chromatograms using a sample to be analyzed (gas sample, the not separated sampling of liquid sample), this method is more accurate, but time-consuming for whole analysis process, and analysis result is relatively higher.Ye You enterprises gas sample, liquid sample separately sample.
《The content of methacrylaldehyde in Propylene By Gas Chromatography acid production catalytic burning tail gas》(author：Lu Junliang；Zhejiang satellite is controlled interest group,《Chemical analysis measures》06 phase in 2009)：The content of methacrylaldehyde in catalytic burning tail gas is produced using capillary gas chromatography acrylic acid.Chromatographic column is FFAP (25m × 0.53mm, 1.0 μm), detector FID, makees internal standard compound with Isosorbide-5-Nitrae-dioxane.Detection is limited to 0.029mg/m3, the relative standard deviation of measurement result is 0.93%~2.48% (n=5), and recovery of standard addition is 97.4%~103.1%.Paper measure level of acrolein is not higher than 4mgL-1, the content of this method methacrylaldehyde suitable for measure acrylic acid production catalytic burning tail gas, that is to say, that suitable for the measure of lower content methacrylaldehyde, such as environmental monitoring.This method makees internal standard compound using Isosorbide-5-Nitrae-dioxane, and capillary gas chromatography acrylic acid produces the content of methacrylaldehyde in catalytic burning tail gas.Internal standard method is a kind of indirect or relative calibration method.In certain constituent content in analyzing determination sample, add a kind of internal standard substance with school who and eliminate for operating condition fluctuation and on caused by analysis result influence, with the correctness of further analysis result.Internal standard method is a kind of important technology in chromatogram ration analysis.During using internal standard method, add a certain amount of standard substance in the sample, it can be leant on by chromatogram it is separated, and not in test sample other component peaks interference, as long as determine internal standard compound and the peak area and relative response of component to be measured, you can obtain the percentage composition of component to be measured in the sample.During using inner mark method ration, the selection of internal standard compound is a highly important job.Ideally, internal standard compound, which should be one, can obtain oneself of pure sample and know compound, so it can be added to past in sample with correct, known amount, it should have essentially identical or as consistent as possible physicochemical properties (such as chemical constitution, polarity, volatility and solubility in a solvent), chromatographic behavior and response characteristic, preferably analyte a homologue with analyzed sample component.
《The research of methacrylaldehyde in gas chromatography measure cigarette》(《Chemistry and bonding》, 05 phase in 2005, author, Liu Ying), the assay method of the methacrylaldehyde in cigarette is have studied, using silica gel absorption methacrylaldehyde, distilled water parsing, gas chromatography is measured.Linear dependence is good in the range of 5ug/ml~300ug/ml, minimum detection limit 5ug/ml, recovery of standard addition 85.90%~91.20%, average coefficient of variation 4.4%.The detection of this method methacrylaldehyde suitable for cigarette.《Methacrylaldehyde in high-efficient liquid phase chromatogram technique analysis cigarette smoke》(《Hefei Teachers College's journal》03 phase in 2008, author：Xie Yueqin) establish the new method of methacrylaldehyde in high performance liquid chromatography measure cigarette smoke.Improve the capture method of cigarette smoke, using being adsorbed with 2, the cambridge filter trapping methacrylaldehyde of 4- dinitrophenylhydrazines (DNPH), the condition of methacrylaldehyde and DNPH derivative reactions on cambridge filter has been investigated, has tested influence of the new flow visualizing to methacrylaldehyde separating effect in cigarette smoke.Realize the quick measure of simplicity of methacrylaldehyde in cigarette smoke.As a result show, this law can eliminate the interference of complicated substrate, and measurement result is accurate.The relative standard deviation of method is 2.35%, and the rate of recovery is limited to 2.5ng/mL in 99.8%~101.2% scope, detection.《Methacrylaldehyde, acetic acid, acrylic acid content in Propylene By Gas Chromatography oxidation production acrylic acid tail gas》(Zhejiang Satellite Petrochemical Co., Ltd., Chen Kejie,《Chemical analysis measures》5th 92-93 pages of the phase in 2013)：The content of methacrylaldehyde, acetic acid, acrylic acid in production acrylic acid tail gas is aoxidized using capillary gas chromatography propylene, chromatographic column is FFAP (30m × 0.53mm, 1 μm), detector is FID, quantified with external standard method, methacrylaldehyde, acetic acid, the detection limit of acrylic acid are respectively 0.025,0.033,0.031mg/m in tail gas sample3, the relative deviation of measurement result is 0.97%-2.63% (n=5), recovery of standard addition 98.29%-103.60%.The paper is recorded：Acrylic acid production process is more to waste water, spent acid, waste gas etc. to carry out harmless treatment using catalytic burning method, and still contains a certain amount of methacrylaldehyde in the tail gas after handling, and can influence atmospheric environment.Air discharge of the country to industrial enterprise's methacrylaldehyde is made that regulation.The content of methacrylaldehyde in incineration tail gas is determined, the technological parameter to adjusting catalytic burning stove, the content of methacrylaldehyde in tail gas is controlled, meets that environmental requirement is very helpful.This method suitable for its waste gas after catalytic burning acrylic acid tail gas methacrylaldehyde, acetic acid, acrylic acid content measure.Methacrylaldehyde, acetic acid, the content of material of acrylic acid three are very low.CN103760270A discloses acrylic acid in one kind air of workplace by ion chromatography：Acrylic acid is gathered with silicone tube, using a kind of environment friendly and pollution-free sodium carbonate/bicarbonate solution as stripping liquid and chromatogram flow phase, establish a kind of quick, sensitive, accurate, environmentally friendly and chromatography of ions cheap cost and detect acrylic acid in workplace air, this provides new feasible way fast and accurately to determine acrylic acid in workplace air, and has widened application of the chromatography of ions in occupational health detection.Good linear relationship is presented in the range of the μ g/ml of 0.1 μ g~4 for acrylic acid in this method.The measure acrylic acid of document above record, methacrylaldehyde, the method for acetic acid are all measure low content acrylic acid, methacrylaldehyde, the method for acetic acid, do not apply to high content acrylic acid, methacrylaldehyde, the measure of acetic acid in measure methacrylaldehyde, acrylic acid production process.
CN201464436U discloses a kind of acrylic acid waste gas chromatographic analysis system of acroleic acid device, and system is made up of PEG-20M packed column (1), four-way valve, the highly polar packed columns of TCEP (2), FID hydrogen flame detectors, P-Q posts packed column (3), six-way valve, TCD thermal conductivity cell detectors and MS-SA molecule sieve separation packed columns (4)；Efficiently solve the separation problem of the medium of saturated liquid containing polarized in acrylic acid waste gas in acrylic acid production device, the pollution of venomous injurant confrontation environment in acrylic acid waste gas can be prevented, pass through this chromatography scheme, the content and propylene of harmful substance in acrylic acid waste gas can be understood in time, the content fluctuation situation of propane, prevent its harm to emission-control equipment operating system, play an important roll to acrylic acid production device long-period stable operation, it provides a good solution to the medium analysis containing saturated liquid in gas, with good application value.《The research of gas chromatographic analysis propylene oxidation reaction gas》(author：Li Luqing,《Lanzhou University》Master's thesis, 2014) paper record：Propylene oxidation reaction gas mainly includes the materials such as propylene, acrylic acid, methacrylaldehyde, acetic acid, oxygen, nitrogen, carbon monoxide, carbon dioxide, water, acetone, and conventional determining method is difficult to the Accurate Determining to these compositions.At present, there has been no the national standard of specification or professional standard to propose assay method to the composition of propylene oxidation reaction gas.The paper by combine Lanzhou Petrochemical Company acroleic acid device actual conditions, under the actual conditions of device different load, constantly grope sampling optimum condition, it is determined that how the method for accurately taking sample.Meanwhile using the situation of the existing gas chromatograph in laboratory, work out one kind and sample gas is repeatedly switched into different chromatographic columns (two using two six-way valves and a four-way valvePEG-20M10%Shimalite-TPA posts, onePorapak Q posts and oneMolecular Sieve13X posts) gas chromatography, this method can once analyze the composition rather than liquid sample of the various needs of propylene oxidation reaction gas.
Propylene gas phase catalytic oxidation reaction prepares methacrylaldehyde, acrylic acid is strong exothermal reaction, moment assembles substantial amounts of reaction heat in reactor, form hot localised points, if reaction heat can not be removed timely and effectively, the moment heat of accumulation is constantly accumulated, and by the loss for causing catalyst activity component, comes off, so that catalyst activity reduction, the lost of life, and cause to aggravate the formation of accessory substance because over oxidation reacts, or even cause runaway reaction, make sintering of catalyst.And one section of reaction temperature, substantially more than 320 DEG C, second-stage reaction temperature is substantially more than 230 DEG C, it is therefore desirable to frequently reaction system liquid sample, gas sample content are analyzed, to Instructing manufacture or adjustment catalyst performance.Methacrylaldehyde, acetaldehyde content particularly methacrylaldehyde content to the conversion ratio of second-stage reaction, yield, selectivity have conclusive effect.The production and scientific research of Accurate Analysis methacrylaldehyde, the content of acetaldehyde to acrylic acid are all significant.
The content of the invention
The method that the present invention provides acetaldehyde in measure liquid phase mixture, particularly relate to the measure for reacting acetaldehyde in liquid product that acrolein oxidation prepares acrylic acid.
At present, legal system acrylic acid, i.e. generally use fixed bed reactors are mainly industrially aoxidized with propylene two-step, for propylene initial oxidation into methacrylaldehyde (one section of reaction), methacrylaldehyde is reoxidised into acrylic acid (second-stage reaction).Contain acrylic acid, methacrylaldehyde, the material such as acetic acid, also a small amount of acetaldehyde in second-stage reaction liquid product.
The method of acetaldehyde in present invention measure liquid phase mixture, mainly contains acrylic acid, methacrylaldehyde, acetic acid in liquid phase mixture, a small amount of acetaldehyde, using butanone as internal standard compound, the content of acetaldehyde in inner mark method ration analysis prepare liquid.
The main continuous mode of content of acetaldehyde is as follows：
1) standard curve is made
Using butanone as internal standard compound, the acetaldehyde titer of various concentrations is configured, chromatogram detection, according to the ratio between peak area of acetaldehyde and butanone and weight ratio, standard curve is made, calculates the relative correction factor of acetaldehyde；
2) sampled from reactor, prepare liquid is used as after constant volume, prepare liquid adds butanone, obtains prepare liquid and butanone weight by essence title, chromatogram detection, obtains the peak area of butanone, acetaldehyde, the content of acetaldehyde in prepare liquid is calculated according to relative correction factor.
The concentration of above-mentioned standard solution is not particularly limited, can be changed according to the reactant in reaction and the actual conditions of product, for example, the making of standard curve can be carried out according to the following procedure：
Using butanone as internal standard compound, configure acetaldehyde titer of 2~10 concentration ranges in 0.00001~0.00009mol/L, essence claims to obtain the weight content of butanone, acetaldehyde, by titer into gas chromatograph sample introduction, the peak area of butanone, acetaldehyde is obtained, is ordinate with the weight ratio of obtained acetaldehyde and internal standard compound, the area ratio of acetaldehyde and internal standard compound is abscissa, standard curve is made, relative correction factor f is obtained by standard curve.
Above-mentioned making standard curve, essence claim to obtain the weight of acetaldehyde and butanone, preferably weigh 2~3 times and average.
Above-mentioned sampling procedure detailed process is as follows：
17L gas samples are taken from second stage reactor sample tap, condensed absorbent adds water to groove after the liquid sample in 1000mL volumetric flasks, obtained, shaken up standby as prepare liquid；
Prepare liquid and butanone weight are obtained above by essence title, preferably weighs 2~3 times and averages.
Chromatogram is gas-chromatography, and chromatographic column is using non-isothermal temperature-gradient method to 160~180 DEG C；By prepare liquid into gas chromatograph sample introduction, obtain the peak area of acetaldehyde and internal standard compound, by following equation calculate prepare liquid in acetaldehyde molar concentration, i.e.,
C：The molar concentration of acetaldehyde in prepare liquid
Aa：Acetaldehyde peak area
f：Relative correction factor, obtained by standard curve
M：Acetaldehyde molal weight, i.e. molecular weight
Ms：Internal standard compound weight (g)
As：Internal standard compound peak area
V：Prepare liquid volume.
Chromatographic column uses non-isothermal temperature-gradient method, i.e., 110 DEG C 1~5min of holding, is then warming up to 130~140 DEG C, preferably 20~25 DEG C/min with 20~30 DEG C/min heating rates, then be warming up to 160~180 DEG C with 10~15 DEG C/min heating rate.
All substances weight of the present invention smart will claim, and so-called essence claims to be accurate to 0.0001g.
Propylene oxidation production methacrylaldehyde, acrylic acid are exothermic reactions, and one section of reaction temperature is more than 320 DEG C, and second-stage reaction temperature is more than 230 DEG C, and acetaldehyde belongs to volatile organic matter.The best external condensation of sampling bottle in above-mentioned sampling procedure, condensation temperature can use the water condensation below 20 DEG C below 20 DEG C, most handy mixture of ice and water condensation.Good using external condensation method sampling acetaldehyde liquefaction effect, content is high, makes analysis result closer to the true composition of product.
Internal standard method is to do internal standard compound with a certain amount of pure material, is added in the sample of precise, and according to tested sample and the quality of internal standard compound, when the ratio between corresponding chromatographic peak area, calculating are tested the content of component.
Mi=fiAi,Ms=fsAs,Relative correction factor f is obtained according to standard curveis, the calculation formula of the content of a components is
As,
Ma：The weight (g) of a components in prepare liquid
Aa：A component peak areas
fis：Relative correction factor, obtained by standard curve
Ms：Internal standard compound weight (g)
As：Internal standard compound peak area
The key of internal standard method is to determine internal standard compound, and the present invention can accurately and reliably determine the content that Propylene Selectivity oxidation prepares acetaldehyde in methacrylaldehyde, acrylic acid reaction product using butanone as internal standard compound, thus complete the present invention.
Contain water in methacrylaldehyde, acrylic acid liquid phase mixture, chromatographic column may be sensitive to water content, if water content is high, it is understood that there may be adsorption phenomena, so as to which the poor reproducibility of appearance time can be caused.And then the accuracy of impact analysis result.
The present invention uses non-isothermal temperature-gradient method, i.e., 110 DEG C 1~5min of holding, the state for allowing chromatograph off working state to be in more than 100 DEG C, is advantageous to reduce influence of the absorption of post to measurement result, improves the reappearance of appearance time.Post pollution can be reduced simultaneously.Then 130~140 DEG C are warming up to 20~30 DEG C/min heating rates, then 160~180 DEG C is warming up to 10~15 DEG C/min heating rate.By non-isothermal temperature-gradient method, i.e., using two kinds of different heating rates first quick and back slow, reduce the influence being rapidly heated to measurement result, make baseline more stable, do not drift about.The interference of non-methacrylaldehyde, acetaldehyde, acrylic acid, acetic acid impurity peak can be eliminated simultaneously, make measurement result accurate, it is reproducible.
The method of present invention measure acetaldehyde aoxidizes the analysis of acetaldehyde production methacrylaldehyde, acrylic acid liquid product suitable for propylene, and methacrylaldehyde, the content of acrylic acid are higher, and general acrylic acid yield is more than 78%.The assay method cost of the present invention is low, easy to operate, requires low to test environment, is not required to large-scale analytical equipment, method is simple and quick, and measurement result is accurate, reproducible.
In order to illustrate assay method of the present invention, by embodiment, the invention will be further elaborated, but the present invention is not limited in these embodiments.
Embodiment
Instrument and reagent
Agilent 5890A gas chromatographicanalyzers, equipped with chromatographic work station
10 μ l microsyringes, internal standard compound：Butanone (analysis level), assay balance, conical flask with stopper：250ml
Spherical pipette：0.5ml, 1ml, 10ml, graduated pipette：1ml, 5ml, 10ml
Embodiment 1
5890 chromatographicconditions
Detector；Flame ionization ditector (FID), chromatographic column：Packed column 3mm × 3m, temperature of vaporization chamber：180 DEG C, detector temperature：190 DEG C, load volume：(N2) 50mL/min, amounts of hydrogen：100mL/min, air capacity：30mL/min.
Reagent is the pure commercially available prod of analysis.
1) standard curve is made
Using butanone as internal standard compound, configure acetaldehyde titer of 7 concentration ranges in 0.00001~0.00009mol/L, essence claims to obtain the weight content of butanone, acetaldehyde, by titer into gas chromatograph sample introduction, the peak area of butanone, acetaldehyde is obtained, is ordinate with the weight ratio of obtained acetaldehyde and internal standard compound, the area ratio of acetaldehyde and internal standard compound is abscissa, standard curve is made, relative correction factor f is obtained by standard curve.Establish internal standard analysis method.
Take 17L gas sample mixture of ice and water condensed absorbents to add water to groove after the liquid sample in 1000mL volumetric flasks, obtained from second stage reactor sample tap, shake up standby as prepare liquid；
Chromatogram selects internal standard method, and chromatographic column uses non-isothermal temperature-gradient method, i.e., 110 DEG C holding 4min, is then warming up to 140 DEG C with 25 DEG C/min heating rates, then be warming up to 180 DEG C with 15 DEG C/min heating rate.0.5ml internal standard compound butanone is taken, keeps off inwall, is put in the 50ml conical flask with stopper that advance essence claimed and (is claimed with assay balance essence, it is accurate to O.0001g), then 10ml prepare liquids are added, essence claims, as detection liquid (quality for obtaining butanone and prepare liquid).Sample introduction 2l in the gas chromatograph that analysis condition according to determination has been stablized to baseline, obtains the peak area of acetaldehyde and internal standard compound, the molar concentration of acetaldehyde is calculated by following equation, i.e.,Analysis result, C=0.00004mol/L are read by chromatographic work station.
Embodiment 2
With embodiment 1, essence claims to obtain the weight of acetaldehyde and butanone determination step, weighs 2 times and averages.Chromatographic column uses non-isothermal temperature-gradient method, i.e., 110 DEG C holding 1min, is then warming up to 135 DEG C with 20 DEG C/min heating rates, then be warming up to 180 DEG C with 10 DEG C/min heating rate.0 DEG C of ice water condensation of sampling bottle.C=mol/L.
Embodiment 3
With embodiment 1, essence claims to obtain prepare liquid and butanone weight determination step, weighs 3 times and averages.Chromatographic column uses non-isothermal temperature-gradient method, i.e., 110 DEG C holding 4min, is then warming up to 140 DEG C with 30 DEG C/min heating rates, then be warming up to 180 DEG C with 10 DEG C/min heating rate.Sampling bottle 5 DEG C of water condensations, C=0.00008mol/L.
Embodiment 4
Determination step with embodiment 1, unlike, chromatographic column use non-isothermal temperature-gradient method, i.e., 110 DEG C keep 3min, are then warming up to 140 DEG C with 25 DEG C/min heating rates, then be warming up to 170 DEG C with 10 DEG C/min heating rate.10 DEG C of water condensations of sampling bottle.C=0.00006mol/L.
Claims (11)
1. a kind of method for determining acetaldehyde in liquid phase mixture, mainly contains propylene in liquid phase mixture
Aldehyde, acrylic acid, acetic acid, it is characterised in that using butanone as internal standard compound, inner mark method ration, gas-chromatography point
Analyse the content of acetaldehyde in prepare liquid.
2. assay method according to claim 1, it is characterised in that the acetaldehyde it is main
Continuous mode is as follows：
1) standard curve is made
Using butanone as internal standard compound, the acetaldehyde titer of various concentrations, chromatogram detection, according to acetaldehyde and fourth are configured
The ratio between peak area of ketone and weight ratio, standard curve is made, calculate the relative correction factor of acetaldehyde；
2) sampled from reactor, prepare liquid is used as after constant volume, prepare liquid adds butanone, is obtained by essence title
Prepare liquid and butanone weight, chromatogram detection, obtain the peak area of acetaldehyde and butanone, second are calculated by following equation
The molar concentration of aldehyde,Wherein, C：The molar concentration of acetaldehyde in prepare liquid；Aa：Acetaldehyde
Peak area；f：Relative correction factor, obtained by standard curve；M：Acetaldehyde molal weight；Ms：Internal standard
Thing weight；As：Internal standard compound peak area, V：Prepare liquid volume.
3. assay method according to claim 1, it is characterised in that the chromatogram is gas-chromatography,
Chromatographic column is using non-isothermal temperature-gradient method to 160~180 DEG C.
4. assay method according to claim 3, it is characterised in that the non-isothermal temperature-gradient method,
I.e. 110 DEG C 1~5min of holding, are then warming up to 130~140 DEG C with 20~30 DEG C/min heating rates, then with
10~15 DEG C/min heating rate is warming up to 160~180 DEG C.
5. assay method according to claim 4, it is characterised in that the non-isothermal temperature-gradient method,
I.e. 110 DEG C 1~5min of holding, are then warming up to 130~140 DEG C with 20~25 DEG C/min heating rates.
6. assay method according to claim 2, it is characterised in that the making of the standard curve
Carry out according to the following procedure：Using butanone as internal standard compound, 2~10 concentration ranges of configuration exist
0.00001~0.00009mol/L acetaldehyde titer, essence claim to obtain the weight content of butanone, acetaldehyde, will marked
Quasi- liquid sample introduction into gas chromatograph, obtains the peak area of butanone, acetaldehyde, with obtained acetaldehyde and internal standard compound
Weight ratio be ordinate, the area ratio of acetaldehyde and internal standard compound is abscissa, standard curve is made, by standard
Curve obtains relative correction factor f.
7. assay method according to claim 2, it is characterised in that described to be treated by essence title
Liquid and butanone weight are surveyed, weighs 2~3 times and averages.
8. assay method according to claim 6, it is characterised in that it is described essence claim obtain acetaldehyde with
The weight content of butanone, weigh 2~3 times and average.
9. assay method according to claim 2, it is characterised in that the specific mistake of sampling procedure
Journey is as follows：17L gas samples condensed absorbent is taken after in 1000mL volumetric flasks from second stage reactor sample tap,
Obtained liquid sample adds water to groove, shakes up standby as prepare liquid.
10. assay method according to claim 9, it is characterised in that the sampling procedure sampling bottle
External condensation, condensation temperature is below 20 DEG C.
11. assay method according to claim 9, it is characterised in that the sampling procedure sampling bottle
Outside is condensed with mixture of ice and water.
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