CN107345944B - Method for measuring acetaldehyde content in liquid phase mixture - Google Patents
Method for measuring acetaldehyde content in liquid phase mixture Download PDFInfo
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- CN107345944B CN107345944B CN201610290812.3A CN201610290812A CN107345944B CN 107345944 B CN107345944 B CN 107345944B CN 201610290812 A CN201610290812 A CN 201610290812A CN 107345944 B CN107345944 B CN 107345944B
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- acetaldehyde
- butanone
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- phase mixture
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000007791 liquid phase Substances 0.000 title claims abstract description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 62
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 54
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 35
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 95
- 150000001875 compounds Chemical class 0.000 claims description 32
- 238000005259 measurement Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004587 chromatography analysis Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 238000005070 sampling Methods 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- 238000001514 detection method Methods 0.000 claims description 12
- 238000012937 correction Methods 0.000 claims description 10
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 48
- 239000000126 substance Substances 0.000 abstract description 10
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010813 internal standard method Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 33
- 238000004458 analytical method Methods 0.000 description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 8
- 235000019504 cigarettes Nutrition 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000000779 smoke Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000003965 capillary gas chromatography Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- -1 compound Alkene Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011555 saturated liquid Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 description 1
- JNAHSTZIPLLKBQ-UHFFFAOYSA-N [O].CC=C Chemical compound [O].CC=C JNAHSTZIPLLKBQ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- NBXMJDVWESETMK-UHFFFAOYSA-N acetaldehyde Chemical compound CC=O.CC=O NBXMJDVWESETMK-UHFFFAOYSA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001574 biopsy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 231100000611 venom Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater 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
- G01N30/02—Column chromatography
-
- 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
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention relates to a method for measuring acetaldehyde content in a liquid phase mixture, wherein the liquid phase mixture mainly contains acrolein, acrylic acid and acetic acid, butanone is taken as an internal standard substance, and the acetaldehyde content in a liquid to be measured is quantitatively analyzed by an internal standard method. The determination method of the invention has the advantages of low cost, simple and convenient operation, simple and quick method, accurate determination result and good repeatability.
Description
Technical field
The present invention relates to a kind of methods of acetaldehyde in measurement liquid phase mixture, particularly relate to prepared by acrolein oxidation
The measurement of acetaldehyde in standby acrylic acid reaction liquid product.
Background technique
Currently, industrial mainly aoxidize legal system acrylic acid with propylene two-step, that is, fixed bed reactors are generallyd use, propylene is first
It is oxidized to methacrylaldehyde (Duan Fanying), methacrylaldehyde is reoxidised into acrylic acid (second-stage reaction).
Using propylene as waste methacrylaldehyde (ACR), acrylic acid (AA) catalyst research in, need to reaction product
Distribution and content carry out accurate detection, to screen catalyst formulation, investigate catalyst service life, selecting catalyst it is best
The reliable data of the offers such as process condition.It is mainly methacrylaldehyde in one section of liquid product, there are also acrylic acid, acetic acid, acetaldehyde
Deng.It is mainly acrylic acid in two sections of liquid products, there are also methacrylaldehyde, acetic acid, acetaldehyde etc..Gas phase mainly measures in reaction end gas
CO、CO2、C3 =(propylene), O2、N2Content, content (acetic acid, second of methacrylaldehyde, acrylic acid and its major impurity are measured in liquid phase
Aldehyde).Currently, more the acrylic acid of holonomic system produces analysis professional standard to acrylic acid (AA) industry not yet, there is enterprise's use
One sample continuously enters several chromatographies and is analyzed (gas sample, the not separated sampling of liquid sample), and this method is more accurate, but entire point
Time-consuming for analysis process, and analysis result is relatively higher.Ye You enterprise gas sample, liquid sample separately sample.
" content that Propylene By Gas Chromatography acid produces methacrylaldehyde in catalytic burning tail gas " (author: Lu Junliang；Zhejiang
Satellite is controlled interest group, " chemical analysis metering " 06 phase in 2009): using the production catalysis of capillary gas chromatography acrylic acid
The content of methacrylaldehyde in incineration tail gas.Chromatographic column is FFAP (25m × 0.53mm, 1.0 μm), detector FID, with Isosorbide-5-Nitrae-dioxy
Six rings make internal standard compound.Detection is limited to 0.029mg/m3, the relative standard deviation of measurement result is 0.93%~2.48% (n=5),
Recovery of standard addition is 97.4%~103.1%.The paper measures level of acrolein and is not higher than 4mgL-1, this method is suitable for measurement
Acrylic acid produces the content of methacrylaldehyde in catalytic burning tail gas, that is to say, that suitable for the measurement of lower content methacrylaldehyde, such as ring
Border monitoring.This method makees internal standard compound using Isosorbide-5-Nitrae-dioxane, and capillary gas chromatography acrylic acid produces catalytic burning
The content of methacrylaldehyde in tail gas.Internal standard method is a kind of indirect or opposite calibration method.Certain component contains in analysis measurement sample
When amount, add a kind of internal standard substance with school who and eliminate fluctuation for operating condition and on analyzing resulting influence, with
The correctness of further analysis result.Internal standard method is a kind of important technology in chromatogram ration analysis.When using internal standard method,
Add a certain amount of standard substance in the sample, it can be leant on by chromatography it is separated, and not in test sample other component peaks interference,
As long as measuring the peak area and relative response of internal standard compound and component to be measured, the percentage of component to be measured in the sample can be found out and contained
Amount.When using inner mark method ration, the selection of internal standard compound is a highly important job.Ideally, internal standard compound should be one
A to obtain oneself of pure sample and know compound, it can be added to past in sample in this way with correct, known amount, it should with it is analyzed
Sample component has essentially identical or consistent physicochemical properties (such as chemical structure, polarity, volatility and in a solvent as far as possible
Solubility etc.), chromatographic behavior and response characteristic, preferably analyte a homologue.
" research that gas chromatography measures methacrylaldehyde in cigarette " (" chemistry and bonding ", 05 phase in 2005, author, Liu
Grain husk), have studied the measuring method of the methacrylaldehyde in cigarette, using silica gel absorption methacrylaldehyde, distilled water parsing, gas chromatography into
Row measurement.Linear dependence is good within the scope 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." high-efficient liquid phase color
Methacrylaldehyde in chromatography cigarette smoke " (" Hefei Teachers College's journal " 03 phase in 2008, author: Xie Yueqin) establish height
Effect liquid phase chromatogram measures the new method of methacrylaldehyde in cigarette smoke.The capture method for improving cigarette smoke, using being adsorbed with 2,
The cambridge filter of 4- dinitrophenylhydrazine (DNPH) traps methacrylaldehyde, and it is anti-to have investigated methacrylaldehyde and DNPH derivatization on cambridge filter
The condition answered has tested influence of the new flow visualizing to methacrylaldehyde separating effect in cigarette smoke.Realize cigarette smoke
The quickly measurement of the simplicity of middle methacrylaldehyde.The result shows that this law can eliminate the interference of complicated substrate, measurement result is accurate.Method
Relative standard deviation is 2.35%, and the rate of recovery is limited to 2.5ng/mL in 99.8%~101.2% range, detection." gas chromatography
Measure methacrylaldehyde, acetic acid, acrylic acid content in propylene oxidation production acrylic acid tail gas " (Zhejiang Satellite Petrochemical Co., Ltd.,
Chen Kejie, " chemical analysis metering " the 5th 92-93 pages of phase in 2013): using the oxidation production of capillary gas chromatography propylene
The content of methacrylaldehyde, acetic acid, acrylic acid in acrylic acid tail gas, chromatographic column are FFAP (30m × 0.53mm, 1 μm), and detector is
FID is quantified with external standard method, methacrylaldehyde in tail gas sample, acetic acid, acrylic acid detection limit be respectively 0.025,0.033,
0.031mg/m3, 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: it is harmless that acrylic acid production process mostly uses catalytic burning method to carry out waste water, spent acid, exhaust gas etc.
Change processing, and still contain a certain amount of methacrylaldehyde in treated tail gas, it will affect atmospheric environment.Country is to industrial enterprise third
The atmosphere discharge of olefine aldehydr is made that regulation.The content for measuring methacrylaldehyde in incineration tail gas joins the technique for adjusting catalytic burning furnace
Number controls the content of methacrylaldehyde in tail gas, meets environmental requirement and be very helpful.This method is suitable for catalytic burning acrylic acid
After tail gas in its exhaust gas the content of methacrylaldehyde, acetic acid, acrylic acid measurement.Methacrylaldehyde, acetic acid, three content of material of acrylic acid are very
It is low.CN103760270A discloses a kind of with acrylic acid in air of workplace by ion chromatography: being adopted with silicone tube
Collect acrylic acid, using a kind of environment friendly and pollution-free sodium carbonate/bicarbonate solution as stripping liquid and chromatogram flow phase, establishes one kind
Quickly, acrylic acid in sensitive, accurate, environmentally friendly and low-cost ion chromatography detection workplace air, this is fast
Acrylic acid provides new feasible way in fast accurately measurement workplace air, and has widened the chromatography of ions and defended in occupation
Application in biopsy survey.Good linear relationship is presented within the scope of 0.1 μ of μ g~4 g/ml for acrylic acid in this method.With above
Offer the measurement acrylic acid of record, methacrylaldehyde, acetic acid method be all the method for measuring low content acrylic acid, methacrylaldehyde, acetic acid, no
Be applicable in measurement methacrylaldehyde, in acrylic acid production process high-content acrylic acid, methacrylaldehyde, acetic acid measurement.
CN201464436U discloses a kind of acrylic acid waste gas chromatographic analysis system of acroleic acid device, and system is by PEG-20M
Packed column (1), four-way valve, the highly polar packed column of TCEP (2), FID hydrogen flame detector, P-Q column packed column (3), six-way valve,
TCD thermal conductivity cell detector and MS-SA molecule sieve separation packed column (4) are constituted；It efficiently solves third in acrylic acid production device
The separation problem of the medium of saturated liquid containing polarized in olefin(e) acid exhaust gas, can prevent venomous injurant confrontation ring in acrylic acid exhaust gas
The pollution in border can understand the content of harmful substance and propylene, propane in acrylic acid exhaust gas by this chromatography scheme in time
Content fluctuate situation, prevent its harm to emission-control equipment operating system, to acrylic acid production device long period stablize
Operation plays a significant role, it provides a good solution to the medium analysis in gas containing saturated liquid, has
Good application value." research of gas chromatographic analysis propylene oxidation reaction gas " (author: Li Luqing, " Lanzhou University "
Master's thesis, 2014) paper is recorded: propylene oxidation reaction gas mainly include propylene, acrylic acid, methacrylaldehyde, acetic acid, oxygen,
The substances such as nitrogen, carbon monoxide, carbon dioxide, water, acetone, conventional determining method are difficult to realize the accurate survey to these compositions
It is fixed.Currently, there has been no the national standards of specification or professional standard to propose measuring method to the composition of propylene oxidation reaction gas.The opinion
Text is by combining Lanzhou Petrochemical Company acroleic acid device actual conditions constantly to grope under the actual conditions of device different load
The optimum condition of sampling, it is determined that the method how accurately to take sample.Meanwhile utilizing the existing gas chromatograph in laboratory
Situation, develops a kind of two six-way valves of utilization and sample gas is repeatedly switched into different chromatographic columns (two by a four-way valvePEG-20M10%Shimalite-TPA column, onePorapak Q column and one
RootMolecular Sieve13X column) gas chromatography, this method can once analyze propylene oxygen
Change the composition of the various needs of reaction gas rather than liquid sample.
Propylene gas phase catalytic oxidation reaction prepares methacrylaldehyde, acrylic acid is strong exothermal reaction, and moment assembles in reactor
A large amount of reaction heat forms hot localised points, if reaction heat cannot be removed timely and effectively, the heat of moment accumulation is constantly tired
Product, will lead to the loss of catalyst activity component, falls off, so that catalyst activity reduction, the lost of life, and cause because excessively
Oxidation reaction and the formation for aggravating by-product, or even cause runaway reaction, make sintering of catalyst.And one section of reaction temperature is basic
At 320 DEG C or more, second-stage reaction temperature is substantially at 230 DEG C or more, it is therefore desirable to frequently to reaction system liquid sample, gas sample content into
Row analysis, to Instructing manufacture or adjustment catalyst performance.Methacrylaldehyde, acetaldehyde content especially methacrylaldehyde content to two sections
The conversion ratio of reaction, yield, selectivity have conclusive effect.Accurate Analysis methacrylaldehyde, acetaldehyde content to acrylic acid
Production and scientific research are all significant.
Summary of the invention
The present invention provides the method for acetaldehyde in measurement liquid phase mixture, particularly relates to acrolein oxidation preparation third
The measurement of acetaldehyde in the reaction liquid product of olefin(e) acid.
Currently, industrial mainly aoxidize legal system acrylic acid with propylene two-step, that is, fixed bed reactors are generallyd use, propylene is first
It is oxidized to methacrylaldehyde (Duan Fanying), methacrylaldehyde is reoxidised into acrylic acid (second-stage reaction).Contain in second-stage reaction liquid product
Acrylic acid, methacrylaldehyde, acetic acid, there are also the substances such as a small amount of acetaldehyde.
The method that the present invention measures acetaldehyde in liquid phase mixture mainly contains acrylic acid, propylene in liquid phase mixture
Aldehyde, acetic acid, a small amount of acetaldehyde, using butanone as internal standard compound, inner mark method ration analyzes the content of acetaldehyde in prepare liquid.
The main continuous mode of the content of acetaldehyde is as follows:
1) standard curve is made
Using butanone as internal standard compound, the acetaldehyde titer of various concentration, chromatography detection, according to the peak face of acetaldehyde and butanone are configured
The ratio between product and weight ratio make standard curve, calculate the relative correction factor of acetaldehyde；
2) it is sampled from reactor, prepare liquid is used as after constant volume, butanone is added in prepare liquid, obtains prepare liquid and fourth by essence title
Ketone weight, chromatography detection, obtains the peak area of butanone, acetaldehyde, calculates containing for acetaldehyde in prepare liquid according to relative correction factor
Amount.
The concentration of above-mentioned standard solution is not particularly limited, it can be according to the reality of reactant and product in reaction
Situation is changed, for example, the production of standard curve can carry out according to the following procedure:
Using butanone as internal standard compound, acetaldehyde standard of 2~10 concentration ranges of configuration in 0.00001~0.00009mol/L
Liquid, essence claim obtain the weight content of butanone, acetaldehyde, by titer into gas chromatograph sample introduction, obtain the peak face of butanone, acetaldehyde
Product, the weight ratio with obtained acetaldehyde and internal standard compound are ordinate, and the area ratio of acetaldehyde and internal standard compound is abscissa, make standard
Curve obtains relative correction factor f by standard curve.
Above-mentioned production standard curve, essence claim to obtain the weight of acetaldehyde and butanone, preferably weigh 2~3 times and be averaged.
Detailed process is as follows for above-mentioned sampling procedure:
17L gas sample is taken from second stage reactor sample tap, and after condensed absorbent in 1000mL volumetric flask, obtained liquid sample adds water
To groove, shake up spare as prepare liquid；
Prepare liquid and butanone weight are obtained above by essence title, preferably weighs 2~3 times and is averaged.
Chromatography is gas-chromatography, and chromatographic column is using non-isothermal temperature-gradient method to 160~180 DEG C；By prepare liquid to gas phase color
Sample introduction in spectrometer obtains the peak area of acetaldehyde and internal standard compound, the molar concentration of acetaldehyde in prepare liquid is calculated by following equation, i.e.,
C: the molar concentration of acetaldehyde in prepare liquid
Aa: acetaldehyde peak area
F: relative correction factor is 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., then 110 DEG C 1~5min of holding are heated up fast with 20~30 DEG C/min
Rate is warming up to 130~140 DEG C, preferably 20~25 DEG C/min, then is warming up to 160~180 with the heating rate of 10~15 DEG C/min
℃。
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 at 320 DEG C or more, second-stage reaction
Temperature is at 230 DEG C or more, and acetaldehyde belongs to volatile organic matter.The best external condensation of sampling bottle, cold in above-mentioned sampling procedure
At 20 DEG C hereinafter, 20 DEG C of water condensations below can be used, most handy mixture of ice and water condenses solidifying temperature.It is taken using external condensation method
Sample acetaldehyde liquefaction effect is good, and 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, according to tested sample
When the ratio between corresponding chromatographic peak area, calculating are tested the content of component with the quality of internal standard compound.
Mi=fiAi,Ms=fsAs,It is obtained relatively according to standard curve
Correction factor fis, the calculation formula of the content of a component is
As,
Ma: the weight (g) of a component in prepare liquid
Aa: a component peak area
fis: relative correction factor is obtained by standard curve
Ms: internal standard compound weight (g)
As: internal standard compound peak area
The key of internal standard method is determining internal standard compound, and the present invention can accurately and reliably measure third using butanone as internal standard compound
Alkene selective oxidation prepare methacrylaldehyde, in acrylic acid reaction product acetaldehyde content, thus complete the present invention.
Containing water in methacrylaldehyde, acrylic acid liquid phase mixture, chromatographic column may be sensitive to water content, if water content is high,
There may be adsorption phenomenas, to will lead to the poor reproducibility of appearance time.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 allow chromatograph off working state to be in 100
DEG C or more state, be conducive to influence of the absorption to measurement result for reducing column, improve the reproducibility of appearance time.It simultaneously can
Reduce column pollution.Then 130~140 DEG C are warming up to 20~30 DEG C/min heating rate, then with the heating of 10~15 DEG C/min
Rate is warming up to 160~180 DEG C.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, keeps baseline more stable, does not drift about.Non- methacrylaldehyde, acetaldehyde, propylene can be eliminated simultaneously
The interference of acid, acetic acid impurity peak, keeps measurement result accurate, reproducible.
The method of present invention measurement acetaldehyde acetaldehyde suitable for propylene oxidation production methacrylaldehyde, acrylic acid liquid product
Analysis, methacrylaldehyde, the content of acrylic acid are higher, and general acrylic acid yield is 78% or more.Measuring method cost of the invention
It is low, it is easy to operate, it is low to test environmental requirement, it is not required to large-scale analytical equipment, method is simple and quick, and measurement result is accurate, repeats
Property is good.
In order to illustrate measuring method of the present invention, by embodiment, the invention will be further elaborated, but this hair
It is bright to be not limited to these embodiments.
Specific embodiment
Instrument and reagent
Agilent 5890A gas chromatographicanalyzer is furnished with chromatographic work station
10 μ l microsyringes, internal standard compound: butanone (analysis level), assay balance, triangular flask: 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 commercial product of analysis.
1) standard curve is made
Using butanone as internal standard compound, 7 concentration ranges are configured in the acetaldehyde titer of 0.00001~0.00009mol/L, essence
Title obtain the weight content of butanone, acetaldehyde, by titer into gas chromatograph sample introduction, obtain the peak area of butanone, acetaldehyde, use
The weight ratio of obtained acetaldehyde and internal standard compound is ordinate, and the area ratio of acetaldehyde and internal standard compound is abscissa, makes standard curve,
Relative correction factor f is obtained by standard curve.Establish internal standard analysis method.
From second stage reactor sample tap take 17L gas sample mixture of ice and water condensed absorbent after in 1000mL volumetric flask, obtain
Liquid sample add water to groove, shake up spare as prepare liquid；
Chromatography select internal standard method, chromatographic column use non-isothermal temperature-gradient method, i.e., 110 DEG C holding 4min, then with 25 DEG C/
Min heating rate is warming up to 140 DEG C, then is warming up to 180 DEG C with the heating rate of 15 DEG C/min.0.5ml internal standard compound butanone is taken, no
Inner wall is touched, is put in the 50ml triangular flask that preparatory essence claimed and (is claimed with assay balance essence, be accurate to O.0001g), then
10ml prepare liquid is added, essence claims, as detection liquid (quality for finding out butanone and prepare liquid).According to determining analysis condition to base
Sample introduction 2l in the stable gas chromatograph of line, obtains the peak area of acetaldehyde and internal standard compound, calculates rubbing for acetaldehyde by following equation
That concentration, i.e.,Analysis is read as a result, C=0.00004mol/L 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 is averaged.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 rate, then with 10 DEG C/min
Heating rate be warming up to 180 DEG C.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 is averaged.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 rate, then with 10 DEG C/min
Heating rate be warming up to 180 DEG C.Sampling bottle 5 DEG C of water condensations, C=0.00008mol/L.
Embodiment 4
Determination step with embodiment 1, unlike, chromatographic column uses non-isothermal temperature-gradient method, i.e., 110 DEG C holding 3min,
Then 140 DEG C are warming up to 25 DEG C/min heating rate, then are warming up to 170 DEG C with the heating rate of 10 DEG C/min.Sampling bottle is used
10 DEG C of water condensations.C=0.00006mol/L.
Claims (8)
1. the method for acetaldehyde, mainly contains methacrylaldehyde, acrylic acid, second in liquid phase mixture in a kind of measurement liquid phase mixture
Acid, which is characterized in that using butanone as internal standard compound, inner mark method ration, the content of acetaldehyde, chromatographic column in gas chromatographic analysis prepare liquid
Using non-isothermal temperature-gradient method to 160 ~ 180 DEG C, the non-isothermal temperature-gradient method, i.e., 110 DEG C 1 ~ 5min of holding, then with 20 ~
30 DEG C/min heating rate is warming up to 130 ~ 140 DEG C, then is warming up to 160 ~ 180 DEG C with the heating rate of 10 ~ 15 DEG C/min.
2. the method for acetaldehyde in measurement liquid phase mixture according to claim 1, which is characterized in that the acetaldehyde contains
The main continuous mode of amount is as follows:
1) standard curve is made
Using butanone as internal standard compound, configure the acetaldehyde titer of various concentration, chromatography detection, according to the peak area of acetaldehyde and butanone it
Than and weight ratio, make standard curve, calculate the relative correction factor of acetaldehyde；
2) it is sampled from reactor, prepare liquid is used as after constant volume, butanone is added in prepare liquid, obtains prepare liquid and butanone weight by essence title
Amount, chromatography detection, obtains the peak area of acetaldehyde and butanone, and the molar concentration of acetaldehyde is calculated by following equation,,
In, C: the molar concentration of acetaldehyde in prepare liquid；Aa: acetaldehyde peak area；F: relative correction factor is obtained by standard curve；M: second
Aldehyde molal weight；Ms: internal standard compound weight；As: internal standard compound peak area, V: prepare liquid volume.
3. the method for acetaldehyde in measurement liquid phase mixture according to claim 2, which is characterized in that the standard is bent
The production of line carries out according to the following procedure: using butanone as internal standard compound, 2~10 concentration ranges of configuration 0.00001 ~
The acetaldehyde titer of 0.00009mol/L, essence claim obtain the weight content of butanone, acetaldehyde, by titer into gas chromatograph into
Sample obtains the peak area of butanone, acetaldehyde, and the weight ratio with obtained acetaldehyde and internal standard compound is ordinate, acetaldehyde and internal standard compound
Area ratio is abscissa, makes standard curve, obtains relative correction factor f by standard curve.
4. the method for acetaldehyde in measurement liquid phase mixture according to claim 2, which is characterized in that described to pass through essence
Title obtains prepare liquid and butanone weight, weighs 2 ~ 3 times and is averaged.
5. the method for acetaldehyde in measurement liquid phase mixture according to claim 3, which is characterized in that the essence claims
To the weight content of acetaldehyde and butanone, weighs 2 ~ 3 times and be averaged.
6. the method for acetaldehyde in measurement liquid phase mixture according to claim 2, which is characterized in that the sampling step
It is rapid that detailed process is as follows: from second stage reactor sample tap take 17 L gas sample condensed absorbents after in 1000 mL volumetric flasks, obtain
Liquid sample adds water to groove, shakes up spare as prepare liquid.
7. the method for acetaldehyde in measurement liquid phase mixture according to claim 6, which is characterized in that the sampling step
Rapid sampling bottle external condensation, condensation temperature is at 20 DEG C or less.
8. the method for acetaldehyde in measurement liquid phase mixture according to claim 6, which is characterized in that the sampling step
It is condensed outside rapid sampling bottle with mixture of ice and water.
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| WO2002037990A3 (en) * | 2000-11-10 | 2002-12-19 | Vector Tobacco Ltd | Method and product for removing carcinogens from tobacco smoke |
| CN1697971A (en) * | 2004-03-01 | 2005-11-16 | 三菱化学株式会社 | Method of determining impurity in acrylic acid |
| CN104921221A (en) * | 2015-06-05 | 2015-09-23 | 贵州苗姑娘食品有限责任公司 | Liver tonifying herbaceous plant beverage |
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| WO2002037990A3 (en) * | 2000-11-10 | 2002-12-19 | Vector Tobacco Ltd | Method and product for removing carcinogens from tobacco smoke |
| CN1697971A (en) * | 2004-03-01 | 2005-11-16 | 三菱化学株式会社 | Method of determining impurity in acrylic acid |
| CN104921221A (en) * | 2015-06-05 | 2015-09-23 | 贵州苗姑娘食品有限责任公司 | Liver tonifying herbaceous plant beverage |
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