CN106248808A - Method for analyzing content of unsaturated acid in liquid phase mixture by gas chromatography - Google Patents
Method for analyzing content of unsaturated acid in liquid phase mixture by gas chromatography Download PDFInfo
- Publication number
- CN106248808A CN106248808A CN201510316837.1A CN201510316837A CN106248808A CN 106248808 A CN106248808 A CN 106248808A CN 201510316837 A CN201510316837 A CN 201510316837A CN 106248808 A CN106248808 A CN 106248808A
- Authority
- CN
- China
- Prior art keywords
- acid
- acrylic acid
- acetic acid
- concentration
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002253 acid Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 239000007791 liquid phase Substances 0.000 title claims abstract description 11
- 238000004817 gas chromatography Methods 0.000 title abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 189
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 104
- 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 102
- 238000002479 acid--base titration Methods 0.000 claims abstract description 8
- 238000004458 analytical method Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 14
- 238000004587 chromatography analysis Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 150000007513 acids Chemical class 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 38
- 239000007789 gas Substances 0.000 description 35
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 239000002912 waste gas Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-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
- 238000009825 accumulation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000721047 Danaus plexippus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 238000010521 absorption reaction Methods 0.000 description 1
- WRVRNZNDLRUXSW-UHFFFAOYSA-N acetic acid;prop-2-enoic acid Chemical compound CC(O)=O.OC(=O)C=C WRVRNZNDLRUXSW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011555 saturated liquid Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 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
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004448 titration Methods 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
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for analyzing the content of unsaturated acids in a liquid phase mixture by gas chromatography, wherein the unsaturated acids in the liquid phase mixture comprise acrylic acid and acetic acid. The method comprises the following determination steps: firstly, determining the molar concentration of total acid in a solution to be detected by adopting an acid-base titration method; then the content of acrylic acid and acetic acid is measured by gas chromatography, and finally the molar concentration of acrylic acid is measured. The determination method has the advantages of low cost, simple and convenient operation, low requirement on the test environment, no need of large-scale analysis equipment, simple and quick method, accurate determination result and good repeatability.
Description
Technical field
The present invention relates to a kind of method of content of unsaturated acid in gas chromatographic analysis liquid phase mixture, specifically
Relate to propylene oxidation and prepare the mensuration of acrylic acid content in acrolein reaction product.
Background technology
At present, industrial mainly aoxidize legal system acrylic acid with propylene two-step, the most generally use fixed bed reactors,
Propylene initial oxidation becomes acrylic aldehyde (one section of reaction), and acrylic aldehyde is reoxidised into acrylic acid (second-stage reaction).
It is being waste acrylic aldehyde (ACR) with propylene, in the catalyst research of acrylic acid (AA), needing
The distribution of product detected accurately with content, to give screening catalyst formulation, investigate catalyst
Life-span, the optimised process operating condition of selecting catalyst etc. provides reliable data.Mainly measure reaction
CO, CO in tail gas2、C3 =(propylene), O2、N2Content, acrylic aldehyde in liquid phase, acrylic acid and
The content (acetic acid, acetaldehyde) of major impurity.At present, acrylic acid (AA) industry also the most more holonomic system
Acrylic acid produce and analyze industry standard, have enterprise to use a sample to continuously enter several chromatographs and be analyzed
(gas sample, the not separated sampling of liquid sample), the method is more accurate, but whole analysis process is the longest, analyzes
Result is more relatively high.The separately sampling of Ye You enterprise gas sample, liquid sample.
" Propylene By Gas Chromatography acid produces the content of acrylic aldehyde in catalytic burning tail gas " (author: land
Monarch is good；Zhejiang satellite is controlled interest group, " chemical analysis metering " 06 phase in 2009): use Capillary Gas
Phase chromatography measures acrylic acid and produces the content of acrylic aldehyde in catalytic burning tail gas.Chromatographic column is
FFAP (25m × 0.53mm, 1.0 μm), detector is FID, makees internal standard substance with Isosorbide-5-Nitrae-dioxane.Detection
It is limited to 0.029mg/m3, the relative standard deviation of measurement result is 0.93%～2.48% (n=5), and mark-on reclaims
Rate is 97.4%～103.1%.This paper measures level of acrolein and is not higher than 4mgL-1, the method is applicable to survey
Determine acrylic acid and produce the content of acrylic aldehyde in catalytic burning tail gas, say, that be applicable to lower content acrylic aldehyde
Mensuration, such as environmental monitoring." Propylene By Gas Chromatography oxidation produce acrylic aldehyde in acrylic acid tail gas,
Acetic acid, acrylic acid content " (Zhejiang Satellite Petrochemical Co., Ltd., Chen Kejie, " chemical analysis metering "
5th phase in 2013 92-93 page): use the oxidation of capillary gas chromatography propylene to produce acrylic acid
Acrylic aldehyde, acetic acid, acrylic acid content in tail gas, chromatographic column is FFAP (30m × 0.53mm, 1 μm),
Detector is FID, carries out quantitatively by external standard method, acrylic aldehyde, acetic acid, acrylic acid detection in tail gas sample
Limit is 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 is 98.29%-103.60%.This paper is recorded: acrylic acid production process pair
Waste water, spent acid, waste gas etc. uses catalytic burning method to carry out harmless treatment, and in the tail gas after processing still
Containing a certain amount of acrylic aldehyde, atmospheric environment can be affected.The airborne release of industrial undertaking's acrylic aldehyde is made by country
Go out regulation.Measure the content of acrylic aldehyde in incineration tail gas, the technological parameter to regulation catalytic burning stove, control
The content of acrylic aldehyde in tail gas processed, meets environmental requirement and is very helpful.The method is applicable to catalytic burning
Acrylic aldehyde, acetic acid, the mensuration of acrylic acid content in its waste gas after acrylic acid tail gas.Acrylic aldehyde, acetic acid,
Acrylic acid three content of material is the lowest.The open one of CN103760270A uses ion-chromatographic determination working space
Acrylic acid in air: gather acrylic acid with silica gel tube, with a kind of environment friendly and pollution-free sodium carbonate/carbon
Acid hydrogen sodium solution is stripping liquid and chromatogram flow phase, establishes a kind of quick, sensitive, accurate, environmental protection and one-tenth
Acrylic acid in this cheap chromatography of ions detection workplace air, this is for measuring work fast and accurately
Make acrylic acid in the air of place and provide new feasible way, and widen the chromatography of ions in occupational health inspection
Application in survey.The method presents good linear relationship for acrylic acid in the range of 0.1 μ g～4 μ g/ml.
Document above record measure acrylic acid, acrylic aldehyde, acetic acid method all be measure low content acrylic acid, third
Olefine aldehydr, the method for acetic acid, high-load acrylic acid in inapplicable mensuration acrylic aldehyde, acrylic acid production process, third
Olefine aldehydr, the mensuration of acetic acid.
CN201464436U discloses the acrylic acid waste gas chromatographic analysis system of a kind of acroleic acid device, system by
The packed column (1) of PEG-20M, cross valve, the highly polar packed column of TCEP (2), FID hydrogen flame detector,
P-Q post packed column (3), six-way valve, TCD thermal conductivity cell detector and MS-SA molecular sieving packed column (4)
Constitute；Efficiently solve and acrylic acid production device contains in acrylic acid waste gas polarized saturated solution state medium
Separate a difficult problem, be possible to prevent the pollution of venomous injurant confrontation environment in acrylic acid waste gas, divided by this chromatograph
Analysis scheme, can understand content and propylene, the content fluctuation of propane of harmful substance in acrylic acid waste gas in time
Situation, prevents its harm to emission-control equipment operating system, stable to acrylic acid production device long period
Operation has important function, and it provides a good solution to the medium analysis containing saturated liquid in gas
Scheme, has good application value." research of gas chromatographic analysis propylene oxidation reaction gas " (is made
Person: Li Luqing, " Lanzhou University " Master's thesis, 2014) paper record: propylene oxidation reaction gas master
Propylene to be included, acrylic acid, acrylic aldehyde, acetic acid, oxygen, nitrogen, carbon monoxide, carbon dioxide, water,
The materials such as acetone, conventional determining method is difficult to the Accurate Determining forming these.At present, not yet there are rule
National standard or the industry standard of model propose assay method to the composition of propylene oxidation reaction gas.This paper passes through
In conjunction with Lanzhou Petrochemical Company acroleic acid device practical situation, under the practical situation of device different load, constantly
Grope the optimum condition of sampling, it is determined that the method taking sample the most accurately.Meanwhile, laboratory is utilized
The situation of existing gas chromatograph, works out one and utilizes two six-way valves and a cross valve that sample gas is many
Secondary switch into different chromatographic column (twoPEG-20M10%Shimalite-TPA post,
OnePorapak Q post and oneMolecular Sieve13X
Post) gas chromatography, the method can once analyze the composition of the various needs of propylene oxidation reaction gas.
It is strong exothermal reaction that propylene gas phase catalytic oxidation reaction prepares acrylic aldehyde, and in reactor, moment assembles big
The reaction heat of amount, forms hot localised points, if reaction heat can not be removed timely and effectively, and the heat of moment accumulation
Amount constantly accumulation, will cause the loss of catalyst activity component, comes off, to such an extent as to catalyst activity reduction,
The lost of life, and cause aggravating the formation of by-product because of over oxidation reaction, even cause runaway reaction,
Make sintering of catalyst.And one section of reaction temperature is substantially more than 320 DEG C, it is therefore desirable to frequently to reaction system
System liquid sample, gas sample content are analyzed, in order to Instructing manufacture or adjustment catalyst performance.If able to convenient,
Measure the content of acrylic acid, acrylic aldehyde, acetic acid fast and accurately, not by large-scale instrument, measure environment
Impact, could preferably meet scientific research, being actually needed of production.
Summary of the invention
The present invention provides a kind of method of content of unsaturated acid in gas chromatographic analysis liquid phase mixture, specifically
Relate to propylene oxidation and prepare the mensuration of acrylic acid content in acrolein reaction product.
At present, industrial mainly aoxidize legal system acrylic acid with propylene two-step, the most generally use fixed bed reactors,
Propylene initial oxidation becomes acrylic aldehyde (one section of reaction), and acrylic aldehyde is reoxidised into acrylic acid (second-stage reaction).One
Containing acrylic aldehyde, acrylic acid in Duan Fanying liquid product, the also material such as very small amount acetic acid.
A kind of method of content of unsaturated acid in gas chromatographic analysis liquid phase mixture, main in liquid phase mixture
Acrylic aldehyde to be contained, acrylic acid, acetic acid, comprise the steps:
A) sampling
Take after 17L gas sample condensed absorbent in 1000mL volumetric flask from first stage reactor sample tap, liquid sample
Add water to groove, standby as liquid to be measured after shaking up；
B) first use total acid molar concentration in determination of acid-basetitration liquid to be measured, be designated as CTotal acid；
C) acrylic acid and acetic acid are surveyed by gas chromatogram again: make acrylic acid, acetic acid standard sample known to concentration
The standard curve of molar content and corresponding peak area ratio；Gas chromatogram surveys acrylic acid and face, acetic acid peak
Long-pending: chromatographic column uses non-isothermal temperature-gradient method to 160～180 DEG C；After liquid to be measured is mixed homogeneously with organic solvent
With 10 μ L microsyringe sample introduction 2 μ L, the chromatogram spectrogram obtained determine the peak area of acrylic acid and acetic acid
Ratio, then finds acrylic acid Mole percent specific concentration on the standard curve of acrylic acid and acetic acid content, note
For AAConcentration；Acrylic acid concentration C in liquid to be measuredAA=CTotal acid×AAConcentration。
Survey acrylic acid by gas chromatogram and acetic acid main process be as follows:
A) standard curve is made
With 3～10 known acrylic acid and the standard sample of acetic acid concentration, after chromatography column feed materials, measure propylene respectively
The ratio of the peak area that acid is corresponding with acetic acid is as the molar content conduct of vertical coordinate, acrylic acid and acetic acid
Abscissa, makes acrylic acid, the standard curve of acetic acid content；
B) gas chromatogram surveys acrylic acid and acetic acid peak area
Chromatographic column uses non-isothermal temperature-gradient method, and i.e. 110 DEG C keep 1～5min, then with 25～35 DEG C/min
Heating rate is warming up to 140～150 DEG C, preferably 25～30 DEG C/min, then the intensification speed with 10～20 DEG C/min
Rate is warming up to 160～180 DEG C, preferably 10～15 DEG C/min；Take 2mL liquid to be measured in bottle with cover with 2mL
Organic solvent mix homogeneously, then with 10 μ L microsyringe sample introduction 2 μ L, is determined third by the spectrogram obtained
Olefin(e) acid and the peak area ratio of acetic acid, then find acrylic acid on the standard curve of acrylic acid and acetic acid content
Mole percent specific concentration, is designated as AAConcentration；Acrylic acid concentration C in liquid to be measuredAA=CTotal acid×AAConcentration；
The acids such as acetic acid, acrylic acid generates salt and water with alkali reaction in aqueous, with in alkali and liquid to be measured
Acid reaction, measures the content of total acid, in determination of acid-basetitration of the present invention liquid to be measured total acid molar concentration preferably
The highly basic such as sodium hydroxide, potassium hydroxide.
Utilize gas Chromatographic Determination acrylic acid Mole percent specific concentration, i.e. AAConcentration；Obtain propylene in liquid to be measured
Acid concentration.
In determination of acid-basetitration of the present invention liquid to be measured, total acid molar concentration is measured and is averaged for 2～4 times.To be measured
Also having acetic acid in liquid sample in addition to having acrylic acid, that so measure is total acid (CTotal acid), the content of acetic acid is very
Few, mainly acrylic acid.Organic solvent used by gas chromatogram of the present invention selects the one in acetone or butanone.
The acrylic acid concentration of acetic acid of the present invention and acrylic acid standard sample is between 93.2～99.5mol%.
Acrylic aldehyde, acrylic acid are to be difficult to be polymerized during gaseous state, are easily polymerized during for liquid, and, in determinand
Containing water, chromatographic column may be sensitive to water content, if water content is high, it is understood that there may be adsorption phenomena, thus
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, and i.e. 110 DEG C keep 1～5min, allows chromatograph off working state
It is in the state of more than 100 DEG C, is conducive to reducing the absorption impact on measurement result of post, improve when peak
Between repeatability.Post can be reduced pollute simultaneously.Then it is warming up to 25～35 DEG C/min heating rate
140～150 DEG C, then it is warming up to 160～180 DEG C with the heating rate of 10～20 DEG C/min；Divided by non-isothermal
Duan Shengwen, i.e. uses two kinds of different heating rates first quick and back slow, decreases and be rapidly heated to measurement result
Impact, makes baseline more stable, does not drifts about.Non-acrylic acid, the interference at acetic acid impurity peak can be eliminated simultaneously, make
Measurement result is accurate, reproducible.
The present invention measures acrylic acid and is applicable to propylene oxidation and produces acrylic aldehyde, acrylic acid liquid product and contain
Quantitative analysis, acrylic aldehyde, acrylic acid content are higher, and general acrylic aldehyde yield, more than 78%, is not suitable for
A small amount of acrylic aldehyde, acrylic acid, the mensuration of acetic acid content after working environment and device exhaust, burned waste gas.
The assay method low cost of the present invention, easy and simple to handle, test environment is required low, is not required to large-scale analytical equipment,
Method is simple and quick, and measurement result is accurate, reproducible.
In order to assay method of the present invention is described, by embodiment, the invention will be further elaborated,
But the present invention is not limited in these embodiments.
Detailed description of the invention
Instrument and reagent
Agilent 5890A gas chromatographicanalyzer, HP-3392 integrator
Detector；Flame ionization ditector (FID), chromatographic column: packed column 3mm × 3m, column temperature:
160～180 DEG C, temperature of vaporization chamber: 185 DEG C, detector temperature: 165 DEG C, load volume: (N2) 55mL/min,
Amounts of hydrogen: 65mL/min, air capacity: 210mL/min.
Base buret: 25mL, NaOH solution (0.0114mol/L), conical flask: 250mL,
Graduated pipette: 25mL, 10mL.Other reagent is analytical pure commercially available prod.
Embodiment 1
In 1000mL capacity after single tube reaction unit first stage reactor sample tap 17L gas sample condensed absorbent
In Ping, liquid sample adds water to groove, standby as liquid to be measured after shaking up.Essence takes 10ml liquid to be measured sample and adds three
In the flask of angle, with the NaOH solution titration that concentration is 0.0114mol/L, phenolphthalein is indicator, writes down institute
With the volume number V of NaOH solutionNaOH=2.23mL.Liquid sample to be measured also has in addition to having acrylic acid acetic acid,
That so measure is total acid (CTotal acid), the content of acetic acid is little, mainly acrylic acid.CTotal acid=CNaOH
VNaOH/VTotal acid, VTotal acid=10mL, CTotal acid=0.00254.
Acrylic acid and acetic acid is surveyed again: by 3～10 known acrylic acid and the standard of acetic acid concentration by gas chromatogram
Sample, measures the ratio of the acrylic acid peak area corresponding with acetic acid respectively as vertical coordinate, acrylic acid after sample introduction
With the molar content of acetic acid as abscissa, make acrylic acid, the standard curve of acetic acid content；Gas phase
Chromatograph surveys acrylic acid and acetic acid peak area, and chromatographic column uses non-isothermal temperature-gradient method, and i.e. 110 DEG C keep 3min,
Then it is warming up to 140 DEG C with 30 DEG C/min heating rate, then is warming up to 160 with the heating rate of 15 DEG C/min
℃；Take 2mL liquid to be measured to mix homogeneously with 2mL butanone in bottle with cover, then enter with 10 μ L trace
Sample device sample introduction 2 μ L, is determined the area ratio of acrylic acid and acetic acid by the spectrogram obtained, then at acrylic acid and
Find acrylic acid Mole percent specific concentration on the standard curve of acetic acid content, be designated as AAConcentration=0.984；To be measured
Acrylic acid concentration C in liquidAA=CTotal acid×AAConcentration=0.00250.
Embodiment 2
Determination step is with embodiment 1, and in determination of acid-basetitration liquid to be measured, total acid molar concentration is measured and taken for 2 times
Meansigma methods, mineral acid is nitric acid, and chromatographic column uses non-isothermal temperature-gradient method, and i.e. 110 DEG C keep 4min, so
After be warming up to 150 DEG C with 35 DEG C/min heating rate, then be warming up to 180 with the heating rate of 20 DEG C/min
DEG C, record CAA=0.00290.
Embodiment 3
Determination step is with embodiment 1, and in determination of acid-basetitration liquid to be measured, total acid molar concentration is measured and taken for 3 times
Meansigma methods, chromatographic column uses non-isothermal temperature-gradient method, and i.e. 110 DEG C keep 3min, then with 25 DEG C/min
Heating rate is warming up to 150 DEG C, then is warming up to 170 DEG C with the heating rate of 10 DEG C/min, records
CAA=0.00343.
Embodiment 4
Determination step is with embodiment 1, and chromatographic column uses non-isothermal temperature-gradient method, and i.e. 110 DEG C keep 2min,
Then it is warming up to 150 DEG C with 30 DEG C/min heating rate, then is warming up to 180 with the heating rate of 10 DEG C/min
DEG C, organic solvent is acetone, records CAA=0.00281.
Claims (7)
1. a method for content of unsaturated acid in gas chromatographic analysis liquid phase mixture, in liquid phase mixture not
Saturated acid includes acrylic acid and acetic acid, it is characterised in that Main Analysis step is as follows:
A) sampling: in 1000mL volumetric flask after first stage reactor sample tap takes 17L gas sample condensed absorbent
In, liquid sample adds water to groove, standby as liquid to be measured after shaking up；
B) first use total acid molar concentration in determination of acid-basetitration liquid to be measured, be designated as CTotal acid；
C) acrylic acid and acetic acid are surveyed by gas chromatogram again: make acrylic acid, acetic acid standard sample known to concentration
The standard curve of product molar content and corresponding peak area ratio；Gas chromatogram surveys acrylic acid and acetic acid peak
Area: chromatographic column uses non-isothermal temperature-gradient method to 160～180 DEG C；Liquid to be measured is mixed homogeneously with organic solvent
Afterwards with 10 μ L microsyringe sample introduction 2 μ L, the spectrogram obtained determine the peak area ratio of acrylic acid and acetic acid
Value, then finds acrylic acid Mole percent specific concentration on the standard curve of acrylic acid and acetic acid content, is designated as
AAConcentration；Acrylic acid concentration C in liquid to be measuredAA=CTotal acid×AAConcentration。
Method the most according to claim 1, it is characterised in that described gas chromatogram surveys acrylic acid
As follows with acetic acid main process:
A) standard curve is made: by 3～10 known acrylic acid and the standard sample of acetic acid concentration, chromatograph
The ratio of the acrylic acid peak area corresponding with acetic acid is measured respectively as vertical coordinate, acrylic acid and acetic acid after sample introduction
Molar content as abscissa, make acrylic acid, the standard curve of acetic acid content；
B) gas chromatogram survey acrylic acid and acetic acid peak area: chromatographic column employing non-isothermal temperature-gradient method, i.e. 110
DEG C keep 1～5min, then carry out first paragraph with the heating rate of 25～35 DEG C/min and be warming up to 140～150
DEG C, then carry out second segment with the heating rate of 10～20 DEG C/min and be warming up to 160～180 DEG C, take 2mL and treat
Survey liquid to mix homogeneously with 2mL organic solvent in bottle with cover, then with 10 μ L microsyringe sample introductions
2 μ L, are determined the peak area ratio of acrylic acid and acetic acid, then contain at acrylic acid and acetic acid by the spectrogram obtained
Find acrylic acid Mole percent specific concentration on the standard curve of amount, be designated as AAConcentration；In liquid to be measured, acrylic acid is dense
Degree CAA=CTotal acid×AAConcentration。
Method the most according to claim 2, it is characterised in that described first paragraph heating rate is
25～30 DEG C/min.
Method the most according to claim 2, it is characterised in that described second segment heating rate is
10～15 DEG C/min.
Method the most according to claim 1, it is characterised in that described determination of acid-basetitration is to be measured
In liquid, total acid molar concentration is measured and is averaged for 2～4 times.
Method the most according to claim 1, it is characterised in that organic solvent choosing used by gas chromatogram
By the one in acetone or butanone.
Method the most according to claim 1, it is characterised in that acrylic acid and acetic acid standard sample
Acrylic acid concentration is between 93.2～99.5mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510316837.1A CN106248808B (en) | 2015-06-10 | 2015-06-10 | Method for analyzing content of unsaturated acid in liquid phase mixture by gas chromatography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510316837.1A CN106248808B (en) | 2015-06-10 | 2015-06-10 | Method for analyzing content of unsaturated acid in liquid phase mixture by gas chromatography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106248808A true CN106248808A (en) | 2016-12-21 |
| CN106248808B CN106248808B (en) | 2019-03-12 |
Family
ID=57626848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510316837.1A Active CN106248808B (en) | 2015-06-10 | 2015-06-10 | Method for analyzing content of unsaturated acid in liquid phase mixture by gas chromatography |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106248808B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112540156A (en) * | 2020-11-21 | 2021-03-23 | 山东飞扬化工有限公司 | Device and method for detecting heteropolyacid in fermentation liquor by using physical method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2585232Y (en) * | 2002-12-11 | 2003-11-05 | 中国石油化工股份有限公司上海石油化工研究院 | On-line analysing device for propylene ammonia oxidation resultant |
| CN1506351A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | In-situ analysis method of propylene ammoxidizing product |
| CN101107070A (en) * | 2005-01-21 | 2008-01-16 | 阿尔科马法国公司 | Method for preparing acrylic acid involving a partial oxidation of propane into propylene |
| US20110224397A1 (en) * | 2010-03-09 | 2011-09-15 | Basf Se | Process for preparing polyols using base catalysis |
| CN102749389A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Analytic method of acrylonitrile material |
-
2015
- 2015-06-10 CN CN201510316837.1A patent/CN106248808B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2585232Y (en) * | 2002-12-11 | 2003-11-05 | 中国石油化工股份有限公司上海石油化工研究院 | On-line analysing device for propylene ammonia oxidation resultant |
| CN1506351A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | In-situ analysis method of propylene ammoxidizing product |
| CN101107070A (en) * | 2005-01-21 | 2008-01-16 | 阿尔科马法国公司 | Method for preparing acrylic acid involving a partial oxidation of propane into propylene |
| US20110224397A1 (en) * | 2010-03-09 | 2011-09-15 | Basf Se | Process for preparing polyols using base catalysis |
| CN102749389A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Analytic method of acrylonitrile material |
Non-Patent Citations (3)
| Title |
|---|
| J. DELEPLANQUE 等: "Production of acrolein and acrylic acid through dehydration and oxydehydration of glycerol with mixed oxide catalysts", 《CATALYSIS TODAY》 * |
| 陈科杰 等: "气相色谱法测定丙烯氧化生产丙烯酸尾气中丙烯醛、乙酸、丙烯酸含量", 《化学分析计量》 * |
| 陈绍华: "国产化丙烯两步氧化法生产丙烯酸工艺与催化剂评价实验", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112540156A (en) * | 2020-11-21 | 2021-03-23 | 山东飞扬化工有限公司 | Device and method for detecting heteropolyacid in fermentation liquor by using physical method |
| CN112540156B (en) * | 2020-11-21 | 2022-11-08 | 山东飞扬化工有限公司 | Device and method for detecting heteropolyacid in fermentation liquor by using physical method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106248808B (en) | 2019-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Porter et al. | Flame ionization detection of carbon monoxide for gas chromatographic analysis. | |
| CN102590414B (en) | Method for analyzing contents of trace arsine and phosphine in gas-phase propylene by gas chromatograph | |
| Budiman et al. | Comparison between GC-TCD and GC-FID for the determination of propane in gas mixture | |
| CN103197019A (en) | Capillary gas chromatography analysis method for N-methyldiethanolamine decarbonizer component | |
| CN102507779B (en) | Method for measuring hydrogen sulfide content in desulfurized amine | |
| CN106248808A (en) | Method for analyzing content of unsaturated acid in liquid phase mixture by gas chromatography | |
| CN108663457A (en) | Utilize the method for residual acrylic acid in HS-GC external standard method acrylate copolymers | |
| Lewis et al. | An accurate method for the determination of carboxyhemoglobin in postmortem blood using GC-TCD | |
| CN106248807B (en) | Method for analyzing acetic acid content in propylene oxidation reaction liquid-phase product | |
| CN107345941B (en) | Method for measuring content of acrylic acid in liquid-phase mixture | |
| Xunqiu et al. | Measurement and correlation of vapor-liquid equilibrium for a cyclohexene-cyclohexanol binary system at 101.3 kPa | |
| CN106248845B (en) | Method for measuring content of unsaturated aldehyde in liquid phase mixture | |
| CN103207170B (en) | A kind of method analyzing arsenic morphology in mensuration food liquid condiment | |
| CN108562680A (en) | The Gas Chromatographic Method of dimethyl suflfate in a kind of industrial production | |
| CN105044263B (en) | A kind of gas chromatogram method of inspection of 4-ethyoxyl-2,3-difluorophenol | |
| CN104749271A (en) | Determination method for content of methanol in water of methanol cracking device | |
| CN108072705A (en) | Method for analyzing acetic acid content in propylene oxidation reaction liquid-phase product | |
| CN107345948B (en) | Method for measuring content of unsaturated aldehyde in liquid-phase mixture | |
| CN107345944B (en) | Method for measuring acetaldehyde content in liquid phase mixture | |
| Grant et al. | Systematic study of the quantitative effects of instrument control on analytical precision in flame ionization gas chromatography | |
| CN107345942B (en) | Method for measuring acetic acid content in propylene oxidation reaction liquid-phase product | |
| CN103472169B (en) | Method for measuring content of bromide ions in brine by gas chromatography | |
| CN104407068A (en) | Gas chromatograph | |
| CN108072706A (en) | Method for measuring content of acrolein in liquid phase mixture | |
| CN101210913A (en) | Substance quantitative analysis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |