CN107345941B - The measuring method of acrylic acid content in a kind of liquid phase mixture - Google Patents
The measuring method of acrylic acid content in a kind of liquid phase mixture Download PDFInfo
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- CN107345941B CN107345941B CN201610289254.9A CN201610289254A CN107345941B CN 107345941 B CN107345941 B CN 107345941B CN 201610289254 A CN201610289254 A CN 201610289254A CN 107345941 B CN107345941 B CN 107345941B
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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- 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
Abstract
The present invention relates to a kind of methods with acrylic acid content in gas chromatographic analysis liquid phase mixture, including following determination step: first using total acid molar concentration in determination of acid-basetitration prepare liquid；It recycles gas-chromatography to survey the content of acrylic acid and acetic acid, finally measures acrylic acid molar concentration.Measuring method of the invention is at low cost, easy to operate, to test environmental requirement it is low, be not required to large-scale analytical equipment, method is simple and quick, analysis result closer to product true composition, it is reproducible.
Description
Technical field
The present invention relates to a kind of methods with acrylic acid content in gas chromatographic analysis liquid phase mixture, particularly relate to
Propylene oxidation prepares the measurement of acrylic acid content in acrolein reaction 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.Mainly measure CO, CO in reaction end gas2、C3 =(propylene), O2、N2Content,
The content (acetic acid, acetaldehyde) of methacrylaldehyde, acrylic acid and its major impurity in liquid phase.Currently, acrylic acid (AA) industry not yet compared with
For the acrylic acid production analysis professional standard of holonomic system, there is enterprise to continuously enter several chromatographies using a sample and analyzed
(gas sample, the not separated sampling of liquid sample), this method is more accurate, but time-consuming for entire analytic 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." methacrylaldehyde, acetic acid, acrylic acid content in Propylene By Gas Chromatography oxidation production acrylic acid tail gas " (Zhe Jiangwei
Star petrochemical industry limited liability company, Chen Kejie, " chemical analysis metering " the 5th 92-93 pages of phase in 2013): use capillary gas phase color
Spectrometry measure propylene oxidation production acrylic acid tail gas in methacrylaldehyde, acetic acid, acrylic acid content, chromatographic column be FFAP (30m ×
0.53mm, 1 μm), detector FID is quantified with external standard method, the detection limit of methacrylaldehyde, acetic acid, acrylic acid in tail gas sample
Respectively 0.025,0.033,0.031mg/m3, the relative deviation of measurement result is 0.97%-2.63% (n=5), mark-on reclaims
Rate is 98.29%-103.60%.The paper is recorded: acrylic acid production process mostly uses catalysis to burn waste water, spent acid, exhaust gas etc.
Burning method carries out harmless treatment, and still contains a certain amount of methacrylaldehyde in treated tail gas, will affect atmospheric environment.Country is right
Regulation has been made in the atmosphere discharge of industrial enterprise's methacrylaldehyde.The content for measuring methacrylaldehyde in incineration tail gas, to adjusting catalytic burning
The technological parameter of furnace controls the content of methacrylaldehyde in tail gas, meets environmental requirement and be very helpful.This method is suitable for catalysis
Burn the measurement of the content of methacrylaldehyde, acetic acid, acrylic acid in its exhaust gas after acrylic acid tail gas.Methacrylaldehyde, acetic acid, three object of acrylic acid
Matter content is very low.CN103760270A discloses a kind of with acrylic acid in air of workplace by ion chromatography: with
Silicone tube acquires acrylic acid, using a kind of environment friendly and pollution-free sodium carbonate/bicarbonate solution as stripping liquid and chromatogram flow phase, builds
A kind of quick, sensitive, accurate, acrylic acid in environmentally friendly and low-cost ion chromatography detection workplace air side is found
Method, this provides new feasible way fast and accurately to measure acrylic acid in workplace air, and has widened ion chromatography
Application of the method in occupational health detection.This method is presented acrylic acid good linear within the scope of 0.1 μ of μ g~4 g/ml
Relationship.Document above record measurement acrylic acid, methacrylaldehyde, acetic acid method all be measure low content acrylic acid, methacrylaldehyde, second
The method of acid, be not suitable for 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.
It is strong exothermal reaction that propylene gas phase catalytic oxidation reaction, which prepares methacrylaldehyde, and moment aggregation is a large amount of anti-in reactor
Heat is answered, hot localised points are formed, if reaction heat cannot be removed timely and effectively, the moment heat of accumulation is constantly accumulated, and will lead to
The loss of catalyst activity component falls off, so that catalyst activity reduction, the lost of life, and cause to react because of excessive oxidation
And aggravate the formation of by-product, or even cause runaway reaction, make sintering of catalyst.And one section of reaction temperature is substantially at 320 DEG C
More than, it is therefore desirable to frequently reaction system liquid sample, gas sample content are analyzed, to Instructing manufacture or adjustment catalyst performance
Energy.If the content of acrylic acid, methacrylaldehyde, acetic acid easily and fast, can be measured accurately, not by large-scale instrument, measurement environment
Influence, could preferably meet the actual needs of scientific research, production.
Summary of the invention
The present invention provides a kind of measuring method of acrylic acid content in liquid phase mixture, particularly relates to propylene oxidation system
The measurement of acrylic acid content in standby acrolein reaction product.
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 one section of reaction liquid product
Methacrylaldehyde, acrylic acid, there are also the substances such as minute quantity acetic acid.
The measuring method of acrylic acid content in a kind of liquid phase mixture mainly contains methacrylaldehyde, propylene in liquid phase mixture
Acid, acetic acid, include the following steps:
A) it samples
From first stage reactor sample tap take 17L gas sample condensed absorbent after in 1000mL volumetric flask, when sampling outside sampling bottle
Portion's condensation, condensation temperature at 25 DEG C hereinafter, liquid sample adds water to groove, it is spare as prepare liquid after shaking up；
B) C is first denoted as using total acid molar concentration in determination of acid-basetitration prepare liquidTotal acid；
C) acrylic acid and acetic acid are surveyed with gas-chromatography again: acrylic acid, acetic acid standard sample mole hundred known to production concentration
Divide the standard curve of content and corresponding peak area ratio；Gas-chromatography surveys acrylic acid and acetic acid peak area: chromatographic column is using non-
Isothermal temperature-gradient method is to 160~180 DEG C；Prepare liquid and organic solvent use 10 μ L microsyringe sample introduction, 2 μ L after mixing, by
Obtained chromatogram spectrogram determines the peak area ratio of acrylic acid and acetic acid, then on acrylic acid and the standard curve of acetic acid content
Acrylic acid Mole percent specific concentration is found, AA is denoted asConcentration；Acrylic acid concentration C in prepare liquidAA=CTotal acid×AAConcentration。
Acrylic acid is surveyed with gas-chromatography and acetic acid main process is as follows:
A) standard curve is made
With the standard sample of 3~10 known acrylic acid and acetic acid concentration, acrylic acid and second are measured respectively after chromatography column feed materials
The ratio of the corresponding peak area of acid is used as ordinate, and the molar content of acrylic acid and acetic acid is as abscissa, production propylene
The standard curve of acid, acetic acid content；
B) gas-chromatography surveys acrylic acid and acetic acid peak area
Chromatographic column uses non-isothermal temperature-gradient method, i.e., then 110 DEG C 1~5min of holding are heated up fast with 25~35 DEG C/min
Rate is warming up to 140~150 DEG C, preferably 25~30 DEG C/min, then is warming up to 160~180 with the heating rate of 10~20 DEG C/min
DEG C, preferably 10~15 DEG C/min；2mL prepare liquid is taken to be uniformly mixed in bottle with cover with 2mL organic solvent, it is then micro- with 10 μ L
2 μ L of feeder is measured, the peak area ratio of acrylic acid and acetic acid is determined by obtained spectrogram, is then contained in acrylic acid and acetic acid
Acrylic acid Mole percent specific concentration is found on the standard curve of amount, is denoted as AAConcentration；Acrylic acid concentration C in prepare liquidAA=CTotal acid×
AAConcentration；
The acids such as acetic acid, acrylic acid are reacted with alkali in aqueous solution generates salt and water, is reacted with alkali with the acid in prepare liquid,
Measure the content of total acid, preferred sodium hydroxide, potassium hydroxide in determination of acid-basetitration prepare liquid total acid molar concentration of the present invention
Equal highly basic.
Utilize gas Chromatographic Determination acrylic acid Mole percent specific concentration, i.e. AAConcentration；Obtain acrylic acid concentration in prepare liquid.
Total acid molar concentration is measured 2~4 times and is averaged in determination of acid-basetitration prepare liquid of the present invention.In prepare liquid sample
There are also acetic acid other than having acrylic acid, that measure in this way is total acid (CTotal acid), the content of acetic acid is seldom, mainly acrylic acid.This
Organic solvent used in invention gas-chromatography selects one of acetone or butanone.The third of acetic acid and acrylic acid standard sample of the present invention
Olefin(e) acid concentration is between 93.2~99.5mol%.
Methacrylaldehyde belongs to unsaturated aldehyde, and propylene oxidation production methacrylaldehyde, acrylic acid are exothermic reactions, and one section of reaction temperature exists
320 DEG C or more, second-stage reaction temperature is at 230 DEG C or more, and methacrylaldehyde, acrylic acid belong to volatile organic matter.Above-mentioned sampling
Sampling bottle external condensation in step, at 25 DEG C hereinafter, 25 DEG C of water condensations below can be used, most handy ice water mixes condensation temperature
Object condensation.Good using external condensation method sampling acrylic acid liquefaction effect, content is high, makes analysis result closer to true group of product
At.
Methacrylaldehyde, acrylic acid are difficult to polymerize when being gaseous state, and polymerization is easy when being liquid, moreover, contain water in determinand, color
Composing column may be sensitive to water content, if water content is high, it is understood that there may be adsorption phenomena, to will lead to the reproducibility of appearance time
Difference.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 140~150 DEG C are warming up to 25~35 DEG C/min heating rate, then with the heating of 10~20 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- acrylic acid, acetic acid impurity peak can be eliminated simultaneously
Interference, keep measurement result accurate, it is reproducible.
The present invention measures point that acrylic acid is suitable for propylene oxidation production methacrylaldehyde, acrylic acid liquid product content
Analysis, methacrylaldehyde, the content of acrylic acid are higher, and general methacrylaldehyde yield is not suitable for working environment and device tail 78% or more
The measurement of a small amount of methacrylaldehyde, acrylic acid, acetic acid content after gas, burned waste gas.Measuring method of the invention is at low cost, operation letter
Just, low to test environmental requirement, it is not required to large-scale analytical equipment, method is simple and quick, and measurement result is accurate, reproducible.
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, 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 (0.0112mol/L), conical flask: 250mL, graduated pipette: 25mL,
10mL.Other reagents are the pure commercial product of analysis.
Embodiment 1
After single tube reaction unit first stage reactor sample tap 17L gas sample condensed absorbent in 1000mL volumetric flask, sampling
When sampling bottle condensed with mixture of ice and water.Liquid sample adds water to groove, spare as prepare liquid after shaking up.Essence takes 10ml prepare liquid sample
It is added in conical flask, is titrated with the NaOH solution that concentration is 0.0112mol/L, phenolphthalein is indicator, and it is molten to write down NaOH used
The volume number V of liquidNaOH=2.35mL.There are also acetic acid other than having acrylic acid in prepare liquid sample, what is measured in this way is total acid
(CTotal acid), the content of acetic acid is seldom, mainly acrylic acid.CTotal acid=CNaOH VNaOH/VTotal acid, VTotal acid=10mL, CTotal acid=0.00263.
Acrylic acid and acetic acid are surveyed with gas-chromatography again: with the standard sample of 3~10 known acrylic acid and acetic acid concentration, into
The ratio of acrylic acid and the corresponding peak area of acetic acid is measured after sample respectively as ordinate, the Mole percent of acrylic acid and acetic acid contains
Amount is used as abscissa, the standard curve of production acrylic acid, acetic acid content；Gas-chromatography surveys acrylic acid and acetic acid peak area, chromatography
Column uses non-isothermal temperature-gradient method, i.e., then 110 DEG C holding 3min are warming up to 140 DEG C with 30 DEG C/min heating rate, then with 15
DEG C/heating rate of min is warming up to 160 DEG C；2mL prepare liquid is taken to be uniformly mixed in bottle with cover with 2mL butanone, then with 10
2 μ L of μ L microsyringe sample introduction, the area ratio of acrylic acid and acetic acid is determined by obtained spectrogram, then in acrylic acid and acetic acid
Acrylic acid Mole percent specific concentration is found on the standard curve of content, is denoted as AAConcentration=0.980；Acrylic acid concentration C in prepare liquidAA
=CTotal acid×AAConcentration=0.00258.
Embodiment 2
Determination step is with embodiment 1,10 DEG C of water condensations of sampling bottle when sampling.Total acid in determination of acid-basetitration prepare liquid
Molar concentration is measured and is averaged for 2 times, and chromatographic column uses non-isothermal temperature-gradient method, i.e., 110 DEG C holding 3min, then with 30 DEG C/
Min heating rate is warming up to 150 DEG C, then is warming up to 180 DEG C with the heating rate of 20 DEG C/min, measures CAA=0.00271.
Embodiment 3
Determination step is with embodiment 1, and sampling bottle is condensed with mixture of ice and water when sampling.In determination of acid-basetitration prepare liquid
Total acid molar concentration is measured 3 times and is averaged, and chromatographic column uses non-isothermal temperature-gradient method, i.e., 110 DEG C holding 4min, 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, measure CAA=0.00276.
Embodiment 4
Determination step is with embodiment 1, and sampling bottle is condensed with mixture of ice and water when sampling.Chromatographic column is risen using non-isothermal segmentation
Temperature, i.e., 110 DEG C holding 2min, is then warming up to 150 DEG C with 35 DEG C/min heating rate, then with the heating rate liter of 10 DEG C/min
For temperature to 180 DEG C, organic solvent is acetone, measures CAA=0.00301.
Claims (8)
1. the measuring method of acrylic acid content in a kind of liquid phase mixture, mainly contained in liquid phase mixture methacrylaldehyde, acrylic acid,
Acetic acid, which is characterized in that steps are as follows for Main Analysis:
A) sample: from first stage reactor sample tap take 17 L gas sample condensed absorbents after in 1000 mL volumetric flasks, when sampling, takes
Sample bottle external condensation, condensation temperature at 25 DEG C hereinafter, liquid sample adds water to groove, it is spare as prepare liquid after shaking up；
B) C is first denoted as using total acid molar concentration in determination of acid-basetitration prepare liquidTotal acid；
C) acrylic acid is surveyed with gas-chromatography again and acetic acid, main process are as follows: a) making standard curve: third known to 3~10
The standard sample of olefin(e) acid and acetic acid concentration measures the ratio conduct of acrylic acid and the corresponding peak area of acetic acid after chromatography column feed materials respectively
The molar content of ordinate, acrylic acid and acetic acid makes the standard curve of acrylic acid, acetic acid content as abscissa；
B) gas-chromatography surveys acrylic acid and acetic acid peak area: chromatographic column uses non-isothermal temperature-gradient method, i.e., 110 DEG C keep 1 ~
Then 5min carries out first segment with the heating rate of 25 ~ 35 DEG C/min and is warming up to 140 ~ 150 DEG C, then with the liter of 10 ~ 20 DEG C/min
Warm rate carries out second segment and is warming up to 160 ~ 180 DEG C, and 2 mL prepare liquids is taken to mix in bottle with cover with 2 mL organic solvents
It is even, 10mL microsyringe sample introduction 2mL is then used, the peak area ratio of acrylic acid and acetic acid is determined by obtained spectrogram, then
Acrylic acid Mole percent specific concentration is found on acrylic acid and the standard curve of acetic acid content, is denoted as AAConcentration；Propylene in prepare liquid
Acid concentration CAA = CTotal acid× AAConcentration。
2. measuring method according to claim 1, which is characterized in that with 25 DEG C or less outside the sampling procedure sampling bottle
Water condensation.
3. measuring method according to claim 1, which is characterized in that mixed outside the sampling procedure sampling bottle with ice water
Object condensation.
4. measuring method according to claim 1, which is characterized in that the first segment heating rate is 25 ~ 30 DEG C/min.
5. measuring method according to claim 1, which is characterized in that the second segment heating rate is 10 ~ 15 DEG C/min.
6. measuring method according to claim 1, which is characterized in that total acid rubs in the determination of acid-basetitration prepare liquid
You are averaged for measurement of concetration 2 ~ 4 times.
7. measuring method according to claim 1, which is characterized in that organic solvent used in gas-chromatography selects acetone or fourth
One of ketone.
8. measuring method according to claim 1, which is characterized in that the acrylic acid concentration of acrylic acid and acetic acid standard sample
Between 93.2~99.5 mol%.
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| US3845120A (en) * | 1969-02-22 | 1974-10-29 | Basf Ag | Production of acrylic acid by oxidation of acrolein |
| CN1697971A (en) * | 2004-03-01 | 2005-11-16 | 三菱化学株式会社 | Method of determining impurity in acrylic acid |
| CN1818638A (en) * | 2006-03-21 | 2006-08-16 | 上海华谊丙烯酸有限公司 | On-line chromatographic analytical system and use for gas-solid-phase oxidation reactant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7125821B2 (en) * | 2003-09-05 | 2006-10-24 | Exxonmobil Chemical Patents Inc. | Low metal content catalyst compositions and processes for making and using same |
| DE102004021764A1 (en) * | 2004-04-30 | 2005-06-02 | Basf Ag | Production of acrylic acid with low by-product content, for use as monomer, by heterogeneous catalyzed partial oxidation of 3C hydrocarbon precursor, preferably with post-reaction to oxidize by-products |
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| US3845120A (en) * | 1969-02-22 | 1974-10-29 | Basf Ag | Production of acrylic acid by oxidation of acrolein |
| CN1697971A (en) * | 2004-03-01 | 2005-11-16 | 三菱化学株式会社 | Method of determining impurity in acrylic acid |
| CN1818638A (en) * | 2006-03-21 | 2006-08-16 | 上海华谊丙烯酸有限公司 | On-line chromatographic analytical system and use for gas-solid-phase oxidation reactant |
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