CN108717085A - A kind of headspace extraction method for in-situ evaluation metal catalyst reduction performance - Google Patents
A kind of headspace extraction method for in-situ evaluation metal catalyst reduction performance Download PDFInfo
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- CN108717085A CN108717085A CN201810412758.4A CN201810412758A CN108717085A CN 108717085 A CN108717085 A CN 108717085A CN 201810412758 A CN201810412758 A CN 201810412758A CN 108717085 A CN108717085 A CN 108717085A
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Abstract
The invention discloses a kind of headspace extraction methods for in-situ evaluation metal catalyst reduction performance；The variation for specifically headspace gas chromatography being utilized quickly to measure reactant and product content in chlorinated aromatic compound catalysis dechlorination reaction process evaluates the technology of the performance of catalyst to establish kinetics relation.Its step is：(1) selected and External standards solutions the preparation of model object, (2) optimization of headspace gas chromatography test parameter, (3) blank control experiment is carried out, (4) headspace gas chromatography is used to carry out the detection of sample, (5) calculating and dynamic analysis of result, the evaluation of (6) catalyst performance.The advantages that this method is better than common gas chromatography and high performance liquid chromatography, has and is not necessarily to sample pretreatment, easy to operate, easy grasp, batch processing is efficient.
Description
Technical field
The present invention is to utilize chlorinated aromatic chemical combination in headspace gas chromatography evaluation metallic catalyst catalysis simulated wastewater
The treatment effect of object, belongs to environmental analysis detection field, specifically a kind of for in-situ evaluation metal catalyst reduction performance
Headspace extraction method.
Background technology
Chlorinated aromatic compound is widely present in the production waste water of a variety of industries such as dyestuff, pesticide, papermaking, petrochemical industry
In, with the gradually deflation of environmental protection policy, the discharge standard of waste water is improved constantly, especially to chlorinated aromatic compound
Discharge content have the limitation being increasingly stringenter.129 kinds of priority pollutants names that Environmental Protection Agency (EPA) is announced
Dan Zhong, the halogenated organic matters based on chlorinated aromatic compound account for more than half.China announce " Chinese environmental preferentially pollutes
In object blacklist ", chlorinated aromatic organic matter also accounts for prodigious proportion.In national sewage comprehensive emission standard GB8978-
In 1996, the three-level discharge standard of paracide and 2,4,6- trichlorophenols is 1mg/L, and the three-level discharge standard of metacresol is
0.5mg/L。
Organic matter of the chlorinated aromatic compound as difficult for biological degradation, common processing method have catalytic oxidation, change
Learn oxidizing process, photochemical oxidation method and electrochemical oxidation process, but oxidation process is there may be the chlorinatedorganic of toxicity bigger,
Such as chlorophenol.Since last century the eighties, the reduction dechlorination that zero-valent metal is used as chlorinatedorganic studies the pass for receiving people
Note, wherein Zero-valent Iron (ZVI) are widely used due to advantages such as its non-toxic inexpensives.As that studies Zero-valent Iron gradually gos deep into,
Nano zero valence iron (nZVI) is gradually developed containing Fe Bimetallic System and immobilization containing Fe Bimetallic System.Currently, this
A little metallic catalysts and Bimetallic catalyst system are applied to every field to the reduction dechlorination research of chlorinatedorganic.Meanwhile
It filters out cheap metal and substitutes noble metal, reduce application cost and find good support materials and fix metallic catalyst, make
It can recycle be current metal catalyst reduction dechlorination research one of hot spot.
Chlorinated aromatic compound and the assay method of corresponding content of degradation products usually have high performance liquid chromatography
(HPLC), gas-chromatography (GC), multi-wavelength ultraviolet spectroscopy etc..Wherein HPLC is limited to larger by chromatographic column, and sample is into color
It is needed by complicated preprocessor before spectrum column to prevent from blocking, operating process is cumbersome, and cost is higher；Although GC is not by chromatographic column
Limitation, but need to extract and pre-concentration process, this process would generally use the organic solvent being more toxic, and repeatedly extraction
The loss of test substance can be caused by taking, and lead to experimental error；Multi-wavelength ultraviolet spectroscopy compared to HPLC and GC have it is easy to operate,
The advantages of easily grasping, but it is to the more demanding of solution composition, is typically only capable to for analyzing the less mould of contained substance type
Quasi- waste water, for more complicated mathematical computations can be encountered when analyzing actual waste water and the more simulated wastewater of contained substance type
And resultant error is larger.Therefore, a kind of degradation of efficient detection technique real time on-line monitoring chlorinated aromatic compound is developed
Process establishes kinetic model, has realistic meaning for screening highly efficient cheap catalyst.
Invention content
The shortcomings that it is an object of the invention to overcome the above-mentioned prior art and deficiency provide a kind of for in-situ evaluation metal
The headspace extraction method of catalyst reduction performance.Overcome the disadvantage present in present analysis chlorinated aromatic compound content method
End.Degradation reaction may be implemented using this method and detection is carried out at the same time, be not necessarily to the pre-treatment of sample, it is easy to operate, and can criticize
Amount detection, it is efficient, it is highly practical.
The present invention is achieved through the following technical solutions：
A kind of headspace extraction method for in-situ evaluation metal catalyst reduction performance includes the following steps：
Step 1, selected and External standards solutions the preparation of model object
Absolute ethyl alcohol, the model object to be measured of configuration standard concentration and corresponding reduction are previously added in 100mL volumetric flasks
Product mother liquor takes the single mother liquor of different volumes ratio to be added in ml headspace bottle, adds deionized water and be diluted to fixed body respectively
Product seals ml headspace bottle, rocks uniformly, to be determined；
Step 2, the optimization of headspace gas chromatography test parameter
Solution to be measured in step 1 is placed in head-space sampler, the component in solution reaches gas-liquid point after constant temperature
Then gaseous component in ml headspace bottle is blown into gas-chromatography with nitrogen and is analyzed by balancing；By the way that gradient sample introduction is arranged
Mouth pressure and chromatogram column temperature, it is ensured that the chromatographic signal peak of all substances will not interfere with each other, and the control of appearance duration is reasonable
Range；
Step 3, blank control experiment
It takes prepared model object solution to be measured in step 1 to be diluted to setting concentration, then takes and be quantitatively adding ml headspace bottle
In, sealing；
The optimal head space test parameter of step 2 is taken to be analyzed, concrete operations are as follows：By the head space equipped with model object solution
Bottle, which is placed in injector furnace box, to be balanced, and then nitrogen purging enters gas chromatographic analysis, and furnace box is back to immediately after purging
In balance same time again, and then purging analysis, so recycle (liquid phase extraction) repeatedly, gained gas-chromatography signal peak
The logarithm of area can constitute a standard curve with extraction times；
Step 4 carries out the detection of sample using headspace gas chromatography
It takes prepared model object mother liquor to be measured in step 1 to be diluted to the same same concentration of step three-phase, then takes same step 3
Equivalent solution is added in ml headspace bottle, is rapidly added nano-metal particle or nanometer bi-metal catalyst, seals；
It is analyzed according to the identical test parameter of step 3, concrete operations are as follows：By the ml headspace bottle being sealed be placed in into
It is balanced in sample device furnace box, then nitrogen purging enters gas chromatographic analysis, is back in furnace box after purging and puts down again immediately
Weigh same time, and then purging analysis, so recycles (liquid phase extraction) repeatedly, record gained gas-chromatography signal peak face
Product；
Step 5 degrades to model object by the analysis changed over time to the head space balanced gas in same sample bottle
Dynamics is studied, and according to multiple headspace extraction theory, the peak area that volatile materials is obtained by extraction in sample bottle meets finger
Number decaying, i.e.,：
An=An-1eq=An-2e2q=...=A0enq (1)
ln(An)=nq+ln (A0) (2)
Wherein：A0For the initial peak area of headspace gas, AnWhen being sampled for n-th, obtained peak area, q is the oblique of curve
Rate, n are extraction times；For degradation reaction system, the concentration of model object is reduced with the extension in reaction time, can root
According to, extrapolate it is adjacent twice extract peak area reduced value
△An=An-1eq-An (3)
By testing obtained peak area A1, A2, A3..., An, corresponding Δ A can be calculated1, Δ A2, Δ A3..., Δ
An；
The relationship of reaction time and extraction times is indicated with following formula：
T=jn (4)
T is the reaction time, and j is sampling interval time (equilibration time), and n is extraction times；
The relationship of gas-chromatography peak area and concentration C can be indicated with following formula：
C=kA (5)
Wherein k is response coefficient, can be corrected and be obtained by standard curve backstepping；
It can be derived according to formula (3) and formula (5)：
△Cn=k (An-1eq-An) (6)
The corresponding peak area of extraction every time that record standard slope of a curve and experiment measure, is brought into formula (6) i.e.
The decrement that volatility model object between two sub-samplings can be calculated is converted into the reaction time further according to formula (4) by number is sampled,
Kinetics equation can be established, observed rate constant is calculated；
Step 6, the evaluation of catalyst：The performance of catalyst is evaluated according to the calculated observed rate constant of step 5.
Model object in above-mentioned steps one refers to aromatic compound, i.e. chlorobenzene or chlorophenols, the addition of absolute ethyl alcohol
Amount is 5-40mL, and the ratio between model object mother liquor volume and corresponding dechlorination product mother liquor volume are 0.1:1-1:0.1.
The thermostat temperature of injector furnace box is 40-80 DEG C in above-mentioned steps two to four；Constant temperature time is 5-30min.
Inlet pressure in above-mentioned steps two is 20-40psi；Chromatogram column temperature is 80-140 DEG C；Inlet pressure ladder
Degree is 1-10psi；Chromatogram column temperature gradient is 1-20 DEG C；A length of 1.5-5min when appearance.
A concentration of 40-150mmol/L is set in above-mentioned steps three；Dosage 10-18mL.
It recycles multiple described in above-mentioned steps three and step 4, refer to extraction times is 3~10 times.
Nano-metal particle or nanometer bi-metal catalyst in above-mentioned steps four, for the gold degraded for chlorinatedorganic
Belong to, including iron, palladium, nickel or silver.
The present invention compared with the existing technology, has the following advantages and effect：
(1) it is not necessarily to sample pretreatment, easy grasp easy to operate, processing time is short is efficient.
(2) degradation reaction and detection are carried out at the same time, and avoid in conventional detection technology nano metal ion residues in solution
In, when sampling carries out sample pretreatment, error caused by the reaction time is extended indirectly.
(3) strong antijamming capability, other substances present in sample will not impact measurement, and can be used for practical useless
The processing detection of water.
Description of the drawings
Fig. 1 is the gas-chromatography signal graph of selected model object dichloro-benzenes and corresponding dechlorination product；
Fig. 2 is blank sample and the chromatographic signal peak area logarithm of catalyst sample is added with the variation of extraction times
Figure.
Specific implementation mode
The present invention is more specifically described in detail with reference to specific embodiment.
The present invention is more specifically described in detail with reference to specific embodiment, but embodiments of the present invention are unlimited
In this.Embodiment is only used for explaining the present invention, is not intended to limit the present invention, and the simple change for being related to the present invention should all belong to this
The protection domain of invention.
Embodiment 1
The evaluation of nano-cellulose load iron palladium bimetallic system
(1) selected and External standards solutions the preparation of model object：20mL absolute ethyl alcohols are previously added in 100mL volumetric flasks,
Dichloro-benzenes, chlorobenzene and benzene mother liquor 400mmol/L are prepared, the single mother liquor of 1mL dichloro-benzenes, 0.5mL chlorobenzenes and benzene is taken to be added respectively
In ml headspace bottle, the dilution of 8mL deionized waters is added, ml headspace bottle is sealed, rocked uniformly, it is to be determined.
(2) optimization of headspace gas chromatography test parameter：Solution to be measured in step (1) is placed in head-space sampler,
Then gaseous component in ml headspace bottle is blown into gas-chromatography with nitrogen and is analyzed by solution constant temperature 15min at 40 DEG C.If
It is 5psi to set inlet pressure gradient, and chromatogram column temperature gradient is 10 DEG C, gradually rises temperature according to setting gradient, obtains optimal
Head space test parameter：230 DEG C, pressure 30psi of injector temperature, 105 DEG C of column temperature, 250 DEG C of detector temperature, appearance duration exists
In 2min.
(3) blank control is tested：Prepared 400mmol/L dichloro-benzenes mother liquor in step (1) is taken to be diluted to 40mmol/L,
Then 18mL is taken to be added in ml headspace bottle, sealing.The head space test parameter in step (2) is taken to be analyzed, concrete operations are as follows：It will
It is placed in 40 DEG C of injector furnace boxes equipped with dichlorobenzene solution ml headspace bottle and balances 15min, then nitrogen purging divides into gas-chromatography
It analyses, is back in furnace box immediately after purging and balances 15min again, and then purging analysis, so cycle 6 times, to gained
The natural logrithm value of gas-chromatography signal peak area draws out standard curve with extraction times mapping, and standard curve is calculated
Regression equation ln (An)=7.215-0.046n, R2=0.997.
(4) headspace gas chromatography is used to carry out the detection of sample：Prepared 400mmol/L dichloro-benzenes mother liquor is taken to be diluted to
Then 40mmol/L takes 40mmol/L solution to be added in ml headspace bottle, is rapidly added nano-cellulose load iron palladium bimetallic, close
Envelope.Same step (3) same test parameter is taken to be analyzed, concrete operations are as follows：Dichlorobenzene solution and nano-cellulose will be housed
The bimetallic ml headspace bottle of load iron palladium is placed in 40 DEG C of injector furnace boxes and balances 15min, and then nitrogen purging enters gas-chromatography
It analyzes, is back in furnace box immediately after purging and balances 15min again, and then purging analysis, so cycle 6 times, record
Gained gas-chromatography signal peak area is respectively 1299.1,1193.8,860.4,430.8,330.3,138.7.
(5) result of calculation is as shown in table 1：
Table 1：The chromatographic signal peak area of nano-cellulose load iron palladium bimetallic sample and corresponding result of calculation is added
(6) observed rate constant that can be calculated the degradation reaction by fit time and ln (c) is 0.02min-1。
Embodiment 2
Carboxymethyl cellulose loads the evaluation of Nanoscale Iron
Step (1), (2), (3) are the same as embodiment 1.
(4) headspace gas chromatography is used to carry out the detection of sample：Prepared 400mmol/L dichloro-benzenes mother liquor is taken to be diluted to
Then 40mmol/L takes 40mmol/L solution to be added in ml headspace bottle, be rapidly added the Nanoscale Iron of carboxymethyl cellulose load, close
Envelope.Same step (3) same test parameter is taken to be analyzed, concrete operations are as follows：Dichlorobenzene solution and carboxymethyl cellulose will be housed
The ml headspace bottle of element load Nanoscale Iron, which is placed in 40 DEG C of injector furnace boxes, balances 15min, and then nitrogen purging divides into gas-chromatography
It analyses, is back in furnace box immediately after purging and balances 15min again, and then purging analysis, so cycle 6 times, record institute
It is respectively 1268.4,1153.7,1042.5,663.4,554.6,342.1 to obtain gas phase chromatographic signal peak area；
(5) result of calculation is as shown in table 2
Table 2：The chromatographic signal peak area of carboxymethyl cellulose load nanometer iron sample and corresponding result of calculation is added
(6) observed rate constant that can be calculated the degradation reaction by fit time and ln (c) is 0.011min-1, with
Embodiment 1 compare, can two kinds of metallic catalysts of Fast Evaluation performance.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (7)
1. a kind of headspace extraction method for in-situ evaluation metal catalyst reduction performance, it is characterised in that including walking as follows
Suddenly：
Step 1, selected and External standards solutions the preparation of model object
Absolute ethyl alcohol, the model object to be measured of configuration standard concentration and corresponding reduzate are previously added in 100mL volumetric flasks
Mother liquor takes the single mother liquor of different volumes ratio to be added in ml headspace bottle, adds deionized water and be diluted to fixed volume respectively, close
Bind empty bottle, rocks uniformly, to be determined；
Step 2, the optimization of headspace gas chromatography test parameter
Solution to be measured in step 1 is placed in head-space sampler, it is flat that the component in solution reaches gas-liquid distribution after constant temperature
Gaseous component in ml headspace bottle, is then blown into gas-chromatography with nitrogen and is analyzed by weighing apparatus；By the way that gradient injection port pressure is arranged
Power and chromatogram column temperature, it is ensured that the chromatographic signal peak of all substances will not interfere with each other, and the control of appearance duration is in zone of reasonableness；
Step 3, blank control experiment
It takes prepared model object solution to be measured in step 1 to be diluted to setting concentration, then takes and be quantitatively adding in ml headspace bottle, it is close
Envelope；
The optimal head space test parameter of step 2 is taken to be analyzed, concrete operations are as follows：Ml headspace bottle equipped with model object solution is set
It is balanced in injector furnace box, then nitrogen purging enters gas chromatographic analysis, is back to immediately in furnace box again after purging
Secondary balance same time, and then purging analysis, so cycle are multiple, the logarithm of gained gas-chromatography signal peak area and extraction
Number can constitute a standard curve；
Step 4 carries out the detection of sample using headspace gas chromatography
It takes prepared model object mother liquor to be measured in step 1 to be diluted to the same same concentration of step three-phase, then takes the third amount of same step
Solution is added in ml headspace bottle, is rapidly added nano-metal particle or nanometer bi-metal catalyst, seals；
It is analyzed according to the identical test parameter of step 3, concrete operations are as follows：The ml headspace bottle being sealed is placed in injector
It is balanced in furnace box, then nitrogen purging enters gas chromatographic analysis, is back in furnace box immediately after purging and balances phase again
The same time, and then purging analysis, so cycle are multiple, record gained gas-chromatography signal peak area；
Step 5, by the analysis changed over time to the head space balanced gas in same sample bottle, according to multiple headspace extraction
Theory, the peak area index of coincidence decaying that volatile materials is obtained by extraction in sample bottle, i.e.,：
An=An-1eq=An-2e2q=...=A0enq (1)
ln(An)=nq+ln (A0) (2)
Wherein：A0For the initial peak area of headspace gas, AnWhen being sampled for n-th, obtained peak area, q is slope of a curve, n
For extraction times；For degradation reaction system, the concentration of model object is reduced with the extension in reaction time, can according to, push away
Calculate the adjacent reduced value for extracting peak area twice
△An=An-1eq-An (3)
By testing obtained peak area A1, A2, A3..., An, corresponding Δ A can be calculated1, Δ A2, Δ A3..., Δ An；
The relationship of reaction time and extraction times is indicated with following formula：
T=jn (4)
T is the reaction time, and j is sampling interval time (equilibration time), and n is extraction times；
The relationship of gas-chromatography peak area and concentration C can be indicated with following formula：
C=kA (5)
Wherein k is response coefficient, can be corrected and be obtained by standard curve backstepping；
It can be derived according to formula (3) and formula (5)：
△Cn=k (An-1eq-An) (6)
The corresponding peak area of extraction every time that record standard slope of a curve and experiment measure, being brought into formula (6) can count
The decrement for calculating volatility model object between two sub-samplings is converted into the reaction time further according to formula (4) by number is sampled,
Kinetics equation is established, observed rate constant is calculated；
Step 6, the evaluation of catalyst：The performance of catalyst is evaluated according to the calculated observed rate constant of step 5.
2. being used for the headspace extraction method of in-situ evaluation metal catalyst reduction performance according to claim 1, feature exists
In：Model object in step 1 refers to aromatic compound, i.e. chlorobenzene or chlorophenols, and the addition of absolute ethyl alcohol is 5-
40mL, the ratio between model object mother liquor volume and corresponding dechlorination product mother liquor volume are 0.1:1-1:0.1.
3. being used for the headspace extraction method of in-situ evaluation metal catalyst reduction performance according to claim 1, feature exists
In：The thermostat temperature of step 2 to injector furnace box in four is 40-80 DEG C；Constant temperature time is 5-30min.
4. being used for the headspace extraction method of in-situ evaluation metal catalyst reduction performance according to claim 1, feature exists
In：Inlet pressure in step 2 is 20-40psi；Chromatogram column temperature is 80-140 DEG C；Inlet pressure gradient is 1-
10psi；Chromatogram column temperature gradient is 1-20 DEG C；A length of 1.5-5min when appearance.
5. being used for the headspace extraction method of in-situ evaluation metal catalyst reduction performance according to claim 1, feature exists
In：A concentration of 40-150mmol/L is set in step 3；Dosage 10-18mL.
6. being used for the headspace extraction method of in-situ evaluation metal catalyst reduction performance according to claim 1, feature exists
In：It recycles multiple described in step 3 and step 4, refer to extraction times is 3~10 times.
7. being used for the headspace extraction method of in-situ evaluation metal catalyst reduction performance according to claim 1, feature exists
In：Nano-metal particle or nanometer bi-metal catalyst in step 4, for the metal degraded for chlorinatedorganic, including iron,
Palladium, nickel or silver.
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| CN111024860A (en) * | 2019-12-30 | 2020-04-17 | 华南理工大学 | Method for measuring different forms of moisture in sludge by using headspace gas chromatography |
| CN114894932A (en) * | 2022-05-07 | 2022-08-12 | 安徽工程大学 | Method for detecting trace amount peculiar smell gas components in automobile textile fabric |
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| CN111024860A (en) * | 2019-12-30 | 2020-04-17 | 华南理工大学 | Method for measuring different forms of moisture in sludge by using headspace gas chromatography |
| CN111024860B (en) * | 2019-12-30 | 2022-01-18 | 华南理工大学 | Method for measuring different forms of moisture in sludge by using headspace gas chromatography |
| CN114894932A (en) * | 2022-05-07 | 2022-08-12 | 安徽工程大学 | Method for detecting trace amount peculiar smell gas components in automobile textile fabric |
| CN114894932B (en) * | 2022-05-07 | 2023-08-01 | 安徽工程大学 | Method for detecting trace odor components in textile fabric for automobile |
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