CN108535390B - A kind of magnetic droplet dispersion extraction method for petroleum acids separation - Google Patents
A kind of magnetic droplet dispersion extraction method for petroleum acids separation Download PDFInfo
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- CN108535390B CN108535390B CN201810194339.8A CN201810194339A CN108535390B CN 108535390 B CN108535390 B CN 108535390B CN 201810194339 A CN201810194339 A CN 201810194339A CN 108535390 B CN108535390 B CN 108535390B
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- petroleum acids
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0419—Solvent extraction of solutions which are liquid in combination with an electric or magnetic field or with vibrations
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The present invention provides a kind of magnetic droplet dispersion extraction method for petroleum acids separation, and steps are as follows: carrying out Silanized hydrophobic modification to extraction container；The magnetic-particle of preparation coating extractant in silanization extraction container；Crude oil sample solution is added into silanization extraction container, be vortexed concussion, and the magnetic-particle for coating extractant is scattered in formation magnetic droplet in crude oil sample solution and extracts to the petroleum acids in crude oil sample, after the completion of extraction, under the action of adding magnet outside, takes out raffinate and simultaneously give up；Cleaning solvent is added into silanization extraction container to be cleaned, be vortexed concussion, under the action of adding magnet outside, takes out cleaning solution and gives up；Desorption solvent is added into silanization extraction container to be desorbed, is desorbed solvent dissolved with the fluid extractant of petroleum acids and dissolve and be detached from magnetic-particle, outside plus under the action of magnet, taking-up stripping liquid is simultaneously collected.Method provided by the invention is easy to operate, quick, and solvent consumption is few, can the multiple samples of mass simultaneous processing.
Description
Technical field
The present invention relates to Sample Pretreatment Technique Used field more particularly to a kind of magnetic droplet dispersions for petroleum acids separation
Extracting process.
Background technique
Acid compound, that is, petroleum acids in crude oil, including fatty acid and aphthenic acids are the research origins of oil, biodegrade
Etc. petroleum geochemistries content important molecule marker.In addition, petroleum acid content and composition are also crude oil processing equipment corrosion
The important parameter of protection and environmental risk assessment etc. research.Since crude oil sample is extremely complex, petroleum acids is analyzed in instrument
It needs to carry out Selective Separation to petroleum acids before.Currently, petroleum acids separation mainly uses liquid-liquid extraction and Solid Phase Extraction.Liquid
Liquid extraction is used as a kind of most common sample-pretreating method, has and is easy in the reproduction of different experiments room, low for equipment requirements etc.
Advantage, but that there are solvent consumptions is big, easily emulsification, the cumbersome time-consuming, deficiencies such as flux is low；Solid Phase Extraction can evade these not
Foot, but there is the problems such as needing special installation, particular adsorbent preparation is difficult or at high cost, and be not so good as in different experiments room reproducibility
Liquid-liquid extraction.
Summary of the invention
In view of this, the present invention provides a kind of magnetic droplet dispersion extraction sides for petroleum acids separation easily to operate
Method.
The present invention provides a kind of magnetic droplet dispersion extraction method for petroleum acids separation, comprising the following steps:
S1 carries out Silanized hydrophobic modification to extraction container；
S2, the magnetic-particle of preparation coating extractant in silanization extraction container；
Crude oil sample solution is added into the silanization extraction container of the magnetic-particle equipped with the coating extractant in S3,
Be vortexed concussion, and the magnetic-particle for coating extractant, which is scattered in crude oil sample solution, forms magnetic droplet to the stone in crude oil sample
Oleic acid is extracted, and after the completion of extraction, outside plus under magnet effect, is taken out raffinate and is given up；
Cleaning solvent is added in S4, Xiang Suoshu silanization extraction container to be cleaned, be vortexed concussion, is adding magnet effect outside
Under, it takes out cleaning solution and gives up；
Desorption solvent is added in S5, Xiang Suoshu silanization extraction container to be desorbed, dissolved with the fluid extractant of petroleum acids
It is desorbed solvent and dissolves and be detached from magnetic-particle, outside plus under magnet effect, take out stripping liquid and collect, dry up to get stone is arrived
Oleic acid.
Further, in step S1, it is the glass sample bottle of 2mL~20mL, the silicon that the extraction container, which selects specification,
The process of alkanisation hydrophobic modification are as follows: extraction container is immersed in the n-hexane containing dichlorodimethylsilane, soaking time 4h
The volume ratio of~48h, dichlorodimethylsilane and n-hexane is 1:99~1:9.
Further, in step S2, the detailed process of the magnetic-particle of preparation coating extractant are as follows: extract and hold to silanization
Magnetic-particle is added in device, excessive fluid extractant is then added, be vortexed concussion, and it is extra to be dissociated using the removal of additional magnet
Fluid extractant to get to coating extractant magnetic-particle；The magnetic-particle is magnetic Nano silica gel particle, partial size
For 100nm~500nm, the dosage of the magnetic-particle is 1mg~100mg, and the fluid extractant is ammonium hydroxide, the concentration of ammonium hydroxide
For 0.5wt%~25wt%, the additional amount of the fluid extractant is 0.05mL~0.5mL, and the time for the concussion that is vortexed is 1min
~3min.
Further, in step S3, the crude oil sample solution is diluted in n-hexane by crude oil sample to be obtained, dilution times
Number is 5~20 times, and the time of extraction is 1min~10min.
Further, in step S4, the cleaning solvent is n-hexane, the volume of the cleaning solvent and the crude oil of addition
The volume of sample solution is consistent, and scavenging period is 0.5min~3min, and wash number is 1~3 time.
Further, in step S5, the desorption solvent is acetone, the additional amount of the desorption solvent be 0.1 mL~
0.5mL, desorption time are 1min~10min.
Further, the additional magnet selects square magnet or cylinder-shaped magnet, and additional magnet is placed on silanization
On the outer wall of extraction container, under the magnetic force, magnetic-particle is attracted on the inner wall of silanization extraction container, at this time may be used
The solution in silanization extraction container to be taken out.
Compared with prior art, the beneficial effects of the present invention are:
1, magnetic droplet of the invention using magnetic nanoparticle as carrier, using ammonium hydroxide as extractant, preparation is simple, at low cost
It is honest and clean；
2, magnetic droplet of the invention is nanoscale, and when extraction is dispersed in sample solution, extractant and analysis
Object contact area is big, and mass-transfer efficiency is high, can effectively improve the rate of recovery and sensitivity；
3, the magnetic-particle in magnetic droplet of the invention is reusable, the actual consumption of separation material in extraction process
Only a small amount of ammonium hydroxide has very high practical value；
4, magnetic droplet extracting process provided by the invention is easy to operate, quick, and solvent consumption is few, can mass simultaneous processing
Multiple samples；
5, magnetic droplet extracting process provided by the invention combine dispersive liquid-liquid microextraction and Magnetic solid phases extraction it is excellent
Point, the separation of petroleum acids suitable for all kinds of crude oil samples, effect are prominent.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of the magnetic droplet dispersion extraction method for petroleum acids separation of the present invention.
Fig. 2 is a kind of work flow diagram of the magnetic droplet dispersion extraction method for petroleum acids separation of the present invention.
Fig. 3 is influence result figure of the dosage of magnetic-particle of the present invention to extraction efficiency.
Fig. 4 is influence result figure of the extraction time of the present invention to extraction efficiency.
Fig. 5 is influence result figure of the desorption time of the present invention to extraction efficiency.
Fig. 6 is the recycling feasibility analysis result figure of magnetic-particle of the present invention.
Fig. 7 is the analysis test knot of one embodiment of the invention Central Plains oil samples before and after the processing by method provided by the invention
Fruit figure.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
Fig. 1 and Fig. 2 are please referred to, the embodiment provides a kind of magnetic droplets for petroleum acids separation to disperse extraction
Take method, comprising the following steps:
Step S1, carries out Silanized hydrophobic modification to extraction container, cleans, and drying obtains silanization extraction container；Extraction
It is the glass sample bottle of 2mL~20mL, the process of Silanized hydrophobic modification are as follows: be immersed in extraction container and contain that container, which selects specification,
In the n-hexane of dichlorodimethylsilane, soaking time is 4h~48h, and the volume ratio of dichlorodimethylsilane and n-hexane is 1:
99~1:9.
Step S2, is added magnetic-particle in silanization extraction container, and excessive fluid extractant is then added, using more
Hole turbula shaker is vortexed after concussion 1min~3min, is removing free extra fluid extraction outside plus under the auxiliary of magnet
Agent obtains the magnetic-particle of coating extractant；Magnetic-particle is magnetic Nano silica gel particle, and partial size is 100nm~500nm, magnetic
Property particle dosage be 1mg~100mg, fluid extractant is ammonium hydroxide, and the concentration of ammonium hydroxide is 0.5wt%~25wt%, liquid extraction
The additional amount for taking agent is the mL of 0.05mL~0.5.
Step S3 is added 0.1mL~10mL's into the silanization extraction container of the magnetic-particle equipped with coating extractant
Crude oil sample solution, be vortexed concussion, and the magnetic-particle for coating extractant is scattered in formation magnetic droplet pair in crude oil sample solution
Petroleum acids in crude oil sample is extracted, and extraction time is 1min~10min, after the completion of extraction, in the auxiliary for adding magnet outside
Under, it takes out raffinate and gives up, retain magnetic-particle；Crude oil sample solution is diluted in n-hexane by crude oil sample to be obtained, dilute
Releasing multiple is 5~20 times.
Step S4 is added cleaning solvent into silanization extraction container and is cleaned, and be vortexed concussion, is adding the auxiliary of magnet outside
It helps down, take out cleaning solution and gives up；Cleaning solvent is n-hexane, the body of the crude oil sample solution of the volume and addition of cleaning solvent
Product is consistent, and scavenging period is 0.5min~3min, and wash number is 1~3 time.
Step S5 is added desorption solvent into silanization extraction container and is desorbed, dissolved with the fluid extractant of petroleum acids
It is desorbed solvent and dissolves and be detached from magnetic-particle, outside plus under the auxiliary of magnet, taking out stripping liquid and collecting, gained solution will be collected
After imbibition is dried with nitrogen, petroleum acids is obtained, carries out gas chromatography-mass spectrometry analysis after redissolving petroleum acids and derivatization with n-hexane；
Desorption solvent selects acetone, and the additional amount of desorption solvent is 0.1 mL~0.5mL, and desorption time is 1min~10min.
In step S2~S5, additional magnet selects square magnet or cylinder-shaped magnet, and the specification of square magnet is long 20mm
× wide 10mm × high 5mm~long 50mm × wide 20mm × high 10mm, the specification of cylinder-shaped magnet are diameter 20mm × high 5mm~straight
Diameter 30mm × high 10mm, the course of work of additional magnet are as follows: be placed on additional magnet on the outer wall of silanization extraction container, In
Under the action of magnetic force, magnetic-particle is attracted on the inner wall of silanization extraction container, at this time can be by silanization extraction container
Interior solution takes out.
For a further understanding of the present invention, below with reference to embodiment to the magnetic droplet for petroleum acids separation of the invention
Dispersion extraction method is described in detail.
Embodiment 1:
The glass sample bottle that specification is 2mL is soaked in the hexane solution containing 5% dichlorodimethylsilane, 8h is stood
Glass sample bottle is taken out afterwards, is cleaned to be placed in 60 DEG C of baking ovens with methanol, n-hexane and be dried, obtain silanized glass sample bottle；
Claim 5mg magnetic Nano silica gel particle to be placed in silanized glass sample bottle, the ammonium hydroxide of 0.1mL 10wt% is added, is vortexed and mixes
Afterwards, under the action of square magnet (specification is 20mm × 15mm × 10mm), magnetic Nano silica gel is free on pipettor taking-up
The extra ammonium hydroxide of particle obtains the magnetic Nano silica gel particle of ammonium hydroxide coating；To the magnetic Nano silica gel coated equipped with ammonium hydroxide
The n-hexane sample solution that 1mL contains 0.1g/mL crude oil is added in the silanized glass sample bottle of grain, be vortexed concussion 2min, this
When ammonium hydroxide coating magnetic Nano silica gel particle be scattered in sample in the form of magnetic droplet, after extraction, in rectangular magnetic
Under the action of iron, takes out raffinate and give up；The cleaning of 1mL n-hexane is added into silanized glass sample bottle, be vortexed concussion
0.5min takes out cleaning solution and gives up, repeated washing 2 times under the action of square magnet；Into silanized glass sample bottle
0.2mL acetone is added, by acetone solution and magnetic Nano silica gel particle is detached from dissolved with the ammonium hydroxide extractant of petroleum acids at this time, in side
It under the action of shape magnet, takes out stripping liquid and collects, nitrogen is blown to dry at room temperature, petroleum acids is obtained, after being redissolved with 0.1mL n-hexane
10 μ L N- (t-butyldimethylsilyi)-N- methyl trifluoro acetamides are added to perform the derivatization, it is laggard to shake 5min at room temperature
Row gas chromatography-mass spectrometry analysis.
Embodiment 2:
The present embodiment and the difference of embodiment 1 are only that: the glass sample bottle that specification is 5mL is soaked in containing 8% dichloro
In the hexane solution of dimethylsilane, the dosage of magnetic Nano silica gel particle is 2mg, and the concentration of ammonium hydroxide is 15wt%, crude oil
The additional amount of sample solution is 2mL, and the extension rate of crude oil sample is 6 times, and the additional amount of acetone is 0.3mL；Yu Zeyu is implemented
Example 1 is essentially identical.
Embodiment 3:
The present embodiment and the difference of embodiment 1 are only that: the glass sample bottle that specification is 10mL is soaked in containing 9% 2
In the hexane solution of chlorodimethylsilane, the dosage of magnetic Nano silica gel particle is 10mg, and the concentration of ammonium hydroxide is 18wt%, former
The additional amount of oil samples solution is 4mL, and the extension rate of crude oil sample is 10 times, and the additional amount of acetone is 0.4mL；Yu Zeyu is real
It is essentially identical to apply example 1.
Embodiment 4:
The present embodiment and the difference of embodiment 1 are only that: the glass sample bottle that specification is 18mL is soaked in containing 10% 2
In the hexane solution of chlorodimethylsilane, the dosage of magnetic Nano silica gel particle is 15mg, and the concentration of ammonium hydroxide is 22wt%, former
The additional amount of oil samples solution is 8mL, and the extension rate of crude oil sample is 15 times, and the additional amount of acetone is 0.45mL；Yu Zeyu
Embodiment 1 is essentially identical.
Fig. 3 is influence result figure of the dosage of magnetic-particle to extraction efficiency, the results showed that, the magnetic Nano silica gel of 2mg
Particle can meet requirement of experiment, this is because magnetic Nano silica gel particle has nano-scale, use it to coat as carrier and extract
When agent being taken to be used to extract, extractant and sample solution contact area are big, and extractant utilization rate is high, and a small amount of separation material can be realized
High-recovery extraction.
Fig. 4 is influence result figure of the extraction time to extraction efficiency, and Fig. 5 is influence result of the desorption time to extraction efficiency
Figure, the results showed that, the vortex concussion of 2min can meet experiment demand for extracting and desorbing, this has benefited from the magnetic of nanoscale
High mass transfer efficiency between property drop and sample solution or stripping workshop.
Fig. 6 is the recycling feasibility analysis result figure of magnetic-particle, the results showed that, the magnetic Nano silicon in the present invention
After recycling 30 times, the extraction efficiency for using it to have as carrier coating extractant does not still obviously become glue particle
Change, illustrates that the magnetic Nano silica gel particle is reusable, significantly improve the practicability of the extracting process.
Fig. 7 is the analysis test knot of one embodiment of the invention Central Plains oil samples before and after the processing by method provided by the invention
Fruit figure, the crude oil sample are added to 11 kinds of petroleum acids standard items of 100ng/mL, the results showed that, the sample before processing is directly analyzed
Hydrocarbon compound signal in all crude oil of obtained Spectral Signal, without any petroleum acid signal；And passes through the present invention and provide
Method processing after, in spectrogram substantially only have petroleum acid compound signal, without apparent hydrocarbon compound interference signal, this shows
Method provided by the invention has preferable impurity-eliminating effect, has to petroleum acids more highly selective, has investigated methodology, linearly related
Coefficient is greater than 0.9954, and detection is limited to 0.7~1.9ng/g, is quantitatively limited to 2.5~6.2ng/g, and relative recovery is 79.1%~
112.1%, in a few days and in the daytime RSD is respectively lower than 11.3% and 13.4%, and method is accurate, reliable.
Magnetic droplet of the invention using magnetic nanoparticle as carrier, using ammonium hydroxide as extractant, preparation is simple, at low cost
It is honest and clean；Magnetic droplet of the invention is nanoscale, and when extraction is dispersed in sample solution, extractant and analyte contact surface
Product is big, and mass-transfer efficiency is high, can effectively improve the rate of recovery and sensitivity；The repeatable benefit of magnetic-particle in magnetic droplet of the invention
With the actual consumption of separation material only has a small amount of ammonium hydroxide in extraction process, has very high practical value；Magnetic provided by the invention
Property droplet extraction method it is easy to operate, quick, solvent consumption is few, can mass simultaneous handle multiple samples；Magnetic provided by the invention
Property droplet extraction method combine the advantages of dispersive liquid-liquid microextraction and Magnetic solid phases extract, the stone suitable for all kinds of crude oil samples
The separation of oleic acid, effect are prominent.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of magnetic droplet dispersion extraction method for petroleum acids separation, which comprises the following steps:
S1 carries out Silanized hydrophobic modification to extraction container；
S2, the magnetic Nano silica gel particle of preparation coating ammonium hydroxide in silanization extraction container；
S3, into the silanization extraction container of the magnetic Nano silica gel particle equipped with the coating ammonium hydroxide, addition crude oil sample is molten
Liquid, be vortexed concussion, and the magnetic Nano silica gel particle for coating ammonium hydroxide, which is scattered in crude oil sample solution, forms magnetic droplet to crude oil
Petroleum acids in sample is extracted, and after the completion of extraction, outside plus under magnet effect, is taken out raffinate and is given up；
Cleaning solvent is added in S4, Xiang Suoshu silanization extraction container to be cleaned, be vortexed concussion, in the case where adding magnet effect outside,
It takes out cleaning solution and gives up；
Desorption solvent is added in S5, Xiang Suoshu silanization extraction container to be desorbed, is solved dissolved with the fluid extractant of petroleum acids
Suction solvent dissolves and is detached from magnetic-particle, outside plus under magnet effect, takes out stripping liquid and simultaneously collects, dries up to get petroleum acids is arrived.
2. the magnetic droplet dispersion extraction method for petroleum acids separation as described in claim 1, which is characterized in that step S1
In, it is the glass sample bottle of 2mL~20mL that the extraction container, which selects specification, the process of the Silanized hydrophobic modification are as follows: will
Extraction container is immersed in the n-hexane containing dichlorodimethylsilane, soaking time be 4h~48h, dichlorodimethylsilane with just
The volume ratio of hexane is 1:99~1:9.
3. the magnetic droplet dispersion extraction method for petroleum acids separation as described in claim 1, which is characterized in that step S2
In, the detailed process of the magnetic Nano silica gel particle of preparation coating ammonium hydroxide are as follows: magnetic Nano is added into silanization extraction container
Then excessive ammonium hydroxide is added in silica gel particle, be vortexed concussion, removes free extra ammonium hydroxide using additional magnet to get arriving
Coat the magnetic Nano silica gel particle of ammonium hydroxide；The partial size of the magnetic Nano silica gel particle is 100nm~500nm, the magnetism
The dosage of nanometer silica gel particle is 1mg~100mg, and the concentration of ammonium hydroxide is 0.5wt%~25wt%, and the additional amount of ammonium hydroxide is
0.05mL~0.5mL, the time for the concussion that is vortexed are 1min~3min.
4. the magnetic droplet dispersion extraction method for petroleum acids separation as described in claim 1, which is characterized in that step S3
In, the crude oil sample solution is diluted in n-hexane by crude oil sample to be obtained, and extension rate is 5~20 times, the time of extraction
For 1min~10min.
5. the magnetic droplet dispersion extraction method for petroleum acids separation as described in claim 1, which is characterized in that step S4
In, the cleaning solvent is n-hexane, and the volume of the cleaning solvent and the volume of crude oil sample solution of addition are consistent, cleaning
Time is 0.5min~3min, and wash number is 1~3 time.
6. the magnetic droplet dispersion extraction method for petroleum acids separation as described in claim 1, which is characterized in that step S5
In, the desorption solvent is acetone, and the additional amount of the desorption solvent is 0.1mL~0.5mL, desorption time be 1min~
10min。
7. the magnetic droplet dispersion extraction method for petroleum acids separation as claimed in claim 3, which is characterized in that described outer
Add magnet to select square magnet or cylinder-shaped magnet, additional magnet is placed on the outer wall of silanization extraction container, in magnetic force
Under the action of, magnetic Nano silica gel particle is attracted on the inner wall of silanization extraction container, can be extracted silanization at this time
Solution in container takes out.
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| CN1049374A (en) * | 1990-09-15 | 1991-02-20 | 中国石油化工总公司 | From crude oil, remove the method for petroleum acid |
| CN1235843C (en) * | 2004-03-12 | 2006-01-11 | 北京石油化工学院 | Method for eliminating and reclaiming acid component from oil products |
| US8157986B2 (en) * | 2008-08-27 | 2012-04-17 | Seoul National University Research & Development Business Foundation | Magnetic nanoparticle complex |
| CN103418345A (en) * | 2013-09-09 | 2013-12-04 | 辽宁石油化工大学 | Modified mesoporous carbon adsorbent and manufacturing method thereof |
| WO2015044449A1 (en) * | 2013-09-30 | 2015-04-02 | Mærsk Olie Og Gas A/S | Use of magnetic nanoparticles for depletion of aromatic compounds in oil |
| CN104785229A (en) * | 2014-01-16 | 2015-07-22 | 中国药科大学 | Preparation method of mixed hemi-micelle solid phase extractant based on magnetic carbon nanotubes |
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