CN108469471A - The solid-phase extraction column and application process of different Group Components in separating synthetic gas olefine reaction oil-phase product - Google Patents
The solid-phase extraction column and application process of different Group Components in separating synthetic gas olefine reaction oil-phase product Download PDFInfo
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- 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
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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
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- G01N2030/062—Preparation extracting sample from raw material
Abstract
The solid-phase extraction column and its application process of different Group Components in a kind of separating synthetic gas olefine reaction oil-phase product, mainly solve the problems, such as that alkane in existing separating synthetic gas olefine reaction oil-phase product, alkene, aromatic hydrocarbons and oxygenatedchemicals are difficult.The solid-phase extraction column is made of two-stage solid-phase extraction column, the stationary phase of first order solid-phase extraction column is silica gel, the stationary phase of second level solid-phase extraction column is the silica gel of load water soluble silver salt and mantoquita, the water-soluble silver salt content that stationary phase is calculated on the basis of silica gel is 3~10 mass %, and mantoquita content is 0~5 mass %.The solid-phase extraction column and its application process of different Group component separations, can be used in the Industrial Analysis of alkane in synthesis gas olefine reaction oil-phase product, alkene, aromatic hydrocarbons and oxygenatedchemicals in the synthesis gas olefine reaction oil-phase product.
Description
Technical field
The present invention relates to the solid-phase extraction column of different Group Component in a kind of separating synthetic gas olefine reaction oil-phase product and
Application process.
Background technology
Synthesis gas alkene (syngas to olefins, SGTO) is with synthesis gas (H2+ CO) it is raw material, certain anti-
It answers and C is made under condition and catalyst action2~C4The reaction of alkene and by-product part oil product, belongs to the one of Fischer-Tropsch synthesis
Kind.This method is to convert coal, natural gas to important channel and the coal high-efficiency cleaning of basic chemical industry raw material and chemicals
The effective ways utilized.
In the later stage eighties, some larger oil companies, which start to invest, in the world researches and develops synthesis gas liquefaction (GTL) phase
Pass technology and technique.Currently, South Africa has 3 indirect liquefaction factories, (Mobil is public for Malaysian (Shell companies) and New Zealand
Department) respectively have a natural-gas indirect liquefaction factory.At home, the coal enterprise such as Yi Taihe Shenhuas implement to build base in research
10 10,000 tons technical scale devices of oil tech are synthesized in iron-based slurry bed system, sinopec and the Lushui River peace have been completed solid based on cobalt-based
Fixed bed synthesizes the kiloton commercial side-stream test of oil tech.This indicates that this technology enters the industrialized production stage in China,
China has independently had blank with the industry development of coal liquifaction.SGTO reaction principles are similar with GTL, but to pursue C2~C4Alkene is
Target product, while by-product part oil-phase product.The composition of synthesis gas olefine reaction oil-phase product is extremely complex, including C5-
C40Alkane, alkene, aromatic hydrocarbons, oxygenatedchemicals, paraffin etc., be suitable for producing liquid fuel, lubricating oil, long-chain alpha-olefin and
Alcohol, ketone chemicals.Therefore, separation determination is carried out to Group Component in synthesis gas olefine reaction oil-phase product and monomer component,
Understand Group Component content, type and monomer composition therein to the processing scheme of optimum synthesis gas olefine reaction oil-phase product,
Increasing economic efficiency has great significance.
Synthesis gas olefine reaction oil-phase product structure composition is complicated, only rely on instrument be unable to get accurately Group Component and
Monomer component information, this just needs to carry out it preprocessing process that separative efficiency is high and intersection component is small, obtains different races
Then component could be analysed in depth with eliminating the overlapping of chromatographic isolation for each component.[" the secondary operation bavin such as Liu Zelong
The analysis of alkene in oil " [J] analytical chemistry, 1996,24 (5)：530-534] it reports secondary processing diesel oil using silicagel column
Sample pre-separation is at non-aromatics, aromatic hydrocarbons and colloid three parts, in conjunction with the type in bromine addition/field ionization mass spectroscopy non-aromatics
And content.This method is cumbersome, and analysis time is long.
Solid phase extraction techniques are widely used in the preprocessing process of oil product in recent years.Utilize the double bond energy and Ag of alkene+
Generation mating reaction formation complex, and saturated hydrocarbons and Ag+It, can be by saturated hydrocarbons and alkene almost without the principle of any effect
Separation.Xu Yan frequently waits [" organophosphorous pesticides-flight time mass spectrum measures the carbon number distribution of alkene in diesel oil " [J] stones
Oily journal, 2010,24 (3)：431-436] by Ag+Ag-SiO is made in load on silica2Solid-phase extraction column uses pentane
The saturation point in diesel samples is flushed out, then flushes out the mixing point of aromatic hydrocarbon and alkene with benzene.It is obtained by pre-separation mixed
It closes to divide into gas-chromatography/field ionization-flight time mass spectrum (GC-FI/TOF MS) analysis and obtains the type and carbon number point of alkene
Cloth information.Bai Xue etc. [olefin type and distribution characterize [J] petroleum refinings and chemical industry in catalytic cracking diesel oil and coker gas oil,
2011,42(11)：76-79] propose that twin columns solid phase extraction detaches the alkene in catalytic cracking diesel oil and coker gas oil, upper prop is filled out
Silica gel is filled, lower prop fills Ag-SiO2.CN 102079987B disclose a kind of Solid Phase Extraction and heavy oil are separated into saturated hydrocarbons, aromatic hydrocarbons
With the method for colloid.These documents are not involved with point of synthesis gas olefine reaction oil-phase product Group Component and monomer component
From the more separation without reference to oxygenatedchemicals in synthesis gas olefine reaction oil-phase product.
Invention content
One of problem to be solved by this invention is to provide a kind of Solid phase extraction separation synthesis gas olefine reaction oil phase production
The solid-phase extraction column of alkane, alkene, aromatic hydrocarbons and oxygenatedchemicals difference Group Component in object.
The two of problem to be solved by this invention are to provide that a kind of Solid phase extraction separation initial boiling point is low, olefin(e) centent is high, contains
There is the method for different Group Components in the synthesis gas olefine reaction oil-phase product of oxide.
The three of problem to be solved by this invention be to provide it is a kind of separation and measure synthesis gas olefine reaction oil-phase product
The chromatographic process of middle difference Group Component.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of Solid phase extraction separation synthesis
The solid-phase extraction column of alkane, alkene, aromatic hydrocarbons and oxygenatedchemicals difference Group Component in gas olefine reaction oil-phase product, by two
Grade solid-phase extraction column composition, two-stage solid-phase extraction column can connect or separate operations, and the stationary phase of first order solid-phase extraction column is
Silica gel, the stationary phase of second level solid-phase extraction column are the silica gel of load water soluble silver salt and mantoquita, and stationary phase is on the basis of silica gel
The water-soluble silver salt content of calculating is 3~10 mass %, and mantoquita content is 0~5 mass %.
In above-mentioned technical proposal, the mass ratio of stationary phase contained by the first order/second level solid-phase extraction column be 0.5~
1.5：1, preferably 0.8~1.2：1.
In above-mentioned technical proposal, the silica gel is silica gel for chromatography, and size distribution is 100-300 mesh, preferably 100-200
Mesh, specific surface area are 400~750m2/ g, preferably 500~650m2/ g, pore volume be 0.35~0.90mL/g, preferably 0.35~
0.5mL/g, the hole of 20~35nm of bore dia account for the 40~65% of pore volume.
The preparation method of above-mentioned silica gel solid phase is：Silica gel is 3~8 hours dry in 100~200 DEG C, obtain activated silica gel
Stationary phase.
The silica gel preparation method of load water soluble silver salt and mantoquita is：Silver salt and copper salt solution are added in silica gel, stirring
It is 1~10 hour dry under the conditions of 100~200 DEG C after uniformly, make silver ion and copper ion uniform adsorption in Silica Surface, obtains Ag
(Cu)-SiO2Stationary phase.The preferred silver nitrate of silver salt and mantoquita described in above-mentioned technical proposal and copper nitrate；Wherein, silver salt
Content is preferably 6~8wt%, and the content of mantoquita is preferably 0.5~3wt%.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows：A kind of Solid phase extraction separation synthesis
The method of different Group Components in gas olefine reaction oil-phase product, including use two-stage solid-phase extraction column described in claim 1
When series connection, synthesis gas olefine reaction oil phase sample is added from the upper layer of first order solid-phase extraction column described in claim 1, uses
First eluant, eluent rinses first order solid-phase extraction column, and the mixture of saturated hydrocarbons and alkene is rinsed to second level solid-phase extraction column
Afterwards, twin columns are separated, rinsing first order solid-phase extraction column with the second eluant, eluent extracts aromatic hydrocarbons, then rinses first with third eluant, eluent
Grade solid-phase extraction column extracts oxygenatedchemicals；Then it rinses second level solid-phase extraction column with the first eluant, eluent and extracts alkane,
Second level solid-phase extraction column is rinsed with the 4th eluant, eluent extract alkene again.Using two-stage Solid Phase Extraction described in claim 1
When column separate operations, synthesis gas olefine reaction oil phase is added from the upper layer of first order solid-phase extraction column described in claim 1
Sample rinses first order solid-phase extraction column with the first eluant, eluent, extracts and collect the mixture of saturated hydrocarbons and alkene, washed with second
De- agent rinses first order solid-phase extraction column and extracts aromatic hydrocarbons, then is rinsed first order solid-phase extraction column with third eluant, eluent and extracted and contained
Oxygen compound；Then front some or all of is collected to the mixture of saturated hydrocarbons and alkene from the upper of second level solid-phase extraction column
Layer is added, and rinsing second level solid-phase extraction column with the first eluant, eluent extracts alkane, then rinses the second level with the 4th eluant, eluent and consolidate
Phase extraction column extracts alkene.First eluant, eluent is selected from isopentane, pentane, n-hexane, hexamethylene, normal heptane and stone
At least one of oily ether, the second eluant, eluent are selected from least one of dichloromethane, chloroform, benzene, carbon disulfide, third elution
Agent is selected from least one of acetonitrile, propionitrile, methanol, ethyl alcohol, isopropanol, methyl acetate, ethyl acetate and tetrahydrofuran, and the 4th
Eluant, eluent is selected from dichloromethane or benzene and ethyl alcohol or the mixture of isopropanol.
In above-mentioned technical proposal, the ratio of the synthesis gas olefine reaction oil-phase product sample and stationary phase gross mass is
1：10~60, preferably 1：15~30.
In above-mentioned technical proposal, after the addition synthesis gas olefine reaction oil-phase product sample, by saturated hydrocarbons and alkene
Hydrocarbon elution the first eluant, eluent used and the volume ratio of synthesis gas olefine reaction oil phase sample are 10~100：1, rinse first
The volume ratio of the second eluant, eluent and synthesis gas olefine reaction oil phase sample is 10~60 used in grade Solid Phase Extraction column extracting aromatic hydrocarbons：
1, rinse third eluant, eluent and synthesis gas olefine reaction oil phase sample used in first order Solid Phase Extraction column extracting oxygenatedchemicals
Volume ratio be 10~60：1, rinse the first eluant, eluent and synthesis gas alkene used in the Solid Phase Extraction column extracting saturated hydrocarbons of the second level
The volume ratio for reacting oil phase sample is 10~100：1, rinse second level Solid Phase Extraction column extracting alkene used in the 4th eluant, eluent with
The volume ratio of synthesis gas olefine reaction oil phase sample is 10~60：1.
In above-mentioned technical proposal, the 4th eluant, eluent is dichloromethane and ethyl alcohol mass ratio is 2~5：1 mixing
Liquid.
To solve above-mentioned technical problem three, the technical solution adopted by the present invention is as follows：It is a kind of to detach and measure synthesis gas
The chromatographic process of different Group Components, includes the method separating synthetic gas alkene with claim 4 in olefine reaction oil-phase product processed
Alkane, alkene, aromatic hydrocarbons and the Oxygen-containing Components sample that hydrocarbon reaction oil-phase product obtains are injected separately into gas chromatograph progress
Further separation, obtains the monomer composition of each alkane, alkene, aromatic hydrocarbons and oxygenatedchemicals.
In above-mentioned technical proposal, chromatographic process separation gas chromatograph separation (GC) operating condition used is：Into
Sample amount 1uL, split sampling, split ratio are (10-100)：1, preferably split ratio is (20-50)：1, chromatographic column is HP-1 capillaries
Column, 300 DEG C of injector temperature, column temperature rise program is 50 DEG C of initial temperature, after keeping 5min, then with the heating speed of 2 DEG C/min
Rate rises to 200 DEG C, keeps 20min.Qualitative detection is level four bars mass spectrograph, is quantitatively detected as level four bars mass spectrograph or FID detections
Device.Mass spectrum (MS) operating condition：EI ionizes mode, bombarding voltage 70eV, scanning quality ranging from 20-550, ion source temperature
220℃。
The stationary phase filled in solid-phase extraction column first order extraction column of the present invention is silica gel, and alkane alkene is detached with silica gel
Hydrocarbon and aromatic hydrocarbons are relatively conventional, and the present invention is with the C1-C20 that silica gel emphasis is in separating synthetic gas olefine reaction oil-phase product
Ketone, aldehyde, alcohol, esters oxygenatedchemicals.Eluting alkane alkene and when aromatic hydrocarbons, the first and second eluant, eluent cannot be selected highly polar molten
Agent, third eluant, eluent need to screen suitable solvent and dosage.With standard solution test to the separating capacity of oxygenatedchemicals, mark
Normal heptane content is 24Wt% in quasi- solution, and 1- nonene contents are 60Wt%, and 2-HEPTANONE content is 6.0%, and toluene level is
10.0%；Applied sample amount is 150 μ L, rinses to obtain alkane olefin solution with 2mL pentane solution successively, molten with the dichloromethane of 2mL
Liquid rinses first order solid-phase extraction column, obtains arene solution, is then rinsed with different highly polar solution, obtains oxygenatedchemicals
Solution, the 2-HEPTANONE content in chromatograph oxygenatedchemicals solution, and calculate the rate of recovery of 2-HEPTANONE.Test result is shown
Acetonitrile or acetonitrile are applied in combination with other intensive polar solvents such as ethyl alcohol, methyl acetate, tetrahydrofuran, the elution to oxygenatedchemicals
Effect is preferable, and the rate of recovery of 2-HEPTANONE is higher；The dosage of third eluant, eluent cannot be too small, and elution is incomplete when dosage is less than 1mL.
The stationary phase filled in the extraction column of the solid-phase extraction column second level of the present invention is Ag (Cu)-SiO2, it is therefore an objective to
Alkane and alkene in the separation synthesis gas olefine reaction oil-phase product that initial boiling point is low, olefin(e) centent is high.It is surveyed with standard solution
Try Ag (Cu)-SiO2Stationary phase is to the separating capacity of alkene, and normal heptane content is 40wt% in standard solution, and 1- nonene contents are
60Wt%, applied sample amount are 150 μ L, rinse to obtain alkane solution with 2mL pentane solution successively, are 3 with 2mL volume ratios：The two of 1
Chloromethanes-ethanol solution rinses, and obtains olefin solution, and nC16 internal standards, chromatograph olefin solution are added in olefin solution
In 1- nonene contents, and calculate the 1- nonene rate of recovery.Test result shows that the content of load water soluble silver salt is 6-8 matter
% is measured, when the content of mantoquita is 0.5-3 mass %, the rate of recovery of alkene is higher；The rate of recovery of alkene when silver salt and mantoquita combine
Better than only use silver salt when the rate of recovery.
Solid-phase extraction column provided by the invention and be added eluant, eluent syringe between and first and second grade of solid-phase extraction column
It is connected using adapter when series connection.The isolated alkane of the above method, alkene, aromatic hydrocarbons and oxygenatedchemicals solution, pass through gas
Chromatography detaches component, and quadrupole mass spectrometer or fid detector measure the intersection component contained in each component and (divided
From component) content, judge separating effect.
Solid-phase extraction column and separation method using the present invention, first order solid-phase extraction column use silica gel solid phase, select
Suitable eluting solvent, alkane, alkene, aromatic hydrocarbons and oxygenatedchemicals difference Group Component in synthesis gas olefine reaction oil-phase product
It is detached, with chromatographic isolation and detects separating effect, test result shows the intersection being separated in each separation Group Component
Constituent content is below 1.5 mass %, illustrates to contain low-boiling hydro carbons and oxide with solid phase extraction method of the present invention separation
Synthesis gas olefine reaction oil-phase product in alkane, alkene, aromatic hydrocarbons and oxygenatedchemicals Group Component, good separation,
Mushing error is within the scope of acceptable.The result shows that the intersection component in the method for the present invention separation component (is detached
Component) content is small, there is good separating effect.
Separation using the present invention and the chromatographic process for measuring different Group Components in synthesis gas olefine reaction oil-phase product,
The composition situation of alkane, alkene, aromatic hydrocarbons and each Group Component of oxygenatedchemicals is measured and the list of each Group Component of accurate quantitative analysis
Body forms.Through Solid phase extraction separation, alkane, alkene, aromatic hydrocarbons and each Group Component of oxygenatedchemicals composition measuring can effectively exclude
Interfere with each other, flow out that phenomenon is seldom altogether, alkane, alkene, aromatic hydrocarbons and each Group Component of oxygenatedchemicals monomer composition can be accurate
It is quantitative.
Below by example, present invention be described in more detail, but the present invention is not limited thereto.
Description of the drawings
Fig. 1 is the total ion chromatogram of alkane component in synthesis gas olefine reaction oil-phase product in the method for the present invention.
Fig. 2 is the total ion chromatogram of olefin component in synthesis gas olefine reaction oil-phase product in the method for the present invention.
Fig. 3 is the total ion chromatogram of aromatic component in synthesis gas olefine reaction oil-phase product in the method for the present invention.
Fig. 4 is the total ion current color of Oxygen-containing Components in synthesis gas olefine reaction oil-phase product in the method for the present invention
Spectrogram.
Specific implementation mode
【Embodiment 1】
The silica gel for preparing the load water soluble silver salt and mantoquita of the present invention that can detach high olefin content sample is fixed
Phase.
It takes 3g silver nitrates to be dissolved in wiring solution-forming in 50mL water, takes 50g silica gel, silver nitrate solution is added in silica gel while stirring
In, after stirring evenly, 150 DEG C of dryings 6 hours obtain the Ag-SiO that silver salt content is 5.0 mass %2Stationary phase (ASG-1).It puts
Enter be kept in dark place in drier it is spare.1.5gAg-SiO is loaded in solid-phase extraction column2Stationary phase (ASG-1), is surveyed with standard solution
Try Ag-SiO2Stationary phase (ASG-1) is to the separating capacity of alkene, and normal heptane content is 40wt% in standard solution, and 1- nonenes contain
Amount is 60Wt%, and applied sample amount is 150 μ L, rinses to obtain alkane solution with 2mL pentane solution successively, is 3 with 2mL volume ratios：1
Dichloromethane-ethanol solution rinse, obtain olefin solution, in olefin solution be added nC16 internal standards, chromatograph alkene
1- nonene contents in solution, and the 1- nonene rate of recovery is calculated, it is shown in Table 1.
Table 1
【Embodiment 2】
The silica gel solid phase of load water soluble silver salt and mantoquita is prepared by the method in embodiment 1, the difference is that silver salt contains
Amount is 8.0 mass %, obtained Ag-SiO2Stationary phase (ASG-2).The 1- nonene rate of recovery is tested with identical method, is shown in Table 1.
【Embodiment 3】
The silica gel solid phase of load water soluble silver salt and mantoquita is prepared by the method in embodiment 1, the difference is that silver salt contains
Amount is 10.0 mass %, obtained Ag-SiO2Stationary phase (ASG-3).The 1- nonene rate of recovery is tested with identical method, is shown in Table 1.
【Embodiment 4】
The silica gel solid phase of load water soluble silver salt and mantoquita is prepared by the method in embodiment 1, the difference is that silver salt contains
Amount is 7.5 mass %, and mantoquita content is 0.5 mass %, obtained Ag (Cu)-SiO2Stationary phase (ASG-4).With identical method
The 1- nonene rate of recovery is tested, is shown in Table 1.
【Embodiment 5】
The silica gel solid phase of load water soluble silver salt and mantoquita is prepared by the method in embodiment 1, the difference is that silver salt contains
Amount is 7.0 mass %, and mantoquita content is 1.0 mass %, obtained Ag (Cu)-SiO2Stationary phase (ASG-5).With identical method
The 1- nonene rate of recovery is tested, is shown in Table 1.
【Embodiment 6】
The silica gel solid phase of load water soluble silver salt and mantoquita is prepared by the method in embodiment 1, the difference is that silver salt contains
Amount is 5.0 mass %, and mantoquita content is 3.0 mass %, obtained Ag (Cu)-SiO2Stationary phase (ASG-6).With identical method
The 1- nonene rate of recovery is tested, is shown in Table 1.
【Embodiment 7】
The silica gel solid phase of load water soluble silver salt and mantoquita is prepared by the method in embodiment 1, the difference is that silver salt contains
Amount is 3.0 mass %, and mantoquita content is 5.0 mass %, obtained Ag (Cu)-SiO2Stationary phase (ASG-7).With identical method
The 1- nonene rate of recovery is tested, is shown in Table 1.
【Comparative example 1】
The silica gel solid phase of load water soluble mantoquita is prepared by the method in embodiment 1, mantoquita content is 8.0 mass %,
Obtained Cu-SiO2Stationary phase (ASG-8).The 1- nonene rate of recovery is tested with identical method, is shown in Table 1.
【Embodiment 8】
Different solvent extraction and separation Oxygen-containing Components are selected with solid phase extraction method of the present invention separation.
Silica gel used in example is that column chromatography silica gel obtains activated silica gel (SG) by silica gel in 150 DEG C of dry 5h,
It is put in spare in drier.1.5g silica gel solid phases are loaded in solid-phase extraction column, are tested to oxygenatedchemicals with standard solution
Separating capacity, normal heptane content is 24Wt% in standard solution, and 1- nonene contents are 60Wt%, and 2-HEPTANONE content is 6.0%, first
Benzene content is 10.0%；Applied sample amount is 150 μ L, rinses to obtain alkane olefin solution with 2mL pentane solution successively, with the two of 2mL
Chloromethanes solution rinses first order solid-phase extraction column, obtains arene solution, is rinsed with the acetonitrile solution of 1mL, obtains oxygen-containing chemical combination
Object solution, the 2-HEPTANONE content in chromatograph oxygenatedchemicals solution, and the rate of recovery of 2-HEPTANONE is calculated, it is shown in Table 2.
Table 2
【Embodiment 9】
By the method Solid phase extraction separation Oxygen-containing Components in embodiment 8, the difference is that being rushed with the acetonitrile solution of 2mL
It washes, obtains oxygenatedchemicals solution.The rate of recovery that 2-HEPTANONE is tested with identical method, is shown in Table 2.
【Embodiment 10】
By the method Solid phase extraction separation Oxygen-containing Components in embodiment 8, the difference is that being rushed with the acetonitrile solution of 3mL
It washes, obtains oxygenatedchemicals solution.The rate of recovery that 2-HEPTANONE is tested with identical method, is shown in Table 2.
【Embodiment 11】
By the method Solid phase extraction separation Oxygen-containing Components in embodiment 8, the difference is that being rushed with the ethanol solution of 2mL
It washes, obtains oxygenatedchemicals solution.The rate of recovery that 2-HEPTANONE is tested with identical method, is shown in Table 2.
【Embodiment 12】
By the method Solid phase extraction separation Oxygen-containing Components in embodiment 8, the difference is that the tetrahydrofuran with 2mL is molten
Liquid rinses, and obtains oxygenatedchemicals solution.The rate of recovery that 2-HEPTANONE is tested with identical method, is shown in Table 2.
【Embodiment 13】
By the method Solid phase extraction separation Oxygen-containing Components in embodiment 8, the difference is that the methyl acetate with 2mL is molten
Liquid rinses, and obtains oxygenatedchemicals solution.The rate of recovery that 2-HEPTANONE is tested with identical method, is shown in Table 2.
【Embodiment 14】
By the method Solid phase extraction separation Oxygen-containing Components in embodiment 8, the difference is that using 1mL acetonitriles and 1mL second
Mixed alkoxide solution rinses, and obtains oxygenatedchemicals solution.The rate of recovery that 2-HEPTANONE is tested with identical method, is shown in Table 2.
【Embodiment 15】
By the method Solid phase extraction separation Oxygen-containing Components in embodiment 8, unlike with 1mL acetonitriles and
0.5mL methyl acetates, 0.5mL tetrahydrofuran mixed solutions rinse, and obtain oxygenatedchemicals solution.2- is tested with identical method
The rate of recovery of heptanone, is shown in Table 2.
【Embodiment 16】
With in solid phase extraction method separating synthetic gas olefine reaction oil-phase product of the present invention alkane, alkene, aromatic hydrocarbons and
Oxygenatedchemicals Group Component.
1.5g silica gel solid phases are loaded in first order solid-phase extraction column, and 1.5gAg- is loaded in the solid-phase extraction column of the second level
SiO2Stationary phase (ASG-5).
Take the synthesis gas olefine reaction oil-phase product of 150 30~250 DEG C of μ L boiling ranges that first order solid-phase extraction column is added.With
3mL pentanes elute and collect alkane and olefin component, obtain 1# alkane and olefin solution.Then the dichloromethane of 2mL is used
Alkane solution rinses first order solid-phase extraction column, obtains 2# arene solutions.2mL acetonitrile solutions are used to rinse first order Solid Phase Extraction again
Column obtains 3# oxygenatedchemicals solution.Then take 500 μ L 1# alkane and olefin solution that second level solid-phase extraction column is added,
It rinses to obtain 4# alkane solutions with 2mL pentane solution successively, is 3 with 2mL volume ratios：1 dichloromethane-ethanol solution punching
It washes, obtains 5# olefin solutions.
Above-mentioned 2#, 3#, 4# and 5# solution is detached using gas chromatograph, mass detector and FID is used to examine respectively
Survey device and carry out qualitative and quantitative detection, alkane, alkene, aromatic hydrocarbons and oxygenatedchemicals Group Component total ion chromatogram see respectively
Fig. 1~Fig. 4 has marked the title of key component in attached drawing 1~4, it is shown that the separation situation of each monomer component, alkane, alkene
It is mainly some isomers with non-entitling claims in aromatic hydrocarbons component, not specified oxygenatedchemicals is mainly some ketone in attached drawing 4
The isomers and aldehyde of class, the compound of alcohol, lipid, the separating effect of Solid Phase Extraction is very good, and it is less to interfere with each other situation.
By the intersection constituent content in qualitative and quantitative analysis 2#, 3#, 4# and 5# solution to evaluate solid phase extraction method
Separating effect.Test result is：Olefin(e) centent is less than 0.5 mass % in alkane component, and Determination of Alkane Content is less than 0.9 in olefin component
Quality %, arene content are less than 1.0 mass %, and olefin(e) centent is less than 1.5 mass % in aromatic component, in Oxygen-containing Components
Arene content is less than 1.2 mass %, shows that the intersection constituent content being separated in each separation Group Component is below 1.5 matter
Measure %, illustrate in solid phase extraction method separating synthetic gas olefine reaction oil-phase product of the present invention alkane, alkene, aromatic hydrocarbons and
Oxygenatedchemicals Group Component, good separation, mushing error is within the scope of acceptable.
The above results show that intersection component (by separation component) content in the method for the present invention separation component is small, have good
Good separating effect.
The percentage composition of key component see the table below 3~6 in alkane, alkene, aromatic hydrocarbons and each Group Component of oxygenatedchemicals.Table 3
~6 analysis result is shown, through Solid phase extraction separation, alkane, alkene, aromatic hydrocarbons and each Group Component of oxygenatedchemicals composition measuring
Can effectively exclude to interfere with each other, altogether flow out phenomenon it is seldom, alkane, alkene, aromatic hydrocarbons and each Group Component of oxygenatedchemicals monomer group
At can be with accurate quantitative analysis.
Table 3
| Major monomeric compoent in alkane | Percentage composition/quality % |
| N-hexane | 5.70 |
| Normal heptane | 10.65 |
| Normal octane | 11.34 |
| N -nonane | 9.09 |
| N-decane | 5.97 |
| N-undecane | 3.47 |
| N-dodecane | 1.96 |
| N-tridecane | 1.02 |
| N-tetradecane | 0.54 |
| N-pentadecane | 0.31 |
| Hexadecane | 0.21 |
Table 4
Table 5
| Major monomeric compoent in aromatic hydrocarbons | Percentage composition/quality % |
| Benzene | 1.70 |
| Toluene | 18.35 |
| Ethylbenzene | 9.44 |
| Meta-xylene | 4.37 |
| Paraxylene | 1.42 |
| Ortho-xylene | 7.41 |
| Isopropylbenzene | 1.22 |
| N-proplbenzene | 4.52 |
| M-methyl ethylbenzene | 4.11 |
| P-methyl-ethylbenzene | 1.83 |
| O-methylethylbenzene | 3.07 |
| 1,2,4- trimethylbenzenes | 1.48 |
| Indane | 2.94 |
| 1- methyl indans | 2.63 |
Table 6
【Embodiment 17】
By alkane, the alkene in the method solid phase extraction method separating synthetic gas olefine reaction oil-phase product in embodiment 16
Hydrocarbon, aromatic hydrocarbons and oxygenatedchemicals Group Component.The difference is that the boiling range ranging from 30~360 of synthesis gas olefine reaction oil-phase product
℃.Solid phase extraction separation and qualitative, quantitative test are carried out with identical method, olefin(e) centent is less than 1.8 matter in alkane component
% is measured, Determination of Alkane Content is less than 1.6 mass % in olefin component, and arene content is less than 0.8 mass %, olefin(e) centent in aromatic component
Less than 2.0 mass %, arene content is less than 1.5 mass % in Oxygen-containing Components.
【Comparative example 2】
The silica gel solid phase of load water soluble silver salt and mantoquita is prepared by the method in embodiment 1, the difference is that silver salt contains
Amount is 0.0 mass %, and mantoquita content is 8.0 mass %, obtained Cu-SiO2Stationary phase (ASG-8).It is tested with identical method
The 1- nonene rate of recovery, is shown in Table 1.
Claims (10)
1. the solid-phase extraction column of different Group Components in a kind of separating synthetic gas olefine reaction oil-phase product, which is characterized in that Gu
Phase extraction column is made of two-stage solid-phase extraction column, and two-stage solid-phase extraction column is series connection or separate operations, first order solid-phase extraction column
Stationary phase be silica gel, the stationary phase of second level solid-phase extraction column is the silica gel of load water soluble silver salt or/and mantoquita, stationary phase
The water-soluble silver salt content calculated on the basis of silica gel is 3~10 mass %, and mantoquita content is 0~5 mass %.
2. the Solid Phase Extraction of different Group Components in separating synthetic gas olefine reaction oil-phase product described in accordance with the claim 1
Column, it is characterised in that the first order solid-phase extraction column and the mass ratio of contained stationary phase in the solid-phase extraction column of the second level be
0.5~1.5：1.
3. the Solid Phase Extraction of different Group Components in separating synthetic gas olefine reaction oil-phase product described in accordance with the claim 1
Column, it is characterised in that the silica gel is silica gel for chromatography, and size distribution is 100-300 mesh, and specific surface area is 400~750m2/
G, pore volume are 0.35~0.90mL/g.
4. the method for different Group Components, appoints using in claims 1 to 3 in a kind of separating synthetic gas olefine reaction oil-phase product
It anticipates a kind of solid-phase extraction column, which is characterized in that the solid-phase extraction column is two-stage series connection, from the upper of first order solid-phase extraction column
Synthesis gas olefine reaction oil phase sample is added in layer, first order solid-phase extraction column is rinsed with the first eluant, eluent, by saturated hydrocarbons and alkene
The mixture of hydrocarbon is rinsed to the solid-phase extraction column of the second level, separates twin columns, and first order solid-phase extraction column is rinsed with the second eluant, eluent
To extracting aromatic hydrocarbons, then rinses first order solid-phase extraction column with third eluant, eluent and extract oxygenatedchemicals；Then it is washed with first
De- agent rinses second level solid-phase extraction column and extracts alkane, then rinses second level solid-phase extraction column with the 4th eluant, eluent and extract alkene
Hydrocarbon.
5. the method for different Group Components, appoints using in claims 1 to 3 in a kind of separating synthetic gas olefine reaction oil-phase product
It anticipates a kind of solid-phase extraction column, which is characterized in that the solid-phase extraction column separate operations, from the upper layer of first order solid-phase extraction column
Synthesis gas olefine reaction oil phase sample is added, rinses first order solid-phase extraction column with the first eluant, eluent, extracts and collect saturation
The mixture of hydrocarbon and alkene rinses first order solid-phase extraction column with the second eluant, eluent and extracts aromatic hydrocarbons, then rushed with third eluant, eluent
It washes first order solid-phase extraction column and extracts oxygenatedchemicals；Then the mixed of saturated hydrocarbons and alkene some or all of is collected into front
Object is closed to be added from the upper layer of second level solid-phase extraction column, rinsing second level solid-phase extraction column with the first eluant, eluent extracts alkane,
Second level solid-phase extraction column is rinsed with the 4th eluant, eluent extract alkene again.
6. according to the method for different Group Components in the separating synthetic gas olefine reaction oil-phase product described in claim 4 or 5,
It is characterized in that, first eluant, eluent is in isopentane, pentane, n-hexane, hexamethylene, normal heptane or petroleum ether
At least one, the second eluant, eluent are selected from least one of dichloromethane, chloroform, benzene, carbon disulfide, and third eluant, eluent is selected from second
At least one of nitrile, propionitrile, methanol, ethyl alcohol, isopropanol, methyl acetate, ethyl acetate and tetrahydrofuran, the choosing of the 4th eluant, eluent
From dichloromethane or benzene and ethyl alcohol or the mixture of isopropanol.
7. according to the method for different Group Components in the separating synthetic gas olefine reaction oil-phase product described in claim 4 or 5,
It is characterized in that, synthesis gas olefine reaction oil phase sample and the ratio of the first order or second level solid-phase extraction column stationary phase quality are 1：
10~60.
8. according to the method for different Group Components in the separating synthetic gas olefine reaction oil-phase product described in claim 4 or 5,
It is characterized in that, after synthesis gas olefine reaction oil-phase product sample is added in first order solid-phase extraction column, by saturated hydrocarbons and alkene
The volume ratio of elution the first eluant, eluent used and synthesis gas olefine reaction oil phase sample is 10~100：1, rinse the first order
The volume ratio of second eluant, eluent used in Solid Phase Extraction column extracting aromatic hydrocarbons and synthesis gas olefine reaction oil phase sample is 10~60：1,
Rinse third eluant, eluent used in first order Solid Phase Extraction column extracting oxygenatedchemicals and synthesis gas olefine reaction oil phase sample
Volume ratio is 10~60：1, it is anti-to rinse the first eluant, eluent and synthesis gas alkene used in the Solid Phase Extraction column extracting saturated hydrocarbons of the second level
It is 10~100 to answer the volume ratio of oil phase sample：1, it rinses the 4th eluant, eluent used in the Solid Phase Extraction column extracting alkene of the second level and closes
Volume ratio at gas olefine reaction oil phase sample is 10~60：1.
9. according to claim 4 in separating synthetic gas olefine reaction oil-phase product different Group Components method, it is special
Sign is that the synthesis gas olefine reaction oil-phase product initial boiling point is low, olefin(e) centent is high, contains oxide, and initial boiling point is big
In equal to 30 DEG C, 95% recovered temperature is less than or equal to 365 DEG C；Olefin(e) centent is higher than 50wt%；Contain C1-C20 in oil-phase product
Ketone, aldehyde, alcohol, esters oxide.
10. the chromatographic process of different Group Components in a kind of separating synthetic gas olefine reaction oil-phase product, using claim 4~
Alkane, alkene, aromatic hydrocarbons and the oxygenatedchemicals that any one method separating synthetic gas olefine reaction oil-phase product in 9 obtains
Component sample, which is characterized in that above-mentioned sample is injected separately into gas chromatograph and is further detached, each alkane, alkene are obtained
The monomer composition of hydrocarbon, aromatic hydrocarbons and oxygenatedchemicals.
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