CN105273742B - Method for solid phase extraction separating of components in heavy oil - Google Patents
Method for solid phase extraction separating of components in heavy oil Download PDFInfo
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Abstract
A method for solid phase extraction separating of components in heavy oil comprises the following steps: heavy oil is diluted and added into a stationary phase, the stationary phase is washed orderly by C5-C6 alkanes to obtain saturated hydrocarbon components, the stationary phase is washed by a solvent with the volume ratio of aromatic hydrocarbon and C5-C6 alkanes of 1: 15-25 to obtain light aromatic hydrocarbon components, the stationary phase is washed by a solvent with the volume ratio of aromatic hydrocarbon and C5-C6 alkanes of 1: 3 to 5 to obtain middle aromatic hydrocarbon components, the stationary phase is washed by aromatic hydrocarbon to obtain heavy aromatic hydrocarbon components, the stationary phase is washed by a solvent with the volume ratio of aromatic hydrocarbon and monohydric alcohol of 1: 0.8 to 1.5 to obtain colloid components, the stationary phase is silver-ion-supported alumina, and supported silver ions accounts for 0.5 to 12% of the mass of alumina. According to the method, the silver-ion-supported alumina is used as the stationary phase for separating hydrocarbons with different polar components in the heavy oil, and the stationary phase is easy to be eluted compared with the supported silver ions which are large in sample processing capacity, and high in separation efficiency.
Description
Technical field
The present invention is a kind of method of heavy oil separation Zhong Ge hydrocarbon systems component, is that one kind is divided using Solid-Phase Extraction specifically
The method of different structure hydrocarbon component in heavy oil.
Background technology
Heavy oil is catalytic cracking, hydrofinishing, be hydrocracked primary raw material with the secondary processing process such as coking, and heavy oil
Level of processing is the key factor for affecting refinery's economic benefit.Due to heavy oil structure composition complexity, even if close in boiling range, H/C
In the case of more suitable than bulk properties such as, mean molecule quantities, its detailed hydro carbons composition, carbon number distribution have very big difference.This
A little differences can cause the difference on transformation rule because of chemical reaction difference, accordingly, it would be desirable to be based on to its close quasi-molecule level
Understanding and opposed polarity component reaction performance research selecting the secondary operations technique for most matching therewith, so as to improve heavy oil
Effective rate of utilization and process technology level.
Saturated hydrocarbons in heavy oil are good secondary processing of raw material, but aromatic hydrocarbons therein and heteroatomic compound secondary plus
Work poor-performing.At present, the research to the especially polycyclic aromatic hydrocarbon of the aromatic hydrocarbons in heavy oil is attracted wide attention.But either analyze
Test or the evaluation of processing characteristics are required for highly purified sample, this be accomplished by the component in heavy oil according to polarity difference
Separated, thus required of both proposing to separation process：(1) separation efficiency is high, highly purified sample can be isolated with
Meet the needs of subsequent analysis detection and study on mechanism；(2) quantity of sample handling is big, can more quickly isolate after can meeting
The sample size that continuous reaction and evaluation experimental need；(3) aromatic component can further be separated according to polarity, it is right to realize
The enrichment of mononuclear aromatics, double ring arene and polycyclic aromatic hydrocarbon.
Component seperation is carried out according to polarity to heavy oil, is mainly separated by hydro carbons composition, such as double adsorbent methods are determined
The separation method of the potential content of lubricating oil is exactly that the lube cut after dewaxing is separated into into saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons, weight
Four components of aromatic hydrocarbons.Its basic process is first to carry out benzol-kentone dewaxing, then with aluminium oxide (γ-Al2O3) and the double adsorbent of silica gel be solid
It is fixed mutually to carry out pillar layer separation, with petroleum ether, the petroleum ether-benzene of different volumes ratio, benzene-ethanol (1：1) rinse successively for solvent
Go out saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons, four components of heavy aromatics (Yang Cui is compiled surely etc. Petrochemical Engineering Analysis method. Science Press,
1990:26).This pair of adsorbent post separation method is preferable to the dewaxed oil separating effect of paraffin base lubricating oil distillate, but
The separation accuracy of the heavy oil high for polycyclic aromatic hydrocarbon content and sulfur content is limited, intersects between component serious.Used in the method
Adsorbent be the double adsorbents of aluminium oxide and silica gel, to polycyclic aromatic hydrocarbon and the limited sorption capacity of sulfur-containing compound, separating virtue
During the higher heavy oil of hydrocarbon content, treating capacity is less, and fixing phase deactivation rate is fast, and the absorption reserve capability of each component is declined, and leads
Detached dowel post effect is caused to reduce, each group cross-contamination phenomena isolated is serious.
Fixing phase is carried out certain modified, appropriateness strengthens fixing phase can improve separation effect to the absorbability of aromatic hydrocarbons
Rate, shortens disengaging time, increases treating capacity of the fixing phase to oil product.Gao Xiuxiang (high show perfume (or spice) etc. silver-colored modification infusorial earth material capture
The research of alkene. analytical chemistry, 2003,31 (8):Silver salt 911-914) is adopted to be coated in Silica Surface or with silver ion as cation
Exchanger is separated to alkene and saturated hydrocarbons, and its principle is that the empty sp hybrid orbital of silver ion outer layer can be electric with the π of alkene
There is stronger mating reaction and generate stable coordination compound in son, so retention time on a column increases, and saturated hydrocarbons are not
Containing the functional group that interaction can occur with silver ion, almost do not have an effect with fixing phase, so reach saturated hydrocarbons
With the purpose of separation of olefins.
Tao Xueming (Tao Xueming, Long Yicheng, Lu Wanzhen. high effective liquid chromatography for measuring diesel oil race constitutes. chromatograph, 1995,13
(5):368-372) with silver type sulfonic acid bonded silica gel (Ag-SCX posts) as fixing phase, with the modified normal hexane of benzene as mobile phase,
Alkene (the C of different carbon chain lengths is realized in high performance liquid chromatography14、C16And C18) separate with alkane (white oil) mixture.With
This is similar, and big π keys are contained in aromatic hydrocarbons, can have certain effect with silver ion, and the different aromatic hydrocarbons of number of rings is conjugated journey due to it
The difference of degree is different from the effect degree of silver ion, and the retention time on pillar is also different.Therefore, it can in accordance with this principle
Saturated hydrocarbons are separated with aromatic hydrocarbons, it is possible to which the aromatic hydrocarbons of different number of rings is separated.
Qiang Dongmei (Qiang Dongmei, Lu Wanzhen. the research of cyclohexene and aromatic hydrocarbons separation mechanism on Ag-SCX posts. chromatograph,
1998,16(3):187-190) with Ag-SCX (silver-colored post) as fixing phase, 3 ‰ cyclohexene/hexamethylene is mobile phase, separates object and is
Detergent alkylate, fluorenes and phenanthrene be configured to saturated hydrocarbons (lube cut) respectively 1：1 hexane solution, has investigated cyclohexene
From separation mechanism of the different number of rings aromatic hydrocarbons on silver-colored post.The article pointed out, the chromatographic thermodynamics equilibrium constant of the aromatic hydrocarbons of different number of rings
It is followed successively by 121 (detergent alkylates)>21 (fluorenes)>13.8 (phenanthrene), absorption of the bigger aromatic hydrocarbons of equilibrium constant on silver-colored post is weaker, because
This, adsorption strength of the aromatic hydrocarbons on silver-colored post strengthens with the increase of number of rings.These are both for micro several detailed hydrocarbons mixing
The separation analysis of thing, can only meet the purpose of analysis test, it is impossible to meet the demand that preparation scale separates complicated heavy oil sample.
The reduced pressure distillate oil separating larger for treating capacity, CN102079987A is disclosed and is to have loaded mass fraction
The silica gel of 13.2% silver nitrate is fixing phase, respectively decompressed wax oil is divided into into saturated hydrocarbons, virtue as solvent with normal hexane, benzene, ethanol
The method of three components of fragrant hydrocarbon and colloid, separating effect is preferable.But the method is not further separated to aromatic component,
The needs that the aromatic component to opposed polarity is further analyzed and processed can not be met.Additionally, the fixing phase that the method is used
The silica gel of middle load silver ion is relatively low to the adsorption strength of silver ion, and when glial component is rinsed, device lower end also needs to connect again
Alumina column, is just avoided that the silver ion for being rinsed is entered in each component isolated, while also increasing operation
Step and difficulty.
As a whole, above-mentioned fixing phase or post effect are too low, and separation efficiency is too poor, saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons and weight
Exist between aromatic hydrocarbons than more serious intersection；Or treating capacity is too little, it is impossible to meet the separation requirement of sample during preparation scale is separated；
Or in the case where separation accuracy is suitable, each treating capacity is too little, it is impossible to realize system to polar compound different in heavy oil
The separation of standby level；Or silver ion is eluted in a large number in each component, the component subsequent analysis detection isolated is affected
With the evaluation of processing characteristics.
The content of the invention
It is an object of the invention to provide a kind of method of Solid phase extraction separation heavy oil each component, the method is with load silver ion
Aluminium oxide be fixing phase, the hydro carbons with opposed polarity component in separable heavy oil, fixing phase is big to quantity of sample handling, separate
Efficiency high and load silver ion be difficult to be eluted.
The method of the Solid phase extraction separation heavy oil each component that the present invention is provided, including adding fixing phase after heavy oil is diluted
In, C is then used successively5～C6Alkane rinse fixing phase obtain saturated hydrocarbon component, with aromatic hydrocarbons and C5～C6Alkane volume ratio is 1：
15～25 solvent washing fixing phase obtains light aromatic hydrocarbons component, with aromatic hydrocarbons and C5～C6Alkane volume ratio is 1：3～5 solvent punching
Wash fixing phase and obtain middle aromatic component, rinse fixing phase with aromatic hydrocarbons and obtain heavy aromatics component, be with aromatic hydrocarbons and monohydric alcohol volume ratio
1：0.8～1.5 solvent washing fixing phase obtains glial component, and described fixing phase is the aluminium oxide of load silver ion, is loaded
Silver ion account for the 0.5～12% of quality of alumina.
In the inventive method, the aluminium oxide of load silver ion is adopted for the fixing phase of heavy oil separation, then rushed using different
Lotion is rinsed to the fixing phase for having adsorbed heavy oil sample, according to component polarity, may separate out saturated hydrocarbons, light aromatic hydrocarbons, middle virtue
Hydrocarbon, five components of heavy aromatics and colloid, can be quickly that follow-up analysis test and reaction evaluating provide necessary sample size.
Specific embodiment
The inventive method adopts the aluminium oxide of load silver ion for fixing phase, due to the polarity that aluminium oxide has, to silver from
Son has stronger absorption reserve capability, and silver ion can be made more firmly to be carried on alumina support, so as to significantly decrease extraction
Take eluting of the solvent to silver ion, both ensure that the separation efficiency and treating capacity of fixing phase, reduce again silver ion be rinsed into
Probability in separation component.In addition, the group that the irrigation used by the present invention, i.e. extractant effectively can adsorb fixing phase
Point, separate by the power of its polarity.The relatively heavy oil handling amount of fixation used is high, separation efficiency is good, and the silver for loading
Ion is difficult to be rinsed agent eluting and flow in separation component, so as to be prevented effectively from dirt of the silver ion loss to separation component
Dye, and improve precision of analysis.
The silver ion loaded in the fixing phase that the present invention is provided preferably accounts for the 3.0～10.0% of quality of alumina, and it can be single
Solely use, be preferably used in conjunction with silica gel, i.e., load silica gel on the upper strata of extract and separate post, the oxygen of load silver ion is loaded in middle level
Change aluminum, lower floor can load aluminium oxide, can not also fill aluminium oxide, form spectra unmixing.
In the inventive method, preferred fixing phase includes the oxygen of the silica gel positioned at upper strata, the load silver ion positioned at middle level
Change aluminum and the neutral alumina positioned at lower floor, the silica gel：The aluminium oxide of load silver ion：The mass ratio of aluminium oxide is 1：2.5
～5.0：0～1.2, alternatively 1：2.5～5.0：0.1～1.0.
In fixing phase described in the inventive method, for load silver ion aluminium oxide and spectra unmixing used by oxidation
It is neutral gama-alumina that aluminum preferred surface is neutral aluminium oxide, more preferably surface.
Preferably 50～300 meters of the specific surface area of the aluminium oxide2/ gram, more preferably 120～300 meters2/ gram, pore volume is preferred
0.10～0.55 ml/g, more preferably 0.20～0.35 ml/g, aluminium oxide median pore diameter is that 25～75 nanometers of hole accounts for always
The 50～90% of pore volume.
In spectra unmixing described in the inventive method, preferably 250～850 meters of the specific surface area of silica gel2/ gram, more preferably 350
～750 meters2/ gram, preferably 0.25～0.99 ml/g, more preferably 0.30～0.96 ml/g of pore volume.Described silica gel is excellent
Kiselgel A is selected, its bore dia is that 20～40 nanometers of hole preferably accounts for the 50～95% of total pore volume.
The exterior active center of fixing phase of the present invention is the main body that interaction occurs with mobile phase and sample, thus
The silver ion for making load is distributed in aluminium oxide in eggshell type, and the silver ion that can make load is utilized.Very
Empty infusion process is with the solution impregnation of alumina carrier of silver ion under certain vacuum (reduced pressure), so that activearm
Divide and be more uniformly dispersed in alumina surface.Impregnation liquid under capillary pressure function, by trickle duct into aluminium oxide
Portion permeates, and the concentration of silver ion is bigger, and the Concentraton gradient inside and outside carrier is also bigger, more readily permeable to carrier inside, is more difficult to shape
Into the catalyst of eggshell type, the same dip time that extends deepens also metal ion infiltration, and so as to be difficult to eggshell type point is formed
Cloth.Therefore, when the present invention prepares the aluminium oxide fixing phase of load silver ion, the impregnation liquid dipping of low concentration of silver ions is preferably used
Aluminium oxide, dip time is unsuitable long.
The present invention provide fixing phase preparation method, including by aluminium oxide immerse silver nitrate solution in, after stirring,
Impregnate 0.5～5.0 hour in 20～70 DEG C at reduced pressure conditions, be then dried.
The suitable concentration of the silver nitrate solution preferably 0.2～10.0 mass %, preferably 0.5～6.0 mass %.
With the pressure preferably 20～100kPa of silver nitrate solution oxide impregnation aluminum, the baking temperature after dipping preferably 100～
200℃。
During above-mentioned dipping introduces silver nitrate, the volume of dipping silver nitrate solution used is alumina catalyst support hole body
Long-pending 1～10 times, preferably 2～5 times.After the completion of dipping, impregnate the aluminium oxide of silver salt (silver nitrate) 100～200 DEG C, preferably
120～180 DEG C of dryings, drying time is 1～30 hour, preferably 1～10 hour.Above-mentioned dipping introduces the process of silver nitrate can be entered
Row is multiple, such as 1～3 time.It is standby that the aluminium oxide of the load silver nitrate obtained after drying is positioned over lucifuge storage in exsiccator.
When the fixing phase that the present invention is provided is the spectra unmixing containing multiple components, wherein silica gel, aluminium oxide and load
The aluminium oxide of silver ion can be seated in same extract and separate post, it is also possible in filling in different extract and separate posts.Work as dress
When filling in same extract and separate post, silica gel is loaded on into upper strata, aluminium oxide is loaded on bottom, during the aluminium oxide of load silver ion is located at
Between.When with different extraction columns, by the detached dowel of filling silica gel, the aluminium oxide detached dowel of filling load silver ion, filling oxidation
The detached dowel of aluminum is connected in series successively by upper, middle and lower.
It is in the purpose of detached dowel bottom filling aluminium oxide：When the oil sample for carrying out the absorption of eluting fixing phase using substantial amounts of solvent
During each component, a small amount of silver ion that can be taken out of by solvent using neutral alumina absorption, it is to avoid silver ion enters into separation component
In, cause analysis detection error.
In the inventive method, in Solid phase extraction separation heavy oil, fixing phase is filled in extract and separate post, the weight of dilution
Oil injects fixing phase by top, and saturated hydrocarbons therein, aromatic hydrocarbons and colloid are adsorbed successively according to polarity size by fixing phase.Rushed with alkane
Fixing phase is washed, saturated hydrocarbon component is obtained, then the mixed liquor of the aromatic hydrocarbons with different proportion and alkane goes out successively light aromatic hydrocarbons and middle virtue
Hydrocarbon, with aromatic hydrocarbons heavy aromatics is flushed out, and then with the mixture of aromatic hydrocarbons and monohydric alcohol flushes out glial component again.
In the present invention, it is preferable that in the upper strata filling silica gel of the aluminium oxide fixing phase of load silver ion, processing heavy oil
When, the silica gel on upper strata is contacted prior to the aluminium oxide of load silver ion with heavy oil, is conducive to avoiding the polycyclic aromatic hydrocarbon of high adsorption capacity
With sulfur-containing compound directly with the oxide contact of load silver ion, cause fixing phase quick to the absorption reserve capability of each component
Decline, causing the separation efficiency of fixing phase fast deactivation, detached dowel reduces.
In the inventive method, the preferred C of diluent of heavy oil is diluted5～C6Alkane.The diluent is with the volume ratio of heavy oil
1～10：1st, preferably 2～5：1.
The mass ratio preferably 8～30 of the fixing phase and heavy oil：1st, more preferably 12～21：1.
In irrigation of the present invention for the light aromatic hydrocarbons component for rinsing fixing phase absorption, aromatic hydrocarbons and C5～C6The volume of alkane
Than preferably 1：18～23.
In irrigation for the middle aromatic component for rinsing fixing phase absorption, aromatic hydrocarbons and C5～C6The volume ratio of alkane is preferred
1：3～4.5.
In irrigation for the colloid for rinsing fixing phase absorption, the volume ratio preferably 1 of aromatic hydrocarbons and monohydric alcohol：0.8～
1.2。
In the inventive method, the C used by the irrigation and dilution heavy oil used by the saturated hydrocarbons of fixing phase absorption is rinsed5～C6
The preferred pentane of alkane, normal hexane or petroleum ether.
The preferred benzene of aromatic hydrocarbons rinsed in light aromatic hydrocarbons, middle aromatic hydrocarbons and irrigation used by heavy aromatics or toluene.
The preferred methanol of monohydric alcohol rinsed in irrigation used by colloid or ethanol.
In said method, the volume ratio preferably 1～10, more of irrigation and fixing phase used by fixing phase is rinsed for described each time
It is preferred that 1～6.
In the inventive method, the light aromatic hydrocarbons that Jing Solid phase extraction separations are obtained are the component for being enriched with mononuclear aromatics, and middle aromatic hydrocarbons is
The component of enrichment double ring arene, heavy aromatics is the component for being enriched with three rings and above aromatic hydrocarbons.
Heavy oil described in the inventive method is vacuum distillate, deasphalted oil or catalytic cracked oil pulp.In the heavy oil
Arene content is 5～90 mass %, and sulfur content is 0.1～4.0 mass %.
Below with embodiment, the present invention is further described, but not thereby limiting the invention.
The chromatography neutral alumina that aluminium oxide used is produced for Chemical Reagent Co., Ltd., Sinopharm Group in example, 74
～149 microns, calcination loss≤8.0%, specific surface area is 152m2/ g, pore volume 0.213mL/g, bore dia is received for 25～75
The hole of rice accounts for the 85% of total pore volume.
Silver nitrate is Nanjing Chemistry Reagent Co., Ltd.'s production, analyzes pure, and pH value (50g/L, 25 DEG C) is 5.0～6.0.
The Kiselgel A that silica gel (silicon dioxide) is produced for subsidiary factory of Haiyang Chemical Plant, Qingdao, 74～149 microns, specific surface area
For 479m2/ g, pore volume 0.349mL/g, bore dia is that 20～40 nanometers of hole accounts for the 89% of total pore volume.
Example instrument be level Four bar gas chromatograph-mass spectrometer (GC-MS) (GC/MS), model Agilent7890GC/
5975MS, 7693 auto injection towers.Gas chromatogram (GC) working condition：Empty capillary column (30m × 0.32mm), the μ L of sample size 1,
Split ratio 50：1,310 DEG C of injector temperature, carrier gas is He, and column flow takes constant current mode, flow velocity 1.0mL/min；Column oven liter
Warm program is 40 DEG C of holding 2min, then with the ramp of 60 DEG C/min to 310 DEG C, keeps 8min；Mass Spectrometry Conditions：EI is ionized
Source (70eV), 230 DEG C of ion source temperature, 150 DEG C of MS level Four bars temperature, 300 DEG C of MSD transmission lines；Solvent delay 3min；With complete
Scanning (SCAN) mode gathered data, full scan mass range is 50～700amu.
Example 1
This example be used for illustrate silicon dioxide of the present invention, aluminium oxide and load silver ion aluminium oxide pretreatment and
Preparation process.
By Kiselgel A raw material in aeration cabinet in 150 DEG C of dryings 5 hours, obtain activated silica gel, be positioned over drying
Deposit in device standby.
By neutral alumina in 550 DEG C of roastings 5 hours, activated alumina is obtained, be positioned in exsiccator and deposit standby.
Take 7.41 grams of silver nitrate and be dissolved in 160mL deionized waters and be configured to silver nitrate solution, take 200 grams of neutral aluminas,
Aluminium oxide is added in silver nitrate solution, is stirred, impregnated 4 hours in 60 DEG C under 50kPa pressure, then will impregnate nitre
The aluminium oxide of sour silver was cooled to room temperature, then as stated above with same volume and the nitric acid of concentration in 150 DEG C of dryings 2 hours
Silver-colored aqueous solution impregnates again, is dried, so dipping three times, and third time is dried 4 hours after impregnating, and obtains the load silver ion for activating
Aluminium oxide A, wherein silver ion accounts for the 7.05% of quality of alumina.It is positioned in exsiccator and is bottled after cooling, keeps in dark place standby
With.
Example 2
The effect of the fixed phase separation vacuum distillate each component that the explanation of this example is provided using the present invention.
The bottom filling 30g neutral aluminas in detached dowel, the aluminium oxide A of centre filling 110g load silver ions, upper strata
Filling 30g silica gel；Detached dowel lower end is connected with pumped vacuum systems.The cumulative volume of fixing phase is 150mL.
Tahe vacuum distillate (350～540 DEG C of boiling range) sample 10.20g (11.19mL) is taken, in being dissolved in 30mL normal hexane,
First with the fixing phase of filling in the above-mentioned detached dowel of normal hexane moistening of 100mL, then the hexane solution of above-mentioned oil sample is added to
In detached dowel.Flush out saturated hydrocarbon component, 255mL toluene with 170mL normal hexane respectively：Normal hexane volume ratio is 1：19 solvent
Flush out light aromatic hydrocarbons component, 255mL toluene：Normal hexane volume ratio is 1：4 solvent washing goes out middle aromatic component, 255mL toluene
Flush out heavy aromatics component, 255mL toluene：Ethanol volume ratio is 1：1 solvent washing goes out glial component.
Solvent in saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid is evaporated using rotary evaporator, saturation is obtained
4.94 grams of hydrocarbon, 1.56 grams of light aromatic hydrocarbons, 1.52 grams of middle aromatic hydrocarbons, 0.92 gram of heavy aromatics, 0.91 gram of colloid loses 0.35 gram.
GC/MS analysis show saturated hydrocarbon component in alkylbenzene content be 0.9 mass %, mononuclear aromatics in light aromatic hydrocarbons component
Content be 74.3 mass %, in middle aromatic component the content of double ring arene be 37.1 mass %, in heavy aromatics component three rings with
On arene content be 65.9 mass %.
After the completion of separation, fixing phase is dried, the silver ion in the aluminium oxide of the load silver ion of centre filling is complete
It is oxidized and becomes black, and the neutral alumina of bottom filling still keeps white, illustrates silver ion not from the aluminium oxide of load
Middle loss.
Example 3
By each component of the method heavy oil separation sample of example 2, the Liaohe River decompression of 10.11g (11.09mL) is except for the difference that taken
Distillate (350～540 DEG C of boiling range) sample carries out Solid phase extraction separation.After separation, 5.48 grams of saturated hydrocarbons, light aromatic hydrocarbons 1.24 are obtained
Gram, 1.37 grams of middle aromatic hydrocarbons, 0.73 gram of heavy aromatics, 1.18 grams of colloid loses 0.11 gram.
GC/MS analyses show that the alkyl benzene content in saturated hydrocarbons is 1.4 mass %, and mononuclear aromatics contains in light aromatic hydrocarbons component
Measure as 72.9 mass %, the content of double ring arene is 38.2 mass % in middle aromatic component, more than three rings virtues in heavy aromatics component
The content of hydrocarbon is 67.8 mass %.
After the completion of separation, fixing phase is dried, the silver ion in the fixing phase of the load silver ion of centre filling is complete
It is oxidized and becomes black, and the neutral alumina of bottom filling still keeps white.
Example 4
The aluminium oxide of load silver ion is prepared by the method for example 1, is except for the difference that added when silver nitrate solution is prepared
Silver nitrate is 1.36 grams, through three dippings, obtains the aluminium oxide B of the load silver ion of activation, and wherein silver ion accounts for aluminium oxide
The 1.30% of quality.
The bottom filling 30g neutral aluminas in detached dowel, the aluminium oxide B of centre filling 110g load silver ions, upper strata
Filling 30g silica gel；Detached dowel lower end is connected with pumped vacuum systems.The cumulative volume of fixing phase is 160mL.
Tahe vacuum distillate (350～540 DEG C of boiling range) sample 10.13g (11.11mL) is taken, in being dissolved in 30mL normal hexane,
First with the fixing phase of filling in the above-mentioned detached dowel of normal hexane moistening of 100mL, then the hexane solution of above-mentioned oil sample is added to
In detached dowel.Flush out saturated hydrocarbon component, 255mL toluene with 170mL normal hexane respectively：Normal hexane volume ratio is 1：19 solvent
Flush out light aromatic hydrocarbons component, 255mL toluene：Normal hexane volume ratio is 1：4 solvent washing goes out middle aromatic component, 255mL toluene
Flush out heavy aromatics component, 255mL toluene：Ethanol volume ratio is 1：1 solvent washing goes out glial component.
Solvent in saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid is evaporated using rotary evaporator, saturation is obtained
5.28 grams of hydrocarbon, 1.41 grams of light aromatic hydrocarbons, 1.18 grams of middle aromatic hydrocarbons, 1.01 grams of heavy aromatics, 0.94 gram of colloid loses 0.20 gram.
GC/MS analysis show saturated hydrocarbon component in alkylbenzene content be 6.7 mass %, mononuclear aromatics in light aromatic hydrocarbons component
Content be 56.5 mass %, in middle aromatic component the content of double ring arene be 28.9 mass %, in heavy aromatics it is more than three rings virtue
The content of hydrocarbon is 56.8 mass %.
After the completion of separation, fixing phase is dried, the silver ion in the aluminium oxide of the load silver ion of centre filling is complete
It is oxidized and becomes black, and the neutral alumina of bottom filling still keeps white, illustrates silver ion not from the aluminium oxide of load
Middle loss.
Example 5
The aluminium oxide of load silver ion is prepared by the method for example 1, is except for the difference that added when silver nitrate solution is prepared
Silver nitrate is 5.80 grams, through three dippings, obtains the aluminium oxide C of the load silver ion of activation, and wherein silver ion accounts for aluminium oxide
The 5.52% of quality.
The bottom filling 30g neutral aluminas in detached dowel, centre filling 110g loads the aluminium oxide C of silver nitrate, upper strata
Filling 30g silica gel；Detached dowel lower end is connected with pumped vacuum systems.The cumulative volume of fixing phase is 153mL.
Tahe vacuum distillate (350～540 DEG C of boiling range) sample 10.25g (11.24mL) is taken, in being dissolved in 30mL normal hexane,
First with the fixing phase of filling in the above-mentioned detached dowel of normal hexane moistening of 100mL, then the hexane solution of above-mentioned oil sample is added to
In detached dowel.Flush out saturated hydrocarbon component, 255mL toluene with 170mL normal hexane respectively：Normal hexane volume ratio is 1：19 solvent
Flush out light aromatic hydrocarbons component, 255mL toluene：Normal hexane volume ratio is 1：4 solvent washing goes out middle aromatic component, 255mL toluene
Flush out heavy aromatics component, 255mL toluene：Ethanol volume ratio is 1：1 solvent washing goes out glial component.
Solvent in saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid is evaporated using rotary evaporator, saturation is obtained
4.89 grams of hydrocarbon, 1.59 grams of light aromatic hydrocarbons, 1.47 grams of middle aromatic hydrocarbons, 1.02 grams of heavy aromatics, 1.05 grams of colloid loses 0.23 gram.
GC/MS analysis show saturated hydrocarbon component in alkylbenzene content be 2.4 mass %, mononuclear aromatics in light aromatic hydrocarbons component
Content be 71.8 mass %, in middle aromatic component the content of double ring arene be 34.7 mass %, in heavy aromatics component three rings with
The content of upper aromatic hydrocarbons is 64.4 mass %.
After the completion of separation, fixing phase is dried, the silver ion in the aluminium oxide of the load silver ion of centre filling is complete
It is oxidized and becomes black, and the neutral alumina of bottom filling still keeps white, illustrates silver ion not from the aluminium oxide of load
Middle loss.
Example 6
The aluminium oxide of load silver ion is prepared by the method for example 1, is except for the difference that added when silver nitrate solution is prepared
Silver nitrate is 10.14 grams, through three dippings, obtains the aluminium oxide D of the load silver ion of activation, and wherein silver ion accounts for aluminium oxide
The 9.66% of quality.
The bottom filling 30g neutral aluminas in detached dowel, centre filling 110g loads the aluminium oxide D of silver nitrate, upper strata
Filling 30g silica gel；Detached dowel lower end is connected with pumped vacuum systems.The cumulative volume of fixing phase is 145mL.
Tahe vacuum distillate (350～540 DEG C of boiling range) sample 10.06g (11.03mL) is taken, in being dissolved in 30mL normal hexane,
First with the fixing phase of filling in the above-mentioned detached dowel of normal hexane moistening of 100mL, then the hexane solution of above-mentioned oil sample is added to
In detached dowel.Flush out saturated hydrocarbon component, 255mL toluene with 170mL normal hexane respectively：Normal hexane volume ratio is 1：19 solvent
Flush out light aromatic hydrocarbons component, 255mL toluene：Normal hexane volume ratio is 1：4 solvent washing goes out middle aromatic component, 255mL toluene
Flush out heavy aromatics component, 255mL toluene：Ethanol volume ratio is 1：1 solvent washing goes out glial component.
Solvent in saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid is evaporated using rotary evaporator, saturation is obtained
4.87 grams of hydrocarbon, 1.58 grams of light aromatic hydrocarbons, 1.43 grams of middle aromatic hydrocarbons, 1.05 grams of heavy aromatics, 0.96 gram of colloid loses 0.17 gram.
GC/MS analysis show saturated hydrocarbon component in alkylbenzene content be 0.7 mass %, mononuclear aromatics in light aromatic hydrocarbons component
Content be 74.6 mass %, in middle aromatic component the content of double ring arene be 38.5 mass %, in heavy aromatics component three rings with
The content of upper aromatic hydrocarbons is 68.3 mass %.
After the completion of separation, fixing phase is dried, the silver ion in the aluminium oxide of the load silver ion of centre filling is complete
It is oxidized and becomes black, and the neutral alumina of bottom filling still keeps white, illustrates silver ion not from the aluminium oxide of load
Middle loss.
Comparative example 1
Illustrate that the fixing phase constituted using neutral alumina and silica gel carries out the conventional post separation effect of vacuum distillate.
Lower floor's filling 85g neutral aluminas in detached dowel, upper strata filling 85g silica gel；By detached dowel lower end and evacuation
System is connected.The cumulative volume of fixing phase is 185mL.
Tahe vacuum distillate (350～540 DEG C of boiling range) sample 10.02g (10.99mL) is taken, in being dissolved in 30mL normal hexane,
First with the fixing phase of filling in the above-mentioned detached dowel of normal hexane moistening of 100mL, then the hexane solution of above-mentioned oil sample is added to
In detached dowel.Flush out saturated hydrocarbon component, 255mL toluene with 170mL normal hexane respectively：Normal hexane volume ratio is 1：19 solvent
Flush out light aromatic hydrocarbons component, 255mL toluene：Normal hexane volume ratio is 1：4 solvent washing goes out middle aromatic component, 255mL toluene
Flush out heavy aromatics component, 255mL toluene：Ethanol volume ratio is 1：1 solvent washing goes out glial component.
Using after the solvent that rotary evaporator is evaporated in saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, weigh, obtain
To 4.97 grams of saturation hydrocarbon samples, 2.14 grams of light aromatic hydrocarbons, 1.12 grams of middle aromatic hydrocarbons, 0.76 gram of heavy aromatics, 0.74 gram of colloid, loss 0.29
Gram.
GC/MS analysis show saturated hydrocarbon component in alkylbenzene content be 4.3 mass %, mononuclear aromatics in light aromatic hydrocarbons component
Content be 60.7 mass %, in middle aromatic component the content of double ring arene be 27.5 mass %, in heavy aromatics component three rings with
The content of upper aromatic hydrocarbons is 52.5 mass %.
From this comparative example result, using the aluminium oxide of unsupported silver ion, in isolated each component, mesh is separated
Constituent content it is more of the invention low, illustrate the low separation efficiency of fixing phase.
Comparative example 2
Take 10.14 grams of silver nitrate and be dissolved in 160mL deionized waters and be configured to silver nitrate solution, take 200 grams of Kiselgel As and add
Enter in silver nitrate solution, stir, under vacuum (0.5kPa) impregnates 4 hours in 60 DEG C, then will impregnate nitric acid
The silica gel of silver was cooled to room temperature in 150 DEG C of dryings 2 hours, then as stated above with same volume and the silver nitrate water of concentration
Solution impregnates again, is dried, and such dipping three times, third time is dried 4 hours after impregnating, and obtains the silicon of the load silver ion of activation
Glue, wherein silver ion account for the 9.66% of silica gel quality.
The bottom filling 30g neutral aluminas in detached dowel, the silica gel of centre filling 110g load silver ions, upper strata filling
30g silica gel；Detached dowel lower end is connected with pumped vacuum systems.The cumulative volume of fixing phase is 163mL.
Tahe vacuum distillate (350～540 DEG C of boiling range) sample 10.20g (11.19mL) is taken, in being dissolved in 30mL normal hexane,
First with the fixing phase of filling in the above-mentioned detached dowel of normal hexane moistening of 100mL, then the hexane solution of above-mentioned oil sample is added to
In detached dowel.Flush out saturated hydrocarbon component, 255mL toluene with 170mL normal hexane respectively：Normal hexane volume ratio is 1：19 solvent
Flush out light aromatic hydrocarbons component, 255mL toluene：Normal hexane volume ratio is 1：4 solvent washing goes out middle aromatic component, 255mL toluene
Flush out heavy aromatics component, 255mL toluene：Ethanol volume ratio is 1：1 solvent washing goes out glial component.
Using after the solvent that rotary evaporator is evaporated in saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, weigh, obtain
To 4.84 grams of saturation hydrocarbon samples, 1.71 grams of light aromatic hydrocarbons, 1.36 grams of middle aromatic hydrocarbons, 0.87 gram of heavy aromatics, 0.81 gram of colloid, loss 0.41
Gram.
GC/MS analysis show saturated hydrocarbon component in alkylbenzene content be 1.3 mass %, mononuclear aromatics in light aromatic hydrocarbons component
Content be 73.8 mass %, in middle aromatic component the content of double ring arene be 37.1 mass %, in heavy aromatics component three rings with
The content of upper aromatic hydrocarbons is 65.9 mass %.
After the completion of separation, fixing phase is dried, the silver ion in the fixing phase of the load silver ion of centre filling is complete
It is oxidized and becomes black, and the neutral alumina of bottom filling also all becomes black, this is inclined with the yield of heavy aromatics and colloid
High phenomenon is consistent, and has illustrated that a certain amount of silver ion comes off from silica gel, is rinsed and enters in neutral alumina.
This comparative example result illustrates that the silica gel with load silver ion is as fixing phase, and required silver ion load capacity is big, and negative
The silver ion of load is preferably rinsed solvent eluting.
Comparative example 3
The bottom filling 75g neutral aluminas in detached dowel, centre filling 65g loads the aluminium oxide A of silver nitrate, upper strata dress
Fill out 30g silica gel；Detached dowel lower end is connected with pumped vacuum systems.The cumulative volume of fixing phase is 152mL.
Tahe vacuum distillate (350～540 DEG C of boiling range) sample 10.04g (11.01mL) is taken, in being dissolved in 30mL normal hexane,
First with the fixing phase of filling in the above-mentioned detached dowel of normal hexane moistening of 100mL, then the hexane solution of above-mentioned oil sample is added to
In detached dowel.Flush out saturated hydrocarbon component, 255mL toluene with 170mL normal hexane respectively：Normal hexane volume ratio is 1：19 solvent
Flush out light aromatic hydrocarbons component, 255mL toluene：Normal hexane volume ratio is 1：4 solvent washing goes out middle aromatic component, 255mL toluene
Flush out heavy aromatics component, 255mL toluene：Ethanol volume ratio is 1：1 solvent washing goes out glial component.
Using after the solvent that rotary evaporator is evaporated in saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, weigh, obtain
To 5.12 grams of saturation hydrocarbon samples, 1.41 grams of light aromatic hydrocarbons, 1.27 grams of middle aromatic hydrocarbons, 1.14 grams of heavy aromatics, 1.02 grams of colloid, loss 0.08
Gram.
GC/MS analysis show saturated hydrocarbon component in alkylbenzene content be 4.7 mass %, mononuclear aromatics in light aromatic hydrocarbons component
Content be 75.8 mass %, in middle aromatic component the content of double ring arene be 33.3 mass %, in heavy aromatics component three rings with
The content of upper aromatic hydrocarbons is 50.2 mass %.
After the completion of separation, fixing phase is dried, the silver ion in the fixing phase of the load silver ion of centre filling is complete
It is oxidized and becomes black, and the neutral alumina of bottom filling still keeps white, illustrates silver ion not from the aluminium oxide of load
Middle loss.
This comparative example result is illustrated, the use of the aluminium oxide of less amount of load silver nitrate is fixing phase, and separating obtained is each
In component, alkyl benzene content is more in saturated hydrocarbon component, and the content of three ring above aromatic hydrocarbons is reduced in heavy aromatics component, illustrates to separate
Efficiency is poor.
Comparative example 4
This comparative example illustrates the effect of aromatic component in the irrigation flushing for adopt different volumes ratio.
By method Solid phase extraction separation Tahe vacuum distillate (350～540 DEG C of boiling range) the sample 10.18g of example 2
(11.17mL), except for the difference that in flushing during aromatic component, using 255mL toluene：Normal hexane volume ratio is 1：5.7 solvent
Flush out middle aromatic component.Rotated vaporizer is evaporated after the solvent in saturated hydrocarbons, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid,
Obtain 5.19 grams of saturation hydrocarbon samples, 1.45 grams of light aromatic hydrocarbons, 1.31 grams of middle aromatic hydrocarbons, 1.16 grams of heavy aromatics, 0.97 gram of colloid, loss
0.1 gram.
GC/MS analysis show saturated hydrocarbon component in alkylbenzene content be 1.3 mass %, mononuclear aromatics in light aromatic hydrocarbons component
Content be 75.7 mass %, in middle aromatic component the content of double ring arene be 38.0 mass %, three rings in heavy aromatics component
The content of above aromatic hydrocarbons is 52.5 mass %.
After the completion of separation, fixing phase is dried, the silver ion in the fixing phase of the load silver ion of centre filling is complete
It is oxidized and becomes black, and the aluminium oxide of the unsupported silver ion of low side filling still keeps white.
This comparative example is illustrated, in flushing in the solvent of aromatic component, reduces the ratio of toluene, though virtue in slightly improving
The content of double ring arene in hydrocarbon component, but will cause to rinse under three ring above arene contents are notable in the heavy aromatics component that obtains
Drop.
Claims (14)
1. in fixing phase, then successively a kind of method of Solid phase extraction separation heavy oil each component, add including after heavy oil is diluted
Use C5～C6Alkane rinse fixing phase obtain saturated hydrocarbon component, with aromatic hydrocarbons and C5～C6Alkane volume ratio is 1：15～25 it is molten
Agent is rinsed fixing phase and obtains light aromatic hydrocarbons component, with aromatic hydrocarbons and C5～C6Alkane volume ratio is 1：3～5 solvent washing fixing phase is obtained
To middle aromatic component, rinse fixing phase with aromatic hydrocarbons and obtain heavy aromatics component, be 1 with aromatic hydrocarbons and monohydric alcohol volume ratio：0.8～1.5
Solvent washing fixing phase obtain glial component, described fixing phase for load silver ion aluminium oxide, the silver ion of load accounts for
The 3～10% of quality of alumina, described aromatic hydrocarbons is benzene or toluene, and described monohydric alcohol is methanol or ethanol.
2. in accordance with the method for claim 1, it is characterised in that described fixing phase includes being located at the silica gel on upper strata, is located at
The aluminium oxide and the aluminium oxide positioned at lower floor of the load silver ion of layer, the silica gel：The aluminium oxide of load silver ion：Aluminium oxide
Mass ratio is 1：2.5～5.0：0～1.2.
3. in accordance with the method for claim 2, it is characterised in that the silica gel：The aluminium oxide of load silver ion：Aluminium oxide
Mass ratio is 1：2.5～5.0：0.1～1.0.
4. according to the method described in claim 1 or 2, it is characterised in that the specific surface area of the aluminium oxide is 50～300 meters2/
Gram, pore volume is 0.10～0.55 ml/g.
5. in accordance with the method for claim 4, it is characterised in that the specific surface area of the aluminium oxide is 120～300 meters2/ gram,
Pore volume is 0.20～0.35 ml/g, and bore dia is that 25～75 nanometers of hole accounts for the 30～90% of total pore volume.
6. according to the method described in claim 1 or 2, it is characterised in that the aluminium oxide is neutral aluminium oxide for surface.
7. in accordance with the method for claim 2, it is characterised in that the specific surface area of the silica gel is 250～850 meters2/ gram, hole
Volume is 0.25～0.99 ml/g.
8. in accordance with the method for claim 2, it is characterised in that the specific surface area of the silica gel is 350～750 meters2/ gram, hole
Volume is 0.30～0.96 ml/g, and bore dia is that 20～40 nanometers of hole accounts for the 50～95% of total pore volume.
9. in accordance with the method for claim 1, it is characterised in that silver ion is in eggshell in the aluminium oxide of the load silver ion
Type is distributed in aluminium oxide.
10. in accordance with the method for claim 1, it is characterised in that the diluent used by dilution heavy oil is C5～C6Alkane, dilution
Agent is 1～10 with the volume ratio of heavy oil：1.
11. according to the method described in claim 1 or 10, it is characterised in that described C5～C6Alkane be pentane, normal hexane or
Petroleum ether.
12. in accordance with the method for claim 1, it is characterised in that fixing phase is 8～30 with the mass ratio of heavy oil：1.
13. in accordance with the method for claim 1, it is characterised in that the heavy oil is vacuum distillate, deasphalted oil or catalysis
Cracking slurry oil.
14. in accordance with the method for claim 13, it is characterised in that in the heavy oil arene content be 5～90 mass %, sulfur
Content is 0.1～4.0 mass %.
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