CN105273742A - 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 the method for a kind of heavy oil separation Zhong Ge hydrocarbon system component, specifically, is a kind of method utilizing different structure hydrocarbon component in Solid phase extraction separation heavy oil.
Background technology
Heavy oil is the main raw material of the secondary processing process such as catalytic cracking, hydrofining, hydrocracking and coking, and heavy oil upgrading level is the important factor affecting refinery's economic benefit.Because heavy oil structure composition is complicated, even if close at boiling range, when the bulk properties such as H/C ratio, molecular-weight average are suitable, its detailed hydrocarbon composition, carbon number distribution have very large difference.These differences can cause the difference on transformation rule because chemical reaction is different, therefore, need based on the secondary processing technique selecting the research of its understanding close to quasi-molecule level and opposed polarity component reaction performance to mate most with it, thus improve effective rate of utilization and the processing technology level of heavy oil.
Stable hydrocarbon in heavy oil is good secondary processing of raw material, but the suitability for secondary processing of aromatic hydrocarbons wherein and heteroatomic compound is poor.At present, the research of the aromatic hydrocarbons in heavy oil especially polycyclic aromatic hydrocarbons is attracted wide attention.But be that analytical test or the evaluation of processing characteristics all need highly purified sample, this just needs to be separated the difference of the component in heavy oil according to polarity, thus sepn process is proposed to the requirement of two aspects: (1) separation efficiency is high, highly purified sample can be isolated to meet the needs of subsequent analysis detection and study on mechanism; (2) quantity of sample handling is large, can isolate the sample size that can meet subsequent reactions and evaluation experimental needs more quickly; (3) further can be separated according to polarity aromatic component, realize the enrichment to mononuclear aromatics, double ring arene and polycyclic aromatic hydrocarbons.
According to polarity, Component seperation is carried out to heavy oil, mainly be separated by hydrocarbon composition, the separation method measuring the potential content of lubricating oil as two sorbent material method be exactly by dewaxing after lubricating oil distillate be separated into stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics four components.Its primary process for first to carry out benzol-kentone dewaxing, then with aluminum oxide (γ-Al
2o
3) and the two sorbent material of silica gel be that stationary phase carries out pillar layer separation, with the sherwood oil-benzene of sherwood oil, different volumes ratio, benzene-ethanol (1:1) for solvent flush out successively stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics four components (volume such as Yang Cuiding. Petrochemical Engineering Analysis method. Science Press, 1990:26).This pair of sorbent material post separation method is better to the pressed oil separating effect of paraffin base lubricating oil distillate, but limited for the separation accuracy of polycyclic aromatic hydrocarbon content and the high heavy oil of sulphur content, intersects serious between component.The sorbent material used in the method is aluminum oxide and the two sorbent material of silica gel, to the limited sorption capacity of polycyclic aromatic hydrocarbons and sulfocompound, when the heavy oil that aromatics separation content is higher, treatment capacity is less, stationary phase deactivation rate is fast, decline to the absorption save power of each component, cause separator column post to be imitated and reduce, isolated each group of cross-contamination phenomena is serious.
Carry out certain modification to stationary phase, appropriateness strengthens stationary phase can improve separation efficiency to the adsorptive power of aromatic hydrocarbons, shortens disengaging time, increases stationary phase to the treatment capacity of oil product.Gao Xiuxiang (Gao Xiuxiang etc. the research of silver-colored modification infusorial earth material capture alkene. analytical chemistry, 2003, 31 (8): 911-914) adopt silver salt to be coated in Silica Surface or be that cationite is separated with stable hydrocarbon alkene with silver ions, its principle is that the outer empty sp hybridized orbital of silver ions with the π-electron of alkene, stronger mating reaction can occur and generates stable title complex, so retention time on a column increases, and stable hydrocarbon is containing with silver ions, interactional functional group occurring, almost do not have an effect with stationary phase, so reach capacity the object of hydrocarbon and separation of olefins.
Tao Xueming (Tao Xueming, Long Yicheng, Lu Wanzhen. the group composition of high effective liquid chromatography for measuring diesel oil. chromatogram, 1995,13 (5): 368-372) with silver type sulfonic acid bonded silica gel (Ag-SCX post) for stationary phase, with the normal hexane of benzene modification for moving phase, high performance liquid chromatography achieves the alkene (C of different carbon chain lengths
14, C
16and C
18) with being separated of alkane (white oil) mixture.Similarly, containing large π key in aromatic hydrocarbons, can have certain effect with silver ions, and the different aromatic hydrocarbons of number of rings due to the difference of its conjugated degree different with the effect degree of silver ions, the retention time on pillar is also different.Therefore, in accordance with this principle stable hydrocarbon can be separated with aromatic hydrocarbons, and can be separated the aromatic hydrocarbons of different number of rings.
Qiang Dongmei (Qiang Dongmei, Lu Wanzhen. the research of tetrahydrobenzene and aromatic hydrocarbons separation mechanism on Ag-SCX post. chromatogram, 1998,16 (3): 187-190) with Ag-SCX (silver-colored post) for stationary phase, 3 ‰ tetrahydrobenzene/hexanaphthene is moving phase, separate object is the hexane solution of the 1:1 that dodecylbenzene, fluorenes and phenanthrene are mixed with stable hydrocarbon (lubricating oil distillate) respectively, has investigated tetrahydrobenzene and the separation mechanism of 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 is followed successively by 121 (dodecylbenzene) >21 (fluorenes) >13.8 (phenanthrene), the absorption of aromatic hydrocarbons on silver-colored post that the equilibrium constant is larger is more weak, therefore, the adsorption strength of aromatic hydrocarbons on silver-colored post strengthens with the increase of number of rings.These are all the compartment analysises of several detailed hydrocarbon mixtures for trace, can only meet the object of analytical test, can not meet the demand of the heavy oil sample of preparation scale separate complex.
For the reduced pressure distillate oil separating that treatment capacity is larger, it be the silica gel of 13.2% Silver Nitrate is stationary phase that CN102079987A has disclosed with load massfraction, decompressed wax oil is divided into the method for stable hydrocarbon, aromatic hydrocarbon and colloid three components with normal hexane, benzene, ethanol for solvent respectively, separating effect is better.But the method is not further separated aromatic component, the needs that the aromatic component of opposed polarity is analyzed further and processed can not be met.In addition, in the stationary phase that the method uses, the adsorption strength of silica gel to silver ions of load silver ion is lower, when rinsing glial component, device lower end also needs alumina column of connecting again, the silver ions being rinsed just can be avoided to enter into isolated each component, too increase step and the difficulty of operation simultaneously.
As a whole, above-mentioned stationary phase or post effect too low, separation efficiency is too poor, stable hydrocarbon, light aromatic hydrocarbons, there is more serious intersection between middle aromatic hydrocarbons and heavy aromatics; Or treatment capacity is too little, the separation requirement of sample in preparation scale separation cannot be met; Or when separation accuracy is suitable, each treatment capacity is too little, preparative scale separation can not be realized to dissimilar polarity component in heavy oil; Or silver ions is entered in each component by a large amount of wash-out and goes, affect the evaluation of the detection of isolated component subsequent analysis and processing characteristics.
Summary of the invention
The object of this invention is to provide the method for each component of a kind of Solid phase extraction separation heavy oil, the method with the aluminum oxide of load silver ion for stationary phase, there is in separable heavy oil the hydro carbons of opposed polarity component, stationary phase is large to quantity of sample handling, separation efficiency is high and the silver ions of load not easily by wash-out.
The method of each component of Solid phase extraction separation heavy oil provided by the invention, comprises and adds in stationary phase after being diluted by heavy oil, then use C successively
5~ C
6alkane rinse stationary phase obtain saturated hydrocarbon component, with aromatic hydrocarbons and C
5~ C
6alkane volume ratio is that the solvent washing stationary phase of 1:15 ~ 25 obtains light aromatic component, with aromatic hydrocarbons and C
5~ C
6alkane volume ratio is that the solvent washing stationary phase of 1:3 ~ 5 obtains middle aromatic component, rinse stationary phase with aromatic hydrocarbons and obtain heavy aromatics component, glial component is obtained with the solvent washing stationary phase that aromatic hydrocarbons and monohydroxy-alcohol volume ratio are 1:0.8 ~ 1.5, described stationary phase is the aluminum oxide of load silver ion, and the silver ions of load accounts for 0.5 ~ 12% of quality of alumina.
In the inventive method, the aluminum oxide adopting load silver ion is the stationary phase of heavy oil separation, different irrigations is adopted to rinse the stationary phase adsorbing heavy oil sample again, according to component polarity, separable go out stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid five components, can fast for follow-up analytical test and reaction evaluating provide the sample size of necessity.
Embodiment
The inventive method adopts the aluminum oxide of load silver ion to be stationary phase, due to the polarity that aluminum oxide has, stronger absorption save power is had to silver ions, silver ions can be made to be carried on more firmly on alumina supporter, thus reduce extraction solvent significantly to the wash-out of silver ions, both ensure that separation efficiency and the treatment capacity of stationary phase, and again reduced silver ions and be rinsed possibility in separated portion.In addition, the irrigation that the present invention is used, namely extraction agent effectively by the component that stationary phase adsorbs, can be separated by the power of its polarity.Stationary phase counterweight oil handling amount used is high, separation efficiency good, and the silver ions of load is not easily rinsed agent wash-out and flows in separated portion, thus effectively can avoid the pollution that silver ions runs off to separated portion, and improves precision of analysis.
In stationary phase provided by the invention, the silver ions of load preferably accounts for 3.0 ~ 10.0% of quality of alumina, it can be used alone, preferably jointly use with silica gel, namely at the upper strata of extracting and separating post filling silica gel, the aluminum oxide of middle level filling load silver ion, aluminum oxide can load in lower floor, also can not fill aluminum oxide, forms spectra unmixing.
In the inventive method, preferred stationary phase comprise the silica gel being positioned at upper strata, the load silver ion being positioned at middle level aluminum oxide and be positioned at the neutral alumina of lower floor, described silica gel: the aluminum oxide of load silver ion: the mass ratio of aluminum oxide is 1:2.5 ~ 5.0:0 ~ 1.2, also can be 1:2.5 ~ 5.0:0.1 ~ 1.0.
In stationary phase described in the inventive method, be neutral aluminum oxide, more preferably surface for the aluminum oxide of load silver ion and spectra unmixing aluminum oxide preferred surface used be neutral gama-alumina.
The specific surface area of described aluminum oxide preferably 50 ~ 300 meters
2/ gram, more preferably 120 ~ 300 meters
2/ gram, pore volume preferably 0.10 ~ 0.55 ml/g, more preferably 0.20 ~ 0.35 ml/g, aluminum oxide median pore diameter is that the hole of 25 ~ 75 nanometers accounts for 50 ~ 90% of total pore volume.
In spectra unmixing described in the inventive method, the specific surface area of silica gel preferably 250 ~ 850 meters
2/ gram, more preferably 350 ~ 750 meters
2/ gram, pore volume preferably 0.25 ~ 0.99 ml/g, more preferably 0.30 ~ 0.96 ml/g.The preferred Kiselgel A of described silica gel, its bore dia is that the hole of 20 ~ 40 nanometers preferably accounts for 50 ~ 95% of total pore volume.
The exterior active center of stationary phase of the present invention is, with moving phase and sample, interactional main body occurs, and thus makes the distribution in eggshell type in aluminum oxide of the silver ions of load, the silver ions of load can be made to be utilized.Vacuum impregnation technology is the solution impregnation of alumina carrier with silver ion under certain vacuum tightness (reduced pressure), is more evenly dispersed in alumina surface to make active ingredient.Steeping fluid is under capillary pressure function, by trickle duct to aluminum oxide internal penetration, the concentration of silver ions is larger, concentration gradient inside and outside carrier is also larger, more easily penetrate into carrier inside, the catalyzer of more difficult formation eggshell type, the same dipping time that extends also can make metal ion permeate intensification, thus is difficult to form eggshell type distribution.Therefore, when the present invention prepares the aluminum oxide stationary phase of load silver ion, preferably use the impregnation fluid aluminum oxide of low concentration of silver ions, dipping time is unsuitable long.
The preparation method of stationary phase provided by the invention, comprises and immerses in silver nitrate solution by aluminum oxide, after stirring, floods 0.5 ~ 5.0 hour at reduced pressure conditions in 20 ~ 70 DEG C, then dry.
Concentration preferably 0.2 ~ 10.0 quality %, preferably 0.5 ~ 6.0 quality % that described silver nitrate solution is suitable.
With the pressure preferably 20 ~ 100kPa of silver nitrate solution impregnated alumina, the drying temperature after dipping preferably 100 ~ 200 DEG C.
Above-mentioned dipping is introduced in the process of Silver Nitrate, the volume flooding silver nitrate solution used be 1 ~ 10 times of alumina catalyst support pore volume, preferably 2 ~ 5 times.After having flooded, the aluminum oxide of dipping silver salt (Silver Nitrate) is in 100 ~ 200 DEG C, preferably 120 ~ 180 DEG C drying, and time of drying is 1 ~ 30 hour, preferably 1 ~ 10 hour.The process that above-mentioned dipping introduces Silver Nitrate can be carried out repeatedly, as 1 ~ 3 time.The aluminum oxide of the load Silver Nitrate obtained after drying is positioned over lucifuge in moisture eliminator and deposits for subsequent use.
When stationary phase provided by the invention is the spectra unmixing containing multiple component, wherein the aluminum oxide of silica gel, aluminum oxide and load silver ion can be seated in same extracting and separating post, also can fill in different extracting and separating posts.When filling in same extracting and separating post, silica gel is loaded on upper strata, and aluminum oxide is loaded on bottom, and the aluminum oxide of load silver ion is positioned at centre.When with different column extractor, the aluminum oxide separator column of the separator column of filling silica gel, filling load silver ion, the separator column of filling aluminum oxide are connected in series by upper, middle and lower successively.
In the object of separator column bottom filling aluminum oxide be: when using a large amount of solvents to carry out each component of oil sample of wash-out stationary phase absorption, neutral alumina can be used to adsorb a small amount of silver ions taken out of by solvent, avoid silver ions to enter into separated portion, cause analyzing and testing error.
In the inventive method, when Solid phase extraction separation heavy oil, filled in by stationary phase in extracting and separating post, the heavy oil of dilution injects stationary phase by top, and stable hydrocarbon wherein, aromatic hydrocarbons and colloid are fixed according to polarity size and adsorb successively mutually.Rinse stationary phase with alkane, obtain saturated hydrocarbon component, then go out light aromatic hydrocarbons and middle aromatic hydrocarbons successively with the aromatic hydrocarbons of different ratios and the mixed solution of alkane, flush out heavy aromatics with aromatic hydrocarbons, and then flush out glial component with the mixture of aromatic hydrocarbons and monohydroxy-alcohol.
In the present invention, preferably, at the upper strata of the aluminum oxide stationary phase of load silver ion filling silica gel, when processing heavy oil, the silica gel on upper strata contacts with heavy oil prior to the aluminum oxide of load silver ion, is conducive to avoiding the polycyclic aromatic hydrocarbons of high adsorption capacity and sulfocompound directly and the oxide contact of load silver ion, causes the absorption save power of stationary phase to each component to decline fast, cause stationary phase fast deactivation, the separation efficiency of separator column reduces.
In the inventive method, the preferred C of thinner of dilution heavy oil
5~ C
6alkane.The volume ratio of described thinner and heavy oil is 1 ~ 10:1, preferably 2 ~ 5:1.
Mass ratio preferably 8 ~ 30:1, the more preferably 12 ~ 21:1 of described stationary phase and heavy oil.
The present invention for rinse stationary phase absorption light aromatic component irrigation in, aromatic hydrocarbons and C
5~ C
6preferred 1:18 ~ 23 of volume ratio of alkane.
For rinsing in the irrigation of aromatic component in stationary phase absorption, aromatic hydrocarbons and C
5~ C
6preferred 1:3 ~ 4.5 of volume ratio of alkane.
For rinsing in the irrigation of the colloid of stationary phase absorption, preferred 1:0.8 ~ 1.2 of volume ratio of aromatic hydrocarbons and monohydroxy-alcohol.
In the inventive method, rinse the stable hydrocarbon irrigation used of stationary phase absorption and dilution heavy oil C used
5~ C
6the preferred Skellysolve A of alkane, normal hexane or sherwood oil.
Rinse the preferred benzene of aromatic hydrocarbons in light aromatic hydrocarbons, middle aromatic hydrocarbons and heavy aromatics irrigation used or toluene.
Rinse the monohydroxy-alcohol particular methanol in colloid irrigation used or ethanol.
In aforesaid method, described volume ratio of rinsing stationary phase irrigation used and stationary phase for each time preferably 1 ~ 10, more preferably 1 ~ 6.
In the inventive method, the light aromatic hydrocarbons obtained through Solid phase extraction separation is the component of enrichment mononuclear aromatics, and middle aromatic hydrocarbons is the component of enrichment double ring arene, and heavy aromatics is the component of enrichment three ring and above aromatic hydrocarbons.
Heavy oil described in the inventive method is vacuum distillate, deasphalted oil or catalytically cracked oil.Aromaticity content in described heavy oil is 5 ~ 90 quality %, and sulphur content is 0.1 ~ 4.0 quality %.
The present invention is further described to use embodiment below, but not thereby limiting the invention.
Aluminum oxide used in example is the chromatography neutral alumina that Chemical Reagent Co., Ltd., Sinopharm Group produces, and 74 ~ 149 microns, calcination loss≤8.0%, specific surface area is 152m
2/ g, pore volume 0.213mL/g, bore dia is that the hole of 25 ~ 75 nanometers accounts for 85% of total pore volume.
Silver Nitrate is that Nanjing Chemistry Reagent Co., Ltd. produces, and analytical pure, 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 is 479m
2/ g, pore volume 0.349mL/g, bore dia is that the hole of 20 ~ 40 nanometers accounts for 89% of total pore volume.
Example instrument is level Four bar gas chromatograph-mass spectrometer (GC/MS), and model is Agilent7890GC/5975MS, 7693 automatic sampling towers.Gas-chromatography (GC) working conditions: empty capillary column (30m × 0.32mm), sample size 1 μ L, splitting ratio 50:1, injector temperature 310 DEG C, carrier gas is He, and post flow takes constant current mode, flow velocity 1.0mL/min; Column oven heating schedule be 40 DEG C keep 2min, then with the ramp of 60 DEG C/min to 310 DEG C, keep 8min; Mass Spectrometry Conditions: EI ionizer (70eV), ion source temperature 230 DEG C, MS level Four bar temperature 150 DEG C, MSD transmission line 300 DEG C; Solvent delay 3min; Use full scan (SCAN) mode image data, full scan mass range is 50 ~ 700amu.
Example 1
This example is for illustration of the pre-treatment of the aluminum oxide of silicon-dioxide of the present invention, aluminum oxide and load silver ion 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 in moisture eliminator deposit for subsequent use.
By neutral alumina 550 DEG C of roastings 5 hours, obtain activated alumina, be positioned in moisture eliminator deposit for subsequent use.
Get 7.41 grams of Silver Nitrates to be dissolved in 160mL deionized water and to be mixed with silver nitrate solution, get 200 grams of neutral aluminas, aluminum oxide is joined in silver nitrate solution, stir, flood 4 hours in 60 DEG C under 50kPa pressure, then the aluminum oxide of Silver Nitrate will be flooded in 150 DEG C of dryings 2 hours, be cooled to room temperature, then again flood with the silver nitrate aqueous solution of same volume and concentration as stated above, dry, dipping like this three times, the rear drying of third time dipping 4 hours, obtain the aluminum oxide A of the load silver ion activated, wherein silver ions accounts for 7.05% of quality of alumina.Be positioned over bottling after cooling in moisture eliminator, keep in Dark Place for subsequent use.
Example 2
This example illustrates the effect adopting stationary phase provided by the invention to be separated each component of vacuum distillate.
Bottom filling 30g neutral alumina in separator column, the aluminum oxide A of middle filling 110g load silver ion, upper strata filling 30g silica gel; Separator column lower end is connected with pumped vacuum systems.The cumulative volume of stationary phase is 150mL.
Get Tahe vacuum distillate (boiling range 350 ~ 540 DEG C) sample 10.20g (11.19mL), be dissolved in 30mL normal hexane, first soak the stationary phase of filling in above-mentioned separator column with the normal hexane of 100mL, then the hexane solution of above-mentioned oil sample is joined in separator column.Saturated hydrocarbon component is flushed out respectively with 170mL normal hexane, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:19 goes out light aromatic component, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:4 goes out middle aromatic component, 255mL toluene rinse goes out heavy aromatics component, 255mL toluene: ethanol contend goes out glial component than the solvent washing for 1:1.
Adopt the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, obtain stable hydrocarbon 4.94 grams, 1.56 grams, light aromatic hydrocarbons, 1.52 grams, middle aromatic hydrocarbons, heavy aromatics 0.92 gram, colloid 0.91 gram, lose 0.35 gram.
The content that GC/MS analyzes alkylbenzene in display saturated hydrocarbon component is 0.9 quality %, in light aromatic component, the content of mononuclear aromatics is 74.3 quality %, in middle aromatic component, the content of double ring arene is 37.1 quality %, and the aromaticity content in heavy aromatics component more than three rings is 65.9 quality %.
After separation completes, dry stationary phase, the silver ions in the aluminum oxide of the load silver ion of middle filling is completely oxidized becomes black, and the neutral alumina of bottom filling still keeps white, illustrates that silver ions does not run off from the aluminum oxide of load.
Example 3
By each component of the method heavy oil separation sample of example 2, carry out Solid phase extraction separation unlike Liaohe River vacuum distillate (boiling range 350 ~ 540 DEG C) sample getting 10.11g (11.09mL).After separation, obtain stable hydrocarbon 5.48 grams, 1.24 grams, light aromatic hydrocarbons, 1.37 grams, middle aromatic hydrocarbons, heavy aromatics 0.73 gram, colloid 1.18 grams, lose 0.11 gram.
The alkyl benzene content that GC/MS analyzes in display stable hydrocarbon is 1.4 quality %, in light aromatic component, the content of mononuclear aromatics is 72.9 quality %, in middle aromatic component, the content of double ring arene is 38.2 quality %, and in heavy aromatics component, the content of the above aromatic hydrocarbons of three rings is 67.8 quality %.
After separation completes, dry stationary phase, the silver ions in the stationary phase of the load silver ion of middle filling is completely oxidized becomes black, and the neutral alumina of bottom filling still keeps white.
Example 4
Preparing the aluminum oxide of load silver ion by the method for example 1, is 1.36 grams unlike the Silver Nitrate added when preparing silver nitrate solution, and through three dippings, obtain the aluminum oxide B of the load silver ion activated, wherein silver ions accounts for 1.30% of quality of alumina.
Bottom filling 30g neutral alumina in separator column, the aluminum oxide B of middle filling 110g load silver ion, upper strata filling 30g silica gel; Separator column lower end is connected with pumped vacuum systems.The cumulative volume of stationary phase is 160mL.
Get Tahe vacuum distillate (boiling range 350 ~ 540 DEG C) sample 10.13g (11.11mL), be dissolved in 30mL normal hexane, first soak the stationary phase of filling in above-mentioned separator column with the normal hexane of 100mL, then the hexane solution of above-mentioned oil sample is joined in separator column.Saturated hydrocarbon component is flushed out respectively with 170mL normal hexane, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:19 goes out light aromatic component, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:4 goes out middle aromatic component, 255mL toluene rinse goes out heavy aromatics component, 255mL toluene: ethanol contend goes out glial component than the solvent washing for 1:1.
Adopt the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, obtain stable hydrocarbon 5.28 grams, 1.41 grams, light aromatic hydrocarbons, 1.18 grams, middle aromatic hydrocarbons, heavy aromatics 1.01 grams, colloid 0.94 gram, lose 0.20 gram.
The content that GC/MS analyzes alkylbenzene in display saturated hydrocarbon component is 6.7 quality %, in light aromatic component, the content of mononuclear aromatics is 56.5 quality %, in middle aromatic component, the content of double ring arene is 28.9 quality %, and in heavy aromatics, the content of the above aromatic hydrocarbons of three rings is 56.8 quality %.
After separation completes, dry stationary phase, the silver ions in the aluminum oxide of the load silver ion of middle filling is completely oxidized becomes black, and the neutral alumina of bottom filling still keeps white, illustrates that silver ions does not run off from the aluminum oxide of load.
Example 5
Preparing the aluminum oxide of load silver ion by the method for example 1, is 5.80 grams unlike the Silver Nitrate added when preparing silver nitrate solution, and through three dippings, obtain the aluminum oxide C of the load silver ion activated, wherein silver ions accounts for 5.52% of quality of alumina.
Bottom filling 30g neutral alumina in separator column, the aluminum oxide C of middle filling 110g load Silver Nitrate, upper strata filling 30g silica gel; Separator column lower end is connected with pumped vacuum systems.The cumulative volume of stationary phase is 153mL.
Get Tahe vacuum distillate (boiling range 350 ~ 540 DEG C) sample 10.25g (11.24mL), be dissolved in 30mL normal hexane, first soak the stationary phase of filling in above-mentioned separator column with the normal hexane of 100mL, then the hexane solution of above-mentioned oil sample is joined in separator column.Saturated hydrocarbon component is flushed out respectively with 170mL normal hexane, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:19 goes out light aromatic component, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:4 goes out middle aromatic component, 255mL toluene rinse goes out heavy aromatics component, 255mL toluene: ethanol contend goes out glial component than the solvent washing for 1:1.
Adopt the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, obtain stable hydrocarbon 4.89 grams, 1.59 grams, light aromatic hydrocarbons, 1.47 grams, middle aromatic hydrocarbons, heavy aromatics 1.02 grams, colloid 1.05 grams, lose 0.23 gram.
The content that GC/MS analyzes alkylbenzene in display saturated hydrocarbon component is 2.4 quality %, in light aromatic component, the content of mononuclear aromatics is 71.8 quality %, in middle aromatic component, the content of double ring arene is 34.7 quality %, and in heavy aromatics component, the content of the above aromatic hydrocarbons of three rings is 64.4 quality %.
After separation completes, dry stationary phase, the silver ions in the aluminum oxide of the load silver ion of middle filling is completely oxidized becomes black, and the neutral alumina of bottom filling still keeps white, illustrates that silver ions does not run off from the aluminum oxide of load.
Example 6
Preparing the aluminum oxide of load silver ion by the method for example 1, is 10.14 grams unlike the Silver Nitrate added when preparing silver nitrate solution, and through three dippings, obtain the aluminum oxide D of the load silver ion activated, wherein silver ions accounts for 9.66% of quality of alumina.
Bottom filling 30g neutral alumina in separator column, the aluminum oxide D of middle filling 110g load Silver Nitrate, upper strata filling 30g silica gel; Separator column lower end is connected with pumped vacuum systems.The cumulative volume of stationary phase is 145mL.
Get Tahe vacuum distillate (boiling range 350 ~ 540 DEG C) sample 10.06g (11.03mL), be dissolved in 30mL normal hexane, first soak the stationary phase of filling in above-mentioned separator column with the normal hexane of 100mL, then the hexane solution of above-mentioned oil sample is joined in separator column.Saturated hydrocarbon component is flushed out respectively with 170mL normal hexane, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:19 goes out light aromatic component, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:4 goes out middle aromatic component, 255mL toluene rinse goes out heavy aromatics component, 255mL toluene: ethanol contend goes out glial component than the solvent washing for 1:1.
Adopt the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, obtain stable hydrocarbon 4.87 grams, 1.58 grams, light aromatic hydrocarbons, 1.43 grams, middle aromatic hydrocarbons, heavy aromatics 1.05 grams, colloid 0.96 gram, lose 0.17 gram.
The content that GC/MS analyzes alkylbenzene in display saturated hydrocarbon component is 0.7 quality %, in light aromatic component, the content of mononuclear aromatics is 74.6 quality %, in middle aromatic component, the content of double ring arene is 38.5 quality %, and in heavy aromatics component, the content of the above aromatic hydrocarbons of three rings is 68.3 quality %.
After separation completes, dry stationary phase, the silver ions in the aluminum oxide of the load silver ion of middle filling is completely oxidized becomes black, and the neutral alumina of bottom filling still keeps white, illustrates that silver ions does not run off from the aluminum oxide of load.
Comparative example 1
The conventional column separating effect adopting the stationary phase of neutral alumina and silica gel composition to carry out vacuum distillate is described.
Lower floor's filling 85g neutral alumina in separator column, upper strata filling 85g silica gel; Separator column lower end is connected with pumped vacuum systems.The cumulative volume of stationary phase is 185mL.
Get Tahe vacuum distillate (boiling range 350 ~ 540 DEG C) sample 10.02g (10.99mL), be dissolved in 30mL normal hexane, first soak the stationary phase of filling in above-mentioned separator column with the normal hexane of 100mL, then the hexane solution of above-mentioned oil sample is joined in separator column.Saturated hydrocarbon component is flushed out respectively with 170mL normal hexane, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:19 goes out light aromatic component, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:4 goes out middle aromatic component, 255mL toluene rinse goes out heavy aromatics component, 255mL toluene: ethanol contend goes out glial component than the solvent washing for 1:1.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, weigh, obtain 4.97 grams, stable hydrocarbon sample, 2.14 grams, light aromatic hydrocarbons, 1.12 grams, middle aromatic hydrocarbons, heavy aromatics 0.76 gram, colloid 0.74 gram, lose 0.29 gram.
The content that GC/MS analyzes alkylbenzene in display saturated hydrocarbon component is 4.3 quality %, in light aromatic component, the content of mononuclear aromatics is 60.7 quality %, in middle aromatic component, the content of double ring arene is 27.5 quality %, and in heavy aromatics component, the content of the above aromatic hydrocarbons of three rings is 52.5 quality %.
From this comparative example result, use the aluminum oxide of non-load silver ion, be separated in each component obtained, all comparatively the present invention is low to be separated object component concentration, illustrates that the separation efficiency of stationary phase is low.
Comparative example 2
Get 10.14 grams of Silver Nitrates to be dissolved in 160mL deionized water and to be mixed with silver nitrate solution, getting 200 grams of Kiselgel As joins in silver nitrate solution, stir, (0.5kPa) floods 4 hours in 60 DEG C under vacuum, then the silica gel of Silver Nitrate will be flooded in 150 DEG C of dryings 2 hours, be cooled to room temperature, then as stated above with the silver nitrate aqueous solution of same volume and concentration again flood, dry, dipping like this three times, the rear drying of third time dipping 4 hours, obtain the silica gel of the load silver ion activated, wherein silver ions accounts for 9.66% of silica gel quality.
Bottom filling 30g neutral alumina in separator column, the silica gel of middle filling 110g load silver ion, upper strata filling 30g silica gel; Separator column lower end is connected with pumped vacuum systems.The cumulative volume of stationary phase is 163mL.
Get Tahe vacuum distillate (boiling range 350 ~ 540 DEG C) sample 10.20g (11.19mL), be dissolved in 30mL normal hexane, first soak the stationary phase of filling in above-mentioned separator column with the normal hexane of 100mL, then the hexane solution of above-mentioned oil sample is joined in separator column.Saturated hydrocarbon component is flushed out respectively with 170mL normal hexane, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:19 goes out light aromatic component, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:4 goes out middle aromatic component, 255mL toluene rinse goes out heavy aromatics component, 255mL toluene: ethanol contend goes out glial component than the solvent washing for 1:1.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, weigh, obtain 4.84 grams, stable hydrocarbon sample, 1.71 grams, light aromatic hydrocarbons, 1.36 grams, middle aromatic hydrocarbons, heavy aromatics 0.87 gram, colloid 0.81 gram, lose 0.41 gram.
The content that GC/MS analyzes alkylbenzene in display saturated hydrocarbon component is 1.3 quality %, in light aromatic component, the content of mononuclear aromatics is 73.8 quality %, in middle aromatic component, the content of double ring arene is 37.1 quality %, and in heavy aromatics component, the content of the above aromatic hydrocarbons of three rings is 65.9 quality %.
After separation completes, dry stationary phase, silver ions in the stationary phase of the load silver ion of middle filling is completely oxidized becomes black, and the neutral alumina of bottom filling also all becomes black, this phenomenon higher with the yield of colloid with heavy aromatics conforms to, explanation has a certain amount of silver ions to come off from silica gel, is rinsed and enters into neutral alumina.
This comparative example result illustrates, with the silica gel of load silver ion for stationary phase, required silver ions charge capacity is large, and the silver ions of load should be rinsed solvent elution.
Comparative example 3
Bottom filling 75g neutral alumina in separator column, the aluminum oxide A of middle filling 65g load Silver Nitrate, upper strata filling 30g silica gel; Separator column lower end is connected with pumped vacuum systems.The cumulative volume of stationary phase is 152mL.
Get Tahe vacuum distillate (boiling range 350 ~ 540 DEG C) sample 10.04g (11.01mL), be dissolved in 30mL normal hexane, first soak the stationary phase of filling in above-mentioned separator column with the normal hexane of 100mL, then the hexane solution of above-mentioned oil sample is joined in separator column.Saturated hydrocarbon component is flushed out respectively with 170mL normal hexane, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:19 goes out light aromatic component, 255mL toluene: normal hexane volume ratio is that the solvent washing of 1:4 goes out middle aromatic component, 255mL toluene rinse goes out heavy aromatics component, 255mL toluene: ethanol contend goes out glial component than the solvent washing for 1:1.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, weigh, obtain 5.12 grams, stable hydrocarbon sample, 1.41 grams, light aromatic hydrocarbons, 1.27 grams, middle aromatic hydrocarbons, heavy aromatics 1.14 grams, colloid 1.02 grams, lose 0.08 gram.
The content that GC/MS analyzes alkylbenzene in display saturated hydrocarbon component is 4.7 quality %, in light aromatic component, the content of mononuclear aromatics is 75.8 quality %, in middle aromatic component, the content of double ring arene is 33.3 quality %, and in heavy aromatics component, the content of the above aromatic hydrocarbons of three rings is 50.2 quality %.
After separation completes, dry stationary phase, the silver ions in the stationary phase of the load silver ion of middle filling is completely oxidized becomes black, and the neutral alumina of bottom filling still keeps white, illustrates that silver ions does not run off from the aluminum oxide of load.
This comparative example result illustrates, the aluminum oxide using the load Silver Nitrate of small amount is stationary phase, and in separating obtained each component, in saturated hydrocarbon component, alkyl benzene content is more, and in heavy aromatics component, the content of the above aromatic hydrocarbons of three rings reduces, and illustrates that separation efficiency is poor.
Comparative example 4
The effect of aromatic component during this comparative example illustrates and adopts the irrigation of different volumes ratio to rinse.
By method Solid phase extraction separation Tahe vacuum distillate (boiling range 350 ~ 540 DEG C) the sample 10.18g (11.17mL) of example 2, during aromatic component, 255mL toluene is adopted: normal hexane volume ratio is that the solvent washing of 1:5.7 goes out middle aromatic component unlike in flushing.After the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics and colloid, obtain 5.19 grams, stable hydrocarbon sample, 1.45 grams, light aromatic hydrocarbons, 1.31 grams, middle aromatic hydrocarbons, heavy aromatics 1.16 grams, colloid 0.97 gram, lose 0.1 gram.
The content that GC/MS analyzes alkylbenzene in display saturated hydrocarbon component is 1.3 quality %, in light aromatic component, the content of mononuclear aromatics is 75.7 quality %, in middle aromatic component, the content of double ring arene is 38.0 quality %, and the content of the above aromatic hydrocarbons of three rings in heavy aromatics component is 52.5 quality %.
After separation completes, dry stationary phase, the silver ions in the stationary phase of the load silver ion of middle filling is completely oxidized becomes black, and the aluminum oxide of the non-load silver ion of low side filling still keeps white.
This comparative example illustrates, in flushing aromatic component solvent in, reducing the ratio of toluene, though the content of double ring arene in aromatic component in improving slightly, significantly declining causing rinsing the above aromaticity content of three rings in the heavy aromatics component that obtains.
Claims (17)
1. a method for each component of Solid phase extraction separation heavy oil, comprises and adds in stationary phase after being diluted by heavy oil, then use C successively
5~ C
6alkane rinse stationary phase obtain saturated hydrocarbon component, with aromatic hydrocarbons and C
5~ C
6alkane volume ratio is that the solvent washing stationary phase of 1:15 ~ 25 obtains light aromatic component, with aromatic hydrocarbons and C
5~ C
6alkane volume ratio is that the solvent washing stationary phase of 1:3 ~ 5 obtains middle aromatic component, rinse stationary phase with aromatic hydrocarbons and obtain heavy aromatics component, glial component is obtained with the solvent washing stationary phase that aromatic hydrocarbons and monohydroxy-alcohol volume ratio are 1:0.8 ~ 1.5, described stationary phase is the aluminum oxide of load silver ion, and the silver ions of load accounts for 0.5 ~ 12% of quality of alumina.
2. in accordance with the method for claim 1, it is characterized in that described stationary phase comprise the silica gel being positioned at upper strata, the load silver ion being positioned at middle level aluminum oxide and be positioned at the aluminum oxide of lower floor, described silica gel: the aluminum oxide of load silver ion: the mass ratio of aluminum oxide is 1:2.5 ~ 5.0:0 ~ 1.2.
3. in accordance with the method for claim 2, it is characterized in that described silica gel: the aluminum oxide of load silver ion: the mass ratio of aluminum oxide is 1:2.5 ~ 5.0:0.1 ~ 1.0.
4., according to the method described in claim 1 or 2, it is characterized in that the specific surface area of described aluminum oxide is 50 ~ 300 meters
2/ gram, pore volume is 0.10 ~ 0.55 ml/g.
5. in accordance with the method for claim 4, it is characterized in that the specific surface area of described aluminum oxide is 120 ~ 300 meters
2/ gram, pore volume is 0.20 ~ 0.35 ml/g, and bore dia is that the hole of 25 ~ 75 nanometers accounts for 30 ~ 90% of total pore volume.
6., according to the method described in claim 1 or 2, it is characterized in that described aluminum oxide is the aluminum oxide of surface for neutrality.
7. in accordance with the method for claim 2, it is characterized in that the specific surface area of described silica gel is 250 ~ 850 meters
2/ gram, pore volume is 0.25 ~ 0.99 ml/g.
8. in accordance with the method for claim 2, it is characterized in that the specific surface area of described silica gel is 350 ~ 750 meters
2/ gram, pore volume is 0.30 ~ 0.96 ml/g, and bore dia is that the hole of 20 ~ 40 nanometers accounts for 50 ~ 95% of total pore volume.
9. in accordance with the method for claim 1, it is characterized in that in the aluminum oxide of described load silver ion, silver ions is that eggshell type is distributed in aluminum oxide.
10. in accordance with the method for claim 1, it is characterized in that the silver ions of load in described stationary phase accounts for 2.5 ~ 9.0% of quality of alumina.
11. in accordance with the method for claim 1, it is characterized in that the thinner diluting heavy oil used is C
5~ C
6alkane, the volume of thinner and heavy oil is 1 ~ 10:1.
12. according to the method described in claim 1 or 11, it is characterized in that described C
5~ C
6alkane is Skellysolve A, normal hexane or sherwood oil.
13. in accordance with the method for claim 1, it is characterized in that described aromatic hydrocarbons is benzene or toluene.
14. in accordance with the method for claim 1, it is characterized in that described monohydroxy-alcohol is methyl alcohol or ethanol.
15. in accordance with the method for claim 1, it is characterized in that the mass ratio of stationary phase and heavy oil is 8 ~ 30:1.
16. in accordance with the method for claim 1, it is characterized in that described heavy oil is vacuum distillate, deasphalted oil or catalytically cracked oil.
17. in accordance with the method for claim 16, and it is characterized in that in described heavy oil, aromaticity content is 5 ~ 90 quality %, sulphur content is 0.1 ~ 4.0 quality %.
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| CN114540058A (en) * | 2020-11-20 | 2022-05-27 | 中国石油天然气股份有限公司 | Needle coke prepared from heavy oil and its preparation method |
| CN114563506A (en) * | 2020-11-27 | 2022-05-31 | 中国石油天然气股份有限公司 | Pretreatment method for determining content and composition of olefin compounds in wax oil |
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