CN102079988B - Heavy oil separation method - Google Patents
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Abstract
The invention relates to a heavy oil separation method which comprises the step of making heavy oil contact the stationary phase of silica silica loading with silver ion. The method can be used for preparing the components of the saturated hydrocarbon and the aromatic hydrocarbon through separating the heavy oil into three parts including saturated hydrocarbon, aromatic hydrocarbon, and colloid. The invention has the advantages of high separation efficiency and high handling capacity.
Description
Technical field
The present invention relates to a kind of method that adopts Solid phase extraction separation heavy oil.
Background technology
Heavy oil is the main raw material of refinery's secondary processing process (as catalytic cracking, coking, hydrocracking etc.), thereby the Heavy Oil Processing Technology level is the important factor that affects refinery's economic benefit.But it is very complicated that the heavy oil structure forms, even close at boiling range, in the suitable situation of the bulk properties such as H/C ratio, molecular-weight average, its suitability for secondary processing often also has different significantly.Thereby, only have chemical constitution and the transformation rule thereof of deep understanding heavy oil, could improve the Heavy Oil Processing Technology level.This just need to separate to obtain different components to heavy oil, then for different components, carries out analysis and the reactivity worth research of more deep (molecular level and quasi-molecule level).Thereby sepn process is proposed to two aspects requirements: (1) separation efficiency is high, can prepare the high purity sample to meet the needs of subsequent analysis detection and study on mechanism; (2) quantity of sample handling is larger, can prepare more quickly the sample size that can meet subsequent reactions and evaluation experimental needs.
Heavy oil is carried out to the component separation, is mainly to form and separate by hydrocarbon system, if by residual oil four component separation methods of generally approval and widespread use, exactly residual oil is separated into to stable hydrocarbon, aromatic hydrocarbons, four components of resin and asphalt for many years.In lot of documents monograph and the standard method at home and abroad of four component separation methods, report is arranged all, primary process is for first with normal heptane, being settled out bituminous matter, then with neutral alumina (γ-Al of moisture 1%
2O
3) for sorbent material carries out the column chromatography Solid phase extraction separation, with sherwood oil, benzene and benzene-ethanol be that solvent flushes out saturated minute in turn, fragrance minute and colloid (Liang Wenjie chief editor. petroleum chemistry. press of University of Petroleum, 1995:135; Yang Cui waits volume surely. the Petrochemical Engineering Analysis method. and Science Press, 1990:31).Traditional column chromatography four component separation methods take time and effort usually, and separation accuracy is limited, compare etc. higher requirement is arranged rinsing solvent flux, chromatographic column major diameter.In addition, also have by aromatic hydrocarbons be further divided into gently, in, six component separation methods of heavy aromatics, and by colloid be further divided into gently, in, eight component separation methods of heavy colloid, but sepn process is more complicated, applies that also too late four component method are general.
For vacuum distillate (VGO), therefore because asphaltenes and gum level are very not low substantially, can save the residual oil deasphalting process in above-mentioned four component method, directly be separated into saturated minute, fragrance minute and colloid.For example, the ASTM D2549 method generally adopted at present provides the method for utilizing stable hydrocarbon, aromatic hydrocarbons and colloid in the Solid phase extraction separation heavy oil fraction, the chromatographic column that this method is used is the bulb tube of top band ball-type interface, what with the bulb tube bottom, be connected is a long and narrow column jecket, and column length is 760～1150 millimeters.The top of long and narrow post and bulb tube joint filling stationary phase, the bottom of stationary phase is glass fibre, and middle level is silicon oxide, and upper strata is bauxitic clay.The processing sample amount is 2～10 grams, during extracting operation, first sample is dissolved with Skellysolve A, be poured in the bulb tube of chromatographic column top, make it flow into stationary phase and be adsorbed, then use respectively Skellysolve A, diethyl ether, trichloromethane, alcohol extraction stable hydrocarbon, aromatic hydrocarbon, colloid.The method chromatographic column used is longer, and the sepn process step is many, and velocity of separation is slow.CN1690704A discloses a kind of method of Solid-Phase Extraction and MS VGO hydrocarbon system composition, solid-phase extraction column height used is the 40-70 millimeter, column internal diameter is the 4-9 millimeter, stationary phase is silicon-dioxide, loadings 1.0-2.0 gram, quantity of sample handling 0.1-0.3 gram, respectively with Skellysolve A or normal hexane, methylene dichloride, benzene-alcohol flushing goes out stable hydrocarbon, aromatic hydrocarbons and colloid, the method is compared with ASTM D2549, separation accuracy is (amount of cross-contamination between general stable hydrocarbon and aromatic hydrocarbons is no more than 5%) quite, separate and significantly shorten analysis time, but quantity of sample handling significantly reduces.
As a whole, above-mentioned separation method or treatment capacity are too little, can't meet the requirement to sample size of subsequent reactions and evaluation experimental; Perhaps separation efficiency is poor, between stable hydrocarbon and aromatic hydrocarbons, has more serious crossed contamination; Or it is comparatively harsh that agent-oil ratio (stationary phase and oil sample weight ratio), solvent washing speed etc. are separated to the operational condition requirement.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of method of utilizing Solid phase extraction separation heavy oil and preparing the heavy oil hydrocarbon component, and the method quantity of sample handling is large, and separation efficiency is high.
The invention provides a kind of separation method of heavy oil, comprise the step that heavy oil is contacted with stationary phase, wherein, described stationary phase comprises the silicon-dioxide of load silver ion.
Heavy oil separation method provided by the invention, method by Solid-Phase Extraction is separated into stable hydrocarbon, aromatic hydrocarbons and three parts of colloid by heavy oil, and prepare saturated hydrocarbon component and aromatic component, can adopt lower stationary phase and oil sample weight ratio (catalystoil ratio) and higher solvent washing speed, have than existing methods higher separation efficiency and larger quantity of sample handling, both can be used as a kind of separation method, be used to meeting the requirement of subsequent analysis technology to sample purity; Can be used as again a kind of method for preparing fast contained hydrocarbon sample in heavy oil, for subsequent reactions and evaluation experimental provide necessary sample size.For example, adopting 100g is the silica gel treatment 30 gram grand celebration vacuum distillates (350～410 ℃ of cuts) of 13.2% load Silver Nitrate through 150 ℃ of dryings 4 hours, Silver Nitrate charge capacity, with 600 ml n-hexanes, flush out stable hydrocarbon, with 700 milliliters of benzene, flush out aromatic hydrocarbons, solvent washing speed is 20～40 ml/min, solvent evaporated, obtain stable hydrocarbon 23.87 grams, aromatic hydrocarbons 5.56 grams, post remaining (colloid) and loss be totally 0.57 gram, and it is 0.1% that GC/MS analyzes the aromatic hydrocarbons weight content shown in stable hydrocarbon; And adopt 100g through 150 ℃ of dryings 4 hours but the silica gel treatment 18 gram grand celebration vacuum distillates (350～410 ℃ of cuts) of load silver ion not, control identical solvent ratio and rinse speed, repeat the aforesaid operations step, obtain stable hydrocarbon 15.11 grams, aromatic hydrocarbons 2.66 grams, post remaining (colloid) and loss are 0.23 gram altogether, and it is 5.9% that GC/MS analyzes the aromatic hydrocarbons weight content shown in stable hydrocarbon, shows to have than polyaromatic to enter into stable hydrocarbon.
Embodiment
Heavy oil separation method of the present invention, be included in Solid-Phase Extraction condition under step that heavy oil is contacted with stationary phase, wherein Solid-Phase Extraction stationary phase used comprises the silicon-dioxide of load silver ion, the silicon dioxide compositions of this load silver ion comprises silver salt and silicon-dioxide, the weight of silicon-dioxide of described load silver ion of take is benchmark, wherein the content of silver salt is 1～40 % by weight, and the content of silicon-dioxide is 60～99 % by weight.The silicon-dioxide of described load silver ion is preferably the silicon-dioxide of load Silver Nitrate, the gross weight (weight that comprises Silver Nitrate and silicon-dioxide) of silicon-dioxide of load Silver Nitrate of take is benchmark, in the silicon-dioxide of load Silver Nitrate, the shared ratio of Silver Nitrate is 1～40 % by weight, be preferably 5～20 % by weight, the shared ratio of silicon-dioxide is 60～99 % by weight, is preferably 80～95 % by weight.
The silicon-dioxide of described load silver ion can adopt the preparation of silver salt solution pickling process.For example, the silicon-dioxide of described load Silver Nitrate, can adopt the method preparation of silver nitrate aqueous solution dipping silica gel (silicon-dioxide), the volume of dipping solution is 1-10 times of used silica gel pore volume, preferably 1.5～3 times, by weight, it is 1～40 % by weight that described dipping makes the shared ratio of Silver Nitrate in the silicon-dioxide of resulting load Silver Nitrate, preferred 5～20 % by weight, the shared ratio of silicon-dioxide is 60～99 % by weight, preferably 80～95 % by weight.After silicon-dioxide (silica gel) dipping silver salt, under 100～200 ℃ dry 1～30 hour, preferably under 120～180 ℃ dry 2～10 hours.The silicon-dioxide of dried load Silver Nitrate is positioned over lucifuge in moisture eliminator and deposits standby.The specific surface area of described silicon-dioxide is 200～750 meters
2/ gram, pore volume are 0.35～0.90 ml/g, and preferably, the specific surface area of described silicon-dioxide is 450～750 meters
2/ gram, pore volume are 0.35～0.55 ml/g, the silicon-dioxide mesoporous be the hole of 20～35 nanometers account for total pore volume 40～70%.Described silicon-dioxide is silica gel, can be Kiselgel A or silochrom, and preferred Kiselgel A, more preferably for the Kiselgel A of chromatographic separation.
In heavy oil separation method provided by the invention, described stationary phase also can comprise the not silicon-dioxide of load silver ion, described in stationary phase not the silicon-dioxide proportion of load silver ion be no more than 80 % by weight, preferably be no more than 50 % by weight; In stationary phase, the silicon-dioxide proportion of load silver ion preferably is not less than 20 % by weight.The silicon-dioxide of described not load silver ion can mix with the silicon-dioxide of load silver ion use or layering is used, preferably will be not the silicon-dioxide of load silver ion be placed in the upper strata of load silver ion silicon-dioxide, heavy oil is first through the silicon oxide of load silver ion not, and then, through the silicon-dioxide of load silver ion, can save like this consumption of load silver ion silicon-dioxide; In addition, when processing the higher raw material of sulphur content (sulfur-bearing aromaticity content), cause the stationary phase rapid deactivation in the time of can avoiding a large amount of sulfide directly with load silver ion silicon-dioxide, to contact, thus the guarantee separation efficiency.The silicon-dioxide of described not load silver ion is preferably silica gel, can be Kiselgel A or silochrom, is preferably Kiselgel A, more preferably for the Kiselgel A of chromatographic separation.The specific surface area of the silicon-dioxide of described not load silver ion (silica gel) is 200～750 meters
2/ gram, pore volume are 0.35～0.90 ml/g, and preferably, the specific surface area of the silicon-dioxide of described not load silver ion is 450～750 meters
2/ gram, pore volume are 0.35～0.55 ml/g, aperture be the hole of 20～35 nanometers account for total pore volume 40～70%.
Heavy oil separation method provided by the invention, comprise that the stationary phase that will comprise the silicon-dioxide of load silver ion fills in solid-phase extraction column, uses C
5-C
7Stable hydrocarbon is wetting (to be referred to the solvent of wetting use is added in column extractor, until it, thinks wetting when the column extractor bottom oozes and complete.) stationary phase, then will be dissolved in C
5-C
7Heavy oil sample in stable hydrocarbon is filled in solid-phase extraction column, and heavy oil is contacted with stationary phase; After adding heavy oil, use C
5-C
7Stable hydrocarbon rinses stationary phase, extracts the stable hydrocarbon in heavy oil; And then, with benzene or dichloromethane rinse stationary phase, extract the aromatic hydrocarbons in heavy oil; The component residued in stationary phase is colloid.Described C
5-C
7Stable hydrocarbon can be a kind of in Skellysolve A, normal hexane, normal heptane, sherwood oil or mixture that it is multiple, is preferably normal hexane; When described flushing stationary phase extracted the aromatic component in heavy oil, rinse solvent used was preferably benzene.
The weight ratio of described stationary phase and heavy oil sample is 3～40: 1, is preferably 3～10: 1; The heavy oil sample adopts C
5-C
7When the saturated hydrocarbon solvent dilution was dissolved, the volume ratio of solvent and heavy oil was 5～30: 1, is preferably 10～20: 1; Use C
5-C
7When stable hydrocarbon rinsed the stable hydrocarbon in stationary phase extraction heavy oil, solvent and heavy oil volume ratio were 10～30: 1, were preferably 15～25: 1; During with the aromatic hydrocarbons in benzene or dichloromethane rinse stationary phase extraction heavy oil, solvent and heavy oil volume ratio are 10～40: 1, are preferably 20～30: 1.
In described Solid phase extraction separation process, use C
5-C
7When stable hydrocarbon rinsed the stable hydrocarbon in stationary phase extraction heavy oil, solvent washing speed was preferably 5～30 ml/min, more preferably 10～30 ml/min; During with the aromatic hydrocarbons in benzene or dichloromethane rinse stationary phase extraction heavy oil, solvent washing speed is preferably 20～50 ml/min, more preferably 30～40 ml/min.
Heavy oil separation method provided by the invention, also can comprise saturated hydrocarbon solution and aromatic hydrocarbons solution solvent evaporated that separation is obtained, obtains stable hydrocarbon and aromatic component in heavy oil.The saturated hydrocarbon solution that Solid phase extraction separation obtains and aromatic hydrocarbons solution solvent evaporated in water-bath, obtain stable hydrocarbon and aromatic component, weighs and obtain saturated hydrocarbon content and aromaticity content in heavy oil, and surplus is colloid and loss.
Heavy oil separation method provided by the invention, being applicable to heavy oil separates, described heavy oil is heavy oil for example vacuum distillate, deasphalted oil, catalytically cracked oil or the hydrotreatment oil of the distillate that obtains of atmospheric and vacuum distillation and residual oil and secondary processing process for example, is particularly useful for processing vacuum distillate and hydrotreatment oil.
Below the present invention is further described with embodiment, but not thereby limiting the invention.
The Kiselgel A that in embodiment, silica gel (silicon-dioxide) used is produced for subsidiary factory of Haiyang Chemical Plant, Qingdao, 100～200 orders, specific surface area 635m
2/ g, pore volume 0.36mL/g, the pore volume in the hole of 20～35 nanometers accounts for 56% of total pore volume.AgNO
3For the high-purity chemical reagent factory in Hunan is produced, analytical pure.
The embodiment instrument is quadrupole gas-chromatography～GC-MS (GC/MS), and model is Agilent 6890GC/5973MS, the band fid detector.Gas-chromatography (GC) working conditions: sample size 1.0 μ L, splitting ratio 30: 1, chromatographic column are empty capillary column 30m * 0.25mm, 360 ℃ of injector temperatures, post case temperature kept 2 minutes at 60 ℃, then with 60 ℃ of/minute speed, was warming up to 350 ℃, kept 7 minutes.Mass spectrum (MS) working conditions: EI ionizes mode, bombarding voltage 70eV, sweep limit 50～700amu, 250 ℃ of ion source temperatures, 350 ℃ of GC/MS interface temperature.
Embodiment 1
The present embodiment is for illustrating processing and the preparation of silicon-dioxide of the present invention (silica gel) and load silver ion silicon-dioxide (silica gel) sample.
By Kiselgel A raw material 150 ℃ of dry 4h in baking oven, obtain activated silica gel standby, be numbered SG.Be positioned in moisture eliminator deposit standby.
Take 60.9g AgNO
3Be dissolved in wiring solution-forming in 400g water; Take 400g silica gel, the Kiselgel A raw material is joined to the AgNO prepared
3In solution, the limit edged stirs, and after silica gel adds, then stirs 15min; To flood AgNO
3Silica gel put into 150 ℃ of dry 4h of baking oven, the load silver ion silica gel that obtains activating (load silver ion silicon-dioxide), be numbered ASG, the Silver Nitrate charge capacity is 13.2 % by weight.Being positioned over lucifuge in moisture eliminator deposits standby.
Embodiment 2
The present embodiment adopts the efficient sharp separation vacuum distillate of Solid-Phase Extraction method provided by the present invention and produces stable hydrocarbon and aromatic component wherein for illustrating.
Take grand celebration vacuum distillate (350～410 ℃ of boiling ranges) sample 30g, be dissolved in the 240mL normal hexane; Filling 100 gram ASG in solid-phase extraction column (interior through 28mm, lower same); Solid-phase extraction column is arranged on the solid-phase extraction device with pumped vacuum systems, with the wetting stationary phase of 120 ml n-hexane, the hexane solution of above-mentioned dissolving oil sample is filled in solid-phase extraction column, controls vacuum tightness and make the discharge rate of solution be stabilized in 20 ml/min; After the oil sample filling, with 600 ml n-hexanes, rinse stationary phase and extract stable hydrocarbon, control vacuum tightness and make normal hexane rinse rate stabilization in 20 ml/min; With 700 milliliters of benzene, rinse stationary phase again, rinsing speed is 40 ml/min, the aromatic hydrocarbons in the extraction distillate.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon and aromatic hydrocarbons solution, weigh, obtain stable hydrocarbon sample 23.87 grams, aromatic hydrocarbons sample 5.56 grams, post remaining (colloid) and loss amount to 0.57 gram.It is 0.1 % by weight that GC/MS analyzes the aromatic hydrocarbons weight content shown in stable hydrocarbon.
Embodiment 3
The present embodiment adopts the efficient sharp separation vacuum distillate of Solid-Phase Extraction method provided by the present invention and produces stable hydrocarbon and aromatic component wherein for illustrating.
Take grand celebration vacuum distillate (460～540 ℃ of boiling ranges) sample 15g, be dissolved in the 200mL normal hexane; At the filling 60 gram ASG of solid-phase extraction column lower floor, upper strata filling 40 gram SG; Solid-phase extraction column is arranged on the solid-phase extraction device with pumped vacuum systems, with the wetting stationary phase of 100 ml n-hexane, the hexane solution of above-mentioned oil sample is filled into to the Solid-Phase Extraction column top, from the bottom of column extractor, vacuumize, control vacuum tightness and make solution flow out rate stabilization in 15 ml/min; After the oil sample filling, with 300 ml n-hexanes, rinse stationary phase and extract stable hydrocarbon, control vacuum tightness and make normal hexane rinse rate stabilization in 15 ml/min; With 330 milliliters of benzene, rinse stationary phase again, rinsing speed is 30 ml/min, the aromatic hydrocarbons in the extraction distillate.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon and aromatic hydrocarbons solution, weigh, obtain stable hydrocarbon sample 11.57 grams, aromatic hydrocarbons sample 2.81 grams, post remaining (colloid) and loss amount to 0.62 gram.It is 0.8 % by weight that GC/MS analyzes the aromatic hydrocarbons weight content shown in stable hydrocarbon.
Embodiment 4
The present embodiment adopts the efficient sharp separation vacuum distillate of Solid-Phase Extraction method provided by the present invention and produces stable hydrocarbon and aromatic component wherein for illustrating.
Take VGO in sand (referring to matter crude oil vacuum distillate in Saudi Arabia, 350～540 ℃ of boiling ranges) sample 6g, be dissolved in the 90mL normal hexane; At the filling 50 gram ASG of solid-phase extraction column lower floor, upper strata filling 50 gram SG; Solid-phase extraction column is arranged on the solid-phase extraction device with pumped vacuum systems, with the wetting stationary phase of 100 ml n-hexane, the hexane solution of above-mentioned oil sample is filled in solid-phase extraction column, controls vacuum tightness and make normal hexane rinse rate stabilization in 10 ml/min; After the oil sample filling, continue to rinse stationary phase with 140 ml n-hexanes and extract stable hydrocarbon; With 180 milliliters of benzene, rinse stationary phase again, rinsing speed is 40 ml/min, the aromatic hydrocarbons in the extraction distillate.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon and aromatic hydrocarbons solution, weigh, obtain stable hydrocarbon sample 2.57 grams, aromatic hydrocarbons sample 3.05 grams, post remaining (colloid) and loss be totally 0.38 gram; It is 0.8 % by weight that GC/MS analyzes the aromatic hydrocarbons weight content shown in stable hydrocarbon.。
Embodiment 5
The present embodiment adopts the efficient sharp separation hydrotreatment oil of Solid-Phase Extraction method provided by the present invention and produces stable hydrocarbon and aromatic component wherein for illustrating.
Take hydrotreatment oil (350～410 ℃ of boiling ranges) sample 30g in sand, dissolving and Solid-Phase Extraction process are with embodiment 2.Obtain stable hydrocarbon sample 21.90 grams, aromatic hydrocarbons sample 7.55 grams, post remaining (colloid) and loss amount to 0.55 gram.It is 0.2 % by weight that GC/MS analyzes the aromatic hydrocarbons weight content shown in stable hydrocarbon.
Comparative Examples 1
This Comparative Examples adopts the silica gel of load silver ion not to carry out the situation of the conventional Solid phase extraction separation of vacuum distillate for illustrating.
Take grand celebration vacuum distillate (350～410 ℃ of boiling ranges) sample 18g, be dissolved in the 144mL normal hexane.Solid-Phase Extraction process solvent for use is than identical with embodiment 2 with flushing speed, just stationary phase is replaced with to 100 gram SG, obtain stable hydrocarbon 15.11 grams, aromatic hydrocarbons 2.66 grams, post remaining (colloid) and loss are 0.23 gram altogether, it is 5.9 % by weight that GC/MS analyzes the aromatic hydrocarbons weight content shown in stable hydrocarbon, shows to have than polyaromatic to enter into stable hydrocarbon.
Visible by embodiment 2-5 and Comparative Examples 1, the method for the invention, quantity of sample handling is larger, and separation efficiency is higher, and the aromaticity content in stable hydrocarbon generally is no more than 1 % by weight; And adopt when the silicon-dioxide of load silver ion does not carry out Solid phase extraction separation, even significantly reduce quantity of sample handling, separation efficiency does not still meet the demands, and between stable hydrocarbon and aromatic hydrocarbons, has obvious crossed contamination.
Claims (14)
1. the method for a heavy oil separation, comprise the step that heavy oil is contacted with stationary phase, it is characterized in that, described stationary phase comprises the silicon-dioxide of load silver ion; The weight of silicon-dioxide of load silver ion of take is benchmark, and the silicon-dioxide of described load silver ion contains the silver salt of 1～40 % by weight, the silicon-dioxide of 60～99 % by weight; The silicon-dioxide of described load silver ion adopts the preparation of silver salt solution pickling process, and described silicon-dioxide is silica gel.
2. according to the described method of claim 1, it is characterized in that, the weight of silicon-dioxide of load silver ion of take is benchmark, the silicon-dioxide of described load silver ion contains the silver salt of 1～40 % by weight, the silicon-dioxide of 60～99 % by weight, the silicon-dioxide proportion of load silver ion described in described stationary phase is not less than 20 % by weight.
3. according to the described method of claim 2, it is characterized in that, the silicon-dioxide of described load silver ion contains the silver salt of 5～20 % by weight.
4. according to claim 1,2 or 3 described methods, it is characterized in that, described silver salt is Silver Nitrate.
5. according to claim 1,2 or 3 described methods, it is characterized in that, the specific surface area of described silicon-dioxide is 200～750 meters
2/ gram, pore volume are 0.35～0.90 ml/g.
6. according to the described method of claim 5, the specific surface area of described silicon-dioxide is 450～750 meters
2/ gram, pore volume are 0.35～0.55 ml/g, aperture be the hole of 20～35 nanometers account for total pore volume 40～70%.
7. according to the described method of claim 1, it is characterized in that, described stationary phase also comprises the not silicon-dioxide of load silver ion, and the silicon-dioxide proportion of load silver ion is not no more than 80 % by weight.
8. according to the described method of claim 5, it is characterized in that, in described stationary phase not the silicon-dioxide proportion of load silver ion be no more than 50%.
9. according to the described method of claim 5, it is characterized in that, the silicon-dioxide of described not load silver ion fills in the upper strata of the silicon-dioxide of load silver ion, and heavy oil is first contacted with the silicon-dioxide of not load, then with the silicon-dioxide of load silver ion, contacts.
10. according to claim 7,8 or 9 described methods, it is characterized in that, the silicon-dioxide of described not load silver ion is silica gel, and the specific surface area of described silica gel is 200～750 meters
2/ gram, pore volume are 0.35～0.90 ml/g.
11. according to the described method of claim 1, it is characterized in that, comprise the following steps: use C
5-C
7The wetting stationary phase that comprises the silicon-dioxide of load silver ion of stable hydrocarbon, then make to be dissolved in C
5-C
7Heavy oil in stable hydrocarbon contacts with stationary phase, uses C
5-C
7Stable hydrocarbon rinses stationary phase and extracts the stable hydrocarbon in heavy oil, then with benzene or dichloromethane rinse stationary phase, extracts the aromatic hydrocarbons in heavy oil, and the component residued in stationary phase is colloid; The heavy oil sample adopts C
5-C
7When the saturated hydrocarbon solvent dilution was dissolved, the volume ratio of solvent and heavy oil was 5～30: 1; Use C
5-C
7When stable hydrocarbon rinsed the stable hydrocarbon in stationary phase extraction heavy oil, solvent and heavy oil volume ratio were 10～30: 1; During with the aromatic hydrocarbons in benzene or dichloromethane rinse stationary phase extraction heavy oil, solvent and heavy oil volume ratio are 10～40: 1; Use C
5-C
7When stable hydrocarbon rinsed the stable hydrocarbon in stationary phase extraction heavy oil, solvent washing speed was 5～30 ml/min, and during with the aromatic hydrocarbons in benzene or dichloromethane rinse stationary phase extraction heavy oil, solvent washing speed is 20～50 ml/min.
12. according to the described method of claim 10, it is characterized in that described C
5-C
7Stable hydrocarbon is one or more in Skellysolve A, normal hexane, normal heptane or sherwood oil.
13. according to the described method of claim 1 or 10, it is characterized in that, the part by weight of stationary phase and heavy oil is 3～30: 1.
14., according to the described method of claim 1, it is characterized in that described heavy oil is vacuum distillate, deasphalted oil, catalytically cracked oil or hydrotreatment oil.
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| CN105273742B (en) * | 2014-07-16 | 2017-04-26 | 中国石油化工股份有限公司 | Method for solid phase extraction separating of components in heavy oil |
| CN104165821A (en) * | 2014-08-01 | 2014-11-26 | 湖北富邦科技股份有限公司 | Method for determining colloid in wax oil |
| CN106324158B (en) * | 2015-06-17 | 2018-11-16 | 中国石油天然气股份有限公司 | The method of nitrogenous compound in Solid Phase Extraction diesel oil |
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| "Standard Test Method for Separation of Representative Aromatics and Nonaromatics Fractions of High-Boiling Oils by Elution Chromatography";American Society of Testing Materials;《ASTM D2549》;20070630;1-6 * |
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