CN102079987A - Method for separating heavy oils by solid phase extraction - Google Patents
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- CN102079987A CN102079987A CN2009102498256A CN200910249825A CN102079987A CN 102079987 A CN102079987 A CN 102079987A CN 2009102498256 A CN2009102498256 A CN 2009102498256A CN 200910249825 A CN200910249825 A CN 200910249825A CN 102079987 A CN102079987 A CN 102079987A
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Abstract
A method for separating heavy oils by solid phase extraction comprises the step of the contact of the heavy oils with stationary phase, wherein the stationary phase consists of silica loaded with silver ions and alumina. In the method, solid extraction separation is used to separate the heavy oils to obtain saturated hydrocarbon, aromatic hydrocarbon, and colloid, and then the saturated hydrocarbon, the aromatic hydrocarbon and the colloid are prepared. By using the method, the separation efficiency and the handling capacity can be taken into account, and the rapid and efficient separation of the heavy oils is realized.
Description
Technical field
The present invention relates to a kind of method that adopts Solid-Phase Extraction to separate 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 influences refinery's economic benefit.But the heavy oil structure is formed very complicated, even close at boiling range, under the suitable situation of bulk properties such as H/C ratio, molecular-weight average, its suitability for secondary processing often also has difference significantly.Thereby, have only the chemical constitution and the transformation rule thereof of deep understanding heavy oil, could improve the Heavy Oil Processing Technology level.This just need separate to obtain different components heavy oil, carries out the analysis and the reactivity worth research of more deep (molecular level and quasi-molecule level) again at different components.Thereby sepn process is proposed two aspects require: (1) separation efficiency height, can prepare the high purity sample to satisfy subsequent analysis and detect and the needs of study on mechanism; (2) quantity of sample handling is bigger, can prepare the sample size that can satisfy subsequent reactions and evaluation experimental needs more quickly.
Heavy oil being carried out component separate, mainly is to form by hydrocarbon system to separate, as exactly residual oil being separated into stable hydrocarbon, aromatic hydrocarbons, colloid and four components of bituminous matter by residual oil four component separation methods of generally approval and widespread use 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 being settled out bituminous matter with normal heptane earlier, again with neutral alumina (γ-Al of moisture 1%
2O
3) separate for sorbent material carries out the column chromatography Solid-Phase Extraction, with sherwood oil, benzene and benzene-ethanol be that solvent flushes out saturated branch in turn, fragrance divides and colloid (Liang Wenjie edits. petroleum chemistry. press of University of Petroleum, 1995:135; Yang Cui waits volume surely. the petrochemical complex analytical procedure. and Science Press, 1990:31).Traditional column chromatography four component separation methods take time and effort usually, and separation accuracy is limited, and flushing solvent flux, chromatographic column length-to-diameter ratio etc. are had higher requirement.In addition, also have with aromatic hydrocarbons be further divided into gently, in, six component separation methods of heavy aromatics, and with colloid be further divided into gently, in, heavy gelationus eight component separation methods, but sepn process is more complicated, also too late four component method of application are general.
For vacuum distillate (VGO), because asphaltenes and gum level are very not low substantially, therefore can save the residual oil deasphalting process in above-mentioned four component method, directly be separated into saturated branch, fragrance branch and colloid.For example, the ASTM D2549 method that generally adopts provides and has utilized Solid-Phase Extraction to separate stable hydrocarbon, aromatic hydrocarbons and gelationus method in the heavy oil fraction at present, the chromatographic column that this method is used is the bulb tube of top dribbling type interface, what be connected with the bulb tube bottom 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 a glass fibre, and the middle level is a silicon oxide, and the upper strata is a bauxitic clay.Handling sample size is 2～10 grams, earlier sample is dissolved with Skellysolve A during extracting operation, be poured in the bulb tube of chromatographic column top, make it flow into stationary phase and be adsorbed, use Skellysolve A, diethyl ether, trichloromethane, alcohol extraction stable hydrocarbon, aromatic hydrocarbon, colloid then respectively.The used chromatographic column of this method is longer, and the sepn process step is many, and velocity of separation is slow.CN1690704A discloses a kind of Solid-Phase Extraction and mass spectrometry is measured the method that VGO hydrocarbon system forms, used solid-phase extraction column height is the 40-70 millimeter, column internal diameter is the 4-9 millimeter, stationary phase is a 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, this method is compared with ASTM D2549, separation accuracy is (amount of cross-contamination between general stable hydrocarbon and the 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 satisfy the requirement to sample size of subsequent reactions and evaluation experimental; Perhaps separation efficiency is relatively poor, has more serious crossed contamination between stable hydrocarbon and the aromatic hydrocarbons; Or it is comparatively harsh that agent-oil ratio (stationary phase and oil sample weight ratio), solvent washing speed etc. are separated the operational condition requirement.
Summary of the invention
The problem to be solved in the present invention provides a kind of method of utilizing Solid-Phase Extraction separation heavy oil and preparing the heavy oil hydrocarbon component, and this method quantity of sample handling is big, the separation efficiency height.
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 and the aluminum oxide of load silver ion.
Heavy oil separation method provided by the invention, method by Solid-Phase Extraction with heavy oil be separated into stable hydrocarbon, aromatic hydrocarbons and three parts of colloid, and preparation saturated hydrocarbon component and aromatic component, can adopt lower stationary phase and oil sample weight ratio (catalystoil ratio) and higher solvent washing speed, have higher separation efficiency and bigger quantity of sample handling than existing methods, both can be used as a kind of separation method, be used to satisfy of the requirement of subsequent analysis technology sample purity; Can be used as a kind of quick method for preparing contained hydrocarbon sample in the heavy oil again, for subsequent reactions and evaluation experimental provide necessary sample size.Contain aluminum oxide in the described stationary phase, with in benzene-ethanol or the alcohol flushing gelationus process, can active adsorption by the silver ions on the silicon-dioxide of being carried on of ethanol elution, avoid the pollution of silver ions to the colloid sample.For example, adopt 100g through 150 ℃ of dryings 4 hours, the Silver Nitrate charge capacity is that 13.2% silica gel and 50g are that stationary phase is handled 15 gram grand celebration vacuum distillates (510～570 ℃ of cuts) through 4 hours neutral alumina of 400 ℃ of roastings, flush out stable hydrocarbon with 300 ml n-hexanes, flush out aromatic hydrocarbons with 350 milliliters of benzene, go out colloid with 120 milliliters of ethanol again, solvent washing speed is 20～40 ml/min, solvent evaporated, obtain stable hydrocarbon sample 10.87 grams, aromatic hydrocarbons sample 2.96 grams, colloid 1.12 grams, loss 0.05 gram, it is 0.5% that GC/MS analyzes the aromatic hydrocarbons weight content that shows in the stable hydrocarbon; And adopt through 150 ℃ of dryings 4 hours but the not silica gel treatment 10 gram grand celebration vacuum distillates (510～570 ℃ of cuts) of load silver ion of 100g with reference to ordinary method, control identical solvent ratio and flushing speed, repeat the aforesaid operations step, obtain stable hydrocarbon 7.43 grams, aromatic hydrocarbons 1.82 grams, colloid 0.71 gram, loss 0.04 gram, it is 4.2% that GC/MS analyzes the aromatic hydrocarbons weight content that shows in the stable hydrocarbon, shows to have than polyaromatic to enter into stable hydrocarbon.
Embodiment
Solid-Phase Extraction provided by the invention is separated in the heavy oil method, be included in Solid-Phase Extraction condition under step that heavy oil is contacted with the stationary phase of the silicon-dioxide that comprises load silver ion, wherein, gross weight with the silicon-dioxide of described load silver ion is a benchmark, comprises the silicon-dioxide of 1～40 weight % silver salt, 60～99 weight % in the silicon dioxide compositions of described load silver ion.Described silver salt is preferably Silver Nitrate, and promptly the silicon-dioxide of described load silver ion is preferably the silicon-dioxide of load Silver Nitrate.In the silicon-dioxide of load Silver Nitrate, Silver Nitrate accounts for 1～40 weight %, silica comprises 60～99 weight %; Preferably, it is 5～20 weight % that Silver Nitrate accounts for, silica comprises 80～95 weight %.
The method preparation of the silicon-dioxide available silver salt solution impregnation silicon-dioxide of described load silver ion.For example, when the silicon-dioxide of described load silver ion is the silicon-dioxide of 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, preferred 1.5～3 times, by weight, it is 1～40 weight % that described dipping makes Silver Nitrate shared ratio in the silicon-dioxide of load Silver Nitrate, preferred 5～20 weight %.Silicon-dioxide behind dipping silver salt (Silver Nitrate) 100～200 ℃ dry 1～30 hour down, preferably 120～180 ℃ dry 2～10 hours down, the silicon-dioxide of dried load Silver Nitrate is positioned in the moisture eliminator lucifuge and deposits standby.The specific surface area of described silicon-dioxide is 200～750 meters
2/ gram, pore volume are 0.35～0.90 milliliter/gram, and preferred, described silicon-dioxide specific surface area is 450～750 meters
2/ gram, pore volume be 0.35～0.55 milliliter/gram, the aperture 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 is used for the Kiselgel A of chromatographic separation.
Solid-Phase Extraction provided by the invention is separated in the heavy oil method, described stationary phase comprises the silicon-dioxide and the aluminum oxide of load silver ion, weight with stationary phase is benchmark, silica comprises 20～99 weight % of load silver ion in the stationary phase, and aluminum oxide accounts for 1～80 weight %; Preferably, silica comprises 40～90 weight % of load silver ion, aluminum oxide accounts for 10～60 weight %.Described aluminum oxide is a neutral alumina, and this aluminum oxide is preferable over 200～800 ℃ of following roastings 1～8 hour, more preferably 300～500 ℃ of following roastings 2～4 hours.
Solid-Phase Extraction provided by the invention is separated in the heavy oil method, and the silicon-dioxide of aluminum oxide and load silver ion can be seated in the same extraction equipment, also can fill in the different equipment.When filling in same extraction equipment for example in the column extractor time, the aluminum oxide proportion is 10～60 weight % in the stationary phase, preferred 30～50 weight %, silica comprises 40～90 weight % of load silver ion; Described aluminum oxide preferably fills in the bottom of the silicon-dioxide of load silver ion, and during extraction, the solvent of solvent or dissolving heavy oil at first contacts with the silicon-dioxide of load silver ion, contacts with aluminum oxide then.Preferably, it is that aluminum oxide fills in the different extraction equipments with the silicon-dioxide of load silver ion that described aluminum oxide fills in independent solid-phase extraction column, the aluminum oxide proportion is 10～60 weight % in the stationary phase, silica comprises 40～90 weight % of load silver ion; Under this situation, heavy oil (comprising the solvent that dissolves heavy oil) is introduced in the extraction equipment of the silicon-dioxide that loads load silver ion, extract stable hydrocarbon and aromatic hydrocarbons then, the column extractor that will load aluminum oxide before adopting benzene-ethanol or alcohol flushing colloid is series at after the column extractor of the silicon-dioxide that loads load silver ion, to reduce the resistance in flushing stable hydrocarbon and the aromatic hydrocarbons process; Described C
5～C
7Stable hydrocarbon can be a kind of or its mixture in Skellysolve A, normal hexane, normal heptane, the sherwood oil, is preferably normal hexane; Solvent for use is a benzene during aromatic component in the described flushing stationary phase extraction heavy oil; Solvent for use is an ethanol during glial component in the described flushing stationary phase extraction heavy oil.
In the heavy oil separation method provided by the invention, described stationary phase also can contain the not silicon-dioxide of load silver ion, described in the stationary phase not the silicon-dioxide proportion of load silver ion be no more than 80 weight %, preferably be no more than 50 weight %.Described silicon-dioxide can mix use with the silicon-dioxide of load silver ion or layering is used, preferably silicon-dioxide is placed the upper strata of load silver ion silicon-dioxide, heavy oil is earlier through the silicon oxide of load silver ion not, and then the silicon-dioxide of process load silver ion, to save the consumption of load silver ion silicon-dioxide; In addition, when handling the higher raw material of sulphur content (content of sulfur-bearing aromatic hydrocarbons), cause the stationary phase rapid deactivation in the time of can avoiding a large amount of sulfide directly to contact with load silver ion silicon-dioxide, thus the guarantee separation efficiency.
Separation heavy oil method provided by the invention comprises that the stationary phase that will comprise the silicon-dioxide of load silver ion fills in the solid-phase extraction column, uses C
5～C
7Stable hydrocarbon wetting (refer to the solvent of wetting usefulness is added in the column extractor, treat its think wetting and finish when the column extractor bottom oozes) stationary phase will be dissolved in C then
5～C
7Heavy oil sample in the stable hydrocarbon is filled in the solid-phase extraction column, and heavy oil is contacted with stationary phase; Use C after adding heavy oil
5～C
7Stable hydrocarbon flushing stationary phase extracts the stable hydrocarbon in the heavy oil; And then, extract the aromatic hydrocarbons in the heavy oil with benzene or dichloromethane rinse stationary phase; Go out the colloid that residues in the stationary phase with benzene-ethanol or ethanol again.Described C
5～C
7Stable hydrocarbon can be a kind of in Skellysolve A, normal hexane, normal heptane, the sherwood oil or mixture that it is multiple, is preferably normal hexane; Used rinse solvent is preferably benzene during aromatic component in the described flushing stationary phase extraction heavy oil.
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
7The volume ratio of solvent and heavy oil is 5～30: 1 during saturated hydrocarbon solvent dilution dissolving, is preferably 10～20: 1; Use C
5～C
7Solvent and heavy oil volume ratio are 10～30: 1 during stable hydrocarbon in the stable hydrocarbon flushing stationary phase extraction heavy oil, are preferably 15～25: 1; During with the aromatic hydrocarbons in benzene or the dichloromethane rinse stationary phase extraction heavy oil, solvent and heavy oil volume ratio are 10～40: 1, are preferably 20～30: 1.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
7Solvent and heavy oil volume ratio are 5～30: 1 during saturated hydrocarbon solvent dilution dissolving, are preferably 10～20: 1; Use C
5～C
7Solvent and heavy oil volume ratio are 10～30: 1 during stable hydrocarbon in the stable hydrocarbon flushing stationary phase extraction heavy oil, are preferably 15～25: 1; Solvent and heavy oil volume ratio are 10～40: 1 during with the aromatic hydrocarbons in benzene or the dichloromethane rinse stationary phase extraction heavy oil, are preferably 20～30: 1; During with benzene-ethanol or alcohol flushing colloid, solvent load is 0.5～2.0: 1 with the ratio of stationary phase pore volume, is preferably 0.8～1.2: 1.
In the described Solid-Phase Extraction sepn process, use C
5～C
7Solvent washing speed is preferably 5～30 ml/min during stable hydrocarbon in the stable hydrocarbon flushing stationary phase extraction heavy oil, more preferably 10～30 ml/min; Solvent washing speed is preferably 20～50 ml/min during with the aromatic hydrocarbons in benzene or the dichloromethane rinse stationary phase extraction heavy oil, more preferably 30～40 ml/min; During with benzene-ethanol or alcohol flushing colloid, solvent washing speed is preferably 20～50 ml/min, more preferably 30～40 ml/min.Solvent for use is an ethanol during glial component in the described flushing stationary phase extraction heavy oil.
Heavy oil separation method provided by the invention also can comprise saturated hydrocarbon solution and aromatic hydrocarbons solution and hydrosol solvent evaporated that separation is obtained, obtains stable hydrocarbon, aromatic hydrocarbons and glial component in the heavy oil.Solid-Phase Extraction is separated saturated hydrocarbon solution and the aromatic hydrocarbons solution solvent evaporated in water-bath that obtains, and obtains stable hydrocarbon, aromatic hydrocarbons and glial component, and weighing obtains stable hydrocarbon in the heavy oil, aromatic hydrocarbons and gum level, and surplus is loss.
Heavy oil separation method provided by the invention, be applicable to that heavy oil separates, described heavy oil is the distillate that obtains of atmospheric and vacuum distillation and for example deasphalted oil of heavy oil, catalytically cracked oil or the hydrotreatment oil of residual oil and secondary processing process for example, is particularly useful for handling vacuum distillate and hydrotreatment oil.
The present invention is further described with embodiment below, but not thereby limiting the invention.
The Kiselgel A that used silica gel (silicon-dioxide) is produced for subsidiary factory of Haiyang Chemical Plant, Qingdao among the embodiment, 100～200 orders, specific surface area 635m
2/ g, pore volume 0.36mL/g, the aperture be the hole of 20～35 nanometers account for total pore volume 56%.AgNO
3For the high-purity chemical reagent in Hunan factory produces, analytical pure.Aluminum oxide is that Chemical Reagent Co., Ltd., Sinopharm Group produces 100～200 orders, column chromatography neutral alumina, igloss weightlessness≤8.0%.
The used instrument of embodiment is quadrupole gas chromatograph-mass spectrometer (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 oven temperature, degree kept 2 minutes at 60 ℃, was warming up to 350 ℃ with 60 ℃ of/minute speed then, kept 7 minutes.Mass spectrum (MS) working conditions: EI ionization mode, bombarding voltage 70eV, sweep limit 50～700amu, 250 ℃ of ion source temperatures, 350 ℃ of GC/MS interface temperature.
Embodiment 1
Present embodiment is used to illustrate the processing and the preparation of silica gel of the present invention (silicon-dioxide) and load silver ion silica gel sample.
With Kiselgel A raw material 150 ℃ of dry 4h in baking oven, it is standby to obtain activated silica gel, is numbered SG.Be positioned over deposit in the moisture eliminator standby.
Take by weighing 60.9g AgNO
3Be dissolved in wiring solution-forming in the 400g water; Take by weighing 400g silica gel, silica gel is joined the AgNO for preparing
3In the solution, the limit edged stirs, after silica gel adds, and restir 15min; To flood AgNO
3Silica gel put into 150 ℃ of dry 4h of baking oven, obtain activatory load silver ion silica gel, be numbered ASG, the Silver Nitrate charge capacity is 13.2 weight %.Being positioned in the moisture eliminator lucifuge deposits standby.
Embodiment 2
Present embodiment is used to illustrate and adopts the efficient sharp separation vacuum distillate of Solid-Phase Extraction method provided by the present invention and produce wherein stable hydrocarbon, aromatic hydrocarbons and glial component.
Take by weighing grand celebration vacuum distillate (510～570 ℃ of boiling ranges) sample 15g, be dissolved in the 220mL normal hexane; Filling 100 gram ASG in solid-phase extraction column (interior through 28mm, down together); Solid-phase extraction column is installed on the solid-phase extraction device that has pumped vacuum systems, with the wetting stationary phase of 100 ml n-hexanes (ASG); The hexane solution of above-mentioned oil sample is filled in the solid-phase extraction column, and control vacuum tightness makes the rate stabilization of solution filling in 15 ml/min; After the oil sample filling finishes, extract stable hydrocarbon with 300 ml n-hexanes flushing stationary phase, control vacuum tightness makes normal hexane flushing rate stabilization in 15 ml/min; With 350 milliliters of benzene flushing stationary phase, flushing speed is 30 ml/min, the aromatic hydrocarbons in the extraction distillate subsequently; To be filled with 50g then and be connected in the silicagel column bottom, with 120mL alcohol flushing stationary phase extraction glial component through the solid-phase extraction column of 4 hours neutral aluminas of 400 ℃ of roastings.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, aromatic hydrocarbons and the hydrosol, weigh, obtain stable hydrocarbon sample 10.87 grams, aromatic hydrocarbons sample 2.96 grams, colloid 1.12 grams, loss 0.05 gram, it is 0.5 weight % that GC/MS analyzes the aromatic hydrocarbons weight content that shows in the stable hydrocarbon.
Embodiment 3
Present embodiment is used to illustrate and adopts the efficient sharp separation vacuum distillate of Solid-Phase Extraction method provided by the present invention and produce wherein stable hydrocarbon, aromatic hydrocarbons and glial component.
Take by weighing VGO in the sand (matter crude oil vacuum distillate in the Saudi Arabia, 350～540 ℃ of boiling ranges) sample 6g, be dissolved in the 90mL normal hexane; At solid-phase extraction column lower floor filling 50 gram ASG, upper strata filling 50 gram SG; Solid-phase extraction column is installed on the solid-phase extraction device that has pumped vacuum systems, with the wetting stationary phase of 100 ml n-hexanes, the hexane solution of above-mentioned oil sample is filled in the solid-phase extraction column, and control vacuum tightness makes the filling rate stabilization of solution in 10 ml/min; After the oil sample filling finishes, extract stable hydrocarbon with 140 ml n-hexanes flushing stationary phase, control vacuum tightness makes normal hexane flushing rate stabilization in 15 ml/min; With 180 milliliters of benzene flushing stationary phase, flushing speed is 40 ml/min, the aromatic hydrocarbons in the extraction distillate subsequently; To be filled with 40g then and be connected in the silicagel column bottom, with 100mL alcohol flushing stationary phase extraction glial component through the solid-phase extraction column of 4 hours neutral alumina of 400 ℃ of roastings.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, aromatic hydrocarbons and the hydrosol, weigh, obtain stable hydrocarbon sample 2.57 grams, aromatic hydrocarbons sample 3.05 grams, colloid 0.36 gram, loss 0.02 gram; It is 0.8 weight % that GC/MS analyzes the aromatic hydrocarbons weight content that shows in the stable hydrocarbon.
Embodiment 4
Present embodiment is used for explanation to be adopted the efficient sharp separation deasphalted oil of Solid-Phase Extraction method provided by the present invention (DAO) and produces wherein stable hydrocarbon, aromatic hydrocarbons and glial component.
Take by weighing DAO sample 10g, be dissolved in the 120mL normal hexane; At solid-phase extraction column lower floor filling 70 gram ASG, upper strata filling 30 gram SG; Solid-phase extraction column is installed on the solid-phase extraction device that has pumped vacuum systems, with the wetting stationary phase of 100 ml n-hexanes, the hexane solution of above-mentioned oil sample is filled in the solid-phase extraction column, and control vacuum tightness makes the hexane solution discharge rate be stabilized in 10 ml/min; After the oil sample filling finishes, extract stable hydrocarbon with 180 ml n-hexanes flushing stationary phase, control vacuum tightness makes normal hexane flushing rate stabilization in 10 ml/min; With 220 milliliters of benzene flushing stationary phase, flushing speed is 40 ml/min, the aromatic hydrocarbons in the extraction distillate subsequently; To be filled with 40g then and be connected in the silicagel column bottom, with 140mL alcohol flushing stationary phase extraction glial component through the solid-phase extraction column of 4 hours neutral aluminas of 400 ℃ of roastings.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, aromatic hydrocarbons and the hydrosol, weigh, obtain stable hydrocarbon sample 4.38 grams, aromatic hydrocarbons sample 3.55 grams, colloid 2.03 grams, loss 0.04 gram; It is 0.8 weight % that GC/MS analyzes the aromatic hydrocarbons weight content that shows in the stable hydrocarbon.
Comparative Examples 1
This Comparative Examples is used to illustrate and adopts not the silica gel of load silver ion to carry out the isolating situation of the conventional Solid-Phase Extraction of vacuum distillate.
Take by weighing grand celebration vacuum distillate (510～570 ℃ of boiling ranges) sample 10g, be dissolved in the 150mL normal hexane.Solid-Phase Extraction process solvent for use is than identical with embodiment 2 with flushing speed, just stationary phase is replaced with 100 gram SG, obtain stable hydrocarbon 7.43 grams, aromatic hydrocarbons 1.82 grams, colloid 0.71 gram, loss 0.04 gram, it is 4.2 weight % that GC/MS analyzes the aromatic hydrocarbons weight content that shows in the stable hydrocarbon, shows to have than polyaromatic to enter into stable hydrocarbon.
By embodiment 2～4 and Comparative Examples 1 as seen, the inventive method quantity of sample handling is bigger, separation efficiency is higher, and the aromaticity content in the stable hydrocarbon generally is no more than 1 weight %, can be used for the efficient sharp separation of vacuum distillate, deasphalted oil, hydrotreatment wet goods raw material.
Claims (14)
1. the method that Solid-Phase Extraction is separated heavy oil comprises the step that heavy oil is contacted with stationary phase, it is characterized in that described stationary phase comprises the silicon-dioxide and the aluminum oxide of load silver ion.
2. according to the described method of claim 1, it is characterized in that, is benchmark with the weight of the silicon-dioxide of load silver ion, and the silicon-dioxide of described load silver ion comprises the silver salt of 1～40 weight % and the silicon-dioxide of 60～99 weight %.
3. according to the described method of claim 2, it is characterized in that the silicon-dioxide of described load silver ion comprises the silver salt of 5～20 weight %.
4. according to each described method of claim 1～3, 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 milliliter/gram.
5. according to the described method of claim 4, the specific surface area of described silicon-dioxide is 450～750 meters
2/ gram, pore volume be 0.35～0.55 milliliter/gram, the aperture be the hole of 20～35 nanometers account for total pore volume 40～70%.
6. according to claim 2 or 3 described methods, it is characterized in that described silver salt is a Silver Nitrate.
7. according to the described method of claim 1, it is characterized in that, comprise the silicon-dioxide of the load silver ion of 40～90 weight % in the described stationary phase, the aluminum oxide of 10～60 weight %.
8. according to claim 1 or 7 described methods, it is characterized in that described stationary phase also contains the not silicon-dioxide of load silver ion, the silicon-dioxide proportion of load silver ion is not no more than 50%.
9. in accordance with the method for claim 8, it is characterized in that the silicon-dioxide of described load silver ion is silica gel, the specific surface area of described silica gel is 200～750 meters
2/ gram, pore volume are 0.35～0.90 milliliter/gram.
10. according to the described method of claim 8, 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 contacted with the silicon-dioxide of load silver ion not earlier, contacts with the silicon-dioxide of load silver ion then.
11., it is characterized in that the part by weight of stationary phase and heavy oil is 3～30: 1 according to the described method of claim 1.
12. according to claim 1,2,3,7 or 11 described methods, it is characterized in that, may further comprise the steps: use C
5～C
7The wetting stationary phase that comprises the silicon-dioxide of load silver ion of stable hydrocarbon makes to be dissolved in C then
5～C
7Heavy oil in the stable hydrocarbon contacts with stationary phase, uses C
5～C
7Stable hydrocarbon flushing stationary phase extracts the stable hydrocarbon in the heavy oil, extracts aromatic hydrocarbons in the heavy oil with benzene or dichloromethane rinse stationary phase then, goes out to residue in colloid in the stationary phase with benzene-ethanol or alcohol flushing again.
13., it is characterized in that described C according to the described method of claim 12
5～C
7Stable hydrocarbon is one or more in Skellysolve A, normal hexane, normal heptane or the sherwood oil.
14., it is characterized in that described heavy oil is vacuum distillate, long residuum, vacuum residuum, deasphalted oil, catalytically cracked oil, hydrotreatment oil according to the described method of claim 1.
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| CN108469471A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | The solid-phase extraction column and application process of different Group Components in separating synthetic gas olefine reaction oil-phase product |
| CN109647000A (en) * | 2019-02-15 | 2019-04-19 | 中国石油大学(北京) | A kind of organic matter auxiliary separating device and organic matter assist separation method |
| CN109839448A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | The method of phenolic compound in solid-phase extraction column and Solid phase extraction separation diesel oil |
| WO2022068174A1 (en) * | 2020-09-29 | 2022-04-07 | 上海兖矿能源科技研发有限公司 | Method for determining composition and content of aromatic hydrocarbons in high-temperature fischer-tropsch synthetic oil |
| CN114563516A (en) * | 2020-11-27 | 2022-05-31 | 中国石油天然气股份有限公司 | Method for determining wax oil group composition |
-
2009
- 2009-11-27 CN CN 200910249825 patent/CN102079987B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| AMERICAN SOCIETY OF TESTING MATERIALS: ""Standard Test Method for Separation of Representative Aromatics and Nonaromatics Fractions of High-Boiling Oils by Elution Chromatography"", 《ASTM D2549》 * |
| 陶学明等: ""高效液相色谱法测定柴油族组成"", 《色谱》 * |
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