CN102079987B - Method for separating heavy oils by solid phase extraction - Google Patents
Method for separating heavy oils by solid phase extraction Download PDFInfo
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- CN102079987B CN102079987B CN 200910249825 CN200910249825A CN102079987B CN 102079987 B CN102079987 B CN 102079987B CN 200910249825 CN200910249825 CN 200910249825 CN 200910249825 A CN200910249825 A CN 200910249825A CN 102079987 B CN102079987 B CN 102079987B
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- 239000000295 fuel oil Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000002414 normal-phase solid-phase extraction Methods 0.000 title claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 166
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 71
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 66
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 42
- 239000000084 colloidal system Substances 0.000 claims abstract description 25
- 229960001866 silicon dioxide Drugs 0.000 claims description 89
- 235000012239 silicon dioxide Nutrition 0.000 claims description 69
- 239000004215 Carbon black (E152) Substances 0.000 claims description 60
- 229930195733 hydrocarbon Natural products 0.000 claims description 60
- 150000002430 hydrocarbons Chemical class 0.000 claims description 60
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 48
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 35
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 30
- 239000003921 oil Substances 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 24
- 229910002027 silica gel Inorganic materials 0.000 claims description 21
- 239000000741 silica gel Substances 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 19
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 16
- 238000011010 flushing procedure Methods 0.000 claims description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 12
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000284 extract Substances 0.000 claims description 8
- 238000009736 wetting Methods 0.000 claims description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- -1 silver ions Chemical class 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 description 33
- 238000011049 filling Methods 0.000 description 13
- 230000002518 glial effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000012545 processing Methods 0.000 description 9
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
一种采用固相萃取分离重油分的方法，包括将重油与固定相接触的步骤，其中所述的固定相包括负载银离子的二氧化硅和氧化铝。该方法通过固相萃取分离将重油分离为饱和烃、芳烃和胶质三个部分并制备饱和烃、芳烃和胶质组分，可以兼顾分离效率和处理量，实现重油的高效快速分离。A method for separating heavy oil by solid phase extraction, comprising the step of contacting the heavy oil with a stationary phase, wherein the stationary phase includes silica and alumina loaded with silver ions. The method separates heavy oil into saturated hydrocarbons, aromatic hydrocarbons and colloids through solid phase extraction separation and prepares saturated hydrocarbons, aromatics and colloid components, which can take into account separation efficiency and throughput, and realize efficient and rapid separation of heavy oil.
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 carries out analysis and the reactivity worth research of more deep (molecular level and quasi-molecule level) for different components.Thereby sepn process is proposed two aspects requirements: (1) separation efficiency is high, can prepare the high purity sample to satisfy 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 satisfy subsequent reactions and evaluation experimental needs.
Heavy oil being carried out component separate, is mainly to form by hydrocarbon system to separate, as exactly residual oil being separated into stable hydrocarbon, aromatic hydrocarbons, four components of resin and asphalt 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 first being settled out bituminous matter with normal heptane, 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 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, eight component separation methods of heavy colloid, but sepn process is more complicated, application also too late four component method is 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 that generally adopts 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 be connected bottom bulb tube 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 the middle level is silicon oxide, and the upper strata is bauxitic clay.Processing sample size is 2～10 grams, first 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, 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 that Solid-Phase Extraction and MS VGO hydrocarbon system form, 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 satisfy subsequent reactions and evaluation experimental to the requirement of sample size; Perhaps separation efficiency is relatively poor, has more serious crossed contamination between stable hydrocarbon and 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 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 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 than existing methods higher separation efficiency and larger quantity of sample handling, both can be used as a kind of separation method, and be used for satisfying the subsequent analysis technology to the requirement of sample purity; Can be used as again a kind of quick method for preparing contained hydrocarbon sample in heavy oil, for subsequent reactions and evaluation experimental provide necessary sample size.Contain aluminum oxide in described stationary phase, in the process with benzene-ethanol or alcohol flushing colloid, can active adsorption by the silver ions on silicon-dioxide of being carried on of ethanol elution, avoid silver ions to the pollution of 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 processed 15 gram grand celebration vacuum distillates (510～570 ℃ of cuts) through 400 ℃ of roastings neutral alumina of 4 hours, 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, lose 0.05 gram, it is 0.5% that GC/MS analyzes the aromatic hydrocarbons weight content that shows in stable hydrocarbon, and adopt 100g through 150 ℃ of dryings 4 hours but the silica gel treatment 10 gram grand celebration vacuum distillates (510～570 ℃ of cuts) of load silver ion not with reference to ordinary method, control identical solvent ratio and rinse 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 stable hydrocarbon, shows to have than polyaromatic to enter into stable hydrocarbon.
Embodiment
In Solid phase extraction separation heavy oil method provided by the invention, 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, take the gross weight of the silicon-dioxide of described load silver ion as benchmark, comprise the silicon-dioxide of 1～40 % by weight silver salt, 60～99 % by weight in the silicon dioxide compositions of described load silver ion.Described silver salt is preferably Silver Nitrate, and namely 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 % by weight, and silicon-dioxide accounts for 60～99 % by weight; Preferably, it is 5～20 % by weight that Silver Nitrate accounts for, and silicon-dioxide accounts for 80～95 % by 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 % by weight that described dipping makes Silver Nitrate shared ratio in the silicon-dioxide of load Silver Nitrate, preferred 5～20 % by weight.Silicon-dioxide after dipping silver salt (Silver Nitrate) under 100～200 ℃ dry 1～30 hour, preferably under 120～180 ℃ dry 2～10 hours, the silicon-dioxide of dried load Silver Nitrate was positioned in 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 ml/g, and preferred, described silicon-dioxide specific surface area is 450～750 meters
2/ gram, pore volume are 0.35～0.55 ml/g, 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.
In Solid phase extraction separation heavy oil method provided by the invention, described stationary phase comprises silicon-dioxide and the aluminum oxide of load silver ion, take the weight of stationary phase as benchmark, in stationary phase, the silicon-dioxide of load silver ion accounts for 20～99 % by weight, and aluminum oxide accounts for 1～80 % by weight; Preferably, the silicon-dioxide of load silver ion accounts for 40～90 % by weight, and aluminum oxide accounts for 10～60 % by weight.Described aluminum oxide is neutral alumina, and this aluminum oxide is preferable over 200～800 ℃ of lower roastings 1～8 hour, more preferably 300～500 ℃ of lower roastings 2～4 hours.
In Solid phase extraction separation heavy oil method provided by the invention, the silicon-dioxide of aluminum oxide and load silver ion can be seated in same extraction equipment, also can fill in different equipment.When filling in same extraction equipment for example in column extractor the time, in stationary phase, the aluminum oxide proportion is 10～60 % by weight, preferred 30～50 % by weight, and the silicon-dioxide of load silver ion accounts for 40～90 % by weight; Described aluminum oxide preferably fills in the bottom of the silicon-dioxide of load silver ion, and during extraction, at first the solvent of solvent or dissolving heavy oil contacts with the silicon-dioxide of load silver ion, then contacts with aluminum oxide.Preferably, it is that aluminum oxide fills in different extraction equipments from the silicon-dioxide of load silver ion that described aluminum oxide fills in independent solid-phase extraction column, in stationary phase, the aluminum oxide proportion is 10～60 % by weight, and the silicon-dioxide of load silver ion accounts for 40～90 % by weight; 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, then extract stable hydrocarbon and aromatic hydrocarbons, after the column extractor that will load aluminum oxide before adopting benzene-ethanol or alcohol flushing colloid is series at the column extractor of silicon-dioxide of filling load silver ion, to reduce the resistance in flushing stable hydrocarbon and aromatic hydrocarbons process; Described C
5～C
7Stable hydrocarbon can be a kind of or its mixture in Skellysolve A, normal hexane, normal heptane, sherwood oil, is preferably normal hexane; During aromatic component in described flushing stationary phase extraction heavy oil, solvent for use is benzene; During glial component in described flushing stationary phase extraction heavy oil, solvent for use is ethanol.
In heavy oil separation method provided by the invention, described stationary phase also can contain 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.Described silicon-dioxide can mix with the silicon-dioxide of load silver ion use or layering is used, preferably silicon-dioxide is 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 the silicon-dioxide of process load silver ion, to save the consumption of load silver ion silicon-dioxide; In addition, when processing 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.
Heavy oil separation method provided by the invention comprises that the stationary phase that will comprise the silicon-dioxide of load silver ion fills in solid-phase extraction column, uses C
5～C
7Then stable hydrocarbon wetting (refer to the solvent of wetting use is added in column extractor, think wetting until it when the column extractor bottom oozes and complete) stationary phase 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; Use C after adding heavy oil
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; Go out with benzene-ethanol or ethanol the colloid that residues in stationary phase again.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; During aromatic component in described flushing stationary phase extraction heavy oil, rinse solvent used is 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
7During saturated hydrocarbon solvent dilution dissolving, the volume ratio of solvent and heavy oil is 5～30: 1, is preferably 10～20: 1; Use C
5～C
7When stable hydrocarbon rinses stable hydrocarbon in stationary phase extraction heavy oil, solvent and heavy oil volume ratio are 10～30: 1, are 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.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
7During saturated hydrocarbon solvent dilution dissolving, solvent and heavy oil volume ratio are 5～30: 1, are preferably 10～20: 1; Use C
5～C
7When stable hydrocarbon rinses stable hydrocarbon in stationary phase extraction heavy oil, solvent and heavy oil volume ratio are 10～30: 1, are 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; 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 described Solid phase extraction separation process, use C
5～C
7When stable hydrocarbon rinses stable hydrocarbon in stationary phase extraction heavy oil, solvent washing speed is 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; During with benzene-ethanol or alcohol flushing colloid, solvent washing speed is preferably 20～50 ml/min, more preferably 30～40 ml/min.During glial component in described flushing stationary phase extraction heavy oil, solvent for use is ethanol.
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 heavy oil.The saturated hydrocarbon solution that Solid phase extraction separation obtains and aromatic hydrocarbons solution solvent evaporated in water-bath obtain stable hydrocarbon, aromatic hydrocarbons and glial component, and weighing obtains stable hydrocarbon in heavy oil, aromatic hydrocarbons and gum level, and surplus is loss.
Heavy oil separation method provided by the invention, being applicable to heavy oil separates, described heavy oil is for example deasphalted oil of heavy 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.
The present invention is further described with embodiment for the below, 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 aperture be the hole of 20～35 nanometers account for total pore volume 56%.AgNO
3For the high-purity chemical reagent factory in Hunan is produced, 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 embodiment instrument 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 case temperature kept 2 minutes at 60 ℃, then was warming up to 350 ℃ with 60 ℃ of/minute speed, 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 used for illustrating 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, obtain activated silica gel standby, be numbered SG.Be positioned over deposit in moisture eliminator standby.
Take 60.9g AgNO
3Be dissolved in wiring solution-forming in 400g water; Take 400g silica gel, silica gel is joined the AgNO for preparing
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 is numbered ASG, the Silver Nitrate charge capacity is 13.2 % by weight.Being positioned in moisture eliminator lucifuge deposits standby.
Embodiment 2
The present embodiment is used for explanation to be adopted the efficient sharp separation vacuum distillate of Solid-Phase Extraction method provided by the present invention and produces wherein stable hydrocarbon, aromatic hydrocarbons and glial component.
Take 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, lower same); Solid-phase extraction column is arranged on solid-phase extraction device with pumped vacuum systems, with the 100 wetting stationary phase of ml n-hexane (ASG); The hexane solution of above-mentioned oil sample is filled in solid-phase extraction column, controls vacuum tightness and make the rate stabilization of solution filling in 15 ml/min; After the oil sample filling is complete, rinses stationary phase with 300 ml n-hexanes and extract stable hydrocarbon, control vacuum tightness and make normal hexane rinse rate stabilization in 15 ml/min; Rinse stationary phase with 350 milliliters of benzene subsequently, rinsing speed is 30 ml/min, the aromatic hydrocarbons in the extraction distillate; Then will be filled with 50g and be connected in the silicagel column bottom through the solid-phase extraction column of 4 hours neutral aluminas of 400 ℃ of roastings, with 120mL alcohol flushing stationary phase extraction glial component.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, aromatic hydrocarbons and 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 % by weight that GC/MS analyzes the aromatic hydrocarbons weight content that shows in stable hydrocarbon.
Embodiment 3
The present embodiment is used for explanation to be adopted the efficient sharp separation vacuum distillate of Solid-Phase Extraction method provided by the present invention and produces wherein stable hydrocarbon, aromatic hydrocarbons and glial component.
Take VGO in sand (matter crude oil vacuum distillate in Saudi Arabia, 350～540 ℃ of boiling ranges) sample 6g, be dissolved in the 90mL normal hexane; At the solid-phase extraction column filling 50 gram ASG of lower floor, upper strata filling 50 gram SG; Solid-phase extraction column is arranged on solid-phase extraction device with pumped vacuum systems, with the 100 wetting stationary phase of ml n-hexane, the hexane solution of above-mentioned oil sample is filled in solid-phase extraction column, controls vacuum tightness and make the filling rate stabilization of solution in 10 ml/min; After the oil sample filling is complete, rinses stationary phase with 140 ml n-hexanes and extract stable hydrocarbon, control vacuum tightness and make normal hexane rinse rate stabilization in 15 ml/min; Rinse stationary phase with 180 milliliters of benzene subsequently, rinsing speed is 40 ml/min, the aromatic hydrocarbons in the extraction distillate; Then will be filled with 40g and be connected in the silicagel column bottom through the solid-phase extraction column of 400 ℃ of roastings neutral alumina of 4 hours, with 100mL alcohol flushing stationary phase extraction glial component.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, aromatic hydrocarbons and 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 % by weight that GC/MS analyzes the aromatic hydrocarbons weight content that shows in stable hydrocarbon.
Embodiment 4
The 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 DAO sample 10g, be dissolved in the 120mL normal hexane; At the solid-phase extraction column filling 70 gram ASG of lower floor, upper strata filling 30 gram SG; Solid-phase extraction column is arranged on solid-phase extraction device with pumped vacuum systems, with the 100 wetting stationary phase of ml n-hexane, the hexane solution of above-mentioned oil sample is filled in solid-phase extraction column, controls vacuum tightness and make the hexane solution discharge rate be stabilized in 10 ml/min; After the oil sample filling is complete, rinses stationary phase with 180 ml n-hexanes and extract stable hydrocarbon, control vacuum tightness and make normal hexane rinse rate stabilization in 10 ml/min; Rinse stationary phase with 220 milliliters of benzene subsequently, rinsing speed is 40 ml/min, the aromatic hydrocarbons in the extraction distillate; Then will be filled with 40g and be connected in the silicagel column bottom through the solid-phase extraction column of 4 hours neutral aluminas of 400 ℃ of roastings, with 140mL alcohol flushing stationary phase extraction glial component.
After adopting the solvent in rotatory evaporator evaporate to dryness stable hydrocarbon, aromatic hydrocarbons and 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 % by weight that GC/MS analyzes the aromatic hydrocarbons weight content that shows in stable hydrocarbon.
Comparative Examples 1
This Comparative Examples is used for explanation and adopts the silica gel of load silver ion not to carry out the situation of the conventional Solid phase extraction separation of vacuum distillate.
Take 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, lose 0.04 gram, it is 4.2 % by weight that GC/MS analyzes the aromatic hydrocarbons weight content that shows in 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 larger, separation efficiency is higher, and the aromaticity content in stable hydrocarbon generally is no more than 1 % by weight, can be used for the efficient sharp separation of vacuum distillate, deasphalted oil, hydrotreatment wet goods raw material.
Claims (14)
1. the method for a Solid phase extraction separation heavy oil, comprise the step that heavy oil is contacted with stationary phase, it is characterized in that, described stationary phase comprises silicon-dioxide and the aluminum oxide of load silver ion, take the weight of the silicon-dioxide of load silver ion as benchmark, the silicon-dioxide of described load silver ion comprises the silver salt of 1～40 % by weight and the silicon-dioxide of 60～99 % by weight; The silicon-dioxide of described load silver ion adopts the method preparation of silver salt solution impregnation of silica, and described silicon-dioxide is silica gel.
2. according to the described method of claim 1, it is characterized in that, take the weight of the silicon-dioxide of load silver ion as benchmark, the silicon-dioxide of described load silver ion comprises the silver salt of 1～40 % by weight and the silicon-dioxide of 60～99 % by weight, in stationary phase, the silicon-dioxide of load silver ion accounts for 20～99 % by weight, and aluminum oxide accounts for 1～80 % by 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 % by weight.
4. according to the described method of claim 1～3 any one, 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.
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 are 0.35～0.55 ml/g, the aperture be the hole of 20～35 nanometers account for total pore volume 40～70%.
6. according to the described method of claim 2 or 3, it is characterized in that, described silver salt is Silver Nitrate, and the volume of dipping solution is 1～10 times of used silica gel pore volume, the silicon-dioxide of dipping after Silver Nitrate under 100～200 ℃ dry 1～30 hour.
7. according to the described method of claim 1, it is characterized in that, described stationary phase comprises the silicon-dioxide of the load silver ion of 40～90 % by weight, the aluminum oxide of 10～60 % by weight.
8. according to the described method of claim 1 or 7, it is characterized in that, described stationary phase also contains the not silicon-dioxide of load silver ion, and 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, and the specific surface area of described silica gel is 200～750 meters
2/ gram, pore volume are 0.35～0.90 ml/g.
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 first contacted with the silicon-dioxide of load silver ion not, then contacts with the silicon-dioxide of load silver ion.
11. according to the described method of claim 1, it is characterized in that, the part by weight of stationary phase and heavy oil is 3～30: 1.
12. according to claim 1,2,3,7 or 11 described methods, it is characterized in that, comprise the following steps: use C
5～C
7Then the wetting stationary phase that comprises the silicon-dioxide of load silver ion of stable hydrocarbon makes 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 stable hydrocarbon in heavy oil, then extracts aromatic hydrocarbons in heavy oil with benzene or dichloromethane rinse stationary phase, then goes out to residue in colloid in stationary phase with benzene-ethanol or alcohol flushing.
13. according to the described method of claim 12, 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; Use C
5～C
7It is 5～30 ml/min that stable hydrocarbon rinses speed when rinsing stable hydrocarbon in stationary phase extraction heavy oil; Rinsing speed during with the aromatic hydrocarbons in benzene or dichloromethane rinse stationary phase extraction heavy oil is 20～50 ml/min; Rinsing speed during with benzene-ethanol or alcohol flushing colloid is 20～50 ml/min.
14. according to the described method of claim 1, it is characterized in that described heavy oil is vacuum distillate, long residuum, vacuum residuum, deasphalted oil, catalytically cracked oil, hydrotreatment oil.
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| CN102757810B (en) * | 2012-06-28 | 2014-09-24 | 神华集团有限责任公司 | Method for separating component from direct-coal-liquefaction full distillate oil by utilizing solid-phase extraction method |
| CN104119950B (en) * | 2013-04-25 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of from heavy oil aromatic component the method for aromatics separation and sulfur-bearing aromatic hydrocarbons |
| CN104208905B (en) * | 2013-06-05 | 2016-05-11 | 中国石油天然气股份有限公司 | A kind of solid-phase extraction cartridge loaded with silver ions and its preparation and application |
| CN104345103B (en) * | 2013-07-29 | 2016-04-27 | 中国石油化工股份有限公司 | The separated island form method of aromatic hydrocarbons and sulfur-bearing aromatic hydrocarbons in heavy oil aromatic component |
| CN104749298B (en) * | 2013-12-30 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of solid-phase extraction column and application process that separates different hydrocarbon components in diesel oil |
| CN104084176B (en) * | 2014-06-23 | 2016-02-17 | 镇江出入境检验检疫局检验检疫综合技术中心 | Rich water chromatographic stationary phases of a kind of silver nano-grain-lactose bonded silica gel and preparation method thereof |
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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 |
| CN105778981B (en) * | 2014-12-23 | 2017-09-01 | 中国石油天然气股份有限公司 | Method for Enriching Nitrogenous Compounds in Diesel Oil by Solid Phase Extraction |
| CN106467759B (en) * | 2015-08-21 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of heavy oil pretreatment and the combined method of catalytic cracking |
| CN106467760B (en) * | 2015-08-21 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of processing of heavy oil method |
| CN106947515B (en) * | 2016-01-07 | 2019-01-29 | 中国石油化工股份有限公司 | The method of different type compound in Solid phase extraction separation crude oil or heavy oil |
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