CN1621830A - Method for analyzing composition of alcohol-containing gasoline and alcohol adsorption material used thereby - Google Patents
Method for analyzing composition of alcohol-containing gasoline and alcohol adsorption material used thereby Download PDFInfo
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- CN1621830A CN1621830A CN 200310115505 CN200310115505A CN1621830A CN 1621830 A CN1621830 A CN 1621830A CN 200310115505 CN200310115505 CN 200310115505 CN 200310115505 A CN200310115505 A CN 200310115505A CN 1621830 A CN1621830 A CN 1621830A
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- alcohol
- trap
- pure
- alkene
- quality
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title abstract description 3
- 125000003158 alcohol group Chemical group 0.000 title abstract 2
- 238000001179 sorption measurement Methods 0.000 title description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 57
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000012159 carrier gas Substances 0.000 claims abstract description 26
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003795 desorption Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 2
- 239000001110 calcium chloride Substances 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 abstract 1
- 235000011148 calcium chloride Nutrition 0.000 abstract 1
- 229930195734 saturated hydrocarbon Natural products 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- -1 tert-pentyl alcohols Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229940094933 n-dodecane Drugs 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 108010063955 thrombin receptor peptide (42-47) Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical group CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GCFHZZWXZLABBL-UHFFFAOYSA-N ethanol;hexane Chemical compound CCO.CCCCCC GCFHZZWXZLABBL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003269 fluorescent indicator Substances 0.000 description 1
- 210000003918 fraction a Anatomy 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000148 multi-dimensional chromatography Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001073 sample cooling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The multidimensional gas chromatographic process of analyzing the composition of alcohol containing gasoline includes injecting gasoline sample into multidimensional gas chromatograph to separate aliphatic hydrocarbon and arene from alcohol, leading the aliphatic hydrocarbon flowing out from the polar chromatographic column to olefin well for adsorbing olefin therein, detecting the saturated hydrocarbon from the olefin well, detaching olefin well from the carrier gas flow path, detecting benzene in alcohol well, reverse blowing the polar chromatographic column with carrier gas, adsorbing alcohol in the alcohol well, detecting arene, desorbing and detecting olefin and desorbing and detecting alcohol. The alcohol adsorbing material includes CaCl2 20-50 wt% and diatomite as carrier 50-80 wt%. The said process can detect hydrocarbon, benzene, arene, olefin and alcohol content in gasoline effectively.
Description
Technical field
The present invention analyzes the method that gasoline is formed for a kind of multidimensional gas chromatographic that adopts, and specifically, is a kind of method that alcohol blended fuel is formed of analyzing.
Background technology
Along with the raising day by day of environmental protection requirement, the automobile exhaust emission standard that country formulates is more and more stricter.Therefore, require the refinery to produce premium-type gasoline, to reduce emission of harmful substances.New unleaded gasoline standard (GB17930-1999) regulation arene content≤40 (volume) % that formulates of China, olefin(e) centent≤35 (volume) %, sulfur content≤0.08 (volume) %, benzene content≤2.5 (volume) %.
For reaching above-mentioned standard, improve the burning performance of gasoline simultaneously, normal oxygenatedchemicals such as methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) (ETBE), tert pentyl methyl ether (TAME), Di Iso Propyl Ether (DIPE), methyl alcohol, ethanol, isopropyl alcohol, n-propanol, isobutyl alcohol, the tert-butyl alcohol, sec-butyl alcohol, normal butyl alcohol and the tert-pentyl alcohols (tertiary pentyl alcohol) etc. of adding, wherein Chang Yong adjuvant is MTBE and ethanol.
In order to control the quality of vehicle-use alcohol gasoline, the GB18351-2001 regulation is according to alkene, arene content in fluorescent indicator adsorption method (FIA) the mensuration gasoline of GB/T 11132; Adopt vapor-phase chromatography according to Sinopec standard SH/T0663-1998 (equivalence margin method ASTM D4815-89), switch the separation oxygenatedchemicals by the twin columns valve, detect the content of pure and mild other oxygenatedchemicals again by thermal conductivity detector (TCD) or flame ionic detector; Benzene content is measured according to SH/T 0693 (equivalence margin method ASTM D3606).Pure content also can utilize gas chromatography and oxygen selective fid detector to measure according to the method for ASTM D5599 in the gasoline.
ASTM D6293-98 adopts the multidimensional gas chromatographic method to measure oxygenatedchemicals, alkane, alkene, naphthenic hydrocarbon, aromatic hydrocarbons in the low olefinic fuel.This method is provided with the adsorption trap of various materials in the carrier gas gas circuit, comprise pure trap, polar column, non-polar column, alkene trap, molecular sieve column, ether-alcohol-aromatic hydrocarbons trap and a hydrogenation catalyst section, can be used for measuring the content of alkane in the gasoline, alkene, benzene, aromatic hydrocarbons, ether, alcohol, but its operating process is too complicated, and be higher than 13% gasoline for olefin(e) centent, need dilution to measure.
Summary of the invention
The purpose of this invention is to provide a kind of multidimensional gas chromatographic of using and analyze the method that alcohol blended fuel is formed, this method is easy and simple to handle, analysis time short.
Another object of the present invention provides and analyzes the used pure sorbing material of gasohol content in the said method.
Multidimensional gas chromatographic provided by the invention is analyzed the method that alcohol blended fuel is formed, comprise gasoline sample is injected multidimensional gas chromatograph, bring the polarity chromatographic column into by carrier gas, aliphatic hydrocarbon is separated with alcohol with aromatic hydrocarbons, the aliphatic hydrocarbon that will flow out from the polarity chromatographic column feeds alkene trap absorption alkene wherein, the stable hydrocarbon that will flow out from the alkene trap detects by detecting device, transfer valve makes the alkene trap break away from the carrier gas stream, by carrier gas the benzene in the polar column is carried by pure trap, entering detecting device detects, treat that benzene flows out fully from pure trap after, with carrier gas blowback polarity chromatographic column, make aromatic hydrocarbons and alcohol by pure trap absorption alcohol wherein, aromatic hydrocarbons enters detecting device by pure trap and detects, and transfer valve makes the alkene trap enter the carrier gas stream, heats up to make the alkene desorption in the alkene trap enter the detecting device detection, after treating that alkene flows out fully, make pure desorption wherein enter the detecting device detection pure trap intensification.
The inventive method adds pure adsorption trap in multidimensional gas chromatograph, make the alcohol in the gasoline fraction to be adsorbed by pure trap at a lower temperature, whole desorption from pure trap under higher temperature, and described pure trap adsorption temp and alkene desorption temperature are complementary, and the separation of the alcohol in the gasoline can not influenced the mensuration that other hydrocarbon systems form.Thereby can fast and effeciently analyze the content of stable hydrocarbon in the alcohol blended fuel, benzene, aromatic hydrocarbons, alkene and alcohol.
The used pure sorbing material of said method comprises the CaCl of 3.0-60.0 quality %
2Carrier zeyssatite with 40.0-97.0 quality %.This material can be at a certain temperature the effective alcohol, particularly ethanol in the adsorbed gasoline component, and other component not have influence substantially, and can be at a certain temperature with the alcohol release of absorption, so that analyze its content.
Description of drawings
Fig. 1 analyzes the mode of operation synoptic diagram of each component concentration of ethanol petrol for the present invention adopts multidimensional gas chromatographic.
Fig. 2 measures the gas chromatogram of each component gained of alcohol blended fuel for the inventive method.
Embodiment
The inventive method adopts multi-dimensional chromatograph to analyze the alcohol blended fuel composition, make alcohol blended fuel pass through the polarity chromatographic column earlier, aliphatic hydrocarbon wherein, benzene, aromatic hydrocarbons and alcohol separate in polar column successively, described aliphatic hydrocarbon component, comprise stable hydrocarbon and alkene, do not adsorbed by polar column and enter the alkene trap from wherein flowing out, the alkene in the aliphatic hydrocarbon is adsorbed by the alkene trap, and stable hydrocarbon flows out the alkene trap and enters detecting device and measure its content.Afterwards, make the alkene trap break away from the carrier gas gas circuit, the benzene that adsorbs in the polarity chromatographic column is blown out with carrier gas, and by measuring its content behind the pure trap.And then, make wherein aromatic component and alcohol pass through pure trap, selective adsorption alcohol with carrier gas blowback polarity chromatographic column.The aromatic hydrocarbons that is flowed out by pure trap enters detecting device, measures its content.After treating that aromatic component all flows out, the temperature of rising alkene trap is incorporated it into carrier gas gas circuit, makes the alkene desorption that is adsorbed in the alkene trap, is carried into detecting device by carrier gas, measures the content of alkene.Again pure trap temperature is raise at last,, detect pure content after making the pure desorption that is adsorbed on wherein with carrier gas blowback alcohol trap.
In the said method, the polarity chromatographic column places in the master control temperature post case, and alkene trap and pure trap place in the auxilliary temperature control post case.The temperature independent regulation of master control temperature post case and auxilliary temperature control post case.The operating temperature of master control temperature post case, promptly the operating temperature of polarity chromatographic column is 90-115 ℃, preferred 100-110 ℃.Auxilliary temperature control post oven temperature, degree is regulated as required, when wherein alkene trap adsorbs olefins, its operating temperature is that the alkene adsorption temp is 80-170 ℃, when pure trap absorption alcohol, the temperature of the i.e. alcohol absorption of auxilliary temperature control post oven temperature, degree is 80-180 ℃, preferred 130-180 ℃; When carrying out the alkene desorption, auxilliary temperature control post oven temperature, degree is that the alkene desorption temperature is 180-240 ℃, and when carrying out pure desorption, the temperature that auxilliary control oven temperature, degree is pure desorption is 240-260 ℃.
In the inventive method, the multidimensional gas chromatograph structure of employing and detail operations replace but balance columns wherein is pure trap referring to CN2520508Y, and operating process is basic identical.
The used carrier gas of the present invention is an inert gas, can be helium, argon gas and nitrogen, preferred nitrogen.Used detecting device is a flame ionic detector in the chromatograph.
The used pure sorbing material of pure trap in the inventive method comprises the CaCl of 3.0-60.0 quality %
2With the carrier zeyssatite of 40.0-97.0 quality %, CaCl
2The preferred 20-50 quality of content %, the preferred 50-80 quality of vector contg %.
Described zeyssatite is selected from red zeyssatite, white diatomite or the zeyssatite after pickling, alkali cleaning, glazing or alkylation are handled.The SiO that contains 60-95 quality % in the zeyssatite
2, 3-17 quality % Al
2O
3, 0.5-4 quality % Fe
2O
3, 0.1-1 quality % MgO.
In the present invention's alcohol sorbing material, the diatomaceous surface area of carrier is a 2-100 rice
2/ gram.Preferred 2-50 rice
2It is that the pore volume of 50-10000 nano-pore is 0.6-1.2 milliliter/gram that/gram, mercury intrusion method record the zeyssatite median pore diameter.
The preparation method of pure sorbing material of the present invention is: diatomite powder is mixed with suitable quantity of water, and water and diatomaceous mass ratio are 0.5-6.5: 1, stir, make bulk or other shape, as make bead, stripe shape, particle, dry then, baking temperature is 20-120 ℃.Dry back at 500-1000 ℃, preferred 600-900 ℃ of roasting.Block zeyssatite after the roasting is pulverized, made the particle of 0.18-0.30 millimeter, promptly obtain carrier.
Above-mentioned carrier is flooded with the anhydrous calcium chloride aqueous solution, dipping temperature is 20-100 ℃, preferred 20-50 ℃, preferred 0.5-3.0 of time hour, the concentration of flooding used calcium chloride water is 1.0-40 quality %, maceration extract is 0.9-2.0 with liquid/solid volume ratio of carrier during dipping: 1, and preferred 0.9-1.2: 1.Behind the dipping with solid 80-180 ℃ of drying, promptly make pure sorbing material preferred 0.5-6.0 hour drying time.
Describe the present invention in detail below in conjunction with accompanying drawing and measure the method that alcohol blended fuel is formed.Among Fig. 1, six-way valve is connected with the mode of chromatographic column by state 1, get gasoline sample injector 1 injecting chromatograph of 0.1 microlitre, through vaporizer 2 vaporizations, enter polarity chromatographic column 4 in the master control temperature post case 7 by six-way valve 3, control master control temperature post oven temperature, degree is 90-115 ℃, preferred 100-110 ℃, carbon number is less than 12 aliphatic hydrocarbon, benzene, aromatic hydrocarbons and alcohol adsorptive separation successively on polar column, aliphatic hydrocarbon wherein is not adsorbed, and flows into the alkene trap 5 in the auxilliary temperature control post case 8, the temperature of auxilliary temperature control post case is controlled to be 80-170 ℃, preferred 130-150 ℃, alkene is wherein adsorbed by the alkene trap, and stable hydrocarbon enters detecting device 10 and detects.After treating that stable hydrocarbon all flows out, switch six-way valve 3B position to state 2, make the alkene trap break away from the carrier gas gas circuit, the benzene in the polar column is carried through pure trap 6 by carrier gas and enters the detecting device detection.After treating that benzene all flows out, switch six-way valve 3 positions, the temperature of assisting temperature control post case is risen to 180 ℃ to state 3, with carrier gas polar column is formed recoil, make aromatic hydrocarbons in the polar column and alcohol by pure trap, and alcohol wherein is adsorbed in the pure trap, aromatic hydrocarbons then flows out pure trap and enters detecting device and detect.After treating that aromatic hydrocarbons all flows out, switch six-way valve 3B position again, will assist temperature control post case 8 temperature and transfer to 180-240 ℃, make the alkene desorption that is retained in the alkene trap, enter detecting device and detect to state 4.After treating that alkene all flows out, switch six-way valve 3 and 3B, will assist temperature control post case and be warming up to 240-260 ℃,, make the pure desorption that is retained in the pure trap, enter detecting device and detect with carrier gas blowback alcohol trap 6 to state 2.In The whole analytical process,, the temperature of temperature control clack box 9 should be remained on steady state value for preventing the sample cooling.
The gas chromatogram that the inventive method mensuration gasoline family forms as shown in Figure 2.Among Fig. 2, A
1Be stable hydrocarbon area fraction (appearance time 0.873-2.857 minute, down together), A
2Be benzene area fraction (3.282 minutes), A
3Be aromatic hydrocarbons area fraction (6.948 minutes), A
4Be alkene area fraction (12.298 minutes), A
5Be ethanol area fraction (16.182 minutes) that the quantitative test of each component adopts corrected area normalizing method to calculate, and promptly passes through the area fraction A of each family's component in the chromatogram
iRelative mass correction factor f with each family's component of measuring with correcting sample
i, calculate by following formula:
In formula (1) and (2), m and V are respectively the massfraction and the volume fraction of each component; d
iAverage density for each component in the chromatogram.
Below by example in detail the present invention, but the present invention is not limited to this.
In the example, the specific surface area of carrier is used absorption instrument (U.S. produces the ASAP2400 type), adopts low-temperature nitrogen adsorption method to measure; Pore size distribution uses mercury rate meter (Micromeritics Instrument Corp. U.S.A produces, 9320 types) to measure.Analyze oil product and form use multidimensional gas chromatograph (Research Institute of Petro-Chemical Engineering's development, MGC-8002 type), contain the twin columns case, fid detector, the flow velocity of carrier gas nitrogen are 45 ml/min.
The assay method of alcohol capture capacity is: (Beijing Analytical Instrument Factory produces to adopt gas chromatograph, model SP-3420), get 0.1 microlitre mixed alkanes (containing normal hexane, positive nonane, n-decane, n-undecane, n-dodecane) sample introduction, normal hexane retention time 0.17 minute, under 0.3 minute the temperature of n-dodecane retention time (pure adsorption temp), the ethanol hexane solution of sample introduction 15 quality %, the sample size when being 2.2 minutes with ethanol chromatographic peak leading edge time captures capacity as alcohol.
Example 1
The carrier of the used pure trap of preparation the inventive method.
Diatomite original ore powder (Linqu, Shandong, the prosperous chemical industry in mountain Ltd produce) and deionized water mixed stirring evenly by 1: 1 mass ratio, 110 ℃ of dryings 5 hours, 900 ℃ of roastings 7 hours place deionized water to cool off while hot.Filter, 110 ℃ of dryings 5 hours, pulverize with bowl mill, sieve into the particle of 0.18-0.3 millimeter, occur to there being powder with the deionized water washing, 120 ℃ of dryings 5 hours make carrier Z
1, its physico-chemical property sees Table 1.Table 1 median pore diameter, pore volume, pore size distribution adopt mercury intrusion method to measure, and specific surface area adopts low-temperature nitrogen adsorption method to measure.
Example 2
Method by example 1 prepares carrier Z
2, different is that sintering temperature is 950 ℃, the carrier Z that makes
2Physico-chemical property see Table 1.
Example 3
Method by example 1 prepares carrier Z
3, different is that sintering temperature is 1000 ℃, the carrier Z that makes
3Physico-chemical property see Table 1.
Example 4
Method by example 1 prepares carrier Z
4, different is that sintering temperature is 1150 ℃, the carrier Z that makes
4Physico-chemical property see Table 1.
Example 5
Method by example 1 prepares carrier Z
5, different is that sintering temperature is 800 ℃, the carrier Z that makes
5Physico-chemical property see Table 1.
Example 6
Method by example 1 prepares carrier Z
6, different is that the carrier after the roasting is cooled off in air, the carrier Z that makes
6Physico-chemical property see Table 1.
Example 7
Method by example 1 prepares carrier Z
7, different is to cool off in stove after the roasting, the carrier Z that makes
7Physico-chemical property see Table 1.
Example 8-19
Following examples preparation pure sorbing material of the present invention.
Get 0.7226 gram carrier, use a certain amount of CaCl
2The 2 ml water solution that are made in 25 ℃ the dipping 0.5 hour, liquid/solid volume ratio is 1: 1.Evaporating water obtained pure sorbing material with solid in 5 hours 120 ℃ of dryings.The used CaCl of each examples preparation alcohol sorbing material
2Content, pure sorbing material alcohol capture capacity, pure adsorption temp see Table 2.
Example 20
Get gasoline 0.1 microlitre that ethanol content is about 11.0 quality %, inject filling the present invention alcohol sorbing material A
5Multi-dimensional chromatograph in analyze, that chooses that 19 gasoline samples analyze the results are shown in Table 3.
Table 1
| Instance number | Bearer number | Specific surface area, rice 2/ gram | The pore volume in diameter 50-10000nm hole, milliliter/gram | Pore volume distribution, volume % | Can several apertures, nanometer |
| ????1 | ????Z 1 | ????12.0 | ????0.92 | ????98 | ????1000 |
| ????2 | ????Z 2 | ????5.0 | ????0.80 | ????92 | ????1100 |
| ????3 | ????Z 3 | ????3.1 | ????0.76 | ????97 | ????1200 |
| ????4 | ????Z 4 | ????1.0 | ????0.76 | ????97 | ????1700 |
| ????5 | ????Z 5 | ????25.0 | ????0.91 | ????90 | ????800 |
| ????6 | ????Z 6 | ????11.5 | ????0.88 | ????97 | ????1030 |
| ????7 | ????Z 7 | ????11.0 | ????0.86 | ????97 | ????1050 |
Annotate: pore volume distribution is that diameter accounts for the volume fraction that diameter is the 6-10000nm hole for the 50-10000nm hole.
Table 2
| Instance number | Alcohol trap material numbering | Bearer number | ??CaCl 2Consumption, gram | Alcohol trap material character | ||
| CaCl 2Content, quality % | Alcohol capture capacity, microlitre | The alcohol adsorption temp, ℃ | ||||
| ????8 | ????A 1 | ????Z 1 | ????0.038 | ????5.0 | ????0.8 | ????140 |
| ????9 | ????A 2 | ????Z 1 | ????0.080 | ????10.0 | ????0.9 | ????145 |
| ????10 | ????A 3 | ????Z 1 | ????0.181 | ????20.0 | ????1.1 | ????145 |
| ????11 | ????A 4 | ????Z 1 | ????0.310 | ????30.0 | ????1.4 | ????145 |
| ????12 | ????A 5 | ????Z 1 | ????0.482 | ????40.0 | ????2.0 | ????150 |
| ????13 | ????A 6 | ????Z 1 | ????0.723 | ????50.0 | ????3.0 | ????150 |
| ????14 | ????A 7 | ????Z 2 | ????0.310 | ????30.0 | ????1.2 | ????130 |
| ????15 | ????A 8 | ????Z 3 | ????0.310 | ????30.0 | ????1.0 | ????125 |
| ????16 | ????A 9 | ????Z 4 | ????0.310 | ????30.0 | ????0.8 | ????110 |
| ????17 | ????A 10 | ????Z 5 | ????0.310 | ????30.0 | ????2.5 | ????150 |
| ????18 | ????A 11 | ????Z 6 | ????0.310 | ????30.0 | ????1.5 | ????145 |
| ????19 | ????A 12 | ????Z 7 | ????0.310 | ????30.0 | ????1.4 | ????145 |
Table 3
The preface stable hydrocarbon, volume % alkene, volume % aromatic hydrocarbons, volume % benzene, volume % ethanol, quality %
Number MGC FIA MGC FIA MGC FIA MGC CGC MGC CGC
1?????40.6????39.3????35.3????35.4????12.8????14.2????0.46????0.52????12.38????11.99
2?????39.2????40.0????34.4????35.2????14.5????13.8????0.47????0.49????12.98????11.92
3?????39.7????40.5????34.5????34.7????15.0????13.4????0.47????0.52????11.85????12.30
4?????41.3????43.3????34.1????34.6????14.6????11.8????0.36????0.39????10.95????11.18
5?????41.1????43.1????33.9????33.2????14.1????12.9????0.37????0.39????11.88????11.63
6?????34.3????34.4????40.9????42.1????13.9????13.2????0.35????0.68????11.94????11.12
7?????38.9????40.7????34.9????34.6????14.8????13.8????0.44????0.50????12.47????11.78
8?????39.4????39.4????35.2????36.8????14.5????13.0????0.47????0.51????11.98????11.66
9?????39.7????39.6????35.5????36.0????13.7????13.5????0.46????0.51????12.14????11.81
10????38.2????38.4????35.2????35.5????15.7????15.2????0.58????0.67????11.94????11.79
11????38.7????39.3????35.8????35.8????14.7????13.9????0.54????0.65????11.80????11.94
12????37.0????35.2????36.1????39.1????15.8????14.9????0.57????0.64????11.96????11.71
13????38.6????38.6????35.0????36.5????15.6????14.1????0.51????0.51????11.78????11.64
14????30.9????31.9????44.4????44.8????13.2????12.5????0.39????0.38????12.67????11.64
15????31.4????30.5????44.6????47.6????13.2????11.4????0.42????0.40????11.89????11.35
16????30.9????29.7????46.1????49.4????12.3????10.1????0.35????0.42????11.91????11.66
17????37.0????38.1????33.2????32.3????19.7????18.8????1.00????1.09????10.89????11.72
18????36.5????37.7????33.3????32.7????19.7????18.7????0.93????1.07????11.30????11.74
19????37.0????39.1????33.9????32.6????18.3????17.5????0.95????1.08????11.63????11.73
Sa????????-0.43???????????-0.67???????????1.02????????????-0.07?????????????0.21
Sd????????1.24????????????1.50????????????1.35????????????0.10??????????????0.55
Annotate: MGC-multidimensional chromatography of the present invention, FIA-fluorescence absorption method, the CGC-vapor-phase chromatography, Sa, Sd-are respectively the mean deviation and the standard deviation of the inventive method and FIA, CGC measurement result.
Claims (10)
1, a kind of multidimensional gas chromatographic that utilizes is analyzed the method that alcohol blended fuel is formed, comprise gasoline sample is injected multidimensional gas chromatograph, bring the polarity chromatographic column into by carrier gas, aliphatic hydrocarbon is separated with alcohol with aromatic hydrocarbons, the aliphatic hydrocarbon that will flow out from the polarity chromatographic column feeds alkene trap absorption alkene wherein, the stable hydrocarbon that will flow out from the alkene trap detects by detecting device, transfer valve makes the alkene trap break away from the carrier gas stream, by carrier gas the benzene in the polar column is carried by pure trap, entering detecting device detects, treat that benzene flows out fully from pure trap after, with carrier gas blowback polarity chromatographic column, make aromatic hydrocarbons and alcohol by pure trap absorption alcohol wherein, aromatic hydrocarbons enters detecting device by pure trap and detects, and transfer valve makes the alkene trap enter the carrier gas stream, heats up to make the alkene desorption in the alkene trap enter the detecting device detection, after treating that alkene flows out fully, make pure desorption wherein enter the detecting device detection pure trap intensification.
2, in accordance with the method for claim 1, it is characterized in that described polarity chromatographic column operating temperature is 90-115 ℃.
3, in accordance with the method for claim 1, the temperature that it is characterized in that alkene trap adsorbs olefins is 80-170 ℃, and the temperature of desorption alkene is 180-240 ℃.
4, in accordance with the method for claim 1, it is characterized in that the temperature of pure trap absorption alcohol is 80-180 ℃, the temperature of dealcoholysis is 240-260 ℃.
5, in accordance with the method for claim 1, it is characterized in that described carrier gas is a nitrogen.
6, the used pure sorbing material of pure trap in the described method of a kind of claim 1 comprises the CaCl of 3.0-60.0 quality %
2Carrier zeyssatite with 40.0-97.0 quality %.
7,, it is characterized in that comprising the CaCl of 20-50 quality % according to the described pure sorbing material of claim 6
2Carrier zeyssatite with 50-80 quality %.
8,, it is characterized in that described zeyssatite is selected from red zeyssatite, white diatomite or the zeyssatite after pickling, alkali cleaning, glazing or alkylation are handled according to the described pure sorbing material of claim 6.
9,, it is characterized in that zeyssatite contains the SiO of 60-95 quality % according to the described pure sorbing material of claim 6
2, 3-17 quality % Al
2O
3, 0.5-4 quality % Fe
2O
3, 0.1-1 quality % MgO.
10,, it is characterized in that described diatomaceous surface area is a 2-50 rice according to the described pure sorbing material of claim 6
2/ gram, the zeyssatite median pore diameter that mercury intrusion method records is that the pore volume of 50-10000 nano-pore is 0.6-1.2 milliliter/gram.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102879491A (en) * | 2012-09-21 | 2013-01-16 | 武汉钢铁(集团)公司 | Analyzing apparatus for total carbon content in argon with high purity and analyzing method thereof |
| CN112007383A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Packing column and system for separating and analyzing hydrocarbon components in hydrocarbon fuel |
| CN112014490A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Method for separating and analyzing hydrocarbon components in hydrocarbon fuel |
| CN113385155A (en) * | 2020-03-13 | 2021-09-14 | 东莞市秉晟石化产品检测有限公司 | Reversible adsorbent for olefin content determination, and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3653840A (en) * | 1969-06-05 | 1972-04-04 | Phillips Petroleum Co | Portable air pollution detector |
| US4287752A (en) * | 1979-08-03 | 1981-09-08 | Standard Oil Co. (Indiana) | Apparatus and method for analyzing the hydrocarbon type composition of gasoline |
| US4384471A (en) * | 1980-12-10 | 1983-05-24 | Engelhard Minerals & Chemicals Corporation | Chromatographic analysis of hydrocarbon mixtures |
| US5262645A (en) * | 1991-09-03 | 1993-11-16 | General Motors Corporation | Sensor for measuring alcohol content of alcohol gasoline fuel mixtures |
| CN2520508Y (en) * | 2002-02-07 | 2002-11-13 | 中国石油化工股份有限公司 | Multi-D gas chromatograph |
-
2003
- 2003-11-28 CN CNB2003101155054A patent/CN100389324C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102879491A (en) * | 2012-09-21 | 2013-01-16 | 武汉钢铁(集团)公司 | Analyzing apparatus for total carbon content in argon with high purity and analyzing method thereof |
| CN112007383A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Packing column and system for separating and analyzing hydrocarbon components in hydrocarbon fuel |
| CN112014490A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Method for separating and analyzing hydrocarbon components in hydrocarbon fuel |
| CN112007383B (en) * | 2019-05-31 | 2021-11-16 | 中国石油化工股份有限公司 | Packing column and system for separating and analyzing hydrocarbon components in hydrocarbon fuel |
| CN112014490B (en) * | 2019-05-31 | 2022-06-28 | 中国石油化工股份有限公司 | Method for separating and analyzing hydrocarbon components in hydrocarbon fuel |
| CN113385155A (en) * | 2020-03-13 | 2021-09-14 | 东莞市秉晟石化产品检测有限公司 | Reversible adsorbent for olefin content determination, and preparation method and application thereof |
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|---|---|
| CN100389324C (en) | 2008-05-21 |
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