CA2064833C - Improved octane measuring process and device - Google Patents
Improved octane measuring process and deviceInfo
- Publication number
- CA2064833C CA2064833C CA002064833A CA2064833A CA2064833C CA 2064833 C CA2064833 C CA 2064833C CA 002064833 A CA002064833 A CA 002064833A CA 2064833 A CA2064833 A CA 2064833A CA 2064833 C CA2064833 C CA 2064833C
- Authority
- CA
- Canada
- Prior art keywords
- octane
- absorbance
- process according
- fuel
- blending
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims description 16
- 238000002835 absorbance Methods 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 22
- 238000005259 measurement Methods 0.000 claims abstract description 12
- 238000011160 research Methods 0.000 claims abstract description 5
- 239000000446 fuel Substances 0.000 claims description 15
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims 2
- 238000007620 mathematical function Methods 0.000 claims 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000004611 spectroscopical analysis Methods 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 230000009102 absorption Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- RLPGDEORIPLBNF-UHFFFAOYSA-N 2,3,4-trimethylpentane Chemical compound CC(C)C(C)C(C)C RLPGDEORIPLBNF-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; viscous liquids; paints; inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2829—Oils, i.e. hydrocarbon liquids mixtures of fuels, e.g. determining the RON-number
Abstract
The near infrared absorbance of the methyne band measures octane (pump, RON, and MON) with excellent correlation and can be used for gasoline blending. The absorbance may be measured as the first, second, third, fourth or higher derivative or by other signal processing techniques. The signal can be used to control a multi-component gasoline blending system to produce a preset desired octane. Such continuous or frequent measurement of octane (research octane number, RON; motor octane num-ber, MON; and pump octane number (research plus motor times 0.5)) permits constant or frequent optimization of gasoline blending to produce a target octane which is sufficient to meet motorists' needs, yet uses minimum amounts of the more expen-sive high octane blending stocks.
Description
2 2064833 IMPROVED OCTANE MEASURING PROCESS AND DEVICE
7 Background of Invention 8 Because the well known knock engine method of measuring fuel 9 octane or other measure of knock avoidance is not continuous, requiresan internal combustion engine under load, and involves spark hazard and 12 substantial maintenance; a continuous method for measurement of octane13 number, etc. has long been sought.
Kelly, Barlow, Jinguji and Callis of the University of Washington, 16 Seattle, (Analytical Chem. 61, 313-320,) found gasoline octane numberscould be predicted from near infrared absorbance in the range 660-1215 19 nanometers (nm). They found best correlation between absorbance and octane number to occur at 896, 932 and 1164 nm for research octane 21 number, 930, 940 and 1012 nm for motor octane number, and 896, 932 22 and 1032 nm for pump octane number.
BP (EP-A-0 285 251) teaches NIR absorption in the wave number 26 spectral range from 6667 to 3840 cm to the -1. By spectrometer with 27 optional fiber optics and computer and suggests determining octane 28 number of each storage tank to calculate proportions of product for 29 transferring to the mixing tank.
32 A search in Lexpat (U.S. patents from 1975 forward) under 33 ~infrared, octane, and (gasoline or fuel) within 25 words of each other 34 showed only four patents: U.S. 4,277,326; U.S. 4,264,336; U.S. 3,496,053;
and U.S. 903,020, none of which relate to new techniques for the 36 measurement of octane.
39 The present invention, by measurement of absorbance in a range 40 close to but above the Kelly et al. wavelengths, shows dramatically 2 improved correlation as compared to measurements made in the
7 Background of Invention 8 Because the well known knock engine method of measuring fuel 9 octane or other measure of knock avoidance is not continuous, requiresan internal combustion engine under load, and involves spark hazard and 12 substantial maintenance; a continuous method for measurement of octane13 number, etc. has long been sought.
Kelly, Barlow, Jinguji and Callis of the University of Washington, 16 Seattle, (Analytical Chem. 61, 313-320,) found gasoline octane numberscould be predicted from near infrared absorbance in the range 660-1215 19 nanometers (nm). They found best correlation between absorbance and octane number to occur at 896, 932 and 1164 nm for research octane 21 number, 930, 940 and 1012 nm for motor octane number, and 896, 932 22 and 1032 nm for pump octane number.
BP (EP-A-0 285 251) teaches NIR absorption in the wave number 26 spectral range from 6667 to 3840 cm to the -1. By spectrometer with 27 optional fiber optics and computer and suggests determining octane 28 number of each storage tank to calculate proportions of product for 29 transferring to the mixing tank.
32 A search in Lexpat (U.S. patents from 1975 forward) under 33 ~infrared, octane, and (gasoline or fuel) within 25 words of each other 34 showed only four patents: U.S. 4,277,326; U.S. 4,264,336; U.S. 3,496,053;
and U.S. 903,020, none of which relate to new techniques for the 36 measurement of octane.
39 The present invention, by measurement of absorbance in a range 40 close to but above the Kelly et al. wavelengths, shows dramatically 2 improved correlation as compared to measurements made in the
3 wavelengths described by Kelly et al.
6 Summary of the Invention 7 According to the present invention, any of the three octane 8 numbers (or all of thbm) can be measured (predicted) by measuring the 9 near infrared absorbance in the methyne range (1200 to 1236 nm). This 0 range correlates sufficiently closely to permit in-line (or at-line, measuring a 12 smaller sidestream) measurement to control blending systems to produce gasolines of target octane with close accuracy.
rleferably, the absorbance in the methyne range is converted into an electrical signal which is ,c,r~reraLly combined with signals indicative of 7 absorbance in other ranges, most preferably about 1196nm and 1236 nm.
Octane:
22 As mentioned above, the present invention is useful for the 23 measurement and control of systems producing octanes according to the 24 well known knock engine procedures for RON, MON, and pump [(R+M) 26 /2] octane. Pump octanes measured are preferably in the range of from 27 about 75 to 1 20, and most preferably from about 84 to 95.
29 Signal Processing:
As those skilled in the art will be aware, the absorbance signal from 31 the measurement of the methyne and other bands will preferably be 33 mathematically processed to provide derived signals which are more 34 directly indicative of the octane being measured. P,efe"ed techniques for 35 mathe,llalical processi"g are the first, second, third, and fourth or higher 36 derivative. The technique of dividing the absorbance at one wavelength 37 by the absorbance at all other wavelenytl ,s in order to cancel out background or noise and normalize the signal; s~.ecttal sul-l,a~;tion in 40 which the spectrum background or noise and normalize the signal; spectral subtraction in 5 which the spectrum of one sample is subtracted from the spectrum of 6 another sample in order to differentiate differences in absorbance, and 7 various combinations of these mathematical techniques. Also valuable are 8 well known curve fitting techniques, e.g. Savitsky-Golay curve fit, Kubelka-9 Munk curve fit transformation, and n-point smoothing (signal averaging).
12 Theory:
14 While the invention is claimed independent of any underlying theory, 15 the invention appears to relate to the free radical propagation and stability16 of the fuel being analyzed. It is hypothesized that ease and smoothness 18 f combustion are probably related to the free radical stability of the 19 species generated during the process of combustion, e.g. secondary and 20 tertiary free radicals. The methyne band, along with the tertiary butyl band 21 (1200-1236 nm), is indicative of methyne groups and t-butyl groups, 22 respectively. The presence of methyne groups and t-butyl groups affords 23 a source of stable free radicals which smooth the combustion process in contrast to the less stable compounds which give rise to sudden changes 26 in combustion which result in knocking of the internal combustion engine 27 in which the fuel is being consumed. Octane is the measure of the ability 28 of the engine to run under adverse circumstances and heavy loads 29 without substantial knocking. 1985 Annual Book of ASTM Standards.
3 Volume 05.04 Test Methods for Rating Motor, Diesel and Aviation Fuels, 32 American Society for Testing and Materials; Philadelphia, PA, 1985.
34 Analytical Equipment:
36 Near Infrared spectrometers and modified IR spectrometers of 3 conventional 91 design may be used with the ~,
6 Summary of the Invention 7 According to the present invention, any of the three octane 8 numbers (or all of thbm) can be measured (predicted) by measuring the 9 near infrared absorbance in the methyne range (1200 to 1236 nm). This 0 range correlates sufficiently closely to permit in-line (or at-line, measuring a 12 smaller sidestream) measurement to control blending systems to produce gasolines of target octane with close accuracy.
rleferably, the absorbance in the methyne range is converted into an electrical signal which is ,c,r~reraLly combined with signals indicative of 7 absorbance in other ranges, most preferably about 1196nm and 1236 nm.
Octane:
22 As mentioned above, the present invention is useful for the 23 measurement and control of systems producing octanes according to the 24 well known knock engine procedures for RON, MON, and pump [(R+M) 26 /2] octane. Pump octanes measured are preferably in the range of from 27 about 75 to 1 20, and most preferably from about 84 to 95.
29 Signal Processing:
As those skilled in the art will be aware, the absorbance signal from 31 the measurement of the methyne and other bands will preferably be 33 mathematically processed to provide derived signals which are more 34 directly indicative of the octane being measured. P,efe"ed techniques for 35 mathe,llalical processi"g are the first, second, third, and fourth or higher 36 derivative. The technique of dividing the absorbance at one wavelength 37 by the absorbance at all other wavelenytl ,s in order to cancel out background or noise and normalize the signal; s~.ecttal sul-l,a~;tion in 40 which the spectrum background or noise and normalize the signal; spectral subtraction in 5 which the spectrum of one sample is subtracted from the spectrum of 6 another sample in order to differentiate differences in absorbance, and 7 various combinations of these mathematical techniques. Also valuable are 8 well known curve fitting techniques, e.g. Savitsky-Golay curve fit, Kubelka-9 Munk curve fit transformation, and n-point smoothing (signal averaging).
12 Theory:
14 While the invention is claimed independent of any underlying theory, 15 the invention appears to relate to the free radical propagation and stability16 of the fuel being analyzed. It is hypothesized that ease and smoothness 18 f combustion are probably related to the free radical stability of the 19 species generated during the process of combustion, e.g. secondary and 20 tertiary free radicals. The methyne band, along with the tertiary butyl band 21 (1200-1236 nm), is indicative of methyne groups and t-butyl groups, 22 respectively. The presence of methyne groups and t-butyl groups affords 23 a source of stable free radicals which smooth the combustion process in contrast to the less stable compounds which give rise to sudden changes 26 in combustion which result in knocking of the internal combustion engine 27 in which the fuel is being consumed. Octane is the measure of the ability 28 of the engine to run under adverse circumstances and heavy loads 29 without substantial knocking. 1985 Annual Book of ASTM Standards.
3 Volume 05.04 Test Methods for Rating Motor, Diesel and Aviation Fuels, 32 American Society for Testing and Materials; Philadelphia, PA, 1985.
34 Analytical Equipment:
36 Near Infrared spectrometers and modified IR spectrometers of 3 conventional 91 design may be used with the ~,
4 2 0 6 4 8 3 3 PCT/USgo/04110 2 invention. Preferred modes of operation are 3 transmission, reflectance, and transreflectance.
4 Suitable spectrometers are the NIRSystems Model 6500; LT
Industries Model 1200; and the Guided Wave Model 300 6 Series. The spectrometer can be operated on a batch 7 basis (receiving signals, e.g. by 2 sample feeding 8 arrangement), or, more preferably, on a continuous basis 9 in which the fluid to be measured flows through a cell or a probe immersed in the flowing fluid transmits 11 optically through a fiber-optic cable to the 12 spectrophometer. The techniques - for sampling, 13 measuring, and signal processing can be conventional and 14 are well known to those skilled in thelart.
16 Blending Systems:
18 Blending systems for use with the present invention 19 can.be of conventional design, usually involving the use of proportioning pumps or automatic cohtrol valves which 21 control the addition rate for each of a series of 22 components fed from different tanks or other sources. A
23 computer receiving the output signal from the 24 spectrophotometer can readily process the information to not only provide the target octane number in the 26 finished blended gasoline, but alsd to provide the 27 target octane at m;nimtlm cost, given the relative costs 28 and octane enhancement values of thel components being 29 fed to the blending system.
31 Utility of the Invention 33 As described above, the inventionlwill be useful in 34 the blending of gasoline, less preferably diesel fuels (cetane number) and jet fuels, e.lg. JP4, both in 36 refineries and in large fuel storage terminals.
37 Blending can be into storage tanks, ~tank trucks, rail 38~ cars, barges, or other transportation vehicles. An WO91/03726 ~ ~; 2;~i6~833 I PCT/US90/04110 _ 2 allowance for octane depletion during transportatio..
3 based on expected weather conditions can also be 4 included in determining the target oc~ane for blending.
Additionally, the invention will be useful for 6 monitoring gasoline quality at retail outlets to assure 7 quality control specifications.
9 Brief Description of the D~awin~s 11 Figure 1 is a plot of the Ipreferred second 12 derivative of absorbance versus wavelength (d2A/d 13 ,nanometers) and shows the near infrared band 14 assignments for the methyl, methyne, t-butyl and methylene functional groups.
17 Figure 2 is a plot of multiple correlation versus 18 wavelength, showing the excellent correlation obtained 19 with the methyne and t-buty} groups. Note the change in the correlation at 1228 nm from strongly positive to 21 negative as the scan proceeds from the t-butyl and 22 methyne groups to the methylene.
24 Figure 3 shows the second derivative of the methyne and methyl absorption bands in the near infrared versus 26 the wavelength for some selected compounds. Note the 27 cumene and 2,3,4-trimethyl pentane do not contain 28 methylene groups. This demonstrates that the methyne 29 band position in the second derivative spectrum extends from 1202 to 1236 nm.
32 Figure 4 similarly shows that t-butyl group (e.g.
33 of the methyl tertiary butyl ether, MTBE, a popular 34 gasoline octane enhancer additive) also falls within the - 35 methyne absorption range. The t-butyl band is centered 36 between 1200-1232 nm.
WO 91/03726 ` ' ~ 0 6 Y 8 3 3 Pcr/us90lo4l lO
2 Figure ; is the Savistsky-Goiay curve fit of the 3 spectru:n of 2,3,4-trimethyl pentane and 2-methyl pentane 4 showing the methyne absorbance in the transmission
4 Suitable spectrometers are the NIRSystems Model 6500; LT
Industries Model 1200; and the Guided Wave Model 300 6 Series. The spectrometer can be operated on a batch 7 basis (receiving signals, e.g. by 2 sample feeding 8 arrangement), or, more preferably, on a continuous basis 9 in which the fluid to be measured flows through a cell or a probe immersed in the flowing fluid transmits 11 optically through a fiber-optic cable to the 12 spectrophometer. The techniques - for sampling, 13 measuring, and signal processing can be conventional and 14 are well known to those skilled in thelart.
16 Blending Systems:
18 Blending systems for use with the present invention 19 can.be of conventional design, usually involving the use of proportioning pumps or automatic cohtrol valves which 21 control the addition rate for each of a series of 22 components fed from different tanks or other sources. A
23 computer receiving the output signal from the 24 spectrophotometer can readily process the information to not only provide the target octane number in the 26 finished blended gasoline, but alsd to provide the 27 target octane at m;nimtlm cost, given the relative costs 28 and octane enhancement values of thel components being 29 fed to the blending system.
31 Utility of the Invention 33 As described above, the inventionlwill be useful in 34 the blending of gasoline, less preferably diesel fuels (cetane number) and jet fuels, e.lg. JP4, both in 36 refineries and in large fuel storage terminals.
37 Blending can be into storage tanks, ~tank trucks, rail 38~ cars, barges, or other transportation vehicles. An WO91/03726 ~ ~; 2;~i6~833 I PCT/US90/04110 _ 2 allowance for octane depletion during transportatio..
3 based on expected weather conditions can also be 4 included in determining the target oc~ane for blending.
Additionally, the invention will be useful for 6 monitoring gasoline quality at retail outlets to assure 7 quality control specifications.
9 Brief Description of the D~awin~s 11 Figure 1 is a plot of the Ipreferred second 12 derivative of absorbance versus wavelength (d2A/d 13 ,nanometers) and shows the near infrared band 14 assignments for the methyl, methyne, t-butyl and methylene functional groups.
17 Figure 2 is a plot of multiple correlation versus 18 wavelength, showing the excellent correlation obtained 19 with the methyne and t-buty} groups. Note the change in the correlation at 1228 nm from strongly positive to 21 negative as the scan proceeds from the t-butyl and 22 methyne groups to the methylene.
24 Figure 3 shows the second derivative of the methyne and methyl absorption bands in the near infrared versus 26 the wavelength for some selected compounds. Note the 27 cumene and 2,3,4-trimethyl pentane do not contain 28 methylene groups. This demonstrates that the methyne 29 band position in the second derivative spectrum extends from 1202 to 1236 nm.
32 Figure 4 similarly shows that t-butyl group (e.g.
33 of the methyl tertiary butyl ether, MTBE, a popular 34 gasoline octane enhancer additive) also falls within the - 35 methyne absorption range. The t-butyl band is centered 36 between 1200-1232 nm.
WO 91/03726 ` ' ~ 0 6 Y 8 3 3 Pcr/us90lo4l lO
2 Figure ; is the Savistsky-Goiay curve fit of the 3 spectru:n of 2,3,4-trimethyl pentane and 2-methyl pentane 4 showing the methyne absorbance in the transmission
5 spectrum.
7 Figure 6 is a schematic diagra:n of a gasoline 8 blending system utilizing the octane measurement 9 techniques of the present invention.
11Description of the Preferred Embodiments 13Example I
15A series of samples of about 141 blended gasolines 16 are analyzed for pump octane number (RON p~us MON
17 divided by 2) by measuring the near IR absorbance at 181220, 1196, and 1236 nm. The second derivative is taken 19 of each absorbance measured and is used to perform a 20 multiple regression. The multiple regression analysis 21 of the data essentially fits the curve~
23Y = K(0) + K(1) x second derivative of absorbance 24at 1220 nm 26+ K(2) x second derivative of absorbance 27at 1196 nm 29+ K(3) x second derivative of absorbance 30at 1236 nm 32 all as shown ln Table A.
File name: OCT2ND Re~ression Results 36 Instrument: 6500 Standard error = .345 37 No. of spectra: 141 Multiple R = .9927 Constituent: 3, PUMP
38Math: 2nd derivative 39Segrnent: 20 Gap: 0
7 Figure 6 is a schematic diagra:n of a gasoline 8 blending system utilizing the octane measurement 9 techniques of the present invention.
11Description of the Preferred Embodiments 13Example I
15A series of samples of about 141 blended gasolines 16 are analyzed for pump octane number (RON p~us MON
17 divided by 2) by measuring the near IR absorbance at 181220, 1196, and 1236 nm. The second derivative is taken 19 of each absorbance measured and is used to perform a 20 multiple regression. The multiple regression analysis 21 of the data essentially fits the curve~
23Y = K(0) + K(1) x second derivative of absorbance 24at 1220 nm 26+ K(2) x second derivative of absorbance 27at 1196 nm 29+ K(3) x second derivative of absorbance 30at 1236 nm 32 all as shown ln Table A.
File name: OCT2ND Re~ression Results 36 Instrument: 6500 Standard error = .345 37 No. of spectra: 141 Multiple R = .9927 Constituent: 3, PUMP
38Math: 2nd derivative 39Segrnent: 20 Gap: 0
6 206~833 PCT/~lS90/04110 l 7 3 Constants WavelengthSimple R
4 K(0) = 85.506 K(1) = 70.323 1220 .988 K(2) = 16.465 1196 .385 6 K(3) = 28.61~ 1236 -.951 8 The multiple coefficent of correlation between the 9 octane, y, and the second derivatives of the absorbances is 0.9927, a very close correlation. This is equivalent 11 to a standard error of about plus or minus .345 octane 12 n~bers which is better than can generally be 13 accomplished by a knock engine with a skilled operator 14 (the average of ASTM methods 2699-84 and 2700-84).
16 Example II
18 Figure 1 shows a plot of the second derivative of 19 the near infrared absorption spectra of approximately 142 gasoline samples, analyzed by the techniques of 21 Example I. Also plotted on Figure 1 are the second 22 derivative ranges of the methyl (1174 to 1212 nm), 23 t-butyl/methyne (1212 to 1228 nm), and the methylene 24 (1228 to about 1268 nm). These absorptions are in the second overtone region of the near infrared spectrum.
26 That is, the original absorbance band for the methyl, 27 methyne, t-butyl and methylene groups is at about 3367 28 nm, so these near infrared ranges being measured are 29 overtones similar to harmonics of the original bands.
Working in the second overtone has advantages over the 31 third overtone which was used by Kelly et al. For 32 example, at a total path length of 20 mm, the absorbance 33 measurements in the second overtone region are in the 34 region where the 3eer-Lambert Law is obeyed, whereas in the third overtone region they are not. (Note, Relly et 36 al. used a 20 mm path length, 10 mm cell in reflectance 37 mode.) WO91/03726 ~ PCT/US90/04110 1 X~6~833 Example III ~
4 .able B shows techniques similar to those used in Example I, but utilizing only the lZ20 nm wavelengt~
6 (methyne range). The multiple correlation is 0.9836 and
4 K(0) = 85.506 K(1) = 70.323 1220 .988 K(2) = 16.465 1196 .385 6 K(3) = 28.61~ 1236 -.951 8 The multiple coefficent of correlation between the 9 octane, y, and the second derivatives of the absorbances is 0.9927, a very close correlation. This is equivalent 11 to a standard error of about plus or minus .345 octane 12 n~bers which is better than can generally be 13 accomplished by a knock engine with a skilled operator 14 (the average of ASTM methods 2699-84 and 2700-84).
16 Example II
18 Figure 1 shows a plot of the second derivative of 19 the near infrared absorption spectra of approximately 142 gasoline samples, analyzed by the techniques of 21 Example I. Also plotted on Figure 1 are the second 22 derivative ranges of the methyl (1174 to 1212 nm), 23 t-butyl/methyne (1212 to 1228 nm), and the methylene 24 (1228 to about 1268 nm). These absorptions are in the second overtone region of the near infrared spectrum.
26 That is, the original absorbance band for the methyl, 27 methyne, t-butyl and methylene groups is at about 3367 28 nm, so these near infrared ranges being measured are 29 overtones similar to harmonics of the original bands.
Working in the second overtone has advantages over the 31 third overtone which was used by Kelly et al. For 32 example, at a total path length of 20 mm, the absorbance 33 measurements in the second overtone region are in the 34 region where the 3eer-Lambert Law is obeyed, whereas in the third overtone region they are not. (Note, Relly et 36 al. used a 20 mm path length, 10 mm cell in reflectance 37 mode.) WO91/03726 ~ PCT/US90/04110 1 X~6~833 Example III ~
4 .able B shows techniques similar to those used in Example I, but utilizing only the lZ20 nm wavelengt~
6 (methyne range). The multiple correlation is 0.9836 and
7 is the highest correlation of any single wavelength in
8 the near infrared range (800-2500 nm)jwith motor octane
9 number.
11 TABLE ~
12 File name: OCT2ND Regression Results 13 Instrument: 6500 Standard error =.524 14 No. of spectra:141 Multiple R = .9836 Constituent: 2,MON
15 Math: 2nd derivative 16 Segment: 20 17 Gap: 0 18 Constants Wavelen~th I Simple R
19 K(0) = 75.158 K(1) = 59.949 1220 .984 22 Example IV
24 When techniques similar to those described in 25 Example III on research octane number, the correlatlon 26 between RON and the second derivative of absorbance at 27 the 1220 nm wavelength is 0.9649 indicating a standard 28 error of plus or minus 0.752 octane numbers, the best 29 correlation and lowest stAn~Ard error available with any single wavelength in the near infrared range. (see 31 Table C) 34 File name: OCT2ND Re~aression Results Instrument: 6500 Standard error =.752 No. of spectra: 141 Multiple'R = .9649 36 Constituent: 1, RON
37 Math: 2nd derivative Segment: 20 38 Gap:
WO91/03726 2064833 PCT/~lS90/04110 g 2 C~nstants Wavelength Simple R
3 K(0) = 84.408 ~l `
4 K~1) = 57.980 1220 .965 6 Example V
8 . When techniques similar to those described in 9 Example III are used to determine pump octane number, the correlation between RON and the sefond derivative of 11 absorbance at the 1220 nm wavelength is 0.9878 12 indicating a standard error of plus or minus .442 pump 13 octane numbers, the best correlatiQn and lowest standard 14 error available with any single wavelength in the near 15 infrared range. (see Table D) File name: OCT2ND Regression Results 19 Instrument: 6500 Standard error = .442 No. of spectra: 141 Multiple R = .9878 Constituent: 3, PUMP
21 Math: 2nd derivative 22 Segment: 20 Gap: 0 24 Constants Wavelength Simple R
~C(0) = 79.782 26 Kt 1) = 58.962 1220 .988 28 Example VI
Figure 5 shows the results of subtracting the 31 absorbance versus wavelength spectrum of n-hexane from 32 2,3,4-trimethyl pentane using a Savitski-Golay curve 33 fit. From this figure, one can see that without 34 mathematical treatment the methyl band extends from about 1160-1195 nm, the methylene iband from about 36 1195-120 nm , and the methyne band is from about 37 1230-1250 nm.
WO91/03726 ~ PCT/US90/04110
11 TABLE ~
12 File name: OCT2ND Regression Results 13 Instrument: 6500 Standard error =.524 14 No. of spectra:141 Multiple R = .9836 Constituent: 2,MON
15 Math: 2nd derivative 16 Segment: 20 17 Gap: 0 18 Constants Wavelen~th I Simple R
19 K(0) = 75.158 K(1) = 59.949 1220 .984 22 Example IV
24 When techniques similar to those described in 25 Example III on research octane number, the correlatlon 26 between RON and the second derivative of absorbance at 27 the 1220 nm wavelength is 0.9649 indicating a standard 28 error of plus or minus 0.752 octane numbers, the best 29 correlation and lowest stAn~Ard error available with any single wavelength in the near infrared range. (see 31 Table C) 34 File name: OCT2ND Re~aression Results Instrument: 6500 Standard error =.752 No. of spectra: 141 Multiple'R = .9649 36 Constituent: 1, RON
37 Math: 2nd derivative Segment: 20 38 Gap:
WO91/03726 2064833 PCT/~lS90/04110 g 2 C~nstants Wavelength Simple R
3 K(0) = 84.408 ~l `
4 K~1) = 57.980 1220 .965 6 Example V
8 . When techniques similar to those described in 9 Example III are used to determine pump octane number, the correlation between RON and the sefond derivative of 11 absorbance at the 1220 nm wavelength is 0.9878 12 indicating a standard error of plus or minus .442 pump 13 octane numbers, the best correlatiQn and lowest standard 14 error available with any single wavelength in the near 15 infrared range. (see Table D) File name: OCT2ND Regression Results 19 Instrument: 6500 Standard error = .442 No. of spectra: 141 Multiple R = .9878 Constituent: 3, PUMP
21 Math: 2nd derivative 22 Segment: 20 Gap: 0 24 Constants Wavelength Simple R
~C(0) = 79.782 26 Kt 1) = 58.962 1220 .988 28 Example VI
Figure 5 shows the results of subtracting the 31 absorbance versus wavelength spectrum of n-hexane from 32 2,3,4-trimethyl pentane using a Savitski-Golay curve 33 fit. From this figure, one can see that without 34 mathematical treatment the methyl band extends from about 1160-1195 nm, the methylene iband from about 36 1195-120 nm , and the methyne band is from about 37 1230-1250 nm.
WO91/03726 ~ PCT/US90/04110
- 10-2 Example VII ~
3 2064833 ( Comparative) When techniques similar to those described in 6 Example III are used to determine pump octane number , 7 but using the regression model and wavelengths of Kelly 8 et al., the correlation between pump octane number and 9 the second derivative of absorbance at the 896, 932 and 1032 wavelength is .9841 indicating a standard error of
3 2064833 ( Comparative) When techniques similar to those described in 6 Example III are used to determine pump octane number , 7 but using the regression model and wavelengths of Kelly 8 et al., the correlation between pump octane number and 9 the second derivative of absorbance at the 896, 932 and 1032 wavelength is .9841 indicating a standard error of
11 plus or minus 0.497 pump octane numbers (b~t using 90
12 samples) as set forth in Table E. Thus, the present
13 invention with only a single wavelength measured
14 provides accuracy better than the multiple correlation suggested by Kelly et al.
(Kelly Wavelengths) File name: GASMINUS Regression Results Instrument: 6500 Standard error = .497 21 No. of spectra: 90 MultipleiR = .9841 22 Constituent: 1, PUMP
Math: N-Point smooth 23 Segment: 2 24 Gap: 0 Constants Wavelength Simple R
26 K(0) =100.105 27 K(1) =278.370 896 .236 28 K(2) =-768.856 932 -.943 29 K(3) =305.203 1032 -.453 (Invention) 32 File name: GAS2ND Regression Results Instrument: 6500 Standard error = .414 33 No. of spectra:90 Multiple R = .9887 34 Constituent: 3,PUMP
Math: 2nd Derivative Segment: 20 36 Gap: o 37 Constants Wavelength Simple R
K(0) = 79.756 39 K(1) = 59.253 1220 .989 WO91/03726 .PCTlUS90/04110 ~ 2 Example V~
4 Figure 6 is a schematic diagram of a typical gasoline blending system such as might be used to employ 6 the present invention at a refinery or large terminal.
7 Tanks 10 through 15 contain gasoline blending stocks, 8 e.g. reformates, isomerates, alkylates, etc. Each of 9 these components has its own octane value as well as a price. For example, reformate and alkylate are both 11 high in octane number, but are relatively expensive 12 blending stocks. Each of the tanks has an automatic 13 control valve 16 through 21 which controls the flow of 14 the -particular blending stock from the tank into a common header 22 and thence into mixing tank 23 from 16 which pump 24 moves the blended gasoline through 17 "at-line" analyzer 25 which analyzes the near IR
18 absorbance of a side-stream 30 at 1220 nm, 1196 nm, and 19 1236 nm, and transmits the resulting absorbance measurements to a mathematical conversion device 26 21 which converts the signal into the second derivative and 22 feeds the resulting signal to computer 27. Optional 23 display device 28 can display both the target octane and 24 the measured octane number at all times. The output 25 from computer 27 is fed to each individual control valve 26 ( or proportioning pump) 16 through 21~ and controls the 27 relative flow of each of the gasoline blending 28 components 10 through 15 into the blending tank 23.
29 various adjustments can be made for hold-up in the tank, 30 etc. (Alternately, the functions of the mathematical 31 conversion device 26 can also be performed by computer 32 27.) 34 The resulting gasoline is withLn plus or minus 35 approximately 0.3 octane numbers at all times.
37 In another variation, each of the lines f rom the 38 gasoline blending stock tanks 10-15 ~is f itted with a .r, --`~ ` 2 near IR analyzer (like 25) which inputs a signal to the computer 27 which 3 iS now programmed to control and optimize the blending process based 4 on al! these inputs.
7 In another variation, an operator reads the computer output of 8 octane number and manually or mechanically controls and opli"~i~es the 9 blending process.
Modifications 14 Specific compositions, methods, devices or embodiments
(Kelly Wavelengths) File name: GASMINUS Regression Results Instrument: 6500 Standard error = .497 21 No. of spectra: 90 MultipleiR = .9841 22 Constituent: 1, PUMP
Math: N-Point smooth 23 Segment: 2 24 Gap: 0 Constants Wavelength Simple R
26 K(0) =100.105 27 K(1) =278.370 896 .236 28 K(2) =-768.856 932 -.943 29 K(3) =305.203 1032 -.453 (Invention) 32 File name: GAS2ND Regression Results Instrument: 6500 Standard error = .414 33 No. of spectra:90 Multiple R = .9887 34 Constituent: 3,PUMP
Math: 2nd Derivative Segment: 20 36 Gap: o 37 Constants Wavelength Simple R
K(0) = 79.756 39 K(1) = 59.253 1220 .989 WO91/03726 .PCTlUS90/04110 ~ 2 Example V~
4 Figure 6 is a schematic diagram of a typical gasoline blending system such as might be used to employ 6 the present invention at a refinery or large terminal.
7 Tanks 10 through 15 contain gasoline blending stocks, 8 e.g. reformates, isomerates, alkylates, etc. Each of 9 these components has its own octane value as well as a price. For example, reformate and alkylate are both 11 high in octane number, but are relatively expensive 12 blending stocks. Each of the tanks has an automatic 13 control valve 16 through 21 which controls the flow of 14 the -particular blending stock from the tank into a common header 22 and thence into mixing tank 23 from 16 which pump 24 moves the blended gasoline through 17 "at-line" analyzer 25 which analyzes the near IR
18 absorbance of a side-stream 30 at 1220 nm, 1196 nm, and 19 1236 nm, and transmits the resulting absorbance measurements to a mathematical conversion device 26 21 which converts the signal into the second derivative and 22 feeds the resulting signal to computer 27. Optional 23 display device 28 can display both the target octane and 24 the measured octane number at all times. The output 25 from computer 27 is fed to each individual control valve 26 ( or proportioning pump) 16 through 21~ and controls the 27 relative flow of each of the gasoline blending 28 components 10 through 15 into the blending tank 23.
29 various adjustments can be made for hold-up in the tank, 30 etc. (Alternately, the functions of the mathematical 31 conversion device 26 can also be performed by computer 32 27.) 34 The resulting gasoline is withLn plus or minus 35 approximately 0.3 octane numbers at all times.
37 In another variation, each of the lines f rom the 38 gasoline blending stock tanks 10-15 ~is f itted with a .r, --`~ ` 2 near IR analyzer (like 25) which inputs a signal to the computer 27 which 3 iS now programmed to control and optimize the blending process based 4 on al! these inputs.
7 In another variation, an operator reads the computer output of 8 octane number and manually or mechanically controls and opli"~i~es the 9 blending process.
Modifications 14 Specific compositions, methods, devices or embodiments
15 discussed are intended to be only illustrative of the invention disclosed by
16 this specification. Variation on these compositions, methods, or 7 embodiments will be readily apparent to a person of skill in the art based 19 upon the teachings of this specification and are therefore intended to be 20 included as part of the inventions disclosed herein. For example, 21 individual variations of NIR spectrometers could cause the optimal 22 wavelengths to be shifted slightly since the precise location of any 23 wavelength is inexact. Also, since differing crude oils produce gasolines 2 which are of differing mo!ecular structures, it is highly likely that a dif~renl 26 wavelength might show higher correlations for the selection of the initial 27 wavelength. It should be noted that the methyne group could still be 28 valuable in conjunction with the first wavelength.
3 What is claimed is:
3 What is claimed is:
Claims (9)
1. A process for the measurement of octane number; or other measure of knock avoidance of fuels by near infrared range spectroscopy comprising determining said octane number or other measure of knock avoidance by:
a. measuring infrared absorbance of the fuel in the t-butyl/methyne band;
b. periodically or continuously outputting a signal indicative of the intensity of said absorbance in said band or one mathematical function or a combination of mathematical functions thereof; and c. mathematically converting said signal to an output signal indicative of said octane number or other measure of knock avoidance of said fuel.
a. measuring infrared absorbance of the fuel in the t-butyl/methyne band;
b. periodically or continuously outputting a signal indicative of the intensity of said absorbance in said band or one mathematical function or a combination of mathematical functions thereof; and c. mathematically converting said signal to an output signal indicative of said octane number or other measure of knock avoidance of said fuel.
2. A process according to Claim 1 wherein said fuel flows substantially intermittently or continuously past the point where said measurement is being made.
3. A process according to Claim 1 wherein a first and/or higher derivative of said absorption of said t-butyl/methyne band with respect to wavelength is measured.
4. A process according to Claim 1 wherein the fuel is gasoline and the octane number measured is pump octane number motor octane and/or research octane.
5. A process according to Claim 1 wherein said signal controls a fuel blending system feeding blending components having different octane numbers into a common zone, whereby a fuel product having a desired octane is produced.
6. A process according to Claim 2 wherein said fuel is a gasoline.
7. A process according to Claim 1 wherein absorbance in one or more additional bands is measured and a signal indicative of its respective absorbance is combined with said signal indicative of absorbance in said t-butyl/methyne band.
8. A process according to Claim 7 wherein said one or more additional bands comprise at least one band selected from the group consisting of methyl, methylene, aromatic and substituted aromatic bands.
9. A process according to Claim 5 wherein each component is analyzed by a near infrared analyzer to produce a signal and all such signals are inputted to a computer controlling the blending process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US402,959 | 1989-09-01 | ||
| US07/402,959 US4963745A (en) | 1989-09-01 | 1989-09-01 | Octane measuring process and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2064833A1 CA2064833A1 (en) | 1991-03-02 |
| CA2064833C true CA2064833C (en) | 1996-04-23 |
Family
ID=23593973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002064833A Expired - Fee Related CA2064833C (en) | 1989-09-01 | 1990-07-20 | Improved octane measuring process and device |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US4963745A (en) |
| EP (1) | EP0489748B2 (en) |
| JP (1) | JPH06105219B2 (en) |
| KR (1) | KR940002499B1 (en) |
| AT (1) | ATE94281T1 (en) |
| AU (1) | AU636635B2 (en) |
| BR (1) | BR9007626A (en) |
| CA (1) | CA2064833C (en) |
| DE (1) | DE69003245T2 (en) |
| DK (1) | DK0489748T4 (en) |
| FI (1) | FI101105B (en) |
| HU (1) | HU217483B (en) |
| NO (1) | NO303992B1 (en) |
| RO (1) | RO109484B1 (en) |
| WO (1) | WO1991003726A1 (en) |
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| US4800279A (en) * | 1985-09-13 | 1989-01-24 | Indiana University Foundation | Methods and devices for near-infrared evaluation of physical properties of samples |
| FR2611911B1 (en) * | 1987-02-27 | 1989-06-23 | Bp France | METHOD OF DIRECT DETERMINATION OF AN OCTANE INDEX |
| ATE146880T1 (en) * | 1987-08-18 | 1997-01-15 | Bp Oil Int | METHOD FOR DIRECT DETERMINATION OF THE PHYSICAL PROPERTIES OF HYDROCARBON PRODUCTS |
-
1989
- 1989-09-01 US US07/402,959 patent/US4963745A/en not_active Expired - Lifetime
-
1990
- 1990-07-20 HU HU9200684A patent/HU217483B/en not_active IP Right Cessation
- 1990-07-20 AT AT90911386T patent/ATE94281T1/en active
- 1990-07-20 JP JP2510613A patent/JPH06105219B2/en not_active Expired - Lifetime
- 1990-07-20 KR KR1019910700003A patent/KR940002499B1/en not_active IP Right Cessation
- 1990-07-20 RO RO92-200220A patent/RO109484B1/en unknown
- 1990-07-20 EP EP90911386A patent/EP0489748B2/en not_active Expired - Lifetime
- 1990-07-20 CA CA002064833A patent/CA2064833C/en not_active Expired - Fee Related
- 1990-07-20 DK DK90911386T patent/DK0489748T4/en active
- 1990-07-20 WO PCT/US1990/004110 patent/WO1991003726A1/en active IP Right Grant
- 1990-07-20 DE DE90911386T patent/DE69003245T2/en not_active Expired - Fee Related
- 1990-07-20 AU AU60457/90A patent/AU636635B2/en not_active Ceased
- 1990-07-20 BR BR909007626A patent/BR9007626A/en not_active IP Right Cessation
-
1992
- 1992-02-28 NO NO920806A patent/NO303992B1/en not_active IP Right Cessation
- 1992-02-28 FI FI920921A patent/FI101105B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06105219B2 (en) | 1994-12-21 |
| CA2064833A1 (en) | 1991-03-02 |
| DK0489748T4 (en) | 1999-09-06 |
| RO109484B1 (en) | 1995-02-28 |
| FI920921A0 (en) | 1992-02-28 |
| EP0489748B1 (en) | 1993-09-08 |
| AU6045790A (en) | 1991-04-08 |
| NO303992B1 (en) | 1998-10-05 |
| BR9007626A (en) | 1992-07-07 |
| JPH04503572A (en) | 1992-06-25 |
| DK0489748T3 (en) | 1993-11-29 |
| HUT61844A (en) | 1993-03-01 |
| EP0489748B2 (en) | 1999-01-13 |
| WO1991003726A1 (en) | 1991-03-21 |
| HU9200684D0 (en) | 1992-05-28 |
| AU636635B2 (en) | 1993-05-06 |
| HU217483B (en) | 2000-02-28 |
| US4963745A (en) | 1990-10-16 |
| KR940002499B1 (en) | 1994-03-25 |
| EP0489748A1 (en) | 1992-06-17 |
| NO920806D0 (en) | 1992-02-28 |
| NO920806L (en) | 1992-04-29 |
| DE69003245T2 (en) | 1994-01-05 |
| KR920701812A (en) | 1992-08-12 |
| DE69003245D1 (en) | 1993-10-14 |
| FI101105B (en) | 1998-04-15 |
| ATE94281T1 (en) | 1993-09-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |