CA2220660C - Method for preparing lubricating oils - Google Patents
Method for preparing lubricating oils Download PDFInfo
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- CA2220660C CA2220660C CA002220660A CA2220660A CA2220660C CA 2220660 C CA2220660 C CA 2220660C CA 002220660 A CA002220660 A CA 002220660A CA 2220660 A CA2220660 A CA 2220660A CA 2220660 C CA2220660 C CA 2220660C
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 40
- 239000011159 matrix material Substances 0.000 claims abstract description 29
- 238000012549 training Methods 0.000 claims abstract description 26
- 238000004821 distillation Methods 0.000 claims abstract description 17
- 238000001311 chemical methods and process Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 230000000704 physical effect Effects 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 44
- 239000000523 sample Substances 0.000 claims description 38
- 230000014759 maintenance of location Effects 0.000 claims description 34
- 150000002500 ions Chemical class 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 25
- 239000013074 reference sample Substances 0.000 claims description 17
- 238000004458 analytical method Methods 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000012634 fragment Substances 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 abstract description 26
- 238000007670 refining Methods 0.000 abstract 1
- 238000005070 sampling Methods 0.000 description 18
- 230000003595 spectral effect Effects 0.000 description 17
- 239000003921 oil Substances 0.000 description 14
- 238000012628 principal component regression Methods 0.000 description 14
- 238000011282 treatment Methods 0.000 description 10
- 238000012937 correction Methods 0.000 description 9
- 238000010238 partial least squares regression Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000012417 linear regression Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000002098 selective ion monitoring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- 238000002790 cross-validation Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000012925 reference material Substances 0.000 description 3
- 238000000611 regression analysis Methods 0.000 description 3
- 239000013598 vector Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000004062 acenaphthenyl group Chemical class C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- 210000001217 buttock Anatomy 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 150000002468 indanes Chemical class 0.000 description 2
- 150000002469 indenes Chemical class 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 150000002987 phenanthrenes Chemical class 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 230000008521 reorganization Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 1
- 101150011616 Ctcf gene Proteins 0.000 description 1
- 241000406799 Deto Species 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 101000941356 Nostoc ellipsosporum Cyanovirin-N Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- IOYNQIMAUDJVEI-BMVIKAAMSA-N Tepraloxydim Chemical compound C1C(=O)C(C(=N/OC\C=C\Cl)/CC)=C(O)CC1C1CCOCC1 IOYNQIMAUDJVEI-BMVIKAAMSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000451 chemical ionisation Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001955 cumulated effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 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
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 108700023468 protein-bound SN-C polysaccharide Proteins 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004808 supercritical fluid chromatography Methods 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
Classifications
-
- 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
- G01N33/2888—Lubricating oil characteristics, e.g. deterioration
-
- 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—Mixtures of fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/10—Devices for withdrawing samples in the liquid or fluent state
- G01N1/16—Devices for withdrawing samples in the liquid or fluent state with provision for intake at several levels
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/10—Devices for withdrawing samples in the liquid or fluent state
- G01N1/20—Devices for withdrawing samples in the liquid or fluent state for flowing or falling materials
- G01N1/2035—Devices for withdrawing samples in the liquid or fluent state for flowing or falling materials by deviating part of a fluid stream, e.g. by drawing-off or tapping
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Lubricants (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
A method for controlling the manufacture of lubricating oils involving the steps of distillation, extracting, dewaxing and optionally hydrofining; or for controlling operating units associated with refinery or chemical processes with feed stocks and products boiling above 350 .degree.C. The method comprises selecting one or more chemical or perceptual or physical or performance properties of the lubricating oil or the feedstock, distillate or raffinate used in the manufacturing process; or of the refinery or chemical process feedstocks or products; creating a training set from reference samples which contain characteristic molecular species present in the lubricating oil, feedstock, distillate or raffinate used in the manufacturing process or from the refining or chemical operations. The reference samples are subjected to GC/MS analysis wherein the often collinear data generated is treated by multivaria te correlation methods. The training set produces coefficients which are multiplied by the matrix generated from a GC/MS analysis of an unknown sample to produce a predicted value of the chemical, performance, perceptual or physical property or groups of properties selecte d.
Description
METHOD FOR PREPARING LUBRICATING OILS
BACKGROUND OF THE INVENTION
I . FIELD OF THE INVENTION
This invention relates to a method for preparing lubricating oils by predicting performance, perceptual, chemical or physical properties of streams entering or exiting units in the Tubes manufacturing process using a combination of gas chromatography and mass spectrometry.
BACKGROUND OF THE INVENTION
I . FIELD OF THE INVENTION
This invention relates to a method for preparing lubricating oils by predicting performance, perceptual, chemical or physical properties of streams entering or exiting units in the Tubes manufacturing process using a combination of gas chromatography and mass spectrometry.
2. DESCRIPTION OF THE RELATED ART
Refineries and chemical plants typically control processing of various component streams and certain additives through the use of both on-line analyzers and off-line laboratory analyses to provide quality information. These quality parameters (chemical composition, physical or perceptual or performance properties) are then fed back into a process control computer which contains control software or algorithms which control refinery or chemical plant hardware (distillation towers or proportional flow control valves). The control programs are typically executed more than three times per hour and their output is used to control either processes or proportional flow valves to vary the quality of the finished product which can either go to tankage or directly to pipelines and terminals, trucks, or to ship-loading facilities. Multiple on-line analyzers are typically required for this process control.
Gas chromatograph has been used to predict physical and performance properties of hydrocarbon mixtures boiling in the gasoline range. Crawford and Hellmuth, Fuel, 1990, 69, 443-447, describe the use of gas chromatography and principal components regression analysis to predict the octane values for gasolines blended from different refinery streams. Japanese laid-open patent application 100463 relates to a method of estimating the cetane number for fuel oils by separating an oil sample into its components using gas chromatography, measuring the signal strength of ion intensities at characteristic masses in the mass spectrum, and correlating these ion intensities to cetane number using multiple regression analysis.
Combined gas chromatography/mass spectrometry (GS/MS) analysis has been done on crude oils. U. S. Patent 5,1 I 9,315 discloses a method for aligning sample SUBSTITUTE SHEET (RULE 26) data such as a mass chromatogram with reference data from a known substance.
Williams et al, 12th European Assoc. Organic Geochem., Organic Geochem. Int.
Mtg.
(Germany 09/16-20/85); Organic Geochemistry 1986, Vol. 10 (1-3) 451-461, discusses the biodegradation of crude oils as measured by GC/MS analysis.
It would be desirable to have a single analyzer means for rapidly measuring chemical or physical properties of intermediate streams in the manufacturing process and/or Tube oil products and using these properties to control units within the manufacturing process and/or product quality.
SUMMARY OF THE INVENTION
This invention relates to a process for controlling the manufacture of lubricating oils from a feed having a boiling point of about 350~C or greater by the steps of introducing the feed into a distillation unit, separating the: feed into light, medium. and heavy distillates, introducing the distillates into an extraction unit, extracting the distillates to produce raffinates, introducing the raffinates into a dewaxing unit and dewaxing the raffinates to produce lubricating oils, said process comprising:
(a) obtaining samples of at least one of lubricating oil, feed, distillate and raffinate;
(b) selecting at least one physical, chemical, perceptual or performance property of at least one of lubricating oil, feed, distillate and raf~inate:;
(c) selecting reference samples, said reference samples containing characteristic compound types present in the at least one lubricating oiI, feed, distillate and raffmate and which have known values for the properly or properties selected in step (b);
(d) producing a training set by the steps of (1) injecting each reference sample into a gas chromatograph which is interfaced to a mass spectrometer thereby causing at least a partial separation of the hydrocarbon mixture into constituent chemical components;
SUBSTITUTE SHEET (RULE 26) _3_ (2) introducing the constituent chemical components of each reference sample into the mass spectrometer, under dynamic flow conditions;
Refineries and chemical plants typically control processing of various component streams and certain additives through the use of both on-line analyzers and off-line laboratory analyses to provide quality information. These quality parameters (chemical composition, physical or perceptual or performance properties) are then fed back into a process control computer which contains control software or algorithms which control refinery or chemical plant hardware (distillation towers or proportional flow control valves). The control programs are typically executed more than three times per hour and their output is used to control either processes or proportional flow valves to vary the quality of the finished product which can either go to tankage or directly to pipelines and terminals, trucks, or to ship-loading facilities. Multiple on-line analyzers are typically required for this process control.
Gas chromatograph has been used to predict physical and performance properties of hydrocarbon mixtures boiling in the gasoline range. Crawford and Hellmuth, Fuel, 1990, 69, 443-447, describe the use of gas chromatography and principal components regression analysis to predict the octane values for gasolines blended from different refinery streams. Japanese laid-open patent application 100463 relates to a method of estimating the cetane number for fuel oils by separating an oil sample into its components using gas chromatography, measuring the signal strength of ion intensities at characteristic masses in the mass spectrum, and correlating these ion intensities to cetane number using multiple regression analysis.
Combined gas chromatography/mass spectrometry (GS/MS) analysis has been done on crude oils. U. S. Patent 5,1 I 9,315 discloses a method for aligning sample SUBSTITUTE SHEET (RULE 26) data such as a mass chromatogram with reference data from a known substance.
Williams et al, 12th European Assoc. Organic Geochem., Organic Geochem. Int.
Mtg.
(Germany 09/16-20/85); Organic Geochemistry 1986, Vol. 10 (1-3) 451-461, discusses the biodegradation of crude oils as measured by GC/MS analysis.
It would be desirable to have a single analyzer means for rapidly measuring chemical or physical properties of intermediate streams in the manufacturing process and/or Tube oil products and using these properties to control units within the manufacturing process and/or product quality.
SUMMARY OF THE INVENTION
This invention relates to a process for controlling the manufacture of lubricating oils from a feed having a boiling point of about 350~C or greater by the steps of introducing the feed into a distillation unit, separating the: feed into light, medium. and heavy distillates, introducing the distillates into an extraction unit, extracting the distillates to produce raffinates, introducing the raffinates into a dewaxing unit and dewaxing the raffinates to produce lubricating oils, said process comprising:
(a) obtaining samples of at least one of lubricating oil, feed, distillate and raffinate;
(b) selecting at least one physical, chemical, perceptual or performance property of at least one of lubricating oil, feed, distillate and raf~inate:;
(c) selecting reference samples, said reference samples containing characteristic compound types present in the at least one lubricating oiI, feed, distillate and raffmate and which have known values for the properly or properties selected in step (b);
(d) producing a training set by the steps of (1) injecting each reference sample into a gas chromatograph which is interfaced to a mass spectrometer thereby causing at least a partial separation of the hydrocarbon mixture into constituent chemical components;
SUBSTITUTE SHEET (RULE 26) _3_ (2) introducing the constituent chemical components of each reference sample into the mass spectrometer, under dynamic flow conditions;
(3) obtaining for each reference sample a series of time resolved mass chromatograms;
(4) calibrating the mass chromatograms to correct retention times;
(5) selecting a series of corrected retention time windows;
(6) selecting within each retention time window a series of molecular and/or fragment ions, said ions being representative of characteristic compounds or compound classes expected within the retention time window;
(7) recording the total amount of each characteristic compound or compound group selected in step d(6);
(8) forming the data from steps d(6) and d(7) into a Z-block matrix;
(9) forming the property data selected in (a) for reference samples selected in (b) into a Y-block matrix;
(10) analyzing the data from steps d(8) and d(9) by multivariate correlation techniques including Partial Least Squares, Principal Component Regression, or Ridge Regression to produce a series of coefficients;
(e) subjecting at least one unknown sample of at least one of lubricating oil, feed, distillate and rafl-inate to steps d( 1 ) top d(3) in the same manner as the reference sample to produce a series of time resolved mass chromatograms;
(f) repeating steps d(4) and d(8) for each mass chromatogram from step (e);
(g) multiplying the matrix from step (f) by the coefficients from step d( 10) to produce a predicted value for the property or properties of the at least one lubricating oil, and/or at least one feed, distillate and rafl-inate sample or samples; and SUBSTITUTE SHEET (RULE 26) _ .t _ (h) using the predicted values of the property or properties of the lubricating oil and/or at least one of the feed, distillate and raffinate sample or samples to control operation of at least one of the distillation unit, extraction unit and dewaxing unit.
Another embodiment of the invention relates to a method for controlling or monitoring chemical or refinery processes which utilize feedstocks and/or produce products having boiling points greater than about 350°C which comprises:
(a) obtaining at least one sample of a refinery or chemical feedstock or product;
(b) selecting at least one physical, chemical, perceptual or performance property of at least one refinery or chemical process feedstock or product;
(c) selecting reference samples, said reference samples containing characteristic compound types present in the at least one refinery or chemical process feedstock or product and which have known values for the property or properties selected in step (b);
(d) producing a training set by the steps of (I) injecting each reference sample into a gas chromatograph which is interfaced to a mass spectrometer thereby causing at least a partial separation of the hydrocarbon mixture into constituent chemical components;
(2) introducing the constituent chemical components of each reference sample into the mass spectrometer, under dynamic flow conditions.
(3) obtaining for each reference sample a series of time resolved mass chromatograms;
(4) calibrating the mass chromatograms to correct retention times;
(5) selecting a series of corrected retention time windows;
(6) selecting within each retention time window a series of molecular and/or fragment ions, said ions being representative of characteristic compounds or compound classes expected within the retention time window;
SUBSTITUTE SHEET (RULE 26) -S-(7) recording the total amount of each characteristic compound or compound group selected in step d(6);
(8) forming the data from steps d(6) and d(7) into a X-block matrix;
(9) forming the property data selected in (a) for reference samples selected in (b) into a Y-block matrix;
( I 0) analyzing the data from steps d(8) and d(9) by multivariate correlation techniques including Partial Least Squares, Principal Component Regression, or Ridge Regression to produce a series of coefficients;
(e) subjecting at least one unknown refinery or chemical process feedstock or process sample to steps d( I ) to d(3) in the same manner as the reference samples to produce a series of time resolved mass chromatograms;
(fj repeating steps d(4) and d(8) for each mass chromatogram from step (e);
(g) multiplying the matrix from step (f) by the coefficients from step d(10) to produce a predicted value of the property or properties for the refinery or chemical process feedstocks or products sample or samples; and (h) using the predicted values of the property or properties of the refinery or chemical feedstocks, intermediate or products sample or samples to control the refinery or chemical process.
The gas chromatography/mass spectrometry (GC/MS) method described above can be used to rapidly predict a wide range of perceptual, performance, chemical and/or physical properties of complex mixtures such as intermediate streams in the tubes manufacturing process and lubricating oil products. Such properties include distillation characteristics, pour point, density, aniline point, feedstock quality, cloud point, haze, viscosity and the like as well as specific chemical constituents. The multivariate correlation methods can also treat the collinear data generated by the GC/MS
analyses.
SUBSTITUTE SHEET (RULE 26) -G-BRIEF DESCRIPTION OF THE DRAWING
Figure I is a schematic flow diagram of a manufacturing process for a tube oil.
DETAILED DESCRIPTION OF THE INVENTION
The typical lubricating oil manufacturing process involves a distillation unit, an extraction unit, a dewaxing unit and optionally, a hydrofining unit.
The lubricating oil products are commonly used as base stocks for producing finished oils or may be specialty products such as transformer oils and agricultural oils.
Figure I is a schematic flow diagram showing an on-line manufacturing process. Feed stocks 10 are complex hydrocarbon mixrture;s such as crudes or heavy distillate streams. The feedstock is fed to distillation unit 20 through line 12. Feedstock may be sampled through sampling port 14 which is connected to sampling line 16 .
interrupted by valve 18.
Distillation unit 20 is typically a pipestill which distills the feed stock into a plurality of distillation cuts. For purposes of simplicity, these distillation cuts are shown exiting unit 20 as line 22 which represents a plurality of lines where n is the number of distinct distillation cuts. Each of the lines 22n may be sampled through sampling ports 24n which are connected to sampling lines 26n interrupted by valves 28n.
The distillate cuts are fed to extraction unit :30 where they are extracted using solvents such as phenol, N-methylpyrrolidone and thf; like. The extraction process results in rafl=inates and bottoms. Again for purposes of simplicity, these raffinates are shown exiting the extraction unit 30 as a single line 32n which represents a plurality of lines where n is the number of different rafflnate extracts. Mach of the lines 32n may be sampled through sampling ports 34n which are connected to sampling lines 36n interrupted by valvea 38n. The raffinate extracts are usually stripped of solvent in a stripping unit (not shown) prior to entering the dewaxing unit.
In the dewaxing unit 40, wax is removed by dewaxing aids such as methyl ethyl ketone, propane and the like. As in the previous units, for purposes of simplicity, the dewaxed raffinates are shown exiting the dev~axing unit 40 as a single line 42n where n is the number of dewaxed rafl7nates. Each of lines 42n may be sampled SUBSTITUTE SHEET (RULE 26) _7_ through sampling ports 44n which are connected to sampling lines 46n interrupted by valves 48n.
The dewaxed raf~nates exiting unit 40 through lines 42n may be used as lubricating oils (following removal of dewaxing aid). Typical examples of such Tube oils are known as Iight neutrals, heavy neutrals, bright stocks and the like. These tube oils ' may be sampled for product quality through sampling ports 44n connected to sampling lines 46n interrupted by valves 48n. These tube oils may optionally be subjected to a hydrofinishing step in a hydrofiner unit 50. Hydrofiners use catalysts and conditions well known in the art. The hydrofinished products exit hydrofiner 50 through lines 52m where m represents the number of Tube oils subjected to hydrofinishing. The hydro-finished oils may be sampled through sampling ports 54m connected to sampling lines 56m interrupted by valves 58m.
Each of lines 16, 26n, 36n, 46n and 56m are connected to sampling .
manifold 60. Sampling manifold 60 also includes an optional provision for at-line operation wherein a remote location 70 is connected to the sampling manifold through line 62 interrupted by valve 66 and sampling port 64. Sampling manifold 60 is a central location where all samples to be analyzed are gathered prior to GC/MS
analysis.
Manifold 60 can be purged by sample to be analyzed to remove contaminants and purged material recycled through line 72 interrupted by valve 74.
Sample to be analyzed is fed through line 76 to sample injection valve 80.
Injection valve 80 can likewise be purged by sample to be analyzed through line 82 interrupted by valve 84. Once sample manifold 60 and sample injection valve 80 are purged, sample to be analyzed is injected into GC/MS analyzer. Samples from off line operation can be directly injected through valve 80. Ofd line samples are those collected at remote locations and brought to a central facility for analysis. The raw data generated by GC/MS analyzer 90 is fed to computer 100. Spent sample and purging materials are sent to recycle through line 92 interrupted by valve 94. Computer 100 mathematically treats raw GC/MS data. Output from computer 100 is then fed as an electronic signal through line 102 to control computer 110. Control computer 110 is connected through line 112 to units 20, 30, 40 and 50 and controls operating conditions within said units 20, 30, 40 and 50. The operating conditions in turn controls the quality of Tube oil product exiting unit 40 and/or 50.
SUBSTITUTE SHEET (RULE 26) _g_ The operation of the GC/MS analyzer 90 and computer 100 is described in further detail as follows. The feedstock, distillate cuts and lubricating oil products are all complex hydrocarbon mixtures involving thousands of individual chemical species.
The use of GC/MS to analyze such complex mixtures for chemical and physical properties involves the generation of large amounts of collinear data.
Multiple regression analysis may be employed for treating normal linear data. However, this type of analysis cannot be used for collinear data.
The process according to the invention involves a means for predicting chemical, performance, perceptual and physical properties of feedstock, distillates, rafflnates and Lubricating oils by quantitative identification of components using a combination of retention times from a GC analysis coupled with target fragment and/or molecular ions produced by the MS. . The MS information is compared against a set of known properties from reference samples which form a training set. By mathematically comparing the experimental data with that of the training set, one may predict the desired properties of other feedstocks, distillates, raffinates and lubricating oils.
GC/MS utilizes a gas chromatograph interfaced with a mass spectro-meter. While a chromatographic method such as supercritical fluid chromatography, liquid chromatography or size exclusion chromatography may be used to separate the mixture into components or mixtures of components, gas chromatography, especially capillary gas chromatography is the preferred means for interfacing with a mass spectrometer. Both GC and MS use computer software for instrument control, data acquisition and data reduction. The computer platform should be capable of acquiring at least 2000 mass spectra in about 7 minutes.
The sample mixture to be analyzed is first injected into a GC where the mixture components are separated as a function of retention time, often on the basis of boiling points. Only partial chromatographic resolution of mixture components is necessary. The GC oven temperature is usually programmed for samples with a wide boiling range. Separated components may also be identified by a detector such as a flame ionization detector, atomic emission detector, thermal conductivity detector or electron capture detector.
The separated or partially separated components are then transferred to the mass spectrometer under dynamic flow conditions. SincE~ a GC operates under atmospheric pressure and a MS under vacuum condition (about 10--'kPa), the SUBSTITUTE SHEET (RULE 26) _9_ instrument interface requires a coupling device such as a molecular separator (e.g., jet, membrane, etc.), open split coupler or capillary direct interface to eff=iciently transfer sample while minimizing Garner gas effects.
Depending on the nature of the sample, the mixture may be introduced directly into a MS using a direct insertion probe without a prior GC
separation step.
Other thermal separation techniques not involving a GC may be used to introduce the sample into the mass spectrometer.
In the MS, sample molecules are bombarded with high energy electrons thereby creating molecular ions which fragment in a pattern characteristic of the molecular species involved. A continuous series of mass spectra are obtained over a scan range of at least 10 to at least 800 daltons. The mass spectral data may also~be acquired under selected ion monitoring (SIM) mode. In the selected ion mode, care' must be taken to select ions representative of the components of interest and to operate under repeatable conditions. A variety of MS instruments may be used including low resolution, high resolution, MS/MS (hybrid, triple quadrupole, etc.), ion cyclotron resonance and time of flight. Any ionization technique may be used, such as electron ionization, chemical ionization, multiphoton ionization, field desorption, field ionization, etc., provided that the technique provides either molecular or fragment ions which are suitable for use in the analysis procedure.
The results of sample analysis are a series of ~ mass spectra. The mass spectra are divided into n time intervals where n is an integer from 1 to f.
At least one diagnostic ion is chosen from each of m time intervals where m is an integer from 1 to n.
The term "diagnostic ion" refers to an ion which is representative of a compound, a chemical class or a performance, perceptual or physical property correlated thereto.
Regardless of whether mass spectra are obtained in the scan or selected ion monitoring mode, it is important that the mass spectra be obtained under repeatable conditions.
If the mass spectral data are acquired in the scan mode, the mass range covered during acquisition should be suff=icient to provide acquisition of all of the ions which could be used as diagnostic ions during mathematical treatment of each mass spectral scan. If the mass spectral data are acquired in the selected ion monitoring mode, then care must be taken that the ions selected for monitoring are suitable for use in measuring the components of interest.
SUBSTITUTE SHEET (RULE 26) -!0-The sample mass spectral data are then compared to mass spectral data from a series of reference samples with known performance, perceptual, physical and/or chemical properties. In order to compare reference mass spectral data with sample mass spectral data, it may be desirable to time align the sample data to help ensure the integrity of the comparison. There are commercially available computer programs for such data alignment, for example, Hewlett-Packard~C/MS software G 1034C
version C.01.05.
The reference mass spectral data, and associated properties data, are arranged in matrix form for mathematical treatment as described below. In the case of chemical composition information, one matrix is formed of reference sample ion intensities at given masses and the other matrix contains known ion intensities for molecular fragment ions of known components. The training set for chemical composi-tion data is thus made up of mass spectral data for different components characteristic of compounds or molecular series expected to be found in the sample mixtures.
Similar training sets can be formed for other chemical or perceptual or performance or physical properties of interest. These training sets form one block or matrix of data (Y-block or properties matrix). The actual sample mass spectral data (which may have been time aligned) form the other block (X-block) or matrix of data. These two matrices are subjected to mathematical treatments known as Partial Least Squares (PLS), or Principal Component Regression (PCR), or Ridge Regression (RR) to obtain a mathematically describable relationship between the properties data and mass spectral data, known as a model. Coefficients provided by this model are mathematically combined with the suitably treated mass spectral data from samples with unknown desired properties to:
a) predict desired properties b) assess the suitability of the model for such predictions, and c) diagnose the stability and general correctness of the process that yielded the mass spectral data PLS/PCR/RR are described in the literature, e.g., Wold S., A. Ruhe, H.
Wold, and W. J. Dunn, "The Collinearity Problem in Linear Regression. The Partial Least Squares (PLS) Approach to Generalized Inverses", SIAM J. Sci. Stat.
Comput., 1984 5(3), 735-743, or Geladi P., and B. R. Kowalki, "Partial Least Squares Regression: A Tutorial", Anal. Chem. Acta, 1986, 185, 1-17, or I~i~kuldsson A., "PLS
Regression Methods", J. Chemometrics, 1988, 2, 211-228, or in many other articles in journals such as the Journal of Chemometrics or Intelligent Laboratory Systems; Frank, L, and J. Friedman, "A Statistical View of Some Chemometrics Regression Tools", Technometrics, 1993, Vol. 35, No. 2; Jackson, J. E., "A User's Guide to Principal Components", Wiley-Interscience, New York, 1991; Montogomery, D.C. and E. A.
Peck, "Introduction To Linear Regression Analysis", Wiley-Interscience, New York, - 1990; and Martens, H., and T. Naes, "Multivariable Calibration", Wiley-Interscience, New York, 1989.
When dealing with a complex mixture, it is necessary to select appropriate masses or groups of masses at specific retention times for a particular compound or classes of compounds. The selection of such masses is the basis for a set a rules which then forms the data for the training set. There are no set procedures for such a selection process. The researcher must select appropriate masses for compounds of interest. For example, feed stocks and Tube oils contain a wide range of compound types such as parafflns, cycloparaffms, aromatics, and olefins. It is known that paraf~nic hydrocarbons yield fragment ions at masses 43, 57, 71, 85,...daltons, and these masses may be used as diagnostic of this class of compounds. Moreover, when coupled with retention time data, it is possible to identify concentrations of specific compounds within this class of compounds. In a similar manner, training sets for other chemical, performance, perceptual or physical properties may be developed by correlating compositional data with other properties of interest, e.g., distillation characteristics, viscosities and viscosity index, volatility, refractive index and the like.
The result of a mathematical treatment such as PLS/PCR/RR of the training set is a set of coefficients for the properties of interest.
These coefficients are then multiplied by the data matrix for the sample.
The result is a prediction of the desired property or properties which information can be used to control operating conditions in the distillation unit, extraction unit, dewaxing unit and/or hydrofiner as well as control Tube oil quality. Moreover, variances in properties serve to promptly alert operators of upsets/changes in operating conditions which could influence product quality. The method of the invention is further illustrated by the following examples.
The method for predicting the physical or chemical properties of a complex hydrocarbon mixture is demonstrated in this example using density at 15°C as the specific property for purposes of illustration. The method is generally applicable to a SUBSTITUTE SHEET (RULE 26j range of other physical properties as well as performance or perceptual or chemical properties of such mixtures.
The initial consideration is to establish a set of standard GC/MS
operating parameters so that the GC/MS analytical data used for predicting properties is obtained under consistent operating conditions. The GC/MS instrument used in this example is a Hewlett-Packard 5972 Mass Selective Detector interfaced to a Hewlett Packard 5890 Series II Gas Chromatograph fitted for use with microbore columns.
The GC/MS operating conditions are summarized in Table 1.
(e) subjecting at least one unknown sample of at least one of lubricating oil, feed, distillate and rafl-inate to steps d( 1 ) top d(3) in the same manner as the reference sample to produce a series of time resolved mass chromatograms;
(f) repeating steps d(4) and d(8) for each mass chromatogram from step (e);
(g) multiplying the matrix from step (f) by the coefficients from step d( 10) to produce a predicted value for the property or properties of the at least one lubricating oil, and/or at least one feed, distillate and rafl-inate sample or samples; and SUBSTITUTE SHEET (RULE 26) _ .t _ (h) using the predicted values of the property or properties of the lubricating oil and/or at least one of the feed, distillate and raffinate sample or samples to control operation of at least one of the distillation unit, extraction unit and dewaxing unit.
Another embodiment of the invention relates to a method for controlling or monitoring chemical or refinery processes which utilize feedstocks and/or produce products having boiling points greater than about 350°C which comprises:
(a) obtaining at least one sample of a refinery or chemical feedstock or product;
(b) selecting at least one physical, chemical, perceptual or performance property of at least one refinery or chemical process feedstock or product;
(c) selecting reference samples, said reference samples containing characteristic compound types present in the at least one refinery or chemical process feedstock or product and which have known values for the property or properties selected in step (b);
(d) producing a training set by the steps of (I) injecting each reference sample into a gas chromatograph which is interfaced to a mass spectrometer thereby causing at least a partial separation of the hydrocarbon mixture into constituent chemical components;
(2) introducing the constituent chemical components of each reference sample into the mass spectrometer, under dynamic flow conditions.
(3) obtaining for each reference sample a series of time resolved mass chromatograms;
(4) calibrating the mass chromatograms to correct retention times;
(5) selecting a series of corrected retention time windows;
(6) selecting within each retention time window a series of molecular and/or fragment ions, said ions being representative of characteristic compounds or compound classes expected within the retention time window;
SUBSTITUTE SHEET (RULE 26) -S-(7) recording the total amount of each characteristic compound or compound group selected in step d(6);
(8) forming the data from steps d(6) and d(7) into a X-block matrix;
(9) forming the property data selected in (a) for reference samples selected in (b) into a Y-block matrix;
( I 0) analyzing the data from steps d(8) and d(9) by multivariate correlation techniques including Partial Least Squares, Principal Component Regression, or Ridge Regression to produce a series of coefficients;
(e) subjecting at least one unknown refinery or chemical process feedstock or process sample to steps d( I ) to d(3) in the same manner as the reference samples to produce a series of time resolved mass chromatograms;
(fj repeating steps d(4) and d(8) for each mass chromatogram from step (e);
(g) multiplying the matrix from step (f) by the coefficients from step d(10) to produce a predicted value of the property or properties for the refinery or chemical process feedstocks or products sample or samples; and (h) using the predicted values of the property or properties of the refinery or chemical feedstocks, intermediate or products sample or samples to control the refinery or chemical process.
The gas chromatography/mass spectrometry (GC/MS) method described above can be used to rapidly predict a wide range of perceptual, performance, chemical and/or physical properties of complex mixtures such as intermediate streams in the tubes manufacturing process and lubricating oil products. Such properties include distillation characteristics, pour point, density, aniline point, feedstock quality, cloud point, haze, viscosity and the like as well as specific chemical constituents. The multivariate correlation methods can also treat the collinear data generated by the GC/MS
analyses.
SUBSTITUTE SHEET (RULE 26) -G-BRIEF DESCRIPTION OF THE DRAWING
Figure I is a schematic flow diagram of a manufacturing process for a tube oil.
DETAILED DESCRIPTION OF THE INVENTION
The typical lubricating oil manufacturing process involves a distillation unit, an extraction unit, a dewaxing unit and optionally, a hydrofining unit.
The lubricating oil products are commonly used as base stocks for producing finished oils or may be specialty products such as transformer oils and agricultural oils.
Figure I is a schematic flow diagram showing an on-line manufacturing process. Feed stocks 10 are complex hydrocarbon mixrture;s such as crudes or heavy distillate streams. The feedstock is fed to distillation unit 20 through line 12. Feedstock may be sampled through sampling port 14 which is connected to sampling line 16 .
interrupted by valve 18.
Distillation unit 20 is typically a pipestill which distills the feed stock into a plurality of distillation cuts. For purposes of simplicity, these distillation cuts are shown exiting unit 20 as line 22 which represents a plurality of lines where n is the number of distinct distillation cuts. Each of the lines 22n may be sampled through sampling ports 24n which are connected to sampling lines 26n interrupted by valves 28n.
The distillate cuts are fed to extraction unit :30 where they are extracted using solvents such as phenol, N-methylpyrrolidone and thf; like. The extraction process results in rafl=inates and bottoms. Again for purposes of simplicity, these raffinates are shown exiting the extraction unit 30 as a single line 32n which represents a plurality of lines where n is the number of different rafflnate extracts. Mach of the lines 32n may be sampled through sampling ports 34n which are connected to sampling lines 36n interrupted by valvea 38n. The raffinate extracts are usually stripped of solvent in a stripping unit (not shown) prior to entering the dewaxing unit.
In the dewaxing unit 40, wax is removed by dewaxing aids such as methyl ethyl ketone, propane and the like. As in the previous units, for purposes of simplicity, the dewaxed raffinates are shown exiting the dev~axing unit 40 as a single line 42n where n is the number of dewaxed rafl7nates. Each of lines 42n may be sampled SUBSTITUTE SHEET (RULE 26) _7_ through sampling ports 44n which are connected to sampling lines 46n interrupted by valves 48n.
The dewaxed raf~nates exiting unit 40 through lines 42n may be used as lubricating oils (following removal of dewaxing aid). Typical examples of such Tube oils are known as Iight neutrals, heavy neutrals, bright stocks and the like. These tube oils ' may be sampled for product quality through sampling ports 44n connected to sampling lines 46n interrupted by valves 48n. These tube oils may optionally be subjected to a hydrofinishing step in a hydrofiner unit 50. Hydrofiners use catalysts and conditions well known in the art. The hydrofinished products exit hydrofiner 50 through lines 52m where m represents the number of Tube oils subjected to hydrofinishing. The hydro-finished oils may be sampled through sampling ports 54m connected to sampling lines 56m interrupted by valves 58m.
Each of lines 16, 26n, 36n, 46n and 56m are connected to sampling .
manifold 60. Sampling manifold 60 also includes an optional provision for at-line operation wherein a remote location 70 is connected to the sampling manifold through line 62 interrupted by valve 66 and sampling port 64. Sampling manifold 60 is a central location where all samples to be analyzed are gathered prior to GC/MS
analysis.
Manifold 60 can be purged by sample to be analyzed to remove contaminants and purged material recycled through line 72 interrupted by valve 74.
Sample to be analyzed is fed through line 76 to sample injection valve 80.
Injection valve 80 can likewise be purged by sample to be analyzed through line 82 interrupted by valve 84. Once sample manifold 60 and sample injection valve 80 are purged, sample to be analyzed is injected into GC/MS analyzer. Samples from off line operation can be directly injected through valve 80. Ofd line samples are those collected at remote locations and brought to a central facility for analysis. The raw data generated by GC/MS analyzer 90 is fed to computer 100. Spent sample and purging materials are sent to recycle through line 92 interrupted by valve 94. Computer 100 mathematically treats raw GC/MS data. Output from computer 100 is then fed as an electronic signal through line 102 to control computer 110. Control computer 110 is connected through line 112 to units 20, 30, 40 and 50 and controls operating conditions within said units 20, 30, 40 and 50. The operating conditions in turn controls the quality of Tube oil product exiting unit 40 and/or 50.
SUBSTITUTE SHEET (RULE 26) _g_ The operation of the GC/MS analyzer 90 and computer 100 is described in further detail as follows. The feedstock, distillate cuts and lubricating oil products are all complex hydrocarbon mixtures involving thousands of individual chemical species.
The use of GC/MS to analyze such complex mixtures for chemical and physical properties involves the generation of large amounts of collinear data.
Multiple regression analysis may be employed for treating normal linear data. However, this type of analysis cannot be used for collinear data.
The process according to the invention involves a means for predicting chemical, performance, perceptual and physical properties of feedstock, distillates, rafflnates and Lubricating oils by quantitative identification of components using a combination of retention times from a GC analysis coupled with target fragment and/or molecular ions produced by the MS. . The MS information is compared against a set of known properties from reference samples which form a training set. By mathematically comparing the experimental data with that of the training set, one may predict the desired properties of other feedstocks, distillates, raffinates and lubricating oils.
GC/MS utilizes a gas chromatograph interfaced with a mass spectro-meter. While a chromatographic method such as supercritical fluid chromatography, liquid chromatography or size exclusion chromatography may be used to separate the mixture into components or mixtures of components, gas chromatography, especially capillary gas chromatography is the preferred means for interfacing with a mass spectrometer. Both GC and MS use computer software for instrument control, data acquisition and data reduction. The computer platform should be capable of acquiring at least 2000 mass spectra in about 7 minutes.
The sample mixture to be analyzed is first injected into a GC where the mixture components are separated as a function of retention time, often on the basis of boiling points. Only partial chromatographic resolution of mixture components is necessary. The GC oven temperature is usually programmed for samples with a wide boiling range. Separated components may also be identified by a detector such as a flame ionization detector, atomic emission detector, thermal conductivity detector or electron capture detector.
The separated or partially separated components are then transferred to the mass spectrometer under dynamic flow conditions. SincE~ a GC operates under atmospheric pressure and a MS under vacuum condition (about 10--'kPa), the SUBSTITUTE SHEET (RULE 26) _9_ instrument interface requires a coupling device such as a molecular separator (e.g., jet, membrane, etc.), open split coupler or capillary direct interface to eff=iciently transfer sample while minimizing Garner gas effects.
Depending on the nature of the sample, the mixture may be introduced directly into a MS using a direct insertion probe without a prior GC
separation step.
Other thermal separation techniques not involving a GC may be used to introduce the sample into the mass spectrometer.
In the MS, sample molecules are bombarded with high energy electrons thereby creating molecular ions which fragment in a pattern characteristic of the molecular species involved. A continuous series of mass spectra are obtained over a scan range of at least 10 to at least 800 daltons. The mass spectral data may also~be acquired under selected ion monitoring (SIM) mode. In the selected ion mode, care' must be taken to select ions representative of the components of interest and to operate under repeatable conditions. A variety of MS instruments may be used including low resolution, high resolution, MS/MS (hybrid, triple quadrupole, etc.), ion cyclotron resonance and time of flight. Any ionization technique may be used, such as electron ionization, chemical ionization, multiphoton ionization, field desorption, field ionization, etc., provided that the technique provides either molecular or fragment ions which are suitable for use in the analysis procedure.
The results of sample analysis are a series of ~ mass spectra. The mass spectra are divided into n time intervals where n is an integer from 1 to f.
At least one diagnostic ion is chosen from each of m time intervals where m is an integer from 1 to n.
The term "diagnostic ion" refers to an ion which is representative of a compound, a chemical class or a performance, perceptual or physical property correlated thereto.
Regardless of whether mass spectra are obtained in the scan or selected ion monitoring mode, it is important that the mass spectra be obtained under repeatable conditions.
If the mass spectral data are acquired in the scan mode, the mass range covered during acquisition should be suff=icient to provide acquisition of all of the ions which could be used as diagnostic ions during mathematical treatment of each mass spectral scan. If the mass spectral data are acquired in the selected ion monitoring mode, then care must be taken that the ions selected for monitoring are suitable for use in measuring the components of interest.
SUBSTITUTE SHEET (RULE 26) -!0-The sample mass spectral data are then compared to mass spectral data from a series of reference samples with known performance, perceptual, physical and/or chemical properties. In order to compare reference mass spectral data with sample mass spectral data, it may be desirable to time align the sample data to help ensure the integrity of the comparison. There are commercially available computer programs for such data alignment, for example, Hewlett-Packard~C/MS software G 1034C
version C.01.05.
The reference mass spectral data, and associated properties data, are arranged in matrix form for mathematical treatment as described below. In the case of chemical composition information, one matrix is formed of reference sample ion intensities at given masses and the other matrix contains known ion intensities for molecular fragment ions of known components. The training set for chemical composi-tion data is thus made up of mass spectral data for different components characteristic of compounds or molecular series expected to be found in the sample mixtures.
Similar training sets can be formed for other chemical or perceptual or performance or physical properties of interest. These training sets form one block or matrix of data (Y-block or properties matrix). The actual sample mass spectral data (which may have been time aligned) form the other block (X-block) or matrix of data. These two matrices are subjected to mathematical treatments known as Partial Least Squares (PLS), or Principal Component Regression (PCR), or Ridge Regression (RR) to obtain a mathematically describable relationship between the properties data and mass spectral data, known as a model. Coefficients provided by this model are mathematically combined with the suitably treated mass spectral data from samples with unknown desired properties to:
a) predict desired properties b) assess the suitability of the model for such predictions, and c) diagnose the stability and general correctness of the process that yielded the mass spectral data PLS/PCR/RR are described in the literature, e.g., Wold S., A. Ruhe, H.
Wold, and W. J. Dunn, "The Collinearity Problem in Linear Regression. The Partial Least Squares (PLS) Approach to Generalized Inverses", SIAM J. Sci. Stat.
Comput., 1984 5(3), 735-743, or Geladi P., and B. R. Kowalki, "Partial Least Squares Regression: A Tutorial", Anal. Chem. Acta, 1986, 185, 1-17, or I~i~kuldsson A., "PLS
Regression Methods", J. Chemometrics, 1988, 2, 211-228, or in many other articles in journals such as the Journal of Chemometrics or Intelligent Laboratory Systems; Frank, L, and J. Friedman, "A Statistical View of Some Chemometrics Regression Tools", Technometrics, 1993, Vol. 35, No. 2; Jackson, J. E., "A User's Guide to Principal Components", Wiley-Interscience, New York, 1991; Montogomery, D.C. and E. A.
Peck, "Introduction To Linear Regression Analysis", Wiley-Interscience, New York, - 1990; and Martens, H., and T. Naes, "Multivariable Calibration", Wiley-Interscience, New York, 1989.
When dealing with a complex mixture, it is necessary to select appropriate masses or groups of masses at specific retention times for a particular compound or classes of compounds. The selection of such masses is the basis for a set a rules which then forms the data for the training set. There are no set procedures for such a selection process. The researcher must select appropriate masses for compounds of interest. For example, feed stocks and Tube oils contain a wide range of compound types such as parafflns, cycloparaffms, aromatics, and olefins. It is known that paraf~nic hydrocarbons yield fragment ions at masses 43, 57, 71, 85,...daltons, and these masses may be used as diagnostic of this class of compounds. Moreover, when coupled with retention time data, it is possible to identify concentrations of specific compounds within this class of compounds. In a similar manner, training sets for other chemical, performance, perceptual or physical properties may be developed by correlating compositional data with other properties of interest, e.g., distillation characteristics, viscosities and viscosity index, volatility, refractive index and the like.
The result of a mathematical treatment such as PLS/PCR/RR of the training set is a set of coefficients for the properties of interest.
These coefficients are then multiplied by the data matrix for the sample.
The result is a prediction of the desired property or properties which information can be used to control operating conditions in the distillation unit, extraction unit, dewaxing unit and/or hydrofiner as well as control Tube oil quality. Moreover, variances in properties serve to promptly alert operators of upsets/changes in operating conditions which could influence product quality. The method of the invention is further illustrated by the following examples.
The method for predicting the physical or chemical properties of a complex hydrocarbon mixture is demonstrated in this example using density at 15°C as the specific property for purposes of illustration. The method is generally applicable to a SUBSTITUTE SHEET (RULE 26j range of other physical properties as well as performance or perceptual or chemical properties of such mixtures.
The initial consideration is to establish a set of standard GC/MS
operating parameters so that the GC/MS analytical data used for predicting properties is obtained under consistent operating conditions. The GC/MS instrument used in this example is a Hewlett-Packard 5972 Mass Selective Detector interfaced to a Hewlett Packard 5890 Series II Gas Chromatograph fitted for use with microbore columns.
The GC/MS operating conditions are summarized in Table 1.
GG Conditions Column Phenyl Silicone (such as HP-5) lOm x 0.1 mm, 17 micron film thickness Tem erature Pro ram Initial Tem erature C 180 Initial Time minutes 0 Pro ram Rate C/min 15 Final Tem erature C 310 Final Time minutes 5.33 Pressure Pro ram Initial Pressure ( si 30 Initial Time (minutes 0 Pro ram Rate si/minute) 4 Final Pressure ( si 80 Final Time minutes) 10 Carrier Gas Helium Linear Velocit 25.6 In'ection Port Tem erature 300 C
In~ection Volume pL 0.5 S lit Ratio 500:1 Column Head Press, kPa A rox. 260 Interface Tem erature (C 310 Mass S ectrometer Conditions Ionization Mode Electron Ionization, 70 eV
nominal C cle Time minutes) 0.003 In order to predict properties (density in this example) of an unknown hydrocarbon mixture, it is first necessary to select reference samples having known values of the property or properties of interest. A series of twenty-seven (27) samples of 150N grade waxy raffmates from various crude oils were prepared and used in this example. These reference samples were used to form both training and test sets as described below.
A data treatment method should be selected prior to obtaining raw GC/MS data. Two types of data treatments which may be used are either Chemist's Rules or Hydrocarbon Compound Type Analysis as described, for example, in Robinson, C.J., "Low Resolution Mass Spectrometric Determination of Aromatics and Saturates in Petroleum Fractions", Analytical Chemistry, 1971, 43(11), pp. 1425-1434.
SUBSTITUTE SHEET (RULE 26) Chemist's Rules involve two separate sections: (1) a calibration section to correct retention times, i.e., the time between zero and the time when a given peak , occurs; and (2) the actual Rules which are based on a selectE:d series of masses corresponding to prominent compounds or molecular series expected for the type of , hydrocarbon mixture under investigation. These compounds or compound types are selected on the basis that they have prominent molecular ancUor fragment ions unique to that compound or molecular series. A portion of the Chemist's Rules are shown in Table 2. A full set of Chemist's Rules are shown in its entirety following Example 4.
COMPLETE CHEMIST'S RULES FOR. LUBES
~ Retention Timeu Rules [ Materialb I MaSSeSe Sranir,a Fnriinn 1 n_C_1G -13 57 71 85 99 113 1.00 1.89 2 I/2 G9 83 97 109 123 137 1.00 2.30 rin 3 3/4 149 1G3 177 189 203 217 1.00 2.30 rin 4 4/S 229 243 257 2G9 283 297 1.00 2.30 rin G rill 309 223 337- . 1.00 2.30 -G -G 91 105 119 133 147 1G1 1.00 2.30 7 -G.1 92 lOG 120 134 148 1G2 1.00 2.30 8 -8/-10 11S 117 129 131 143 145 1.00 2.30 9 -12 128 141 142 155 156 169 1.00 2.30 -14/-IG151 153 1G5 IG7 179 181 1.00 2.30 I1 -18 178 l91 192 205 20G 219 1.00 2.30 12 -20 202 215 22G 239 228 2.11 1.00 2.30 13 nCl7 43 S7 71 85 99 113 1.89 1.98 13 nCl7 43 57 71 8S 99 _ 1.89 1.98 . 113 14 isoPara-13 S7 71 85 99 113 1.98 2.30 nCl8 .13 57 71 85 99 113 2.30 2.-10 1G isoPara43 57 71 85 99 113 1.980 2.30() 17 I/2 G9 83 97 109 12 137 2.400 3.22() rin 3 18 3/4 1.19 1G3 177 189 _ 217 2.400 3.220 rin 203 19 4/5 229 2.13 257 269 283 297 2.400 3.22() rin 172 -8/-1U 115 117 129 131 143 145 12.07 14.00 173 -12 128 141 142 155 _ 1G9 12.07 14.0() 174 -141-IGI51 153 IGS IG7 179 181 12.07 1.1.00 175 -18 178 191 192 205 20G 219 12.07 14.00 17G -20 202 2I5 22G 239 228 241 12.07 1.1.00 177 nC39 .13 57 71 85 99 113 12.83 12.87 178 isoPara-13 57 71 85 99 113 12.88 14.00 ~ ~
SUBSTITUTE SHEET (RULE 26) -1~-a) Rule number, integer index b) Compound or group of compound rule applies to:
I/2 ring I/2 ring cycloparaflins 3/4 ring 3/4 ring cyclopara~ns 4/5 ring 4/5 ring cycloparafflns 6 ring 6 ring cycloparafflns -6 CnH2n-6 alkylated benzenes -6.1 CnH2n-6 linear alkkylated benzenes -8/-10 CnH2n_g alkylated indanes, CnH2n-10 alkylated indenes -12 CnH2n-12 aIkylated naphthalenes -14/16 CnH2n-14 alkylated acenaphthenes/CnH2n_16 alkylated acenaphthalenes -18 CnH2n-18 alkylated phenanthrenes/anthracenes -20 CnH2n-20 alkylated naphthenophenanthrenes c) Masses used in Rule jup to n may be specified, where n is an integer which is equial to the number of masses scanned during the time interval (d)].
d) Retention time for both starting and ending expected retention times based on historical averages in minutes.
A reference retention time is then determined for each mass spectral ion grouping selected for use in the Chemist's Rules for each of the selected molecular types or molecules identified in Table 2. Such corrections are necessary due to slight shifts in retention times which may result from column degradation, column head pressure fluctuations, changes in column carrier gas linear velocity, or minor fluctuations in the GC column oven temperatures or other causes. The calibration step generates a series of correction factors for the entire GC/MS data file. There are commercially available programs which will perform retention time corrections. The results of applying such corrections are shown in Table 3.
SUBSTITUTE SHEET (RULE 26) REFERENCE CALIBRATION
MASSa TIMEb TYPEc LMTd TIlWe CORRCTIONf 268 2.800 P O.IS 2.794 -0.006 282 3.276 P 0.15 3.272 -0.004 366 6.260 P 0.15 6.266 0.006 422 7.953 P 0.15 7.953 0.000 57 10.556 P 0.15 10.-'i91 0.035 a) Mass or compound selected for the calibration b) Expected occurrence time, typically based on average of several analyses c) P=Peak or maximum occurrence, F=First occurrence of the material d) Range (~ minutes) for reference material fj Correction to be applied between reference materials (column a). Correction for first material is from initial time to calibration time; correction for second material is between first and second reference materials; and last correction is applied to end of data acquisition.
Once the correction coefficients are determined, the actual Rules are then determined. In the case of density preduction, a total of 178 Rules is used based on compound or compound series identification. For each Rule, a set of characteristic mass numbers are determined. These characteristic mass numbers can range from 1 to n, where n is an integer representing the entire mass range scanned or the number of selected ions being monitored. In this case, six characteristic; mass numbers are illustrated. The ion intensities of the masses for each Rule are summed within the upper and lower retention time limits for that rule. The results are shown for a sampling of the 178 Rules in Table 4 for this demonstration analysis. A full set of rules is shown in its entirety following Example 4.
SUBSTITUTE SHEET (RULE 2S) o ~ ~ c o 0 o c o W W ~ W W W
o o o o~o o~
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. N U ~ O N N N N N N N N N N ~ N N
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SU8ST1TUTE SHEET (RULE 26) _ 18 0 0 0 0 ~ ~~ ~ ~ W W W
~ n o 0 0 00 0 0 0 ~ o 00~ro o . . . 0 00 0 0 0 0 0 .oa.0 0 00 0 0 .-rr o0 'n-..oo - ~p ~r ~ o~~c o~~ ~n ~ o - c~~
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N N N N , . O OO O O Q~O
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SUBSTITUTE SNEET (RULE 26) Total Raw Abundance (TIC): total area observed in the GC/MS analysis.
Chemist Rule: total area found using the Chemist's Rules;
based on experience, should be greater than 30% of total raw abundance.
Air Leakage: total ionization due to a.ir (m/z 28, 32, 40, 44) useful diagnostic for instrumentation problems.
Average Scan Rate (Min/Max): shows the minimum, average and maximum scan rates during the GC/MS analysis and is a useful diagnostic to identify instrumental problems.
Number of records: is the number of mass spectral scans acquired during the analysis.
The analysis summarized in Table 4 is done for each reference sample.
The results from these respective analyses form a training set which is subjected to mathematical treatment. The goal is develop a model that can be used to predict the unknown properties of future samples using their mass spectral data only. The mathe-matical treatments are described by multivariate correlation 'techniques such as Projection to Latent Structures (PLS) or otherwise known a.s Partial Least Squares (PLS), Principal Component Regression (PCR), and Ridge Regression (RR). These techniques are superior to ordinary multiple linear regression in their ability to treat colIinearity amongst variables in the X-block or GC/MS data matrix (and Y-block or properties matrix for PLS), and in their ability to handle the quantity of data generated by the Chemist's Rules. Ordinary Multiple Linear Regression cannot be used to treat collinear variables.
PLS/PCR/RR are numerical analysis techniques for detecting and formulating a mathematical structure (model) within a data set comprising observations associated with multiple objects. Each object has associated. without observations for multiple variables, the latter being common to all objects. These multiple variables are assigned into two categories, known as X-block and Y-block (GC/MS data in this case).
Observations associated with all variables in the X-block are realized from a common process. Observations associated with variables in the Y-block (known properties in this SUBSTITUTE SHEET (RULE 26) case) are realized from processes that may be dii~erent for each variable. The data set used to construct this mathematical model is referred to as the model calibration data set.
The common use of PLS/PCR/RR is to apply the model developed from the calibration data set to X-block observations realized for new objects (not in the calibration data set) to predict values for the corresponding variables in the Y-block for these new objects, without having to execute the Y-block processes used in the calibration data set. Using diagnostics that are simultaneously generated by the PLS/PCR1RR model, assessment of whether the new objects can be adequately described by the model, and whether the model is used in an extrapolation mode versus interpolation mode can be performed. , PLS/PCR addresses the collinearity features in the X-block and Y-block, by suitably reducing the dimensionality in both X- and Y-blocks (for PLS), and X-block only (for PCR) to form the model. Collinearity is a term referring to the existence of relationships between variables within the block itself. In the PLS modeling algorithm a number of independent dimensions in the X- and Y- blocks are identified by forming pseudo-variables known as principal components or latent vectors through different sets of linear combinations of original variables in each block. Each set of such combinations constitutes an independent dimension. It comprises a set of coefficients that each value associated with each variable in the block is to be weighted by to arrive at the new value for this dimension. The values for the new, reduced dimensions in the Y-block are regressed onto their counterparts in the new, reduced dimensions of the X-block to arrive at the most parsimonious dimension size (number of latent vectors) and their associated weights, with the final goal of one linear equation generated to permit predic-tion of Y-block variables using X-block variables. The number of dimensions used to construct the model is determined through optimization of a criterion known as PRESS
(Prediction Error Sum of Squares), cumulated by a Cross Validation (CV) technique using the training data set, and, following the general model parsimony principle.
For PCR, the number of independent dimensions in the X-block are first selected and identified in a similar fashion as in PLS by forming principal components.
Then, for each variable in the Y-block, a model is obtained by performing ordinary multiple linear regression using the Principal Components as "Prediction Variables".
SUBSTITUTE SHEET (RULE 26) F'or Ridge Regression, the collinearity problem is dealt with in a different manner than PLS/PCR. Here a diagonal matrix known as the Lambda Matrix is added to the Covariance Matrix of the X-block with the net erect of stabilizing the numerical computation needed to obtain the model coefficients. The selection of Lambda values is through optimization of PRESS criterion using cross validation of the training set.
Thus, the Chemist's Rule data for the various; reference samples derived from GC/MS analysis form the X-block variables. PLS/PCIt/RR treatment may require preliminary reorganization of the X-block data, such as transposition and removal of redundant data and constants or mathematical transformations. The Y-block variables are the property (or properties) to be predicted, and may also require mathematical transformations such as logarithmic or geometric, as well as reorganization.
The data blocks may be represented by: - .
X-BLOCK MATRIX
jChemist's Rules (n samples x 178 columns)]
X1,1 X1,2 X1,3 ... XI,176 X1,177 x1,178 X2,1 X2,2 X2,3 ... X2,176 X2, I77 X2,178 X3,1 X3.2 X3.3 ... X3,176 X3,177 X3,178 Xn, Xn,2 Xn,3 ... Xn,176 Xn,177 Xn,178 l Y-BLOCK VECTOR
[Measured property or properties (n samples)]
Yn SUBSTITUTE SHEET (RULE 26) The Y-block may be a single observation per set of Chemist's Rules as shown above, or it may be a n x m matrix of observations where there are m different properties to be predicted.
The results of PLS treatment of the training set data are a series of coe~cients. Raw GC/MS data from an unknown sample (or samples) are then treated by the Chemist's Rules first to correct the retention times and then to form the ion summations. Each value for the Chemist's Rule ion summation result is then multiplied by the training set coefficients and summed to generate the prediction of the desired property. Table 5 illustrates the quality of the predicted density values for both the training set and the unknown test set for density at 15°C.
Predicted vs. Measured Waxy Raffinate Density Values @ 15°C (g/ml) Measured* Predicted Trainin Set 1 0.8478 0.8481 2 0.8597 0.8608 3 0.8642 0.8649 4 0.8614 0.8645 5 0.8657 0.8690 6 0.8616 0.8610 7 0.8680 0.8665 8 0.8596 0.8593 9 0.8596 0.8609 10 0.8640 0.8637 11 0.8645 0.8661 12 0.8762 0.8772 13 0.8849 0.8863 14 0.8607 0.8589 15 0.8675 0.8652 16 0.8622 0.8635 17 0.8699 0.8691 18 0.8749 0.8743 19 0.8636 0.8636 20 0.8636 0.8632 21 0.8794 0.8771 22 0.8724 0.8722 23 ~ 0.8600 0.8613 SUBSTITUTE SHEET (RULE 26) Test Set 24 0.8695 0.8fi91 25 0.8664 0.8fi44 ' 26 0.8665 0.8fi45 27 0.8768 0.8 758 * measured by ASTM D 4052-91 The procedure of Example 1 was repeated for predicting refractive index @ 75°C for the suite of 150N grade waxy raf$nates. The same 22 samples were used for the training set, while the remaining five samples were used as a test set. The results for the refractive index at 75°C are summarized in Table 6.
Predicted vs. Measured Refractive Index @ 75°C
Measured* Predicte;d Trainin Set 1 1.4441 1.4434 2 _ 1.4504 1.4505 3 1.4534 1.452!
4 1.4509 1.452E~
1.4540 1.4551 6 I .4509 1.450 7 7 I .4550 1.4540 8 I .4504 I .4499 9 1.4495 1.4500 1.4523 1.4514 11 1.4525 I .4532 12 1.4573 1.457 7 13 1.4628 1.4626 14 1.4506 1.4500 1.4542 1.4535 I 1.4528 1.453 8 17 1.4575 1.4571 18 1.4581 1.4575 19 1.4505 1.4519 1.4512 1.4519 2 I .4616 1.4609 I
22 1.4576 1.4582 SUBSTITUTE SHEET (RULE 26) Test Set 23 1.4497 1.4503 ' 24 1.4546 1.4546 25 1.4525 1.4522 26 1.4530 1.4526 27 1.4582 1.4579 ~
*measured by ASTM D 1218-92 The procedure of Example 1 was repeated for predicting viscosity at 100°C for ISON grade waxy raffinates. The same 22 samples were used for the training set, while the remaining five samples were used as a test set. The results for density prediction are summarized in Table 7.
Predicted vs. Measured Viscosity @ 100°C (cSt) Measured* Predicted Trainin Set 1 5.38 5.37 2 4.72 4.74 3 4.79 4.79 4 4.68 4.74 5 4.74 4.79 _ 6 4.48 4.48 7 4.49 4.42 8 4.35 4.27 -9 4.38 4.34 I 0 4.44 4.3 8 11 4.41 4.53 12 4.61 4.66 13 4.76 4.84 14 4.49 4.45 I S 4.59 4.56 ' 16 4.84 4.88 I 7 4.96 5.00 I 8 4.74 4.62 19 4.16 4.39 20 4.91 4.88 21 5.19 S. I4 SUBSTITUTE SHEET (RULE 26) Test Set 22 5..07 5.07 23 4.3 5 4.45 24 4.67 4.51 25 4.39 4.41 26 5.00 4.90 27 4.81 4.79 *measured by ASTM D 445-8f~
The procedure of Example 1 was repeated for predicting weight percent wax content for 1 SON grade waxy raffmates. The same 22 samples were used for the training set, while the remaining five samples were used as a test set. The results for density prediction are summarized in Table 8. ~ .
Predicted vs. Measured Wax Content (Wt%) Measured* Predicted Trainin Set I 21.8 22.0 2 25.7 23.5 3 20.0 21.5 4 20.6 20.0 19.1 17.8 6 29.6 29.5 7 17.5 18.6 8 20.0 21.4 9 20.8 19.9 19.4 18.8 I 1 18.8 19.8 12 3.6 3.6 13 2.4 0.9 14 I 8.4 20.8 IS 16.9 18.0 16 16.2 16.5 I 7 14.6 14.4 I 8 6.7 7.5 19 20.2 17.4 21.2 21.1 SUBSTITUTE SHEET (RULE 26) Test Set 21 10.4 10.4 22 1 1.6 12.3 23 23.5 22.5 24 7.6 9.4 25 18.1 I 7.5 26 20.4 20.2 g.6 8.4 *measured by ASTM D 3235-88 Other properties of various grades of lubricating intermediate streams or.
finished products, such as, cloud point, flash point, viscosity index, pour point, basic nitrogen content, distillation and volatility characteristics, viscosity at 40°C, aniline point, sulfur content, etc., could be predicted using the method according to the invention.
The subject method can also be applied for predicting properties of other types of complex hydrocarbon mixtures in similar boiling ranges, such as catalytic cracker feedstock quality, feed to extraction or dewaxing units, feedstocks to distillation or stripping towers, and to blending considerations.
SUBSTITUTE SHEET (RULE 26) COMPLETE CHEMIST'S RULES FOR LUBES
Retention Rulea ~ Materialb ~ Masseso ~ Starting ~ Ending I nC 16 43 57 71 85 99 113 1.00 1.89 2 I/2 rin 69 83 97 109 123 137 1.00 2.30 3 3/4 rin 149 163 177 189 203 217 1.00 2.30 4 4/5 rin 229 243 257 269 283 297 1.00 2.30 6 rin 309 223 337 1.00 2.30 6 -6 91 105 119 133 147 161 1.00 2.30 7 -6.1 92 106 120 134 148 162 1.00 2.30 8 -8/-10 115 117 129 131 143 145 1.00 2.30 9 -12 128 141 142 155 156 169 1.00 2.30 -14/-16 151 153 165 167 179 181 1.00 2.30 11 -18 178 191 192 205 206 219 1.00 ~ ~
2.30 12 -20 202 215 226 239 228 241 1.00 2.30 13 nC I 7 43 57 71 85 99 1 1.89 1.98 14 isoPara 43 57 71 85 99 113 1.98 2.30 1~ nCl8 43 57 71 85 99 113 2.30 2.40 16 isoPara 43 57 71 85 99 113 2.40 3.22 17 1 /2 rin 69 83 97 109 I 13 2.40 3 .22 18 3/4 rin 149 163 177 189 203 217 2.40 3.22 19 4/5 rin~ 229 243 257 269 283 297 2.40 3.22 6 rin 309 223 337 2.40 3.22 21 -6 91 105 119 133 147 161 2.40 3.22 22 -6.1 92 106 120 134 148 162 2.40 3.22 23 -8/-10 115 117 129 131 143 145 2.40 3.22 24 -12 128 141 142 155 I56 169 2.40 3.22 -14/-16 151 153 165 167 179 18I 2.40 3.22 26 -18 178 191 192 205 206 219 2.40 3.22 27 nC 19 43 57 7I 85 99 1 2.70 2.85 28 isoPara 43 57 71 85 99 113 2.85 3.22 29 nC20 43 57 71 85 99 113 3.22 3.34 isoPara 43 57 71 85 99 I13 3.34 3.70 31 1 /2 rin 69 83 97 109 123 13 3 .34 4.20 = 7 32 3l4 rin 149 163 177 189 203 217 3.34 4.20 33 4/5 rin 229 243 257 269 283 297 3.34 4.20 34 6 rin 309 223 337 3.34 4.20 -6 91 105 119 133 147 161 3.34 4.20 36 -6.1 92 106 120 134 148 162 3.34 4.20 37 -8/-10 115 117 129 131 143 145 3.34 4.20 38 -12 128 141 142 155 156 I69 3.34 4.20 39 -14/-16 151 153 I65 167 179 181 3.34 4.20 SUBSTITUTE SHEET (RULE 26) 40 -18 178 191 192 205 206 219 3.34 ~ 4.20 41 -20 202 215 226 239 228 241 3.34 4.20 42 nC21 43 57 71 85 99 113 3.70 3.83 43 isoPara 43 57 71 85 99 113 3.84 4.20 44 nC22 43 57 71 85 99 I13 4.20 4.33 45 isoPara 43 57 71 85 99 113 4.33 4.72 46 1/2 rin 69 83 97 109 123 137 4.33 5.20 47 3/4 rin 149 163 177 189 203 217 4.33 5.20 48 4/5 rin 229 243 257 269 283 297 4.33 5.20 49 6 rin 309 223 337 4.33 5.20 50 -6 91 105 119 133 147 161 4.33 5.20 51 -6.1 92 106 120 134 148 162 4.33 5.20 52 -8/-10 I15 117 129 131 143 145 4.33 5.20 53 -12 128 141 142 155 156 169 4.33 5.20 54 -14/-16 151 153 165 167 179 181 4.33 5.20 55 -18 178 191 192 205 206 219 4.33 5.20 56 -20 202 215 226 239 228 241 4.33 ~ 5.20 57 nC23 43 57 71 85 99 113 4.72 4.83 58 isoPara 43 57 71 85 99 113 4.83 5.20 59 nC24 43 57 71 85 99 113 5.20 5.37 60 isoPara 43 57 71 85 99 113 5.38 5.64 61 1/2 rin 69 83 97 109 I23 137 5.38 6.15 62 3/4 rin 149 163 177 189 203 217 5.38 6.15 63 4/5 rin 229 243 257 269 283 297 5.38 6.15 64 6 rin 309 223 337 5.38 6.15 65 -6 91 105 119 133 147 161 5.38 6.15 66 -6.1 92 106 120 134 148 I62 5.38 6.15 67 -8/-10 115 117 129 131 143 145 5.38 6.15 68 -12 128 141 142 155 156 169 5.38 6.15 69 -14/-16 151 153 165 167 179 I81 5.38 6.15 70 -18 178 191 192 205 206 219 5.38 6.15 71 -20 202 215 226 23 9 228 241 5.3 8 6.1 S
72 nC25 43 57 ?I 85 99 113 5.65 5.85 73 isoPara 43 57 71 85 99 113 5.85 6.15 74 nC26 43 57 71 85 99 113 6.15 6.32 75 isoPara 43 57 71 85 99 113 6.33 6.64 76 I/2 rind 69 83 97 109 123 137 6.33 7.04 77 3/4 rin 149 163 177 189 203 217 6.33 7.04 78 4/5 rin 229 243 257 269 283 297 6.33 7.04 79 6 rin 309 223 337 6.33 7.04 80 -6 91 105 119 133 147 161 6.33 7.04 81 -6.1 92 106 120 134 148 162 6.33 7.04 82 -8/-10 115 117 129 131 143 145 6.33 7.04 83 -12 128 141 142 155 156 169 6.33 7.04 SUBSTITUTE SHEET (RULE 26) 84 -14/-16 151 153 165 167 179 181 6.33 7.04 85 -18 178 191 192 205 206 219 6.33 7.04 86 -20 202 215 226 239 228 241 6.33 7.04 87 nC27 43 57 71 85 99 113 6.65 6.75 88 isoPara 43 57 71 85 99 113 6.76 7.04 89 nC28 43 57 71 85 99 113 7.05 7.20 90 isoPara 43 57 71 85 99 113 7.21 7.45 91 1/2 rin 69 83 97 109 123 137 7.21 7.85 92 3/4 rin 149 163 177 189 203 217 7.21 7.85 93 4/5 rin 229 243 257 269 283 297 7.21 7.85 =
94 6 rin 309 223 337 7.21 7.85 95 -6 91 105 119 133 147 I61 7.21 7.85 96 -6.1 92 106 120 134 148 162 7.21 7.85 97 -8/-10 115 117 129 131 143 145 7.21 7.85 98 -12 128 141 142 155 156 169 7.21 7.85 99 -14/-16 151 153 165 167 179 181 7.21 7.85 100 -18 178 191 192 205 206 219 7.21 7.85 101 -20 202 215 226 239 228 241 7.21 7.85 102 nC29 43 57 71 85 99 113 7.46 7.65 103 isoPara 43 57 71 85 99 113 7.66 7.85 104 nC30 43 57 71 85 99 lI3 7.85 8.00 105 isoPara 43 57 71 85 99 113 8.OI 8.30 106 I/2 rin 69 83 97 109 123 137 8.01 8.65 107 3/4 rin 149 163 177 189 203 217 8.01 8.65 108 4/5 rin 229 243 257 269 283 297 8.01 8.65 109 6 rin 309 223 337 8.01 8.65 110 -6 91 105 119 133 147 161 8.01 8.65 II1 -6.1 92 106 120 134 148 162 8.01 8.65 112 -8/-10 II5 117 129 131 143 145 8.01 8.65 113 -12 128 141 142 155 156 169 8.01 8.65 114 -14/-16 151 153 165 167 179 181 8.01 8.65 115 -18 178 191 192 205 206 219 8.01 8.65 116 -20 202 215 226 239 228 241 8.01 8.25 117 nC31 43 57 71 85 99 113 8.30 8.37 118 isoPara 43 57 71 85 99 113 8.38 8.65 119 nC32 43 57 71 85 99 113 8.66 8.79 120 isoPara 43 57 71 85 99 113 8.77 8.99 121 1/2 rin 69 83 97 109 123 137 8.77 9.45 122 3/4 rin 149 163 177 189 203 217 8.77 9.45 123 4/5 rin 229 243 257 269 283 297 8.77 9.45 124 6 rin 309 223 337 8.77 9.45 125 -6 91 105 119 133 147 161 8.77 9.45 126 -6.1 92 106 120 134 148 162 8.77 9.45 127 -8/-10 115 117 129 131 143 145 8.77 9.45 SUBSTITUTE SHEET (RULE 26) 128 -12 128 141 142 155 156 169 8.77 9.45 129 -14/-16 I 153 165 167 179 I 8.77 9.45 I
130 -18 178 191 192 205 206 219 8.77 _ 9.45 131 -20 202 215 226 23 228 241 8.77 9.45 132 nC33 43 57 71 85 99 113 8.95 9.11 133 isoPara 43 57 71 85 99 113 9.11 9.50 134 nC34 43 57 71 85 99 113 9.50 9.56 135 isoPara 43 57 71 85 99 113 9.56 9.92 136 1/2 rin 69 83 97 109 123 137 9.56 _ 10.51 137 3/4 rin 149 163 177 189 203 217 9.56 10.51 138 4/5 rin 229 243 257 269 283 297 9.56 10.51 139 6 rin 309 223 337 9.56 10.5 140 -6 91 105 119 133 147 161 9.56 _ 10.51 141 -6.1 92 106 120 134 148 162 ~ 9.56 10.51 142 -8/-10 115 1 129 131 143 145 9.56 10.51 143 -12 128 141 142 155 156 169 9.56 10.51 144 -14/-16 I51 153 165 1'67 I79 181 9.56 10:51 145 -18 178 191 192 205 206 219 9.56 10.51 146 -20 202 215 226 239 228 241 9.56 1Ø51 147 nC35 43 57 71 85 99 113 9.93 10.04 148 isoPara 43 57 71 85 99 113 10.04 10.51 149 nC36 43 57 71 85 99 113 10.51 10.67 150 isoPara 43 57 71 85 99 113 10.67 11.16 151 I/2 rin 69 83 97 109 123 137 10.67 I 1.93 152 3/4 rin 149 163 177 189 203 217 10.67 11.93 153 4/5 rin 229 243 257 269 283 297 10.67 11.93 154 6 rin 309 223 337 10.67 1 1.93 155 -6 91 105 119 133 147 161 10.67 11.93 156 -6.1 92 106 120 134 148 162 10.67 11.93 157 -8/-I0 115 117 129 131 143 145 10.67 11.93 158 -12 128 141 142 I55 156 169 10.67 11.93 159 -14/-16 I51 153 165 167 179 181 10.67 11.93 160 - I 8 178 191 192 205 206 219 10.67 11.93 161 -20 202 215 226 239 228 241 10.67 11.93 162 nC37 43 57 71 85 99 113 11.17 11.28 163 isoPara 43 57 71 85 99 113 11.29 11.93 164 nC38 43 57 71 85 99 113 11.94 12.06 165 isoPara 43 57 71 85 99 113 12.07 12.83 166 I/2 rin 69 83 97 109 123 137 12.07 14.00 167 3/4 rin 149 163 177 189 203 217 12.07 14.00 168 4/5 rin 229 243 257 269 283 297 12.07 14.00 169 6 rin 309 223 337 12.07 14.00 170 -6 91 105 119 133 147 161 12.07 14.00 171 -6.1 92 106 120 134 148 162 12.07 14.00 SUBSTITUTE SHEET (RULE 26) 172 -8/-10 115 117 129 131 143 145 12.07 14.00 173 -12 128 14I 142 155 156 169 12.07 14.00 174 -14/-16 151 153 165 167 179 181 12.07 14.00 175 -18 178 I91 192 205 206 219 12.07 14.00 176 -20 202 215 226 239 228 241 12.07 14.00 17_7_ nC39 43 57 71 85 99 113 12.83 12.87 178 isoPara 43 57 71 85 99 113 12.88 14.00 ~
a) Rule number, integer index b) Compound or group of compound rule applies to:
1/2 ring 1/2 ring cycloparaffins 3/4 ring 3/4 ring cycloparaffins 4/5 ring 4/5 ring cycloparaffins 6 ring 6 ring cyclopara~ns ' -6 CnH2n-6 alkylated benzenes -6.1 CnH2n-6 linear alkylated ben2:enes -8/-10 CnH2n_g alkylated indanes, CnH2n-10 alkylated indenes -12 CnH2n-12 alkylated naphthalenes -14/-16 CnH2n-14 alkylated acenaphthenes/CnH2n-16 alkylated acenaphthalenes -18 CnH2n-18 alkylated phenanthrenes/anthracenes -20 CnH2n-20 alkylated naphthenophenanthrenes c) Masses used in Rule jup to n may be specified, where n is an integer which is equal to the number of masses scanned during the time interval (d)]
d) Retention time for both starting and ending expected retention times based on historical averages in minutes.
SUBSTITUTE SHEET (RULE 26) o a a ~ o O ~ O O O O O O O O O O N ~ - t~
~ O O O O O O O O O O O O O O O O
U
C
cC
'fl = M ~tO O O O O O O O O O ~ ~O~n~
N ~ I~ InN ~n l 00 N O M ~DvD
~ N M M I~h ~ M 00 ~O~ et ~fct M
~h V1V7V1V1h V1 N V1t~N N '~ V1V1 ' O O O O O O O O O O O O O O O O
C O O O O O O O O O O O O O O O O
U o o cio C o o c o 0 o c o 0 0 0 t -n o0 0~o~a~ a~o~a~ o~a' a'c~ o~c~ o~o~
0 o C ~ N N N N N N N N N N N O~ N M N
M U ~ N N N N N N N N N N N ~ N N M
r O N
~ O N
N N N N N N N N N N N N V' rtv1v1 ' N OD O O O O O O O O O O O O O O O O
,_,O O O O C O O O O O O O O O O O
O C O C O O C C O O O O O C O O O
00 000000 000000 0000 0000 0ova ~G~;~n ~ a~ o\v.o~ o~a.o~ o.o~ o~o, a oo ~ o~Q.
R ~ O~~ ~ C~O~~ C~C~ Q~O~ O~00 O~N M
O 00~ N ~T C%~O O O O O O O O O O O O ~ ~ N N
v~ ~ ~ ~ ~
V'1N N 00 n ~ I~ N
N ~ N
e~ O O O O O O O O O O O O O O O O
n ~ O~ O O O O O O O O O O O 00 O O N
00 M M M M M M M M M M M O~ M ~ N
Li. M = ~ N N N N N N N N N N N ~ N N M
~
r~
O O O O O O O O O O O O O O O O
O O O O O O O O O O O O ~ 00O O
Q! R O O O O O O O O O O O O 00 O~M ~
C/1 ~ ~ N N
v X M f~t~l~ ~ N V1~ ~ ~ ~ M M M M
U 'r ~ N N ~ ~ ~ ~ N
N ~
J
_ U C7 ~ 4\ M M M f~00 M ~O O~~O 00O~ O~O~O~
O~ N O 00 ~ C 'Y~ (~O N Qv OvO~U
R pn - N N ~ N N
~ ~ ~ ~
e~
V1 U ~ Q~ M ~ ~ u1 f~1!1 O~V'1 N ~ V1 ~ 00 O 00 M M 0 O 00 000000 C ~ ~ N ~ ~ ~ ~
y N
C ."_, N
V
ec _sy L In c~ ,r ~ c~t~t~ t~O~O a'N ~nN ~O~ ~
cc-~.. G I~ ~ n v1 M ~ N N ~' ~DO~ N I~ I~(~
~
_eG~ ~--~ ' ~ N M ~ .- N
O _C._>
E- U Q Q Z
t~ M M M M V7~O I~~ M ~ V1t~ I~C~I~
v1 00~O~ N O O ~-C' ~1Ov ~ v1 1!1V W
!1 ~ N N ~ ~ N
M Q1Q1~ Q~~ N V100 ~ 00 N M M M M
~ ~O'cTN O Q\O~--N m I~O V I ~ ~T
rf N M -- ~ ~ N
-fl C
C
\p R cC
r- C C C v _ _ C .
L L ~L 1 ~ R ~ R
= '- ~ c -U U N ~ ~n~. W N o0O p p C ~ M ~ ~O~ ~0 00~ 1 i N C .NG .
' 1 R - INM ~Tv1vOlf~~00~0~C ~~~NM eT
~
.
~L I
L~I
SUBSTITUTE SHEET (RULE 26) 0 0 0 o a o .o.o~oo ~ 0 0 0 0 0 0 0 0'0 0 0 y \ o o~o.o.a \ o yy y \ \ o \ y y y y y y ~
~nO O O ~O- - M N O N O~~Ov~~OC O G ~ON h v~~pN -O O O O O O O O O M M ~O00O~~ O O ~ N N N N O O
0 0 0 0 0 0 o c o 0 0 0 00 .-o o c.0 0 0 0 0 o co I
~OO~O O v~N ~Ov~v'1O ~D~OMO~N N v'1C>etM v'1h C~Q~O~
00 O - ~Dm n h O~~M oo~ Ov Own Ow0 h O~~O
01~O O ~ O 00h ~ ~DMv0h 0000 ~ et_ ~ M O O
O ~ N O M - vD - Ovhh M er~ 00N Cv~ m ~Ov~
h ~nV N O ~O ~D~DN~O~ - et~Oh - M h M
h N N ~n~DM OO~ 0000O O O
- NM h V V V''~~h~ C'rtC'C ~D~f'et-M
O O O O O O O O O O O O OO O O O C)O O O O O O O
t ~ i ~ ~ i i i ~ ~ ~ ~ ~ ~O~ ~O~O~O~T~p~ph Q1O~C~QYO~O~Q~O~C~O~O~
O O O O D O
_ _ _ _ _ _ MO~O~O O~CrQ O O O O~C O
~ ~ ~ ~ ~ ~ ~
N N N N N N N N N N 00N M~O~ _ _ _ _ _ _ _ M M M M M M M M M M N M MM rr!r!rd'~ ~ ~ ~ ~ Q ~-V1V1V1V1V'1V7~!1V1V7V1~O~O!r~ !r'~T!rd'lT'~~'~ ~!'~ Q
O
O O O O O O O O O O O OO O O O C)C)O O O O O O
O O O O O O O O O O O O OO O O O C)O O O O O O O
O O O O O O O O O O O O OO O O O C)O O O O O O O
~ n n n ~ n n n n n n n n n n n n n a n n n n.
.
~!1V1v-)v1V1V1~nV1V1~n~ ~!'~O~O~D~O~OK)~O~D~D~O~O~O~O
O~Q~U O~'fit~M M M M C~1M M M M M M M
M M M M M M M M M M ~O00NM M M M ('~)M M M M M M M
N N N N N N f'!('JN N N N MM M M M (r1M M M r1r1r7r1 ~ ~ f f O O O O O O C C O O O O OO O O O C)O O O O O O O
N N N N N c~JN c~JN N ~nN ~rO O O O C)O O O O O O O
N N N N N N c~Jc~1N cV00N Mh N N N CJN N N N N N N
M M M M M M M r1M M N M MM ~ !r'~!~' O O O O O O O O O O O O OO O O O C)O O O O O O O
O O O O O O O O O O O ~nNC'Q et~ crV ~t~ V'~ ~ ~t 'C~r~ 'cfQ rSrf'T~r'~h 00NM M M M ('~1M M M M M M M
N N N N N N N tVN N N N MM M M M t~~r1eh!Y1ehM t~th h l h - N V~G~~ O~M M MM h h h .. N V7Ov- Ov-~ --M _ ~ ~O~DW D 00- _ M ~ ~ \DC'~D00.-.' ~ N N - N - - N N ~ N N
M M M h 00M ~CU ~OQ~Q~OvO~M M M h 00M \OO~~O00 I ~ ~
N O 00 ~Scf'Tv:h C OvOvQvQ~N O 00 ~f~ ~rW h O N
( - N N ~ ~ ~ ~ N - N N - N N
' ~ ~
O~O~O~ M Q - h U1~!1V'1v1V1U O~O~ M ~ ~ V1h v1O
v1 ~
O 00v0 r1M r~~ 'VO 00000000O 00vD M M M V1~0O M
~ I I ~
v :
.-N -i-_ ~ ~ ~ ~~ - N y - N N
.-~.J i h h h h Q~O G~ ~nN - - ~.-h ~ h h O~O O~N v'1N ~O
( ~ h ~
c~J
~
O~h W M - t~J~ fVG~h h hh O~h v~r~- N N Q ~OO~N
N
i T
-~N r1- - ~ N r~- - N
- -M M M M ~!1vp[~~ M - (~h (~[~M M M r7V1l0h - M v1 -0ov0V'N O O - ~Tv~O wevtv~~no0~Dctc~JO O ~ ~'W Qv-N N ~ ~ N c,~- - N
O~O~O~U - f'!v-)i - 00M M MM O~O~O~d'1._N V100- 00N
vO~rN 0 ~ 0~- lt~dv~t~~ ~ C'~ ~ ~SN C C~- N w t~C
- N ~"~ ~ ~ - N r~ ~ N
-~
~
W.~.C ~ O~R pR '''y~
~
N ef'v1' ~ c~!"~S'00"~C1.NC1. ' ' ~ \
i=
N ct~ni~ W N V 00O
.p~ oo- ._U 0 U0 - M Q ~Oi i n ~ ~ n C .NC.~- M ~ V7~ ~O00~ ~ s (V
n h iooo.o - rn~-mr ~ni.~-cmooic~c i-.N M -rv,~ ihoo~o~o -~ , ~ - ~ N N c~!f'J ~ ~ ~ N ~M M M r7M M M I M 'CC' i N (~JN N M M
f~J
SUBSTITUTE SHEET (RULE 26) 0 0 o a ~ a W W W W W ~ o ~ o o~ ~ ~ ~ ~ ~ ~ ~ ~ ~ y M M ~ ~ ~ ~'N V C~N ~ h h h~O~O~ O h ~ ~!1~-O M O~
~ ~ ~DN O M O O O ~n~O~n~n~O oov0~n~ vp~ ~ ~ M v0 ~ N erO O O ~ O O O O OO ~ N N N efO C O ~ C
N O N O ~Do0Ovh M O o0M O OvN vDO Ov~ ~ O Ovo00000 ~O ~'h h M N M C'0000~ 00~!1(~N N 00Qvh _ ~ h v1O
~n N M OW~ ~ 1 ~ 00N ~nN OvN~ M N M h O 00~'~DOvh h N 00N N ~no0O ~Do000~ Ovh~wD ~ O pvooN M M O ~O
_ _ M O ~n~D~O~t~n~ON o0W pM Ovo0w N O~00N ~ ~ M
v1 h v100Q~M - N O v1N N ~ON M M C~~Dct[~et~ M h C vWD OO~n~ ~ N N N N t~O Qv0000~ v'1N
N ~ N N N N N N N N N NN N M ~ V~v1v'1tnv1v~
O O O O O O O O O O O O O OO O O O O O O O O O O
O O O O O O O O O O O O O OO O O O O O O O O O O
O O O O O O O O O O O O O CO O O O O O C O O O O
00 C.CvO N N N N N N N N N NN ~ N M ~ va~nv1~w ~n N OvN N O O O O O O O O O OO M O h V v~~ v v v w n 1 1 1 00 ~ M h N N N N N N N N N NN 00N M v0~ _ _ _ _ M er~trt~nw viviw n m u1v1viv~~ viV1v1~D~O~D~D~O~O
N M M M M M M M
O O O O O O O O O O O O O OO O O O O O O O O O O
O O O O O O O O O O O O O OO O O O O O O O O O O
O O O O O O O O O O O O O OO O O O O O O O O O O
~ ~ i i ~
O ~ N M M M M M M M
Ov M OvN N N N N N N N N N NN N M O 00000000000000 ~D 00~ M M M M M M M M M M MM h ODN M M M M M M M
M M ~ ~fQ '~TV'ct~''t1'C'~f~ ~C'~ ~fV1V'1V1~!1V1V'tV1V1 O O O O O O O O O O O O O OO O O O O O O O O O C
M O M N O O O O O O O O O OO M O h C v1v~vWn ~nv~
00 N M h N N N N N N N N N NN 00N M ~ ~
M ~ C'etv~m m w n ~nw ~nownv'i~t~n~1viv0~D~O~D~O~O
O O O O O O O O O O O O O OO O O O O O O O O O O
O ~ O M M M M M M M M M M MM N M O 00000000000000 h 00N M M M M M M M M M M MM h 00N M M M M M M M
M M '~TC'~ ~fV'C'~ ~f'Cr~t~ ~~f'lT'~lN V1V1V1V7V1V1V1 M M M M h h h ~ N ~nO~~ O~~ M M M M h h h ~ N
~ M ~ U ~O~O~t~D00~~ ~ ~ M ~ ~ ~O~O
~ N N ~ NN ~ ~ N N
O~Q~M M M h 00M ~OO~~00O~O~O~Q~M M M h 00 O~ OvOv~ N O o0 !TT V w h ON OvOvOvOvN O o0 ~
~ N cV ~ ~ NN ~ N N
~
v!1V1V1t!1O~O~~ M cf--V1h V1QvV1V1vf'1V1C~O~O M
00 0000~ O 00~O ~ M y v0N o0000000O o0 ~ ~ ~ ~ N
~
~ h h h h U O . N ~nN~O.-.~ - - h h h h O~O
~ O~ ~ I
I
I~ h h h O~h vl~M- N fVa*~OO~N h h h h O~h ~11M ~ N
N M - ~ ~N ~ N M ~ -t h h h h M M M M V1~Oh ~ M ~V7h h h h M M M M ~1~O
~n v W ~n00~OetN O O ~ Q v1Ov~ m ~n~nW o0v0C'N O C
n ~ N N ~ ~N ~ N N ~
~
M M M M O~O~01Q~--N V100- OON M M M M Q1U ~ O~~ N
C ~'~ V ~D~TN O O~~ ~ N ~nhO ~ Q '~TC'~O'SN O CJ~G~
I
~ N M ~N ~ N M ~
~ C C C ~ v v N . _ _ .. O C .C_C
''' ' M ~ ~T''~v:W W
N O.N O. _ ._ W . ... _ ._ ' N N
U p U p N C ~ W. W N eTo00 ~ ~ N C W 'v:.
~D00~
C .~C .~~ M C'~O~ n y C ~ C ~ ~ M C'~O
i . .
N M Q'~ w0h I O~C ~-I M ~f WpI 00~ O ~ N M C'~nv7 o0 N h U
Q Q'~ ~ ~tC''T ~DvD~O~Dv0vCSCI
SUBSTITUTE SHEET (RULE 26) a a ~ o o a o a oa o 0 0 o a o a o o a a a a a o M M V1M f~0001~OO~00V1...O 00M N V100V'7.~~ 00~OM
00t~t~N .-.~Dv~M ~OM v1~ .~M v100[~I~N ~ ~ON ~
O O O O O N N N NetO O O ~ O O O O O O ~ N ~-.-.ri O CvO weM ~ C't~00~ N ~nN N ~ Q~Ovo0etv~Cvo0OvOv O o0N O oo~ - ooNO O N twD M ~w0 M o0~n~nM ~ N O
~O~Ov7~DN ~ M O~O~n~DvWn v1et~nM ~ Wit"v~Ov00~nOvN
00N O etN O ~OI~Q~ ~pO O ~DN N M 00O~N N ~O00N N
N ~ Ovt~- M o0M Ov~ ~ 00N 00.-.Ow0 ~D~ OvU N 00N W
M 0000~ V1~ON V1~'C'M V1'V'~ M N 00Q~~ V1M O~~OO C' M N N O O O~Ot~N ~nN M N N ~ ~D00~OI~~' V7H V1V'1N ~ V'1V7VM M M M M M M M M M M !TM N O
O O O O O O O O OO O O O O O O O O O O O O O O O
O O O O O O O O OO O O O O O O O O O O O O O O O
O O O O O O O O OO O O O O O O O O O O O O O O O
V1~1~1V1C'V1~!1~f'M M M M M M M M M M M C'M N ~ O
v~vmn ~nv~u1~nN ~er~f~'et~ etC'rtet~ ~ ~n~!'O ~mn ~ ~ ~ ~ ~ 00~ M ~DO O O O O O O O O O O t~O N ~to0 ~D~G~O~O~D~i~D~O~On l~n n t~n I~f~t~t~n ~On n n t~
M M M M M !f!fV1~V1t!1Y1V1V1V1Y1V1V1V1~!1!f'~'M N N
O O O O O O O O OO O O O O O O O O O O O O O O O
O O O O O O O O OO O O O O O O O O O O O O O O O
O O O O O O O O OO O O O O O O O ~ O O O O O O O
O
M M M M M V'~fV1V1V'1V1V1V1V1Y1V1~ V1'h V1~ ~ M N N
N ~ N MM M M M M M M M M M M V)~Ov'f.-.
M M M M M ~O00~ MM M M M M M M M M M M ~O~ O N N
~nv~~nv~V~~nvw0 v0~O~O~Dv0~OvD~D~Ov0~Ov0~D~Dn n n O O O O O O O O OO O O O O O O O O O O O O O O O
' W v1V ~nvWn W N C'C''ctcf'~ V 'vTC'Q ~TC Q ~!1~tO vWn ~ 00~ M ~OO O O O O O O O O O O t~O N V o0 ~D~O~D~O~O~n~O~D~Dn n n (~n n l~h n n t~vDI~n (~n O O O O O O O O OO O O O O O O O O O O O O O O O
0000000000V1~ V'1MM M M M M M M M M M M V1~DV)~
M M M M M ~D00~ MM M M M M M M M M M M ~O~ O N N
v1~nv~~nown v~~O~O~D~D~D~OvD~O~O~O~D~O~D~O~Ot~n n M M M MI~I~(~ N ~101~ O~~ M M M M l~
!T~O00~-~ ~ ~M ~ \D~ ~O00~ tT~ -rM
~ N N ~ N N .-N N ~
M ~OO~~D00Q~~ ~ Q~M M M I~00M ~OO~~D00O~01O~O~M
~nt~O N OvG1O~OvN O 00 ~ ~ e*m I~O N OvOvQvO~N
~ N N ~ ~ N N ~ N N
V1C~V1Q~V'fv1V1v1Q~O~01 M ~f'~ ult~V7O~~!1V1~!11!701 ~
M V1~OO M ~ OOI00OpO 00vp M M M ~ ~OO M 00000000C
--N N ~ ~ ~ ~ N --N N
O~N V1N ~D~ - .-n (~t~I~O~O O~N V~N ~O~ ~ .-- f~
1 ~
-N !S~OO~N I~I~ t~C~I~v1M ~ N N C ~OC~N t~I~l~
t~
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~ M V1L~t~(~I~M M M M V1~Oh .~M V1I~(~(~C~M
~ ~ ~nO w-~ w ~n~noo~DetN O O ~ et~nC~~ ~nv~~n~no0 .~.N .-..N N , ...N
~100~ 00N M M M MO~~ O1Qv~ N V100.~00N M M M M U
~
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t~00OvO ~ N M ~ ~n~D~ 00OvO ~ N ~ ~ v~~DI~00~ O --rt' t~ M
SUBSTITUTE SHEET (RULE 26) o o a ~ ~ ~ o a ~ \ \ \ o ~ ~ 0 0 0 0oN f O ~Df vDN ~nN vD~ ~nW O o0~nM .-~ ~ N f ~ et ~O~ O ~ ~tvDw D M ~ f N N ~nf erO O o0M f V ~tM O
O O O ~ O O O O O O .- ~ N O O O O O O O O O O
f v0N oo.-f M ~DOvOvN M M N ~n.--~Cvo0pvp~M f vDm O~
00OvO ~ N N OvV'O 0000Ovf ~n00M o0~n~DOvN etN ~ ~D
v D
O _ f 00u1f N N M v .-~M OvN 00 ~nv7~pvp~ pp_ v~
O
~tf ~ M f M ~n00W D _ v'1a000.-.Iwp f N N f f f v0~D
O o0~D~C--~D~ ~nf o0O w ~nf ~nO O~N etet~Ov00oM f f eTN M 00~DN etM ~tOvOvCv_ f Ov~ ~-.N M Ow0 00N
N rt~ N N N ~ v0~tcW0 O .-. M ...
O O O O O O O O O O O O etO~Q~O~p~O~p~p~p~p~p~
O O O O O O O O O O O O O O O O O O O O O O O O O
O O O O O O O O O O O C O O O O O O O O O O O O O
O O O O O O O O O O O O O O O O O C O O O C O O O
O O O O O O O O O O ~ O O O~T p~O~C~C~p~p~p~p~p~et ' ' V v1v1tnh V v~V'1h ~!1v1~ O OvV1v)V'1v1v1v1V'fV'1V1V1Y1 00000000000000000000~Oo0O N ~O~Ov0~D~O~Dv0~Ov0~DN
f f f f (~f f f f f n 00OG0000pppppppppppppppppp f N N N N N N N N N N O O O O O O O O O O O O O
O O O O O O O O O O O O O O O O O O O O O O O O O
O O O O O O O O O O O O O O O O O O O O O O O O O
O O O C C O O O O O O O O O O O O O O O O O C O O
N N N N N N N N N N ~ ~ O O O O O O O O O O O O O
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ N N N N N N N N N N ~V~ O~00 0 0 0 0 0 0 0 0 0 0 0 f f f f f f f f f n f f 000000OOopOQQppppppppppp f O O O O O O O O O O O O O v~O O O O O O O O O O O
V1V1V1V~~!1V1N'1~!1V7V1V1t!1O O~V1V1V'1V1~ N V1tnV1V7V1 00000000000000000000v000O N ~Gv0vOvD~O~O~Cv0vO~ON
f f f f f f f f f f f f 0000op00op00OOpppppppppppp O O O O O O O O O O ~ ~ O O O O O O O O O O O O O
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ N N N N N N N N N N et~OooO O O O O O O O O O O O
n f f f f f f f f f f f f 000000OOpppppppppppppppp f f N v1O~~ p~~ M M M M f f f N v'1~ ~ O
~
N ~ ~ V ~O00 N ~ .._~ ~p~Oet~O00_ f N N N N ~ N N
M M f 00M ~O~ ~O00Q~Q~Q~Q~M M M f 00M \OO~~O00 rP'~tv~f O N OvCvOvQvN O 00 etetetv~f O N
N N ~ ~ N ~ N N ~ N N
N
OvO~ M ~ ~ ~1f v~O~v1v~v1v~QvT O~ M ~ ~ v7f v~'Cv 00~O M M M v'1~DO M 00000000O 00~O M M M ~1~DO M
N ~ N N ~ N .-.N N
f f f p~O O~N v1N ~O~ --.-.-f f f f O~O O~N v~N ~O
f v~M .-N N V ~OO~N f f f f O~f v1M - N N rY~OO~N
N M ~ ~-N ~ N M -- ~-N
M M M N ~ f - M ~ v1f f f f M M M M h ~Of ~ M ~1 ~O~!'N O O ~ W n O~~ v mnW o 00~O'ctN O O -~~tv1Ov-N N ~ .-N ~ N N ~ ~ N
Cv~ N ~!100.-.00N M M M M O~O~C~Qv~ N ~!100 00N
C'N O CvCv- N m f O C'~ r!'W p ~ N O C~O~- N ~nf O
~ N M ~ N ~ N M .-N
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N M eTv1vDf 00.n.O --N M C'v w0f 00OvO ~ N M ~t ~D
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O~U O~O~O~O~~ U O C O O O O O O O O ~
=
SUBSTITUTE SHEET (RULE 26) a ~a o o a o o a o a a o o a o 0 o a a ~ o o a a ~n N~ t~00~tO - t~ooCvM Qv~ N M o00oO 0000O O ~O~D
~O ~~O~OQ N O O C'- N N N N O v7I~.-eft~O O O N O
O ~O O ~ O O O O O O O O O O O O O O O O O O O O
Ov N~OM o0._O O ~nt~Cv~ t~(~M Ovt~M O~~ v~O O o0~O
N V1V1O ~O00M M M O 00V'I~00C~~ ~ Op~ ~ M
t~ C 00O N 00C~00(~t~cfV1tn~ rl'M M 00O
M OvO M O~V M o0O wlN o0~Ov~ I~0000O 00O ~ ~G
00 ~D~D~D~ ~n._.M ~n~ ~ ~ M ~ QvOvooO _ ~ O N M
etv1vDooOv oot~~ O~~ oo O O two .-.M O N
N efN N ~n N M ~ M
~n O~~ etO O O O O O O O O O O ~ O vp~ ~ et~ ete~
n O O_ ~ N N N N N N N N N N N _ N N N M M M M M M
O OO O O O O O O O O O O O O O O O O O O O O O O
O OO O O O O O O O O C O O O O O O O O O O O O O
~'O O O O O O O O O O O v'1v~00vp~ eter~ ~t~
~
t ~O O P-f~t~f~t~t~t~t~t~C'~t~N ~ t~er~ eteteter~
M ~D00O etC'~!'~ er'~etrtet~'et~ ~n~nOwn ~n~nN ~nv~
00 0000O~O~O~O~C~C~Q~O~~ C~O~C~O~O~C~C~O O O O O O
V1O~~ .-..-..-..~......-..-..--.~ ~ ~ M V1O
O OO -N N N N N N N N
O OO O O O O O O O O O O O O O O
O O O O O O O O
O OO O C O O O O O O O O O O O O O O G O O O O C
O v~O~~ ._.-...-.~.-..-.....~._.~ _ _ O 00v0000000000000OQ0000000000~ N .-.00000000000000 M M~Ot't~t~t~t~h t~t~t~t~t~I~O~~ V1V1V'1V7tf'1V1V1V1 OO 00000000000000000000OpOOppOp00Q~OvCvO~O~C~C~p~T
O OO O O O O O O O O O O O O O ~nt~O O O O O O O
V1OvO W tf1vWn v~v1v1~!1v1v'1v1.~Q~V1N ~ .-M ~Dt~Q~~ C '~'Q C'C'~Y'Q ~ ~ C'~ d'h ~ V1V'1N t/1V1V'1 00 000000O~O~~ Q~U~O~O~O~O~~ C~O~Q~O~O~O O O O O O
~O OO O O O O O O O O O O O O O O ~nO O O O O O O
O~ 00~On n I~n f~I~(~n n t~t~I~N .--~C~~D~O~D~O~ ~D~D
N M~Ot~n t~n t~t~t~t~t~t~t~t~Ov~ ~fanv'~v~~nv7v~v~
00 000000000000OOppOp000000OCOOa001Qv01O~01OvOvOvO~
~ ~ M ~ ~ ~ ~ ~ M M t~t t~ N
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O~O~O~M M M t~00M ~OO~~O00CTO~~ O~M M M t~00 Ov O~OvOvN O oo C C ~t~nt~O N OvQvOvOvN O 00 ~T~T
~-N N ~ ~ N N ~ N N
V'fV1V1V1~ O~O~ M ~f- v'1t~~l1O~v1V1V1V1QvO~Q1 M
00 000000O 00~O M M M V1\OO M 00000000O 00~O M M
'-N ~ --N N .-N
i (~t~t~t~OvO OvN m N ~O~ .-.-~.~~~ c~t~T O
I I
t~ t~t~f~O~t~v'1M - N N ef~OO~I t~I~t~I~~ (~v'1M --N
N
N M - - N ~-N M --~ M M M M V1~Ot~~ M ~ V'1t~t~[~t~M M M M V1~O
ow nan~n00t0C'N O O .-~ v~Ov--own own o0~ ~fN O O
N N -~ .-N ~ N N ~
M MM M ~ O~QvQv~ N Y100~ 00N M M M M O~O~QvOv--N
~t etet~ ~O~tN O OvOv~ N ~nt~O ~t~T~ ~ ~O~ N O QvOv N M ~ ~-~ ~-~ M
N N
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N ' ~ ' r ' C W L N C 00O N ~tv1'W
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rf ~ . .
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N N N INN N ~NN N N M ~MM M M M M r~fC~1M ~TC' I l I I I I I I I
SUBSTITUTE SHEET (RULE 26) 0 0 o a a o ~ o o a o a o 0 0 0 o a \ 0 0 o a a o 0 N o0M ~nO C~~ O ~D--O O O ~nO O O O O O et-'N t~~nO
~ O ~ O O ~ M -r~ M O O O O O O O O O O O ~ O O O O
O O O O O O O O O O O O O O O O O O O O O O O O O O
O N ~ O~~ etM O O 00O O O 00O O N o0 N O
~ O ~ ~ i ~ ~OC w C ~ 0 Own O O vON O rtef p v0eth ~nOv e O ' p t M et~ h N C ~ N N ~
Q'00!t'tnv1V7~ V1tn1f'1V1N V7N tnV1V1V1V1V11nV1 M M M M M N M M M M M M M M M M M M M M M M M M M M
O
O O O O O O O O O O O O O O O O O O O O O O O O O
O O O O O O O O O O O O O O O O O O O O O O O O O O
Wit'~t~'00C V'1h V1V1t!7h V~h V1~!1h ~!1N V1V1V1V1V1V1 ' ' C ~ etV et~DetO O~~O~O~O~D~O~O~O~O~O~O~O.~~OO~~DM M
~ ' n W ~nv v1O v~h ~ OvOvOvCvOvC~OvOvOvOyOvM CvO o0O O
f O O O O O O O O ~ -.--~ . t . . .-N N e et ~ .-.~~ ~ .-.~
~O00C'~ V'1tnV'1h V1V1N ~ V1V1V1V1V1V1V1V1V1 N N
N N N N N M M M M M M M M M M M M M M M M M M M
O O O O O O O
O O O O O O O O O O O O O O O O O O O
O O O O O O O O O O O O O O O O O O O O O O O O O O
~ O 00~ V~V1~!1N V1V1V1V1~nN V1V1H V1V1V1V'fV1 00000000~n~O'cO O O O O O O O . O O O O N h O O O
O
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C~O~O~T O~O~O O O O O O O O O O O O O O ~ ~ N N N
O O O O O O O O O O O O O O O O O O O O O O O O O
_ _ _ _ O
h ~DM M M M M M M M M M M 00M ~OM O O
~nW o v~~nO ~n~D--CvOvO~OvO~OvOvCvOvCvOvN CvO o0O O
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O~O~C~C~O~O~O O O O O O O O O O O O O O ~ .--~N N N
V1O~~ Q~~ M M M ~ M ~ M M h ' ~ ~Oo0 O~ ~O~O!t~D00~ '~~ .-. ~ M
-~~.
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N N ~ N N ~ ~ N
w n h ~nO~~mn v~~nO~U O~ M ~t~ ~nh ~nO~~n~n~n~nOvOv M ~1~DO M 000000OpO pp~p M M M v'W O M 00000000O 00 p ~
N N '-N ~ N N
O~N v1N ~O.-._ .-.-h h h h O~O O~N v1N ~O~ - --~ h h N ~ ~OO~N h l~h h O~h v~M .-.N N Q ~OO~N h h h h C~h N ._N M .-. ._N
h ~ M V1h h (~h M M M M V1\ph ~.M V1h h h h M M
~nQv~ v~~n~mn o0~C~ N O O ~ ~tw C~~ v~~n~nv~oo~D
~ N ~ N N ~ ~ N
V700~ ODN M M M M ~ 01O~Q~ N V100.-~00N M M M M G1C~
N v~h O ~fQ et~ ~O~tN O QvOv~ N ~nh O ~ rfC ~t~Dv N ~ N M ..N
~O cQ cC
~ = C C
~ vl~ ~Oe ~ _ _ O ~ h R OOcC'~'C
C ~ C
n N C O00 M O..M CS. ~ ~ M M "
' U ~ U ~ N ~ ~ i. W N ~ OOO ~ ~ N
i N ~O0 ~ v n iiC . C .N~-M V ~D~ 0 ~ n ~ N C N C N ~ M
. .
N M etm D h 00O~O ~ N M V ~w0 h ~ ~ O ~ N M ~Tv~~Ch ' ' 00C~
~!C V Q'C'C''S~T~n~nW o v m ~nv~v~~n~O~D~O~D~O~DvD~D
SUBSTITUTE SHEET (RULE 26) a a o ~ a ~ ~ a a ~ ~ o O O O O O O O O O O M O
O O O O O O O O O O O O
O O O O O O O O O O O O
O
O O O O O O O O O ~ Q' 00 ~ ~O et n ~D
O rt , M
O~
M
N H h ~ h N ~ ~ h N ~
M M M M M M M M M M M
O O O O O O O O O O O
O O O O O O O O O O O
h V'1~!1V1V1V1t!1N tnV1V1 II
M M M M M M M M M O M
O O O O O O O O O C~O
'~tV'~ et~ ~ ~tet~'N ~
V'1V'fV1V1V1V1V1N t!1V1tf'f M M M M M M M M M M M
O O O O O O O O O O O
O O O O O O O O O O O
~ H N N N ~ ~ ~ N h ~
O O 0 0 O O O O O ~O~
_ _ _ _ _ _ _ _ 0001 N N N N N N N N N N N
O O O O O O O O O O O
O O O O O O O O O I~O
O O O O O O O O O o0O
eteTet~trtet~t~ ~fN ~
O O O O O O O O O O O
I~(~f~n C~n n N n M 0O
O O O O O O O O O o000 N N N N N N N N N N N
~ ~ ~ ~ M
~O~ ~ 00 ~
N ~ N N
M l~00M ~DO~~OODO~O~
efQ etv~t~O QvOv N
O
O~ M C ~ V1(~V1O~v1V1 _ N tn O M M M V1~OO M 0000 ~ N
N - N N ~ C
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t~l'~O~O OvN v1N vp.~_ y U
M .-.N N C v0OvN t~(~
N M ~ .-.N C N -a U
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N N ~ ~ N ' ' ' ~
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' U
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U ~ M C' ~O n n 00O~O .-N M V w vDn o0 ~ ~ ~ ~ ~ ~ I~I~~ ~ ~ I I
SUBSTITUTE SHEET (RULE 2S~
In~ection Volume pL 0.5 S lit Ratio 500:1 Column Head Press, kPa A rox. 260 Interface Tem erature (C 310 Mass S ectrometer Conditions Ionization Mode Electron Ionization, 70 eV
nominal C cle Time minutes) 0.003 In order to predict properties (density in this example) of an unknown hydrocarbon mixture, it is first necessary to select reference samples having known values of the property or properties of interest. A series of twenty-seven (27) samples of 150N grade waxy raffmates from various crude oils were prepared and used in this example. These reference samples were used to form both training and test sets as described below.
A data treatment method should be selected prior to obtaining raw GC/MS data. Two types of data treatments which may be used are either Chemist's Rules or Hydrocarbon Compound Type Analysis as described, for example, in Robinson, C.J., "Low Resolution Mass Spectrometric Determination of Aromatics and Saturates in Petroleum Fractions", Analytical Chemistry, 1971, 43(11), pp. 1425-1434.
SUBSTITUTE SHEET (RULE 26) Chemist's Rules involve two separate sections: (1) a calibration section to correct retention times, i.e., the time between zero and the time when a given peak , occurs; and (2) the actual Rules which are based on a selectE:d series of masses corresponding to prominent compounds or molecular series expected for the type of , hydrocarbon mixture under investigation. These compounds or compound types are selected on the basis that they have prominent molecular ancUor fragment ions unique to that compound or molecular series. A portion of the Chemist's Rules are shown in Table 2. A full set of Chemist's Rules are shown in its entirety following Example 4.
COMPLETE CHEMIST'S RULES FOR. LUBES
~ Retention Timeu Rules [ Materialb I MaSSeSe Sranir,a Fnriinn 1 n_C_1G -13 57 71 85 99 113 1.00 1.89 2 I/2 G9 83 97 109 123 137 1.00 2.30 rin 3 3/4 149 1G3 177 189 203 217 1.00 2.30 rin 4 4/S 229 243 257 2G9 283 297 1.00 2.30 rin G rill 309 223 337- . 1.00 2.30 -G -G 91 105 119 133 147 1G1 1.00 2.30 7 -G.1 92 lOG 120 134 148 1G2 1.00 2.30 8 -8/-10 11S 117 129 131 143 145 1.00 2.30 9 -12 128 141 142 155 156 169 1.00 2.30 -14/-IG151 153 1G5 IG7 179 181 1.00 2.30 I1 -18 178 l91 192 205 20G 219 1.00 2.30 12 -20 202 215 22G 239 228 2.11 1.00 2.30 13 nCl7 43 S7 71 85 99 113 1.89 1.98 13 nCl7 43 57 71 8S 99 _ 1.89 1.98 . 113 14 isoPara-13 S7 71 85 99 113 1.98 2.30 nCl8 .13 57 71 85 99 113 2.30 2.-10 1G isoPara43 57 71 85 99 113 1.980 2.30() 17 I/2 G9 83 97 109 12 137 2.400 3.22() rin 3 18 3/4 1.19 1G3 177 189 _ 217 2.400 3.220 rin 203 19 4/5 229 2.13 257 269 283 297 2.400 3.22() rin 172 -8/-1U 115 117 129 131 143 145 12.07 14.00 173 -12 128 141 142 155 _ 1G9 12.07 14.0() 174 -141-IGI51 153 IGS IG7 179 181 12.07 1.1.00 175 -18 178 191 192 205 20G 219 12.07 14.00 17G -20 202 2I5 22G 239 228 241 12.07 1.1.00 177 nC39 .13 57 71 85 99 113 12.83 12.87 178 isoPara-13 57 71 85 99 113 12.88 14.00 ~ ~
SUBSTITUTE SHEET (RULE 26) -1~-a) Rule number, integer index b) Compound or group of compound rule applies to:
I/2 ring I/2 ring cycloparaflins 3/4 ring 3/4 ring cyclopara~ns 4/5 ring 4/5 ring cycloparafflns 6 ring 6 ring cycloparafflns -6 CnH2n-6 alkylated benzenes -6.1 CnH2n-6 linear alkkylated benzenes -8/-10 CnH2n_g alkylated indanes, CnH2n-10 alkylated indenes -12 CnH2n-12 aIkylated naphthalenes -14/16 CnH2n-14 alkylated acenaphthenes/CnH2n_16 alkylated acenaphthalenes -18 CnH2n-18 alkylated phenanthrenes/anthracenes -20 CnH2n-20 alkylated naphthenophenanthrenes c) Masses used in Rule jup to n may be specified, where n is an integer which is equial to the number of masses scanned during the time interval (d)].
d) Retention time for both starting and ending expected retention times based on historical averages in minutes.
A reference retention time is then determined for each mass spectral ion grouping selected for use in the Chemist's Rules for each of the selected molecular types or molecules identified in Table 2. Such corrections are necessary due to slight shifts in retention times which may result from column degradation, column head pressure fluctuations, changes in column carrier gas linear velocity, or minor fluctuations in the GC column oven temperatures or other causes. The calibration step generates a series of correction factors for the entire GC/MS data file. There are commercially available programs which will perform retention time corrections. The results of applying such corrections are shown in Table 3.
SUBSTITUTE SHEET (RULE 26) REFERENCE CALIBRATION
MASSa TIMEb TYPEc LMTd TIlWe CORRCTIONf 268 2.800 P O.IS 2.794 -0.006 282 3.276 P 0.15 3.272 -0.004 366 6.260 P 0.15 6.266 0.006 422 7.953 P 0.15 7.953 0.000 57 10.556 P 0.15 10.-'i91 0.035 a) Mass or compound selected for the calibration b) Expected occurrence time, typically based on average of several analyses c) P=Peak or maximum occurrence, F=First occurrence of the material d) Range (~ minutes) for reference material fj Correction to be applied between reference materials (column a). Correction for first material is from initial time to calibration time; correction for second material is between first and second reference materials; and last correction is applied to end of data acquisition.
Once the correction coefficients are determined, the actual Rules are then determined. In the case of density preduction, a total of 178 Rules is used based on compound or compound series identification. For each Rule, a set of characteristic mass numbers are determined. These characteristic mass numbers can range from 1 to n, where n is an integer representing the entire mass range scanned or the number of selected ions being monitored. In this case, six characteristic; mass numbers are illustrated. The ion intensities of the masses for each Rule are summed within the upper and lower retention time limits for that rule. The results are shown for a sampling of the 178 Rules in Table 4 for this demonstration analysis. A full set of rules is shown in its entirety following Example 4.
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SUBSTITUTE SNEET (RULE 26) Total Raw Abundance (TIC): total area observed in the GC/MS analysis.
Chemist Rule: total area found using the Chemist's Rules;
based on experience, should be greater than 30% of total raw abundance.
Air Leakage: total ionization due to a.ir (m/z 28, 32, 40, 44) useful diagnostic for instrumentation problems.
Average Scan Rate (Min/Max): shows the minimum, average and maximum scan rates during the GC/MS analysis and is a useful diagnostic to identify instrumental problems.
Number of records: is the number of mass spectral scans acquired during the analysis.
The analysis summarized in Table 4 is done for each reference sample.
The results from these respective analyses form a training set which is subjected to mathematical treatment. The goal is develop a model that can be used to predict the unknown properties of future samples using their mass spectral data only. The mathe-matical treatments are described by multivariate correlation 'techniques such as Projection to Latent Structures (PLS) or otherwise known a.s Partial Least Squares (PLS), Principal Component Regression (PCR), and Ridge Regression (RR). These techniques are superior to ordinary multiple linear regression in their ability to treat colIinearity amongst variables in the X-block or GC/MS data matrix (and Y-block or properties matrix for PLS), and in their ability to handle the quantity of data generated by the Chemist's Rules. Ordinary Multiple Linear Regression cannot be used to treat collinear variables.
PLS/PCR/RR are numerical analysis techniques for detecting and formulating a mathematical structure (model) within a data set comprising observations associated with multiple objects. Each object has associated. without observations for multiple variables, the latter being common to all objects. These multiple variables are assigned into two categories, known as X-block and Y-block (GC/MS data in this case).
Observations associated with all variables in the X-block are realized from a common process. Observations associated with variables in the Y-block (known properties in this SUBSTITUTE SHEET (RULE 26) case) are realized from processes that may be dii~erent for each variable. The data set used to construct this mathematical model is referred to as the model calibration data set.
The common use of PLS/PCR/RR is to apply the model developed from the calibration data set to X-block observations realized for new objects (not in the calibration data set) to predict values for the corresponding variables in the Y-block for these new objects, without having to execute the Y-block processes used in the calibration data set. Using diagnostics that are simultaneously generated by the PLS/PCR1RR model, assessment of whether the new objects can be adequately described by the model, and whether the model is used in an extrapolation mode versus interpolation mode can be performed. , PLS/PCR addresses the collinearity features in the X-block and Y-block, by suitably reducing the dimensionality in both X- and Y-blocks (for PLS), and X-block only (for PCR) to form the model. Collinearity is a term referring to the existence of relationships between variables within the block itself. In the PLS modeling algorithm a number of independent dimensions in the X- and Y- blocks are identified by forming pseudo-variables known as principal components or latent vectors through different sets of linear combinations of original variables in each block. Each set of such combinations constitutes an independent dimension. It comprises a set of coefficients that each value associated with each variable in the block is to be weighted by to arrive at the new value for this dimension. The values for the new, reduced dimensions in the Y-block are regressed onto their counterparts in the new, reduced dimensions of the X-block to arrive at the most parsimonious dimension size (number of latent vectors) and their associated weights, with the final goal of one linear equation generated to permit predic-tion of Y-block variables using X-block variables. The number of dimensions used to construct the model is determined through optimization of a criterion known as PRESS
(Prediction Error Sum of Squares), cumulated by a Cross Validation (CV) technique using the training data set, and, following the general model parsimony principle.
For PCR, the number of independent dimensions in the X-block are first selected and identified in a similar fashion as in PLS by forming principal components.
Then, for each variable in the Y-block, a model is obtained by performing ordinary multiple linear regression using the Principal Components as "Prediction Variables".
SUBSTITUTE SHEET (RULE 26) F'or Ridge Regression, the collinearity problem is dealt with in a different manner than PLS/PCR. Here a diagonal matrix known as the Lambda Matrix is added to the Covariance Matrix of the X-block with the net erect of stabilizing the numerical computation needed to obtain the model coefficients. The selection of Lambda values is through optimization of PRESS criterion using cross validation of the training set.
Thus, the Chemist's Rule data for the various; reference samples derived from GC/MS analysis form the X-block variables. PLS/PCIt/RR treatment may require preliminary reorganization of the X-block data, such as transposition and removal of redundant data and constants or mathematical transformations. The Y-block variables are the property (or properties) to be predicted, and may also require mathematical transformations such as logarithmic or geometric, as well as reorganization.
The data blocks may be represented by: - .
X-BLOCK MATRIX
jChemist's Rules (n samples x 178 columns)]
X1,1 X1,2 X1,3 ... XI,176 X1,177 x1,178 X2,1 X2,2 X2,3 ... X2,176 X2, I77 X2,178 X3,1 X3.2 X3.3 ... X3,176 X3,177 X3,178 Xn, Xn,2 Xn,3 ... Xn,176 Xn,177 Xn,178 l Y-BLOCK VECTOR
[Measured property or properties (n samples)]
Yn SUBSTITUTE SHEET (RULE 26) The Y-block may be a single observation per set of Chemist's Rules as shown above, or it may be a n x m matrix of observations where there are m different properties to be predicted.
The results of PLS treatment of the training set data are a series of coe~cients. Raw GC/MS data from an unknown sample (or samples) are then treated by the Chemist's Rules first to correct the retention times and then to form the ion summations. Each value for the Chemist's Rule ion summation result is then multiplied by the training set coefficients and summed to generate the prediction of the desired property. Table 5 illustrates the quality of the predicted density values for both the training set and the unknown test set for density at 15°C.
Predicted vs. Measured Waxy Raffinate Density Values @ 15°C (g/ml) Measured* Predicted Trainin Set 1 0.8478 0.8481 2 0.8597 0.8608 3 0.8642 0.8649 4 0.8614 0.8645 5 0.8657 0.8690 6 0.8616 0.8610 7 0.8680 0.8665 8 0.8596 0.8593 9 0.8596 0.8609 10 0.8640 0.8637 11 0.8645 0.8661 12 0.8762 0.8772 13 0.8849 0.8863 14 0.8607 0.8589 15 0.8675 0.8652 16 0.8622 0.8635 17 0.8699 0.8691 18 0.8749 0.8743 19 0.8636 0.8636 20 0.8636 0.8632 21 0.8794 0.8771 22 0.8724 0.8722 23 ~ 0.8600 0.8613 SUBSTITUTE SHEET (RULE 26) Test Set 24 0.8695 0.8fi91 25 0.8664 0.8fi44 ' 26 0.8665 0.8fi45 27 0.8768 0.8 758 * measured by ASTM D 4052-91 The procedure of Example 1 was repeated for predicting refractive index @ 75°C for the suite of 150N grade waxy raf$nates. The same 22 samples were used for the training set, while the remaining five samples were used as a test set. The results for the refractive index at 75°C are summarized in Table 6.
Predicted vs. Measured Refractive Index @ 75°C
Measured* Predicte;d Trainin Set 1 1.4441 1.4434 2 _ 1.4504 1.4505 3 1.4534 1.452!
4 1.4509 1.452E~
1.4540 1.4551 6 I .4509 1.450 7 7 I .4550 1.4540 8 I .4504 I .4499 9 1.4495 1.4500 1.4523 1.4514 11 1.4525 I .4532 12 1.4573 1.457 7 13 1.4628 1.4626 14 1.4506 1.4500 1.4542 1.4535 I 1.4528 1.453 8 17 1.4575 1.4571 18 1.4581 1.4575 19 1.4505 1.4519 1.4512 1.4519 2 I .4616 1.4609 I
22 1.4576 1.4582 SUBSTITUTE SHEET (RULE 26) Test Set 23 1.4497 1.4503 ' 24 1.4546 1.4546 25 1.4525 1.4522 26 1.4530 1.4526 27 1.4582 1.4579 ~
*measured by ASTM D 1218-92 The procedure of Example 1 was repeated for predicting viscosity at 100°C for ISON grade waxy raffinates. The same 22 samples were used for the training set, while the remaining five samples were used as a test set. The results for density prediction are summarized in Table 7.
Predicted vs. Measured Viscosity @ 100°C (cSt) Measured* Predicted Trainin Set 1 5.38 5.37 2 4.72 4.74 3 4.79 4.79 4 4.68 4.74 5 4.74 4.79 _ 6 4.48 4.48 7 4.49 4.42 8 4.35 4.27 -9 4.38 4.34 I 0 4.44 4.3 8 11 4.41 4.53 12 4.61 4.66 13 4.76 4.84 14 4.49 4.45 I S 4.59 4.56 ' 16 4.84 4.88 I 7 4.96 5.00 I 8 4.74 4.62 19 4.16 4.39 20 4.91 4.88 21 5.19 S. I4 SUBSTITUTE SHEET (RULE 26) Test Set 22 5..07 5.07 23 4.3 5 4.45 24 4.67 4.51 25 4.39 4.41 26 5.00 4.90 27 4.81 4.79 *measured by ASTM D 445-8f~
The procedure of Example 1 was repeated for predicting weight percent wax content for 1 SON grade waxy raffmates. The same 22 samples were used for the training set, while the remaining five samples were used as a test set. The results for density prediction are summarized in Table 8. ~ .
Predicted vs. Measured Wax Content (Wt%) Measured* Predicted Trainin Set I 21.8 22.0 2 25.7 23.5 3 20.0 21.5 4 20.6 20.0 19.1 17.8 6 29.6 29.5 7 17.5 18.6 8 20.0 21.4 9 20.8 19.9 19.4 18.8 I 1 18.8 19.8 12 3.6 3.6 13 2.4 0.9 14 I 8.4 20.8 IS 16.9 18.0 16 16.2 16.5 I 7 14.6 14.4 I 8 6.7 7.5 19 20.2 17.4 21.2 21.1 SUBSTITUTE SHEET (RULE 26) Test Set 21 10.4 10.4 22 1 1.6 12.3 23 23.5 22.5 24 7.6 9.4 25 18.1 I 7.5 26 20.4 20.2 g.6 8.4 *measured by ASTM D 3235-88 Other properties of various grades of lubricating intermediate streams or.
finished products, such as, cloud point, flash point, viscosity index, pour point, basic nitrogen content, distillation and volatility characteristics, viscosity at 40°C, aniline point, sulfur content, etc., could be predicted using the method according to the invention.
The subject method can also be applied for predicting properties of other types of complex hydrocarbon mixtures in similar boiling ranges, such as catalytic cracker feedstock quality, feed to extraction or dewaxing units, feedstocks to distillation or stripping towers, and to blending considerations.
SUBSTITUTE SHEET (RULE 26) COMPLETE CHEMIST'S RULES FOR LUBES
Retention Rulea ~ Materialb ~ Masseso ~ Starting ~ Ending I nC 16 43 57 71 85 99 113 1.00 1.89 2 I/2 rin 69 83 97 109 123 137 1.00 2.30 3 3/4 rin 149 163 177 189 203 217 1.00 2.30 4 4/5 rin 229 243 257 269 283 297 1.00 2.30 6 rin 309 223 337 1.00 2.30 6 -6 91 105 119 133 147 161 1.00 2.30 7 -6.1 92 106 120 134 148 162 1.00 2.30 8 -8/-10 115 117 129 131 143 145 1.00 2.30 9 -12 128 141 142 155 156 169 1.00 2.30 -14/-16 151 153 165 167 179 181 1.00 2.30 11 -18 178 191 192 205 206 219 1.00 ~ ~
2.30 12 -20 202 215 226 239 228 241 1.00 2.30 13 nC I 7 43 57 71 85 99 1 1.89 1.98 14 isoPara 43 57 71 85 99 113 1.98 2.30 1~ nCl8 43 57 71 85 99 113 2.30 2.40 16 isoPara 43 57 71 85 99 113 2.40 3.22 17 1 /2 rin 69 83 97 109 I 13 2.40 3 .22 18 3/4 rin 149 163 177 189 203 217 2.40 3.22 19 4/5 rin~ 229 243 257 269 283 297 2.40 3.22 6 rin 309 223 337 2.40 3.22 21 -6 91 105 119 133 147 161 2.40 3.22 22 -6.1 92 106 120 134 148 162 2.40 3.22 23 -8/-10 115 117 129 131 143 145 2.40 3.22 24 -12 128 141 142 155 I56 169 2.40 3.22 -14/-16 151 153 165 167 179 18I 2.40 3.22 26 -18 178 191 192 205 206 219 2.40 3.22 27 nC 19 43 57 7I 85 99 1 2.70 2.85 28 isoPara 43 57 71 85 99 113 2.85 3.22 29 nC20 43 57 71 85 99 113 3.22 3.34 isoPara 43 57 71 85 99 I13 3.34 3.70 31 1 /2 rin 69 83 97 109 123 13 3 .34 4.20 = 7 32 3l4 rin 149 163 177 189 203 217 3.34 4.20 33 4/5 rin 229 243 257 269 283 297 3.34 4.20 34 6 rin 309 223 337 3.34 4.20 -6 91 105 119 133 147 161 3.34 4.20 36 -6.1 92 106 120 134 148 162 3.34 4.20 37 -8/-10 115 117 129 131 143 145 3.34 4.20 38 -12 128 141 142 155 156 I69 3.34 4.20 39 -14/-16 151 153 I65 167 179 181 3.34 4.20 SUBSTITUTE SHEET (RULE 26) 40 -18 178 191 192 205 206 219 3.34 ~ 4.20 41 -20 202 215 226 239 228 241 3.34 4.20 42 nC21 43 57 71 85 99 113 3.70 3.83 43 isoPara 43 57 71 85 99 113 3.84 4.20 44 nC22 43 57 71 85 99 I13 4.20 4.33 45 isoPara 43 57 71 85 99 113 4.33 4.72 46 1/2 rin 69 83 97 109 123 137 4.33 5.20 47 3/4 rin 149 163 177 189 203 217 4.33 5.20 48 4/5 rin 229 243 257 269 283 297 4.33 5.20 49 6 rin 309 223 337 4.33 5.20 50 -6 91 105 119 133 147 161 4.33 5.20 51 -6.1 92 106 120 134 148 162 4.33 5.20 52 -8/-10 I15 117 129 131 143 145 4.33 5.20 53 -12 128 141 142 155 156 169 4.33 5.20 54 -14/-16 151 153 165 167 179 181 4.33 5.20 55 -18 178 191 192 205 206 219 4.33 5.20 56 -20 202 215 226 239 228 241 4.33 ~ 5.20 57 nC23 43 57 71 85 99 113 4.72 4.83 58 isoPara 43 57 71 85 99 113 4.83 5.20 59 nC24 43 57 71 85 99 113 5.20 5.37 60 isoPara 43 57 71 85 99 113 5.38 5.64 61 1/2 rin 69 83 97 109 I23 137 5.38 6.15 62 3/4 rin 149 163 177 189 203 217 5.38 6.15 63 4/5 rin 229 243 257 269 283 297 5.38 6.15 64 6 rin 309 223 337 5.38 6.15 65 -6 91 105 119 133 147 161 5.38 6.15 66 -6.1 92 106 120 134 148 I62 5.38 6.15 67 -8/-10 115 117 129 131 143 145 5.38 6.15 68 -12 128 141 142 155 156 169 5.38 6.15 69 -14/-16 151 153 165 167 179 I81 5.38 6.15 70 -18 178 191 192 205 206 219 5.38 6.15 71 -20 202 215 226 23 9 228 241 5.3 8 6.1 S
72 nC25 43 57 ?I 85 99 113 5.65 5.85 73 isoPara 43 57 71 85 99 113 5.85 6.15 74 nC26 43 57 71 85 99 113 6.15 6.32 75 isoPara 43 57 71 85 99 113 6.33 6.64 76 I/2 rind 69 83 97 109 123 137 6.33 7.04 77 3/4 rin 149 163 177 189 203 217 6.33 7.04 78 4/5 rin 229 243 257 269 283 297 6.33 7.04 79 6 rin 309 223 337 6.33 7.04 80 -6 91 105 119 133 147 161 6.33 7.04 81 -6.1 92 106 120 134 148 162 6.33 7.04 82 -8/-10 115 117 129 131 143 145 6.33 7.04 83 -12 128 141 142 155 156 169 6.33 7.04 SUBSTITUTE SHEET (RULE 26) 84 -14/-16 151 153 165 167 179 181 6.33 7.04 85 -18 178 191 192 205 206 219 6.33 7.04 86 -20 202 215 226 239 228 241 6.33 7.04 87 nC27 43 57 71 85 99 113 6.65 6.75 88 isoPara 43 57 71 85 99 113 6.76 7.04 89 nC28 43 57 71 85 99 113 7.05 7.20 90 isoPara 43 57 71 85 99 113 7.21 7.45 91 1/2 rin 69 83 97 109 123 137 7.21 7.85 92 3/4 rin 149 163 177 189 203 217 7.21 7.85 93 4/5 rin 229 243 257 269 283 297 7.21 7.85 =
94 6 rin 309 223 337 7.21 7.85 95 -6 91 105 119 133 147 I61 7.21 7.85 96 -6.1 92 106 120 134 148 162 7.21 7.85 97 -8/-10 115 117 129 131 143 145 7.21 7.85 98 -12 128 141 142 155 156 169 7.21 7.85 99 -14/-16 151 153 165 167 179 181 7.21 7.85 100 -18 178 191 192 205 206 219 7.21 7.85 101 -20 202 215 226 239 228 241 7.21 7.85 102 nC29 43 57 71 85 99 113 7.46 7.65 103 isoPara 43 57 71 85 99 113 7.66 7.85 104 nC30 43 57 71 85 99 lI3 7.85 8.00 105 isoPara 43 57 71 85 99 113 8.OI 8.30 106 I/2 rin 69 83 97 109 123 137 8.01 8.65 107 3/4 rin 149 163 177 189 203 217 8.01 8.65 108 4/5 rin 229 243 257 269 283 297 8.01 8.65 109 6 rin 309 223 337 8.01 8.65 110 -6 91 105 119 133 147 161 8.01 8.65 II1 -6.1 92 106 120 134 148 162 8.01 8.65 112 -8/-10 II5 117 129 131 143 145 8.01 8.65 113 -12 128 141 142 155 156 169 8.01 8.65 114 -14/-16 151 153 165 167 179 181 8.01 8.65 115 -18 178 191 192 205 206 219 8.01 8.65 116 -20 202 215 226 239 228 241 8.01 8.25 117 nC31 43 57 71 85 99 113 8.30 8.37 118 isoPara 43 57 71 85 99 113 8.38 8.65 119 nC32 43 57 71 85 99 113 8.66 8.79 120 isoPara 43 57 71 85 99 113 8.77 8.99 121 1/2 rin 69 83 97 109 123 137 8.77 9.45 122 3/4 rin 149 163 177 189 203 217 8.77 9.45 123 4/5 rin 229 243 257 269 283 297 8.77 9.45 124 6 rin 309 223 337 8.77 9.45 125 -6 91 105 119 133 147 161 8.77 9.45 126 -6.1 92 106 120 134 148 162 8.77 9.45 127 -8/-10 115 117 129 131 143 145 8.77 9.45 SUBSTITUTE SHEET (RULE 26) 128 -12 128 141 142 155 156 169 8.77 9.45 129 -14/-16 I 153 165 167 179 I 8.77 9.45 I
130 -18 178 191 192 205 206 219 8.77 _ 9.45 131 -20 202 215 226 23 228 241 8.77 9.45 132 nC33 43 57 71 85 99 113 8.95 9.11 133 isoPara 43 57 71 85 99 113 9.11 9.50 134 nC34 43 57 71 85 99 113 9.50 9.56 135 isoPara 43 57 71 85 99 113 9.56 9.92 136 1/2 rin 69 83 97 109 123 137 9.56 _ 10.51 137 3/4 rin 149 163 177 189 203 217 9.56 10.51 138 4/5 rin 229 243 257 269 283 297 9.56 10.51 139 6 rin 309 223 337 9.56 10.5 140 -6 91 105 119 133 147 161 9.56 _ 10.51 141 -6.1 92 106 120 134 148 162 ~ 9.56 10.51 142 -8/-10 115 1 129 131 143 145 9.56 10.51 143 -12 128 141 142 155 156 169 9.56 10.51 144 -14/-16 I51 153 165 1'67 I79 181 9.56 10:51 145 -18 178 191 192 205 206 219 9.56 10.51 146 -20 202 215 226 239 228 241 9.56 1Ø51 147 nC35 43 57 71 85 99 113 9.93 10.04 148 isoPara 43 57 71 85 99 113 10.04 10.51 149 nC36 43 57 71 85 99 113 10.51 10.67 150 isoPara 43 57 71 85 99 113 10.67 11.16 151 I/2 rin 69 83 97 109 123 137 10.67 I 1.93 152 3/4 rin 149 163 177 189 203 217 10.67 11.93 153 4/5 rin 229 243 257 269 283 297 10.67 11.93 154 6 rin 309 223 337 10.67 1 1.93 155 -6 91 105 119 133 147 161 10.67 11.93 156 -6.1 92 106 120 134 148 162 10.67 11.93 157 -8/-I0 115 117 129 131 143 145 10.67 11.93 158 -12 128 141 142 I55 156 169 10.67 11.93 159 -14/-16 I51 153 165 167 179 181 10.67 11.93 160 - I 8 178 191 192 205 206 219 10.67 11.93 161 -20 202 215 226 239 228 241 10.67 11.93 162 nC37 43 57 71 85 99 113 11.17 11.28 163 isoPara 43 57 71 85 99 113 11.29 11.93 164 nC38 43 57 71 85 99 113 11.94 12.06 165 isoPara 43 57 71 85 99 113 12.07 12.83 166 I/2 rin 69 83 97 109 123 137 12.07 14.00 167 3/4 rin 149 163 177 189 203 217 12.07 14.00 168 4/5 rin 229 243 257 269 283 297 12.07 14.00 169 6 rin 309 223 337 12.07 14.00 170 -6 91 105 119 133 147 161 12.07 14.00 171 -6.1 92 106 120 134 148 162 12.07 14.00 SUBSTITUTE SHEET (RULE 26) 172 -8/-10 115 117 129 131 143 145 12.07 14.00 173 -12 128 14I 142 155 156 169 12.07 14.00 174 -14/-16 151 153 165 167 179 181 12.07 14.00 175 -18 178 I91 192 205 206 219 12.07 14.00 176 -20 202 215 226 239 228 241 12.07 14.00 17_7_ nC39 43 57 71 85 99 113 12.83 12.87 178 isoPara 43 57 71 85 99 113 12.88 14.00 ~
a) Rule number, integer index b) Compound or group of compound rule applies to:
1/2 ring 1/2 ring cycloparaffins 3/4 ring 3/4 ring cycloparaffins 4/5 ring 4/5 ring cycloparaffins 6 ring 6 ring cyclopara~ns ' -6 CnH2n-6 alkylated benzenes -6.1 CnH2n-6 linear alkylated ben2:enes -8/-10 CnH2n_g alkylated indanes, CnH2n-10 alkylated indenes -12 CnH2n-12 alkylated naphthalenes -14/-16 CnH2n-14 alkylated acenaphthenes/CnH2n-16 alkylated acenaphthalenes -18 CnH2n-18 alkylated phenanthrenes/anthracenes -20 CnH2n-20 alkylated naphthenophenanthrenes c) Masses used in Rule jup to n may be specified, where n is an integer which is equal to the number of masses scanned during the time interval (d)]
d) Retention time for both starting and ending expected retention times based on historical averages in minutes.
SUBSTITUTE SHEET (RULE 26) o a a ~ o O ~ O O O O O O O O O O N ~ - t~
~ O O O O O O O O O O O O O O O O
U
C
cC
'fl = M ~tO O O O O O O O O O ~ ~O~n~
N ~ I~ InN ~n l 00 N O M ~DvD
~ N M M I~h ~ M 00 ~O~ et ~fct M
~h V1V7V1V1h V1 N V1t~N N '~ V1V1 ' O O O O O O O O O O O O O O O O
C O O O O O O O O O O O O O O O O
U o o cio C o o c o 0 o c o 0 0 0 t -n o0 0~o~a~ a~o~a~ o~a' a'c~ o~c~ o~o~
0 o C ~ N N N N N N N N N N N O~ N M N
M U ~ N N N N N N N N N N N ~ N N M
r O N
~ O N
N N N N N N N N N N N N V' rtv1v1 ' N OD O O O O O O O O O O O O O O O O
,_,O O O O C O O O O O O O O O O O
O C O C O O C C O O O O O C O O O
00 000000 000000 0000 0000 0ova ~G~;~n ~ a~ o\v.o~ o~a.o~ o.o~ o~o, a oo ~ o~Q.
R ~ O~~ ~ C~O~~ C~C~ Q~O~ O~00 O~N M
O 00~ N ~T C%~O O O O O O O O O O O O ~ ~ N N
v~ ~ ~ ~ ~
V'1N N 00 n ~ I~ N
N ~ N
e~ O O O O O O O O O O O O O O O O
n ~ O~ O O O O O O O O O O O 00 O O N
00 M M M M M M M M M M M O~ M ~ N
Li. M = ~ N N N N N N N N N N N ~ N N M
~
r~
O O O O O O O O O O O O O O O O
O O O O O O O O O O O O ~ 00O O
Q! R O O O O O O O O O O O O 00 O~M ~
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v X M f~t~l~ ~ N V1~ ~ ~ ~ M M M M
U 'r ~ N N ~ ~ ~ ~ N
N ~
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O~ N O 00 ~ C 'Y~ (~O N Qv OvO~U
R pn - N N ~ N N
~ ~ ~ ~
e~
V1 U ~ Q~ M ~ ~ u1 f~1!1 O~V'1 N ~ V1 ~ 00 O 00 M M 0 O 00 000000 C ~ ~ N ~ ~ ~ ~
y N
C ."_, N
V
ec _sy L In c~ ,r ~ c~t~t~ t~O~O a'N ~nN ~O~ ~
cc-~.. G I~ ~ n v1 M ~ N N ~' ~DO~ N I~ I~(~
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O _C._>
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t~ M M M M V7~O I~~ M ~ V1t~ I~C~I~
v1 00~O~ N O O ~-C' ~1Ov ~ v1 1!1V W
!1 ~ N N ~ ~ N
M Q1Q1~ Q~~ N V100 ~ 00 N M M M M
~ ~O'cTN O Q\O~--N m I~O V I ~ ~T
rf N M -- ~ ~ N
-fl C
C
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r- C C C v _ _ C .
L L ~L 1 ~ R ~ R
= '- ~ c -U U N ~ ~n~. W N o0O p p C ~ M ~ ~O~ ~0 00~ 1 i N C .NG .
' 1 R - INM ~Tv1vOlf~~00~0~C ~~~NM eT
~
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SUBSTITUTE SHEET (RULE 26) 0 0 0 o a o .o.o~oo ~ 0 0 0 0 0 0 0 0'0 0 0 y \ o o~o.o.a \ o yy y \ \ o \ y y y y y y ~
~nO O O ~O- - M N O N O~~Ov~~OC O G ~ON h v~~pN -O O O O O O O O O M M ~O00O~~ O O ~ N N N N O O
0 0 0 0 0 0 o c o 0 0 0 00 .-o o c.0 0 0 0 0 o co I
~OO~O O v~N ~Ov~v'1O ~D~OMO~N N v'1C>etM v'1h C~Q~O~
00 O - ~Dm n h O~~M oo~ Ov Own Ow0 h O~~O
01~O O ~ O 00h ~ ~DMv0h 0000 ~ et_ ~ M O O
O ~ N O M - vD - Ovhh M er~ 00N Cv~ m ~Ov~
h ~nV N O ~O ~D~DN~O~ - et~Oh - M h M
h N N ~n~DM OO~ 0000O O O
- NM h V V V''~~h~ C'rtC'C ~D~f'et-M
O O O O O O O O O O O O OO O O O C)O O O O O O O
t ~ i ~ ~ i i i ~ ~ ~ ~ ~ ~O~ ~O~O~O~T~p~ph Q1O~C~QYO~O~Q~O~C~O~O~
O O O O D O
_ _ _ _ _ _ MO~O~O O~CrQ O O O O~C O
~ ~ ~ ~ ~ ~ ~
N N N N N N N N N N 00N M~O~ _ _ _ _ _ _ _ M M M M M M M M M M N M MM rr!r!rd'~ ~ ~ ~ ~ Q ~-V1V1V1V1V'1V7~!1V1V7V1~O~O!r~ !r'~T!rd'lT'~~'~ ~!'~ Q
O
O O O O O O O O O O O OO O O O C)C)O O O O O O
O O O O O O O O O O O O OO O O O C)O O O O O O O
O O O O O O O O O O O O OO O O O C)O O O O O O O
~ n n n ~ n n n n n n n n n n n n n a n n n n.
.
~!1V1v-)v1V1V1~nV1V1~n~ ~!'~O~O~D~O~OK)~O~D~D~O~O~O~O
O~Q~U O~'fit~M M M M C~1M M M M M M M
M M M M M M M M M M ~O00NM M M M ('~)M M M M M M M
N N N N N N f'!('JN N N N MM M M M (r1M M M r1r1r7r1 ~ ~ f f O O O O O O C C O O O O OO O O O C)O O O O O O O
N N N N N c~JN c~JN N ~nN ~rO O O O C)O O O O O O O
N N N N N N c~Jc~1N cV00N Mh N N N CJN N N N N N N
M M M M M M M r1M M N M MM ~ !r'~!~' O O O O O O O O O O O O OO O O O C)O O O O O O O
O O O O O O O O O O O ~nNC'Q et~ crV ~t~ V'~ ~ ~t 'C~r~ 'cfQ rSrf'T~r'~h 00NM M M M ('~1M M M M M M M
N N N N N N N tVN N N N MM M M M t~~r1eh!Y1ehM t~th h l h - N V~G~~ O~M M MM h h h .. N V7Ov- Ov-~ --M _ ~ ~O~DW D 00- _ M ~ ~ \DC'~D00.-.' ~ N N - N - - N N ~ N N
M M M h 00M ~CU ~OQ~Q~OvO~M M M h 00M \OO~~O00 I ~ ~
N O 00 ~Scf'Tv:h C OvOvQvQ~N O 00 ~f~ ~rW h O N
( - N N ~ ~ ~ ~ N - N N - N N
' ~ ~
O~O~O~ M Q - h U1~!1V'1v1V1U O~O~ M ~ ~ V1h v1O
v1 ~
O 00v0 r1M r~~ 'VO 00000000O 00vD M M M V1~0O M
~ I I ~
v :
.-N -i-_ ~ ~ ~ ~~ - N y - N N
.-~.J i h h h h Q~O G~ ~nN - - ~.-h ~ h h O~O O~N v'1N ~O
( ~ h ~
c~J
~
O~h W M - t~J~ fVG~h h hh O~h v~r~- N N Q ~OO~N
N
i T
-~N r1- - ~ N r~- - N
- -M M M M ~!1vp[~~ M - (~h (~[~M M M r7V1l0h - M v1 -0ov0V'N O O - ~Tv~O wevtv~~no0~Dctc~JO O ~ ~'W Qv-N N ~ ~ N c,~- - N
O~O~O~U - f'!v-)i - 00M M MM O~O~O~d'1._N V100- 00N
vO~rN 0 ~ 0~- lt~dv~t~~ ~ C'~ ~ ~SN C C~- N w t~C
- N ~"~ ~ ~ - N r~ ~ N
-~
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W.~.C ~ O~R pR '''y~
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N ef'v1' ~ c~!"~S'00"~C1.NC1. ' ' ~ \
i=
N ct~ni~ W N V 00O
.p~ oo- ._U 0 U0 - M Q ~Oi i n ~ ~ n C .NC.~- M ~ V7~ ~O00~ ~ s (V
n h iooo.o - rn~-mr ~ni.~-cmooic~c i-.N M -rv,~ ihoo~o~o -~ , ~ - ~ N N c~!f'J ~ ~ ~ N ~M M M r7M M M I M 'CC' i N (~JN N M M
f~J
SUBSTITUTE SHEET (RULE 26) 0 0 o a ~ a W W W W W ~ o ~ o o~ ~ ~ ~ ~ ~ ~ ~ ~ ~ y M M ~ ~ ~ ~'N V C~N ~ h h h~O~O~ O h ~ ~!1~-O M O~
~ ~ ~DN O M O O O ~n~O~n~n~O oov0~n~ vp~ ~ ~ M v0 ~ N erO O O ~ O O O O OO ~ N N N efO C O ~ C
N O N O ~Do0Ovh M O o0M O OvN vDO Ov~ ~ O Ovo00000 ~O ~'h h M N M C'0000~ 00~!1(~N N 00Qvh _ ~ h v1O
~n N M OW~ ~ 1 ~ 00N ~nN OvN~ M N M h O 00~'~DOvh h N 00N N ~no0O ~Do000~ Ovh~wD ~ O pvooN M M O ~O
_ _ M O ~n~D~O~t~n~ON o0W pM Ovo0w N O~00N ~ ~ M
v1 h v100Q~M - N O v1N N ~ON M M C~~Dct[~et~ M h C vWD OO~n~ ~ N N N N t~O Qv0000~ v'1N
N ~ N N N N N N N N N NN N M ~ V~v1v'1tnv1v~
O O O O O O O O O O O O O OO O O O O O O O O O O
O O O O O O O O O O O O O OO O O O O O O O O O O
O O O O O O O O O O O O O CO O O O O O C O O O O
00 C.CvO N N N N N N N N N NN ~ N M ~ va~nv1~w ~n N OvN N O O O O O O O O O OO M O h V v~~ v v v w n 1 1 1 00 ~ M h N N N N N N N N N NN 00N M v0~ _ _ _ _ M er~trt~nw viviw n m u1v1viv~~ viV1v1~D~O~D~D~O~O
N M M M M M M M
O O O O O O O O O O O O O OO O O O O O O O O O O
O O O O O O O O O O O O O OO O O O O O O O O O O
O O O O O O O O O O O O O OO O O O O O O O O O O
~ ~ i i ~
O ~ N M M M M M M M
Ov M OvN N N N N N N N N N NN N M O 00000000000000 ~D 00~ M M M M M M M M M M MM h ODN M M M M M M M
M M ~ ~fQ '~TV'ct~''t1'C'~f~ ~C'~ ~fV1V'1V1~!1V1V'tV1V1 O O O O O O O O O O O O O OO O O O O O O O O O C
M O M N O O O O O O O O O OO M O h C v1v~vWn ~nv~
00 N M h N N N N N N N N N NN 00N M ~ ~
M ~ C'etv~m m w n ~nw ~nownv'i~t~n~1viv0~D~O~D~O~O
O O O O O O O O O O O O O OO O O O O O O O O O O
O ~ O M M M M M M M M M M MM N M O 00000000000000 h 00N M M M M M M M M M M MM h 00N M M M M M M M
M M '~TC'~ ~fV'C'~ ~f'Cr~t~ ~~f'lT'~lN V1V1V1V7V1V1V1 M M M M h h h ~ N ~nO~~ O~~ M M M M h h h ~ N
~ M ~ U ~O~O~t~D00~~ ~ ~ M ~ ~ ~O~O
~ N N ~ NN ~ ~ N N
O~Q~M M M h 00M ~OO~~00O~O~O~Q~M M M h 00 O~ OvOv~ N O o0 !TT V w h ON OvOvOvOvN O o0 ~
~ N cV ~ ~ NN ~ N N
~
v!1V1V1t!1O~O~~ M cf--V1h V1QvV1V1vf'1V1C~O~O M
00 0000~ O 00~O ~ M y v0N o0000000O o0 ~ ~ ~ ~ N
~
~ h h h h U O . N ~nN~O.-.~ - - h h h h O~O
~ O~ ~ I
I
I~ h h h O~h vl~M- N fVa*~OO~N h h h h O~h ~11M ~ N
N M - ~ ~N ~ N M ~ -t h h h h M M M M V1~Oh ~ M ~V7h h h h M M M M ~1~O
~n v W ~n00~OetN O O ~ Q v1Ov~ m ~n~nW o0v0C'N O C
n ~ N N ~ ~N ~ N N ~
~
M M M M O~O~01Q~--N V100- OON M M M M Q1U ~ O~~ N
C ~'~ V ~D~TN O O~~ ~ N ~nhO ~ Q '~TC'~O'SN O CJ~G~
I
~ N M ~N ~ N M ~
~ C C C ~ v v N . _ _ .. O C .C_C
''' ' M ~ ~T''~v:W W
N O.N O. _ ._ W . ... _ ._ ' N N
U p U p N C ~ W. W N eTo00 ~ ~ N C W 'v:.
~D00~
C .~C .~~ M C'~O~ n y C ~ C ~ ~ M C'~O
i . .
N M Q'~ w0h I O~C ~-I M ~f WpI 00~ O ~ N M C'~nv7 o0 N h U
Q Q'~ ~ ~tC''T ~DvD~O~Dv0vCSCI
SUBSTITUTE SHEET (RULE 26) a a ~ o o a o a oa o 0 0 o a o a o o a a a a a o M M V1M f~0001~OO~00V1...O 00M N V100V'7.~~ 00~OM
00t~t~N .-.~Dv~M ~OM v1~ .~M v100[~I~N ~ ~ON ~
O O O O O N N N NetO O O ~ O O O O O O ~ N ~-.-.ri O CvO weM ~ C't~00~ N ~nN N ~ Q~Ovo0etv~Cvo0OvOv O o0N O oo~ - ooNO O N twD M ~w0 M o0~n~nM ~ N O
~O~Ov7~DN ~ M O~O~n~DvWn v1et~nM ~ Wit"v~Ov00~nOvN
00N O etN O ~OI~Q~ ~pO O ~DN N M 00O~N N ~O00N N
N ~ Ovt~- M o0M Ov~ ~ 00N 00.-.Ow0 ~D~ OvU N 00N W
M 0000~ V1~ON V1~'C'M V1'V'~ M N 00Q~~ V1M O~~OO C' M N N O O O~Ot~N ~nN M N N ~ ~D00~OI~~' V7H V1V'1N ~ V'1V7VM M M M M M M M M M M !TM N O
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SUBSTITUTE SHEET (RULE 26)
Claims (12)
1. A method for controlling the manufacture of lubricating oils from a feed having a boiling point of about 350°C or greater by the steps of introducing the feed into a distillation unit, separating the feed into light, medium and heavy distillates, introducing the distillates into an extraction unit, extracting the distillates to produce raffinates, introducing the raffinates into a dewaxing unit and dewaxing the raffinates to produce lubricating oils, said method comprising:
(a) ~obtaining samples of at least one lubricating oil, feed, distillate and raffinate;
(b) ~selecting at least one physical, chemical, perceptual or performance properties of at least one of lubricating oil, feed, distillate and raffinate;
(c) ~selecting reference samples, said reference samples containing characteristic compound types present in the at least one lubricating oil, feed, distillate and raffinate and which have known values for the property or properties selected in~
step (b);
(d) ~producing a training set by the steps of:
(1) ~injecting each reference sample into a gas chromatograph which is interfaced to a mass spectrometer thereby causing at least a partial separation of the hydrocarbon mixture into constituent chemical components;
(2) ~introducing the constituent chemical components of each reference sample into the mass spectrometer, under dynamic flow conditions:
(3) ~obtaining for each reference sample a series of time resolved mass~~
chromatograms;
(4) ~calibrating the mass chromatograms to correct retention times;
(5) ~selecting a series of corrected retention time windows;
(6) ~selecting within each retention time window a series of molecular and/or fragment ions, said ions being representative of characteristic compounds or compound classes expected within the retention time window;
(7)~recording the total amount of each characteristic compound or compound group selected in step d(6);
(8) ~forming the data from steps d(6) and d(7) into a X-block matrix in the order of the selected retention time windows from d(5) to yield for each selected reference sample a row in the training set X-block matrix;
(9) ~forming the property data selected in (b) for reference samples selected in (c) into a Y-block matrix;
(10) ~analyzing the data from steps d(8) and d(9) by multivariate correlation techniques to produce a series of coefficients;
(e) ~subjecting at least one unknown sample of at least one of lubricating oil, feed, distillate and raffinate to the steps d(1) and d(3) in the same manner as the reference samples to produce a series of time resolved mass chromatograms;
(f) ~repeating steps d(4) and d(8) for each mass chromatogram from step (e);
(g) ~multiplying the matrix from step (f) by the coefficients from step d(10) to produce a predicted value for the property or properties for the at least one lubricating oil, feed, distillate and raffinate sample or samples; and (h) ~using the predicted values of the property of properties of the at least one lubricating oil, feed, distillate and raffinate sample or samples to control operation of at least one of the distillation unit, extraction unit and dewaxing unit.
(a) ~obtaining samples of at least one lubricating oil, feed, distillate and raffinate;
(b) ~selecting at least one physical, chemical, perceptual or performance properties of at least one of lubricating oil, feed, distillate and raffinate;
(c) ~selecting reference samples, said reference samples containing characteristic compound types present in the at least one lubricating oil, feed, distillate and raffinate and which have known values for the property or properties selected in~
step (b);
(d) ~producing a training set by the steps of:
(1) ~injecting each reference sample into a gas chromatograph which is interfaced to a mass spectrometer thereby causing at least a partial separation of the hydrocarbon mixture into constituent chemical components;
(2) ~introducing the constituent chemical components of each reference sample into the mass spectrometer, under dynamic flow conditions:
(3) ~obtaining for each reference sample a series of time resolved mass~~
chromatograms;
(4) ~calibrating the mass chromatograms to correct retention times;
(5) ~selecting a series of corrected retention time windows;
(6) ~selecting within each retention time window a series of molecular and/or fragment ions, said ions being representative of characteristic compounds or compound classes expected within the retention time window;
(7)~recording the total amount of each characteristic compound or compound group selected in step d(6);
(8) ~forming the data from steps d(6) and d(7) into a X-block matrix in the order of the selected retention time windows from d(5) to yield for each selected reference sample a row in the training set X-block matrix;
(9) ~forming the property data selected in (b) for reference samples selected in (c) into a Y-block matrix;
(10) ~analyzing the data from steps d(8) and d(9) by multivariate correlation techniques to produce a series of coefficients;
(e) ~subjecting at least one unknown sample of at least one of lubricating oil, feed, distillate and raffinate to the steps d(1) and d(3) in the same manner as the reference samples to produce a series of time resolved mass chromatograms;
(f) ~repeating steps d(4) and d(8) for each mass chromatogram from step (e);
(g) ~multiplying the matrix from step (f) by the coefficients from step d(10) to produce a predicted value for the property or properties for the at least one lubricating oil, feed, distillate and raffinate sample or samples; and (h) ~using the predicted values of the property of properties of the at least one lubricating oil, feed, distillate and raffinate sample or samples to control operation of at least one of the distillation unit, extraction unit and dewaxing unit.
2. ~A method for controlling or monitoring chemical or refinery processes which utilize feedstocks and/or product products having boiling points greater than about 350°C which comprises:
(a) ~obtaining at least one sample of a refinery or chemical feedstock or product;
(b) selecting at least one physical, chemical, perceptual or performance property of at least one refinery or chemical process feedstock or product;
(c) selecting reference samples, said reference samples containing characteristic compound types present in the as least one refinery or chemical process feedstock or products and which have known values for the property or properties selected in step (b);
(d) producing a training set by the steps of:
(1) injecting each reference sample into a gas chromatograph which is interfaced to a mass spectrometer thereby causing at least a partial separation of the hydrocarbon mixture into constituent chemical components;
(2) introducing the constituent chemical components of each reference sample into the mass spectrometer, under dynamic flow conditions;
(3) obtaining for each reference sample a series of time resolved mass chromatograms;
(4} calibrating the mass chromatograms to correct retention times;
(5) selecting a series of corrected retention time windows;
(6) selecting within each retention time window a series of molecular and/or fragment ions, said ions being representative of characteristic compounds or compound classes expected within the retention time window;
(7) recording the total amount of each characteristic compound or compound goup selected in step d(6);
(8) forming the data from steps d(6) and d(7) into a X-block matrix in the order of the selected retention time windows from d(5) to yield for each selected reference sample a row in the training set X-block matrix;
(9) forming the property data selected in (b) for reference samples selected in (c) into a Y-block matrix;
(10) analyzing the data from steps d(8) and d(9) by multivariate correlation techniques to produce a series of coefficients;
(e) subjecting at least one unknown refinery or chemical process feedstock or process sample to steps d(1) and d(3) in the same manner as the reference samples to produce a series of time resolved mass chromatograms;
(f) repeating steps d(4) and d(8) for each mass chromatogram from step (e);
(g) multiplying the matrix from step (f) by the coefficients from step d(10)to produce a predicted value for the property or properties for the refinery or chemical process feedstocks or products sample or samples; and (h) using the predicted values of the property or properties of the refinery or chemical feed stocks or products sample or samples to control the refinery or chemical process.
(a) ~obtaining at least one sample of a refinery or chemical feedstock or product;
(b) selecting at least one physical, chemical, perceptual or performance property of at least one refinery or chemical process feedstock or product;
(c) selecting reference samples, said reference samples containing characteristic compound types present in the as least one refinery or chemical process feedstock or products and which have known values for the property or properties selected in step (b);
(d) producing a training set by the steps of:
(1) injecting each reference sample into a gas chromatograph which is interfaced to a mass spectrometer thereby causing at least a partial separation of the hydrocarbon mixture into constituent chemical components;
(2) introducing the constituent chemical components of each reference sample into the mass spectrometer, under dynamic flow conditions;
(3) obtaining for each reference sample a series of time resolved mass chromatograms;
(4} calibrating the mass chromatograms to correct retention times;
(5) selecting a series of corrected retention time windows;
(6) selecting within each retention time window a series of molecular and/or fragment ions, said ions being representative of characteristic compounds or compound classes expected within the retention time window;
(7) recording the total amount of each characteristic compound or compound goup selected in step d(6);
(8) forming the data from steps d(6) and d(7) into a X-block matrix in the order of the selected retention time windows from d(5) to yield for each selected reference sample a row in the training set X-block matrix;
(9) forming the property data selected in (b) for reference samples selected in (c) into a Y-block matrix;
(10) analyzing the data from steps d(8) and d(9) by multivariate correlation techniques to produce a series of coefficients;
(e) subjecting at least one unknown refinery or chemical process feedstock or process sample to steps d(1) and d(3) in the same manner as the reference samples to produce a series of time resolved mass chromatograms;
(f) repeating steps d(4) and d(8) for each mass chromatogram from step (e);
(g) multiplying the matrix from step (f) by the coefficients from step d(10)to produce a predicted value for the property or properties for the refinery or chemical process feedstocks or products sample or samples; and (h) using the predicted values of the property or properties of the refinery or chemical feed stocks or products sample or samples to control the refinery or chemical process.
3. The method of claim 1 or claim 2 wherein the multivariate correlation techniques are Partial Least Squares, Principle Component Regression or Ridge Regression.
4. The method of any one of claims 1 to 3 wherein the gas chromatograph is a capillary gas chromatograph and the mass spectrometer is a quadrupole mass spectrometer.
5. The method of any one of claims 1 to 3 wherein the gas chromatograph and mass spectrometer are operated under repeatable conditions.
6. The method of any one of claims 1 to 5 wherein the selection of a series of molecular and/or fragment ions characteristic of compounds or compound classes is accomplished using Chemist's Rules.
7. The method of any one of claims 1 to 5 wherein the selection of a series of molecular and/or fragment ions characteristic of compounds or compound classes is accomplished using Hydrocarbon Type Analysis.
8. The method of any one of claims 1 to 7 wherein data from the gas chromatograph and mass spectrometer are stored in a computer.
9. The method of any one of claims 1 to 8 wherein data from steps (c) and (g) are treated in a computer.
10. The method of any one of claims 1 to 9 further comprising selecting a further chemical performance, perceptual or physical property of the hydrocarbon mixture.
11. The method of any one of claims 1 to 10 wherein the data are collinear.
12. The method of any one of claims 1 to 11 wherein the multivariate correlation technique is Partial Least Squares.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/494,643 | 1995-06-23 | ||
| US08/494,643 US5699270A (en) | 1995-06-23 | 1995-06-23 | Method for preparing lubrication oils (LAW232) |
| PCT/US1996/007174 WO1997000926A1 (en) | 1995-06-23 | 1996-05-17 | Method for preparing lubricating oils |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2220660A1 CA2220660A1 (en) | 1997-01-09 |
| CA2220660C true CA2220660C (en) | 2007-04-03 |
Family
ID=37951719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002220660A Expired - Lifetime CA2220660C (en) | 1995-06-23 | 1996-05-17 | Method for preparing lubricating oils |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2220660C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20240076563A1 (en) * | 2020-12-30 | 2024-03-07 | Chevron U.S.A. Inc. | Improved Process to Make Finished Base Oils and White Oils from Dewaxed Bulk Base Oils |
-
1996
- 1996-05-17 CA CA002220660A patent/CA2220660C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20240076563A1 (en) * | 2020-12-30 | 2024-03-07 | Chevron U.S.A. Inc. | Improved Process to Make Finished Base Oils and White Oils from Dewaxed Bulk Base Oils |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2220660A1 (en) | 1997-01-09 |
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