CA1272891A

CA1272891A - Chromatographic analyzer

Info

Publication number: CA1272891A
Application number: CA000509915A
Authority: CA
Inventors: Robert E. Robinson; Julius J. Szakasits
Original assignee: Shell Canada Ltd
Current assignee: Shell Canada Ltd
Priority date: 1985-06-28
Filing date: 1986-05-26
Publication date: 1990-08-21
Anticipated expiration: 2007-08-21
Also published as: US5049509A; EP0207537A2; EP0207537A3; JPS625179A; EP0207537B1; DE3687484D1

Abstract

A B S T R A C T

CHROMATOGRAPHIC ANALYZER

Method and apparatus for analyzing a hydrocarbon sample are provided. The apparatus employs a highly polar column to separate the aromatics from non-aromatic components. The non-aromatic effluent from the highly polar column is passed to a 13X MSCOT
(molecular sieve coated open tubular) column and a first less polar column. In a second configuration the highly polar column is backflushed into a second less polar column. The 13X MSCOT (molecular sieve coated open tubular) column separates isoparaffins and any coeluting olefins, normal paraffins and naphthenes by carbon number while the first less polar column individually separates the paraffins, naphthenes and olefins. Thus, the individual olefins may be removed from the data of the 13X molecular sieve column. The second less polar column is employed to separate individual aromatics.
The method for analyzing a hydrocarbon sample separates the aromatics of the sample from the isoparaffins, normal paraffins, naphthenes and olefins. The isoparaffins and any coeluting olefins, normal paraffins and naphthenes are then separated and detected by carbon number. Simultaneously, the individual non-aromatic components are separated and detected. The aromatics that have been previously separated are then individually separated and detected.
The apparatus and method may also include a fifth column for detecting quantities of a preselected inorganic compound.

Description

CHROMATOGRAPHIC ANALYZER

This invention relates generally to analysis of samples by gas chromatography and more particularly, relates to the analysis of hydrocarbon samples by gas chromatography.
It is important to be-able to analyze a hydrocarbon sample quickly and cheaply. This importanc~ is particularly acute in the petrochemical and chemical industries. This is because ~here may be frequent changes in the composition of feedstocks employed in the various processes that are involved in either the petrochemical or chemical industries. This has created the need for an on-site instrument which can quickly provide an analysis of the feed and/or product composition during plant operation to ensure that the feed and product composition are within desired ranges. The failure to recognlze poor plant performance, wh~ch may result in out of specification products, at an early stage can lead to a serious loss in economic revenues.
Prior art analysis has generally consisted of a combination of gas chromotography and analytical chemistry methods conducted in some central laboratory which is normally remote from the chemical or petrochemical plant. The employment of these two (gas chromoto-graphy and analytical chemistry) methods is usually a ~ime consuming and expensive proposition. ~urther, it often results in a leng~hy time period between the time when the sample is actually taken and when the results are made available to the plant. This may exacer-bate any potential economic loss due to poor plant performance during this time.
These and other limitations and dlsadvan~ages of the prior art are overcome by the present invention. It is ~herefore an object of the present invention to provide an improved gas chromatographic method and apparatus for analyzing hydrocarbon samples. The inven-tion therefore provides a method for analyzing a hydrocarbon . .
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product sampIe for isoparaffins, normal paraffins, naphthen0s, and aromatics, comprising the steps of separating said aromatics of said sample from said isoparaffins, normal paraffins and naphthenes of said sample;
separating and detecting said isoparaffins, normal paraffins and naphthenes by carbon number; and individually separating and detecting said aromatics of said sample. The invention also provides an apparatus for analyzing a hydrocarbon product sample for isoparaffins, normal paraffins, naphthenes and aromatics, comprising:
means for separating said aromatics of said sample from said isoparaffins, normal paraffins and naphthenes of said sample;
means for separating and detecting said isoparaffins, normal paraffins and naphthenes by carbon number; and means for individually separating and detecting said aromatics of said sample.
The method of the invention for analyzing a hydrocarbon sample analyzes the sample for isoparaffins, normal paraffins~ naphthenes, aromatics (and olefins, if present). This method separates the aromatics of the sample fro~ the isoparaffins, normal paraffins, naphthenes (and olefins) and thereafter, the individual aromatics are separated and detected. The fraction containing separated isoparaffins, normal paraffins, naphthenes (and olefins) are Çurther separated and detected by isoparaffins (with coeluting olefins), normal paraffins and naphthenes~by carbon number. The method also separates and detects individual saturated and unsatura-ted components of the sample; the detection of individual saturated and unsaturated components allows for the contribution of the indi~idual olefins to be subtracted out of the contribution of isoparaffins and coeluting olefins by carbon number. When olefins are not present 9 this step of separating and detecting individual saturated and unsaturated components may be omitted.
The apparatus of the invention for analyzing a hydrocarbon sample consists of ~our gas chromatography columns with an optional fifth column. A suitable sample injector injects a sample into the ' . ': '.,, :
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~irst column. The first column is a highly polar column which is employed to separate the aromatics fraction from ~he non-aromatics fraction, i.e. unsatura~ed and saturated components. This highly polar column is selectively interconnectable with a second column, which is a 13X molecular sieve column, and a third column, which is a first less polar column than the highly polar column, or with a fourth column. The highly polar column is interconnectable with the fourth column so that the highly polar column may be backflushed into the fourth column, which is a second less polar column than the highly polar column. The optional fifth column may be employed to measure preselected inorganic components, such as for example, but not limited to, hydrogen, nitrogen, sulphur compounds9 or other heteroatom components, and may receive a portion of the sample from the sample injector. The i3X molecular sieve coated capillary column separates isoparaffins and coeluting olefins, normal paraffins and naphthenes by carbon number. The first less polar column separates the individual paraffins and naphthenes and olefins. The second less polar column separates the individual aromatics.
~ The apparatus of the invention also includes appropriate valve means, detection means, means for controlling the temperature of each column and means for supplying appropriate carrier gases at appropriate flow rates to the various columns.
The present invention provides detailed analysis in approxi-mately one and one-half hours of the isoparaffins, normal paraffins, naphthenes, aromatics and olefins of a hydrocarbon sample boiling below about 255 C, including the C5/C6 ring naphthenes distribution within that sample. The data provided by the present invention can be used as, for example but not limited to, an input into a plant model to determine what control actions are necessary to optimize a reformer process.
The present invention uses a plurality of columns and detectors to expand the analyzer scope and to shorten ths analysis time by performing various analyses concurrently. As noted hereinabove, in an alternative embodiment the present invention can be provided with a means for splitting the~sample before it is passed through the highly polar column and a portion that is split off before the ~, . . . .
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~L~ 7;~3a3:3 highly polar column is supplied to a column having a material for separating predetermined inorganic compounds. The column having material for separating at least one predetermined inorganic compound has an appropriate detector means for de~ecting the amount of predetermined component that is separated by this column.
The invention will now be described by way of example in more detail with reference to the accompanying drawings in which:
Fig. 1 is a diagrammatic view of one embodiment of a chromato-graphic analyzer according to the present invention;
Fig. 2 is a diagrammatic view of a portion of the analyzer depicted in Fig. 1 in a different operating position;
Fig. 3 is a simplified flow diagram of the analyzer of Fig. 1 in one operating configuration;
Fig. 4 is a simplified flow diagram of the apparatus of Fig. 1 in a second operating configuration;
Fig. 5 is a typical chromatogram of the component-by-component separation of a non-aromatic fraction of a typical hydrocarbon sample with the first less polar column of the analyzer of Fig. 1;
Fig. 6 is a chromatogram of the normal paraffins, naphthenes, and isoparaffins with coeluting olefins by carbon number separation of a typical hydrocarbon sample with the 13X MSCOT (molecular sieve coated open tubular) column of the analyzer of Fig. l;
Fig. 7 is a chromatogram showing the separation of the aromatics from a typical hydrocarbon sample with the second less polar column of the analyzer of Fig. l; and Fig. 8 is an alternative embodiment of the present invention.
~eferring now to Fig. 1 there may be seen a simplified dia-grammatic view of one embodiment of a chromatographic analyzer of the present invention. More particularly, there may be seen four columns, i.e. column 100, column 200, column 300 and column 400.
There may also be seen a lO-port valve 50, sample injector 10 and carrier gas supply lines 20, 36 and 37. It should be noted that the valve 50 has two operating positions and is depicted in its first operating position in Fig. 1 and in its second operating position in Fig. 2.

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Continuing to refer to Fig. 1, a suitable inert carrier gas, which may be nitrogen, is injected into a line 20 which sweeps a hydrocarbon sample, which has been injected in the sample in~ector 10 by appropriate means, from the sample injector 10 through a line 21 into the valve 50. The line 21 is connected to a port B of the valve 50. The valve port B is internally connected to a valve port C when the valve 50 is in its first operating position. The valve port C is, in turn, connected to a line 22 which is, in turn, connected to the column 100, which may be a highly polar column.
The column 100 may be any suitable metal tubing and may have a length of from about 1 to about 3 metres and an inside diameter of from about 1.5 to about 3.0 millimetres. The column 100 may be a stainless steel ~ube having a length of about 3 metres and an inside diameter of about 2.3 millimetres to make the non-aromatics from aromatics separation. The mesh size is for example about 100/120 mesh.
The column 100 may be contained in a suitable temperature programmable oven 101 for maintaining the temperature of the column 100 at a constant temperature, as determined by a suitable controller ~0 or computer 600. The outlet from the column 100 is a line 23 which is interconnected with a splitter 24. The effluent from the highly polar column 100 in the line 23 is split into three portions by a splitter 24. A portion of the effluent travels down each of three lines 25, 26, 27. The line 27 includes a flow restricter 28 and a normally open solenoid valve 29. The outlet of the solenoid valve 29 is normally vented to the atmosphere.
The line 25 is connected to port G of the valve ~0. However, the line 25 may also have a flow restricter 33 in its line. The port G of the valve 50 is connected ~o a port F of the valve 50 when the valve 50 is in its first operating position. The port F, in turn, is connected to a line 34 which is interconnected with the column 300. The column 300 is for example a 13X molecular sieve coa~ed open tubular (MSCOT) column.
Finely ground 13X molecular sieve is combined with water to form a slurry which is pressured through a clean length of any , ~ .
-' suitable metal (such as stainless steal) 9 fused silica, or glass capillary tubing. An inert gas purge is maintained through the tubing to dry the column and the temperature of the inert gas may be increased after the column is "dried" to stabilize the column and leave the 13X sieve particles attached to the wall of the tubing. The details of preparing such a column are not part of the present invention and will not be described in detail.
The finely divided particle layer provides a high resolution separation of naphthenes, normal paraffins, and isoparaffins with any coeluting ol~fins boiling up to about 255 C by carbon number.
The column 300 may be from abou~ 50 metres to about 150 metres in length and may have an inner diameter of from about 0.1 millimetres to about 0.5 millimetres. The column 300 is for example about 100 metres of a fused silica capillary tube with an inner diameter of about 0.5 millimetres, for general analysis use. Fused silica can be used because of its ability to operate at lower temperatures and because it is inert. While metal tubing may be employed, some metals may cause "cracking" of the sample, and create a large "tail" from impurities which are sometimes found in metal tubing.
For analysis o feedstocks that also are analyzed by the column 400 (as noted later herein) the column 300 has for example a length of about 50 metres. However, for analysiQ of products that do not contain olefins and if a C5/C6 ring naphthene separation is not important the column 400 may be eliminated and the column 300 then has for example a length of about 100 metres to achieve essentially the same separations as the column 400 would achieve. If a C5/C6 ring naphthene separation is important, the column 400 may still be eliminated (if no olefins are present) if the naphthene content is less than about 5%.
The column 300 may also be in a suitable temperature pro-grammable oven 301. The temperature of the oven 301 may be programmed by, for example, a suitable computer or controller 600 to provide suitable heating of the column 300 to facilitate analysis of a sample. The heating program employed for the oven 301 depends upon the type and length of the column 300. For example, for an ' ' ' ' - ` : ,: ,.

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approximately 100 me~res fused silica column having an about 0.50 millimetres inner diameter, the multi-level temperature programming may be: starting at about 70 C, having an increasing ramp of about 10 C/min up to about 150 C, then 5 C/min to about 240 C and then a slower ramp of abou~ 2 C/min to about 320 C to enhance separaeion. Other temperature programs may also be employed, as are ~ell known in the art. The effluent from the column 300 is connected by a line 35 to a sultable detector 302. The detector 302 is for example a flame ioni~ation detector.
A line 26 is connected to the port A of the valve 50. However, the line 26 preferably includes a flow restricter 30 in its line.
The port A is interconnected with a port J of the valve 50 when the valve 50 is in its first operating position. The port J of the valve 50 is connected to a line 31 which is also interconnected with the column 400.
The column 400 is for example a less polar column than the highly polar column 100. The column 400 may be from about 100 metres to about 125 metres in length and have an inner diameter of from about 0.25 millimetres to about 0.32 millimetres and contain a uniform film of a less polar phase than column 100 of thickness from about 0.75 microns to about 1.0 microns. Examples of such less polar phases that are stabIe are methyl and phenyl silicone in fixed ratios, methyl silicone by itself 9 vinyl-phenyl-methyl silicone, polyethylene-polypropylene glycol or cyano-propyl silicone.
~5 The column 400 may be made from any suitable metal, fused silica, or glass tubing. For example, the column 400 is fused silica tubing h~ving a length of about 100 metres and an inside diameter of about 0.~5 millimetres, containing a uniEorm film of methyl silicone about 1.0 microns thick.
The column 400 may also be disposed in a suitable temperature programmable oven 401. The temperature of the oven 401 may be programmed by a-suitable controller or computer 600 to provide suitable heating to the column 400 during its analysls. For example, for a 100 metres fused sillca column having a 0.25 millimetres inner diameter containing a uniform 1.0 micron thick film of methyl silicone, ~he multi-level programming may be: starting at about .

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30 C, having a gradually increasing rate of increase from about 1 C/min to about 60 C and then increasing the rate to about 5 C/min to about 90 C, and then about 20 C/min to about 200 C.
Other temperature programs may be employed, as are well known in the art. The effluent from the column 400 is connected to a suitable detector 402 by line 32. For example, the detector 402 is a flame ioniæation detector.
Fig, 3 depicts, in a simplified flow diagram, the hereinbefore described flow paths of Fig. 1 when the valve 50 is in its first operating position, but omits the valve 50. Fig. 2 illustrates the second operating position of the valve 50. In this second position the port A is in~erconnected with the port B, the port C is connected with the port D, the port E is connected with the port F, the port G is interconnected with the port H, and the port I is interconnected with the port J. This second operating position of the valve 50 which is illustrated in Fig. 2 is employed to backflush the aromatics portion of a hydrocarbon sample from the column 100 into the column 200. ~hile this backflushing operation is occurring, separation is occurring on the columns 300 and 400.
Fig. 4 is a simplified flow diagram of the apparatus of Fig. 1 when the valve 50 is in its second operating position, but omits the valve 50.
Referring now to Fig. 1 and to Fig. 4, it may be seen that an appropriate inert carrier gas, which is preferably helium, is supplied to and flows down the lines 36 and 37 to the valve 50. The line 37 is connected to the port I of the valve 50 which, in the second operating position of the valve 50, is interconnected with the port J tsee Fig. 2). The port J, in turn, is connected with the line 31 which is interconnected with the column 400. Thus, the line 37 supplies a carrier gas to the column 400 to allow this column to continue its analysis of the portion of the hydrocarbon sample which has been injected upon it, while the highly polar column 100 is being backflushed onto the column 200, and also during the analysis of the arom-~ics backf1ushed onto the column 200.

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Continuing to refer to Fig. 1 and Fig. 4, the line 36 is interconnected with the port ~ of the valve 50 which, in its second operating position, is interconnected with the port F (see Fig. 2).
The port F is, in turn, connected to the line 34 which is intercon-nected with the column 300. Thus, the line 36 supplies an appropriatein~rt carrier gas, which is preferably helium, to the column 300 during the backflushing of the highly polar column 100 onto the column 200 and also during the analysis of the aromatics backflushed onto the column 200.
Carrier gas 20 flowing through the injector 10 and the line 21 is interconnected with the line 26 when the valve 50 is in its second operating position (see Fig. 2). This allows the carrier gas 20 to flow through the line 26 into the splitter 24 9 the back down line 23, into the polar column 100. The retarded materials on the column 100 are then backflushed down the line 22 to the port C of the valve 50. The port C of the valve 50 is interconnected with the port D, when the valve 50 is in its second operating position (see Fig. ~). These backflushed materials pass out of the port D of the valve 50 down the line 38 to the splitter 39 where a portion of the effluent goes through the line 40 and the flow resis~or 41. Also in the flowline 40 is a three-way solenoid valve 42, which connects to the line 43 containing a flow restrictor 45, and a line 44 which is normally vented to the atmosphere. The valve 42 is normally open and connects the line 40 to the line 44. HoweverJ when the valve 42 shuts, it interconnects ~he line 43 with the line 40, as depicted in Fig. 4.
The alternate path for the effluent from the column 100 is down the line 46 which is interconnected with the column 200. The column 200 is preferably a less polar column than the highly polar column 100. However, the column 200 may contain substantial amounts of polar material to enhance the separation of the aromatic compo-nents, but should be less polar t;han the highly polar column 100.
Examples of such less polar ma~erials are phenyl and methyl silicone in various ratios or methyl silicone alone, or any other material noted hereinbefore for use in the column 400. The column 200 may be .
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from about 10 metres to about 25 metres in length and have an inner diameter of from about 0.30 millimstres to about 0.50 millimetres and contain a uniform phase layer having a thickness of about 1 micron to about 8 microns. The column 200 may be made from any suitable metal, fused silica, or glass capillary tubing. For example, the column 200 is a fused silica tubing having a length of about 25 metres and an inside diameter of about 0.32 millimetres, containing a uniform layer of methyl silicone or phenyl-methyl silicone about 5.0 microns thick.
The column 200 may also be contained in a temperature pro-grammable o~en 201. The oven 201 is preferably the same as the oven 401, i.e. the oven 401 may contain both the column 200 and the column 400. When the column 200 is in the oven 401, the length and coating thickness of the column 200 as well as the flow rate of carrier gas through the column 200 are optimized for the best separaeion of aromatics while undergoing the temperature program of the oven 401. When the column 200 is in its own separate oven 201, a suitable temperature program may be employed depending upon the length, coating thickness and flow rate of the column 200. Suitable temperature programs are well known in the art. The column 200 is preferably interconnected with a suitable detector 202 by a line 47. For example, tha detector 202 is a flame ionization detector.
The operation of the analyzer, including operation of the valves, the temperature programming of the ovens 9 and the recording ~5 of any output from the detectors may be under the control of a suitable computer/controller 600. This computer/controller may also include suitable data manipulation and output formating functions.
The detectors (202, 302, 402) may alternatively include appropriate chart recorders and/or analog-to-digltal converters for input into the computer/controller 600.
The operation of the process analyzer of the present invention is described as follows. The sample is injected into the analyzer through the sample injector 10 and carried by the carrier gas 20 into the column 100. The column 100 retards the aromatics of the sample and allows the remainder of the sample and carrier gas to .

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pass out through the line 23. The effluent from the column 100 is then split with a portion of it venting to atmosphere and the remaining portions being diverted to the column 300 and the column 400 through appropriate valving and line connections as discussed hereinabove. This is most easily seen in ~ig. 3.
Before benæene would elute from the column 100, the valve 50 is switched from its first operating position to its second operating position (which is indicated in Fig. 2). Simultaneously with the switching of the valve 50, the normally open solenoid valve 29 is closed and the flow restrictor 49 in the line 48 is employed with the flo~ restrictor 33 in the line 25 to prevent incomplete back-flushing of the column 100. The carrier gas from the line 37 is now supplied to-the column 400 as noted hereinabove and the oven 401 begins its temperature program. The carrier gas from the line 36 is now supplied to the column 300 as noted hereinabove and the oven 301 begins its temperature program.
The column 300 which is preferably a 13X MSCOT (molecular sieve coated open tubular) column separates the isoparaffins and any coeluting olefins, normal paraffins and naphthenes by carbon number. These isoparaffins and any coeluting olefins, normal paraffins, and naphthenes, are detected by the detector 302 by carbon number. The column 400 which is for example fused silica less polar coated column, is used to separate individually the paraffins, naphthenes and olefins, which are detected by a suitable ~5 detector 40~. As noted hereinbefore, if there i~ less than about 5%
naphthenes (when C5/C6 ring separation is important) and there are no olefins present (typically a product as opposed to a feedstock) then the column 400 may be eliminated and the column 300 lengthened somewhat to obtain better component separations.
Concurrent with the separation occurring on the columns 300 and 400, the column lOO is being backflushed into the column 200.
This is most clearly illustrated in ~ig. 4. This backflushing of the column 100 sweeps the aromatics that were retarded on the column 100 into the column~200. After the aromatics are swept from the column lOi into the column 200 the carrier gas flow through the .: ., . :

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column 200 is increased in a stepwise manner. This is accomplished by closing the three-way valve 42 which then places the ~low restric~or 45 into the flow path and accordingly more carrier gas is injected into the column 200. This increased gas flow is the gas flow for optimal separation on the column 200, as noted hereinbefore.
The time to increase the carrier flow for the column 200 is related to ~he ~ime employed to switch the valve 50 from its first operating position to its second operating position. That is, ~he carrier flow is increased at approximately two and one-half times the length of time at which the valve 50 is switched to its second operating position.
Separation by carbon number of the normal paraffins, iso-paraffins with coeluting olefins, and naphthenes occur on the 13X
~ISCOT (molerular sieve coated open tubular) column. At the end of the run the olefins may be subtracted out of this data based on the identification of the individual olefins from the column 400. This leaves, by carbon number, the paraffins, both iso and normal, and the naphthenes obtained from the 13X MSCOT (molecular sieve coated open tubular) column. The column 400 includes a detailed component separation of the individual naphthenes through at least about C8.
As noted hereinabove, the individual olefins are also identified on this column.
For ehose products or feedstocks that do not contain olefin~
and contain less than about 5% naphthenes (when C5/C6 ring splits ~5 are important), the separation of individual components from the column 400 may be duplicative of the separation obtained on only the column 300 if the column 300 is lengthened slightly, as discussed hereinbefore. Thus, when no olefins (or a minimal amount of olefins) and less than about 5% naphthenes (when C5/C6 ring splits are important), are present, the column 400 may be eliminated and thP
column 300 increased in length to achieve essentially the same separation.
For those products or feedstocks that have a very high naphthene content (i.e. such that binaphthenes and higher naphthenes are present), any bi- and higher naphthenes will not elute before , ' benzene and will thus be included in the held up aromatics portion in the column 100. However, these bi- and higher naphthenes may be separated and detected separately from the aromatics by the column 200 and its associated detector 202. The computer/controller 600 may then take the data for these bi- and higher naphthenes and insert it in the appropriate table or chart corresponding to the components identified by the column 400 and/or the column 300.
Thus, the computer/controller 600 may know for all the columns employed what elution times (and corresponding peaks) correspond to what components by column and may make appropriate data ad~ustments, such as ehose described hereinbefore, for the final output data ~rom the analyzer of the present invention.
Fig. 5-7 depict component separations that reasonably portray ehe actual data from the columns of the apparatus of the present invention.
Fig. 5 depicts the component separation of a representative hydrocarbon sample, including olefins, from the column 400 as detected by the detector 402. The column 400 separates the sample by individual components from C1 through at least C11. The column used for this chromatogram was an approximately 100 metres fused silica tubing having an inside diameter of about 0.25 millimetres, containing a uniform coating of methyl silicone about 1.0 microns thick and subjected to the temperature program noted hereinbefore as an example for the column 400. Normally, only Cl through abou~
~5 Cg are identified from a practical standpoint, as extensions beyond about Cg require the identification of a large number of peaks that are usually of little or no interest. The peaks identified in Figo 5 are defined in Table 1.
Fig. 6 depicts the component separation of the representative sample of E'ig. 5 obtained by the eolumn 300 as detected by the detector 302. It illustrates the separation of the normal paraffins and isoparaffins with coeluting olefins from the naphthenes by carbon number through C11. The column used for this chromatogram was an approximately 100 metres stainless-steel tubing having an inside diameter of about 0.5 millimetres, prepared as noted : ` , ' . ' ` ,: ` ' . " ''`' , '~ ' .

hereinbefore, and subjected to the tempe~a~ure program noted hereinbefore as an example for the column 300. The normal paraffin peak (P) is denoted by an asterisk immediately above the peak for each carbon number between C5 and Cll, as shown in the example, Fig. 6; however, separation of paraffins, naphthenes and olefins can be made through C14 Fig. 7 depicts the aromatic components separaticn of the sample of Fig. 5 obtained by the column 200 as de~ected by the detector 202. The column used to obtain this chromatogram was an 1~ approximately 25 metres fused silica tubing having an interior diameter o~ about 0.32 millimetres, containing about a 5 micron thick coating of 5~ phenyl/95% methyl silicone, and subjected to the temperature program of column 400, noted hereinbefore as an example. The peaks identified in Fig. 7 are defined in Table 2. As l~ illustrated in Fig. 7, additional peaks are detected but are not normally identified for practical reasons, as noted hereinbefore, but are summed all together to obtain a greater than about C
iden~ification. The start of the summation is indlcated at A.
The column employed as the column 100 to make the aromatics from non-aromatics separa~ion for Fig. 5-7 was an approximately 3 metres stainless steel tubing having an inside diameter of about

2.3 millimetres, and held isothermally at a eemperature of 120 C.
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Identification of Chromatogram (Fig. 1) l. Isopentane 2. n-Pentane

3. 3,3-Dimethyl-l-butene

4. Cyclopen~ene

5. Cyclopentane

6. 2,3-Dimethylbutane :
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7. 2,3-Dimethyl-l-butene

8. 2-Methylpentane

9. 3-Methylpentane

10. 2-Methyl-l-pentene

11. l-Hexene

12. n-Hexane

13. t-Hexene-2

14. 4~4-Dimethyl-l-pentene

15. Methylcyclopentane

16. 2 J 4-Dimethylpentane

17. 2,3-Dimethyl-2-butene

18. 2,2,3-Trimethylbutane

19. Cyclohexane

20. Cyclohexene

21. 2-Methylhexane

22. 2,3-Dimethylpentane

23. l,l-Dimethylcyclopentane

24. 4-Methyl-l-hexene

25. 3-Methylhexane

26. C-1,3-Dimethylcyclopentane

27. t~l,3-Dimethylcyclopentane

28. 3-Ethylpentane

29. t-1,2-Dimethylcyclopentane

30. l-Heptene

31. 2,2,4-Trimethylcyclopentane

32. n-Heptane

33. t-2-Hep~ene

34. 2,4,4-Trimethyl-l-pentene

35. c-2-Heptene

36. 1-c-2-Dimethylcyclopentane

37. Nethylcyclohexane ~
; 38. 1,1,3-Trimethylcyclopentane 39. 2?4-Dimethylhexane + 2,5-dimethylhexane 40. 2,2,3-Trimethylpentane + 3,3-dimethylhexane 41. 1-t-c-4-Trimethylcyclopentane ': ~
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42. 2,2~3-Trimethylpentane 43. c,t~c-1,2,3-Trimethylcyclopentane + t,c,t-1,2,3-trimethyl-cyclopentane 44. 2,3,4-Trimethylpentane 45. 2,3,3-Trlmethylpentane 46. 2,3-Dimethylhexane 47. 3-Ethyl-2-methylpentane ~ 1,1,2-trimethylcyclopentane 48. 2-Methylheptane 49. 4-Methylheptane 50. 3~Ethyl-3-Methylpentane + 4-dimethylhexane 51. c,c,t-1,2,4-Trimethylcyclopentane ~ 3-methylheptane 52. 3-Ethylhexane 53. 1-c-3-Dimethylcyclohexane + c,c,c-1,2,3-trimethylcyclopentane 54. t-1,4-Dimethylcyclohexane 55. 1~1-Dimethylcyclohexane 56. t-1-Ethyl-3-methylcyclopentane + l-octene 57. c-1-Ethyl-3-methylcyclopentane 58. t-1-Ethyl-2-methylcyclopentane S9. t-1,2-Dimethylcyclohexane 60. n-Octane 61. c,c,c-1,2,3-Trimethylcyclopentane 62. c-1,4-Dimethylcyclohexane + t-1,3-dimethylcyclohexane 63. Isopropylcyclopentane ~ c-2-octene 64. c~1-Ethyl-2-methylcyclopentane 65. 2,4-Di~ethylheptane 66. c-1,2-Dime~thylcyclohexane 67. n Propylcyclopentane 68. Ethylcyclohexane 69. 2,5-Dimethylheptane 70. 1-Nonene 71. c-3-Nonene 72. 1-Decsne 73. t-3-Decene 74. 1-Undecene 75. 1-Dodecene .

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Aromatics Column Separation 1. Benzene 2. Toluene 3. Ethylbenzene 4. m,p-Xylene 5. o-~ylene 6. Isopropylbenzene 7. n-Propylbenzene 8. 1-Methyl-3-ethylbenzene, 1-methyl-4-ethylbenzene 9. 1,3,5-Trimethylbenzene 10. 1-Methyl-2-ethylbenzene 11. 1,2,4-Trimethylbenzene 12. sec-Butylbenzene, n-butylbenzene 13. Unknown 14. 1-Methyl-3-isopropylbenzene 15. 1,2,3-Trimethylbenzene Methyl-2-isopropylbenzene ~
17. 1-Methyl-3-n-propylbenzene, 1,3-diethylbenzene 18. 1~Methyl-4-n-propylbenzene, n-butylbenzene, 1,4-diethylbenzene, 1,2-dimethyl-5-ethylbenzene 19. 1,2-Dimethylbenzene 20. 1-Methyl_2-n~propylbenzene 21. 1,4-Dimethyl-2-ethylbenzene 22. 1,3-Di~ethyl-4-ethylbenæene 23.~ 1,2-Dimethyl-4-ethylbenzene 24. 1,3-Dimethyl-2-eehylbenzene 25. Unknown ~ ~
26. 1,2-Dimethyl-3-ethy1benzene , - : . - . . ~ , . -. - .
- : . . .. . .

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27. 1,2,4,5-Tetramethylbenzene 28. 1,2,3,5-~etramethylbenzene 29. Unknown 30. Unknown 31. Unknown 32. 1,2,3,4-Tetramethylbenzene 33. Unknown 34~ Unknown 35. Unknown 36. Unknown 37. Naphthalene _ As noted hereinbefore, the computer/controller 600 may be employed to shift data corresponding to various components from one column to another based upon known component elution times for each column. Accordingly, the olefins present in Fig. 6 may be subtracted out based upon the amoun~ and specific olefin present, as identified in Fig. 5 (Table 1).
Referring to Fig. 8 an alternative embodiment of the present invention is provided in which an additional fifth column for detecting a preselected inorganic component is incorporated with the apparatus of Flg. l.~More particularly, a fifth column 500 to measure a preselected inorganic component, is added to the apparatus of Fig. 1. In a similar manner, the method of the present invention may also include a step for determining at least one preselected inorganic component of a hydrocarbon sample.
The column 500 may be a packed column suitable for determining the amount of hydrogen in the sample. Alternatively, the column 500 may be a column for determining nitrogen, the amount of sulphur components or other heteroatom components in the sample.
The sample to be analyzed may again be in;ected into the sample injector 10. The sample is carried from the in~ector 10 by - .: .
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carrier gas from the line 20 into a line 61. The line 61 is connected to the port X of the valve 60. The valve 60 is a two-position si~-port valve~ In its first operating position, the ports of the valve 60 are interconnected as indicated in Fig. 8 by the solid lines. In its second operating position, the ports of the valve 60 are interconnected as indicated by the dashed lines.
The first position of the valve 60 may be employed to allow a sample from the injector 10 to be supplied to the various columns for analysis. That is, the port X is interconnected with the port Y
to which the line 62 is connected. Thus, the sample is swept into the line 62 from injector 10 by the carrier gas supplied by the line 20. The line 62 is also connected to the splitter 63 which diverts a portion of the sample to the line 64 and to the line 21.
The line 21 is the sample supply line for the apparatus of Fig. 1 which operates as described hereinbefore.
The line 64 is the sample supply line for the column 500 and is connected to the port M of the valve 70. The valve 70 is a two-position four-port valve. In its first operating position, as indicated by solid lines in Fig. 8, the port M is interconnected with the port N. The port N is connected to the line 65 which is also connected to the input of the column 500.
The column 500 is employed to analyze the sample for preselected inorganic components such as hydrogen, nitrogen, sulphur compounds, or other heteroatom components. For hydrogen gas, the column 500 is ~S preferably a stainless steel tubing of about 1.5 metres in length and having an inside diameter of about 2.3 millimetres. The column 500 may also be in a temperature programmable oven 501, which may also be controIled by the controlIer 600 (see Fig. 1).
The column 500 is also connected to the line 66. The line 66 is also connected to the port P of the valve 70. In its first operating position, as indicated by solid 11nes in Fig. 8, the port P is interconnected to the port Q. The port Q is connected to the line 67 which also is connected to a detector 502. For hydrogen detection, the detector 502 is for example a thermal conductivity detector.

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The valve 70 in its second operating position, as indicated by the dashed lines in Fig. 8, is employed to backflush the column 500 into the detector 502. When the detector 502 is a thermal conduc-tivity detector it may also need a separate supply of carrier gas ~hich is supplied by line 68.
As also depicted in Fig. 8, the valve 60 may be employed to circulate a portion of a product or feedstock through a sample loop 82 on the valve 60 through a supply line 81 and a return line 83.
When this portion of the apparatus depicted in Fig. 8 is so employed, the injector 10 need not be used to provide a sample for analysis.
When the valve 60 is moved to its second position, the carrier gas from the line 20 sweeps the sample from the sample loop 82 into the line 62 ~here it is split and analyzed as noted hereinbefore. The valve 60 may be so employed with the apparatus of Fig. 1 even when the column 500 is not employed with the apparatus of Fig. 1.
Many other variations and modifications may be made in the apparatus and techniques hereinbefore described by those having experience in this technology without departing from the concepts of the present invention. Accordingly, it should be understood that the apparatus and methods depicted in the accompanying drawi~gs and referred to in the foregoing description are illustrative only and are not intended as a limitation on the scope of the invention.

' - ~ '' ~ ' . ' ' , : ' ' .

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method for analyzing a hydrocarbon product sample for isoparaffins, normal paraffins, naphthenes, and aromatics, com-prising the steps of:
separating said aromatics of said sample from said iso-paraffins, normal paraffins and naphthenes of said sample;
separating and detecting said isoparaffins, normal paraffins and naphthenes by carbon number; and individually separating and detecting said aromatics of said sample.

2. The method as claimed in claim 1 for analyzing a hydro-carbon sample for isoparaffins, normal paraffins, naphthenes, aromatics and olefins, further comprising the steps of:
separating said aromatics of said sample from said iso-paraffins, normal paraffins, naphthenes and olefins of said sample;
separating and detecting said isoparaffins and any co-eluting olefins, normal paraffins and naphthenes by carbon number;
separating and detecting individual non-aromatic com-ponents of said sample.

3. The method as claimed in claim 2, further comprising the step of subtracting any coeluting olefins from said isoparaffins in functional relationship with said separating and detecting of individual non-aromatic components.

4. The method as claimed in claim 2 or 3, further compris-ing the step of separating and detecting a predetermined inorganic component in said sample.

5. The method as claimed in claim 2 or 3 wherein said step of separating and detecting of said individual non-aromatic com-ponents is for components having a number of carbon atoms substan-tially in the range from one carbon atom to nine carbon atoms.

6. The method as claimed in claim 2 or 3, wherein said step of separating and detecting said isoparaffins and any coeluting olefins, normal paraffins and naphthenes by carbon number is for components having a number of carbon atoms substantially in the range from one carbon atom to fourteen carbon atoms.

7. The method as claimed in claim 2 or 3 wherein said step of separating of aromatics from said isoparaffins, normal paraf-fins, naphthenes and olefins is performed with a gas chromatograph column and is stopped in functional relationship to the elution of benzene from said column.

8. An apparatus for analyzing a hydrocarbon product sample for isoparaffins, normal paraffins, naphthenes and aromatics, comprising:
means for separating said aromatics of said sample from said isoparaffins, normal paraffins and naphthenes of said - 22a - 63293-2655 sample, means for separating and detecting said isoparaffins, normal paraffins and naphthenes by carbon number; and means for individually separating and detecting said aromatics of said sample.

9. The apparatus as claimed in claim 8 for analyzing a hydrocarbon sample for isoparaffins, normal paraffins, naphthenes, aromatics and olefins, further comprising:
means for separating aromatics of said sample from iso-paraffins, normal paraffins, naphthenes and olefins of said sample;
means for separating and detecting said isoparaffins and any coeluting olefins, normal paraffins and naphthenes by carbon number;
means for separating and detecting individual non-aromatic components of said sample.

10. The apparatus as claimed in claim 9, further comprising means for separating and detecting at least one preselected inorganic component.

11. The apparatus as claimed in claim 9 comprising:
a 13X molecular sieve coated capillary column for sepa-rating isoparaffins and any coeluting olefins, normal paraffins and naphthenes by carbon number;
a first less polar column for individually separating paraffins, naphthenes and olefins;

a second less polar column for separating individual aromatics;
and a highly polar column for separating aromatics from non-aromatic components selectively interconnectable with said 13X molecular sieve column and first less polar column, and with said second less polar column.

12. The apparatus as claimed in claim 11, further comprising means for controlling the temperature of said 13X molecular sieve column.

13. The apparatus as claimed in claim 12, further comprising means for controlling the temperature of said first less polar column.

14. The apparatus as claimed in claim 11, further comprising gas chromatographic column means for separating at least one preselected inorganic component of said sample operatively interconnected with said highly polar column.

15. The apparatus as claimed in claim 11, wherein said highly polar column is selectivity interconnected with said second less polar column in functional relationship to the elution time of benzene from said highly polar column.

16. The apparatus as claimed in claim 11, further comprising computer/controller means for operating said 13X molecular sieve column, said first less polar column, said second less polar column and said highly polar column.

17. The apparatus as claimed in claim 8, wherein said means for separating said aromatics comprises a highly polar column.

18. The apparatus as claimed in claim 8, wherein said means for separating and detecting said isoparaffins, normal paraffins and naphthenes comprises a 13X molecular sieve coated capillary column.

19. The apparatus as claimed in claim 8, wherein said means for individually separating and detecting said aromatics comprises an at least slightly polar column.