CA2094939A1 - Method and apparatus for determining sulphur concentrations in complex compounds - Google Patents
Method and apparatus for determining sulphur concentrations in complex compoundsInfo
- Publication number
- CA2094939A1 CA2094939A1 CA 2094939 CA2094939A CA2094939A1 CA 2094939 A1 CA2094939 A1 CA 2094939A1 CA 2094939 CA2094939 CA 2094939 CA 2094939 A CA2094939 A CA 2094939A CA 2094939 A1 CA2094939 A1 CA 2094939A1
- Authority
- CA
- Canada
- Prior art keywords
- light
- sample
- reaction
- ozone
- introducing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
- G01N21/766—Chemiluminescence; Bioluminescence of gases
-
- 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
- G01N33/2835—Oils, i.e. hydrocarbon liquids specific substances contained in the oil or fuel
- G01N33/287—Sulfur content
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
A METHOD AND APPARATUS FOR THE SELECTIVE DETERMINATION OF
VARIOUS SULFUR COMPONENTS IN COMPLEX COMPOUNDS IN A REALTIME, CONTINUOUS APPLICATION COMPRISING SEPARATION OF THE CONSTITUENT
COMPONENTS OF A PETROLEUM PRODUCT SAMPLE BY CHROMATOGRAPHY;
REACTING, BY FLAMELESS COMBUSTION, THE EXITING SAMPLE IN A REDUCING
ENVIRONMENT OF HYDROGEN AND AIR; INTRODUCING THE PRODUCTS OF THE
REACTION TO AN OZONE LADEN CHEMILUMINESCENCE DETECTOR; FILTERING
THE RESULTANT LIGHT EMISSIONS TO EXCLUDE INFRARED PRODUCED BY RE-ACTING NITROGEN COMPOUNDS; MATHEMATICALLY MANIPULATING THE RE-SULTANT ULTRAVIOLET LIGHT INDUCED ELECTRICAL SIGNAL TO OBTAIN A RE-ALTIME MEASUREMENT OF THE SULPHUR CONCENTRATIONS.
A METHOD AND APPARATUS FOR THE SELECTIVE DETERMINATION OF
VARIOUS SULFUR COMPONENTS IN COMPLEX COMPOUNDS IN A REALTIME, CONTINUOUS APPLICATION COMPRISING SEPARATION OF THE CONSTITUENT
COMPONENTS OF A PETROLEUM PRODUCT SAMPLE BY CHROMATOGRAPHY;
REACTING, BY FLAMELESS COMBUSTION, THE EXITING SAMPLE IN A REDUCING
ENVIRONMENT OF HYDROGEN AND AIR; INTRODUCING THE PRODUCTS OF THE
REACTION TO AN OZONE LADEN CHEMILUMINESCENCE DETECTOR; FILTERING
THE RESULTANT LIGHT EMISSIONS TO EXCLUDE INFRARED PRODUCED BY RE-ACTING NITROGEN COMPOUNDS; MATHEMATICALLY MANIPULATING THE RE-SULTANT ULTRAVIOLET LIGHT INDUCED ELECTRICAL SIGNAL TO OBTAIN A RE-ALTIME MEASUREMENT OF THE SULPHUR CONCENTRATIONS.
Description
` 2094~3'~
This invention relates to the field of continuous analysis and measurement of sulphur components in complex compounds, more particularly, the analysis and measurement of such components in petroleum products by chemiluminescence means.
Present methods of analysis and measurement of sulphur compounds in petroleum os products generally consist of the use of gas chromatography in combination with a flame photom-etric detector.
It is customary for a grab sample to be obtained from the above mentioned apparatus and delivered to an offsite or onsite laboratorywhere analysis takes place. The results of such analysis may typically be unavailable for hours, or in some cases days.
lo The time delay in obtaining valid analysis in turn delays the processing of the petroleum product and, therefore, a considerable advantage is to be had from a system of analysis that operates on a realtime, continuous basis.
In addition to the delay factor, the known art method of analysis and measurement suffers from the following shortcomings:
15 (a) it results in a non linear response to varying concentrations of sulphur;
(b) the analysis is subject to interferences from other compounds;
(c) it is subject to quenching from non-sulphur containing compounds;
(d) it provides different response factors for different sulphur species; and - , -, . :; . : ~ ~ -: . ...
-` 209~939 (e) due to the reactive nature of the sulphur compounds of interest, stable process samples are relatively difficult to obtain.
It is an object of the present invention, then, to selectively determine the concentration of various sulphur components in complex compounds in a realtime, continuous process 05 application by providing: -(a) a measurement device and method wherein the response is linear from low ppb to ppm concentrations.
~b) a measurement device and method which is substantially free from known interferences;
(c) a measurement device and method which is substantially immune to quenching from other 10 compounds;
(d) a measurement device and method wherein substantially the same response factor can be used regardless of the sulphur specie under analysis;
:, (e) a measurement device and method located and performed on site, at the process, thus ensuring a representative sample is analyzed; and 15 (i ) a measurement device and method, the realtime continuous functioning of which facilitates adjustment of the process before product not meeting established specifications is actually produced.
Further objects and advantages of the present invention will become apparent from a consideration of the ensuing description and drawings.
This invention relates to the field of continuous analysis and measurement of sulphur components in complex compounds, more particularly, the analysis and measurement of such components in petroleum products by chemiluminescence means.
Present methods of analysis and measurement of sulphur compounds in petroleum os products generally consist of the use of gas chromatography in combination with a flame photom-etric detector.
It is customary for a grab sample to be obtained from the above mentioned apparatus and delivered to an offsite or onsite laboratorywhere analysis takes place. The results of such analysis may typically be unavailable for hours, or in some cases days.
lo The time delay in obtaining valid analysis in turn delays the processing of the petroleum product and, therefore, a considerable advantage is to be had from a system of analysis that operates on a realtime, continuous basis.
In addition to the delay factor, the known art method of analysis and measurement suffers from the following shortcomings:
15 (a) it results in a non linear response to varying concentrations of sulphur;
(b) the analysis is subject to interferences from other compounds;
(c) it is subject to quenching from non-sulphur containing compounds;
(d) it provides different response factors for different sulphur species; and - , -, . :; . : ~ ~ -: . ...
-` 209~939 (e) due to the reactive nature of the sulphur compounds of interest, stable process samples are relatively difficult to obtain.
It is an object of the present invention, then, to selectively determine the concentration of various sulphur components in complex compounds in a realtime, continuous process 05 application by providing: -(a) a measurement device and method wherein the response is linear from low ppb to ppm concentrations.
~b) a measurement device and method which is substantially free from known interferences;
(c) a measurement device and method which is substantially immune to quenching from other 10 compounds;
(d) a measurement device and method wherein substantially the same response factor can be used regardless of the sulphur specie under analysis;
:, (e) a measurement device and method located and performed on site, at the process, thus ensuring a representative sample is analyzed; and 15 (i ) a measurement device and method, the realtime continuous functioning of which facilitates adjustment of the process before product not meeting established specifications is actually produced.
Further objects and advantages of the present invention will become apparent from a consideration of the ensuing description and drawings.
,~
:-~ 209~939 According to one aspect the present invention is a method to selectively determine the concentration of a variety of sulphur components in complex compounds in a realtime continuous process application comprising the steps of:
introducing a sample of a petroleum product through a chromatograph column;
05 reacting, by flameless combustion, the sample exiting the chromatograph with a reducing mixture of hydrogen and air such that S02~H2=SO+H20;
introducing ozone into an evacuated chemiluminescence cell;
mixing the products of the reaction with the ozone to produce light in the ultraviolet spectrum suchthat; S0+03=S~+02+LIGHI;
10 filtering the light output to substantially eliminate interference of infrared light emmissions from the reaction of nitrogen compounds;
detecting the light output; and displaying the light output in human readable form. : :
According to another aspect the invention is an apparatus to selectively determine the 15 concentration of various sulphur components in complex compounds in a realtime, continuous application comprising;
a sampliing means for introducing a process product sample to a chromotograph column;
209~93!~
means for reacting by flameless combustion the sample exiting the chromatograph column with a reducing mixture of hydrogen and air;
: `:
means for introducing ozone to an evacuated chemiluminescence detector and mixing the product of the reaction with the ozone so that light is emitted in the ultraviolet spectrum and the light is 05 linearly proportional to the sulphur concentration of the sample.
means for filtering the emitted light so that interference from chemiluminescence reaction of nitrogen compounds emitting light in the infrared region is substantially eliminated;
A description of the presently preferred embodiment of the instant invention now follows having regard to the drawing wherein;
10 Figure 1 is a block diagram of the system showing the relationship of the functional sub-systems.
A sample 10 of a process product, typically a petroleum product, is introduced into a conventional thick film, methyl silicone liquid phase, open tubular chromatograph column 12 which provides separation of sulphur species of interest as well as hydrocarbons.
A flow metering system 14 comprised of conventional valving, well known to those sldlled in the art, accepts an incoming supply of hydrogen 16 and air 18; mixes the hydrogen 16with the air 18and transfers a controlledflow of the hydrogen/air mixture 20substantiallyfree frompressure fluctuations, toan electricallypowered, flameless ovenæwhichismaintained atatemperatureof appro~imately 850 degrees Celsius by means of a temperature control ævia electrical signal path 26. ' ,. , ~ . ., :, , ~ :
, -2~94939 Upon receipt of an electrical command signal 28, transmitted from a microprocessor based, system control 30to the chromatograph column 12, the separated sample 10ais transferred from the chromatograph column 12 to the oven 22 where the sample 10a reacts with the reducing mixture of hydrogen/air 20.
' ' os The detector 34is evacuatedby operationof avacuum pump 36 which pump 36 maintains a gauge pressure of approximately 25 inches Hg within the reaction chamber of the detector 34.
Ozone 38, produced by the actions of an ozone generator 40 of conventional design is introduced into the evacuated reaction chamber of the detector 34 and the products of the reaction 32 are conveyed by any suitable means from the oven æ to the ozone 381aden reaction chamber of the detector34wherein reactionwiththe ozone 38 produces ultraviolet lightemission which is linearly proportional to the sulphur concentration of the sample 10.
An opticalfilter42substantiallyeliminatesinterference fromany chemiluminescence ::
reactions of nitrogen compounds which may also be present in the sample 10 by blocking light emissions in the infrared region. ..
.:
The filtered light from the detector 34 is transferred as an analog electrical signal 44 to the system control 3Q
~ .
The system control 30 is comprised of a microprocessor and associated electricalcomp4nentsoperatingunderthe direction and supervision of control software, to accomplish the digitization of theanalogsignal44;tocalculatetheareas underthe peaks of the analog signal 20 44; and correlate those areas to the elution times, thereby determining the concentrations of each sulphur component of the sample 10; to control the timing of the transfer of sample 10afrom the chromatograph column 12tothe oven 22; to periodicallybackflush the chromatograph column ~ 2094939 with helium; and to provide status indicators and appropriate drive signals to a user interface system.
The description herein should not be construed as limiting the scope of the present invention but rather as setting forth the presently preferred embodiment of the invention. Thus 05 the scope of the invention should be determined by the appended claims and their legal equiva-lents.
. ~ . . .
.-:;
:-~ 209~939 According to one aspect the present invention is a method to selectively determine the concentration of a variety of sulphur components in complex compounds in a realtime continuous process application comprising the steps of:
introducing a sample of a petroleum product through a chromatograph column;
05 reacting, by flameless combustion, the sample exiting the chromatograph with a reducing mixture of hydrogen and air such that S02~H2=SO+H20;
introducing ozone into an evacuated chemiluminescence cell;
mixing the products of the reaction with the ozone to produce light in the ultraviolet spectrum suchthat; S0+03=S~+02+LIGHI;
10 filtering the light output to substantially eliminate interference of infrared light emmissions from the reaction of nitrogen compounds;
detecting the light output; and displaying the light output in human readable form. : :
According to another aspect the invention is an apparatus to selectively determine the 15 concentration of various sulphur components in complex compounds in a realtime, continuous application comprising;
a sampliing means for introducing a process product sample to a chromotograph column;
209~93!~
means for reacting by flameless combustion the sample exiting the chromatograph column with a reducing mixture of hydrogen and air;
: `:
means for introducing ozone to an evacuated chemiluminescence detector and mixing the product of the reaction with the ozone so that light is emitted in the ultraviolet spectrum and the light is 05 linearly proportional to the sulphur concentration of the sample.
means for filtering the emitted light so that interference from chemiluminescence reaction of nitrogen compounds emitting light in the infrared region is substantially eliminated;
A description of the presently preferred embodiment of the instant invention now follows having regard to the drawing wherein;
10 Figure 1 is a block diagram of the system showing the relationship of the functional sub-systems.
A sample 10 of a process product, typically a petroleum product, is introduced into a conventional thick film, methyl silicone liquid phase, open tubular chromatograph column 12 which provides separation of sulphur species of interest as well as hydrocarbons.
A flow metering system 14 comprised of conventional valving, well known to those sldlled in the art, accepts an incoming supply of hydrogen 16 and air 18; mixes the hydrogen 16with the air 18and transfers a controlledflow of the hydrogen/air mixture 20substantiallyfree frompressure fluctuations, toan electricallypowered, flameless ovenæwhichismaintained atatemperatureof appro~imately 850 degrees Celsius by means of a temperature control ævia electrical signal path 26. ' ,. , ~ . ., :, , ~ :
, -2~94939 Upon receipt of an electrical command signal 28, transmitted from a microprocessor based, system control 30to the chromatograph column 12, the separated sample 10ais transferred from the chromatograph column 12 to the oven 22 where the sample 10a reacts with the reducing mixture of hydrogen/air 20.
' ' os The detector 34is evacuatedby operationof avacuum pump 36 which pump 36 maintains a gauge pressure of approximately 25 inches Hg within the reaction chamber of the detector 34.
Ozone 38, produced by the actions of an ozone generator 40 of conventional design is introduced into the evacuated reaction chamber of the detector 34 and the products of the reaction 32 are conveyed by any suitable means from the oven æ to the ozone 381aden reaction chamber of the detector34wherein reactionwiththe ozone 38 produces ultraviolet lightemission which is linearly proportional to the sulphur concentration of the sample 10.
An opticalfilter42substantiallyeliminatesinterference fromany chemiluminescence ::
reactions of nitrogen compounds which may also be present in the sample 10 by blocking light emissions in the infrared region. ..
.:
The filtered light from the detector 34 is transferred as an analog electrical signal 44 to the system control 3Q
~ .
The system control 30 is comprised of a microprocessor and associated electricalcomp4nentsoperatingunderthe direction and supervision of control software, to accomplish the digitization of theanalogsignal44;tocalculatetheareas underthe peaks of the analog signal 20 44; and correlate those areas to the elution times, thereby determining the concentrations of each sulphur component of the sample 10; to control the timing of the transfer of sample 10afrom the chromatograph column 12tothe oven 22; to periodicallybackflush the chromatograph column ~ 2094939 with helium; and to provide status indicators and appropriate drive signals to a user interface system.
The description herein should not be construed as limiting the scope of the present invention but rather as setting forth the presently preferred embodiment of the invention. Thus 05 the scope of the invention should be determined by the appended claims and their legal equiva-lents.
. ~ . . .
.-:;
Claims (2)
1. A method to selectively determine the concentration of a variety of sulphur components in complex compounds in a realtime continuous process application comprising the steps of:
introducing a sample of a petroleum product through a chromatograph column;
reacting, by flameless combustion the sample exiting the chromatograph with a reducing mixture of hydrogen and air such that SO2+H2=SO+H2O;
introducing ozone into an evacuated chemiluminescence cell;
mixing the products of the reaction with the ozone to produce light in the ultraviolet spectrum such that; SO+O3=SO2+O2+LIGHT;
filtering the light output to substantially eliminate interference of infrared light emmissions from the reaction of nitrogen compounds;
detecting the light output; and displaying the light output in human readable form.
introducing a sample of a petroleum product through a chromatograph column;
reacting, by flameless combustion the sample exiting the chromatograph with a reducing mixture of hydrogen and air such that SO2+H2=SO+H2O;
introducing ozone into an evacuated chemiluminescence cell;
mixing the products of the reaction with the ozone to produce light in the ultraviolet spectrum such that; SO+O3=SO2+O2+LIGHT;
filtering the light output to substantially eliminate interference of infrared light emmissions from the reaction of nitrogen compounds;
detecting the light output; and displaying the light output in human readable form.
2. An apparatus to selectively determine the concentration of various sulphur components in complex compounds in a realtime, continuous application comprising;
a sampling means for introducing a process product sample to a chromotograph column;
means for reacting by flameless combustion the sample exiting the chromotograph column in a reducing mixture of hydrogen and air;
means for introducing ozone to an evacuated chemiluminescence detector and mixing the product of the reaction with the ozone so that light is emitted in the ultraviolet spectrum and the light is linearly proportional to the sulphur concentration of the sample; and means for filtering the emitted light so that interference from chemiluminescence reaction of nitrogen compounds emitting light in the infrared region is substantially eliminated.
a sampling means for introducing a process product sample to a chromotograph column;
means for reacting by flameless combustion the sample exiting the chromotograph column in a reducing mixture of hydrogen and air;
means for introducing ozone to an evacuated chemiluminescence detector and mixing the product of the reaction with the ozone so that light is emitted in the ultraviolet spectrum and the light is linearly proportional to the sulphur concentration of the sample; and means for filtering the emitted light so that interference from chemiluminescence reaction of nitrogen compounds emitting light in the infrared region is substantially eliminated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2094939 CA2094939A1 (en) | 1993-04-26 | 1993-04-26 | Method and apparatus for determining sulphur concentrations in complex compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2094939 CA2094939A1 (en) | 1993-04-26 | 1993-04-26 | Method and apparatus for determining sulphur concentrations in complex compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2094939A1 true CA2094939A1 (en) | 1994-10-27 |
Family
ID=4151533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2094939 Abandoned CA2094939A1 (en) | 1993-04-26 | 1993-04-26 | Method and apparatus for determining sulphur concentrations in complex compounds |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2094939A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11402333B2 (en) * | 2016-09-06 | 2022-08-02 | Ac Analytical Controls B.V. | Method for chemiluminescent sulphur detection and a furnace |
| US11493449B2 (en) * | 2018-09-04 | 2022-11-08 | Shimadzu Corporation | Sulfur chemiluminescence detector analysis system, display control method and non-transitory computer readable medium |
-
1993
- 1993-04-26 CA CA 2094939 patent/CA2094939A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11402333B2 (en) * | 2016-09-06 | 2022-08-02 | Ac Analytical Controls B.V. | Method for chemiluminescent sulphur detection and a furnace |
| US11493449B2 (en) * | 2018-09-04 | 2022-11-08 | Shimadzu Corporation | Sulfur chemiluminescence detector analysis system, display control method and non-transitory computer readable medium |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |