US20020029802A1 - Integrated valve design for gas chromatograph - Google Patents
Integrated valve design for gas chromatograph Download PDFInfo
- Publication number
- US20020029802A1 US20020029802A1 US09/850,954 US85095401A US2002029802A1 US 20020029802 A1 US20020029802 A1 US 20020029802A1 US 85095401 A US85095401 A US 85095401A US 2002029802 A1 US2002029802 A1 US 2002029802A1
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- United States
- Prior art keywords
- valve
- plates
- valve assembly
- gas
- heating zone
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- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/201—Injection using a sampling valve multiport valves, i.e. having more than two ports
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- 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
- G01N30/66—Thermal conductivity detectors
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- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/6416—With heating or cooling of the system
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/8158—With indicator, register, recorder, alarm or inspection means
Definitions
- This invention relates to the field of gas chromatography.
- this invention relates to a new gas chromatograph.
- this invention relates to a new gas chromatograph having multiple valves and detectors.
- the field of gas chromatography is concerned with analyzing gas samples flowing through a process pipeline.
- a sample is provided to a gas chromatography which then separates the sample into portions and uses a variety of detectors to analyze the concentration of particular components in the process stream.
- a disclosed embodiment of the invention is a multi-valve assembly including a plurality of plates and diaphragms attached together to form multiple valves. Each of these valves is individually actuatable by an outside source and includes a plurality of valve ports.
- the assembly may also include a reception area where at least one fluid properly detector, such as a TCD, may be inserted.
- the assembly preferably includes an open area in the body of plate that holds a spool.
- the spool includes a heater and heats a gas sample to a predetennined temperature while the remainder of the plates heat carrier gas to a second predetermined temperature by use of a band heater.
- the disclosed embodiment also includes two sets of screws, a first set attaching a top plate of the invention to at least one middle plate, and a second set attaching a bottom plate of the invention to at least one middle plate, the top plate being removable without the bottom plate becoming detached.
- the invention comprises a combination of features and advantages which enable it to overcome various problems of prior devices.
- the various characteristics described above, as well as other features, will be readily apparent to those skilled in the art upon reading the following detailed description of the preferred embodiments of the invention, and by referring to the accompanying drawings.
- FIG. 1 is a simplified diagram of a gas chromatograph system.
- FIG. 2 is a simplified schematic of a gas chromatograph.
- FIG. 3A is a schematic diagram of a valve in an ON configuration.
- FIG. 3C is a schematic diagram of a multiple valve system for analyzing a sample.
- FIG. 4 is an illustrative cut-away view of a valve.
- FIG. 5 is an illustrative cut-away view of a solinoid.
- FIG. 6 is an exploded isometric view of an embodiment of a multi-valve block.
- FIG. 7A is a top view of an upper piston plate for the multi-valve block of FIG. 6.
- FIG. 7B is a bottom view of an upper piston plate for the multi-valve block of FIG. 6.
- FIG. 8B is a bottom view of a lower piston plate for the multi-valve block of FIG. 6.
- FIG. 9A is a top view of a base plate for the multi-valve block of FIG. 6.
- FIG. 9B is a bottom view of a base plate for the multi-valve block of FIG. 6.
- FIG. 11 is a sealing diaphragm for the multi-valve block of FIG. 6.
- FIG. 12 is a cushion diaphragm for the multi-valve block of FIG. 6.
- FIG. 13A is an upper actuator diaphragm for the multi-valve block of FIG. 6.
- FIG. 13B is a lower actuator diaphragm for the multi-valve block of FIG. 6.
- FIG. 14 is a cut-away view of a multi-valve assembly during operation.
- FIG. 15 is a top view of the bottom piece of insulation for a multi-valve assembly oven.
- FIG. 16 is a cross-section view of an embodiment of the multi-valve assembly.
- FIG. 1 shows a gas chromatograph system generally built in accordance with the teachings herein.
- Gas flows through a process pipeline 1 I 10 , a sample of which is taken by a sample probe 120 prior to being introduced to gas chromatograph (GC) 100 .
- the gas sample may be filtered and heat traced generally along tubing 130 before flowing into gas chromatograph 100 . This heating may be required for gases that may condense into a part gas, part liquid flow at cooler temperatures.
- the gas sample is either returned into the process pipeline 110 , or vented to the atmosphere.
- gas chromatograph 100 includes valve assembly 210 connected to multiple columns 220 and detectors 230 , in this case, thermal conductivity detectors (TCD).
- a gas sample generally follows path 240 through valve assembly 210 , columns 220 and TCDs 230 .
- the valve assembly allows the selection of columns 220 which contain a liquid phase, or porous polymer, or other material that acts to separate the gas sample into multiple portions, each portion being sequentially released to the TCDs 230 .
- a gas sample may contain various molecular weight hydrocarbon components.
- Column 220 could separate the gas sample so that lower molecular weight hydrocarbon components would elute from the column first, followed by a higher molecular weight component, etc.
- Valve 300 includes a plurality of valve ports, labeled 1 - 6 . It will be appreciated that more or fewer number of ports may also be used.
- Incoming line 310 provides a gas sample to valve 300 .
- Exhaust line 320 expels the gas sample from the valve 300 .
- Solid lines 330 show open passages between ports, whereas dotted lines 340 indicate blocked passages between the ports.
- a solenoid places valve 300 into either an ON position, as shown in FIG. 3A, or an OFF position, as shown in FIG. 3B.
- a valve When a valve is in the ON position, gas flows from incoming line 310 , through port 1 to port 6 , through line 315 and finally through port 3 to port 2 and out exhaust line 320 .
- Wien the valve is in the OFF position, gas flows from incoming line 310 , through port 1 to port 2 and out through exhaust line 320 .
- FIGS. 3C and 3D illustrate how a pair of valves may operate either alone or in combination with additional valves (not shown).
- a first valve 300 includes ai array of 6 valve ports.
- a second valve 350 also includes an array of 6 valve ports.
- Associated tubing 310 , 315 , 320 , 325 and 390 , and columns 360 and 370 are also shown as well as dual TCD 380 .
- Incoming line 310 is attached to a sample transport line (not shown).
- a sample transport line (not shown).
- gas sample flows from incoming line 310 to port 1 to port 2 of the valve 300 and out exhaust line 320 .
- valve 300 is in an ON position, however, gas sample flows from port 1 to port 6 and then through sample loop 315 . That gas then flows from port 3 to port 2 of valve 300 and is expelled out exhaust line 320 .
- the sample loop 315 is filled with a gas sample. This means that, if valve 300 is turned OFF at this time, a gas sample is trapped within the sample loop 315 .
- valve 350 when it is in an OFF configuration, carrier gas flows from carrier gas input line 390 through port 2 of valve 350 , to port 1 and then through carrier tubing 325 .
- valve 300 is also in an OFF configuration, so that the carrier gas in tubing 325 is forced through port 5 to port 6 and through gas sample tubing 315 . Consequently, this action forces the (gas sample down column 360 via ports 3 and 4 . The gas sample can then additionally be forced through column 370 and into the dual TCD 380 via ports 4 and 3 .
- Many other port combinations also exist and are within the skill of one in the art.
- the valves may be connected in series to form “channels.”
- Each channel feeds into a corresponding TCD pair (a measurement TCD and a reference TCD).
- Use of more than one TCD pair results in a simultaneous analysis by the TCD's of the sample flowing through their corresponding attached columns.
- This parallel analysis results in a increased analysis speed as compared to serial analysis.
- the number of chanmels in use at any particular time is limited both by the number of valves and by the number of detectors. Of course, the greater the number of valves, the greater the number of potential channels, and the more potential for more parallel processing and a faster overall system.
- a greater number of valves results in a greater number of channels from which to choose for each TCD.
- a multi-valve system may have sufficient valves to operate eight channels. Even if only two detector pairs exist, such that only two channels can be in use at any one time, the detector pairs can be designed to select which chaimel among those eight channels it is conmected to. This dramatically increases the flexibility of the presently disclosed gas chromatograph system.
- Valve 400 includes a base plate 410 with activation ports 412 and 414 , a lower actuator diaphragm 420 , a lower piston plate 430 with associated long piston 435 , upper actuator diaphragm 440 , upper piston plate 450 with associated short piston 455 , cushion diaphragm 460 , sealing diaphragm 465 , and primary plate 470 with valve ports 472 and 474 therein.
- These valve ports suitably could be ports 1 and 6 as shown in FIG. 3.
- gas sample 480 enters valve port 472 .
- This gas sample 480 travels out valve port 474 when long piston 435 is in an elevated (closed) position and short piston 455 is not.
- Long piston 435 is elevated by gas pressure applied to activation port A 412 . This pressure deforms lower actuator diaphragm 420 and forces long piston 435 in an upward direction in lower piston plate 430 . Upper end of long piston 435 then abuts against primary plate 470 .
- short piston 455 is actuated by gas pressure from activation port B 414 , and forces gas sample 480 to path 485 .
- FIG. 5 generally illustrates the operation of a solenoid.
- Solenoid 500 includes a common line port 510 , exit port 520 corresponding to activation port A, exit port 530 corresponding to activation port B, release port 525 for exit port A exit port B, and control leads 540 .
- Tubing 550 connects to each of common line port 510 , and exit ports 520 and 530 .
- Exit ports A and B connect to activation ports A and B in FIG. 4, respectively.
- Common line port 510 conmects to a gas under pressure.
- Gas pressure applied to either of activation port A or activation port B controls whether the corresponding valve is in an ON or OFF position.
- Electrical control signals from leads 540 control whether common line 510 is connected to exit port A or exit port B, and thus whether gas pressure is applied to activation port A or activation port B.
- FIG. 6 shows an exploded view of an embodiment of the multi-valve block 600 including an open area 605 , base plate 610 with associated dowel pins to align components, a lower activator diaphragm 620 , a lower piston plate 630 with associated long pistons 635 , an upper activator diaphragm 640 , an upper piston plate 650 with associated short pistons 655 , a cushion diaphragm 660 , a sealing diaphragm 665 , and a primary plate 670 .
- Each piston includes a lower base portion with a pole extending therefrom. Hole sets 680 and 690 are suitable for two pairs of TCD's.
- First set of screws 615 for insertion through base plate 610 , lower piston plate, and upper piston plate are shown as well as a second set of screws 675 for insertion through primary plate 670 , upper piston plate 650 , lower piston plate 630 , and base plate 610 .
- five solenoids are also present, each controlling a different valve.
- the multi-valve device 600 includes 5 valves, with each valve having six ports.
- a compact device is achieved that can separate a gas sample into a large number of columns as discussed above. This facilitates faster and more precise analysis of the gases contained in the gas sample. Manufacturing costs can also be reduced.
- the teachings herein can be used to integrate more or fewer than 5 valves into a single unit, and more or fewer valve ports per valve. For example, if a greater number of valves is desired, up to 7 valves can easily be located in the embodiment shown in FIG. 6.
- FIG. 6 One manner in which the embodiment of FIG. 6 makes faster and more precise analysis of the gas sample is reduction of what is known as “dead volume.” Increased dead volume results when the components of a gas chromatograph are widely spaced and undue mixing of the fluid occurs. This mixing of the gas or fluid sample results in a “band broadening.” Band broadening is undesirable because the area of each band of an analysis corresponds to a concentration measurement and these bands should not overlap. Consequently, a series of broad bands results in a much slower analysis than is possible with a series of short bands. Therefore, an integrated, compact design is particularly desirable from a performance perspective. Further, the illustrated geometry provides sufficient area for a first and second set of TCD's.
- TCD's may be located outside the multi-valve block if desired (e.g. to integrate a greater number of valves into the multi-valve block), the inclusion of the TCD's in the multi-valve block helps further miniaturize the device and make it more compact.
- FIGS. 7A and 7B show top and bottom views respectively of the upper piston plate of FIG. 6. Refeiring to the top view of FIG. 7A, locations 701 - 705 for 5 valves are shown. Screw holes, generally at 720 , are also shown for accepting screws to tighten together the primary plate with other plates. Holes 750 are for screws from the bottom, to tighten the plates together, while holes 760 are for dowel pins to position the valves. Tuniing to the bottom view of the upper piston plate shown in FIG. 7B, locations 701 - 707 are similarly shown. Each valve includes sufficient room 730 . 735 for 3 piston bases and 3 piston poles. Raised edges 740 around the perimeter of each valve location are also shown.
- the raised surfaces defined by the raised edges exist on both sides of the upper and lower piston plates. A raised edge of 0.032 inches could be used, for example. These raised edges 740 reduce the surface area upon which the screws 615 and 675 provide force and thereby reduce the chance of leakage.
- a bottom set of screws 615 extends tirough the base plate 610 , lower piston plate 630 , and upper piston plate 650 . Screws 615 attach these plates together.
- a top set of screws 675 extends through the primary plate, the upper piston plate, and the base plate to hold those plates together. This dual screw set approach simplifies maintenance because the loosening and removal of screws 675 allows access and replacement of the sealing diaplragm 665 and cushion diapliragm 660 without disassembly of a greater number of plates than necessary.
- the sealing diapliragm that becomes most contaminated by the dirty gas that flows through the multi-valve.
- a relatively low torque of about 10 ft/lbs. has been found acceptable for these screw sets while making the removal of these screws as easy as possible.
- the multi-valve configuration also simplifies maintenance because, by virtue of multiple valves in an integrated unit, replacement of only one diaplragm is necessary rather than the multiple diaphragms that would othervise be necessary for multiple valves.
- FIGS. 8A and 8B show the lower piston plate of FIG. 6.
- FIGS. 8A and 8B are the upper and lower views respectively of the lower piston plate.
- locations 801 - 805 are provided for the five valves, in addition to an area for two sets of TCDs.
- Holes 820 and holes 825 accept tightening screws.
- Also shown are five triangular grooves 830 and accompanying holes 840 within each groove. Gas from the solenoids travels tlrough the actuation holes 840 to the grooves 830 . These grooves 830 provide a path for the actuation gas that elevates the short pistons.
- valves of the illustrated embodiment have six ports, and thus three short pistons per valve, a triangular shape is convenient (but not necessary) to actuate all three short pistons simultaneously.
- locations 801 - 807 are shown.
- holes 840 are also generally shown at 840 are holes connected to an actuator port through which gas exerts pressure. These holes 840 correspond to the grooves 830 of FIG. 8A. As can be seen, space 830 is provided for the base of long pistons 635 .
- FIGS. 9A and 9B show the top and bottom views respectively of the base plate.
- a plurality of grooves 930 are shown, with each groove encompassing a hole 940 for actuator gas.
- actuator holes 945 traveling up to the lower piston plate are additionally shown.
- FIG. 9B illustrates the bottom view of the base plate. Illustrated are slot 960 and holes 970 , 980 , and 990 .
- Slot 960 is present because it simplifies the removal of plates upon disassembly. In particular, after a valve has been assembled, the diaphragms tend to stick to a contact surface, and the slots provide an area where the plates can be easily grabbed onto.
- Hole 970 is a port A and B common line that coinects to port A and B on solenoids via tubing. Holes 980 and 990 are screw holes. FIG. 9B also shows cross-drill lines 962 and 964 representing drilled areas for insertion of carrier and sample gas tubing. Holes at the entrance to each insertion area are also shown. The carrier and sample gas are quickly and reliably preheated in the insertion areas defined by cross-drill lines 962 and 964 from the warmth in the multi-valve block.
- FIGS. 10A and 10B show the upper and lower view of a primary plate of FIG. 6.
- TCD holes 1050 - 1053 and associated tubing holes 1060 - 1063 are also shown.
- a hole 1070 suitable for a RTD heat sensor is also shown.
- FIG. 10B shows a bottom view of the primary plate. Included are holes 1010 to accept screws and 1020 to accept dowel pins.
- FIGS. 11 - 13 illustrate the diaphragms of FIG. 6.
- FIG. 11 shows the sealing diaphragm of FIG. 6.
- the sealing diaphragm is preferably made from 2 mil thick KaptonTM made by DuPont with a 0.5 mil teflon coating on each side.
- FIG. 12 shows the cushion diaphragm of FIG. 6.
- the cushion diaphragm is preferably about 0.002′′ thick and is made from Nomax paper by DuPont.
- FIGS. 13A and 13B illustrate upper and lower actuator diaphragms. Both actuator diaphragms are preferably made from 3 mil thick KaptonTM made by DuPont.
- FIG. 14 illustrates a multi-valve block 1400 including a spool 1410 with areas for a first RTD (Resistance Thermal Detector) 1420 and two TCD pairs 1425 , an exterior surface 1430 to the multi-valve block 1400 , a band heater 1440 outside of the exterior surface 1430 , carrier gas preheat tubing 1450 located between the exterior surface 1430 and the band heater 1450 , and a base plate 610 as part of the multi-valve block.
- Spool 1410 contains one or more cartridge heaters 1460 and a second RTD 1465 . Referring back to FIG. 6, a hole or open area 605 is present in the middle of the multi-valve block.
- the open area 605 accommodates spool 1410 that protrudes fiom the base plate 610 .
- Columns 1470 wraps around the spool 1410 .
- solinoids 1480 connected via tubing 1485 to the base plate at its lower end 1490 .
- Band heater 1440 is an AC band heater of approximately 200 Watts power.
- a gas sample flows through tubing or conduits 315 (not shown in FIG. 14) in the multi-valve block prior to flowing through the piping of the columns 1470 .
- the carrier gas flows through the carrier gas preheat tubing 1450 prior to flowing through columns 1470 .
- the carrier gas preheat tubing may be located at different positions to heat the carrier gas to a predetermined temperature.
- the carrier gas preheat tubing may be just inside the band heater as shown in FIG. 14, or it may preferably occupy insertion areas in the multi-valvc block, as explained in reference to FIG. 9.
- both the carrier gas and the as sample are heated to approximately the temperature of the multi-valve block.
- this arrangement provides for two heating zones.
- the area proximate to the spool 1410 defines a second heating zone.
- a first heating zone is defined by the temperature of the remainder of the multi-valve block.
- the first RTD located in the multi-valve block at 1420 measures the temperature of the first heating zone.
- the second RTD located at 1465 within the spool 1410 measures the temperature of the second heating zone.
- Two separate heating zones are important because the gas flowing through the columns 1470 should ideally be about 3-5° C. higher than the temperature at each TCD (the temperature of the first heating zone).
- the TCD's in the first heating zone should be kept to within about 0.1° C. of a predetermined temperature for accurate analysis.
- the temperature variation in the second heating zone should also be maintained within about a 0.1° C. tolerance. More heating zones may be added when desired to allow the analysis of the complex samples.
- an “oven” is created from a thermal insulation material.
- This oven is essentially a cylindrical sleeve that surrounds the rest of the multi-valve device and keeps its temperature stable, except for the solinoids, which must be kept away from the heat inside the oven.
- FIG. 15 an illustrative bottom 1500 of this insulation cylinder or sleeve is shown. As can be seen, it contains a number of holes 1510 , through which extend the tubing for the solinoids and the legs of the base stand.
- FIG. 16 illustrates the insulation 1610 for the “coven” including the bottom 1500 of the insulation cylinder.
- base plate 610 is adjacent to the bottom of the insulation cylinder 1500 .
- Legs 1600 to create stand-off are made from TeflonTM 1605 .
- tubing 1485 that extends through the bottom piece 1500 to the lower surface 1490 of the multi-valve block 1400 .
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Abstract
A gas chromatograph with multiple valves is disclosed. An embodiment of the multi-valve gas chromatograph includes multiple valves and multiple thermal conductivity detectors (TCD's). This allows separation and measurement of a gas sample in one compact integrated unit.
Other features may also be present. For example, a first heating zone may include a band heater placed around the multi-valve block to heat the carrier gas and to keep the multi-valve block at a desired temperature. A second heating zone may include a spool and a cartridge heater to heat the columns through which the gas sample flows. Two sets of screws, one through the top of the multi-valve and one through the bottom, may be included to simplify maintenance of the multi-valve system. Insulation defining an oven can be placed around the assembly to stabilize the temperature of the multi-valve assembly.
Description
- Not Applicable.
- Not Applicable.
- 1. Field of the Invention
- This invention relates to the field of gas chromatography. In particular, this invention relates to a new gas chromatograph. Even more particularly, this invention relates to a new gas chromatograph having multiple valves and detectors.
- 2. Description of the Related Art
- The field of gas chromatography is concerned with analyzing gas samples flowing through a process pipeline. A sample is provided to a gas chromatography which then separates the sample into portions and uses a variety of detectors to analyze the concentration of particular components in the process stream.
- Before now, a number of problems have existed with gas chromatographs. For example, fast and accurate measurements are desirable for any gas chromatograph. A gas stream flowing through the process pipeline may be composed of many different classes of components and ideally, each of these components would be analyzed. However, conventional gas chromatographs cannot respond to process changes as quickly as desired. Futher, liquid contaminants in the process stream can introduce further complications to any analysis.
- Another problem with previous gas chromatographs is a lack of flexibility in analysis of the gas stream. It would often be desirable to analyze different characteristics of the gas stream without switching to another gas chromatograph. However, previous gas chromatographs are restricted because of their limited number of valves and their lack of flexibility. As such, a gas chromatograph is needed that can analyze complex process streams with greater accuracy and speed.
- Other problems with gas chromatographs have also existed in the valve system contained in gas chromatographs. For example, these valves are not easy to service. Maintenance may be necessary because often the flows through a gas chromatograph are dirty, and this contamination can affect the performance of key components in the gas chromatograph. Substitution of clean components in the gas chromatograph can minimize the problem, but disassembling the gas chromatograph has in the past been a difficult and frustrating experience. Thus, a need for a new gas chromatograph exists.
- As known by those of ordinary skill, the prior art also presents other problems that should be solved or minimized.
- A disclosed embodiment of the invention is a multi-valve assembly including a plurality of plates and diaphragms attached together to form multiple valves. Each of these valves is individually actuatable by an outside source and includes a plurality of valve ports. The assembly may also include a reception area where at least one fluid properly detector, such as a TCD, may be inserted. The assembly preferably includes an open area in the body of plate that holds a spool. The spool includes a heater and heats a gas sample to a predetennined temperature while the remainder of the plates heat carrier gas to a second predetermined temperature by use of a band heater.
- The disclosed embodiment also includes two sets of screws, a first set attaching a top plate of the invention to at least one middle plate, and a second set attaching a bottom plate of the invention to at least one middle plate, the top plate being removable without the bottom plate becoming detached.
- The invention comprises a combination of features and advantages which enable it to overcome various problems of prior devices. The various characteristics described above, as well as other features, will be readily apparent to those skilled in the art upon reading the following detailed description of the preferred embodiments of the invention, and by referring to the accompanying drawings.
- For a more detailed description of the preferred embodiment of the present invention, reference will now be made to the accompanying drawings, wherein:
- FIG. 1 is a simplified diagram of a gas chromatograph system.
- FIG. 2 is a simplified schematic of a gas chromatograph.
- FIG. 3A is a schematic diagram of a valve in an ON configuration.
- FIG. 3B is a schematic diagram of a valve in an OFF configuration.
- FIG. 3C is a schematic diagram of a multiple valve system for analyzing a sample.
- FIG. 4 is an illustrative cut-away view of a valve.
- FIG. 5 is an illustrative cut-away view of a solinoid.
- FIG. 6 is an exploded isometric view of an embodiment of a multi-valve block.
- FIG. 7A is a top view of an upper piston plate for the multi-valve block of FIG. 6.
- FIG. 7B is a bottom view of an upper piston plate for the multi-valve block of FIG. 6.
- FIG. 8A is a top view of a lower piston plate for the multi-valve block of FIG. 6.
- FIG. 8B is a bottom view of a lower piston plate for the multi-valve block of FIG. 6.
- FIG. 9A is a top view of a base plate for the multi-valve block of FIG. 6.
- FIG. 9B is a bottom view of a base plate for the multi-valve block of FIG. 6.
- FIG. 10A is a top view of a primary plate for the multi-valve block of FIG. 6.
- FIG. 10B is a bottom view of a primary plate for the multi-valve block of FIG. 6.
- FIG. 11 is a sealing diaphragm for the multi-valve block of FIG. 6.
- FIG. 12 is a cushion diaphragm for the multi-valve block of FIG. 6.
- FIG. 13A is an upper actuator diaphragm for the multi-valve block of FIG. 6.
- FIG. 13B is a lower actuator diaphragm for the multi-valve block of FIG. 6.
- FIG. 14 is a cut-away view of a multi-valve assembly during operation.
- FIG. 15 is a top view of the bottom piece of insulation for a multi-valve assembly oven.
- FIG. 16 is a cross-section view of an embodiment of the multi-valve assembly.
- FIG. 1 shows a gas chromatograph system generally built in accordance with the teachings herein. Gas flows through a process pipeline1I10, a sample of which is taken by a
sample probe 120 prior to being introduced to gas chromatograph (GC) 100. The gas sample may be filtered and heat traced generally alongtubing 130 before flowing intogas chromatograph 100. This heating may be required for gases that may condense into a part gas, part liquid flow at cooler temperatures. After being analyzed by the gas chromatograph, the gas sample is either returned into theprocess pipeline 110, or vented to the atmosphere. - Referring to FIG. 2,
gas chromatograph 100 includesvalve assembly 210 connected tomultiple columns 220 anddetectors 230, in this case, thermal conductivity detectors (TCD). A gas sample generally followspath 240 throughvalve assembly 210,columns 220 andTCDs 230. The valve assembly allows the selection ofcolumns 220 which contain a liquid phase, or porous polymer, or other material that acts to separate the gas sample into multiple portions, each portion being sequentially released to theTCDs 230. For example, a gas sample may contain various molecular weight hydrocarbon components.Column 220 could separate the gas sample so that lower molecular weight hydrocarbon components would elute from the column first, followed by a higher molecular weight component, etc. - Refering to FIGS. 3A and 3B, the operation of a valve is shown.
Valve 300 includes a plurality of valve ports, labeled 1-6. It will be appreciated that more or fewer number of ports may also be used.Incoming line 310 provides a gas sample tovalve 300.Exhaust line 320 expels the gas sample from thevalve 300.Solid lines 330 show open passages between ports, whereasdotted lines 340 indicate blocked passages between the ports. - A solenoid (not shown) places
valve 300 into either an ON position, as shown in FIG. 3A, or an OFF position, as shown in FIG. 3B. When a valve is in the ON position, gas flows fromincoming line 310, through port 1 toport 6, throughline 315 and finally throughport 3 toport 2 and outexhaust line 320. Wien the valve is in the OFF position, gas flows fromincoming line 310, through port 1 toport 2 and out throughexhaust line 320. - FIGS. 3C and 3D illustrate how a pair of valves may operate either alone or in combination with additional valves (not shown). A
first valve 300 includes ai array of 6 valve ports. Asecond valve 350 also includes an array of6 valve ports.Associated tubing columns dual TCD 380. -
Incoming line 310 is attached to a sample transport line (not shown). Whenfirst valve 300 in an OFF position, gas sample flows fromincoming line 310 to port 1 toport 2 of thevalve 300 and outexhaust line 320. Whenvalve 300 is in an ON position, however, gas sample flows from port 1 toport 6 and then throughsample loop 315. That gas then flows fromport 3 toport 2 ofvalve 300 and is expelled outexhaust line 320. At this time, thesample loop 315 is filled with a gas sample. This means that, ifvalve 300 is turned OFF at this time, a gas sample is trapped within thesample loop 315. - Turning now to
valve 350, when it is in an OFF configuration, carrier gas flows from carriergas input line 390 throughport 2 ofvalve 350, to port 1 and then throughcarrier tubing 325. At this time,valve 300 is also in an OFF configuration, so that the carrier gas intubing 325 is forced throughport 5 toport 6 and throughgas sample tubing 315. Consequently, this action forces the (gas sample downcolumn 360 viaports column 370 and into thedual TCD 380 viaports - Each channel feeds into a corresponding TCD pair (a measurement TCD and a reference TCD). Use of more than one TCD pair results in a simultaneous analysis by the TCD's of the sample flowing through their corresponding attached columns. This parallel analysis results in a increased analysis speed as compared to serial analysis. Further. because tecluology currently limits the channels and the detector pairs to a one-to-one correspondence, the number of chanmels in use at any particular time is limited both by the number of valves and by the number of detectors. Of course, the greater the number of valves, the greater the number of potential channels, and the more potential for more parallel processing and a faster overall system. But even if the number of detectors limits the number of channels being used at any one time, a greater number of valves results in a greater number of channels from which to choose for each TCD. For example, a multi-valve system may have sufficient valves to operate eight channels. Even if only two detector pairs exist, such that only two channels can be in use at any one time, the detector pairs can be designed to select which chaimel among those eight channels it is conmected to. This dramatically increases the flexibility of the presently disclosed gas chromatograph system.
- Referring to FIG. 4, a cross-section of a partial valve assembly is shown.
Valve 400 includes abase plate 410 withactivation ports lower actuator diaphragm 420, alower piston plate 430 with associatedlong piston 435,upper actuator diaphragm 440,upper piston plate 450 with associatedshort piston 455,cushion diaphragm 460, sealingdiaphragm 465, andprimary plate 470 withvalve ports ports 1 and 6 as shown in FIG. 3. - Referring back to FIG. 4,
gas sample 480 entersvalve port 472. Thisgas sample 480 travels outvalve port 474 whenlong piston 435 is in an elevated (closed) position andshort piston 455 is not.Long piston 435 is elevated by gas pressure applied toactivation port A 412. This pressure deformslower actuator diaphragm 420 and forceslong piston 435 in an upward direction inlower piston plate 430. Upper end oflong piston 435 then abuts againstprimary plate 470. Similarly,short piston 455 is actuated by gas pressure from activation port B414, and forcesgas sample 480 topath 485. - Whether a valve is in an ON or OFF position depends upon a solenoid that applied gas pressure alternately to either activation port A or activation port B. FIG. 5 generally illustrates the operation of a solenoid.
Solenoid 500 includes acommon line port 510,exit port 520 corresponding to activation port A,exit port 530 corresponding to activation port B,release port 525 for exit port A exit port B, and control leads 540.Tubing 550 connects to each ofcommon line port 510, andexit ports Common line port 510 conmects to a gas under pressure. Gas pressure applied to either of activation port A or activation port B controls whether the corresponding valve is in an ON or OFF position. Electrical control signals fromleads 540 control whethercommon line 510 is connected to exit port A or exit port B, and thus whether gas pressure is applied to activation port A or activation port B. Some variation to the particulars of this design is possible while still staying within the teachings of the invention. - FIG. 6 shows an exploded view of an embodiment of the
multi-valve block 600 including anopen area 605,base plate 610 with associated dowel pins to align components, alower activator diaphragm 620, alower piston plate 630 with associatedlong pistons 635, anupper activator diaphragm 640, anupper piston plate 650 with associated short pistons 655, acushion diaphragm 660, a sealingdiaphragm 665, and aprimary plate 670. Each piston includes a lower base portion with a pole extending therefrom. Hole sets 680 and 690 are suitable for two pairs of TCD's. First set ofscrews 615 for insertion throughbase plate 610, lower piston plate, and upper piston plate are shown as well as a second set ofscrews 675 for insertion throughprimary plate 670,upper piston plate 650,lower piston plate 630, andbase plate 610. In addition, because there are five valves, five solenoids (not shown) are also present, each controlling a different valve. - As can be seen, the
multi-valve device 600 includes 5 valves, with each valve having six ports. By integrating multiple valves into a single multi-valve block, a compact device is achieved that can separate a gas sample into a large number of columns as discussed above. This facilitates faster and more precise analysis of the gases contained in the gas sample. Manufacturing costs can also be reduced. The teachings herein can be used to integrate more or fewer than 5 valves into a single unit, and more or fewer valve ports per valve. For example, if a greater number of valves is desired, up to 7 valves can easily be located in the embodiment shown in FIG. 6. - One manner in which the embodiment of FIG. 6 makes faster and more precise analysis of the gas sample is reduction of what is known as “dead volume.” Increased dead volume results when the components of a gas chromatograph are widely spaced and undue mixing of the fluid occurs. This mixing of the gas or fluid sample results in a “band broadening.” Band broadening is undesirable because the area of each band of an analysis corresponds to a concentration measurement and these bands should not overlap. Consequently, a series of broad bands results in a much slower analysis than is possible with a series of short bands. Therefore, an integrated, compact design is particularly desirable from a performance perspective. Further, the illustrated geometry provides sufficient area for a first and second set of TCD's. While these TCD's may be located outside the multi-valve block if desired (e.g. to integrate a greater number of valves into the multi-valve block), the inclusion of the TCD's in the multi-valve block helps further miniaturize the device and make it more compact.
- FIGS. 7A and 7B show top and bottom views respectively of the upper piston plate of FIG. 6. Refeiring to the top view of FIG. 7A, locations701-705 for 5 valves are shown. Screw holes, generally at 720, are also shown for accepting screws to tighten together the primary plate with other plates.
Holes 750 are for screws from the bottom, to tighten the plates together, whileholes 760 are for dowel pins to position the valves. Tuniing to the bottom view of the upper piston plate shown in FIG. 7B, locations 701-707 are similarly shown. Each valve includessufficient room 730. 735 for 3 piston bases and 3 piston poles. Raisededges 740 around the perimeter of each valve location are also shown. The raised surfaces defined by the raised edges exist on both sides of the upper and lower piston plates. A raised edge of 0.032 inches could be used, for example. These raisededges 740 reduce the surface area upon which thescrews - Referring back to FIG. 6, it can be seen that two sets of screws are shown corresponding to
holes tlirough holes screws 615 extends tirough thebase plate 610,lower piston plate 630, andupper piston plate 650.Screws 615 attach these plates together. A top set ofscrews 675 extends through the primary plate, the upper piston plate, and the base plate to hold those plates together. This dual screw set approach simplifies maintenance because the loosening and removal ofscrews 675 allows access and replacement of the sealingdiaplragm 665 and cushion diapliragm 660 without disassembly of a greater number of plates than necessary. It is the sealing diapliragm that becomes most contaminated by the dirty gas that flows through the multi-valve. A relatively low torque of about 10 ft/lbs. has been found acceptable for these screw sets while making the removal of these screws as easy as possible. The multi-valve configuration also simplifies maintenance because, by virtue of multiple valves in an integrated unit, replacement of only one diaplragm is necessary rather than the multiple diaphragms that would othervise be necessary for multiple valves. - FIGS. 8A and 8B show the lower piston plate of FIG. 6. FIGS. 8A and 8B are the upper and lower views respectively of the lower piston plate. Referring to FIG. 8A, once again, locations801-805 are provided for the five valves, in addition to an area for two sets of TCDs.
Holes 820 andholes 825 accept tightening screws. Also shown are fivetriangular grooves 830 and accompanyingholes 840 within each groove. Gas from the solenoids travels tlrough the actuation holes 840 to thegrooves 830. Thesegrooves 830 provide a path for the actuation gas that elevates the short pistons. Because the valves of the illustrated embodiment have six ports, and thus three short pistons per valve, a triangular shape is convenient (but not necessary) to actuate all three short pistons simultaneously. Turning now to the bottom view of FIG. 8B, locations 801-807 are shown. Also generally shown at 840 are holes connected to an actuator port through which gas exerts pressure. Theseholes 840 correspond to thegrooves 830 of FIG. 8A. As can be seen,space 830 is provided for the base oflong pistons 635. - FIGS. 9A and 9B show the top and bottom views respectively of the base plate. Referring to FIG. 9A, similar to FIG. 8A, a plurality of
grooves 930 are shown, with each groove encompassing ahole 940 for actuator gas. In addition actuator holes 945 traveling up to the lower piston plate are additionally shown. FIG. 9B illustrates the bottom view of the base plate. Illustrated areslot 960 andholes Slot 960 is present because it simplifies the removal of plates upon disassembly. In particular, after a valve has been assembled, the diaphragms tend to stick to a contact surface, and the slots provide an area where the plates can be easily grabbed onto.Hole 970 is a port A and B common line that coinects to port A and B on solenoids via tubing.Holes cross-drill lines cross-drill lines - FIGS. 10A and 10B show the upper and lower view of a primary plate of FIG. 6. Referring now to FIG. 10A shown are TCD holes1050-1053 and associated tubing holes 1060-1063. Also shown is a
hole 1070 suitable for a RTD heat sensor. FIG. 10B shows a bottom view of the primary plate. Included areholes 1010 to accept screws and 1020 to accept dowel pins. - FIGS.11-13 illustrate the diaphragms of FIG. 6. FIG. 11 shows the sealing diaphragm of FIG. 6. The sealing diaphragm is preferably made from 2 mil thick Kapton™ made by DuPont with a 0.5 mil teflon coating on each side. FIG. 12 shows the cushion diaphragm of FIG. 6. The cushion diaphragm is preferably about 0.002″ thick and is made from Nomax paper by DuPont. FIGS. 13A and 13B illustrate upper and lower actuator diaphragms. Both actuator diaphragms are preferably made from 3 mil thick Kapton™ made by DuPont.
- FIG. 14 illustrates a
multi-valve block 1400 including aspool 1410 with areas for a first RTD (Resistance Thermal Detector) 1420 and twoTCD pairs 1425, anexterior surface 1430 to themulti-valve block 1400, aband heater 1440 outside of theexterior surface 1430, carriergas preheat tubing 1450 located between theexterior surface 1430 and theband heater 1450, and abase plate 610 as part of the multi-valve block.Spool 1410 contains one ormore cartridge heaters 1460 and asecond RTD 1465. Referring back to FIG. 6, a hole oropen area 605 is present in the middle of the multi-valve block. Theopen area 605 accommodatesspool 1410 that protrudes fiom thebase plate 610.Columns 1470 wraps around thespool 1410. Also shownt are solinoids 1480 connected viatubing 1485 to the base plate at itslower end 1490.Band heater 1440 is an AC band heater of approximately 200 Watts power. - During operation, a gas sample flows through tubing or conduits315 (not shown in FIG. 14) in the multi-valve block prior to flowing through the piping of the
columns 1470. In contrast, the carrier gas flows through the carriergas preheat tubing 1450 prior to flowing throughcolumns 1470. The carrier gas preheat tubing may be located at different positions to heat the carrier gas to a predetermined temperature. The carrier gas preheat tubing may be just inside the band heater as shown in FIG. 14, or it may preferably occupy insertion areas in the multi-valvc block, as explained in reference to FIG. 9. Thus, prior to being warmed by the spool, both the carrier gas and the as sample are heated to approximately the temperature of the multi-valve block. - Thus, this arrangement provides for two heating zones. The area proximate to the
spool 1410 defines a second heating zone. A first heating zone is defined by the temperature of the remainder of the multi-valve block. The first RTD located in the multi-valve block at 1420 measures the temperature of the first heating zone. The second RTD located at 1465 within thespool 1410 measures the temperature of the second heating zone. Two separate heating zones are important because the gas flowing through thecolumns 1470 should ideally be about 3-5° C. higher than the temperature at each TCD (the temperature of the first heating zone). In addition, the TCD's in the first heating zone should be kept to within about 0.1° C. of a predetermined temperature for accurate analysis. The temperature variation in the second heating zone should also be maintained within about a 0.1° C. tolerance. More heating zones may be added when desired to allow the analysis of the complex samples. - In order to stabilize the temperatures in heating zones, an “oven” is created from a thermal insulation material. This oven is essentially a cylindrical sleeve that surrounds the rest of the multi-valve device and keeps its temperature stable, except for the solinoids, which must be kept away from the heat inside the oven. Referring to FIG. 15, an
illustrative bottom 1500 of this insulation cylinder or sleeve is shown. As can be seen, it contains a number ofholes 1510, through which extend the tubing for the solinoids and the legs of the base stand. - FIG. 16 illustrates the
insulation 1610 for the “coven” including thebottom 1500 of the insulation cylinder. As part of themmulti-valve block 1400,base plate 610 is adjacent to the bottom of theinsulation cylinder 1500.Legs 1600 to create stand-off are made fromTeflon™ 1605. Also shown istubing 1485 that extends through thebottom piece 1500 to thelower surface 1490 of themulti-valve block 1400. - While preferred embodiments of this invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments described herein are exemplary only and are not limiting. Many variations and modifications of the system and apparatus are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but is only limited by the claims that follow, the scope of which shall include all equivalents of the subject matter of the claims.
Claims (20)
1. A multi-valve assembly, comprising:
a unit including a plurality of plates and diaphragms attached together to form multiple valves, each of said valves being individually actuatable and having a plurality of valve ports.
2. The multi-valve assembly of claim 1 , wherein said unit forms a reception area for at least one fluid property detector.
3. The multi-valve assembly of claim 2 , wherein said fluid property detector is a thermal conductivity detector.
4. The multi-valve assembly of claim 1 , wherein a number of said plates have a ring shape forming an open area in the body of each of said number of plates.
5. The multi-valve assembly of claim 4 , wherein said integrated unit further includes a spool occupying a portion of said open area, said plates defining at least a first heating zone and said spool defining at least a second heating zone.
6. The multi-valve assembly of claim 5 , wherein each of said first and said second heating zones include at least one temperature detector and wherein said first heating zone is maintained about a first predetenrined temperature and said second heating zone is maintaned at about a second predetermined temperature.
7. The multi-valve of claim 5 , wherein said first heating zone is maintained by a band heater located approximately concentrically around at least one of said plates and said second heating zone is maintained by a second heater in said spool.
8. The multi-valve assembly of claim 5 , wherein gas sample tubing and carrier gas tubing( attach to said valve ports, at least a portion of said gas sample tubing being inside said second heating zone and at least a portion of said carrier gas tubing being in said first heating zone.
9. The multi-valve assembly of claim 1 , further comprising a plurality of actuator ports in at least one of said plates, each of said valves corresponding to a pair of actuator ports.
10. The multi-valve assembly of claim 9 , further comprising a plurality of solenoids, each of said solenoids being attached to one of said pairs of actuator ports via tubing, each of said solenoids capable of actuating a corresponding one of said valves.
11. The multi-valve assembly of claim 2 . further comprising:
a plurality of fluid property detectors located in said reception area;
a temperature detector proximate to at least one of said fluid property detectors.
12. The multi-valve assembly of claim 1 , further comprising:
an insulative housing surrounding said plurality of plates.
13. The multi-valve assembly of claim 1 , further comprising a first set of screws and a second set of screws, wherein said multi-valve assembly includes at least three plates, said plates being in a generally stacked arrangement, wherein a first of said plates is a top plate, a second of said plates is a bottom plate and a third of said plates is a middle plate, said first set of screws being inserted through said top plate, said second set of screws begin inserted through said bottom plate, wherein said at least three plates are attached together, said top plate being detachable from said middle plate upon removal of said first set of screws from said top plate while said middle plate and said lower plate remain attached while said second set of screws remain inserted through said bottom plate.
14. The multi-valve assembly of claim 1 , wherein each valve corresponds to ane area on said plurality of plates, at least one of said plurality of plates including an elevated surface at each of said areas.
15. The multi-valve assembly of claim 1 , further comprising:
a set of a plurality of pistons corresponding to each valve, said each of sets of pistons having first and second subsets wherein each valve is in either an ON condition or an OFF condition, with said first subset being, actuated when each valve is in an ON condition and with said second subset being actuated when each valve is in an OFF condition.
16. A multi-valve device comprising:
an integrated block having multiple valves and multiple detectors, each of said valves being suitable to direct selectively a fluid flow and each of said detectors positioned to analyze at least a portion of said fluid flow.
17. The multi-valve device of claim 16 , further comprising:
a plurality of fluid sample detectors at least partially within said integrated block.
18. The multi-valve device of claim 16 ,wherein said multi-valve device defines first and second heating zones, said second heating zone being, concentrically surrounded by said first heating, zone.
19. The multi-valve device of claim 18 , wherein a gas sample is heated in said second heating, zone and a carrier gas is heated in said first heating zone.
20. The multi-valve device of claim 16 , further comprising:
a first set and a second set of screws tightened paitially through said multi-valve device, said multi-valve device being, conifigured to paitially disassemble upon removal of said first set of screws.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US09/850,954 US20020029802A1 (en) | 1998-10-16 | 2001-05-07 | Integrated valve design for gas chromatograph |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/174,203 US6227034B1 (en) | 1998-10-16 | 1998-10-16 | Integrated valve design for gas chromatograph |
US09/850,954 US20020029802A1 (en) | 1998-10-16 | 2001-05-07 | Integrated valve design for gas chromatograph |
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US09/174,203 Continuation US6227034B1 (en) | 1998-10-16 | 1998-10-16 | Integrated valve design for gas chromatograph |
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US20020029802A1 true US20020029802A1 (en) | 2002-03-14 |
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US09/174,203 Expired - Lifetime US6227034B1 (en) | 1998-10-16 | 1998-10-16 | Integrated valve design for gas chromatograph |
US09/850,954 Abandoned US20020029802A1 (en) | 1998-10-16 | 2001-05-07 | Integrated valve design for gas chromatograph |
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US09/174,203 Expired - Lifetime US6227034B1 (en) | 1998-10-16 | 1998-10-16 | Integrated valve design for gas chromatograph |
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Cited By (1)
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CN105351662A (en) * | 2015-09-25 | 2016-02-24 | 中海福建天然气有限责任公司 | System for cooling pipeline through boil off gas (BOG) |
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US6701774B2 (en) * | 2000-08-02 | 2004-03-09 | Symyx Technologies, Inc. | Parallel gas chromatograph with microdetector array |
US6834531B2 (en) * | 2000-12-29 | 2004-12-28 | Christopher J. Rust | Gas chromatograph modular auxiliary oven assembly and method for analyzing a refinery gas |
US7059199B2 (en) | 2003-02-10 | 2006-06-13 | Invensys Systems, Inc. | Multiphase Coriolis flowmeter |
US7188534B2 (en) * | 2003-02-10 | 2007-03-13 | Invensys Systems, Inc. | Multi-phase coriolis flowmeter |
CN101986152B (en) * | 2005-02-22 | 2012-05-30 | 机械分析公司 | Diaphragm seal valve, chromatographic analysis system and using method thereof |
WO2006089389A1 (en) * | 2005-02-22 | 2006-08-31 | Mecanique Analytique Inc. | Diaphragm-sealed valve, analytical chromatographic system and method using the same |
US7216528B2 (en) | 2005-02-22 | 2007-05-15 | Mecanique Analytique Inc. | Diaphragm-sealed valve, analytical chromatographic system and method using the same |
US7524363B2 (en) * | 2006-05-16 | 2009-04-28 | Alliant Techsystems Inc. | Gas chromatograph column assembly |
US7635005B2 (en) * | 2006-05-16 | 2009-12-22 | Alliant Techsystems Inc. | Very small high pressure regulator |
US7735352B2 (en) * | 2006-05-16 | 2010-06-15 | Alliant Techsystems Inc. | Multi-dimensional portable gas chromatograph system |
US7485176B2 (en) * | 2006-05-16 | 2009-02-03 | Alliant Techsystems Inc. | Compact thermal conductivity detector |
CN102699516B (en) * | 2007-02-28 | 2015-03-18 | 沃特世科技公司 | Liquid-chromatography apparatus having diffusion-bonded titanium components |
DE102007031680A1 (en) | 2007-07-06 | 2009-01-08 | Thermo Fisher Scientific (Bremen) Gmbh | Apparatus for providing gases, in particular for the isotope ratio analysis |
WO2010129189A1 (en) * | 2009-05-04 | 2010-11-11 | Cameron International Corporation | Flow distributed buffered/educted gas seal |
DE102009043947B4 (en) * | 2009-09-04 | 2011-07-07 | G+R Technology Group AG, 93128 | Plant for the production of polycrystalline silicon with a device for discharging gaseous measuring samples |
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US3095746A (en) * | 1960-02-15 | 1963-07-02 | Phillips Petroleum Co | Fluid-actuated valve |
US3139755A (en) * | 1960-09-01 | 1964-07-07 | Phillips Petroleum Co | Pneumatically-actuated diaphragm valve |
DE1171177B (en) * | 1961-08-18 | 1964-05-27 | Bodenseewerk Perkin Elmer Co | Three-way switch valve for gas chromatograph |
US3393551A (en) * | 1964-08-17 | 1968-07-23 | Minnesota Mining & Mfg | Gas chromatograph valve |
US3386472A (en) * | 1965-03-25 | 1968-06-04 | Leeds & Northrup Co | Valves for gas chromatography |
US3627992A (en) * | 1969-08-18 | 1971-12-14 | Bio Logics Inc | Reading encoded devices |
US3916465A (en) * | 1972-10-26 | 1975-11-04 | Hooker Chemicals Plastics Corp | Multi-stream gas chromatographic method and apparatus |
US3975946A (en) * | 1974-02-27 | 1976-08-24 | Micromeritics Instrument Corporation | Liquid chromatography sample measuring and introducing apparatus |
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US5581028A (en) * | 1994-06-23 | 1996-12-03 | Hewlett Packard Company | Fluid property sensors incorporating plated metal rings for improved packaging |
US5567868A (en) * | 1995-01-23 | 1996-10-22 | Hewlett-Packard Company | Planar manifold assembly |
US5767387A (en) * | 1996-10-22 | 1998-06-16 | Hewlett-Packard Co. | Chromatograph having pneumatic detector |
-
1998
- 1998-10-16 US US09/174,203 patent/US6227034B1/en not_active Expired - Lifetime
-
2001
- 2001-05-07 US US09/850,954 patent/US20020029802A1/en not_active Abandoned
Cited By (1)
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CN105351662A (en) * | 2015-09-25 | 2016-02-24 | 中海福建天然气有限责任公司 | System for cooling pipeline through boil off gas (BOG) |
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