This specification relates to the treatment of emissions related to the dehydration of natural gas.
The following is not an admission that anything discussed below is citable as prior art or part of the common general knowledge of persons skilled in the art.
Natural gas must be dehydrated before transportation in pipelines to avoid hydrate formation and corrosion. Most dehydrators use a TEG (tri-ethylene glycol) solvent or other glycol solvent to remove the water in the gas, and a gas re-boiler is used to boil the water off the glycol. The dehydrator releases waste gases and vapors, principally through venting, flaring or incineration.
U.S. Pat. No. 6,010,674 (National Tank Company) describes a combustor to incinerate the organics from the off-gas mixture.
U.S. Pat. No. 6,789,288 (Membrane Technology & Research) describes a pervaporation process for glycol drying.
U.S. Pat. No. 6,984,257 (R. T. Heath and F. D. Heath) and U.S. Pat. No. 5,766,313 (R. T. Heath) describe a process in which off-gas from a re-boiler is condensed and re-injected to the burner. However the quantity of off-gas is normally larger than the requirement of the burner.
U.S. Pat. No. 6,551,379 and RE39,944 (R. T. Heath) describe using a portion of the TEG flow through an ejector to create a vacuum to improve the separation of non-condensable gases.
International Patent Application No. PCT/CA2004/001047 to Cranford et al., filed on Jul. 16, 2004 and published as WO 2005/007277 A1 on Jan. 27, 2005, describes an asymmetric integrally skinned membrane comprising a polyimide and another polymer selected from the group consisting of polyvinylpyrrolidone, sulfonated polyetherketones and mixtures thereof. The membrane is substantially insoluble in an organic solvent, substantially defect free and is useful as a vapor separation membrane. Methods for preparing asymmetric integrally skinned polyimide membranes are also disclosed. The membranes can have a vapor permeance to water at least 1×10−7 mol/m2sPa at a temperature of about 30° C. to about 200° C. The membrane may have a vapor permeance selectivity of at least 50, preferably at least 250, for water/ethanol at a temperature of about 140° C. This International publication number WO 2005/007277 A1 is incorporated herein in its entirety by this reference to it.
The following introduction is not intended to limit or define any claim. One or more inventions may reside in any combination of one or more process steps or apparatus elements drawn from a set of all process steps and apparatus elements described below or in other parts of this document, for example the detailed description, claims or figures.
The off-gas, for example from the stripping system of an existing glycol-based dehydration unit, contains water vapor, methane, BTEX (benzene, toluene, ethylbenzene, xylene), and VOCs (volatile organic compounds)). This off-gas is sent to a gas separation membrane system for dehydration. The gas separation membrane has a high selectivity for water over organic compounds and may be an integrally skinned asymmetric polyimide membrane as described in WO2005/007277A1. The driving force for water permeation is established by applying a vacuum on the permeate side of the membrane unit or by flowing a sweep gas, for example warm and dry air, through the permeate side of the unit. The basic glycol based dehydration process components such as the contactor and stripping system, for example still and flash tanks, are still used on the front end. The dehydrated off-gas is recycled to the product natural gas stream, for example to the inlet of the pipeline compressor or in its gas fuel line, to the inlet of the dehydrator or directly into the pipeline. This process reduces, or substantially eliminates, the emission of toxic organic compounds and green-house gases from the dehydrator, recovers valuable methane gas and ultimately reduces operating costs. The membrane unit can be retro-fitted to existing glycol dehydrators or made as part of a new system.
Various apparatuses or processes will be described below to provide an example of an embodiment of each claimed invention. No embodiment described below limits any claimed invention and any claimed invention may cover processes or apparatuses that are not described below. The claimed inventions are not limited to apparatuses or processes having all of the features of any one apparatus or process described below or to features common to multiple or all of the apparatuses described below. It is possible that an apparatus or process described below is not an embodiment of any claimed invention.
The key elements of a prior art natural gas glycol (or TEG) dehydrator are illustrated in
Methane emissions and consumption come from gas-driven TEG pumps, fuel-process consumption, instrument gas consumption and stripping gas as described in Table 1. The total amount of methane emitted represents about 0.5% of the methane treated. Hydrocarbons and BTEX which are carried by TEG from the contactor to the stripping system are also emitted with the off-gas. Water vapor is also present in the off-gas which makes the off-gas very corrosive and difficult to treat.
Because of the health and environmental impacts of glycol dehydrator emissions, regulations are becoming more stringent and address both the emission of health-related contaminants such as BTEX and green-house gases such as methane. There is a need to improve existing installations to design new dehydrators to have lower emissions.
A dehydration system 10 using a gas or vapor separation membrane unit 14 is shown in
The system 10 is based on a conventional TEG dehydration unit 12 having a TEG contactor 6 and a TEG regeneration unit 8. Wet natural gas 9 flows into an inlet 38 of the dehydration unit 12. Rich TEG 4 flows from the TEG contactor 6 to the regeneration unit 8. Lean TEG 2 flows from the regeneration unit 8 to the contactor 6. Gases leave the dehydration unit 12 through an outlet 3 optionally after passing through a heat exchanger 5 which the lean TEG 2 also flows through.
The gas that would ordinarily be released from the dehydration unit 12 as a contaminated off-gas 16 is sent to a membrane unit 14 for dehydration. Gas 16 to be sent to the membrane unit 14 can be taken from the still, the flash tank, both the still and flash tank, or another part of the dehydrator where these gases are collected and can be released. A collector 15 may be used to collect, for example, flash tank emissions 17 and TEG regenerator emissions 19. A vacuum can be applied to the permeate outlet 18 of the membrane unit 14 by a permeate compressor 20, or vacuum pump, as shown in
The dehydrated gas 28 can be sent to an inlet 38 of the dehydration unit 12, the inlet of a pipeline compressor upstream of the dehydration unit, directly into the product natural gas pipeline or otherwise reused for example by burning it to generate steam or electricity. In
All or substantially all of the off-gas can be sent to the membrane unit 14. Because the dehydrated gas is recycled, the system 10 reduces emissions, preferably bringing the emissions close to zero. A side-by-side comparison of a conventional dehydrator using an electric glycol pump and stripping gas and the process and apparatus of
The membrane unit 14 removes water vapor selectively from the off-gas. The water vapor may be discharged to the atmosphere. The selective removal of water from the off-gas enables recompression of the methane and BTEX since compressors are sensitive to water vapor. The water is released as vapour and so the process does not produce a liquid discharge.
This is a non-provisional of, and claims priority from, U.S. application Ser. No. 61/034,559, filed on Mar. 7, 2008 by Gaetan Noel and Pierre Cote entitled EMISSION TREATMENT PROCESS FROM NATURAL GAS DEHYDRATORS, which is incorporated herein in its entirety by this reference to it.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/CA2009/000282 | 3/6/2009 | WO | 00 | 10/22/2010 |
Number | Date | Country | |
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61034559 | Mar 2008 | US |