Abstract:
The off-gas from the still and flash tank of an existing glycol-based dehydration unit (containing water vapor, methane, BTEX (benzene, toluene, ethylbenzene, xylene), VOCs (volatile organic compounds)) is sent directly to a gas separation membrane system for dehydration. The gas separation membrane has a high selectivity for water over organic compounds (for example, the membrane 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, dry air through the permeate side of the unit.

Description:
[0001]    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. 
     
    
     FIELD 
       [0002]    This specification relates to the treatment of emissions related to the dehydration of natural gas. 
       BACKGROUND 
       [0003]    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. 
         [0004]    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. 
         [0005]    U.S. Pat. No. 6,010,674 (National Tank Company) describes a combustor to incinerate the organics from the off-gas mixture. 
         [0006]    U.S. Pat. No. 6,789,288 (Membrane Technology &amp; Research) describes a pervaporation process for glycol drying. 
         [0007]    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. 
         [0008]    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. 
         [0009]    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/m 2 sPa 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. 
       INTRODUCTION 
       [0010]    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. 
         [0011]    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. 
     
    
     
       FIGURES 
         [0012]      FIG. 1  is a schematic diagram of a dehydration system with a membrane unit. 
           [0013]      FIG. 2  shows a prior art natural gas dehydrator. 
           [0014]      FIG. 3  shows a process flow diagram of a system as in  FIG. 1  as used in a 10 MMSCFD natural gas dehydration system. 
       
    
    
     DETAILED DESCRIPTION 
       [0015]    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. 
         [0016]    The key elements of a prior art natural gas glycol (or TEG) dehydrator are illustrated in  FIG. 2 . Natural gas is dehydrated in a contactor, counter-current with a glycol solution. The glycol solution is regenerated in a stripping system (still and flash tank) and recycled. Water vapor, methane, BTEX and other VOCs are emitted from the stripping system and released to the atmosphere. Glycol dehydrators are described in Chapter 20 of the Engineering Data Book published by the Gas Processors Supply Association (2004) which is incorporated herein by this reference to it. The emissions of BTEX, VOCs and methane are health and environmental hazards. The emitted methane is a greenhouse gas and also a product that could otherwise be sold. 
         [0017]    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. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Estimated consumption/emission of methane  
               
               
                 for a 10 MMscfd dehydrator 
               
             
          
           
               
                   
                   
                 Methane 
                 Energy 
               
               
                   
                 Source 
                 Nm 3 /y 
                 GJ/y 
               
               
                   
                   
               
             
          
           
               
                   
                 Glycol pump 
                 211,000 
                 7,827 
               
               
                   
                 Reboiler fuel 
                 66,000 
                 2,437 
               
               
                   
                 Stripping gas 
                 191,000 
                 7,096 
               
               
                   
                 Instruments 
                 5,000 
                 195 
               
               
                   
                 Total 
                 473,000 
                 17,555 
               
               
                   
                   
               
             
          
         
       
     
         [0018]    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. 
         [0019]    A dehydration system  10  using a gas or vapor separation membrane unit  14  is shown in  FIGS. 1 and 3 . The vapor separation membranes in the membrane unit  14  may be as described in WO2005/007277A1. A module suitable for use with such membranes is described in U.S. patent application Ser. No. 12/117,007, filed on May 8, 2008, entitled HOLLOW FIBRE MEMBRANE MODULE, which is incorporated herein in its entirety by this reference to it. Such membranes and membrane separation units  14  are available under the trade-mark SIFTEK from Vaperma Inc. 
         [0020]    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. 
         [0021]    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  FIG. 3 , to withdraw water vapor  26  from the gas stream and thereby produce a dehydrated gas  28  at the retentate outlet  30  of the membrane unit  14 . Optionally, a sweep gas  22  can be passed into an inlet  24  on the permeate side of the membrane unit  14 , through the permeate side of the membrane unit  14 , and out of the permeate outlet  18 , as shown as an option in  FIG. 1 , if desired to assist with water vapour removal. The flow of dehydrated gas  28  may be driven by a retentate compressor  32 . The off-gas  16  from the dehydration unit  12  contains a large portion of the water vapour present in the wet natural gas  9  fed to the inlet  38  of the dehydration unit, but in a much smaller gas flow. The concentration of water vapour in the off-gas  16  may be twenty times or more than the concentration of water vapour in the wet natural gas  9 . A pump or compressor capable of handling the off-gas  16  would be very expensive because water vapour in high concentration tends to condense when pressurized in a pump or compressor. Placing retentate compressor  32  downstream of the membrane unit  14 , where the water content is low, avoids operation in a high water vapour concentration. Permeate compressor  20  operates in a high water vapour concentration but operates at or below atmospheric pressure where the problems of condensation are not as significant. If necessary, a condenser may be added in line between the membrane unit  14  and the permeate compressor  20 . 
         [0022]    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  FIG. 3 , the outlet  30  from the membrane unit  14  is connected to the inlet  34  of a contactor inlet compressor  36 . The dehydrated recovered emission gas (REG)  28 , which is the retentate from the membrane unit  14 , is compressed by a retentate compressor  32  to the inlet pressure of a contactor inlet compressor  36 . Compared to an alternative connection of the membrane unit  14  retentate line to the gas outlet  3  from the contactor  6 , this reduces the required pressure gain through retentate compressor  32 . The water content of the REG  28  also only needs to be reduced sufficiently to be able to compress the REG  28  to mix into the natural gas upstream of the dehydrator  12  rather than to the specifications of the pipeline. 
         [0023]    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  FIG. 3  is presented in Table 2 below, showing a 97.7% reduction of emissions and a 3 year pay-back. Various operating parameters for the system  10  are shown in Table 3 below. The stream numbers 1 to 5 in Table 3 correspond to the flows through pipes in  FIG. 3  marked with a diamond having the corresponding stream number inside of the diamond. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Value Proposition-10 MMSCFD DehydrationPlant 
               
             
          
           
               
                   
                   
                 Conventional 
                 Membrane 
               
               
                   
               
             
          
           
               
                 Capital Cost, k$ 
                   
                 0 
                 250 
               
               
                 Operating 
                 Gas 
                 56.5 
                 0.2 
               
               
                 cost (k$/yr) 
                 Electricity 
                 0.0 
                 6.9 
               
               
                   
                 Membrane replacement 
                 0.0 
                 3.3 
               
               
                   
                 Water disposal 
                 0.0 
                 1.0 
               
               
                   
                 Maintenance &amp; Labour 
                 0.0 
                 2.0 
               
               
                   
                 Miscellaneous 
                 0.0 
                 2.0 
               
               
                   
                 Total Annual Cost 
                 56.5 
                 15.4 
               
               
                 Emissions 
                 BTEX 
                 2.4 
                 0.0 
               
               
                 (mt/yr) 
                 HAP 
                 3.5 
                 0.0 
               
               
                   
                 VOC 
                 19.2 
                 0.1 
               
               
                   
                 Methane-ethane-others 
                 153.3 
                 0.4 
               
               
                 GHG 
                 equivalent CO2 (mt/yr) 
                   
                 2673 
               
               
                 emission 
                   
                   
                   
               
               
                 reduction 
                   
                   
                   
               
             
          
           
               
                   
                 Carbon Trading @15 $US/ton CO2 (k$/yr) 
                 44.1 
               
             
          
           
               
                 profitability 
                 Capital, k$ 
                   
                 250 
               
               
                   
                 Savings, k$/yr 
                 Gas Recovered 
                 41 
               
               
                   
                   
                 GHG credits 
                 44 
               
               
                   
                   
                 total 
                 85 
               
               
                   
                 Payback, years 
                   
                 2.9 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                   
                   
                 MEM 
                   
                 MEM 
                   
               
               
                   
                   
                 retentate 
                   
                 permeate 
                 MEM 
               
               
                   
                 off gas 
                 to com- 
                 MEM 
                 to atmos- 
                 retentate  
               
               
                   
                 to MEM 
                 pressor 
                 permeate 
                 phere 
                 to pipeline 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 stream no 
                 1 
                 2 
                 3 
                 4 
                 5 
               
               
                 flow rate, 
                 37.0 
                 19 
                 17.71 
                 17.71 
                 19 
               
               
                 kg/hr 
                   
                   
                   
                   
                   
               
               
                 vapor 
                 1.0000 
                 1.0000 
                 1.0000 
                 1.0000 
                 1.0000 
               
               
                 fraction (1  
                   
                   
                   
                   
                   
               
               
                 or 0 only) 
                   
                   
                   
                   
                   
               
               
                 rest of gas, 
                 8.96% 
                 17.16% 
                 0.02% 
                 0.02% 
                 17.16% 
               
               
                 % wt 
                   
                   
                   
                   
                   
               
               
                 methane,  
                 38.34% 
                 73.43% 
                 0.11% 
                 0.11% 
                 73.43% 
               
               
                 % wt 
                   
                   
                   
                   
                   
               
               
                 water  
                 52.70% 
                 9.41% 
                 99.88% 
                 99.88% 
                 9.41% 
               
               
                 content, 
                   
                   
                   
                   
                   
               
               
                 % mass 
                   
                   
                   
                   
                   
               
               
                 T, deg. C. 
                 100.0 
                 100.0 
                 100.0 
                 230.6 
                 172.8 
               
               
                 P, kPa abs 
                 101.3 
                 98.6 
                 10.00 
                 101.33 
                 750.0 
               
               
                 enthalpy, 
                   
                   
                 2671.1 
                 2916.9 
                   
               
               
                 kJ/kg 
                   
                   
                   
                   
                   
               
               
                 GJ/hr 
                   
                   
                 0.047 
                 0.052 
                   
               
               
                 m3/hr  
                 62.4 
                 33.1 
                 305 
                 41 
                 5.2 
               
               
                 (gas) or  
                   
                   
                   
                   
                   
               
               
                 l/min (lid.) 
                   
                   
                   
                   
                   
               
               
                 V, m3/kg  
                 1.6856 
                 1.7179 
                 17.2295 
                 2.2955 
                 0.2700 
               
               
                 (gas) or  
                   
                   
                   
                   
                   
               
               
                 kg/l (liq.) 
                   
                   
                   
                   
                   
               
               
                 Cp, kJ/kg-K 
                   
                   
                 1.884 
                 1.884 
               
               
                   
               
             
          
         
       
     
         [0024]    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.