EP0770667B1 - Procédé de séchage de gaz au glycol incluant la purification des rejets gazeux - Google Patents

Procédé de séchage de gaz au glycol incluant la purification des rejets gazeux Download PDF

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Publication number
EP0770667B1
EP0770667B1 EP96402157A EP96402157A EP0770667B1 EP 0770667 B1 EP0770667 B1 EP 0770667B1 EP 96402157 A EP96402157 A EP 96402157A EP 96402157 A EP96402157 A EP 96402157A EP 0770667 B1 EP0770667 B1 EP 0770667B1
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EP
European Patent Office
Prior art keywords
btex
liquid
liquid desiccant
desiccant
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP96402157A
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German (de)
English (en)
French (fr)
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EP0770667A1 (fr
Inventor
Benoit Landreau
Alexandre Rojey
Jean-Claude Amande
Nicole Doerler
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IFP Energies Nouvelles IFPEN
Nouvelles Applications Technologiques NAT
Original Assignee
IFP Energies Nouvelles IFPEN
Nouvelles Applications Technologiques NAT
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Publication of EP0770667A1 publication Critical patent/EP0770667A1/fr
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Publication of EP0770667B1 publication Critical patent/EP0770667B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
    • C10G5/04—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas with liquid absorbents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas

Definitions

  • the invention relates to a method for dehydrating gas using a liquid desiccant (glycol) including an effluent purification step gaseous emitted during the regeneration of said liquid desiccant.
  • the invention relates more particularly to a process making it possible to reduce pollution due to gaseous emissions from natural gas drying units, pollution mainly due to the following aromatic compounds: benzene, toluene, ethyl benzene, xylene (BTEX).
  • Dehydration of a gas for example a natural gas or a gas of refinery, is a classic operation. It allows to control the point of dew "water” of the gas, to avoid the formation of hydrates or ice during transportation or use of this gas, reduce the risk of corrosion, or for all other reasons.
  • TEG triethylene glycol
  • MEG monoethylene glycol
  • DEG diethylene glycol
  • T4EG tetraethylene glycol
  • a conventional gas dehydration unit with a liquid desiccant for example a glycol
  • the wet gas enters, by line 1, at the bottom of a column of absorption A1, operating under pressure, where it contacts by circulation to counter-current the liquid desiccant introduced at the head by line 3.
  • the water contained in the gas is absorbed by the desiccant.
  • the gas dehydrated comes out at high pressure from the head of the absorption column A1 by the line 2. Leaving the bottom of column A1, the desiccant loaded with water is sent by line 4 to the head of the regeneration unit R1 where it is used as coolant.
  • the desiccant charged with water is sent to a flash separation tank S1, in which the pressure is lower than in the absorption column A1.
  • a flash separation tank S1 in which the pressure is lower than in the absorption column A1.
  • Much of the gas absorbed at high pressure by the desiccant is separated from the liquid phase in this balloon S1. This gas can either be released to the atmosphere through line 5, or used as fuel gas during the desiccant regeneration stage. It is then sent to the reboiler burner R2 of the regeneration device R1.
  • the liquid desiccant containing water but being separated from the gas absorbed at strong pressure comes from the flash separation balloon through line 7. After its passage in at least one heat exchanger El, it is sent by the line 7 in the thermal regeneration device R1, in which part of the water absorbed by the desiccant will be vaporized and eliminated at the top by the line 8, while the regenerated desiccant which comes out at the bottom through line 3 crosses the exchanger El and is sent by a pump P1, in a cooler E4, then at the top of the absorption column A1.
  • a conventional means consists in following the thermal reconcentration step with a step of stripping with dry gas or with a low water content, for example part of the gas stream dehydrated by the desiccant, as described in particular in US-A-3,105,748.
  • BTEX aromatic compounds
  • TEG- which is also a solvent for the compounds aromatic
  • the vapors emitted by a TEG reboiling unit can have a very high total aromatic content (greater than 30%).
  • a specific composition (Treatment of the Whitney Canyon natural gas field, Wyoming, United States) is given for information below (% by weight): - Water 45.2% - Nitrogen 7.7% - Benzene 4.6% - Toluene 15.6% - Ethyl benzene 0.9% - Xylene 12.7% - Other hydrocarbons 13.3%
  • composition of the discharges varies according to the nature of the gas to be treated, the temperature and flow rate of TEG circulating in the installation. These releases must be reduced in order to respond to the new constraints linked to toxic products in the atmosphere. For example, in the United States, the "Clean Air Act Amendment", published in 1990, drastically reduces rates acceptable releases of BTEX to the atmosphere in the United States. Any unit discharging more than 100 tonnes / year of BTEX or 25 tonnes / year of any combination of these 4 compounds is subject to control and regulation.
  • Incineration of vapors which can be carried out by a flame incinerator powered by the fuel oil produced by the unit, has the disadvantage of requiring a very important investment.
  • US-A-5,209,762 describes an improvement to the previous process eliminating the aromatics dissolved in the liquid water extracted from the three-phase balloon.
  • Another technique involves installing a steam circuit on the primary condenser, followed by a screw compressor, vapors not condensables being reintroduced into the processing unit.
  • Yet another technique implements the drying and treatment of a gas, using a solvent composed of glycol, N-methyl-caprolactam and water, the glycol concentration (preferably TEG) being between 80 and 97%.
  • a solvent composed of glycol, N-methyl-caprolactam and water, the glycol concentration (preferably TEG) being between 80 and 97%.
  • the invention relates to a new process using condensation vapors from the desiccant regeneration device.
  • the process of the invention has the particular advantage of producing purified gaseous effluents, which can be discharged directly to the atmosphere or to a conventional torch system (without incinerator) or well to reuse in the installation.
  • step (a) the flow of wet gas 1 is brought into contact with the flow of liquid desiccant 3, against the current in an absorption column A1, this which produces a dry gaseous effluent 2 leaving at the top and a flow of desiccant liquid 4 loaded with water and BTEX, leaving at the bottom of said column absorption A1.
  • the wet gas enters the production pressure (generally from 20 to 150 bar) and at a temperature below 50 ° C. If the temperature of gas production is greater than this value, said gas will be cooled, by example by an air cooler, before entering column A1.
  • the liquid desiccant introduced at the head of column A1 is conventionally at a temperature approximately 5 ° C higher than that of the gas to be treated.
  • step (b) the flow of charged liquid desiccant 4 is sent to a flash separation tank S1, in which a vapor effluent is separated 5 leaving the head, mainly containing methane, water vapor and BTEX and, leaving the bottom, a liquid phase 7 containing mainly the desiccant liquid loaded with water and BTEX.
  • the flow of liquid desiccant loaded with water and BTEX leaves by line 4 at the temperature of the gas to be treated; it is usually sent as cooling fluid at the top of the distillation column D1 of the regeneration device R1, where the temperature of said desiccant increases in general about 10 ° C.
  • the desiccant, then sent to the flask flash separation S1, is relaxed at a pressure of 2 to 5 bar, its temperature, depending on operating conditions, which can vary from 50 to 85 ° C.
  • step (c) the flow of liquid desiccant 7 is sent through a heat exchanger El, to the distillation column D1 of the regeneration R1, which further comprises a reboiler R2; of said device regeneration R1, it leaves a steam effluent 8 at the head containing water and BTEX and in the bottom a liquid effluent 3, constituting the liquid desiccant regenerated, which is sent, through the heat exchanger El and the pump P1, at the top of the absorption column A1 of step (a).
  • the flow of liquid desiccant is heated in the exchanger El, dimensioned so as to cause a temperature variation of at least minus around 100 ° C on stream 7 (warmed) and stream 3 (cooled).
  • the effluent steam 8 from the distillation column D1 generally leaves at a temperature about 80 to 90 ° C and at atmospheric pressure.
  • the liquid desiccant regenerated leaves the reboiler R2 at the bottom at a temperature of around 200 ° C. and undergoes a temperature drop of at least about 100 ° C in the exchanger El as already indicated above.
  • the temperature of the regenerated desiccant is adapted to the conditions of column A1: it is cooled, generally in a exchanger E4, up to a temperature approximately 5 ° C higher than that of gas to be treated. Its pressure is also adapted, by the pump P1, to that prevailing in the absorption column A1.
  • step (d) said gaseous effluent 8 leaving at the head of the column of distillation D1 of the regeneration device R1 is condensed in a condenser C1 and sent to a three-phase separation flask B1, hence exits, at the top, a gaseous effluent 9 containing BTEX, laterally, a hydrocarbon phase 10 containing BTEX and at the bottom, an aqueous liquid phase 11.
  • the overhead effluent from the distillation column D1 is cooled through the condenser C1, generally an air cooler, up to about 50 ° C, or less depending on operating conditions.
  • the three-phase separation flask B1 is at this temperature and at atmospheric pressure; the same is true of the gaseous effluent 9.
  • step (e) the gaseous effluent 9 is sent in updraft in a washing column L1, in which it is brought into contact against the current with a liquid flow 12, taken from the liquid desiccant circuit regenerated. From said washing column L1, a desiccant flow comes out at the bottom liquid 13 having absorbed BTEX, which is returned to the device for regeneration R1, and at the top a gaseous effluent free of BTEX.
  • the regenerated liquid desiccant flow used for washing generally represents 3 to 10% of the flow injected into the supply of the absorption column A1.
  • the temperature of the desiccant used is advantageously at least 5 ° C higher than that of the gaseous effluent to be treated. This temperature will be adapted to the conditions operating, generally by means of an E3 heat exchanger.
  • the injected desiccant comes out at the bottom of the washing column L1 at temperature of the gaseous effluent to be treated.
  • the regenerated desiccant used for washing the gaseous effluents of the three-phase separator B1 can be taken from the supply of the absorber A1, according to the arrangement shown in FIGS. 4 to 6. This configuration avoids the installation of an exchanger and a pump on site.
  • the desiccant loaded with BTEX, leaving at the bottom of the wash L1 by line 13 can be sent to feed 7 of the column distillation D1 upstream of the heat exchanger E1, as shown figure 4.
  • the desiccant loaded with BTEX leaving the washing column L1 by the line 13 can also be sent to the feed 7 of the distillation column D1 downstream of said heat exchanger E1, as shown in FIG. 5. It can also be injected directly at the top of the distillation column D1 of the regeneration device R1, or at an intermediate level as indicated in dotted lines in Figure 5.
  • the stream of regenerated liquid desiccant 12 supplying the washing column L1 at the head can still be taken from the reboiler R2 by a pump P2 and pass through a heat exchanger E2, and if necessary in an exchanger E3, in which it is cooled, and the liquid desiccant 13 having absorbed BTEX and leaving the bottom of the column L1 is returned through the E2 heat exchanger, where it is reheated to reboiler R2.
  • a configuration is shown in figure 3.
  • the stripping agent liquid from step 4 is partially vaporized during a first heating stage, generating a vapor phase enriched with water, which is returned upstream of step 4 and a liquid phase depleted in water, which is vaporized before being sent to step 1.
  • This arrangement allows stripping the liquid desiccant by a vapor phase containing practically no more water and thus being able to obtain a very thorough regeneration of the liquid desiccant.
  • the charge to be treated arrives via line 4 at the head of the distillation device D1. After passing through the flash separation tank S1, it is sent by the line 7 to the exchanger E1, where it is heated by the liquid desiccant regenerated arriving by line 3. Leaving the exchanger El by line 7, the charge enters the distillation device D1, which overcomes successively from top to bottom a reboiling zone R2, a zone of stripping S2 and a tank B2.
  • the temperature in the reboiling zone R2 is generally understood between 150 ° C and 250 ° C.
  • the absolute pressure in the assembly consisting of the distillation device D1, reboiler R2, stripping zone S2 and balloon B2 is generally between 0.5 and 2 bar.
  • the regenerated liquid desiccant leaves the flask B2 through line 3, crosses exchanger E1, where it is cooled by the load arriving via line 7, and is reinjected at the head of the absorption column A1, by the pump P1.
  • the lighter compounds are removed from the process in the form gas via line 9; the water is evacuated from the process by line 11 with the other hydrophilic products; stripping agent and other products hydrophobic are sent, saturated with water, by line 10 and through the pump P2, to the exchanger E5, where they are partially vaporized and sent by line 17 to balloon B3.
  • the vapor phase generated in the E5 exchanger can be drained from the process.
  • the liquid phase leaving balloon B3 via line 18, leaner in water than liquid arriving via line 10, is divided so as to keep constant the flow of stripping agent in the loop: a fixed part is sent to the evaporator E6 via line 20; possible excess, due to absorption by the desiccant of part of the gas stream treated during the step of dehydration, is evacuated from the process by line 19.
  • a mode of operation used in the North Sea to compensate for variations in the aromatics contained in the gas produced consists of alternating periods of normal use of the process with periods during which fuel gas is used as stripping agent. These last periods allow the constitution of a reserve of stripping agent.
  • the aromatics arriving in the charge accumulate in balloon B1 and the purge carried out through line 19 can be operated so as to maintain the constant amount of stripping agent in the B1 flask, per example by controlling the purge flow by level regulation.
  • the purge can be carried out either at the outlet of the B1 tank under control of level in balloon B1, i.e. at the exit of balloon B3 under level control in ball B3.
  • the latter arrangement has the advantage of producing a dehydrated liquid fraction. This liquid fraction can either be remixed with the gas while being vaporized, or valued separately.
  • gaseous effluent 5 from the flash separation flask S1 can be injected into the three-phase balloon B1, where it can be injected partly condensed.
  • the vapor joins that already separated in the balloon B1 and which leaves therefrom line 9 to be treated in the washing column L1 according to the invention. This possibility is shown in dotted lines in Figure 4.
  • washing column L2 supplied at the head by regenerated liquid desiccant, with the same sampling possibilities and than those described above for the washing column L1.
  • the gaseous effluent leaving column L1 via line 14 is freed from the fraction of BTEX but is also dehydrated. It can therefore be recompressed by a compressor K1 and mixed with the gas treated as indicated on the diagram in Figure 4.
  • a compressor K1 can be associated with effluent 14.
  • effluents 2, 5 and 14 effluent 5 or effluent gas from a washing column L2 treating effluent 5 can be associated with effluent 14.
  • Said effluent 14 can also be used as fuel for heating of reboiler R2 of regeneration system R1.
  • the gas is sent to a conventional working dehydration unit with TEG, as shown in Figure 1.
  • the gas is dehydrated with a conventional unit having a condenser, lowering the temperature of the vapors from the regeneration column R1 at 55 ° C, and a three-phase gravity separation flask (Figure 2). All the operating conditions are identical to those of the example described above.
  • the gas is dehydrated with a unit having a condenser, lowering the temperature of the vapors from the regeneration column 4 at 55 ° C. and a three-phase gravity separation balloon.
  • the vapors coming out of this balloon are taken up in a washing column L1 described in FIG. 4.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Drying Of Gases (AREA)
EP96402157A 1995-10-27 1996-10-10 Procédé de séchage de gaz au glycol incluant la purification des rejets gazeux Expired - Lifetime EP0770667B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9512689 1995-10-27
FR9512689A FR2740468B1 (fr) 1995-10-27 1995-10-27 Procede de sechage de gaz au glycol incluant la purification des rejets gazeux

Publications (2)

Publication Number Publication Date
EP0770667A1 EP0770667A1 (fr) 1997-05-02
EP0770667B1 true EP0770667B1 (fr) 2000-08-23

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EP96402157A Expired - Lifetime EP0770667B1 (fr) 1995-10-27 1996-10-10 Procédé de séchage de gaz au glycol incluant la purification des rejets gazeux

Country Status (7)

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US (1) US6004380A (no)
EP (1) EP0770667B1 (no)
CA (1) CA2188825C (no)
DE (1) DE69609922T2 (no)
DK (1) DK0770667T3 (no)
FR (1) FR2740468B1 (no)
NO (1) NO315566B1 (no)

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US6605138B2 (en) * 1999-04-21 2003-08-12 Matthew T. Frondorf Apparatus and method for exclusively removing VOC from regeneratable solvent in a gas sweetening system
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US6238461B1 (en) 1999-06-15 2001-05-29 Rodney T. Heath Natural gas dehydrator
US7531030B2 (en) 1999-06-15 2009-05-12 Heath Rodney T Natural gas dehydrator and system
US6251166B1 (en) * 1999-08-18 2001-06-26 Anderson Controls, Lc Glycol regeneration system having a pressurized reboiler to remove BTEX compounds
US6183540B1 (en) * 1999-08-27 2001-02-06 Kinder Morgan, Inc. Method and apparatus for removing aromatic hydrocarbons from a gas stream prior to an amine-based gas sweetening process
US20020117391A1 (en) * 2001-01-31 2002-08-29 Beam Craig A. High purity CO2 and BTEX recovery
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US6955705B1 (en) * 2004-06-02 2005-10-18 Rdc Research Llc Method and system for compressing and dehydrating wet natural gas produced from low-pressure wells
US9353315B2 (en) 2004-09-22 2016-05-31 Rodney T. Heath Vapor process system
US20070151292A1 (en) * 2004-09-22 2007-07-05 Heath Rodney T Vapor Recovery Process System
FR2884154B1 (fr) 2005-04-07 2007-12-21 Inst Francais Du Petrole Procede de purification d'un gaz naturel par adsorption des mercaptans
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US8163680B2 (en) * 2006-09-28 2012-04-24 Chevron Oronite Company Llc Method of demulsing a natural gas dehydrator
US8052847B2 (en) * 2007-09-14 2011-11-08 Niagara Blower Company System and method for removing moisture from liquid desiccant
US8529215B2 (en) 2008-03-06 2013-09-10 Rodney T. Heath Liquid hydrocarbon slug containing vapor recovery system
CA2716870A1 (en) * 2008-03-07 2009-09-11 Vaperma Inc. Emission treatment process from natural gas dehydrators
US20100281775A1 (en) * 2009-05-11 2010-11-11 Gly-Tech Services, Inc. System for dehydrating natural gas
US9695373B2 (en) 2010-04-08 2017-07-04 Moneyhun Equipment Sales System and method for natural gas dehydration
CA2736223A1 (en) 2010-04-08 2011-10-08 Joseph A. Witherspoon Ultra-low emission natural gas dehydration unit with continuously fired reboiler
US8491712B2 (en) * 2010-09-13 2013-07-23 General Electric Company Dehydration systems and methods for removing water from a gas
US8864887B2 (en) * 2010-09-30 2014-10-21 Rodney T. Heath High efficiency slug containing vapor recovery
FR2981280B1 (fr) 2011-10-17 2015-12-18 IFP Energies Nouvelles Procede de captage d'un compose contenu dans un gaz par adsorption sur lit vertical
FR2990140B1 (fr) * 2012-05-07 2015-01-02 Gdf Suez Sa Procede de traitement du gaz naturel par absorption avec un solvant dessicant
US10052565B2 (en) 2012-05-10 2018-08-21 Rodney T. Heath Treater combination unit
US9527786B1 (en) 2013-03-15 2016-12-27 Rodney T. Heath Compressor equipped emissions free dehydrator
US9291409B1 (en) 2013-03-15 2016-03-22 Rodney T. Heath Compressor inter-stage temperature control
US9932989B1 (en) 2013-10-24 2018-04-03 Rodney T. Heath Produced liquids compressor cooler
WO2016155678A1 (es) * 2015-03-30 2016-10-06 Francisco Javier Velasco Valcke Dispositivo para la extracción de agua del medio ambiente
JP6656843B2 (ja) * 2015-08-21 2020-03-04 株式会社神戸製鋼所 ガス処理システム及びガス処理方法

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Also Published As

Publication number Publication date
NO964540L (no) 1997-04-28
NO315566B1 (no) 2003-09-22
DE69609922D1 (de) 2000-09-28
EP0770667A1 (fr) 1997-05-02
FR2740468B1 (fr) 1997-12-12
DE69609922T2 (de) 2000-12-28
US6004380A (en) 1999-12-21
CA2188825C (fr) 2006-01-03
FR2740468A1 (fr) 1997-04-30
DK0770667T3 (da) 2000-11-13
CA2188825A1 (fr) 1997-04-28
NO964540D0 (no) 1996-10-25

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