EP2588216A2 - Procédé et dispositif de désorption de solutions détergentes aminées chargées provenant de processus de lavage de gaz - Google Patents

Procédé et dispositif de désorption de solutions détergentes aminées chargées provenant de processus de lavage de gaz

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Publication number
EP2588216A2
EP2588216A2 EP11745938.8A EP11745938A EP2588216A2 EP 2588216 A2 EP2588216 A2 EP 2588216A2 EP 11745938 A EP11745938 A EP 11745938A EP 2588216 A2 EP2588216 A2 EP 2588216A2
Authority
EP
European Patent Office
Prior art keywords
gas
zone
detergent solution
separation
flushing gas
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.)
Withdrawn
Application number
EP11745938.8A
Other languages
German (de)
English (en)
Inventor
Ralf Boback
Sebastian Wohlrab
Felix FRÖHLICH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Leibniz-Institut fur Katalyse Ev An Der Universitat Rostock
Original Assignee
Leibniz-Institut fur Katalyse Ev An Der Universitat Rostock
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Leibniz-Institut fur Katalyse Ev An Der Universitat Rostock filed Critical Leibniz-Institut fur Katalyse Ev An Der Universitat Rostock
Publication of EP2588216A2 publication Critical patent/EP2588216A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/0005—Degasification of liquids with one or more auxiliary substances
    • B01D19/001—Degasification of liquids with one or more auxiliary substances by bubbling steam through the liquid
    • B01D19/0015—Degasification of liquids with one or more auxiliary substances by bubbling steam through the liquid in contact columns containing plates, grids or other filling elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B01D71/0281—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention relates to a process for the desorption and regeneration of laden amine-containing detergent solutions from gas scrubbing processes in which C0 2 and / or sulfur compounds such as H 2 S are chemically bound and to an apparatus for carrying out the process.
  • gases such as biogas, waste gases from chemical processes or natural gas and earth gases contain C0 2 and / or sulfur compounds which must be separated from further use or safe discharge into the atmosphere.
  • Chemical and physical gas scrubbing methods are suitable for this purpose, in which case a chemical scrubbing preferably takes place by means of an amine-containing detergent solution in which CO 2 and sulfur compounds are chemically bound.
  • a biogas upgrading plant which binds by physical solution under pressure inter alia C0 2 in the detergent.
  • the regeneration takes place by carrying out a first expansion step, a heating of the detergent with subsequent second expansion and a final stripping with ambient air.
  • Air stripping is a process known for physical adsorption installations for CO 2 and / or sulfur compounds, and is suitable for oxidation-stable detergents.
  • detergent solutions containing amine are characterized by a low oxidation stability.
  • the separation of the condensed water content is carried out by phase separation in the liquid phase naphtha - water.
  • the water to be removed is withdrawn liquid from the system.
  • Noncondensing portions of the stripping gas are discharged from the system in gaseous form.
  • the recovered by condensation Naphtaanteil is evaporated again.
  • a portion of the separated water is added to adjust a reflux to the top of the stripping column.
  • Fischer-Tropsch reaction products u. the stripping of physical, physio-chemical and chemical detergents and solvents with gases other than air.
  • EP 1 543 874 A2 describes a combined absorption and high pressure stripping in which the pressure of the stripping is above the absorption pressure and in which the stripping gas is exposed to two different pressure stages.
  • stripping gases natural gas, nitrogen and C2 to C5 hydrocarbons are given.
  • the stripping with water vapor and with product gas, especially for gas purification and especially for the removal of one or all acidic gas components such as hydrogen sulfide and carbon dioxide from gas streams such as natural gas and industrial gases by chemisorption in a two-circuit process includes the DE 698 09 393 T2 (US 6,139,605).
  • the process improves the desorption level of the detergent used in the fine cleaning and internally shifts the CO 2 desorption performance to the classical water vapor desorption of the semi-lean branch.
  • the method can thus achieve a higher desorption of the detergent, but retains the already outlined disadvantages of classical steam desorption.
  • Deposition of C0 2 other methods are known, which are deepened below.
  • a common treatment process of hydrocarbons based on the separation of higher hydrocarbons by deep-freeze condensation and upstream adsorptive drying by means of glycol.
  • the deep-freeze condensation is a process and energy consuming process that causes a compression of the gas streams after the relaxation. In some cases, an additional pre-cooling of the gas streams is required.
  • a suitable membrane process for the fine depletion of hydrocarbons the energy requirement and thus the costs can be reduced because the gases do not have to be subjected to the above-mentioned preconditioning.
  • the membrane process thus represents a more environmentally friendly process.
  • Hinners describes the testing of polymer-based membranes for the separation of HKW from natural gases under elevated pressure conditions. These show the disadvantage of swelling due to the moisture and HKW contained in the gas stream, whereby the selectivity decreases. The prerequisite for the use of such membranes would therefore be complete predrying of the gas streams.
  • membranes made of inorganic-non-metallic materials do not have this swelling capacity and are therefore more versatile.
  • their high chemical resistance, pressure and pressure swing resistance and thermal stability A prerequisite for a selective separation is a uniform pore size of the inorganic membrane material in the molecular size of the components to be separated. Therefore, zeolite membranes are suitable because they have an inherent, defined pore system.
  • the hydrophobic silicalite or low-aluminum ZSM-5 from the group of MFI zeolites is particularly suitable for the separation of nonpolar components.
  • WO 94/01209 describes the synthesis of dense ZSM-5 layers and their use in selective adsorption and the like. a. from hydrocarbons to an applied feed pressure of 100 kPa.
  • the invention has for its object to provide a process for the desorption of an obtained in the purification of gases amine-containing detergent solution in which C0 2 and / or sulfur compounds are chemically bonded to provide low exhaust gas consumption, a substantial desorption of the loaded detergent solution and thereby the significantly reduce the oxidative load on the detergent solution, thereby increasing its service life and thus significantly delaying aging.
  • Another object is to ensure a minimum content of the flushing gas in the C0 2 -Off gas.
  • Another object of the method is to use those technically usable existing heat potentials, which are below the boiling point of Waschstoffiösung.
  • the method consists in that
  • the heated detergent solution in a stripping zone with a chemically inert flushing gas is contacted intensively for a mean residence time of 3 minutes to 180 minutes, preferably from 30 to 80 minutes, wherein the amine-containing detergent solution stripped from the flushing gas and dissolved C0 2 or dissolved sulfur compounds be driven off (process step B), wherein the intensive contact mitteis bubble, packing, packing columns, membrane contactors or spray columns or a column containing static mixing elements, in which a portion of the laden detergent solution is passed in countercurrent to the flushing gas can take place;
  • the flushing gas is recovered as a gas component from the mixture with the desorbed C0 2 or the sulfur compound or the two parts through a two-stage separation at least, wherein carried out in a stage by cooling or by a combination of cooling and pressure increase condensation of the flushing gas , So that a first Flushgasanteil from the offgas stream after condensation is present as a separable liquid and at the exit as a liquid of this condensation zone together with other mitauskondensierenden gas components such.
  • B. water is withdrawn, z. B. after a gas liquefier (process step C);
  • step D the remaining, uncondensed second Flushgasanteil within the C0 2 or sulfur compounds such as H 2 S or both containing Offgasgemisches in a second process step (step D) is transferred to a Flushgasfeinabtrennung and there:
  • step E the liquid or gaseous flue gas is used again in the stripping and recirculated (step E) by the condensed liquid flushed gas evaporated in a heated evaporation zone and introduced via a first entry path together with already gaseous Flushgasan turnover also in gaseous form in the stripping zone and the laden detergent solution is brought into intensive contact, or the remaining after passing through the evaporation zone liquid Flushgasanteile liquid in the filled with the desorbed Waschschiösung heating and / or Are brought to the contact zone or that the flushing gas is spent together with the washing solution in a pressurized Heäzzone and brought via a nozzle by flash evaporation for proportional evaporation or that a second entry path, the flushing gas in the liquid state directly into the filled with the desorbed detergent solution heating zone and / or spent in the stripping zone, and here in the washing medium solution is evaporated, wherein non-evaporating condensate, in particular water, are taken up by the amine-containing
  • the separation of the flushing gas from the offgas stream may also comprise its water content, e.g. for drying the off-gas or for regulating the water content of the amine-containing detergent solution can also be deducted separately.
  • the coalescing and foam separation zone may be omitted if
  • water-soluble chemically inert organic substances suitable for adsorption and absorption in washing solutions, e.g. in polar solvents or
  • the separation membrane material for separating the CO 2 -flush gas mixture in a) is characterized by its tightness in the form of leakage.
  • Membrane materials can therefore be: ceramic, dense microporous layers (zeolite membranes) or dense polymer membranes. Zeolite membranes work on the principle of adsorption, preferably via pore condensation. Polymer membranes preferably work on the principle of solution diffusion. Preference is given to inorganic zeolite membranes.
  • H 2 S is understood here to mean in general sulfur compounds which can usually be present, such as thiols, H 2 S, COS or mercaptans.
  • Particularly preferred materials for porous layer inorganic membranes are densely grown zeolite-based crystallites, most preferably MF1, FAU, LTA, MOR, FER, MEL, BEA; ITR and KFi, preferably MFI and FAU, and here particularly preferably the MFI structure with Silikalithmembranen without AI share or MFi membranes with an aluminum content.
  • Particularly preferred in MFI membranes with aluminum contents are Si / Al units of greater than 75.
  • Further preferred zeolites are CIT-1, DAF-1, Stilbite, Beta, Boggsite, EMC-2 and STA-1.
  • the pore sizes are in the range of Moiekül micr the hydrocarbons to be separated at 0.3 - 2 nm, preferably 0.5 - 0.8 nm.
  • amorphous inorganic membranes are preferred. Particularly preferred herein are silica membranes and carbon membranes having pore sizes in the range of 0.5-2 nm.
  • the membranes should be dense and thus leak-free and thus allow only adsorptive processes on the inner surface, whereby the mass transfer thus proceeds only through the intra-crystalline pore system.
  • Advantageous for the separation process are membranes that allow high permeate flows due to their small layer thickness.
  • the thickness of the separating layer is therefore preferably less than 50 ⁇ m, for example 2 to 40 ⁇ m, more preferably less than 30 ⁇ m, for example 2 to 20 ⁇ m.
  • Membranes of asymmetric construction are preferred, as explained below.
  • a mesoporous layer is produced by applying a slurry of ground commercial zeolite materials ( ⁇ 1 ⁇ , advantageously ⁇ 500 nm) and subsequent temperature treatment at 500 - 700 ° C. Thereafter, to produce the microporous layer on the mesoporous layer, the latter with a synthesis solution at 140 to 200 ° C, treated hydrothermally for 12 to 72 hours and z. B. coated with silicalite.
  • composition of a silicalite synthesis solution can vary depending on the synthesis method, the reagents used, the physical synthesis parameters as well as the desired membrane properties with respect to selectivity and flux.
  • SDA may be, for example, tripropylammonium hydroxide or tripropylammonium bromide or a mixture of both.
  • macroporous refers to pores of> 1,000 nm, mesoporous pores of 2 to 50 nm and microporous pores of 0.1 to 2 nm.
  • washing processes for binding the gaseous liquid gas component e.g. utilizing a selective solubility of the flushing gas in a solvent to minimize the discharge of flushing gas from the system.
  • flush gas is understood to mean a substance which is chemically inert for the substances involved in the process and which is at least partially gaseous at the temperature of the amine-containing detergent solution or which changes into the gaseous state when introduced into the detergent solution, and which stripping the chemically and physically fixed in the detergent solution C0 2 or chemically bonded sulfur compounds or both in the discharged offgas.
  • flush gas is understood to mean a condensable gas which boils in the defined temperature range, a low heat of vaporization and is compatible with the product gas. The condensation of the flushing gas must be in the range of 5 to 98 ° C at a pressure in the range of 0.1 to 6 bar (a).
  • Low heat of vaporization is understood to mean a range of 10 to 60 kJ / mol.
  • An advantageous temperature range is 60-95 ° C, preferably 80-92 ° C.
  • Another preferred range is 90-95 ° C. If the Waschmitteilves is under pressure, the temperature can be up to 120 ° C. A preferred temperature range is then 90-1 10 ° C.
  • Suitable as a flush gas in the context of the present process are, for example, saturated linear and cyclic alkanes such as n-pentane, cyclopentane, n-hexane. Cyclohexane, n-heptane, cycloheptane, 2,2-dimethylbutane, 2-methylpentane, 3-methylpentane, mixtures thereof; Ethers such as tert-butyl ether, tert-butyl ethyl ether, isopropanol, di-n-propyl ether and mixtures thereof; primary, secondary and tertiary alcohols such as ethanol, i-propanol, n-propanol, secondary and tertiary butyl alcohol and mixtures thereof.
  • saturated linear and cyclic alkanes such as n-pentane, cyclopentane, n-hexane. Cyclohexane, n-heptane
  • saturated hydrocarbons or mixtures thereof in particular pentanes or hexanes, especially n-pentane or n-hexane, and tert-butyl ether and tert-butyl ethyl ether.
  • Also preferred for the selection of the flushing gas is a small temperature difference between the boiling temperature of the flushing gas and the operating temperature, i. the temperature range in which the stripping of Waschmitteiites takes place.
  • “Chemically inert” for the flush gas means that the flush gas does not undergo any chemical reaction with any of the components of the wash solution to interfere with the functionality of the reversible bond detergent with respect to CO 2 and sulfur compounds.
  • Heat sources preferred for the invention for heating the amine-containing Waschmitteilves in the heating zone to the operating temperature are heat transfer such as cooling liquids or gases with waste heat from combined heat and power plants (CHP), which are typically available with temperatures up to +98 ° C, or those of heat pumps from Geothermal or solar plants or waste heat or process heat of other industrial processes. These heat sources in the form of water or thermal oil can be brought to the level of desorption temperature by heat pumps.
  • Particularly suitable amine-containing wash-solution solutions for the present process are those which are used in the scrubbing of C0 2 from gas mixtures such as biological sewage, ground and mine gas and which are liquid at normal temperature. Preferably, these are aqueous solutions.
  • Such detergent solutions react chemically with C0 2 , but also chemically bind sulfur compounds as well as H 2 S, thiols, mercaptans or mixtures thereof. Furthermore, C0 2 and gaseous sulfur compounds can also be physically dissolved to a lesser extent. With the aid of the flushing gas, both the chemically bound sulfur compounds and the C0 2 are stripped off.
  • detergent solutions are those obtained in the amine scrubbing in other chemical processes, or resulting from the scrubbing of natural gas or associated gas.
  • the degree of loading of the detergent to determine the actual desorption of WaschmitteNösung is measured by the pH, the conductivity, the density, the speed of sound, the spectroscopic properties of the detergent solution or in their combination and used as a demolition criterion of desorption.
  • the achievable degree of desorption is dependent on the effective stripping time and stripping intensity, the type of aqueous amine washing solution and its temperature for temperatures around 90-95 ° C at about 50% of the chemical C0 2 absorption capacity of a loaded amine-containing detergent solution.
  • the stripping can be carried out at low temperatures just above the Gieich.stician "absorption of C0 2 to desorption of C0 2 ", since the stripping shifts the equilibrium in the desorption reaction in favor of the released gas C0 2 .
  • the lowest possible desorption temperature can be used.
  • Another important advantage of the invention is that the flushing gas used for stripping can be recovered almost completely with relatively little technical and energy expenditure and reused in the circuit.
  • the detergent solution undergoes a C0 2 discharge of 50 to 60% of its inlet-side initial charge.
  • the discharge achieved can be determined directly on the basis of parameters for the degree of loading of the washing liquid such as pH, density, refractive index, conductivity and as a criterion for achieving the required average residence time of the detergent solution in the stripping.
  • the direct spectrometric or titrimethsche determination of the detergent loading level is possible.
  • Another method is the direct determination of the discharged C0 2 amount in the offgas stream using the CO 2 concentration and the off-gas volume flow.
  • the device for carrying out the method according to the invention comprises the following functional elements which are in the interaction of action:
  • a subsequent primary deposition zone consisting of a gas liquefier or a region in which flash evaporation can take place
  • Separation zone for separating the non-condensed parts of the gas stream, consisting on the one hand of CO 2 , H 2 S, methane, amine detergent, water vapor and on the other hand, the gaseous in vapor pressure remaining fractions of the flushing gas; and means for recirculating the flushing gas into the circuit.
  • the device is supplemented by:
  • a flush gas line from the evaporation zone to the stripping zone h) a connecting line from the evaporator zone to the heating zone, i) a circulation line with feed pump between heating zone (sump) and stripping zone for a multiple circulation of the amine-containing detergent solution,
  • the sensor mentioned under b) can measure the ratio of CO 2 to flush gas, both as direct CO 2 measurement or Flushgaskonzentrationsteil or both, by determining mixture characteristics such as speed of sound, density, heat of condensation of the offgas stream. He can also evaluate the ratio of effective Flushgasvolumenstrom to change the loading of the detergent in the course of desorption.
  • the liquid-gas separation in the coalescing and Schaumabscheidezone preferably takes place by mechanically acting separation elements such as perforated bends, screens, Koaleszenzabscheider, filter elements, foam domes u. ä .. It is also possible to use spray elements for spraying WaschmitteH ⁇ sung or water or energy-carrying facilities, such as ultrasonic actuators, evaporation lines, infrared radiant heat sources or electromagnetic heating in the RF or microwave range, which act effectively on foams or foam surfaces and allow such a liquid-gas separation.
  • the addition of surface-active chemical foam inhibitor is possible to prevent unwanted transport of liquid in the laxative gas path of the offgas Flushgasgemischs.
  • the membrane is characterized by impermeability (leak-free) and preferably consists of ceramic, dense microporous layers (zeolite membranes) or dense polymer membranes, which operate on the principle of adsorption diffusion or, preferably, pore condensation. Preference is given to zeolite membranes.
  • a fundamental positive effect of the method is that the risk of premature oxidation and aging of the detergent solution can be substantially reduced by the low process temperatures and that heat sources with relatively low heat level can be used effectively and thus energy optimization is achieved. Due to the lower process temperatures, the aniagenischen requirements can be lowered and thus their durability and availability can be increased. Also, the expenses for the operation and maintenance of the plant are lower, resulting in an overall more economical advantage.
  • the plant is part of a biogas upgrading plant that removes CO 2 and / or sulfur compounds by amine scrubbing.
  • DGA® diglycolamine
  • the loaded Rich detergent solution having an amine concentration of about 50%, a temperature of 60 ° C and a loading of 0.35 mol C0 2 per mole of amine is fed through the Rich-detergent line 1 to the stripping zone 3.
  • the stripping zone 3 can be equipped with surface-enlarging elements such as structured packings, random packings, contactors, spray nozzles.
  • the Rich detergent solution flows through these elements in the running as a heating zone 4 section.
  • the volume of the heating zone 4 and the stripping zone 3 including a connecting line 6 between the heating zone 4 and the stripping zone 3 is dimensioned so that the average residence time of the detergent solution is 30 minutes.
  • the heat transfer medium of the heating zone 4 is supplied from a technical low-temperature source of 94 ° C, so that the detergent solu ung in the heating zone 4 is maintained at a temperature in the range of 86 - 92 ° C.
  • the flushing gas n-hexane with a boiling point at atmospheric pressure of 69 ° C is passed through the stripping zone 3 and possibly from the heating zone 4 in the stripping zone 3 in countercurrent to the detergent solution and causes the stripping effect in gaseous form and thus the desorption of the detergent solution.
  • Part of the dissolved in the detergent solution CO2 and / or H 2 S is stripped by the Flushgasstrom in an advantageous and surprising manner already at temperatures below about 105 ° C, the previous minimum temperature for effective DGA® desorption desorbed, ie the Detergent solution does not need to be boiled.
  • the Flushgastrom circulates over surface enlarging internals in the stripping zone 3. Thus, the flushing gas is intensively swirled in countercurrent with the detergent solution.
  • the stripping effect is maximally enhanced and effective depletion of the fixed CO2 and the sulfur compounds in the amine-containing detergent solution is effected.
  • the depleted detergent solution is withdrawn from the device via the Lean Detergent 2 line for reuse.
  • the liquid flushing gas can be heated with the detergent to achieve a superheated liquid state under pressure and by Relaxing of the detergent flushing gas mixture by a nozzle arrangement in the stripping zone evaporation of the flushing gas can be brought about.
  • the mixture of both mixture components can also be done directly in front of the nozzle. The method is particularly advantageous when the difference between the boiling temperature of the flushing gas and the temperature of the available heat source is small, ie less than 10K.
  • a CO2 sensor 9 measures the C0 2 concentration of the gaseous fuel gas offgas mixture discharged from the coalescing and foam separation zone 8. Since the desorption of the detergent solution via the heating zone 4 and stripping zone 3 is kinetikümiert, it is expedient to limit the volume flow of flushing gas used to a point at which a maximum CO 2 discharge coincides with a minimum Flushgasvolumenstrom, since the enthalpy of enthalpy of Flushgas- phase transition in addition to the chemical desorption enthaiphie the detergent solution and to heat both substances / substance mixtures is applied. For this purpose, the signal of the CO 2 sensor 9 is used to regulate an optimum value in the ratio of CO 2 desorption to generated Flushgasvolumenstrom. This is done in an operative manner via the heat input into the evaporation zone 17 or by regulation of the circulation of the liquid flushing gas when it is evaporated directly in the detergent solution.
  • the volume ratio of expelled CO 2 and / or sulfur compounds to the circulating Flushgasstrom is 1: 1 to 1:20.
  • the Kinetiklimit ist results from the first reaction at about + 82 to 85 ° C reverse reaction of the carbamate to DGA® under CO 2 release at a reduced reaction rate. Therefore, the possible release of C0 2 is limited by the stripping with the flushing gas. For others, z. B. non-carbamate-forming amine detergent this applies in a comparable manner.
  • the detergent solution is circulated from a feed pump 7 from the heating zone 4 via connecting line 6 to the top of the stripping zone 3.
  • From the outlet of the coalescing and Schaumabscheidezone 8 enriched with C0 2 and H 2 S gas stream is passed via connecting line 10 in a gas liquefier 11, in which a thermal condensation of the flushing gas takes place; at least a part of the flush gas is thereby transferred into the liquid state of matter.
  • the cooling takes place via a cooling medium, which is tempered below the boiling point of the flushm medium. This may be the detergent stream itself or else a separate coolant stream, for example that of a cold water salt.
  • An alternative known to a person skilled in the art is liquefaction by a pressure increase or a combination of cooling and pressure change.
  • the gas liquefier 11 alone constitutes a liquified gas separation zone when the stripping zone 3 serves as a flash evaporation zone.
  • the condensate which also contains non-flushing gas fractions, e.g. Contains water is withdrawn liquid from the gas liquefier 11 and fed via the connecting line 13 of the evaporation zone 17.
  • non-flushing gas fractions e.g. Contains water
  • the transition from liquid to gaseous flushing gas takes place.
  • the recirculated flushing gas is returned via the flushing gas line 18 directly into the stripping zone 3 into the process via the first entry path.
  • the unevaporated liquid portions of the flushmium including the co-condensed Wasseranteiie be derived from the evaporation zone 17 via the connecting line 19 and the injector 20 in the heating zone 4.
  • the detergent solution then evaporates the remaining Flushgasanteil.
  • the main circuit of the Flushgasstroms is closed.
  • the liquid present Flushmedium can be introduced with the co-condensed water without upstream evaporation phase directly via the connecting line 19 and injector 20 in the heating zone 4.
  • the flushing gas is evaporated in the detergent solution heated above the flushing gas boiling point.
  • the uncondensed in the gas liquefier 1 1 part of the gas stream consists of C0 2 , sulfur compounds, traces of methane, traces of amine, water vapor, dissolved permanent gases and the gaseous vapor pressure in the remaining parts of the flushmium.
  • the gas liquefier 11 is connected via a connecting line 12 to a second process stage in the form of a fine-gas recirculation 15. within the Flushgasfeinabtrennung 15, the separation is gaseous
  • the membrane unit used is an MFI membrane bundle consisting of individual MFI-coated corundum monoco channels with an asymmetrical structure.
  • Compressor or vacuum pumps are reinforced (not shown here).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne des procédés et un dispositif pour régénérer des solutions détergentes aminées chargées provenant de processus de lavage de gaz tels que des biogaz, effluents gazeux issus de processus chimiques, gaz naturel et gaz associé, dans lesquels du CO2 et/ou des composés sulfurés sont liés chimiquement. La solution détergente est portée à une température de 20 - 96 °C et mise en contact avec un gaz de rinçage, soumise à un strippage pendant 3 à 180 min, puis, une fois les constituants du gaz de rinçage séparés, acheminée sous forme de condensat à une membrane ou à une unité de séparation similaire où la fraction de gaz de rinçage non condensée est séparée. Le gaz de rinçage condensé est de nouveau évaporé et réintroduit dans le circuit. La désorption est très efficace et pratiquement complète. En raison de la faible température nécessaire à l'élévation de température, des sources de basses températures techniques peuvent être utilisées, telles que la chaleur perdue provenant de l'eau de refroidissement de centrales thermiques de type bloc, la chaleur solaire, l'énergie géothermique, la chaleur perdue d'origine industrielle et/ou la chaleur de processus.
EP11745938.8A 2010-07-01 2011-06-30 Procédé et dispositif de désorption de solutions détergentes aminées chargées provenant de processus de lavage de gaz Withdrawn EP2588216A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010025819A DE102010025819A1 (de) 2010-07-01 2010-07-01 Verfahren und Einrichtung zur Regeneration aus Gaswäschen stammender aminhaltiger Waschmittellösungen
PCT/EP2011/061054 WO2012001125A2 (fr) 2010-07-01 2011-06-30 Procédé et dispositif de désorption de solutions détergentes aminées chargées provenant de processus de lavage de gaz

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EP2588216A2 true EP2588216A2 (fr) 2013-05-08

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EP11745938.8A Withdrawn EP2588216A2 (fr) 2010-07-01 2011-06-30 Procédé et dispositif de désorption de solutions détergentes aminées chargées provenant de processus de lavage de gaz

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EP (1) EP2588216A2 (fr)
DE (1) DE102010025819A1 (fr)
WO (1) WO2012001125A2 (fr)

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FR2982169B1 (fr) * 2011-11-03 2014-06-06 Ifp Energies Now Procede de captation de co2 par un solvant aux amines avec regeneration du solvant par utilisation d'une source geothermale
EP3507259B1 (fr) * 2016-08-30 2024-02-07 Mojj Engineering Systems Ltd. Procédé d'évaporation de liquide de lavage épuisé bio-méthanisé en utilisant un système de dégazage à étages multiples

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Publication number Publication date
WO2012001125A3 (fr) 2012-04-12
WO2012001125A2 (fr) 2012-01-05
DE102010025819A1 (de) 2012-01-05

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