EP2132280A2 - Procédé de traitement de gaz de fumées dans des centrales et autres installations - Google Patents

Procédé de traitement de gaz de fumées dans des centrales et autres installations

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Publication number
EP2132280A2
EP2132280A2 EP08717769A EP08717769A EP2132280A2 EP 2132280 A2 EP2132280 A2 EP 2132280A2 EP 08717769 A EP08717769 A EP 08717769A EP 08717769 A EP08717769 A EP 08717769A EP 2132280 A2 EP2132280 A2 EP 2132280A2
Authority
EP
European Patent Office
Prior art keywords
alkali
plant
flue gas
reactor
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Withdrawn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
EP08717769A
Other languages
German (de)
English (en)
Inventor
Florian Krass
Ingo Krossing
Günther STEINFELD
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.)
Silicon Fire AG
Albert Ludwigs Universitaet Freiburg
Original Assignee
Silicon Fire AG
Albert Ludwigs Universitaet Freiburg
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
Priority claimed from EP07104246A external-priority patent/EP1961479A3/fr
Priority claimed from EP07113903A external-priority patent/EP1958683A3/fr
Priority claimed from PCT/EP2008/051097 external-priority patent/WO2008110405A2/fr
Application filed by Silicon Fire AG, Albert Ludwigs Universitaet Freiburg filed Critical Silicon Fire AG
Priority to EP08717769A priority Critical patent/EP2132280A2/fr
Publication of EP2132280A2 publication Critical patent/EP2132280A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • 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 methods and corresponding devices are to be designed to find wide acceptance by using materials that can be recycled as much as possible, or that can be used in various stages of the process sub-processes and that have a commercial value. This should enable a technical implementation on a broad basis.
  • the process according to the invention is based on a novel concept which binds the CO 2 in an alkali metal hydrogencarbonate using existing starting materials. Especially for binding, storing or storing CO 2 , sodium bicarbonate (NaHCO 3 , also known as
  • alkali lye and / or alkaline earth liquor which in the following will be referred to simply by the generic term alkali lye.
  • alkali metal hydroxides also called alkali hydroxides
  • alkaline earth metal hydroxides also called alkaline earth hydroxides
  • alkali metal hydroxide is to be understood in particular as meaning the following substances: NaOH; LiOH; KOH; Be (OH) 2 ; Mg (OH) 2 ; Ca (OH) 2 .
  • alkali solutions of only one alkali metal or alkaline earth metal, or else solutions of different alkali metal hydroxides and / or alkaline earth metal hydroxides can be used.
  • Alkali carbonate According to the invention - depending on the specific embodiment - alkali carbonate is produced. This generic term is used to describe the following carbonates: sodium carbonate (Na 2 CO 3 ); Lithium carbonate (Li 2 CO 3 ); Potassium carbonate (K 2 CO 3 ); Beryllium carbonate (BeCO 3 ); Magnesium carbonate (MgCO 3 ); Calcium carbonate (CaCO 3 ).
  • the amalgam method A is ideally started with 310-280 g NaCl in 11 solution.
  • the salt concentration should be at least 260 g / l.
  • the concentrated alkali salt brine 24 thus preferably has a salinity which is greater than 170 g / l, and is preferably greater than 280 g / l (depending on the electrolysis process, A., B. or C., slightly different values of salinity may be used here) , It is particularly advantageous to monitor the total salt content (salinity) of the concentrated alkali salt brines 24 by a conductivity measurement.
  • the total salt content can also be monitored by measuring the density and thereby controlling the entire process. Particularly preferred is the combination, for example, of a conductivity measurement with the density measurement, e.g. to control the electrolysis process. Additionally or alternatively, a pH measurement can be carried out to give an indication of the NaOH concentration.
  • alkali salt sols 24 e.g., a NaCl sol
  • sea water was provided.
  • the salt can be e.g. from salt mines that do not deliver clean and edible salt, or from seawater near the sea. In Germany, there are still large salt deposits that could be used.
  • an alkali lye 31 is used, which is particularly inexpensive and easy to manufacture.
  • the alkali lye 31 is provided by converting the alkali salt brines 24 while supplying energy (see box 205 in Fig. 12).
  • the alkali salt brine 24 is preferably purified (see box 202.1 in FIG. 12). This step is optional and the corresponding box in Fig. 12 is therefore shown in phantom. It is also possible to purify the alkali lye 31 (not shown in FIG. 12). This step is also optional.
  • a device 30 (eg in the form of a filling tower) is filled with alkali lye 31.
  • the filling can take place continuously or discontinuously through an inlet 35.
  • a distribution head 34.1 is mounted inside the device 30.
  • injection nozzles or similarly acting agents can also be used in order to be able to inject or pump in the CO 2 into the alkali lye 31.
  • a large number of bubbles are formed, which increases the effective surface area and hence the efficiency of the reaction.
  • the process which preferably proceeds in the device 30, is exothermic and, with evolution of heat, the alkali bicarbonate 26 (eg, sodium bicarbonate; NaHCOs) precipitates.
  • the alkali metal bicarbonate 26 is highly schematic in the lower part of the Device 30 is shown.
  • the process can also be conducted in such a way that alkali metal carbonate (eg sodium carbonate, Na 2 CO 3 ) is formed.
  • alkali hydrogen carbonate 26 can be converted by the supply of energy (energy expenditure 2, E2) into alkali carbonate.
  • cooling means 32 should be used to dissipate the heat generated during the exothermic reaction.
  • Such cooling devices can also be used analogously in the reactors shown in FIGS. 8, 9, 10 and 11.
  • This cooling device 32 can be cooled with water (eg sea water), as indicated in FIGS. 6B and 6C.
  • water eg sea water
  • the seawater is thus (further) preheated before it is finally brought to a temperature above 100 ° C. in the heating 12 (see FIG. 2).
  • the cooling device 32 may be traversed by a heat transfer medium that transports heat through tubes to the heater 12 to assist in heating the seawater. In this case, the cooling device 32 is not flowed through by the seawater.
  • the cooling loops 16 and the cooling device and 32 are connected in series and successively flowed through by seawater, before then the heated seawater passes through the input-side feed line 11 into the device 10.
  • sodium bicarbonate (NaHCO 3 ) can be formed as alkali metal bicarbonate 26 (see box 208 in FIG. 12).
  • the sodium bicarbonate (NaHCO 3 ) can be stored to permanently bind the CO 2 .
  • sodium bicarbonate can also be used in downstream chemical (industrial) processes in which as far as possible no CO 2 is produced (see box 209 in FIG. 12).
  • the flue gases (see flue gas supply 200 in FIG. 1 and FIG. 12) of the power plant are introduced into a highly concentrated alkali lye 31 (see reference numeral 206 in FIG. 12).
  • sodium bicarbonate 31 NaHCO 3
  • the alkali metal bicarbonate 26 eg sodium bicarbonate, NaHCO 3
  • Decisive for a rapid absorption is the greatest possible common interface between the liquid and the gaseous phase, ie, for example, the NaOH solution and the purified (of SO 2 and NO x -frereitem) flue gas, or CO 2 -containing gas mixtures or pure CO 2 -GaS.
  • the gaseous phase ie, for example, the NaOH solution and the purified (of SO 2 and NO x -frereitem) flue gas, or CO 2 -containing gas mixtures or pure CO 2 -GaS.
  • As large as possible common interfaces are preferably obtained by blowing the gas in the form of small gas bubbles as possible from below into the solution, which then move vertically upwards due to their lower density through the solution.
  • aqueous NaOH solution of 1.0 g / l (higher concentrations are even better), one can expect pure CO 2 (> 90%) over a path length of several Centimeters (in about 10 cm) almost completely (> 90%, preferably> 99%) as long as the pH of the resulting solution is strongly basic (eg pH> 12). If the pH drops by absorption of CO 2 , this slows down and longer path lengths are necessary. At a pH of about 8 no absorption takes place. At a pH of about 8, all the NaOH in the system was chemically converted to NaHCO 3 .
  • the path lengths also lengthen when using gas mixtures, the longer they extend the lower the original fraction of CO 2 was in this gas mixture. In principle, it is possible with such a system to absorb arbitrarily large amounts of CO 2 almost completely from mixtures, provided that sufficient NaOH or another alkali lye 31 is available.
  • the systems and systems according to the invention for avoiding or reducing CO 2 emissions should be optimized to use the existing base equivalents as completely as possible, ie For example, completely convert existing NaOH into NaHCO 3 . In addition, it is easier to obtain pure products (NaHCO 3 , Na 2 CO 3 ) that can be used further.
  • Na 2 CO 3 is desired as a product, some process parameters can be chosen almost arbitrarily.
  • solubility of NaOH (and also that of Na 2 CO 3 ) is much better than that of NaHCO 3 , so that rather low NaOH concentrations, preferably less than 5 g / l, are suitable for the starting solution 31 in order to prevent the precipitation of NaHCO 3 in the wrong places of the plant 30 to avoid.
  • Fig. 8 is a schematic diagram in Fig. 8.
  • Countercurrent tube 38 has an upper end inlet 35 for caustic 31 (preferably NaOH).
  • CO 2 inlet 34 At the lower end of the countercurrent tube 38 is the CO 2 inlet 34, through which CO 2 -GaS (eg flue gas or purified flue gas) enters the device 30.
  • CO 2 -GaS eg flue gas or purified flue gas
  • the inlet side (ie at the inlet 35 for the alkali lye 31) results in a flow direction of the liquid, which leads from the inlet 35 to an underlying outlet 37 (the direction of flow of the liquid is indicated in Fig. 8 by the arrow FF).
  • a gas outlet 36 NaHCO 3 solution can be removed.
  • the clean gas released from the CO 2 exits the upper end of the counterflow tube 38 through a gas outlet 36.
  • the filling level FH is located in the counterflow pipe 38 above the inlet 35 for the alkali lye 31st
  • an atomizer or a similar means is arranged to produce the smallest possible gas bubbles.
  • the counterflow tube 38, or the potential reaction region 39 of the countercurrent tube 38 must be as long as possible. That is, the limits as to when NaOH (denoted by Y1 in FIG. 8) and CO 2 (denoted by Y2 in FIG. 8) are completely fixed are not fixed.
  • the boundary Y1 and Y2 only have to be above the CO 2 inlet 34 or below the inlet 35 for the alkali lye 31 (preferably NaOH). Another problem arises that at too high flow rate of the solution (the direction of flow of the liquid is indicated in Fig.
  • the gas (the direction of flow of the gas is indicated in Fig. 8 by the arrow FG) entrained downwards is and can not exit at the top of the gas outlet 36.
  • the working pressure on the input side ie, at the inlet 35 for the caustic 31
  • the working pressure on the input side is controlled to be in a predetermined relation to the gas pressure at the CO 2 inlet 34. Fluctuations in the gas pressure can therefore be best compensated by the working pressure on the inlet side of the alkali lye 31 is adjusted accordingly control technology.
  • Fig. 9 is a schematic diagram in Fig. 9.
  • a device 30 is used whose essential component is a batch reactor 44.
  • the batch reactor 44 has an upper end inlet 35 for the caustic 31 (preferably NaOH).
  • the CO 2 inlet 34 At the lower end of the batch reactor 44 is the CO 2 inlet 34, through which CO 2 -GaS (eg flue gas or purified flue gas) enters the device 30.
  • the filling level is designated FH. It is here preferably below the inlet 35 for the alkali lye 31.
  • the batch reactor 44 further comprises an underlying outlet 37. At this outlet 37 NaHC ⁇ 3 solution can be removed. The clean gas released from the CO 2 exits the upper end of the batch reactor 44 through a gas outlet 36.
  • a nebulizer 46 or similar means is preferably arranged so that the incoming CO 2 -GaS is divided or disassembled by the nebulizer 46 into small bubbles and then these bubbles through the liquid in the Batch reactor 44 rise through it.
  • porous material can also be used to achieve bubble formation.
  • the batch reactor 44 is filled with NaOH solution 31, then the inlet 35 is closed again.
  • the gas outlet 36 is typically always open and provides for pressure equalization in the batch reactor 44 during the feed.
  • the CO 2 inlet 34 is opened and CO 2 -containing gas is blown / pumped.
  • the CO 2 -free gas flows out of the reactor 44 through the gas outlet 36.
  • a pH meter 45 or detector is used to continuously or discontinuously adjust the pH of the liquid in the batch reactor
  • Measuring devices for the volume flow at the CO 2 inlet 34 and at the gas outlet 36 can additionally control the course of the process. These measuring devices may alternatively or in addition to the pH meter
  • FIG. 10 is a schematic diagram in FIG. Because this double-batch process in the
  • the double-batch process works analogously to the batch process according to FIG. 9.
  • the advantage of this device 30 with a double-layout system lies in the continuous decrease of CO 2 -containing gas. While a batch, for example, in the first batch reactor 44.1 with CO 2 -containing gas is added, the other batch is pumped out in the second batch reactor 44.2 and refilled.
  • This double-batch process therefore runs intermittently. It can be processed a continuously accumulating flue gas stream.
  • the valve 47 is a valve which releases either the inlet to the first batch reactor 44.1 or the inlet to the second batch reactor 44.2. That is, the CO 2 -containing gas flows either into one or the other batch reactor 44.1 or 44.2.
  • Fig. 11 is a schematic diagram in Fig. 11. Since this multiple-batch process is based essentially on the batch process already described, reference is made to the description of FIGS. 9 and 10 for the basic aspects.
  • the multiple-batch process works analogously to the batch process according to FIG. 9.
  • the advantage of this device 30, for example with a five-fold design, lies in the fact that not only the CO 2 removal works continuously, but also the inflow of NaOH solution , as well as the effluent of NaHCO 3 solution.
  • reactor II While the finished NaHCO 3 solution is pumped out of the reactor I (batch reactor 44.1) through the underlying outlet 37 (sinking filling level FH, as indicated by the arrow pointing downwards in the interior of the reactor I), reactor II (batch reactor 44.2) is in Waiting state and is pumped off as soon as reactor I (batch reactor 44.1) is empty. At the same time, CO 2 -containing gas is blown into the reactor III (batch reactor 44.3) through the CO 2 inlet 34, as indicated by the arrow pointing to the left in the CO 2 inlet 34. It results in the reactor III (Batch Reactor 44.3) temporarily a slightly increased fill level FH, since the gas reduces the effective density of the solution in the reactor. Of the
  • Reactor IV (Batch Reactor 44.4) is in the standby state and is charged with CO 2 -containing gas as soon as the completion of the reaction in Reactor III (Batch Reactor 44.3) is diagnosed.
  • the reactor V (batch reactor 44.5) is simultaneously filled with NaOH solution (increasing filling level FH, as indicated by the arrow pointing upwards inside the reactor V). Filling with NaOH Solution is indicated in the region of the inlet 35 by the arrow pointing to the left.
  • alkali lye 31 preferably NaOH
  • the filling with alkali lye 31 occurs through the inlet 35.
  • the CO 2 -containing gas is blown through the CO 2 inlets 34 and the final NaHCO 3 solution is pumped or removed through the underlying outlets 37.
  • the multiple-batch process can also be reduced to 3 reactors 44.1 to 44.3.
  • Inlet 35 and 34 and the outlets 37 would be more susceptible to disturbances or changing CO 2 content in the (smoke) gas. In any case, more would be needed
  • Sensors are needed to control the progress of the reaction, for example, to adjust the strength of the CO 2 flow.
  • This process is indicated schematically in FIG. This requires an energy expenditure, which is designated in FIG. 5 with energy expenditure 2.
  • the fresh water produced during heating is collected.
  • the heating is preferably carried out at a temperature between 80 0 C and 300 0 C, preferably at 170 0 C to 180 0 C and the liberated CO 2 is recycled via a return 204 in the circuit, as in Fig. 5 by the perpendicular to above arrow and indicated in Fig. 12 by the dashed line 204.
  • the same procedure can be followed with the other alkali bicarbonates 26.
  • the alkali carbonate (eg sodium carbonate) can be stored to permanently bind the CO 2 .
  • the alkali carbonate (eg sodium carbonate) can also be used in chemical processes in which no possible CO 2 is formed (see box 209 in Fig. 12).
  • the flue gases (see flue gas supply 200 in FIG. 1 and FIG. 12) of the power plant 41 are introduced into a highly concentrated caustic 31, as mentioned (see 206 in FIG. 12).
  • alkali bicarbonate 26 and / or alkali carbonate which is more or less polluted, because in the flue gas other gases and substances may be (depending on which other sub-processes 214, 207, 217 this cleaning process is performed).
  • an alkali lye 31 is used, as mentioned.
  • three different approaches for providing or producing alkali lye 31 are designated by the reference symbols 210, 211 and 212.
  • chloralkali electrolysis processes have different advantages and disadvantages in terms of energy consumption (A.>B.> C), purity of the starting materials (C>A.> B.) And purity of the products (A.>C> B.) As well as the maintenance effort of plants (big at C). If particularly pure alkali bicarbonate products or alkali carbonate products are needed for further processing, then currently the process A. is preferred, although this process requires somewhat more energy A. When it comes to generating permanently storable or interposable alkaline bicarbonate or alkali carbonate, then process B is best suited.
  • alkaline-state chlor-alkali electrolysis processes have been deliberately chosen because these processes do not cause direct CO 2 emissions and energy consumption can be met by coupling to a power plant.
  • the chloralkali electrolysis process produces alkali lye 31 (eg sodium hydroxide, NaOH) without direct CO 2 emission.
  • reaction equations (7) and (8) are examples of alkali solutions.
  • CO 2 can be converted directly to the desired products of soda or sodium carbonate when working with caustic soda (NaOH).
  • NaOH caustic soda
  • the other alkali solutions can be used analogously.
  • the corresponding process control is shown schematically in FIG.
  • the chloralkali electrolysis for example, of a specially produced NaCl solution, or of pre-purified, concentrated seawater, yields the following valuable products: sodium hydroxide (NaOH), chlorine (Cl 2 ) and hydrogen (H 2 ).
  • the hydrogen (H 2 ) can either be returned to the power plant to be used there as an energy supplier, or the hydrogen can be stored or transported away. In this way, power plants could produce additional hydrogen in the future.
  • the hydrogen is particularly suitable as a temporary energy storage and the energy of the stored hydrogen, for example, can be released (by combustion or in a fuel cell) when peak loads occur.
  • the process according to the invention has further inherent advantages, since the substances that are needed (educts) or produced (products or recyclables), form a group of materials in other contexts in the vicinity of a power plant 41 or other industrial process, as well as of heaters or Incineration plants, can be used advantageously (see sub-processes 214, 207 and 217 in Fig. 12).
  • Ammonia may optionally be added e.g. for denitrification (box 217 in Fig. 12) of the power plant exhaust gases (flue gas) can be used, as indicated in the following equation (9):
  • a catalyst is needed in this process.
  • Ammonia can be prepared by directly combining nitrogen and hydrogen according to equation (10): JM 2 + 3 H 2 ⁇ 2 NH 3 + 92 fcJ (10)
  • the ammonia synthesis according to equation (10) is exothermic (reaction enthalpy - 92.28 kJ / mol). It is an equilibrium reaction that proceeds with volume reduction.
  • the nitrogen can be provided, for example, according to the Linde method, in which, on the one hand, the oxygen and, on the other hand, the nitrogen are separated from the ambient air, as represented schematically by the method block 41 in FIG. The corresponding
  • Process block 41 may be part of the overall system 40 for NH 3 synthesis.
  • the overall system 40 for NH 3 synthesis can again be part of the flue gas cleaning 51 of the overall system 50 (see FIG. 1).
  • the NH 3 synthesis is carried out in a NH 3 synthesis reactor, for example in the form of a cooled pressure vessel 43.
  • a cooling device 42 which in turn is part of a series circuit of seawater cooled cooling devices 16, 32 and 42.
  • the NH 3 synthesis according to (10) may, in a preferred embodiment, provide a portion of the energy needed, for example, to operate the thermal distillation process to provide the alkali salt brines 24, assuming seawater as the salt source.
  • the energy can also be used for the electrolysis (energy expenditure 1, El) and production of the alkali lye 31.
  • cooling with a heat transfer medium can also be carried out here, as described above, in order to convey the energy to the heating area 12.
  • urea can also be prepared from the ammonia (NH 3 ) according to the following equation (11) if required.
  • this sub-process is indicated by reference numeral 219. In this process, a portion of the CO 2 is bound again.
  • This optional sub-process (11) can be used if, for example, in the parallel power plant or industrial process, urea is needed to remove soot particles or other pollutants from the exhaust gases (flue gas).
  • the urea discharge is indicated by reference numeral 214 in FIG.
  • the urea can also be used as an energy storage, since urea can be easily and easily stored and / or transported.
  • sodium bicarbonate can be used analogously to the Neutrec® process or sodium bicarbonate ("bicarbonate”) process to neutralize the acidic constituents of the flue gas (hydrochloric acid, sulfur dioxide, hydrofluoric acid, etc.) (see box 207 in FIG. 12)
  • the acidic constituents of the flue gas hydroochloric acid, sulfur dioxide, hydrofluoric acid, etc.
  • heavy metals as well as dioxins and furans can be separated by addition of activated charcoal or hearth furnace coke.
  • the sodium compounds (sodium chloride, sodium sulphate, sodium fluoride, sodium carbonate, etc.) resulting from the neutralization of the acid flue gas components are separated from the flue gases by filtering techniques
  • Sodium chloride may optionally be reused (see box 216 in Figure 12).
  • the neutralization of the acidic components by the sodium hydrogencarbonate can be described by the following reaction equations:
  • the sodium bicarbonate is brought into contact with the hot flue gases. Thereby, it is thermally activated and converted into sodium carbonate (soda; Na 2 CO 3 ) having a high specific surface area and porosity, as indicated by the following equation (15):
  • the neutralization process 207 can be made even better and more ecological by replacing sodium bicarbonate (NaHCO 3 ) with sodium carbonate (soda, Na 2 CO 3 ).
  • This soda falls according to the invention as a product of the process and can be used in part in the same plant for the neutralization of the acidic components of the flue gas.
  • Another essential aspect of the invention is seen in the fact that when binding CO 2 , which comes from a combustion, pyrolysis or other industrial process, in addition to the valuable alkali carbonate (eg soda) also drinking water / fresh water is produced.
  • This water is virtually a waste product and can be used eg for drinking water supply or irrigation.
  • the inventive method for flue gas cleaning comprises in summary the following steps:
  • alkali hydrogen carbonate eg NaHCO 3
  • alkali carbonate eg Na 2 CO 3
  • alkaline hydrogen carbonate eg NaHCO 3
  • Alkali carbonate eg Na 2 CO 3 .
  • the alkali hydrogen carbonate (eg NaHCO 3 ) and / or alkali metal carbonate (eg Na 2 CO 3 ) is used to form a sub-process for neutralizing the flue gas (Box 207). to dine with it.
  • this sub-process is performed before the sub-process after step 4.
  • sodium salt e.g., NaCl
  • flue gas cleaning residue e.g., from the sodium products resulting from neutralization, Box 207.
  • This sodium salt may be reused in the process according to the invention (see box 216 in FIG. 12).
  • the sodium salt thus obtained can therefore be used to supplement the salt feed 26 from seawater (box 201) or the production of brine from solid salts (box 203).
  • the inventive method can be operated efficiently and safely, in which case preferably should be used with the amalgam method A.
  • the use of contaminated brine would have the consequence that the resulting NaOH and also the resulting NaHCO 3 would be contaminated accordingly.
  • the nitrogen oxides in the flue gas can be eliminated (box 217).
  • the NOx in the flue gases may be purified by a catalyst system (eg, SCR; selective catalytic reduction), as previously mentioned.
  • a catalyst system eg, SCR; selective catalytic reduction
  • urea is used as the reducing agent in such a system for eliminating or reducing the nitrogen oxides.
  • SCR technology can be used particularly advantageously as one of the last sub-processes for flue gas treatment, since it is also able to eliminate ammonia residues in the flue gas. That can be important if the flue gas contains ammonia per se, as may be the case with the flue gases of a cement plant, or that may be important if in other sub-processes ammonia is used.
  • the removal of nitrogen oxides may also be effected by the injection of ammonia into the firing space (e.g., in the boiler of a power plant 41) by the non-catalytic denitrification (SNCR) process.
  • SNCR non-catalytic denitrification
  • the nitrogen produced in the SCR process in addition to water vapor can e.g. used in the Haber-Bosch process.
  • the apparatus technical effort is particularly low according to the invention, since similar or related substances are used in all sub-procedures. With a suitable, cascade-like coupling of the sub-processes, even products of one sub-process can be used in other sub-processes, as described.
  • salt and coal are the most important raw materials that Germany owns.
  • the salt can be used to provide the alkali salt sols.
  • all important raw materials are available on site.
  • the method described here and the corresponding system 50 can be used not only in stationary but also in mobile systems.
  • the method can also be used for cleaning the exhaust gases of vehicles, the apparatus design must be adjusted accordingly.
  • the pathway shown in the present application is significantly better and less risky than pumping gaseous CO 2 gas into calcareous rock strata.
  • the present process also has significant advantages over the processes in which rock is spread and ground to capture CO 2 gas by carbonate formation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne un procédé et un dispositif (30) de liaison de CO<SUB>2</SUB> gazeux. Le procédé fait intervenir une saumure concentrée transformée en lessive de soude caustique (31) par électrolyse. Le CO<SUB>2</SUB> à lier est ensuite introduit dans la lessive de soude caustique (31). Il se forme alors de l'hydrogénocarbonate de sodium et/ou du carbonate de sodium. D'autres constituants des gaz de fumées peuvent être éliminés ou considérablement réduits dans d'autres processus partiels antérieurs ou ultérieurs.
EP08717769A 2007-03-15 2008-03-13 Procédé de traitement de gaz de fumées dans des centrales et autres installations Withdrawn EP2132280A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08717769A EP2132280A2 (fr) 2007-03-15 2008-03-13 Procédé de traitement de gaz de fumées dans des centrales et autres installations

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP07104246A EP1961479A3 (fr) 2007-01-11 2007-03-15 Procédé et dispositif de liaison de CO2 gazeux en relation avec la désalinisation de l'eau de mer
EP07113903A EP1958683A3 (fr) 2007-01-11 2007-08-07 Procédé destiné au traitement de gaz de fumée pour centrales et autres installations
PCT/EP2008/051097 WO2008110405A2 (fr) 2007-03-15 2008-01-30 Procédé et dispositif de liaison de co2 gazeux et de traitement de gaz de combustion à l'aide de composés carbonate de sodium
EP08717769A EP2132280A2 (fr) 2007-03-15 2008-03-13 Procédé de traitement de gaz de fumées dans des centrales et autres installations
PCT/EP2008/053025 WO2008110609A2 (fr) 2007-03-15 2008-03-13 Procédé de traitement de gaz de fumées dans des centrales et autres installations

Publications (1)

Publication Number Publication Date
EP2132280A2 true EP2132280A2 (fr) 2009-12-16

Family

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EP08717769A Withdrawn EP2132280A2 (fr) 2007-03-15 2008-03-13 Procédé de traitement de gaz de fumées dans des centrales et autres installations

Country Status (2)

Country Link
EP (1) EP2132280A2 (fr)
WO (1) WO2008110609A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1400114B1 (it) * 2010-05-21 2013-05-17 Eni Spa Procedimento per la fissazione dell'anidride carbonica proveniente da una centrale termica alimentata tramite combustibile fossile.
WO2022101287A1 (fr) * 2020-11-10 2022-05-19 Shell Internationale Research Maatschappij B.V. Systèmes et procédés de génération d'un acide carboxylique à partir d'un flux de gaz co2
DE102022119806A1 (de) 2022-08-05 2024-02-08 Metaliq GmbH Verfahren und System zur Natriumcarbonatherstellung

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US2792283A (en) * 1953-01-28 1957-05-14 Diamond Alkali Co Process of making sodium bicarbonate from sodium hydroxide cell liquor
US3368866A (en) * 1962-08-13 1968-02-13 Solvay Process for the manufacture of sodium carbonate
US3707453A (en) * 1971-05-06 1972-12-26 Olin Corp Mercury cell having rotating anodes
JPS5891179A (ja) * 1981-11-24 1983-05-31 Chlorine Eng Corp Ltd イオン交換膜法電解槽
US5830422A (en) * 1995-06-23 1998-11-03 Ormiston Mining And Smelting Co. Ltd. Method for production of sodium bicarbonate, sodium carbonate and ammonium sulfate from sodium sulfate
NO317918B1 (no) * 2002-02-15 2005-01-03 Sargas As Fremgangsmate for fremstilling av ferskvann og rensing av karbondioksyd
FI118629B (fi) * 2005-06-15 2008-01-31 Metso Power Oy Menetelmä ja laitteisto hiilidioksidin poistamiseksi rikkidioksidipitoisista savukaasuista

Non-Patent Citations (1)

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Title
See references of WO2008110609A2 *

Also Published As

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WO2008110609A3 (fr) 2010-09-23
WO2008110609A2 (fr) 2008-09-18

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