|Publication number||WO2006022885 A1|
|Publication date||2 Mar 2006|
|Filing date||12 Apr 2005|
|Priority date||6 Aug 2004|
|Also published as||CA2574633A1, CA2574633C, EP1781400A1, EP1781400A4, EP1781400B1, US7641717, US8308849, US20080072762, US20100064889|
|Publication number||PCT/2005/12794, PCT/US/2005/012794, PCT/US/2005/12794, PCT/US/5/012794, PCT/US/5/12794, PCT/US2005/012794, PCT/US2005/12794, PCT/US2005012794, PCT/US200512794, PCT/US5/012794, PCT/US5/12794, PCT/US5012794, PCT/US512794, WO 2006/022885 A1, WO 2006022885 A1, WO 2006022885A1, WO-A1-2006022885, WO2006/022885A1, WO2006022885 A1, WO2006022885A1|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (4), Non-Patent Citations (2), Referenced by (130), Classifications (17), Legal Events (17)|
|External Links: Patentscope, Espacenet|
ULTRA CLEANING OF COMBUSTION GAS INCLUDING THE
REMOVAL OF CO2
FIFiLD OF THE INVENTION
The present invention relates to systems and methods for ultra cleaning of combustion gas followed by the capture and regeneration of CO2.
Most of the energy used in the world today is derived from the combustion of carbon and hydrogen containing fuels such as coal, oil and natural gas. In addition to carbon and hydrogen, these fuels contain oxygen, moisture and contaminants such as ash, sulfur, nitrogen compounds, chlorine, mercury and other trace elements. Awareness to the damaging effects of the contaminants released during combustion triggers the enforcement of ever more stringent limits on emissions from power plants, refineries and other industrial processes. There is an increased pressure on operators of such plants to achieve near zero emission of contaminants and to reduce CO2 emission.
The art teaches various processes and technologies designed to reduce the emission of contaminants from combustion gases. Baghouses, electrostatic precipitators and wet scrubbers are typically used to capture particulate matter, various chemical processes are used to reduce sulfur oxides, HCl and HF emissions, combustion modifications and NOx reduction processes are used to reduce NOx emission and processes are being developed to capture mercury and other trace elements from combustion gas.
Significant progress has been made in the last 20-30 years and plants today are a lot cleaner and safer to the environment than in the past. However, there are growing indications that even small concentration of particulate matter and especially the very fine, less than 2.5 micron size particles (PM2.5), sulfur oxides, acid mist and mercury are harmful to human health and need to be controlled.
Controlling the residual emission is still a challenge and with existing technologies the cost of capturing the last few percents of harmful contaminants is very high.
In addition, in the last few years, there is a growing concern related to the accumulation of CO2, a greenhouse gas, in the atmosphere. The accelerated increase of CO2 concentration in the atmosphere is attributed to the growing use of fuels, such as coal, oil and gas, which release billions of tons of CO2 to the atmosphere every year.
Reduction in CO2 emission can be achieved by improving efficiency of energy utilization, by switching to lower carbon concentration fuels and by using alternative, CO2 neutral, energy sources. However, short of a major breakthrough in energy technology, CO2 emitting fuels will continue to be the main source of energy in the foreseeable future. Consequently, a low cost low energy consuming process for capturing and sequestering CO2 is needed to reverse the trend of global warming. State of the art technologies for capturing CO2 are not suitable for operation with dirty, low pressure, low CO2 concentration, and oxygen containing combustion gases. Available commercial technologies for CO2 capture are energy intensive and high cost. If applied they would impose a heavy toll on the cost of energy utilization.
An applicable process currently available for post combustion CO2 capture is the amine process using Mono-Ethanol-Amine (MEA) or similar amines to react with CO2. The MEA process is capable of achieving high capture efficiency and of generating a concentrated CO2 stream for sequestration. However, the process has several drawbacks including:
• The MEA reagent is expensive and degrades in oxygen and CO2 environment.
• The MEA is corrosive and can be used only in a relatively diluted form.
• The reaction of MEA with CO2 is highly exothermic.
• Regeneration is energy intensive.
• The process is a large consumer of heat and auxiliary power.
The cost of the amine process and system is very high and the net power output of a power plant equipped with amine system to capture CO2 is greatly reduced.
To achieve clean burning of fuels with near zero emission, including the emission of CO2, there is a need for a low cost low energy process that:
• Captures residual contaminants
• Captures CO2 and releases it in a concentrated and high pressure form for sequestration. Accordingly, it would be considered an advance in the art to develop new systems and methods to overcome the current problems and shortcomings.
SUMMARY OF THE INVENTION
The present invention is an integrated method and system to efficiently and cost effectively reduce the emission of residuals, such as SO2, SO3, HCl, HF and particulate matter including PM2.5, from combustion gas, downstream of conventional air pollution control systems, to near zero levels. Further, the system of the current invention reduces CO2 emission by capturing and delivering it to sequestration in a concentrated form and at high pressure. It is the objective of this invention that the process would be relatively uncomplicated, would utilize low cost reagent, would generate no additional waste streams and most importantly, would be a low cost and low energy consumer.
The present invention is a wet method and system whereby the saturated combustion gas, downstream of conventional air pollution control equipment and system, is cooled to well below its ambient saturation temperature. The cooling is achieved by direct contact with cold water in dedicated vessels. The direct contact between the gas and the liquid, combining with massive condensation of moisture from the saturated gas, is a very efficient wet scrubber. Optionally, alkaline materials such as sodium or ammonium carbonate can be added to the direct contact cooler to enhance the capture of the acidic species in the gas. The direct cooling to low temperature can be achieved in one or more cooling stages. Continuous bleed from the direct contact cooler, prevents the accumulation of the captured contaminants in the direct contact coolers. In a preferred embodiment, the chilled water will be generated in cooling towers with additional cooling, to low temperature in the range of 0-20, or even 0-10, degrees Celsius, by efficient mechanical vapor compression where the water itself is used as the refrigerant.
In accordance with the, current invention, cooling of the gas substantially reduces its moisture content. The cooled and low moisture gas has relatively low volume and relatively high CO2 concentration thus making the efficient capture of CO2 easier and lower cost.
The invention further involves the mass transfer and the reaction of gaseous CO2 from the combustion gas with CO2-lean ammoniated solution to form CO2-rich ammoniated solution. According to the current invention, the absorption reaction occurs in a CO2 absorber operating at about atmospheric pressure and at low temperature preferably in the temperature range of 0-20, or even 0-10, degrees Celsius. The low temperature enhances mass transfer of CO2 to the solution while substantially reducing the vapor pressure of ammonia and preventing its evaporation into the gas stream. One or more stages of CO2 absorption can be used depending on the capture efficiency requirements.
Further, in accordance with the current invention, the pressure of the CO2-rich solution from the CO2 absorber is elevated by high-pressure pump to the range of 30-2000 psi and it is heated to the temperature range of 50-200 degrees Celsius and preferably to the temperature range of 100-150 degrees Celsius. Under the conditions above the CO2 separates from the solution and evolves as a relatively clean and high-pressure gas stream. The high pressure CO2 gas stream contains low concentration of ammonia and water vapor, which can be recovered by cold washing of the CO2 gas steam. The regeneration reaction is endothermic. However, the heat of reaction is low and the overall heat consumption of the process is relatively low. Moreover, the high-pressure regeneration minimizes the evaporation of ammonia and water thus minimizing the energy consumed in the process. Also, low-grade heat can be used for the regeneration of the CO2 to further reduce the impact of the CO2 capture on the overall efficiency of the plant. The CO2-lean solution used in the absorber to capture the CO2 contains NH3/CO2 mole ratio in the range of 1.5-4.0 and preferably in the range of 1.5-3.0. The CO2-rich solution sent for regeneration contains NH3/CO2 mole ratio in the range of 1.0-2.0 and preferably in the range of 1.0-1.5.
The present invention has the advantage of high efficiency low cost capture of residual contaminants from the combustion gas followed by high efficiency low cost capture and regeneration of CO2. Low temperature absorption and high-pressure regeneration are critical to successful operation of the process and system. The simple, low cost and efficient system has notable advantage over other cleaning and CO2 capturing processes and it is a real breakthrough in achieving the objective of near zero emission of contaminants.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other advantages of this invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which: FIG. 1 is a schematic representation of the integrated system to capture residual contaminants and CO2 from combustion gas downstream of conventional air pollution control systems. The system includes gas cleaning, CO2 absorption and CO2 regeneration.
FIG. 2 is a schematic of the subsystems for the cooling of the gas and for deep cleaning of residual contaminants.
FIG. 3 is a schematic of the CO2 capture and regeneration subsystems. It includes CO2 absorber which operates at low temperature and CO2 regenerator which operates at moderate temperature and at high pressure.
DETAILED DESCRPTION OF THE INVENTION
In accordance with the present invention, a process and system to remove most contaminants, including CO2, from gas streams is provided. These gases are typically resulting from the combustion or gasification of coal, liquid fuels, gaseous fuels and organic waste materials. The contaminants include residual of e.g. SO2, SO3, HCl, HF, CO2, particulate matter including PM2.5, mercury and other volatile matter. The high removal efficiency of the contaminants is achieved by saturation and efficient cooling of the gas to below its adiabatic saturation temperature and preferably to as low as 0-20, or even 0-10, degrees Celsius. Fine particles and acid mist are nucleation sites for the condensation of water. Thus, practically all fine particles and acid mist are removed from the gas stream. The low temperature creates an environment of low vapor pressure of SO2, SO3, HCl, HF, Mercury and other volatile matter, which condense into the cold water as well.
The cooling of the flue gas enables the efficient capture of CO2 in CO2-lean ammoniated solution or slurry. Absorption of the CO2 is achieved at low temperature preferably at as low as 0-20 degrees Celsius or at as low as 0-10 degrees Celsius. The absorbent is regenerated by elevating the temperature of the solution or slurry to the range of 50-200 degrees Celsius and to pressures in the range of 30-2000 psig. The low temperature of absorption and the high pressure of regeneration result in high CO2 capture efficiency, low energy consumption and low loss of ammonia through evaporation. The CO2 absorption takes place in the aqueous NH3-CO2-H2O system where the ammonia can be in the form of ammonium ion, NH4 +, or in the form of dissolved molecular NH3. The CO2 can be in the form of carbonate, C03 =, bicarbonate, HCO3 " or in the form of dissolved molecular CO2. The capacity of the solution to absorb CO2 and the form in which the species are present depends on the ammonia concentration, on the NH3/CO2 mole ratio and on the temperature and pressure.
High NH3/CO2 mole ratio increases the vapor pressure of ammonia and results in ammonia losses through evaporation. Low NH3/CO2 ratio increases the vapor pressure of CO2 and decreases its capture efficiency. Thus, the optimal NH3/CO2 mole ratio for absorption is in the range of 1.0-4.0 and preferably in the range of 1.5 to 3.0. High temperature increases the vapor pressure of both ammonia and CO2. As a result, the absorber should operate at the lowest practical temperature and preferably in the 0-20 degrees Celsius temperature range or even in the 0-10 degrees Celsius temperature range.
At high concentration and lower temperature the solubility limits may be reached and solids particles precipitate. These solids particles are typically in the form of ammonium carbonate (NH4)2CO3 for high NH3/CO2 ratio and ammonium bicarbonate NH4HCO3 for low NH3/CO2 ratio.
The mass transfer and absorption reactions for concentrated low temperature slurries are the following:
• CO2 (g) ^ CO2 (aq)
• CO2 (aq) + H2O -» H+ + HCO3 " • (NH4)2CO3 (s) -^ 2NH4 +-KX)3 '
• H++CO3 = ^ HCO3-
• HCO3^NH4 + ^ NH4HCO3 (s)
Where CO2 captured from the gas converts ammonium carbonate to ammonium bicarbonate. The reactions above are reversible and CO2 is stripped from the liquid phase at elevated temperature.
Depending on the operating conditions, side undesired reactions may occur such as:
• NH4 ++CO3 = -» NH3 (g) + HCO3-
• NH4 ++HCO3- ■* NH3 (g) + CO2 (g) + H2O
Causing emission OfNH3 into the gas phase. Lower temperature and lower NH3/CO2 ratio in the absorber suppresses these undesired reactions. However, during the regeneration and at elevated temperature, gaseous ammonia is formed. To prevent ammonia from escaping from the liquid phase (and for other reasons) the regenerator is deigned to operate under elevated pressure and under conditions where the solubility of ammonia in the solution is very high and the emission of gaseous ammonia is very low.
FIG. 1 is a schematic representation of the integrated process, which includes cleaning and cooling of the gas, CO2 absorption into CO2-lean ammoniated solution and CO2 regeneration from the CO2-rich solution. Stream 102 is a gas stream from combustion or industrial process containing residual contaminants, CO2 and inert gas species. The CO2 concentration of the gas is typically 10-15% for coal combustion and 3-4% for natural gas combustion. Subsystem 130 represents a series of conventional air pollution control processes which, depending on the source of the gas may include particulate collectors, NOx and SO2 control, acid mist capturing device and more. The contaminants collected in the system are removed in stream 112. Stream 104, downstream of the conventional cleaning devices, contains residual contaminants not collected by the conventional systems. It is typically water saturated and in the temperature range of 40-70 degrees Celsius. Subsystem 132 is a series of one or more Direct Contact Coolers (DCC), where cold water generated in cooling towers and chillers (not shown) is used to wash and scrub the gas, capture its residual contaminants and lower its moisture content. Stream 114, is a bleed from subsystem 132 designed to purge all the residual contaminants captured.
Stream 106 is a cooled gas suitable for CO2 capture in the CO2 absorber. Subsystem 134 represents the CO2 absorber and may comprise of a series of absorber stages, depending on the removal efficiency required and the operating conditions of the plant. The clean gas with low CO2 concentration, stream 108, is released to the atmosphere. Stream 124 is a cooled CO2-lean ammoniated solution from the regenerator, subsystem 136, which is used as the absorbent to capture the CO2 in the absorber. The resultant stream 120 is a CO2-rich ammoniated solution sent for regeneration.
The regenerator, subsystem 136, operates at high pressure and elevated temperature and may be a single or a series of regeneration reactors. The pressure of the ammoniated solution fed to the regenerator is elevated using high pressure pump, pump 138, to yield stream 122 which is CO2-rich and at high pressure. Typically, the pressure of stream 122 is in the range of 50-2500 psi, higher than the regenerator pressure to prevent premature evaporation of CO2. Heat is provided to the regenerator by heating stream 126 in heater 140. The high pressure and high temperature in the regenerator cause the release of high- pressure gaseous CO2, stream HO. The high-pressure regeneration has major cost and energy advantage. Low quality thermal energy is used to generate the high pressure CO2 stream instead of high- value electric power.
FIG. 2 is a schematic representation of the cooling and cleaning subsystems, which may optionally include waste heat recovery, heat exchanger 240, for utilization of the residual heat in the gas. The residual heat in stream 202 can be extracted in heat exchanger 240 by transferring of the heat to a cooling medium streams 220 and 222. The heat can then be used downstream for CO2 regeneration.
Vessel 242 is a wet direct contact scrubber used to adiabatically cool and saturate the gas. If the gas contains high concentration of acid species, such as gas from coal or oil fired power
J plants, then reactor 242 is used for flue gas desulfurization. Acid absorbing reagent, such as limestone, stream 226, is added to vessel 242 and the product, such as gypsum, stream 224, is withdrawn. Make up water, stream 227, is added to vessel 242 from the Direct Contact Cooler (DCC) 244. The make up stream contains all the contaminants collected in the direct contact coolers. These contaminants are removed from the system with the discharge stream 224. Gas stream 202 in coal fired boiler is typically at temperature in the range of 100-200 degrees Celsius, gas stream 204 is typically at temperature range of 80-100 degrees Celsius and gas stream 206 is typically water-saturated and at temperature range of 40-70 degrees Celsius.
Two stages of direct contact cooling and cleaning, vessels 244 and 246, are shown in FIG. 2. The actual number of direct contact coolers may be higher and it depends on optimization between capital cost, energy efficiency and cleaning efficiency requirements. Gas stream 206 is cooled in DCC 244 to just above the cooling water temperature of stream 230. The temperature of the cooling water, stream 230, depends on the ambient conditions and on the operation and process conditions of Cooling Tower 250. Cooling Tower 250 can be of the wet type with temperature slightly below or slightly above ambient temperature, or the dry type with temperature above ambient temperature. Ambient air, Stream 212 provides the heat sink for the system and the heat is rejected in Stream 214, which absorbs the heat from water stream 228. The resultant cooled water stream 230, is typically at temperature range of 25-40 degrees Celsius and the resultant cooled combustion gas stream from DCC 244 is at about 1-3 degrees Celsius higher temperature. Alkaline materials such as ammonium or sodium carbonate can be added to DCC 244 to neutralize the acidic species captured. The alkaline materials can be added in makeup water, stream 225.
The cleaner and lower temperature, Stream 208 flows to DCC 246, which is similar to DCC 244 except for the fact that colder water, stream 234, is used for cooling. Stream 234 is a chilled water stream cooled by Chiller 248, which is preferably a mechanical vapor compression machine with water as its refrigerant. Heat from Chiller 248 is rejected via stream 236 to Cooling Tower 250 with returning stream 238. Cooling water stream 234 can be as cold as 0-3 degrees Celsius or higher resulting in combustion gas temperature, stream 210, exiting DCC 246 being at 0-10 degrees Celsius temperature or few degrees higher. The heat absorbed from the gas stream is removed from DCC 246 via water stream 232. More condensation occurs in DCC 246 and further capture of contaminants. These contaminants are bled from the system to vessel 242. (Bleed stream is not shown). Gas Stream 210, the product of the cooling and cleaning subsystem shown in FIG. 2, is at low temperature; it contains low moisture and practically has no particulate matter, acidic or volatile species.
FIG. 3 is a schematic representation of the CO2 capture and regeneration subsystem. Stream 302 is a clean and cooled gas stream, similar to stream 210 in FIG. 2. It flows into the CO2 absorber 350, where the CO2 is absorbed by a cooled CO2-lean ammoniated solution or slurry, Stream 324 containing NH3/CO2 mole ratio in the range of 1.5-4.0 and preferably 1.5-3.0. Depending on the absorber design and the number of absorption stages used, more than 90% of the CO2 in Stream 302 can be captured to yield a cold and CO2 depleted gas stream 304. Residual ammonia in stream 304 can be washed in vessel 356 by cold water or by cold and slightly acidic solution, stream 338. Stream 338 is cooled in heat exchanger 368. As a result of the cooling, cleaning and CO2 capture, the gas stream discharged from the system, Stream 306, contains mainly nitrogen, oxygen and low concentration of CO2 and H2O.
Stream 324 is a CO2-lean stream from the regenerator, which is cooled in the regenerative heat exchanger 354 and further by chilled water in heat exchanger 362. It captures CO2 in absorber 350 and discharges from the absorber, Stream 312, as a CO2-rich stream with NH3/CO2 mole ratio in the range of 1.0-2.0 and preferably with NH3/CO2 mole ratio in the range of 1.0-1.5. In a preferred embodiment, stream 312 contains high concentration of dissolved and suspended ammonium bicarbonate. A portion of stream 312 is optionally recycled back to the absorber while the balance, Stream 314, is pressurized in high pressure pump 360 to yield high pressure ammoniated solution stream 316. Stream 316 is heated in regenerative heat exchanger 354, by exchanging heat with the hot and CO2-lean stream from the regenerator, stream 322, which is a portion of stream 320 discharged at the bottom of regenerator 352.
The CO2-rich stream from the regenerative heat exchanger 354, stream 318, can be further heated with waste heat from the boiler or from other sources. It flows into the regenerator 352, which has one or more stages of regeneration. More heat is provided to the regenerator from heat exchanger 364, which heats stream 330. The heat provided to the system from the various sources, elevates the regenerator temperature to 50-150 degrees Celsius or higher, depending on the desired pressure of the CO2 stream 308 and subject to cost optimization consideration. The higher the temperature the higher will be the pressure of the CO2 that evolves from the solution, stream 308. The higher the pressure the lower will be the ammonia and water vapor content of stream 308. To generate low temperature and highly concentrated CO2 stream, stream 308 is washed and cooled in direct contact vessel 358 with cold water, stream 336 from heat exchanger 366. Excess water and NH3 captured in vessel 358, stream 332, flows back to regenerator 352 while the balance, stream 334, is cooled and recycled to the wash chamber, vessel 358.
The present invention has now been described in accordance with several exemplary embodiments, which are intended to be illustrative in all aspects, rather than restrictive. Thus, the present invention is capable of many variations in detailed implementation, which may be derived from the description contained herein by a person of ordinary skill in the art. All such variations and other variations are considered to be within the scope and spirit of the present invention as defined by the following claims and their legal equivalents.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US4515760 *||21 Dec 1983||7 May 1985||Linde Aktiengesellschaft||Non-precipitating regulation of ammonia content in sour gas solvent scrubbing systems|
|US5318758 *||9 Mar 1992||7 Jun 1994||Mitsubishi Jukogyo Kabushiki Kaisha||Apparatus and process for removing carbon dioxide from combustion exhaust gas|
|US6485547 *||28 Nov 2000||26 Nov 2002||Mitsubishi Heavy Industries, Ltd.||Exhaust gas cooling system|
|US20030140786 *||17 Dec 2002||31 Jul 2003||Masaki Iijima||Exhaust heat utilization method for carbon dioxide recovery process|
|2||*||See also references of EP1781400A4|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|WO2007012143A1 *||28 Jul 2006||1 Feb 2007||Commonwealth Scientific And Industrial Research Organisation||Recovery of carbon dioxide from flue gases|
|WO2008094777A1 *||21 Jan 2008||7 Aug 2008||Alstom Technology Ltd||Use of so2 from flue gas for acid wash of ammonia|
|WO2008101293A1||20 Feb 2008||28 Aug 2008||Hunwick Richard J||System, apparatus and method for carbon dioxide sequestration|
|WO2008134770A1 *||1 May 2008||6 Nov 2008||Powerspan Corp.||Removal of carbon dioxide from flue gas streams using mixed ammonium/alkali solutions|
|WO2008135150A1 *||18 Apr 2008||13 Nov 2008||Evonik Energy Services Gmbh||Method for purifying flue gases from incinerators and then producing urea|
|WO2008141195A1 *||9 May 2008||20 Nov 2008||Powerspan Corp.||Carbon dioxide scrubbing with ammonium carbonate and ammonia vapor control|
|WO2009000025A1||23 Jun 2008||31 Dec 2008||Commonwealth Scientific And Industrial Research Organisation||An improved method for co2 transfer from gas streams to ammonia solutions|
|WO2009003891A1 *||25 Jun 2008||8 Jan 2009||Alstom Technology Ltd.||Removal of carbon dioxide from flue gas with ammonia comprising medium|
|WO2009009725A1 *||11 Jul 2008||15 Jan 2009||Powerspan Corp||Scrubbing of ammonia with urea ammonium nitrate solution|
|WO2009055419A1 *||22 Oct 2008||30 Apr 2009||Alstom Technology Ltd||Multi-stage co2 removal system and method for processing a flue gas stream|
|WO2009056830A1 *||30 Oct 2008||7 May 2009||Alstom Technology Ltd||Carbon capture system and process|
|WO2009063041A1 *||14 Nov 2008||22 May 2009||Basf Se||Method for removing carbon dioxide from fluid flows, in particular combustion exhaust gases|
|WO2009068594A1 *||27 Nov 2008||4 Jun 2009||Shell Internationale Research Maatschappij B.V.||Process for removal of carbon dioxide from flue gas with ammonia cooled by vaporised liquefied natural gas|
|WO2009073422A1 *||24 Nov 2008||11 Jun 2009||Alstom Technoloby Ltd||Promoter enhanced chlled ammonia based system and method for removal of co2 from flue gas stream|
|WO2009080994A2 *||11 Dec 2008||2 Jul 2009||L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude||Cogeneration or trigeneration process using first and second h<sb>2</sb>s and/or co<sb>2</sb> capture units operating in parallel|
|WO2009080994A3 *||11 Dec 2008||24 Jun 2010||L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude||Cogeneration or trigeneration process using first and second h<sb>2</sb>s and/or co<sb>2</sb> capture units operating in parallel|
|WO2009091437A1 *||31 Oct 2008||23 Jul 2009||Powerspan Corp.||Removal of carbon dioxide from a flue gas stream|
|WO2009153351A1 *||19 Jun 2009||23 Dec 2009||Shell Internationale Research Maatschappij B.V.||Process for the removal of carbon dioxide from a gas|
|WO2010005797A2 *||25 Jun 2009||14 Jan 2010||Shell Oil Company||A method of treating a hydrocarbon gas stream having a high carbon dioxide concentration by using a lean solvent containing aqueous ammonia|
|WO2010005797A3 *||25 Jun 2009||4 Mar 2010||Shell Oil Company||Method of treating natural gas with high carbon dioxide concentration using aqueous ammonia|
|WO2010020017A1 *||24 Aug 2009||25 Feb 2010||Commonwealth Scientific And Industrial Research Organisation||Treatment of co2-depleted flue gases|
|WO2010039612A1 *||25 Sep 2009||8 Apr 2010||Alstom Technology Ltd||Chilled ammonia based co2 capture system and method with water wash|
|WO2010103392A1||11 Mar 2010||16 Sep 2010||Alstom Technology Ltd||Flue gas treatment system and the method using amonia solution|
|WO2010110939A1 *||1 Feb 2010||30 Sep 2010||Alstom Technology Ltd||Gas stream processing|
|WO2010146167A2||18 Jun 2010||23 Dec 2010||Shell Internationale Research Maatschappij B.V.||Process for the removal of carbon dioxide and/or hydrogen sulphide from a gas|
|WO2011034725A1||1 Sep 2010||24 Mar 2011||Alstom Technology Ltd||Method for removal of carbon dioxide from a process gas|
|WO2011034726A1||1 Sep 2010||24 Mar 2011||Alstom Technology Ltd||Method and system for removal of carbon dioxide from a process gas|
|WO2011034873A1 *||15 Sep 2010||24 Mar 2011||Alstom Technology Ltd||Method and system for regenerating a solution used in a wash vessel|
|WO2011046441A1 *||15 Oct 2010||21 Apr 2011||Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno||Method for absorption of acid gases using amino acids|
|WO2011058426A1||11 Nov 2010||19 May 2011||Alstom Technology Ltd||Flue gas treatment system|
|WO2011084254A1||23 Nov 2010||14 Jul 2011||Alstom Technology Ltd||Ammonia removal, following removal of co2, from a gas stream|
|WO2011084508A2||15 Dec 2010||14 Jul 2011||L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude||Method of obtaining carbon dioxide from a carbon dioxide-containing gas mixture|
|WO2011084512A1||15 Dec 2010||14 Jul 2011||L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude||Method of obtaining carbon dioxide from a carbon dioxide-containing gas mixture|
|WO2011084516A1||15 Dec 2010||14 Jul 2011||L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude||Method of obtaining carbon dioxide from a carbon dioxide - containing gas mixture by means of a membrane and condensing|
|WO2012035411A1||14 Sep 2011||22 Mar 2012||Alstom Technology Ltd||Raw gas collection system|
|WO2012036946A2||7 Sep 2011||22 Mar 2012||Alstom Technology Ltd||Process gas treatment system|
|WO2012038794A1||14 Sep 2011||29 Mar 2012||Alstom Technology Ltd||Trace component removal in c02 removal processes by means of a semipermeable membrane|
|WO2012071125A2||26 Oct 2011||31 May 2012||Alstom Technology Ltd||System and method of managing energy utilized in a flue gas processing system|
|WO2012071125A3 *||26 Oct 2011||10 Oct 2013||Alstom Technology Ltd||System and method of managing energy utilized in a flue gas processing system|
|WO2012071126A2||26 Oct 2011||31 May 2012||Alstom Technology Ltd||System and method of managing energy utilized in a flue gas processing system|
|WO2012104693A1||25 Jan 2012||9 Aug 2012||Alstom Technology Ltd||Process gas treatment system|
|WO2012106125A1||19 Jan 2012||9 Aug 2012||Alstom Technology Ltd||Gas treatment process and system|
|WO2012112336A1||7 Feb 2012||23 Aug 2012||Alstom Technology Ltd||Process and system for cleaning a gas stream|
|WO2012150493A1||1 May 2012||8 Nov 2012||Alstom Technology Ltd||Gas/liquid contacting vessel and the use thereof in a flue gas treatment system|
|WO2013006390A2||29 Jun 2012||10 Jan 2013||Alstom Technology Ltd||Chilled ammonia based co2 capture system with ammonia recovery and processes of use|
|WO2013006390A3 *||29 Jun 2012||10 May 2013||Alstom Technology Ltd||Chilled ammonia based co2 capture system with ammonia recovery and processes of use|
|WO2013042088A1||21 Sep 2012||28 Mar 2013||Alstom Technology Ltd||Heat integration of a cement manufacturing plant with an absorption based carbon dioxide capture process|
|WO2013108191A1||16 Jan 2013||25 Jul 2013||Alstom Technology Ltd||A method of forming urea by integration of an ammonia production process in a urea production process and a system therefor|
|WO2013108213A1||17 Jan 2013||25 Jul 2013||Alstom Technology Ltd||Control of a chilled ammonia process for co2 removal from a flue gas|
|WO2013111097A1||24 Jan 2013||1 Aug 2013||Alstom Technology Ltd||Ammonia capturing by co2 product liquid in water wash liquid|
|WO2013144899A3 *||28 Mar 2013||23 Jan 2014||Alstom Technology Ltd||Flue gas treatment system with ammonia solvent for capture of carbon dioxide|
|WO2013159215A1 *||14 Mar 2013||31 Oct 2013||Co2 Solutions Inc.||Co2 capture using low concentration ammonia based absorption solutions in presence of enzymes|
|WO2014059961A1||15 Oct 2013||24 Apr 2014||Hermann Büttner||Method for the synchronous absorption of carbon dioxide from flue gas and synthesis of dialkyl carbonates and alkylene carbonates|
|WO2016205057A1||9 Jun 2016||22 Dec 2016||Saudi Arabian Oil Company||Integrated process for co2 capture from internal combustion engines of mobile sources and use in thermal power production cycle|
|CN101600489B||21 Jan 2008||14 Nov 2012||阿尔斯托姆科技有限公司||Use of so2 from flue gas for acid wash of ammonia|
|CN101784329B||23 Jun 2008||12 Mar 2014||联邦科学及工业研究组织||Improved method for CO2 transfer from gas streams to ammonia solutions|
|CN102083513B||24 Nov 2008||18 Sep 2013||阿尔斯托姆科技有限公司||Promoter enhanced chilled ammonia based system and method for removal of CO2 from flue gas stream|
|CN102345873A *||5 Jul 2011||8 Feb 2012||巴布科克和威尔科克斯能量产生集团公司||Integrated flue gas dehumidification and wet cooling tower system|
|CN102345873B *||5 Jul 2011||30 Sep 2015||巴布科克和威尔科克斯能量产生集团公司||集成烟气除湿和湿式冷却塔系统|
|CN102438730B *||25 Sep 2009||5 Aug 2015||阿尔斯托姆科技有限公司||捕集系统和方法|
|CN102711959A *||11 Nov 2010||3 Oct 2012||阿尔斯通技术有限公司||Flue gas treatment system|
|CN103328074A *||7 Feb 2012||25 Sep 2013||阿尔斯通技术有限公司||Process and system for cleaning a gas stream|
|DE102011015466A1 *||31 Mar 2011||25 Oct 2012||Immoplan Verfahrenstechnik||Device for purifying air containing ammonia and carbon dioxide, has gas scrubber, saline solution and two Peltier heat pumps, where Peltier heat pump is comprised of two Peltier elements that are connected in parallel|
|DE102012020141A1||15 Oct 2012||17 Apr 2014||Hermann Büttner||Verfahren zur synchronen Absorption von Kohlenstoffdioxid aus Rauchgas und Synthese von Dialkylcarbonaten und Alkylencarbonaten|
|EP1998870B2 †||16 Mar 2007||2 Sep 2015||Basf Se||Process for contacting two phases whose contact is accompanied by heat evolution|
|EP2014347A1 *||3 Jul 2007||14 Jan 2009||ALSTOM Technology Ltd||Removal of carbon dioxide from flue gas|
|EP2117683A1 *||17 Dec 2007||18 Nov 2009||Sinvent AS||Method for capturing co2 from exhaust gas|
|EP2117683A4 *||17 Dec 2007||9 Nov 2011||Sinvent As||Method for capturing co2 from exhaust gas|
|EP2175967A1 *||23 Jun 2008||21 Apr 2010||Commonwealth Scientific and Industrial Research Organisation||An improved method for co2 transfer from gas streams to ammonia solutions|
|EP2175967A4 *||23 Jun 2008||18 Apr 2012||Commw Scient Ind Res Org||An improved method for co2 transfer from gas streams to ammonia solutions|
|EP2311545A1 *||15 Oct 2009||20 Apr 2011||Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO||Method for absorption of acid gases|
|EP2322265A1||12 Nov 2009||18 May 2011||Alstom Technology Ltd||Flue gas treatment system|
|EP2340886A1||3 Dec 2010||6 Jul 2011||Alstom Technology Ltd||Desulfurization of, and removal of carbon dioxide from, gas mixtures|
|EP2404653A1 *||6 Jul 2011||11 Jan 2012||Babcock & Wilcox Power Generation Group, Inc.||Integrated flue gas dehumidification and wet cooling tower system|
|EP2431499A1||17 Sep 2010||21 Mar 2012||Alstom Technology Ltd||Raw gas collection system|
|EP2433700A1||23 Sep 2010||28 Mar 2012||Alstom Technology Ltd||Trace component removal in CO2 removal processes by means of a semipermeable membrane|
|EP2481470A1||1 Feb 2011||1 Aug 2012||ALSTOM Technology Ltd||Process gas treatment system|
|EP2520352A1||2 May 2011||7 Nov 2012||Alstom Technology Ltd||Gas/liquid contacting vessel and the use thereof in a flue gas treatment system|
|EP2617708A1||17 Jan 2012||24 Jul 2013||Alstom Technology Ltd||A method of forming urea by integration of an ammonia production process in a urea production process and a system therefor|
|EP2653210A1 *||18 Apr 2012||23 Oct 2013||Siemens Aktiengesellschaft||Combustion assembly with flue gas washing and CO2 removal and method for operating same|
|EP2724770A1||26 Oct 2012||30 Apr 2014||Alstom Technology Ltd||Absorption unit for drying flue gas|
|EP2754480A1||9 Jan 2013||16 Jul 2014||Alstom Technology Ltd||Flue gas treatment method|
|EP2757071A1 *||17 Jan 2013||23 Jul 2014||Alstom Technology Ltd||Integrated carbon dioxide removal and ammonia-soda process|
|EP3184162A1||7 Sep 2011||28 Jun 2017||General Electric Technology GmbH||Removal of non-volatiles from ammonia-based co2-absorbent solution|
|EP3192581A1||7 Sep 2011||19 Jul 2017||General Electric Technology GmbH||Removal of non-volatiles from ammonia-based co2-absorbent solution|
|US7846240||9 Sep 2009||7 Dec 2010||Alstom Technology Ltd||Chilled ammonia based CO2 capture system with water wash system|
|US7862788||18 Nov 2008||4 Jan 2011||Alstom Technology Ltd||Promoter enhanced chilled ammonia based system and method for removal of CO2 from flue gas stream|
|US7867322||17 Jan 2008||11 Jan 2011||Alstom Technology Ltd||Use of SO2 from flue gas for acid wash of ammonia|
|US8034166||11 May 2007||11 Oct 2011||Basf Se||Carbon dioxide absorbent requiring less regeneration energy|
|US8063246||18 Apr 2008||22 Nov 2011||Evonik Energy Services Gmbh||Method for purifying flue gases from combustion plants and then producing urea|
|US8075673||19 Oct 2006||13 Dec 2011||Basf Se||Absorption medium and method for removing carbon dioxide from gas streams|
|US8182577||21 Oct 2008||22 May 2012||Alstom Technology Ltd||Multi-stage CO2 removal system and method for processing a flue gas stream|
|US8292989||30 Oct 2009||23 Oct 2012||Alstom Technology Ltd||Gas stream processing|
|US8293200||29 Oct 2010||23 Oct 2012||Alstom Technology Ltd||Desulfurization of, and removal of carbon dioxide from, gas mixtures|
|US8312738||20 Nov 2007||20 Nov 2012||Exxonmobil Upstream Research Company||Integrated controlled freeze zone (CFZ) tower and dividing wall (DWC) for enhanced hydrocarbon recovery|
|US8329128||1 Feb 2011||11 Dec 2012||Alstom Technology Ltd||Gas treatment process and system|
|US8343445||18 Mar 2009||1 Jan 2013||Alstom Technology Ltd||System and method for enhanced removal of CO2 from a mixed gas stream|
|US8354261||30 Jun 2011||15 Jan 2013||Codexis, Inc.||Highly stable β-class carbonic anhydrases useful in carbon capture systems|
|US8354262||30 Jun 2011||15 Jan 2013||Codexis, Inc.||Chemically modified carbonic anhydrases useful in carbon capture systems|
|US8377173||7 Nov 2008||19 Feb 2013||The University Of Akron||Amine absorber for carbon dioxide capture and processes for making and using the same|
|US8388738||14 Nov 2008||5 Mar 2013||Basf Se||Method for removing carbon dioxide from fluid flows, in particular combustion exhaust gases|
|US8398749||12 Dec 2006||19 Mar 2013||Basf Se||Process for the recovery of carbon dioxide|
|US8414853||18 Mar 2009||9 Apr 2013||Alstom Technology Ltd||System and method for enhanced removal of CO2 from a mixed gas stream via use of a catalyst|
|US8420364||30 Jun 2011||16 Apr 2013||Codexis, Inc.||Highly stable beta-class carbonic anhydrases useful in carbon capture systems|
|US8470077||17 Nov 2011||25 Jun 2013||Alstom Technology Ltd||Low pressure stripping in a gas purification process and systems thereof|
|US8512989||20 Dec 2012||20 Aug 2013||Codexis, Inc.||Highly stable beta-class carbonic anhydrases useful in carbon capture systems|
|US8518148||8 Jul 2011||27 Aug 2013||Babcock & Wilcox Power Generation Group, Inc.||Integrated flue gas dehumidification and wet cooling tower system|
|US8518156||3 Aug 2010||27 Aug 2013||Alstom Technology Ltd||Method and system for regenerating a solution used in a wash vessel|
|US8541619||9 Sep 2011||24 Sep 2013||Steag Energy Services Gmbh||Method for purifying flue gases from combustion plants and then producing urea|
|US8569031||20 Dec 2012||29 Oct 2013||Codexis, Inc.||Chemically modified carbonic anhydrases useful in carbon capture systems|
|US8623307||14 Sep 2010||7 Jan 2014||Alstom Technology Ltd.||Process gas treatment system|
|US8623314||21 Feb 2012||7 Jan 2014||Alstom Technology Ltd||Chilled ammonia based CO2 capture system with ammonia recovery and processes of use|
|US8663364||1 Jul 2010||4 Mar 2014||L'Air Liquide, Société Anonyme pour l'Étude et l'Éxploitation des Procédés Georges Claude||Method of obtaining carbon dioxide from carbon dioxide-containing gas mixture|
|US8690992||19 Mar 2013||8 Apr 2014||Alstom Technology Ltd||Low pressure stripping in a gas purification process and systems thereof|
|US8703082||17 Dec 2007||22 Apr 2014||Sinvent As||Method for capturing CO2 from exhaust gas|
|US8728209||2 Aug 2011||20 May 2014||Alstom Technology Ltd||Method and system for reducing energy requirements of a CO2 capture system|
|US8734569||1 Jul 2010||27 May 2014||L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude||Method of obtaining carbon dioxide from carbon dioxide-containing gas mixture|
|US8758484||25 Jun 2008||24 Jun 2014||Alstom Technology Ltd||Removal of carbon dioxide from flue gas with ammonia comprising medium|
|US8864879||30 Mar 2012||21 Oct 2014||Jalal Askander||System for recovery of ammonia from lean solution in a chilled ammonia process utilizing residual flue gas|
|US8926927||19 Jun 2009||6 Jan 2015||Shell Oil Company||Process for the removal of carbon dioxide from a gas|
|US9028784||15 Feb 2011||12 May 2015||Alstom Technology Ltd||Process and system for cleaning a gas stream|
|US9149761||30 Nov 2010||6 Oct 2015||Exxonmobil Upstream Research Company||Removal of acid gases from a gas stream, with CO2 capture and sequestration|
|US9162177||25 Jan 2012||20 Oct 2015||Alstom Technology Ltd||Ammonia capturing by CO2 product liquid in water wash liquid|
|US9174168||11 Nov 2010||3 Nov 2015||Alstom Technology Ltd||Flue gas treatment system|
|US9278306||16 Mar 2007||8 Mar 2016||Basf Se||Process for contacting two phases whose contact is accompanied by heat evolution|
|US9428449||23 Jun 2014||30 Aug 2016||Alstom Technology Ltd||Method of forming urea by integration of an ammonia production process in a urea production process and a system therefor|
|US9463410||14 Sep 2011||11 Oct 2016||General Electric Technology Gmbh||Trace component removal in CO2 removal processes by means of a semipermeable membrane|
|US9469547||16 Jan 2014||18 Oct 2016||Alstom Technology Ltd||Integrated carbon dioxide removal and ammonia-soda process|
|US9598993||19 Jun 2015||21 Mar 2017||Saudi Arabian Oil Company||Integrated process for CO2 capture and use in thermal power production cycle|
|US20100170397 *||25 Jun 2008||8 Jul 2010||Nader Padban||Removal of carbon dioxide from flue gas with ammonia comprising medium|
|Cooperative Classification||Y02E20/326, B01D53/62, F23J2215/50, F23J2219/50, B01D53/75, B01D53/1475, F23J15/06, Y02C10/04, B01D2252/102, F23J15/006, B01D2251/2062, Y02C10/06|
|European Classification||B01D53/14H6, B01D53/62, F23J15/06, F23J15/00P, B01D53/75|
|2 Mar 2006||AL||Designated countries for regional patents|
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