Approved and Issued by the Chemical Industry Vision2020 Technology Partnership An electronic copy of this plan can be found at: www.chemicalvision2020.org

Copyright Information The information in this document is meant to be distributed widely throughout the chemical industry and the broader research community. The authors encourage reproduction and dissemination of portions of or the entire document with attribution and without changes.

Acknowledgements This study was carried out by James A. Ritter and Armin D. Ebner under a subcontract with Oak Ridge National Laboratory (Managed by UT-Battelle, LLC for the Department of Energy under contract DE-AC05-00OR22725) and sponsored by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy, Industrial Technologies Program. The programmatic support of Dickson Ozokwelu, the Chemicals Industry of the Future team lead who funded this effort, is greatly appreciated. We would also like to thank members of the Chemical Industry Vision2020 Technology Partnership committee who contributed to this study: Francis Via of Fairfield Resources (Chair); Sharon Robinson of Oak Ridge National Laboratory (Vice Chair); Linda Curan of BP; Timothy Frank, Parick H. Au-Yeung, and John G. Pendergast, Jr. of Dow; Scott Barnicki of Eastman Chemical; Hans Wijmans of Membranes Research & Technology, Inc.; Krish R. Krishnamurthy and Stevan Jovanic of BOC; Dante Bonaquist and Neil Stephenson of Praxair, Inc.; Santi Kulprathipanja of UOP; Dilip Kathold of Air Products and Chemicals, Inc.; Charles G. Scouten of The Fusfeld Group; Brendan Murray of Shell; and Greg Chambers of GE. H. Lee Schultz and Borys Marriza of BCS, Incorporated participated in final preparation of this document.

This report was prepared as an account of work sponsored in part by agencies of the United States Government. Neither the United States Government, nor any agency thereof, nor any of their employees make any warranty, expressed or implied, or assume any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represent that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. This report represents the views and opinions of the chemical industry and not those of the United States Government or any agency thereof.


Carbon Dioxide Separation Technology: R&D Needs For the Chemical and Petrochemical Industries November 2007 iv .

................................................................................................................. 2 Overview of CO2 Emissions and Production Processes ..................................................................................................Carbon Dioxide Separation Technology: R&D Needs For the Chemical and Petrochemical Industries Table of Contents FOREWORD.............................................................................................. 37 SUPPORTIVE INFORMATION ON ENVIRONMENTAL CO2 EMISSIONS ............................................. 18 Membranes ........................................................................................................................................................................................................................... 25 Hybrid Membranes ............................................................................................................ 29 RECOMMENDATIONS FOR FUTURE R&D...................................................................................... 35 Long-Term Flow Sheet Augmentation with Adsorption and Membrane Processes .......... 10 Summary of Current Commercial Practices................................................ 17 Selective Adsorbents......... 1 CURRENT COMMERCIAL PRACTICES................................................. 32 Near-Term Adsorption Process Development.. 36 Long-Term Advanced Adsorbent Materials and Process Development for CO2 Removal .......................................................................................................................................................... 31 Near-Term Membrane Development......................................................................................................... 27 Conclusions from Background Survey .......................................................................................... 20 Facilitated Transport Membranes............... 7 Membrane Processes........................................................... 12 Adsorption Process Refinements ............................................................ ES-1 INTRODUCTION......................... 4 Absorption Processes .............................................................................................. 5 Adsorption Processes ............................................................................ 12 Sorption Enhanced Reaction (Periodic Adsorptive Separating Reactors) ........................................................................ 33 Near-Term Absorbent and Absorption Process Development ................................................................................................................................................................................................................................... x EXECUTIVE SUMMARY .......................................................................................................................................................................................................... 36 Long-Term Advanced Membrane Materials for CO2 Removal........................................................................................................................... 26 Hollow Fiber Gas-Liquid Contactors............ 9 Cryogenic Liquefaction Processes............................................................................ 20 Polymeric Membranes ....................................................................................... 23 Inorganic Membranes................ 31 Near-Term Adsorbent Development........................................................................................................................................................................................................................................................ 12 Adsorption ............................ 38 v ....................................... 2 CO2 Removal Processes...................................... 38 Main Sources of Industrial CO2 Emissions .............................. 11 EMERGING LITERATURE CONCEPTS.........................................................................

............................................... 51 Sulfur Recovery Processes........... 48 Natural Gas Production .................................................................................................................................................................... 59 Conceptual Flow Sheets for Additional Guidance..................................................................................................................................................... 41 Iron and Steel Manufacture ......................... 54 Fermentation to Produce Ethanol............... 50 Aluminum Manufacture ............................................................. 132 Glossary ........................................................................................................................................Combustion Processes ................................................................................................................................................................................. 45 Lime and Cement Production ............................................................. 56 Mitigation Approaches to Combat CO2 Emissions................................................................................................ Syngas............................. 53 Landfill and Coal Bed Methane Gases ...... 61 References.......................................... 133 vi .......................................................................................................... and NH3 Production ............................................................................................... 46 Hydrogen................ 71 Vision 2020 for the Chemical Industry Separations Committee Members.............................................................................................................. 39 Coal Gasification .......................... 56 Expanding the Definition of CO2 Capture Approaches used in Power Plants ............

............. ............... 97 Summary of 2002 U.......................................... 106 Major types of acid gas absorbent processes...... .............................................. 129 Typical capacities and gas flows for processes in Figures 4 to 14............................................................. 108 Typical capacities of commercial and developmental CO2 and CO selective adsorbents...... 105 Characteristics of key alkanolamines used in gas treating............. ..................... 130 Largest IGCC and NGCC plants in the world as of January 2000............................................................ 110 Permeabilities and permeances of membrane materials used for CO2 separations.......................S............. 99 Number of patents and peer review manuscripts per researcher or research group on CO2 related separation processes since 1995 and 2002....................... Table 2....S........... Table 11................ 111 Trans-membrane flux for different capillary hollow fiber membrane contactors reported in the literature........ ... 98 Average U.............................. ............ 104 Licensors of CO2 separation processes...................................................................................................S............................. CO2 emissions..... Table 9...... CO2 emissions....... and number of plants worldwide.....List of Tables Table 1............. ....................... 100 Number of patents per company on CO2 related separation processes since 1995 and 2002.............. Table 3.................................... Table 5............... production rate... ................ ................. Table 6............... 131 vii ............. ........ 109 Performances of various PSA cycle configurations investigated for CO2 concentration from flue gas.............................. Table 14......... Table 15. Table 12..... Table 13..... CO2 emissions per plant within several industries............ ...................................... 107 Number of papers since 2000 containing in the title the indicated alkanolamine and other absorbents for CO2 removal...................................... 1990 and 2004 Worldwide and U........... ......... ........... ..... ... Table 7.............. Table 8...................... Table 10............. 127 Typical molar fraction concentrations in each of the streams listed in Figures 4 to 14... Table 4.......... .............. .......... Table 16.......... type of process............

.. 53 Figure 13....... Flow sheet of a typical........... U......List of Figures Figure 1................... Industry 2002 CO2 emissions in MMt: non-energy related processes.. IGCC) plants for power generation/H2 production.................... and electric arc furnace (EAF).................. 51 Figure 12....... Flow sheet of a typical.......................................... Flow sheet of typical................ 2 Figure 2........................................... 50 Figure 11... Post-combustion. state-of-the-art stainless steel production plant consisting of a coke oven................................. .............. Industry 2002 CO2 Emissions in MMt .......................... 61 Figure 17............. flaring..................... combustion process that includes burners....................... ... ... 64 Figure 20............ .. Industrial..... 49 Figure 10..... blast furnace. 2002 CO2 emissions in MMt: Total........................................................... . U. 62 Figure 18............. 43 Figure 7...S. Pre-combustion and post-combustion approaches for capture and concentration of CO2 in the ammonia manufacture industry for streams 1 through 4 in Figure 9........................ state-of-the-art................................ incinerators.............................................. .......... 45 Figure 8.............. state-of-the-art coal gasification (also referred to as integrated gasification combined cycle............... state-of-the-art process for the manufacture of lime and cement.. 56 Figure 15............. Flow sheet of typical................ and oxyfuel combustion approaches for capture and concentration of CO2 in the stainless steel industry for the streams 1 through 4 defined in Figure 7……… ........................... 38 Figure 4...…………… ........ U......... Pre-combustion approaches for the capture and concentration of CO2 in the coal gasification industry for stream 1 in Figures 5 and 6.......................... Flow sheet of a typical................... Post-combustion and oxyfuel-combustion approaches for the capture and concentration of CO2 in combustion processes for stream 1 in Figure 4...... etc........ Transportation.............. 60 Figure 16.. IGCC) plants for power generation/syngas production....................... Flow sheet of a typical.... sinter plant........ The three conventional approaches for CO2 capture in the fossil fuel power plant industry are defined here in broader terms for use in any CO2 producing industrial process (Figures 16 to 23).........S..... pre-combustion.... Flow sheet of typical.. 63 Figure 19.................................................. Residential and Commercial.................. basic oxygen furnace (BOF)........... state-of-the-art fermentation process for the production of ethanol typically out of corn-starch............. state-of-the-art H2 or NH3 production plant..................................................................... utility boilers......................................................... 65 viii . ...... Flow sheet of a typical............................................... Flow sheet of a typical............................................... Post-combustion and oxyfuel-combustion approaches for capture and concentration of CO2 in the cement and lime industry for stream 1 defined in Figure 8. Flow sheet of a typical........... 3 Figure 3...... Flow sheet of a typical.. state-of-the-art a) solid waste landfill gas recovery process and b) coal bed methane gas recovery process........................................ state-of-the-art Claus-SCOT process for the production of sulfur from a stream rich in sulfur-bearing compounds.... 40 Figure 5.......... ... state-of-the-art process for the production of natural gas....................... state-of-the-art processes for the manufacture of aluminum................. state-of-the-art coal gasification (also referred to as integrated gasification combined cycle............................... Electric Power.................... ..................S... 47 Figure 9.……… ...................... 55 Figure 14.................. 42 Figure 6...............

............................. Post-combustion and pre-combustion approaches for capture and concentration of CO2 in the aluminum industry for the streams 1 and 2 defined in Figure 12... and landfill gas industries for stream 1 defined in Figures 10 and 13.......... ......... 18.. 20 and 22 that contain N2.... 70 ix ... CO or CH4 as permanent gases (PG) as well as sulfur bearing compounds (e.......................................... coal...................................... .. COS................................... O2...... 66 Figure 22........ ........ CO or CH4 as permanent gases (PG) in addition to CO2....................................................... 68 Figure 24. 67 Figure 23..................................... 68 Figure 25........) in addition to CO2.... Post-combustion approach for capture and concentration of CO2 in the ethanol production industry for stream 1 defined in Figure 14.. Flow diagram representing a CO2 separation and concentration step for streams in Figures 17.. Pre-combustion approach for capture and concentration of CO2 in the natural........... O2.....................................g.............................. 19 and 22 that contain N2.................. CO or CH4 as permanent gases (PG) as well as significant concentrations of H2 in addition to CO2.................. etc. 69 Figure 26.. Flow diagram representing a CO2 separation and concentration step for streams in Figure 21 that contain N2..... O2............................Figure 21................. H2S................................. 18.......... Flow diagram representing a CO2 separation and concentration step for streams in Figures 16..... ....

is directed to commercial. industrial CO2 production. Several chemical production processes were selected for review and two topics. hydrogen and carbon dioxide separations. formed a committee to identify research and development needs for separation technology to drive equilibrium processes for the Chemical and Petrochemical Industry. x . This report. were developed into full studies. the second of two. This committee was established in June 2004 and chartered with the responsibility to define the drivers and R&D requirements of the chemical and petrochemical industries for equilibrium separations.FOREWORD The Vision2020 Technology Partnership. an industry-led organization for accelerated innovation and technology development.

appear rather apparent. For near-term adsorbent development: 1) Develop high-capacity.EXECUTIVE SUMMARY A Chemical Industry Vision 2020 sub-committee was established in June 2004 and chartered with the responsibility of identifying research and development needs for separation technology to drive equilibrium processes for the Chemical and Petrochemical Industry. and sequestration.2%) of U. Full details including scope of scientific space to be explored and justifications are provided in the report starting on page 31. other means besides CO2 consumption must be considered to mitigate the CO2 emissions. In reviewing this section. CO2-selective adsorbents to operate at elevated temperatures and pressures in the presence of sulfur and steam.S.e. The overall goal of this review is to foster the development of new adsorption. There are many programs outside the scope of this report addressing these issues (e. 3-4 mol/kg. Current industrial practices are summarized with the use of flow sheets. and makes recommendations for future research.g. transport. and membrane technologies to improve manufacturing efficiency and reduce CO2 emissions. The need for improving the energy intensive separation processes involving CO2 are well recognized. new power plant design. A very small portion (0. Department of Energy has shown that the separation of CO2 represents 75% of the overall cost associated with its separation.S. 7 – 15 years) research. ES-1 . Kyoto protocol. is designed to summarize and present recommendations for improved CO2 separation technology for industrial processes. Energy efficient CO2 separation technologies with improved economics are needed for industrial processing and for future options to capture and concentrate CO2 for reuse or for sequestration.. The U. the second in a series. The recommendations of this Vision 2020 Chemical Industry team are summarized below. The growing concern about global warming is placing greater demand on improving energy efficiency and reducing CO2 emissions. The first report on hydrogen manufacture and separation has been published as a review article and as a DOE report [1]. absorption. CO2 emissions is separated for industrial or commercial use.. 2) the current commercial separation technologies and 3) emerging adsorption and membrane technologies for CO2 separation.e. Hence. This report. carbon tax structure. at times. please be patient as a summary of recommendations can. This report provides an overview of 1) the principal CO2 producing processes. Flow sheets of existing CO2 producing processes are provided for guidance and new conceptual flow sheets have also been designed. sequestration). 0 – 5 years) and longer-range (i. This study focuses on the chemical and petrochemical industries. storage. Recommendations are set-forth for future R&D in CO2 separation and recovery for both nearterm (i.

amines). where a pure heavy product like CO2 is more desirable than pure light product such as H2. 6) Develop CO2 permselective hybrid mixed-matrix membranes with improved selectivity. 5) Develop more selective absorbents. CO2 over sulfur species.g. develop new PSA cycles that take advantage of the heavy reflux concept. N2.For near-term membrane development: 1) Develop CO2 permselective polymeric glassy or rubbery membranes with CO2/H2 selectivity of >15-20. Rethink bed designs for rapid heating and cooling. 4) Develop CO2 permselective inorganic membranes with selectivity of > 15-20. natural gas and coal bed methane). 2) Specific Goal: Develop polymeric glassy or rubbery membranes for CO2/CH4 that have selectivity > 50.g. For example. for processes with H2S and COS species present (e. and stability. For near-term adsorption process development: 1) Develop new pressure swing adsorption (PSA) cycle designs that take advantage of new or existing CO2 selective adsorbents.. 4) Develop absorbents that are stable to trace contaminants (e. 3) Develop CO2 permselective facilitated transport membranes that can operate in the absence of water for long periods of time. 2) Develop new regeneration techniques. For long-term flow sheet augmentation with adsorption and membrane processes: 1) Develop hybrid technology for H2 production (e.. possibly temperature swing adsorption (TSA) or PSA/TSA hybrid cycles. to be conducted at high pressure. 2) Improve efficiency for thermal management in the design of TSA and PSA/TSA hybrid cycles. for steam methane reforming by combining the reactor with a CO2 selective adsorbent and an H2 permeable membrane). 3) Develop absorbents that work on high temperature gases. 2) Develop new CO2 adsorbent and membrane technologies that are amenable to integrated gasification combined cycle (IGCC) and related power and chemical production technologies with CO2 sequestration as a potential long term objective. For near-term absorbent and absorption process development 1) Develop absorbents with improved capacity and greatly improved heat of absorption.g. and CH4. with high flux and high temperature stability. 7) Develop CO2 permselective hollow fiber membrane contactors with improved permeance and stability. permeance. ES-2 .. as opposed to thermal or vacuum regeneration. 5) Develop CO2 permselective selective surface flow membranes with higher CO2 selectivity with H2. double the current commercial membrane CO2 flux. resists plasticizing and is stable to heavy oil.

For long-term advanced adsorbent materials and process development for CO2 removal: 1) Develop advanced structured adsorbent materials for use in rapid-cycle PSA. ES-3 . mass transfer limitations).investigate the relationship between adsorbent particle size. possibly coupled with adsorption or membranes processes.quantify the effect on cycle time and bed sizes for a forced temperature swing/PSA cycle. and hybrid cycles. 5) Develop improved CO2 separations with sorption enhanced reaction processes using PSA. and accelerated cycle times (i.3) Specific Goal: Develop hybrid technology. 4) Develop TSA and or PSA/TSA hybrid cycles with improved materials . TSA. that removes CO2 by chemical reaction in the chemical process. surface properties..e. For long-term advanced membrane materials for CO2 removal: 1) Develop next generation membrane materials with high selectivity for CO2 (> 100). operating at high temperatures and pressures and with resistance to fouling and cracking or embrittlement. 2) Develop improved designs for rapid-cycle PSA for CO2 capture and concentration with both heavy and dual reflux cycles steps. 3) Reduce cycle time in rapid PSA to improve throughput .

ES-4 .

This report provides an overview of 1) the principal CO2 producing processes.S. and sequestration. are needed to accelerate these developments? These questions constitute the overall focus and direction of this study. While reading this report. Carbon dioxide production is ubiquitous in combustion. sulfur tolerance)? What is the estimated time of development for a new commercial application without additional action? What will it take to deliver a new commercial application in 3-5 years? What will it take to accelerate these developments? What breakthroughs.. Department of Energy has shown that the separation of CO2 represents 75% of the overall cost associated with its separation. while most is produced in the generation of power through the combustion of fossil fuels. and membrane technologies for CO2 separation.g. transport. if any. Direct answers are dependent on specific applications. The U. storage. costs. absorption. Some CO2 is produced as a by product of chemical manufacturing. absorption. Furthermore. The underlying economic and environmental drivers are encouraging the development of more energy-efficient CO2 separation technologies. This report provides specific recommendations for improving only adsorption. and membrane technologies for CO2 separation. energy generation and manufacturing processes. and 3) the emerging adsorption. more energy-efficient CO2 separation processes are needed.INTRODUCTION The overall goal of this review is to foster the development of new adsorption. it is recommended that the following questions be kept in mind: • • • • • • What are the generic technologies with the most promise? What are the high-level technical issues to be overcome in commercializing a new CO2 separation technology (e. and membrane technologies for CO2 separation. The growing concern about global warming is placing greater demands on improving the energy efficiency of processes and on reducing CO2 emissions. 2) the current commercial separation technologies. Hence. and makes recommendations for future separations research and development. recommendations have been developed for certain technologies that might meet the CO2 separation challenge. 1 . absorption.

The general concern is that the continued production of CO2 will 2 . an overview of sources CO2 and environmental emissions is provided in the supportive information section starting on page 38.CURRENT COMMERCIAL PRACTICES This section provides an overview of the sources of CO2 emissions and CO2 production processes. These are absorption. The four most widely used. Total US 2. Transportation 4. All four processes are commercially important. Transportation. Electric Power. Overview of CO2 Emissions and Production Processes The literature on the production and emissions of CO2 from the chemical and petrochemical industries is rapidly expanding. 2002 CO2 emissions in MMt: Total. adsorption. as shown in Figure 1. Electric Power 3. 5752 2250 1868 1042 365 227 % 39 32 18 6 4 U. demonstrating that CO2 separation and capture technologies are of growing importance. commercial CO2 removal processes are reviewed. membrane. Residential Homes 6.S. Absorption is the most prevalent of CO2 removal methods. Residential and Commercial While the focus of this report is on industrial separation technology associated with the purification of gas streams containing CO2 or the production of CO2. 7000 6000 5000 4000 3000 2000 1000 0 1 2 3 4 5 6 1. Commercial Buildings Figure 1. Most of the CO2 emissions originate from the generation of electricity. and cryogenic processing. Industrial Processes 5. Industrial.

flue gas from fossil fuel combustion processes.043 million metric tons (MMt). lime and aluminum production. 3 . By 2015 this number is expected to increase by 23% to 33. Table 2 provides a breakdown of the leading industries that produce the most (non-energy related) emissions.2 11.752 MMt of CO2 emissions or about 22% of the world’s total. total. Industry 2002 CO2 Emissions in MMt . and natural gas wells [4].S. sodium phosphate manufacture. In 2002 the U. Process Generated 4.284 MMt. processes including from electric or other power generation. and with the rise of developing countries.685 MMt of CO2 or about 29% of the U.S. Commercial Use 1685 1486 192 7 % 88. and by 2025 it is expected to increase by 43% to 38. development efforts are underway to improve the efficiency of production and separation possesses and to mitigate CO2 emissions. a 26% increase over the 1990 emissions. Figure 2. electric power generation was responsible for 2. natural gas.4 Figure 2.S. 3. was responsible for 5. It is no surprise that CO2 emissions track very well with population growth. The main sources of commercial CO2 include synthetic ammonia and hydrogen plants.S. The energy related CO2 emissions are also given for comparison. As shown in Table 2 industrial production accounts for 29% of CO2 emissions. These numbers are shown in Figure 1. fermentation. compared to that produced solely by the process and that consumed by other processes. however. Only 11% of industrial emissions are associated with chemical or petrochemical processing. Table 1 (tables begin on page 97) provides a summary of worldwide CO2 emissions. etc.250 MMT. Table 2 summarizes the CO2 emissions from various U. Overall. Hence. When adding the CO2 equivalence for the electricity consumed by industry.adversely impact global warming [2]. etc. or 39% of the total. It appears that the CO2 emissions from the energy generated to support the chemical and petrochemical 1800 1600 1400 1200 1000 800 600 400 200 0 1 2 3 4 1. Industrial Processes 2. cement. then industry was responsible for 1. industrial activities accounted for 1. ammonia. reveals that 88% of these emissions are associated with energy generation.S. These CO2 industries include iron and steel. sources in 2002 with a further breakdown for fuel type. limekiln operations.4 0. It is noteworthy that about 98% of the CO2 emissions were from burning fossil fuels to produce energy.790 MMt [3]. U. Steam. Energy. which in 2004 were estimated at 27. U.042 MMt of CO2 emissions or about 18% of the total. steam.

N2. flue gas. 8) oil well secondary recovery. in 2004 [5]. 11% (see Figure 2). other means besides CO2 consumption must be considered to mitigate the CO2 emissions from industrial and energy-related sources. it is clear from the CO2 production and emission numbers (Figure 2) that the industrial consumption of CO2 constitutes only a negligible fraction of all the CO2 produced by human activities and it is doubtful that this fact will change in the foreseeable future [6. and even landfill gas and coal bed methane gas. This complication is generally not present in natural gas. new power plant design. 5) foundry-mold preparation. flue gas.. but. In fact. H2O. and much of this CO2 finds its way to the atmosphere because the end use does not consume the CO2. 7) mining operations.7]. 88% vs. Hence. None of the other commercial uses of CO2 actually consume CO2. In spite of the Kyoto Protocol and potential penalties and taxes associated with CO2 emissions. 9) rubber tumbling. CO2 is being removed from a valuable product gas. coal bed methane and some landfill gases contain O2 that can interfere with certain CO2 separation systems. other contaminants generally must be removed or handled. Most of these processes were developed for natural gas sweetening or H2 recovery from syngas. The main uses of CO2 include 1) beverage carbonization. 6) greenhouses.e. most landfill gas. and in most cases there is no place to put the CO2 once it is captured. There are many programs outside the scope of this report addressing these issues (e. Along with CO2.. 4) food freezing and processing. as a saleable product. At the moment these processes are simply too expensive to use. where it is eventually emitted to the atmosphere as a waste by-product. and in most cases. However. Table 3 illustrates average point-source (plant) CO2 emissions for a number of industrial sectors. Natural gas. CO2 is recovered from a process gas. H2S. In addition. and 12) extraction processes [4]. CO2 is recovered simply to prevent it from being released into the atmosphere. reacted to form a different carbon-containing chemical). 10) therapeutical work. 2) chemical manufacture.g. commercial CO2 gas treatment plants are usually 4 . and C2+ hydrocarbons and trace elements in various oxidation states. CO2 production was nineteenth on the list of the top 50 highest volume chemicals produced in the U. only in the manufacture of chemicals (#2) is CO2 consumed (i. there is little if any use of commercially available CO2 capture processes for this purpose. Recently. A very small portion of the produced CO2 is recovered for industrial or commercial use. Second. of the twelve uses listed above. Most significantly. this necessarily requires sequestration of the recovered CO2. as mentioned above. For these reasons. landfill gas. CO2 Removal Processes There are three incentives to remove CO2 from a process stream. First. Kyoto protocol. or H2 systems. purification of this CO2 may be required.S. interest has built on the capture of CO2 from flue gas. and coal bed methane gas systems are more complex than the typical H2 system. such as in ethanol production. sequestration).industries overwhelms the CO2 emissions from the actual chemicals or petrochemical processes. Depending on the application. such as H2. only a modest fraction of the CO2 produced is marketed as a saleable product. 3) firefighting. Third. Processes to remove CO2 from gas streams vary from a simple once-through wash or treatment operations to complex multistep recycle systems. carbon tax structure. 11) welding. Among these are particulates. Nevertheless.

Table 7 lists the most widely used absorbents. H2.integrated gas processing systems. diisopropanolamine (DIPA). cement. combinations of physical solvents and reactive absorbents may be used in tandem. Four different CO2 removal technologies are widely practiced in industry. 2) adsorption. methyldiethanolamine (MDEA). the production of natural gas requires the removal of CO2 in order to be effectively utilized). Ethanolamine has the highest capacity and the lowest molecular weight. 5 .g. Some commonly used physical solvents are methanol (Rectisol Process) and glycol ethers (Selexol Process). Ammonia and alkaline salt solutions are also used as absorbents for CO2. Table 8 also lists the major types of CO2 and acid gas absorption processes that are commonly used in gas treating. A variety of liquid absorbents are being used to remove CO2 from gas streams. and aluminum industries and from combustion is virtually non-existent. In many industrial applications. in all cases solvent recycling is energy and capital intensive. Absorption processes generally can be divided into two categories. but only at high pressures where solubility becomes appreciable. Tables 4 and 5 provide information on CO2 removal technologies in terms of the number of patents and or peer-reviewed articles published by a company or research team since 1995 and since 2005. utilize absorption processes for removing CO2 and or acid gases. 3) membranes. syngas. For these applications alkanolamines are commonly used as reactive absorbents. Physical absorption processes are those where the solvent only interacts physically with the dissolved gas.. These are 1) absorption. the use of CO2 scrubbers for the production of CO2 from the iron and steel. natural gas. as well as coal gasification. Absorption Processes The overwhelming majority of CO2 removal processes in the chemical and petrochemical industries take place by absorption (see Table 6). Table 6 lists the licensors of CO2 separation processes as of 2004 [9]. Processes where the solvent chemically reacts with the dissolved gas are referred to as chemical absorption processes. Here a solvent is used as an absorbent with thermodynamic properties such that the relative absorption of CO2 is favored over the other components of the gas mixture. These include monoethanolamine (MEA). and 4) cryogenic processes [8]. Other examples include the removal of CO2 from the circulating gas stream in ammonia manufacture or ethylene oxide manufacture. The chemical process industries (CPI) removes CO2 to meet process or product requirements (e. Water is used as a CO2 absorbent. However. Tables 7 and 8 compare key properties of some of the important alkanolamines used in acid gas treating. Of the CO2 producing processes listed above. As far as the authors are aware. and NH3 production. few are designed simply for CO2 removal. lime. It offers the highest removal capacity on either a unit weight or a unit volume basis. both chemical and physical. and diglycolamine (DGA). diethanolamine (DEA).

etc. Thus. the by-product is additional CO2. if any. More serious is the MEA loss by evaporation. where absorption processes are being used. and very low vapor pressure. using MEA to meet pipeline specifications for H2S may be difficult. If water gas shift is used to make more H2. DIPA can remove COS and is selective for H2S removal over CO2 removal. they lead to different products that cause fewer filtration and plugging problems. As a result. for synthetic natural gas (SNG) production via coal gasification followed by methanation. MDEA selectively removes H2S in the presence of CO2. for making methanol or acetic acid). Diglycolamine has the same reactivity and capacity as DEA. has good capacity. ammonium bicarbonate. as discussed above. MEA also reacts with CO2 to give a series of products that lead to slow losses of this alkanolamine. Recovery of the CO2 requires treating a gas stream rich in CH4 and H2O. The most commonly used treating solutions are aqueous solutions of the ethanolamines or alkali carbonates. syngas and NH3 production plants. although a considerable number of other treating agents have been developed in recent years. Coal gasification to produce syngas (mostly CO + H2) also yields some CO2 that generally must be removed before using the syngas (e. Absorption processes similar to those used in H2. and it contains a variety of other gasous species and particulates that make CO2 recovery difficult and expensive.5+ vol% pure. the flue gas is very hot. some CO2 is recovered. syngas and NH3 production via methane stream reforming is recovered using hot carbonate absorption or MEA absorption. Also.g.. with a lower vapor pressure and lower evaporation losses. MEA systems generally are capable of recovering a CO2 stream that is 99. a hot carbonate solution or one of the physical solvents is economical preferred. Here the scrubber delivers a high-purity CO2 product which requires little. CO2 is being recovered from flue gas for commercial use [9]. Nevertheless. saleable CO2 is being recovered from H2. or when only partial removal is necessary. syngas and NH3 production also are used in coal gasification. flaring. incineration. good reactivity. Indeed. The hot carbonate systems used in many ammonia plants typically afford 95-97 vol% CO2 byproduct. DEA has a lower capacity than MEA and it reacts more slowly. Most of the newer treating agents rely on a combination of physical absorption and chemical reaction. utility boilers. By-product CO2 from H2. When only CO2 is to be removed in large quantities.Natural gas is treated to remove the acid gas constituents (H2S and CO2) by contacting the natural gas with an alkaline liquid. but reacts irreversibly with COS and CS2. contain significant amounts of CO2. In addition to the main desired. as illustrated in Tables 6 to 8. readily-reversible product. DIPA is used in the Sulfinol and Shell Adip processes to treat gas to pipeline specifications. Triethanolamine has been almost completely replaced in sour gas treating because of its low reactivity toward H2S. this CO2 is generally of low quality because its concentration tends to be low. However. Its vapor pressure is much higher that those of the other compounds in Table 7. MEA has good thermal stability. A train of separation and purification equipment is being used. further purification. Although its reactions with COS and CS2 are slower. with the CO2 being removed via MEA absorption 6 . MDEA is a preferred solvent for gas treating. Flue gas from combustion processes associated with burners.

titanosilicate molecular sieves.technology. Mitsubishi Heavy Industries Ltd. has 24 Econamine FG plants operating worldwide and producing a saleable CO2 product for both the chemical and food industries. With CO2 emissions becoming more of a concern worldwide. a review of the recent literature on absorption processes for the removal of CO2 and other acid gases from process streams would be quite valuable. fermentation ethanol. the low temperature CO shift reactor and the methanation reactor. the family of amines is clearly dominant. NH3. CO2 adsorption capacities of typical commercial adsorbents are given in Table 10. As of April 2005. the adsorbents include activated carbons for sulfur compounds and trace contaminant removal. This eliminated the CO2 scrubber. The adsorption processes include pressure swing adsorption (PSA). and 0. 100 ppmv CH4. A review of the recent literature identified about 230 articles since 2000. new H2 plants were being built with PSA units as the main H2 purification process. and hybrid PSA/TSA. The PSA unit offers advantages of improved H2 product purity (9999. temperature swing adsorption (TSA). and activated carbons. and 5A zeolite for 1 Kansai-Mitsubishi proprietary Carbon Dioxide Recovery Process 7 . silica gel or alumina for water. Randall Gas Technologies. which was developed in the 1970s and 1980s for enhanced oil recovery [8]. has four installations of similar technology operating on coal fired boilers. It is noteworthy that a recent review article on this subject was not found during this search. Although other reactive absorbents are represented. Modern PSA plants for H2 purification generally utilize layered beds containing 3 to 4 adsorbents (e.. Two of these plants produce chemical grade CO2 and the other two plants produce food grade CO2. natural gas. Adsorption Processes Only a few classes of adsorbents and adsorption processes are being used to remove CO2 from gas streams. and combustion are beginning to use adsorption processes for removing or purifying CO2. they have agreed to license two KD CDR Process1 plants to a fertilizer company in India. activated carbon for CO2. Clearly. also has commercialized a flue gas CO2 recovery process. 10-50 ppmv carbon oxides.0 vol% N2) with capital and operating costs comparable to those of wet scrubbing. By-product CO2 from H2 production via methane stream reforming is recovered using PSA in lieu of absorption. and with absorption processes dominating CO2 removal from industrial streams. making them the world’s largest CO2 recovery plants. It appears that these are the only examples of marketing flue gas CO2 recovery technology.g. silica gels for light hydrocarbon removal. Other classic adsorbents are being used to remove contaminants from CO2 streams destined for commercial use. only H2.99 vol% H2. bauxite. and silica gels for moisture removal. These adsorbents include aluminosilicate zeolite molecular sieves. Of the CO2 producing processes listed above. In the early 1980s. the literature on the subject of CO2 removal has grown substantially in the last few years. Each plant can capture 450 metric tons per day of CO2. and activated aluminas. Table 9 lists the number of papers and the corresponding absorbent that was studied. ABB Lummus Global Inc. In this case. syngas. KS-2 and KS-3). based on their newly developed and proprietary hindered amine solvents (KS-1.1-1. Fluor Enterprises Inc.

absorption. Since landfill gas and coal bed methane gas are somewhat similar in composition to natural gas. PSA systems are under development to process this tail gas into H2 and CO2 rich streams. The crude by-product is typically 99. and cryogenic and membrane separation. But the product is wet (saturated with water at ambient temperature) and not odor-free. Fermentation to produce ethanol has recently emerged as a major source of CO2 by-product for industrial use. Axens has over 60 installations operating worldwide that treat a variety of natural gas and industrial process streams [9]. Axens has commercialized natural gas purification technology. they yield a by-product CO2 stream that is only about 50 vol% pure. The gas is finally dried with activated alumina. and N2 removal). When destined for large-scale industrial use (urea. including adsorption.. However. a train of separation processes. To remove CO2 from coal bed methane. The molecular gate adsorption technology commercialized by Engelhard Corporation uses a titanosilcate adsorbent combined with a PSA process in a vacuum swing adsorption mode to remove N2 and/or CO2 from natural gas streams. or silica gel before compression and cooling to the liquid or solid form. Hydrogen recovery depends on the desired purity. The composition of natural gas varies widely depending on the location of the well. and organics. Low purity makes this tail gas stream less attractive as a commercial CO2 source. bauxite. as described in detail above. PSA technology is beginning to supplant some of the absorption technology in natural gas treatment. but ranges between 60 and 90%. The recovery of CO2 from flue gas by adsorption technology is not commonly practiced by 8 . N2. they are included here for convenience. with the tail gas (i. Similarly. The alumina removes trace and bulk contaminants in the natural gas other than CO2 through both chemisorption and physisorption mechanisms. Because of the complexity and variability of the composition of natural gas. SO2. The CO2 concentration in natural gas varies between 3 and 40 vol%. Engelhard Corporation uses molecular gate adsorption technology with a more traditional PSA mode with compressed feeds ranging in pressure from 80 to 800 pounds per square inch gauge (psig) [10].8% pure CO2 on a dry basis. the purification is not as exacting as it is for food grade CO2. etc. Ten of these units are being built and three are in operation for upgrading methane from abandoned coal mines [10]. especially in the so called shut-in natural gas wells that previously contained too much N2 to justify processing. the CO2 is usually washed with a simple water scrubber to remove water soluble compounds. based on alumina and zeolite molecular sieve adsorbents and a TSA regeneration mode. from four to sixteen columns are used in tandem. Although PSA systems are increasingly used for H2 recovery.). Two of these units were in operation as of 2004 [9]. CO. enhanced oil recovery. Depending on the production volume requirements. and H2) generally being used as fuel for the reformer. CO2. industrial inerting. may be used to process it into pipeline quality methane. the desorbed gas containing H2O. CO. The PSA unit is operated at ambient temperature with a feed pressure ranging between 20 and 60 atm. as discussed later in the Emerging Literature Concepts section (see page 12). After recovery.CH4. CO2 traditionally has been removed using an amine-based scrubbing process.e. The zeolite molecular sieve serves to remove CO2 and other contaminants via physisorption. but it could be as high as 80 vol%. CH4. It is then treated with activated carbon to remove traces of H2S.

By the end of the 1980s companies such as Natco (Cynara). CO2 is a very small gas molecule.8 Å).industry. the membrane market devoted to CO2 separation from natural gas is about 20%. the elevated processing costs associated with regeneration and phase change are eliminated. The first commercial cellulose acetate membrane units for CO2 removal from natural gas were implemented only few years after the introduction in 1980 of the first commercial PRISM membrane air separation system developed by Monsanto [14. Membranes are used in situations where the produced gas contains high levels of CO2. to a lesser extent landfill gas production.3 Angstrom units (Å)) than lighter gases. Today. Finally. which is especially suitable for retrofitting applications. polyimides. As a consequence. Hence. which is only 2% of the total separations market for natural gas. the CO2 appears not to be used for commercial applications. membrane systems involve small footprints compared to other processes and require low maintenance. Neither the flow sheet nor the purity of the recovered CO2 is known. Membrane systems potentially or actually commercialized for gas separations are listed in Tables 4 and 5. syngas.. CO2 also has a relatively high molecular weight and a large quadruple moment. Membranes are an appealing option for CO2 separation.15]. They are also compact and lightweight and can be positioned either horizontally or vertically. it neither requires a separating agent nor involves phase changes. However.64 Å) and CH4 (3. UOP (Separex) and Kvaerner (Grace Membrane Systems) were producing membrane plants for this purpose. 3. mainly because of the inherent permeating properties of this species. more selective polyimides and only recently polyaramides were slowly introduced to displace the old cellulose acetate systems. Currently. with a smaller kinetic radius (i. only natural gas production.46 Å). N2 (3. molecular sieves. and several other inorganic materials. In addition. a key sensitivity with these current membranes is that they must be protected from the heavier C5+ hydrocarbons present in wet 9 . and polyaramides). as shown in Table 6. the modular aspect of membrane units allow for multi-stage operation and linear scale up costs. but. Membrane Processes In general. First. These properties give rise to very high CO2 permeation rates and selectivities over many other gas species. such as glassy and rubbery polymers.59 Å) and H2 (2. sometimes even higher than H2 and He. and NH3 production are beginning to use membrane processes for removing or purifying CO2. The only example was obtained from a recent report in the literature that indicated CO2 is being recovered from flue gas commercially using a layered PSA bed containing X and A type zeolites and activated carbon in Japan [11]. Of the CO2 producing processes listed above. and H2. CO2 is a fast diffusing gas in many membrane materials.89 Å) are smaller than CO2. only He (2. Amine-based absorption processes dominate this market.e. In fact. A few years later. such as O2 (3. among permanent gases. membrane technology for separating gas streams is attractive for many reasons [1219]. enabling it naturally to adsorb more strongly to or dissolve at much higher concentrations in these membrane materials compared to many other gas species. commercial membrane technology for CO2 separation is largely based on glassy polymeric materials (cellulose acetate. with the number commercialized given in Table 6. On the other hand.

Cryogenic separation of CO2 is most applicable to highpressure gas streams. As gleaned from above. Both are based on polymeric asymmetric membrane materials composed of a single polymer or layers of at least two different polymers. respectively. membrane processes. are used for this purpose. including ones with separating layers made of cellulose acetate. sheet-type contactor. consisting of H2 and CO2 with low concentrations of CO and CH4. which includes most of the industrial sources of CO2 emissions. such as water and heavy hydrocarbons. particularly in dilute gas streams. natural gas for use as a salable product are a relatively recent development. like those available in precombustion and oxyfuel combustion processes [2]. Cryogenic CO2 recovery is typically limited to streams that contain high concentrations of CO2. One exception is for the production of ethanol through fermentation. which can be readily transported. The disadvantages associated with the cryogenic separation of CO2 are the amount of energy required in refrigeration. Relatively pure H2 containing a very low concentration of CO2 leaves these units in the low pressure permeate stream. petrochemical. current membranes have been designed generally to remove unwanted CO2 from a desired product. with a lower limit of about 50 vol%. Air Products and Chemicals and Ube are marketing membrane systems for EOR and landfill gas upgrading.natural gas streams. polysulfone. that tend to freeze and block the heat exchangers. The PRISM system is based on a hollow fiber design and Polysep is a spiral-wound. for example. and the requirement to remove gases. The advent of enhanced oil recovery (EOR) projects using CO2 has changed this situation. can be used as fuel. Membranes for large-scale recovery of CO2 from. with the active polymer layer being a polyimide. Details about this cryogenic CO2 process are not readily available. This stream can be sent to a methanator for CO2 removal and further purification. It is not considered to be a viable CO2 capture technology for streams that contain low concentrations of CO2. Cryogenic Liquefaction Processes Recovery of CO2 by cold liquefaction has the advantage of enabling the direct production of very pure liquid CO2. liquefaction is generally practiced in this case to produce a highly pure liquid CO2 product. rather than to recover CO2 for its own value. A variety of membranes. For example. 10 . and polyimide. Natural gas fields in West Texas now recover CO2 that is pipelined to areas where it is needed for EOR. Both are used to recover H2 from refinery streams at purities ranging from 70 to 99 vol% and with recoveries ranging from 70 to 95%. Liquefaction technology for CO2 recovery is still incipient. Liquefaction is achieved by the dual action of external refrigeration and the Joule-Thompson effect that results from the compression and adiabatic expansion of the stream. however. such as the Polysep membrane systems developed by UOP and the PRISM membrane systems developed by Monsanto and now sold by Air Products and Chemicals [9] recover H2 from various refinery. Membrane units have also been commercialized for H2 purification in reforming processes (UOP. Exposure to these compounds immediately degrades performance and can cause irreversible damage to the membranes. In fact. but with a preferred concentration of > 90 vol%. and chemical process streams. The high-pressure retentate stream. Air Products and Chemicals).

For a more detailed review of CO2 emissions and sources. 11 . absorption. This report is designed to promote the development of new adsorption. An overview of the sources of CO2 emissions and CO2 production processes is provided to exemplify that although most of the CO2 emissions are from the generation of electricity. no commercial operational units of this technology have been reported. and cryogenic processing. Currently. membranes. Gas & Process Ltd. only ethanol production and H2. This technology exploits liquefaction to separate CO2 from H2 and other gases in the tail gas of a H2 purification PSA unit. absorption. Summary of Current Commercial Practices The four most widely used commercial CO2 removal processes are: absorption. Emerging concepts for new approaches in separation are highlighted in the next section of this report. Of the CO2 producing processes listed above. Tables 4 and 6 provide some information on the cryogenic systems that are described in the literature. Recently. However. Absorption is by far the most prevalent CO2 removal process. and membrane technologies for CO2 recovery and capture from commercial processes. industrial point sources can be significant. cryogenic CO2 recovery is increasingly being used commercially for purification of CO2 from streams that already have high CO2 concentrations (typically > 90%). and membrane processes in CO2 removal from industrial process streams are reviewed. That section is followed by recommendations for future R&D.Nevertheless. also developed a CO2 liquefaction process called CO2LDSEP. The uses of adsorption. see Supportive Information on Environmental CO2 Emissions section on page 38. Fluor Enterprises Inc. has commercialized a CO2 liquefaction process with around seven units installed worldwide. The process is assisted by membrane technology to treat streams with CO2 fractions greater than 90 vol%. Costain Oil. Special emphasis has been placed on fostering the development of separation technologies that are economically sound and effective under the operating conditions of CO2-producing processes. some of the information dates back a few decades. and NH3 production utilize (or are beginning to utilize) cryogenic processes for removing or purifying CO2. adsorption. syngas.

These are well known cyclic adsorption processes with many commercialized gas separation and purification applications. These include the H2.. Modifications to improve separation efficiency have included additional beds. a focus has been placed on emerging concepts in the separation sciences to overcome the limitations of current CO2 removal processes. Many opportunities are identified. To this end. TSA and PSA technologies). emerging literature concepts in adsorption and membrane technology for CO2 removal are reviewed and recommendations are set forth for future R&D. For this review. key factors must be considered: 1) the large scale and conditions of industrial production. To set forth recommendations for future R&D on CO2 removal processes. Adsorption Process Refinements Adsorption-based CO2 separation and capture technologies are based primarily on thermal and pressure swing regeneration processes (i.e. and NH3 production processes. which include landfill gas and coal bed methane gas. typically 7 to 10 beds [20] as many as 16 beds [21]. and 4) purity demands of gases involved. The concepts presented in these studies have the potential for both nearterm and longer-term impact on adsorption technology for the removal of CO2 from industrial process streams. Valuable guidance for this report has been provided by the Vision 2020 committee of industrial scientists active in the field and leading academic scientists referenced at the beginning and end of this report. 2) materials requirements. syngas. The performance. Another key to success in both PSA and TSA processes is matching the adsorbent with the cycle configuration. and reliability of the adsorbent used arekey to its successful commercial acceptance. and tanks for storing intermediate process streams 12 . sorption enhanced reaction processes (SERP) or periodic adsorptive separating reactors. cost. Adsorption The emerging literature concepts on the use of adsorbents and adsorption processes in the chemical and petrochemical industries that produce CO2 have focused on a few processes. and the natural gas production processes. multi-layer PSA process. including hybrid systems that have the potential for significant improvement in separation technology.EMERGING LITERATURE CONCEPTS The goal of this report is to achieve energy savings and to improve CO2 separation process performance and economics. Tables 10 and 11 respectively provide a list of adsorbents and PSA cycle configurations currently being investigated for CO2 removal. 3) economic goals and drivers. Emerging literature concepts on the use of adsorbents and adsorption processes to remove CO2 from flue gas generated from fossil fuel combustion also have been identified. A survey of the recent literature in these areas is given below. and selective adsorbents for CO2 are discussed. The latest developments in PSA and TSA process refinements. The potential for novel adsorbents and membranes and associated processes are outlined. Major breakthroughs in PSA technology for large-scale H2 purification and associated CO2 removal were realized in the early 1970’s with the development of a 4-bed.

between cycle stages. Along with these additional beds and tanks came more complex cycle sequencing to achieve higher throughputs with the same or even less volume of adsorbent distributed in the additional beds. Each bed in a PSA plant undergoes adsorption and regeneration cycle steps. These steps include 1) pressurization, 2) high pressure feed, 3) co-current depressurization, 4) counter-current depressurization, 5) counter-current purge (light reflux), and 6) several equalization (pressurization/depressurization) steps between two beds. Improvements, not only in H2 purification PSA plants but also in CO2 concentration and recovery PSA plants, can be realized by 1) further refinement of these cycle steps, 2) addition of new cycle steps, and 3) novel refinement of the cycle sequencing to create a more effective separation processes. The evolution of H2 PSA technology is a good example of how simple cycle modifications can have a significant impact on the process performance, and shows that intuition may not always be correct. Whysall and Wagemans of UOP [21] recently demonstrated that the duration of the purge step does not have to be equal to or less than the duration of the adsorption step and, by extending the purge step, the production capacity of a PSA H2 plant for the first time could exceed 110 Nm3/hr using 16 beds. Baksh et al. of Praxair Technology, Inc. [22,23] decreased the number of PSA beds with the judicious use of storage tanks to collect and reuse gas during cycle steps so as to increase H2 production per unit adsorbent. [23] also shows that the PSA process performance can be improved significantly by first removing N2 from the feed stream using modified (via cation exchange) X-type zeolite adsorbent, which also advantageously remove CO2. Xu and Weist of Air Products and Chemicals [24] modified the pressure equalization steps by using four steps with just six beds, and decreasing the cycle time for pressure equalization between beds [25]. Most of these changes are not obvious but have provided a path way for improved separations. Sircar and Golden [26] describe several other novel approaches to PSA cycle sequencing for both H2 purification and simultaneous H2 and CO2 purification. The latter PSA cycle involves two interconnected cascades of PSA beds each operating with their own unique cycle sequence and number of beds. The complexity between the different cycle steps in a H2 purification PSA unit has recently been reported by Waldron and Sircar [27]. Many improved and novel PSA cycle sequences are anticipated for use in CO2 recovery plants, based on continued industrial and academic research. Another way to improve the performance of a PSA process is to decrease the cycle time, which allows more gas to be processed using less adsorbent. This is referred to as rapid-cycle PSA. For example, QuestAir recently announced an improved H2 purification technology employing a rapid-cycle PSA unit with a rotary valve. This technology is planned for installation in the largest liquid H2 plant in Asia, which will be fabricated in Japan. Rapid-cycle PSA is not a new concept; however, it required major innovations in process design for handling the gas streams before commercialization became feasible. This innovation has been reported in a series of patents by Keefer and Doman of QuestAir Technologies [28-30] which describe the rotary valve and multi-bed cycle sequencing approaches. The same rapidcycle PSA concepts based on a rotary valve are now being applied by QuestAir to remove CO2 from natural gas and landfill gas. 13

Adsorbent attrition and intraparticle mass transfer effects still limit how rapidly the cycle sequencing can be carried out. This problem partly has been alleviated with the recent development of novel structured adsorbents, incorporating very small commercially available adsorbent particles or crystals, like activated carbons and zeolites, in a support material like a sheet of paper. In this way, the effects of mass transfer and adsorbent attrition are minimized. Structured adsorbent materials are described in the recent patents by Golden et al. of Air Products and Chemicals [31-33], and by Keefer et al. [34]. With the development of a very thin, paper like, structured adsorbent material by QuestAir came the development of a second generation, ultra rapid-cycle PSA H2 purification system. In this system, a rotary adsorbent bed concept has supplanted the rotary valve concept, with the rotary adsorbent bed being comprised of multiple beds within one cylindrical adsorber unit [35]. This unique configuration has resulted in a very compact PSA unit that can be operated at very short cycle times and thus very high H2 production rates. ExxonMobil recently partnered with QuestAir Technologies to design and build a rotary bed PSA plant for the recovery of H2 from the tail gas of a conventional H2 PSA plant [36]. This rotary adsorbent bed concept is certainly applicable to CO2 capture and concentration from a variety of process streams. However, further improvements in this technology are required for this application, including the continued development of new structured, multilayered adsorbents, with each layer containing an adsorbent that is selective to one or more of the gases to be separated. A comprehensive review of relevant studies that deal with removing and concentrating CO2 from simulated flue and stack gases by various PSA cycles has been given recently by Reynolds and co-workers [37]. Table 11 provides a summary of the performances of these various PSA cycles. All utilize a light, heavy, dual, or even a no reflux PSA cycle configuration, intermixed with various cocurrent and or countercurrent depressurization steps, feed, light product, and heavy product pressurization steps, and null (delay) and pressure equalization steps. Note the heavy and dual (light and heavy) reflux cycle steps have been included to concentrate the heavy component (e.g., CO2). H2 PSA plants, which have been designed specifically for producing a very pure light component (e.g., H2,) only include a light reflux step. The heavy reflux step, or so called high pressure rinse step, has been introduced in several PSA patents with only limited commercialization. Not surprisingly, the fairly complicated two-cascade PSA system developed by Sircar and Golden [26] utilizes a heavy reflux step in the cascade that produces the concentrated CO2; the other cascade uses only the light reflux purge step to produce the high purity H2. In addition, these PSA cycles being studied for removing and concentrating CO2 from simulated flue and stack gases also utilize 1) a vacuum swing cycle with the high pressure set just above atmospheric pressure and the low pressure set at some vacuum level, or 2) a more conventional pressure swing cycle with the purge or low pressure set at or near atmospheric pressure and the feed set at a higher pressure. To concentrate and recover CO2 from flue or stack gas, most PSA cycles utilize one or more commercially available adsorbents that exhibit a high capacity for CO2 at ambient temperature and pressure (e.g., activated carbon, carbon molecular sieve, and X and Y type aluminosilicate zeolites). Some of these cycles also utilize a developmental adsorbent (i.e., a K-promoted hydrotalcite-like (HTlc) adsorbent that exhibits a high capacity for CO2 at elevated


temperatures (e.g., 300 to 500oC) and ambient pressure). It is clear from the summary in Table 11 that there are numerous designs for operating PSA processes. This also illuminates the challenge associated with choosing one PSA cycle over another one for a given application. After carefully examining the results summarized in Table 11, in most cases it is still not clear which PSA cycle would be more advantageous. For example, it could easily be reasoned by the expert that it would be inappropriate to use a no reflux cycle or just a light reflux cycle in an attempt to concentrate a heavy component by PSA. But even in this light reflux only case, a particular PSA cycle outperformed a PSA cycle with heavy reflux, depending on many factors like the process conditions, cycle times, bed sizes, adsorbent CO2 capacity, or even the addition of a light end equalization step [38], all of which are interrelated. So, it appears that a PSA cycle with light reflux for concentrating a heavy component can be considered for separating CO2, especially since a light reflux-only PSA cycle reduces the capital and operating costs by avoiding the use of an additional compressor for implementing a heavy reflux step. Hence, PSA cycle configurations are difficult to predict, understand, and interpret, even for an expert. A better understanding of these heavy and dual reflux cycles through R&D clearly is warranted so that more efficient PSA processes can be developed for current commercial separations and for concentrating CO2 from stack and flue gases. This is true in regard to both the more conventional multi-bed PSA process and to the new rotary bed process described above. TSA is also being explored for CO2 capture and concentration from stack and flue gases. For example, Ding and Alpay [39] used K-promoted HTlc as the adsorbent in a TSA process for CO2 removal from high temperature streams. In a TSA mode, the adsorbent bed is usually regenerated by using a hot purge gas to effect desorption of CO2. This purge gas (e.g., steam) can be any gas that does not adsorb appreciably on the adsorbent at the desorption temperature. PSA processes are also being developed for CO2 removal from natural gas [40-42], and even landfill gas [43,44] and coal bed methane [10, 45-48]. For example, Engelhard Corporation developed a PSA process to remove H2O, CO2, and heavier hydrocarbons from methane using their Molecular Gate adsorbent technology. These adsorbents are comprised of titanium silicate molecular sieves that were originally developed to remove only N2 from natural gas by kinetic separation. This class of materials was subsequently found to provide uniquely higher kinetic and adsorption selectivities for CO2 and H2O, exceeding those of more traditional aluminosilicate molecular sieves. A typical PSA system using the Molecular Gate adsorbent to separate CO2 from CH4 rich gas streams at feed pressures between 100 and 800 psia produces a product stream containing CH4 at concentrations of > 90 vol%. This commercial technology is able to process gas streams containing up to 30 vol% CO2 with favorable economics [40,42]. Over the past decade, academic researchers also have focused on the development, understanding, and optimization of new PSA cycle configurations for gas separation and purification. For example, Jiang and co-workers [49] are developing important optimization tools for multi-bed PSA processes, especially for H2 purification and CO2 recovery. Process design and fine tuning offers opportunities for significant improvements in the PSA process


51]. more research needs to be done with these PSA cycles that mimic multi-component distillation operations. top.performance. Warmuzinski and Tanczyk [50. Another novel feature includes feeding a PSA column at intermediate position between the ends of the column. Dong et al. the feed can be introduced at high (stripping) or low (enriching) pressure. In this mode. This concept was demonstrated by separating a ternary gas mixture (i. and Reynolds et al. recycling. Most published work involving the purification of H2 simply reports the performance of a given layered bed. It appears that the vast majority (> 99%) of the PSA literature involves only the stripping PSA cycle concept. such as natural gas. they do not address optimizing the number of layers. The possibility of treating complex gas streams containing multiple components. however.e. Hence. landfill gas. very little is known about the operation and performance of an enriching PSA cycle [56-59]. CO2-CH4-N2) into three enriched products. Reynolds and co-workers [55]. and or collecting gases. Hence. [60. The feed step is maintained at low pressure and the adsorbent bed enriches the gas phase with the heavy component due to desorption [61]. This type of PSA process mimics the behavior of a distillation column. Lee and coworkers [52-54]. whereas the word “enriching” is used to denote that the feed step is carried out at the low pressure and that the adsorbent bed enriches the gas phase with the heavy component due to desorption [61].. In one case activated carbon was used in both sets of columns. Clearly. 16 . However. with multiple adsorbents appears feasible with these PSA cycles. an enriching PSA cycle functions in a reversed or inverted mode compared to a stripping PSA cycle. types of adsorbents. and light and heavy reflux operations can be carried out simultaneously at the respective ends of the column. Multi-layed beds are the industrial standard. from a gas streams. like CO2. or depth of each layer. These uncommon enriching PSA cycles operate in stark contrast to common stripping PSA cycle configurations. Some very novel PSA cycles were introduced to the literature by Diagne and co-workers in Japan [56-59] followed by the work of Mcintyre et al.64]. More PSA R&D is needed in the area of recovering the heavy component. [65] borrowed ideas from distillation and applied them to PSA by interconnecting two or more sets of twin columns through side. and or bottom ports for feeding. and others are studying the design of multi-layered adsorbent beds through mathematical simulation and bench scale experimentation. This kind of PSA cycle was first described by Wilson [62] and has recently appeared in two patents [63. very little information has been published on the design and optimization of layered bed PSA processes. Both groups are studying PSA cycles to concentrate the heavy component in gas streams. and coal bed methane gas streams. The word “stripping” is used to denote that the feed step is carried out at the high pressure and that the adsorbent strips the heavy component from the gas phase due to selective adsorption. in two other cases they used activated carbon in one set of columns and layered 13X zeolite and carbon molecular sieve in the other set of columns. this work needs to be extended to include the number of beds and all possible cycle steps for robust optimization.61].

or related combined cycle processes. and reduced sensitivity to moisture and other poisons are required for this approach to become of commercial interest. especially for CO2 removal and concentration. An emphasis is placed on the judicious use of these different adsorptive reactors to optimize the production of H2. SERP is a fixed bed process with the reactor containing a mixture of a conventional catalyst and a selective. natural gas combined cycle (NGCC). For this approach a high temperature CO2 selective adsorbent is mixed with a typical reforming catalyst to conduct the steam methane reforming and water gas shift reactions in one unit and at lower temperatures. [79] involves the development of precombustion decarbonization technology for CO2 capture from to integrated gasification combined cycle (IGCC). larger working capacity. or syngas from the reforming of methane. Reforming can be practiced at these lower temperatures because of the in situ removal of CO2 [71. In a series of patents [69-73] and three publications [74-76]. beginning with the work of Vaporciyan and coworkers [66-68]. the development of new adsorbents is needed specifically for these high temperature applications. The general idea is to use the adsorbent to selectively remove one or more of the products formed from an equilibrium limited reaction to shift the equilibrium in favor of increased conversion. A team at Air Products and Chemicals has developed adsorptive separating reactors using the SERP process. Some very recent work on the SERP concept by Hufton et al. activated aluminas or silica gels is lacking at the higher operating temperatures which is typical of the regeneration conditions. These separation characteristics are required at elevated process temperatures. high-temperature adsorbent. The feed for this unit was obtained from a conventional steam methane reformer [77]. Medium purity H2 production (~ 95%) was achieved by conducting this SERP process in a water gas shift reactor containing the catalyst and a CO2 selective adsorbent. In the third case.Sorption Enhanced Reaction (Periodic Adsorptive Separating Reactors) Conducting reaction and adsorptive separation in a single fixed bed reactor configuration dates back to 1987. For an equilibrium limited reaction. this group discusses a redesign of the methane reforming operation. methane reforming with CO2 can be revamped by using CO or H2 selective adsorbents. a simple pressure swing in the bed can be used for regeneration. There appears to be significant potential for the development of additional applications of and new adsorbents for the SERP concept. CO is converted to CO2 which is quickly removed by the CO2 selective 17 . Improved adsorbents with greater selectivity. Because performance of most commercial adsorbents like zeolites. This process is referred to as sorption enhanced water gas shift. It involves a multibed PSA process operating at high temperature with the columns again packed with catalyst and K-promoted HTlc. activated carbons. CO. the adsorbent shifts the equilibrium in favor of higher conversion through Le Chatlier’s principal. In the first case steam methane reforming is driven using CO2 and or CO selective adsorbents. When the adsorbent becomes saturated with the product. In a more general patent. three uses of the SERP concept are discussed [78]. more rapid adsorption and desorption kinetics.73]. The adsorbent is then regenerated with a pressure or temperature swing. In the second case. H2O selective adsorbents are used in the production of CO using a reverse water gas shift reactor.

The capacities of these materials would be less than 0. Han and Harrison [80]. They can reduce or eliminate downstream separation and purification units currently associated with the production of high purity H2. and 0. especially high temperature adsorbents. X and Y zeolites. or syngas when removing CO2 for recovery or sequestration.1 mol/kg at the temperatures associated with the steam methane 18 . and silica gel [69. water gas shift. Zou and Rodrigues[83]. After a series of PSA cycle steps. FeTi. which decreases to 0. with metal oxides and mixed metal oxides of Mg. and clay minerals such as sepiolite and dolomite [71-73.70. Similarly. The overall conclusion is that activated carbons and zeolites are superior to metal oxides and HTlcs for ambient temperature applications. [91] covered activated carbons. aliminosilicate zeolites. MgNi.90] have been studying the performance of the SERP for the steam reforming of methane in a single unit using a PSA cycle to remove CO2 reversibly from the reaction product gas using a K-promoted HTlc. The continued experimental validation of modeling analyses. La and Ca. and to optimizing its performance. coupled with the study of various PSA cycle sequences. A H2 product free of CO2 is produced at high pressure and temperature. 5A zeolite exhibits ~ 3. typical activated carbons exhibit 1. The preferred H2O adsorbents include commercially available A. Selective Adsorbents New selective adsorbents can play a key role in both H2 and CO2 production. and Ortiz and Harrison [82] have been researching SERP for the steam reforming of methane in a single unit using a TSA cycle to remove CO2 reversibly from the reaction product gas with CaO.77]. A recent review of CO2 absorbents by Yong et al. and/or reverse water gas shift reactors to operate at reduced temperatures or pressures. Clearly. should contribute to the understanding of this type of adsorptive reactor system. PdAg. modified double layer hydroxides.5 to 2. mordenites.0 mol/kg CO2 adsorption at 25 oC and 500 torr.0 mol/kg at 25 oC and 500 torr. metal oxides and HTlcs for reversible adsorption. [84].78]. The preferred CO2 adsorbents include: K-promoted HTlc. and Ding and Alpay [89.1 to 0. Mn. but for high-temperature applications metal oxides and HTlcs are preferred. This CO2 product could be recovered. and LaNi [78]. and modified spinels. This in situ removal of CO2 facilitates more conversion of the CO to CO2 through Le Chatlier’s principal. The preferred CO adsorbents include Cu(I) or Ag(I) on silica-alumina [78]. Again. The preferred H2 adsorbents include metal hydrides such as Pd. a concentrated CO2 product is produced at low pressure. It is clear that these SERPs allow steam methane reforming. The success of the SERP relies on CO2. Harrison and Peng [81]. Xiu and Rodrigues [85-88]. This gas is burned in a high efficiency gas turbine. further implementation of SERP would be fostered with the development of improved adsorbents. Although the SERP concept seems to work well. spinels. As shown in Table 10. CO. H2O and even H2 selective adsorbents.76. aluminas. a wide range of commercially available and developmental adsorbent materials can be used in the SERP concept.2 mol/kg at 250 oC and 500 torr. and either sold for industrial or commercial use or further processed for sequestration.adsorbent.2 mol/kg at 250 to 300 oC and 500 torr. as discussed above. Xiu et al. industrial acceptance of this technology has been limited. including a heavy reflux step.

These adsorbents are attractive not only for SERPs. The sensitivity of these materials to H2O vapor has not been reported. [102] in Japan. For selective adsorbents.98]. For example. as shown recently by Reynolds et al. Lithium zirconate and CaO can function as high-temperature. Double layer hydroxides exhibit even higher reversible capacities in the presence of steam. The CO2. typically of around 1. with regeneration carried out at 900 oC in N2 [106]. CH4 and H2O capacities of theses various Molecular Gate adsorbents are proprietary. [103[. Table 10 compares the capacities of these developmental CO2 selective adsorbents to established commercial materials.93]. the reversible CO2 capacities typically range between 0. with reasonable regeneration rates exhibited at 780 oC that improve with CO2 free purge gas [100] (see Table 10). the material pore size of 3. Typical CO2 adsorption capacities are high at 3. water gas shift.90]. These materials are also showing high CO2 capacities at high temperatures with reasonable regeneration rates.06 (undoped) to 0.5 mol/kg at 500 oC and 760 torr.7 angstroms is effective at excluding methane from its pores while accepting nitrogen and other smaller and far more adsorbing molecules such as CO2 and H2O into its pores [10]. The recent work by Engelhard Corporation involves the development of novel adsorbent materials for CO2 separation from natural gas streams. Han and Harrison [80]. but also for high temperature PSA processes. even in the presence of steam. The Molecular Gate technology. and reverse water gas shift reactive adsorbers.4 to 4. the K-promoted HTlc materials exhibit a high and pressure-reversible CO2 capacity at temperatures compatible with steam methane reforming. Several teams are also exploring alumina as a high temperature and pressure-reversible CO2 adsorbent for use in a PSA cycle [91. selective CO2 adsorbents with temperature-reversibility. Mayorga et al. Ida and Lin [100].5 mol/kg at 375 oC and 230 torr [93]. CaO adsorbents are being investigating by Iyer et al. [99]. Based on titanium silicate molecular sieves. Ortiz and Harrison [82]. was also found to be uniquely attractive for CO2 and H2O separation from natural gas. and Abanades [107] in Spain.97]. [105]. [61. Overall.3 mol/kg at 300 oC and 500 torr (see Table 10). The CO2 capacity of aluminas undoped and doped with metal oxides and carbonates ranges from 0. Gupta et al.reforming. which is similar to that reported by Yong et al [91] for commercially available basic aluminas. This performance is highly dependent on the synthesis and pretreatment conditions [96]. Xiong et al. Harrison and Peng [81]. [94] and Yong and Rodrigues [95] have characterized HTlcs for CO2 adsorption at ambient and elevated temperatures. as are Nair et al. Gupta and Fan [104]. Yong et al. which was originally targeted for kinetic separation of N2 from natural gas.52 (doped with 9 wt% Li2O) mol/kg at 400 oC and 500 Torr [98]. [106] in Japan. and water gas shift and reverse water gas shift applications [92. A similarly high CO2 capacity of 7 mol/kg 19 . [101] are exploring the zirconates. [93] at Air Products and Chemicals report synthesis procedures and operational capacities for both HTlcs and double layer hydroxides. Kuramoto et al. and Ida et al. Despite the small differences of kinetic radius between nitrogen and methane. the Molecular Gate process takes advantage of the unique ability to adjust pore size opening of the material within an accuracy of 0. typical reversible CO2 capacities range between 4 and 8 mol/kg at 500 oC and 150 torr.7 mol/kg at 300 and 400 oC and 200 and 700 torr. ~ 0. N2.1 angstrom.4 and 0. as have Ding and Alpay [89.

resulted for a CaO exposed to 76 torr of CO2 and cycled over 50 times at 700 oC using N2 for purge. This is a large reversible CO2 capacity (see Table 10). These CaO adsorbents are very sensitive to sulfur but the sensitivity to H2O vapor has not been reported [103]. The operating temperature range of this material may be too high for most steam methane reforming (SMR), the water gas shift (WGS) and reverse water gas shift reactors, however. United Technologies working with NASA in the mid to late 1990s developed novel low temperature solid amine-based CO2 adsorbents that are pressure and or temperature regenerable [108,109]. One variant of this novel material consists of a liquid amine, such as polyethyleneimine (PEI) chemically bonded to polymethyl methacrylate with poly(ethylene glycol), a second liquid phase, used to enhance mass transfer [110]. This solid amine adsorbent has a reversible CO2 capacity of around 0.9 mol/kg at 25 oC and 15.2 torr of CO2, it can be regenerated using PSA at a moderate vacuum of 1 torr, and its capacity markedly improves in the presence of water vapor [110]. More recently, Xu et al. at Pennsylvania State University, in a series of works [111-113], have been developing a similar reversible solid amine-based adsorbent for CO2 using MCM-41 as the support and PEI as the CO2 active amine. Depending on the Si/Al ratio of the MCM-41 and the loading of PEI ranging from 30 to 75 wt%, typical CO2 adsorption capacities range from 1.5 to 3.0 mol/kg at 75 oC and 1 atm of CO2, with complete reversibility achieved simply by purging with pure N2 at 75 oC [112]. However, the adsorption and desorption kinetics are generally quite slow with 150 minutes required in each case. Most recently they investigated its effectiveness for treating simulated flue gas comprised of 14.9, 4.25 and 80.85 vol% CO2, O2 and N2, respectively [113]. The results at 75 oC were encouraging with CO2/N2 selectivites of over 1000 and CO2/O2 selectivites of over 180. This supported solid amine-based adsorbent has limited applications as it is unstable at 100 oC. Membranes A wide variety of membrane materials and membrane gas contactors are being developed for gas separation and purification applications involving CO2. A survey of the recent literature is given below. The latest developments in polymeric, facilitated transport, inorganic, and hybrid organic/inorganic membranes are reviewed. This is followed by a brief assessment of hollow fiber gas-liquid contactors. Ideas presented in these studies have the potential for both near-term and longer-term impact of membrane applications on the removal of CO2 from process streams, including flue gas or combustion gas streams. Tables 12 and 13, respectively, provide the permeability and permeance of membrane materials used for CO2 separation, and the transmembrane flux data for different capillary hollow-fiber membrane contactors reported in the literature. Polymeric Membranes Polymeric membranes are attractive because they can be manufactured into units with very high surface areas, either in the form of hollow fibers arranged in the tube-and-shell configuration (85% of the market) or in the form of flat sheets packaged as spiral-wound modules with less area but more resilience against adverse conditions [14,15,19]. There are two types of polymeric


membranes. Those that are referred to as glassy polymeric membranes have a glass transition temperature that is higher than room temperature. In contrast, those that have a glass transition temperature that is well below room temperature are referred to as rubbery polymeric membranes. Table 12 summarizes the permeability and permeance obtained with these kinds of membrane materials when used for CO2 separation. Most commercial membrane systems in gas separations are based on glassy polymeric materials as opposed to their rubbery counterparts because of their superior mechanical properties and overall permeability-selectivity tradeoffs [114-116]. Common glassy polymeric materials include polysulfones [117-127], polyimides [116,128-150], polyaramides and polycarbonates [151-154], polyphenylene oxides [155-163] and cellulose derivatives [164-168]. Although there are less than 10 commercial membrane processes available today [14,15], these glassy polymeric membranes are still receiving significant attention in the literature [169-176]. As indicated earlier, the selectivity of a large fraction of glassy polymeric membranes depends largely on their ability to discriminate gas species by size and diffusivities through the membrane structure. Such ability is for a large group of glassy polymeric membranes consistent with the solution-diffusion model [14-19,177-180]. In the solution-diffusion model, the transport of molecules is regulated mainly by thermal oscillations of the semi-rigid polymer structure that allows diffusion selectivities based upon subtle changes in size. However, there is a small fraction of stiff glassy polymeric materials (described below) where the diffusion selectivity is governed by a size selection mechanism similar to that found in inorganic molecular sieves [178187]. Because the performance of most glassy polymers is structure dependent, physical or chemical attacks upon it can lead to a significant deterioration of performance. Glassy membranes that become overexposed for extended periods of time to large concentrations of CO2 or even traces of vapors from organic solvents may lead to undesirable compaction, swelling, and plasticization that irreversibly change the morphology, and hence may lead to reduced membrane performance [13-19,128-130,135,142,144,145,188-204]. Plasma and thermal treatment (i.e., annealing) [135,188,190,200,202,204] and chemical cross-linking methods [128-130,142,144,145,193199,201,203], which improve the membrane resistance by increasing the polymer rigidity, are the most frequently used strategies to improve durability. Thermal treatments of polymeric material for membranes with cross linking agents improve resistance to plasticization and other attacks. Thermally induced densified structures are being investigated with charge transfer complexes [194-198,202], diols [128-130,193-198] and diamines [129,142,144,145,193,203]. The improved resistance against structural modification is realized via covalent bonding of neighboring polymeric strands. These approaches lead to reductions in permeability, sometimes with improvements in selectivity. Others have observed further success by attempting a mixed approach of both techniques [194-198]. Thermal annealing, for example, can further drive cross-linking reactions to stabilize the polymer properties. The addition of inorganic materials can also lead to further stabilization of the membrane. In this regard, polymers crosslinked with inorganic monomers [205-209], typically alkoxy-silanes,


improve stability and also improve performance. These materials belong to a different class of materials normally regarded as organic-inorganic hybrid materials and are discussed later. Glassy polymers, characterized by a very rigid ultramicroporus structure, posses pores sufficiently small for gas separation [178,179]. Molecule diffusion in these polymer molecular sieves is similar to that in inorganic molecular sieves. Examples of these materials are polypyrrolone copolymers [178-180,184-187] and the recently developed intrinsic microporous polymers [181-183,210]. In general, these polymeric membranes are very attractive because they display performances normally above the upper bound for conventional polymeric materials and enhanced stability [178,179]. Another type of glassy polymer is di-substituted acetylene-based polymers [116,211-231]. Disubstituted polyacetylenes are known for their unique gas transport properties, characterized mainly by enormous gas permeability, high fractional free volumes (typically > 20%), and unusually high vapor/gas selectivities [116,217,220,221,230,231]. Within polyacetylenes, poly(1-trimethylsilyl-1-propyne) (PTMSP) displays the largest gas permeability of all known polymers [116]. It is believed that the large permeability associated with these polymers is due mainly to a concerted action of the rigid double bonds of the polymeric backbone and the bulky side groups, hindering chain segmental motion and restraining polymer chains from packing efficiently [215]. The resulting effect is a polymeric matrix with large, possibly interconnected, free volume that provides a very efficient permeation pathway for transporting molecules. Also, unlike the rest of the glassy polymers, polyacetylenes do not discriminate permeates based on diffusivity but rather on solubility, which provides them with the ability to permeate heavier and more soluble organic molecules and CO2 over smaller gases. Due to this reason, polyacetylenes such as PTMSP [216,217,220-222,224,225,229,230] and Poly(1-methyl-1pentyne) [217-219,230,231] have been investigated as potential materials for the separation of light hydrocarbon gases and vapors (C3+) from natural gas and off-gas H2-containing streams (e.g., from fluidized catalytic crackers) in refineries. As result of their selectivity towards CO2 over H2, polyacetylenes also have found potential use in hydrogen/syngas production processes (e.g., reforming). However, the CO2/H2 selectivities so far displayed by these polymers (i.e., < 6) are still only moderate. This limitation, due mainly to the prohibitive losses of high-pressure H2 in the low-pressure permeate, reduces the commercial potential for these polymer membranes. Another major concern behind polyacetylenes is their lack of chemical resistance and performance loss over time [215,224,225]. Polyacetylenes tend to incur irreversible structural changes and degraded performance with long exposures to feed gases. Several approaches have been attempted to overcome these problems with some success and sometimes with loss of performance. These approaches include the addition of silica fillers [223,232-234] to manipulate the molecular polymer chain packing. They also include the addition, preparation, or use of other polyacetylenes more resistant to aggressive feeds, such as poly(4-methyl-2-pentyne) [230], poly(1-phenyl-1-propyne) [231], and diphenylacetylene [215]. Chemical treatments such as fluorination and desilylation [211-215] also have been explored.


solubility) between gas penetrants and the polymeric phase. However.264. In the past.]. rubbery polymeric materials allow membrane technology to be a viable option for this industrial application. Table 12 summarizes the permeabilities and permeances obtained with these kinds of membrane materials when used for 23 .240.235-239. plasticization and other adverse attacks than their glassy counterparts [13.235255]. 6-10) and show significantly higher CO2/N2 or CO2/CH4 selectivities (40-60) than commercially available glassy membranes.235-238. particularly ether oxygen atoms.e. semi-organic rubbery polymers such as silicone membranes (in particular poly(dimethylsiloxane) (PDMS)). rubbery polymers seem to offer significant space for improvement with a great potential for future commercial use.. the preparation of block copolymers containing low molecular weight rubbery polymer segments and glassy polymers such as nylons [175. rubbery polymers suffer from modest permeabilities. it is possible for rubbery polymeric materials to be more selective towards heavier gases such as CO2 or H2S over smaller molecules such as H2 or He [13. including the addition of hydrophobic pendant groups [240. given relatively low temperatures. It is believed that polar groups in the polymer backbone. are largely responsible for the enhanced selectivity for CO2. These materials display the largest CO2/H2 selectivities (i. their further study as possible membrane materials is somewhat discouraged. because these materials have suffered from reduced selectivities. but they posses the unique ability to be selective towards CO2 over H2. Thus. In this regard. The utilization of cross linking agents that keep rubbery polymer segments small has also been investigated [242243. Facilitated Transport Membranes Facilitated transport membranes (FTMs) have received considerable attention because of their extremely elevated selectivities and relatively high fluxes [17]. The transport of molecules in rubbery polymers also can be explained by the solution-diffusion model. Despite the large selectivities. have received considerable attention for their high intrinsic permeabilities [116.264. This cross linking improves the mechanical consistency that is normally lacking in rubbery polymers. rubbery polymers tend to display lower performance than their glassy counterparts. In general. coal and waste gasification and partial oxidation.265] and polyethers [175. polyimides [267-269] and others [158.252.266. Despite all these challenges..264. The fact that rubbery polymers do not rely on diffusion selectivity makes their performance much less likely to be affected by swelling.247.256-263].175.267. several approaches have been implemented to minimize the existence of crystalline phases within these polymers.241. and other similar processes.253].242-254] are the rubbery polymers receiving the greatest attention.265].245-247].241.265].The increasing demands for purer and cheaper H2 has fostered the development of technologies that selectively remove CO2 from H2/syngas under high pressure from reforming. polyphosphazenes [240. particularly for the CO2/H2 system.241. principally as a consequence of the large degree of crystallinity associated with them [235238. However. However. in this case the selectivity of rubbery polymers relies upon the physical interactions (i.e.235-239].159. Today.

Several approaches have been attempted with moderate success to control evaporation. At partial pressures over 0. dendrimers [274. In waterswollen membranes [288-290]. 24 . Similarly. evaporation losses have been reduced by alternatively using non-volatile solvents such as carbonate-glycerol [271]. the carrier is ionic and physically binds to the ion exchange membrane via attractive electrostatic forces.274]. The carrier solution is forced to permeate through the membrane and then is continuously recycled to the feed side. of most FTMs is their characteristically strong decay of permeability as the partial pressure of the favored molecule increases [274-277. where CO2 is to be removed. and. the membrane physically interacts and retains water. stability problems due to evaporation of the carrier solution.280282. glycine-Na-glycerol [272. observed with traditional FTMs.275]. The high selectivity in FTMs is achieved through the existence of carriers within the membrane that selectively interact with given molecules and facilitate their transport through the membranes. Clearly. are widely known for their stability problems. In ionic exchange membranes (IEMs) [282-287]. However. their selectivity severely deteriorates. to sustain their uniquely high selectivity. This behavior limits their use to feeds with low partial pressures of this species.CO2 separation. perhaps a minor one. In BLFMs. A particularly novel approach to FTM technology is that associated with the “bulk flow liquid membrane” (BFLM) concept.288. causing swelling which improves the transport of the solute. even if present in low concentrations. which are a particular type of IEM.273].5 atm most carriers rapidly approach saturation and the permeation rates become severely limited. The most successful facilitated transport membranes are the so called fixed carrier membranes (FCMs) [291-293]. which are also ILMs. however.293]. mainly as a result of the evaporation of the carrier medium – a problem that is particularly acute in immobilized liquid membranes (ILMs) [270].292. particularly with water. Otherwise. the evaporation is reduced by using non-volatile polyelectrolytes as molten salts or salt hydrates as solvents. reforming and coal gasification. such as in reforming. In some FTMs. FTMs may overcome these problems in applications where humidification preconditioning is not a requirement. are avoided. most FTMs still require feed preconditioning. Membranes where the carriers are tightly bound to the polymer also have been developed to counteract degradation. In FCMs the carrier consists of secondary amines or carbonates that are chemically bonded to the backbone of the membrane. Despite all this work on FTMs. which was introduced by the group of Teramoto [294-296]. glycerol carbonate [270. where water serves as the carrier. the chemically bound carrier alleviates the evaporation and migration problems associated with the free liquid FTMs. FTMs. Another problem. FTMs that are selective towards CO2 can have a great impact on reducing processing costs or improving equilibrium driven processes such as natural gas sweetening. more successfully. where H2O actively participates. in polyelectrolyte membranes (PEM) [276-281]. and with the exception of some ILMs and FCMs. and flue gas treatment.

e.342-350]. the CO2/H2 selectivities of these membranes (< 5 for most species . Most of the literature regarding inorganic membranes that rely on diffusion selectivity for CO2 separation has been focused on the CO2/N2 or CO2/CH4 systems. in so called selective surface flow (SSF) membranes.Briefly. Table 12 summarizes the permeabilities and permeances obtained with these kinds of membrane materials when used for CO2 separation.148. The flexibility of this process is such that both microporous and capillary membranes can be successfully used. BFLM units do not require the use of special membranes. In addition. or porous stainless steel that also provide structural consistency. Because the membrane is always wetted with carrier solution. Recently others [262. condensation is so important that even the smaller and faster diffusing species become the less permeable ones. with BFLMs the carrier solution is continuously mixed with the feed gas and the carrier selectively reacts with the solute. [294. For example.306-313. Also. Upon leaving the unit the absorbed CO2 is released and the regenerated carrier is recycled back to the feed for reuse. However.135. Any small amount of carrier solution that does not permeate the membrane is later separated from the treated gas and returned through the receiving side of the membrane to join the carrier that is permeating through the membrane. The first SSF membranes were developed by Air Products and Chemicals and have been extensively studied [71. non-selective inorganic materials. sometimes to the point of becoming totally excluded.138.295] showed CO2/N2 selectivities over 500 and permeances and greater than 300 GPUs2 for a wide variety of BFLMs containing capillary polyethersulfone membranes 250 microns thick.. In other materials adsorption and condensation play an additional role. zirconias. An extreme case of diffusion-selective membranes is that of molecular sieves. To improve their productivity.351-359] have reported new types of membranes with SSF 2 GPU = 1 x 10-6 cm3 (STP)/(cm2-s-cm Hg) 25 . Materials typically used as membrane materials include carbon molecular sieves from a wide variety of organic polymeric precursors [134. but also because they are more resistant to high temperatures and pressures. thick and porous membranes with sufficient mechanical strength and durability can be used as long as they do not severely restrict the transport of the carrier.see Table 12) so far are too low to be of any economic value. and silicas [337-341]. Inorganic Membranes Inorganic membranes are very attractive not only because they have significantly better performance in terms of permeability and selectivity over organic membranes. Once inside the membrane unit the carrier permeates the membrane with the dissolved solute from the feed side (high-pressure side) to the receiving side (low-pressure side). pores unfilled with liquid through which the gas may flow unselectively).297-305. zeolites [314-336].325.].250. Most inorganic membranes exploit diffusion selectivity as the main factor for gas separation. and regeneration treatments. these membranes must be deposited as thin layers upon the surface of other. aggressive feeds. where the molecular spacing within the pores of the membrane is so restricted that the transport of some larger molecules becomes severely impeded. Teramoto et al. fouling. the membrane remains highly selective while devoid of any open pores (i. such as aluminas.

179.388]. The organic or polymeric phase serves as the host [390-392]. titanias [125.209. the inorganic phase. delaying the transport of the less selective species.361-364. In the second type the membrane typically is formed via a sol-gel process whereby hydroxyls of the inorganic monomers (e. Despite all their appealing properties.390398.389.390-395].385388.g. retards the flow of the smaller. In the second type both organic and inorganic phases become intermingled at the molecular level via chemical reactions between monomers of both phases [173.377-383.366. alkoxy silanes) become covalently bonded to the backbone of the organic monomer via organic functional groups.. there has been an abundance of literature reporting that organic-inorganic hybrid membranes can improve the performance of the organic phase.179.g. In the first type the mixing is realized in a slurry that contains both phases dispersed in a solvent that is later removed. Organic-inorganic hybrid membranes generally can be classified into two types.375.389].361-365.397-409. it also has been reported that hybrid membranes exhibit higher stability against aggressive environments [390]. So-called hybrid organic–inorganic membranes seem to offer potential to overcome this limitation.178. In this case. consists of diverse types of silicas [137.205-208. and zeolites [396-409]. due to an improved condensation selectivity in favor of the heavier species. improving the mechanical (e. the inorganic phase may act as a molecular sieve. which is normally in dispersed form. its permeability [178.361-387].375.] or in the form sol-gel precursors that are subsequently incorporated into the organic phase [137. Polymeric membranes have shown little progress since Robeson set the permeability-selectivity trade-off upper limit in 1991 [360].205-209. more 26 .361-364.179.402]. potentially addressing many of the current needs of the membrane industry [178. carbon materials [178. Hybrid membranes have been shown to significantly increase the selectivity of the polymer while keeping. Their inherent brittleness and the elevated manufacturing costs associated with making modules that are crack free and have large surface areas are still serious issues that limit their utility. Table 12 summarizes the permeabilities and permeances obtained with these kinds of membrane materials when used for CO2 separation.376.. The first one is due to the particular interactions that the inorganic phase establishes with the favored gas species. by increasing bursting pressures) and thermal properties of the inorganic phase and providing the manufacturing flexibility and ductility associated with the organic phase [207.390-392]. In the first type the inorganic phase consists of either preformed submicron particles (fillers) [125. These membranes are attractive because they synergistically exploit the desired properties of both phases. There are two main reasons for the enhanced performance observed in hybrid membranes [207].characteristics.371.205-208.390-395. It is doubtful that this will change in the near future.179.376].173.389.401. In these membranes.365. In addition. and sometimes also increasing. Further.389. or as a SSF material which.389-395]. Hybrid Membranes In the past two decades there has been much interest in the development of hybrid membranes consisting of mixtures of organic and inorganic phases. inorganic membranes are not commercially used for CO2 separation.

hybrid membranes are used only to improve the mechanical strength of membranes for liquid separations.399-402.375.379. A strongly interacting inorganic phase can inhibit chain or backbone mobility (i.L. A polymeric phase that is otherwise too permeable or too impermeable may lead to undesirable gas bypassing (i. increase stiffness) and open inter-chain packing (i. hybrid membranes currently are not being used. interacting mixtures containing zeolites and rubbery polymers [401-402]. Gore and Associates GmbH.205-209. reverse osmosis. Hollow Fiber Gas-Liquid Contactors The concept of using a hollow fiber membrane unit to serve as a gas-liquid contactor for absorption was first introduced by Zhang and Cussler [414. The second reason for the improved performance is a consequence of morphological changes that take place in the polymer structure as a result of the strong interactions now existing between the two phases.. which reduces selectivity.367. Limited or no success has been achieved where phase separation occurs (e. while the transport of the less selective species is delayed. etc. for example.371. ion exchange.410] to reduce surface tension has been demonstrated. Defects at the interface and phase separation lead to gas bypassing.e. low selectivity) or poor membrane productivity (i. with mixtures of silicas or zeolites and glassy polymers) [390392].. Some success has been achieved by using coupling agents and sol-gel techniques with organic polymers functionalized with. hollow fiber contactors may be very attractive for CO2 27 ..411]. commercialization is looming.. In this regard.e. or carbon based materials with glassy polymers [178.e.361364. a handful of companies including Kvaerner Oil & Gas. trialkoxysilane groups or alkoxysilane monomers containing functional groups [137. and TNO Environment Energy and Process Innovation have successfully developed larger-scale units [416-418].391.380. However. The same bonding concept has been successfully exploited with in situ prepared hybrid membranes where bonding reactions result in the formation of nano-microcomposites [173.. low permeability). the most critical decision in making a hybrid membrane with improved performance lies in the correct selection of the membrane materials [207. in some cases significantly better. because of the inherent high selectivity and relatively large flows.179. Both selected phases should facilitate the transport of the more selective gas species. respectively. Currently. The simplest approach to insure interfacial adhesion is to select phases that are physically and chemically compatible with each other and to assure that interfacial surface tension is minimized.392].376]. matching the permeabilities of the favored gas species in both phases is an important consideration. W.389-395] have led to better performing membranes. For example. Perhaps. The use of polymeric compatibilizers [173. At present.415]. simultaneously improving both the selectivity and permeability of the organic phase. such as those used in ultrafiltration.diffusing species. [412.g.382. Alternative approaches have been attempted to improve adhesion of poorly interacting phases.e. Nevertheless.209.413].366. In the gas separation industry. backbone inter-distance). It is also imperative that the phases display good adhesion at the interface.

or other hydrocarbons through the permeate. foaming. particularly in feeds with low CO2 concentrations. which is significantly higher than the typical 100-500 m2/m3 observed in packed bed systems. Also. methane. clogging. The pores of the membrane must be kept completely gas filled. Superficial velocities in these membrane processes easily can exceed 2 cm/s. The non-wetted pores in the membrane are such that the membrane does not offer any selectivity over the gas species.421-424. kLa) can still be larger than that attained in a packed bed [441-443].. wetting) increases the overall mass transfer coefficient of the process. which is a limit in their packed bed counterparts.e. Furthermore.separations in processes such as reforming and gas sweetening. The presence of stagnant liquid within the pores (i. and liquid entrainment [418].426-445. These membrane contactors also offer advantages over selective membranes. Hollow fiber gas-liquid contactors are flexible and can be operated over a wider range of conditions. The larger surface area in these contactors is perhaps the most attractive advantage. channeling. The result of having a large surface area is that despite the typically lower mass transfer coefficients associated with the laminar regime of the liquid phase in these membrane contactors. and the particular modularity of the membrane contactors allows their design to be simple and scaled linearly. All these facts could lead to significant operational and capital cost savings.]. Membrane wetting largely depends on an adequate selection of membrane and liquid absorbent. Table 13 provides a summary of the trans-membrane flux being achieved for different capillary hollow fiber membrane contactors reported in the literature.. Because of its advantages over conventional absorption towers. the liquid absorbent assumes this role [416-425]. the membrane must only allow the solute to diffuse through with little resistance before reaching the absorbent. The performance of hollow fiber membrane contactors depends almost exclusively on the liquid absorbent. Thus. membrane contactors may display transmembrane surface areas between 500-3000 m2/m3. In spite of their positive attributes. and swelling of the polymer [316.418]. a great deal of research has been conducted on gas-liquid contactors in acid gas sweetening of natural gas and flue gas streams [416-418. the extremely high selectivity towards CO2 that can be achieved with these membrane contactors limits their loss of primary gases such hydrogen. The initial high resistance against liquid penetration into the membrane pores tends to break down with time as a result of combined mechanisms that include surface wetting. 28 . the contacting area is fixed and does not vary with process conditions.e. This problem has significantly limited commercial interest. as they are not subject to the common limitations observed in packed beds such as flooding. and unlike dense or selective membranes it is not significantly affected by plasticization and other structural attacks. hollow fiber gas-liquid contactors are unable to sustain processing conditions for prolonged periods of time. The ability to stop a liquid from wetting or penetrating into the pores of the membrane depends directly on the surface tension of the liquid and inversely on the size of the membrane pores. unlike packed bed systems. The process basically uses a non-selective membrane that serves only as a physical barrier between the gas and the liquid phase. Depending on the diameter and thickness of the hollow fibers. the volumetric mass transfer coefficient (i. surface modification and reaction.

More hydrophobic membranes. the interfacial surface tension tends to decrease considerably with increasing alkanolamine concentration. Another significant problem associated with these gas-liquid contactors is pore blocking. which corresponds to the mean free path and is equivalent to 70 nm for CO2. but then recovers as the CO2 loading increases [418]. However.442] have shown that adding significant concentrations of triethanolamine (TEA) into the absorbent also can improve membrane stability against wetting. the use of hydrophobic membranes. alkanolamines. but.417]. diethyl or di-methyl glycine. Pores. ensures large surface tensions. In addition. Drioli et al. recommendations are presented for future work on promising adsorption and membrane technologies. have been developed to resolve this problem. the selected solvent must be compatible with long-term stability of the membrane. For example. and Klaassen et al. and some amino acid salts tend to react with the CO2 and form precipitates that eventually cause pore clogging and fouling. Conclusions from Background Survey This survey identified several areas where major improvements or breakthroughs may be achieved in CO2 removal with the judicious use of adsorption and membrane processes. it requires less energy consumption and does not react with CO2. in combination with aqueous based absorbents. In the next section. the membrane becomes selective. which improve the lower mass transfer coefficients of the traditional contactors [416. In several other areas the path forward is potentially blocked by fundamental material limitations. Recently. However. can be used but are more expensive. such as polytetrafluoroethylene (PTFE). Yeon et al. for example. A summary of membrane contactors can be found in the reviews of Li and Chen [445]. In alkanolamines. which is related to solvent stability. For example. [419.420]. Korikov and Sirkar [433] showed that aqueous solutions containing polyamidoamine dendrimers as absorbents also may improve membrane stability. surface tension may also vary with the absorbent concentration and CO2 loading.With higher surface tension and smaller pores it is less likely that the membrane can be wetted. cannot be so small that they restrict the flow of solute across the membrane. however. in particular monoethanolamine (MEA). Below the lowest limit. which offer similar absorption characteristics to aqueous alkanolamines and do not degrade polyolefin membranes. [441. It is anticipated that breakthroughs in adsorption and membrane 29 . PTFE is expensive and the PTFE membrane contactors exhibit only limited contacting areas. Most recent efforts are directed towards developing cross-flow membrane contactors. such as inexpensive polyolefin membranes. alkanolamines tend physically to interact and breakdown the hydrophobicity of polyolefin membranes. [425]. In general. Another way to restrict membrane wetting is by reducing the pore size. Amino acid salts made from glycine. alanine. TEA offers a lower absorption rate than the alkanolamines. Membranes containing this alkanolamine displayed stable performances for over 3000 hours. such as suspensions of alkanolamines or carbonates.

environmental impacts and feedstock requirements.technologies will lead to significant reductions in energy consumption. 30 . and thereby provide considerable improvements in process economics.

7 – 15 years).. and zirconates for CO2 structured adsorbents for rapid PSA. as mentioned throughout this report. CaOs. Crosscutting Recommendation: the development of pre-cleaning technologies to remove a wide variety of contaminants from CO2 streams may be critical to the successful development and implementation of any or most membrane and some adsorption processes.e. As a guide. These recommendations are set-forth for both the near-term time frame (i. these materials have potential for commercial use in CO2 capture. carbon fiber molecular sieves) In general. 1 – 5 years) and longer. Near-Term Adsorbent Development Overarching Goal: Develop high-capacity CO2-selective adsorbents with rapid adsorptiondesorption kinetics. the classes of adsorbent materials being studied today include: • • • Low-temperature activated carbons..e.RECOMMENDATIONS FOR FUTURE R&D Recommendations are set-forth for future CO2 separations R&D needs based on this technology and industrial assessment. However. improved selectivity.. or PSA/TSA processes (e. carbon molecular sieves. they all suffer from one or more of the following deficiencies: • • too expensive insufficient working capacity 31 . The near-term developments in CO2 separations technology are divided into four categories: • • • • Near-Term Adsorbent Development Near-Term Membrane Development Near-Term Adsorption Process Development Near-Term Absorbent and Absorption Process Development The long-range developments in CO2 separations technology are divided into three categories: • • • Long-Term Flow Sheet Augmentation with Adsorption and Membrane Processes Long-Term Advanced Adsorbent Materials and Process Development for CO2 Removal Long-Term Advanced Membrane Materials for CO2 Removal It must be emphasized that streams containing CO2 tend to be dirty and contain many different contaminants. and zeolites for CO2 High-temperature hydrotalcites. and operational stability.range research (i. This fact is very important and provides the basis for a crosscutting recommendation for adsorption and membrane materials and process development.g.

Recommendations: 1) Specific Goal: Develop high-capacity CO2-selective adsorbents that can operate at elevated temperatures in the presence of sulfur-bearing compounds and possibly steam. As a guide. that exhibit high permeability. sulfur bearing compounds. ionic exchange membranes. they all suffer from one or more of the following deficiencies: • • polymeric glassy membranes generally suffer from chemical attack by CO2. which is similar to commercial low temperature adsorbents like 5A zeolite for CO2. and exhibit good mechanical stability under high differential pressures.. The operating pressures should be in the range that corresponds to this working capacity range (e. Working capacities at elevated temperatures in the range of 3-4 mol/kg are desirable. water swollen membranes.g. these types of membranes or membrane contactors show commercial potential with energy saving impact in CO2 capture.and high-temperature membranes that are selective only to CO2. and organic solvents polymeric rubbery membranes generally suffer from low permeabilities and low 32 . Any improvement in these capacities will be highly desirable. fixed carrier membranes.• • • • • • • insufficient selectivity slow adsorption or desorption or mass transfer kinetics moisture sensitivity vulnerability to poisons like CO or S too rectangular of an adsorption isotherm shape making regeneration difficult with pressure too strong of a physiochemical interaction requiring regeneration with relatively high temperature instead of pressure limited rapid cycling capability because commercial pellet materials tend to crumble if the cycling is too fast Table 10 provides some insight into the CO2 capacities now being achieved. However. and polyelectrolyte membranes inorganic membranes including molecular sieves and selective surface flow membranes hybrid mixed matrix membranes including inorganic-organic hybrid materials hollow fiber membrane contactors that operate with absorbents In general. the general classes of membrane materials being studied today include: • • • • • polymeric membranes including glassy and rubbery membrane materials facilitated transport membranes including immobilized liquid membranes. 1 to 40 atm). are robust and resistant to fouling and degradation. Near-Term Membrane Development Overarching Goal: Develop low.

with at least 2 times higher CO2 flux than current commercial membranes. Any improvement in these properties will be highly desirable. bypassing. 2) Specific Goal: Develop polymeric glassy or rubbery membranes for CO2/CH4 that have selectivity > 50. avoid vapor conditioning. 6) Specific Goal: Develop CO2 permselective hybrid mixed matrix membranes with improved selectivity and permeance. Near-Term Adsorption Process Development Overarching Goal: Develop new or modify existing adsorption process technology that offers increased energy savings at lower capital and operating costs. 3) Specific Goal: Develop CO2 permselective facilitated transport membranes that can operate in the absence of water for long periods of time. and minimize the strong dependence between CO2 permeance and partial pressure as often observed in these materials. and plasticization for the case with matrices made of glassy polymer. N2. etc.• • • • • selectivities towards CO2 over H2 facilitated transport membranes suffer from being too dependent on the presence of moisture to maintain selectivity inorganic membranes tend to be brittle and have low surface areas selective surface flow membranes tend to have low selectivities hybrid mixed-matrix membranes suffer from phase separation hollow fiber membrane contactors suffer from plasticization and tend to lose their resistance to wettability with time Table 12 and 13 provide some insight into the properties of these various membranes towards selective CO2 separations. wetting. Recommendations: 1) Specific Goal: Develop CO2 permselective polymeric glassy or rubbery membranes with CO2/H2 selectivity of > 15-20. and stability against phase separation. etc. 4) Specific Goal: Develop CO2 permselective inorganic membranes with selectivity of > 1520 or higher as these systems provide the desirable temperature stability. double the current commercial membrane CO2 flux. and with higher stability to syngas production conditions of 200oC or higher. affords higher reliability. 7) Specific Goal: Develop CO2 permselective hollow fiber membrane contactors with improved permeance and prolonged stability against solvent dissolution. and 33 . 5) Specific Goal: Develop CO2 permselective selective surface flow membranes with a much higher CO2 selectivity toward gases such as H2. control or eliminate carrier evaporation. CH4. and pore blocking. resists plasticizing and is stable to heavy oil.

where a pure heavy product like (CO2) is more desirable than pure light product (like H2) foster a clear understanding of the design of such a PSA cycle. Recommendations: 1) Specific Goal: Develop new PSA cycle designs that take advantage of new or even existing CO2 selective adsorbents. adsorption process technology being studied today includes: • • • various pressure swing adsorption cycles at ambient and elevated temperatures temperature swing adsoprtion for some CO2 separations sorption-enhanced reaction processes. No attempt has been made to recover CO2 from the tail gas of H2 PSA plants. mainly for H2 production In general. Any improvement in these performances will be highly desirable. which appears to be lacking compared to the commercial light reflux PSA processes. the application of the heavy reflux PSA concept for H2 production is a desirable near term target Some existing adsorbents with potential include: • • molecular sieve zeolites molecular gate silicotitanates 34 . As a guide. hence.reduces footprint and environmental impact. possibly TSA or PSA/TSA hybrid cycle designs could be envisioned. state-of-the-art cyclic adsoption processes suffer from the following: • • • • • • CO2 is typically the heavy component discarded in the tail gas of a PSA unit poor enrichment of CO2 in typical PSA units TSA is limited to long cycle times and hence low feed throughputs PSA generally is limited to ambient or near ambient temperature operation PSA feed pressures tend to be very high PSA and TSA beds tend to be very large Table 11 provides some insight into the performances of PSA processes for the recovery of CO2 from stack and flue gas. Some ideas for improvement include: • • • • • • • • rethink the use of the tail gas or heavy product from PSA processes revamp existing PSA plants through cycle modification use lower or even higher purge gas pressure replace one or more of the adsorbents with more efficient ones decrease the number of adsorbent vessels add storage tanks to replace some of the adsorbent beds develop new PSA cycles that take advantage of the heavy reflux concept.

4) Specific Goal: Develop absorbents that are stable to trace contaminants (e. Some ideas include: • • rethink bed designs for rapid heating and cooling because the long times required to heat conventional beds for regeneration and then cool them to the feed temperature give rise to long cycle times and thus exceedingly large columns take advantage of the many heat sources that are available throughout some of the CO2 producing plants that may lend themselves to a TSA or a PSA/TSA hybrid cycle configuration for selective CO2 removal from a process stream Near-Term Absorbent and Absorption Process Development Overarching Goal: Develop new or modify existing absorption process technology that offers increased energy savings with lower capital and operating costs.. one approach might be to develop reactive solvents that can convert sulfur species directly to elemental sulfur. amines are more likely to develop problems than most physical solvents).• activated carbons Some new adsorbents with potential include: • • • hydrotalcites CaO zirconates 2) Specific Goal: Need improved efficiency for thermal management in the design of TSA and PSA/TSA hybrid cycles. natural gas and coal bed methane). as opposed to thermal or vacuum regeneration. Recommendations: 1) Specific Goal: Develop absorbents with improved capacity and greatly improved heat of absorption.. while simultaneously or later absorbing CO2. 35 . 2) Specific Goal: Develop new regeneration techniques. and affords higher reliability and reduces footprint and environmental impact. 3) Specific Goal: Develop absorbents that work on high temperature gases. in particular develop regeneration techniques that can be done at high pressure to cut down on compression costs for sequestration or enhanced oil recovery uses. 5) Specific Goal: Develop more selective absorbents (CO2 over sulfur species) for processes with H2S and COS species present (e.g.g.

This design would not only shift the equilibrium of the reforming reaction favorably. These adsorbents should have comparable working capacity under operational conditions for the current and new non-structured adsorbents mentioned above. that removes CO2 by chemical reaction in the chemical process. 3) Specific Goal: Minimize the cycle time in rapid PSA to improve its throughput and 36 . The recommended approach involves the development of new adsorbent and membrane separation materials.g. 3) Specific Goal: Develop hybrid technology. It appears that highly selective and highly permeable membranes will always be very difficult to fabricate. this includes exploring rapid-cycle PSA with the incorporation of both heavy and dual reflux cycles steps. so a less selective membrane with a high flux may suffice. but it also would facilitate the WGS reaction. However. multi-separation designs. with hybrid multi-reactive. Long-Term Advanced Adsorbent Materials and Process Development for CO2 Removal Overarching Goal: Develop new adsorbent materials and CO2 process technology that offers increased energy savings with lower capital and operating costs.Long-Term Flow Sheet Augmentation with Adsorption and Membrane Processes Overarching Goal: Develop new adsorption and membrane process technology that offers lower capital and operating costs and affords higher reliability on stream with improved energy savings. develop a multifunctional hybrid reactor for steam methane reforming by combining the reactor with a CO2 selective adsorbent and an H2 permeable membrane). possibly coupled with adsorption or membranes processes. Driving equilibrium processes in this way can greatly improve manufacturing process efficiencies. the criteria for selectivity or permeability may be relaxed.. Recommendations: 1) Specific Goal: Develop advanced structured adsorbent materials for use in rapid-cycle PSA. and affords higher reliability and reduces footprint and environmental impact. In particular. 2) Specific Goal: Further develop the design of rapid-cycle PSA for CO2 capture and concentration. 2) Specific Goal: Develop new CO2 adsorbent and membrane technologies that are amenable to IGCC and related power and chemical production technologies with CO2 sequestration as a potential long term objective. Recommendations: 1) Specific Goal: Develop hybrid technology for H2 production (e.

while resisting fouling and cracking or embrittlement. surface properties. thermal swing. 37 . Long-Term Advanced Membrane Materials for CO2 Removal Overarching Goal: Develop new membrane materials that offer increased energy savings wiht lower capital and operating costs. In particular. and while withstanding high temperatures and pressures that could save substantial energy associated with operation by replacing existing CO2 and acid gas removal equipment. and accelerated cycle times. In particular. and affords higher reliability and reduces footprint and environmental impact. Recommendations: 1) Specific Goal: Next generation membrane materials are needed that offer very high selectivity for CO2 (> 100). or even hybrid pressure and thermal swing regeneration methods.hence efficiency by investigating the limiting relationship between adsorbent particle size. a deeper understanding of the PSA/TSA hybrid cycle is needed to quantify the effect on the cycle time and bed sizes when adding a forced temperature swing/PSA cycle. 4) Specific Goal: Develop TSA and or PSA/TSA hybrid cycles with improved materials for use in CO2 separation technologies. 5) Specific Goal: Develop improved CO2 separations with sorption enhanced reaction processes using pressure swing. the mass transfer limitations associated with ultra fast cycling need to be quantified.

00 50. Limestone and Dolomite Use 6. Petrochemical Production 9. Listed in order of decreasing CO2 generation. Lime Manufacture 5. U. Main Sources of Industrial CO2 Emissions 60. 4) lime and cement production.76 43. Note that with the exception of some of the combustion and gasification processes. These approaches include the worldwide Kyoto Protocol that is designed to cut CO2 emissions to below 1990 levels. Process flowsheets are provided that illustrates where the CO2 is produced. some of the approaches that have been proposed to combat these CO2 emissions are summarized. should be helpful in defining performance and operating condition requirements for the near.08 2.00 1 2 3 4 5 6 7 8 9 10 1. Typical process capacities and gas flow rates for these CO2 producing industries are given in Table 15. The flowsheets associated with each of these industrial CO2 producers is provided in Figures 4 through 14.00 30.00 10. 9) municipal solid waste landfills. and utility boilers. flaring. 5) H2. these flowsheets are 38 .00 0.including burners. and the use of CO2-consuming algae that can be used to make biodiesel fuel. 3) steel manufacture.01 1. Industry 2002 CO2 emissions in MMt: non-energy related for producing industrial CO2 processes.78 2.22 4. and corresponding stream compositions and conditions.and far-term development of new adsorption and membrane processes for CO2 capture from industrial sources. these industrial processes include 1) combustion . incineration. integrated gasification combined cycle power plants that are more efficient.98 4. and 10) fermentation to produce ethanol. in this supportive section. Ten sources (see Figure 3) are reviewed in order of decreasing impact on CO2 emissions.56 12. the main sources of industrial CO2 emissions are reviewed. Aluminum Production 7. and the condition and composition of the various process streams addressed. Ammonia Manufacture & Urea Application 4. Phosphoric Acid Production 53.38 Brief descriptions of the processes most responsible Figure 3. syngas. Soda Ash Manufacture & Use 8.00 40. the process capacity.S. Iron and Steel Production 2. 2) coal gasification. Cement Manufacture 3. The corresponding stream compositions and conditions for each of these flow sheets are given in Table 14.00 20.72 4. and NH3 production. Also. taxation in some parts of Europe on the release of CO2 into the atmosphere.SUPPORTIVE INFORMATION ON ENVIRONMENTAL CO2 EMISSIONS In this supportive section.03 15. Titanium Dioxide Production 10. These flow sheets. 8) Claus/SCOT processes. 6) natural gas production. 7) aluminum manufacture. emissions are discussed below.

Tables 2 and 3 and also Figure 3 present slightly different perspectives on non-energy related CO2 production from various processes. such as coal. or utility boiler is given in Figure 4. or some other type of fossil fuel. incinerators. All of these processes produce CO2 as a by-product of burning or combusting various fuel sources. or steam or to get rid of a waste product. utility boilers. including those that generate power from burning fossil fuels to simple burners. A typical flow sheet for a carbon-based combustion process that could be associated with a burner. and or flares to generate heat. flares. Fossil fuel power plants. natural gas. 39 . Combustion Processes [446-449] This section considers the carbon dioxide generated from all types of industrial combustion processes. six of which were mentioned above and are reviewed below. flare.concerned only with CO2 emissions resulting from chemical and petrochemical processes. as well as many chemical and petrochemical plants. energy. utilize burners. incinerator. solid waste. incinerators. and boilers.

Almost all fossil fuel power plants for the generation of electricity fall into this group. utility boilers. and NOx. the generated heat is used to generate electricity from steam turbines. Tables 1 and 2. Combustion processes that use coal or waste as fuel may require an elaborate cleanup process to remove ash. 40 .. including pulverized coal (PC) and IGCC or NGCC power plants.SOLID WASTE/COAL NATURAL GAS/GAS FUEL Combustion Chamber 1100 oC Incinerator Ash boiler Ash N2+H2O+CO2 +O2 Boiler Combustion Chamber 1100 oC 1 HCl Electrostatic Precipitator 250 oC Acid Scrubber 65 oC Fly Ash Gypsum VOCs SO2 Scrubber Limestone/Lime Adsorbent Activated carbon NH3 Air DeNOx Step SCR Catalyst 300 oC Stack 150 oC 2 N2+H2O+CO2 +O2 CLEANUP PROCESS Figure 4. state-of-the-art. In some plants. SO2. combustion process that includes burners. In power plants and utility boilers. Flaring does not necessarily take place in a chamber. The carbon-based fuel enters a chamber where it is combusted in the presence of air at a temperature of up to 1100oC. incinerators. such as IGCC or NGCC power plants. Flow sheet of a typical. and Figures 1 and 2 provide a breakdown of the energy and non-energy related CO2 emissions from combustion processes. HCl. and capacity and flow rate information is given in Table 15. The compositions of the numbered streams are shown in Table 14. volatile organics. etc. The corresponding stream compositions are given in Table 14. Combustion steps with gas fuels and natural gas may only require a NOx removal step. About 89% of the CO2 emissions in the manufacturing industry are energy-related emissions. flaring.

The gas is then fed into an absorption process for the subsequent removal of HCl and SO2. or even organic solid waste. In this dual mode. The coal or fuel in the gasification unit is exposed to a controlled atmosphere (> 20 atm and 1300oC) of both steam and oxygen to produce syngas (i. Coal gasification not only can be used for power generation. In general. clearly it produces both energy and non-energy related CO2 emissions (Tables 1 to 3 and Figure 3). The existence of these combustion and shift reactions leads to the formation of copious amounts of CO2 that eventually make their way into the atmosphere. Currently. more recent designs include a train of gas phase cleanup processes. Typical flow sheets of coal gasification plants are given in Figures 5 and 6. volatile organic compopunds (VOCs). are emitted to the atmosphere. Coal Gasification [446. and even other chemical production. NOX and other contaminants from the flue gas. and Figures 1 and 2). because of the ever increasing concerns over reducing the emissions of SO2. CO2 generally is not recovered from flue gas. In the case of solid fuels. and Figures 1 and 2). the gas is sent to an adsorption process where activated carbon removes the VOCs.e. petroleum coke. When it is used to generate only power. 41 . The fuel is normally a solid. the chamber is designed to cope with the removal of ash from the bottom. NH3. It can be fed to the gasifier dry or it can be injected in the form of a wet slurry. the cleanup of the exiting flue gas starts with the electrostatic precipitation of particles (fly ash) that could not be removed by the particle separators. The corresponding stream compositions are given in Table 14. but also it can be used for H2. When it is designed to do produce both chemicals and power. Heavy liquid oils can also be used in this process. Also. In this step. Next. for the most part. it is referred to as an IGCC plant. biomass. In the latter case. In the act of producing power or chemicals..gas turbines are also used in addition to steam turbines. such as coal. it is released into the atmosphere in copious amounts that represent nearly 90% of all CO2 emissions from industrial processing (Tables 1 and 2. it falls under the category of combustion (Tables 1 and 2. The cleanup of the flue gas is finished after a deNOx step. This process is carried out continuously at 250oC and removes nearly 100% of the fly ash. while minimizing the fraction of fully combusted carbon. CO + H2). the gas is passed through an aqueous suspension of lime that leads to the formation of CaSO4 (gypsum). and at the flue gas exit cyclones or other devices are used for gas phase particulate removal. syngas.450-452] The increasing need to more efficiently and more cleanly utilize the energy contained within coal motivated the development of coal gasification processes to replace old coal-fired power plants. and capacity and flow rate information is given in Table 15. hence. the NOx is catalytically converted into N2 and H2O using a mixture of air and ammonia at a temperature of about 300oC. coal gasification processes unavoidably produce large amounts of CO2 that.

which is then used to produce sulfuric acid. Tail gas from the cold scrubbing steps is sent to a Claus/SCOT process for sulfur production. HCN. IGCC) plants for power generation/syngas production. state-of-the-art coal gasification (also referred to as integrated gasification combined cycle. In the cold path. 42 . cleanup of acid syngas takes place either through hot (I) or cold sweetening paths (II or III).N2/Air H2SO4 Acid Plant 100 oC > 20 atm N2/Air/SO2 Sulfur Sorber 550 oC > 20 atm Zn based Syngas+ CO2 Coal Petroleum Coke Biomass Organic Solid Waste Warm Water Heavy Oil Slurry Gasification or POX 1300-1350 oC 20-80 bar Raw Syngas Chlorine Guard 550 oC > 20 atm Nahcolite 2 I Steam Air Air Separation O2 Quenching Cyclons and Filters Air Water Soluble Sp. Slag III Chemical Scrubbing 90-120 oC 20-60 atm K2CO3 w/wo MEA/DEA Flow sheet of typical. After a fuel (mostly coal) gasification step that is similar to reforming of CH4. NH3. acid syngas may be treated via physical scrubbing following a COS hydrolysis step (II). The compositions of the numbered streams are shown in Table 14. syngas may not need COS hydrolysis if the syngas is sweetened by chemical scrubbing with K2CO3 (Benfield) (III). sulfur compunds are converted into SO2. Alturnatively. chlorides Syngas+CO2+ H2O Scrubbing H2S/COS/SO2 COS Hydrolysis 350 oC < 200 oC II 20-50 atm TiO2/Al2O3 Claus/SCOT CO2+H2S+SO2 Physical Scrubbing Syngas+ CO2 1 20-50 oC 20-60 atm To Power Selexol/Purisol/Rectisol Generation CO2+H2S+SO2 Syngas+ CO2 Water Slag & Particulate Syngas + CO2+ H2S/SO2 N2 Figure 5. In the hot path.

NH3.N2/Air H2SO4 Acid Plant 100 oC > 20 atm N2/Air/SO2 Air Sulfur Sorber 550 oC > 20 atm Zn based Syngas+ CO2 Coal Petroleum Coke Heavy Oil Chloride Guard 550 oC > 20 atm Nahcolite Warm Water Syngas + Water Soluble Sp.e. path III). Flow sheet of typical. IGCC) plants for power generation/H2 production. sweet shift) identical to those in ammonia production (see Figure 9). the acid syngas may be sweetened before (II) or after (III) shift reactions. In the first case (i. syngas is shifted after sweetening through two water gas shift steps (i..e. The compositions of the numbered streams are shown in Table 14. the sweetening step is just like those shown in paths II and III in Figure 5 (only that of path II is shown here) before going through two sweet shift steps. path II)..e. sweetening takes place via physical scrubbing after two sour shift reactions that are specially prepared to deal with sulfur bearing species while chemically converting them into H2S. In the case of the hot sweetening path (see Figure 5). 43 . SO2. In the second case (i. state-of-the-art coal gasification (also referred to as integrated gasification combined cycle. The process is similar to that shown in Figure 5 except that the syngas gas is further shifted for both H2 production and pre-combustion capture of CO2. chlorides Syngas + COS CO2/H2S/COS Hydrolysis H2O 350 oC Scrubbing o 20-50 atm < 200 C II TiO2/Al2O3 Physical Scrubbing 20-50 oC 20-60 atm Selexol/Purisol/Rectisol H2S+CO2+SO2 1 Syngas +CO2 High Temperature Clean Shift 315-430 oC 20 atm Fe3O4/Cr2O3 Low Temperature Clean Shift 205-230 oC 20 atm CuO/ZnO I Slurry Raw Syngas Steam Air Air Separation Gasification or POX 1300-1350 oC Quenching O2 20-80 bar Claus/SCOT H2 + CO2 Cyclons and Filters Water Slag & Particulate H2S+CO2+SO2 Physical Scrubbing 20-50 oC 20-60 atm Selexol/Purisol/Rectisol H2 + CO2 III High Temperature Sour Shift 315-430 oC 20-50 atm CoMo based Low Temperature Sour Shift 205-230 oC 20-50 atm CoMo Based H2 + CO2/H2S 2 N2 Slag To H2 Purification In Figure 9 Figure 6. In the case of the cold sweetening path (see Figure 5). CO2/H2S HCN.

In hot sweetening. HCN. Note that a COS-CS2 hydrolysis unit is not always required. In the chloride guard reactor. as described below in the H2. The following reaction takes place: HCl + NaHCO3 → NaCl + H 2O + CO2 (1) In the HGCU unit. However. heat exchanging).Most gasifiers are provided with purified oxygen (> 95 vol%) to significantly reduce the size of the unit and its operational costs (e. a chemical scrubbing unit operating as a CGCU at 90-120oC that contains K2CO3 has proven to be successful in hydrolyzing COS and CS2. two different processes have evolved for producing power or H2 (chemicals) from cold-sweetened sour syngas. At this point. due to the additional costs associated with the air separation unit. By simple chemical exchange. which contains all the sulfur compounds and a large fraction of CO2. followed by a hot gas cleanup unit (HGCU). if not all. where elemental sulfur is produced. and NH3 present in the gas stream. the gas is first sent to a COS hydrolysis unit (350oC). the resulting syngas is sent to a series of shift reactors and purification units that are based on the same processes used in steam reforming.g. Syngas. This also is done to minimize the generation of NOx. SO2. the sour syngas is sent to so a called sour shift reactor located upstream of the CGCU. a considerable number of gasifiers operate with air. The resulting syngas is sent to a series of shift reactors and purification units that are based on the same processes used in steam reforming. and NH3 Production section. It is cooled by quenching and heat exchanging. traces of HCl are removed from the gas by reacting with sodium bicarbonate (nahcolite) in the form of pellets. and other traces of sulfur-containing gases are removed. is sent to a sulfur recovery process. Gasifiers produce both solids and gases as products. such as the Claus/SCOT process. such as a Selexol unit or some similar process. as described below in the Hydrogen. the gas first goes through a column filled with a solid absorbent that contains ZnO. The particulates are removed using cyclones and filters. This unique shift reactor contains a sulfur resistant catalyst made of Co and Mo to 44 . while simultaneously removing sulfur-containing species all in one step. The CGCU tail gas. A fraction of the sweet gas produced in this step is recycled and mixed with hot air to regenerate the HGCU unit (or one that operates in parallel) once the ZnO is spent or saturated. Finally. and NH3 Production section. the gas leaves the filters at about 550oC and more than 20 atm and enters a chloride guard reactor. Syngas. the ZnO reacts at about 550oC with all the sulfur containing compounds in the gas and converts them into ZnS. Then it is sent to a cold gas cleanup unit (CGCU). In the first process. The cooled and particulate-free sour syngas is then sent through either a hot or cold sweetening process to be used either for power generation or H2 (chemical) production. The resulting gas is very hot and contains particulate matter. In the second process.. the gas leaves the filters at a much lower temperature (350oC) and enters an acid scrubber where water is used to remove most. where H2S. of the HCl. In cold sweetening. This regeneration reaction takes place at a temperature above 750oC and the SO2-rich gas leaving the unit is sent to an acid plant to produce sulfuric acid. The solid slag is easily removed from the bottom of the gasifier. whereby a TiO2/Al2O3 catalyst converts most of the COS and even CS2 into H2S.

and capacity and flow rate information is given in Table 15.453-456] The manufacture of steel constitutes the largest industrial producer of non-energy related CO2. basic oxygen furnace (BOF). Because COS and CS2 hydrolysis takes place inside this reactor. coal-coke conversion. CO. which involves the carbonization of coal at high temperature (1100°C) in an oxygen deficient atmosphere to produce coke. a separate hydrolysis unit is not needed in this case. and electric arc furnace (EAF). It operates at high pressure (> 20 atm) and in two steps: one at an intermediate temperature (315-430oC) and the other one at a lower temperature (205-230oC). The gas leaving the coke oven is composed mainly of CH4 and H2 plus CO2. The corresponding stream compositions are given in Table 14. Iron and Steel Manufacture [446. blast furnace. Lime. A typical flow sheet for the manufacture of steel is given in Figure 7.Silica) Basic Oxygen Furnace 1700 oC Steel Electric Arc Furnace >1600 oC N2 +CO2+CO+H2 CO +CO2 3 To Flaring Steel Scrap Air 4 Graphite Electrodes Figure 7. and heavier 45 . which is enriched in carbon relative to the raw coal. state-of-the-art stainless steel production plant consisting of a coke oven.P. The compositions of the numbered streams are shown in Table 14. CO2 and CO are produced from burning methane. Steel manufacture starts with the coke making process.treat the sour syngas. being responsible for about 29% of those CO2 emissions (Tables 2 and 3. Ca carbide O2 Slag (S. sinter plant. NH3. Sulfates Coal Coke Fines Dust Sinter Plant Flue gas Iron Ore Limestone Fines Coke Oven Battery 1100 oC Iron Ore H2+NG+ N2+H2O 1 Sintered pellets N2 +CO2+CO+H2 Air Dust Separator 2 To Fuel or Flaring Coke+ NG Air Slag Blast Furnace 1500-1900 oC N2+CO+CO2+H2+Dust Molten Iron Mg. and Figure 3). Water Tar. and carbon removal from pig iron through all steps. Flow sheet of a typical.

This step is where most of the CO2 is generated that does not come from the burning of fuels. and NOx emissions are produced during this step. phosphorus. calcium. This flue gas is used either as fuel or it is flared. and a balance of silicon. Although it can process pig iron in the feed. about 4% carbon. along with desulfuring agents such as lime. In the blast furnace. which ultimately reduces the iron oxide in both the iron ore and the sinter into metallic iron according to the following reaction: Fe2O3 + 3CO → 2 Fe + 3CO2 (2) The limestone is used to remove the silica present in the ore in the form of fusible calcium silicate. With a moving lance. About 75% of the hot metal from the blast furnace is poured into a pear-shaped basic oxygen furnace (BOF) that tilts sideways for charging and pouring.hydrocarbons. All CO produced in this and other steps in the steel industry is utilized as a reducing agent and in the generation of heat. Lime and Cement Production [446. which is carried out in a sinter plant. Without limestone. and magnesium. while silica. limestone. and as it burns. This step is followed by a step that utilizes a basic oxygen furnace (BOF). CO is produced and leaves the reactor. certain proportions of coke. and traces of sulfur. and magnesium phosphates and sulfides become part of the slag that is separated from the molten steel. resulting in a loss of metallic iron. the steel forms in the same way. The coke as a reactant is essentially burned as a fuel to heat the furnace. These small agglomerates allow the passage of hot gases during the subsequent blast furnace operation. Fine particles of iron ore. manganese. Instead of a BOF. iron ore. the EAF process has been designed more specifically for the recuperation of steel from scrap. an electric arc furnace (EAF) is also used.457] The manufacture of cement and lime from limestone and dolomite constitute the second and fifth largest sources of CO2 produced in non-energy related industrial processes (Tables 2 and 3. The result is a semi-molten mass called sinter that solidifies into porous pieces of appropriate size and strength for feeding into the blast furnace. as such. Whether the BOF or EAF are used. In this furnace. it gives off CO. calcium carbide. iron silicate is formed. and collected dust are agglomerated by combustion with air (1200oC). it is easy to separate. sinter. and limestone are mixed together and heated to temperatures of around 1500 to 1700oC with a controlled supply of air to produce the so called pig iron. and 46 . VOCs. energy is supplied electrically via graphite electrodes or chemically via mixing natural gas and oxygen through lances to melt the mixture. is a pre-treatment step in the production of iron. Large quantities of CO2. The next step. The heat released due to these reactions raises the furnace temperature (> 1600oC) and facilitates melting of the mixture. This hot metal is then mixed with 25% purchased scrap metal. CO. coke. The pig iron produced in this step contains about 92% iron. while producing CO and slag. which floats to the top of the molten metal. pure oxygen is injected into the mix at various places in the BOF to combine with carbon and other unwanted elements such as silicon and phosphorus that are present in the pig iron.

constituting together about 32 % of this total.. is blended with the ground clinker. A review of the global cement industry and its associated CO2 emissions has been given by Worrell et al. Final products are obtained following fine milling steps. Most CO2 is produced from the decomposition of carbonates and burning of kiln fuel. The first step consists of a calcination step at 800900oC where the calcium carbonate (i. The final product is then milled to produce a fine powder. and capacity and flow rate information is given in Table 15. The composition of the numbered stream is shown in Table 14. limestone) in the pellets undergoes decomposition with the release of CO2 according to: CaCO3 → CaO + CO2 (3) The CO2 is produced at around 22 vol%. clinker) of uniform quality. The corresponding stream compositions are given in Table 14. A typical flow sheet for the manufacture of cement and lime is given in Figure 8. This lime powder may be 47 . After a preparation and raw milling step. Farther down in the kiln. This relatively high concentration of CO2 makes it ideal for recovery as a saleable product. This calcination step again produces CO2 according to the reaction depicted in Equation 3.e.. CO2 + N2 Limestone Ingredients 1 KILN Preparation & Raw Milling Calcination 800-950 oC Clinkering 1350-1450 oC Air Lime Milling Gypsum Ball Milling Cement Figure 8. The manufacture of cement is finished with a milling of the clinker to produce a fine grey powder.e. Cement is produced in a further clinkering step and much more elevated temperatures. Cement normally is produced in three steps. along with other materials. to produce finished cement. After an extraction and coarse milling process. [458]. with it ranging from 14% to 33 vol%. the pellets are inserted into a rotary kiln where they undergo two steps. The major difference between them is that the rotary kiln is operated in one step to form the pellets during calcination at 800-900˚C. the raw limestone is mixed with mineral additives and water in proportions that lead to the formation of pellets (i.Figure 3). additional clinkering completes the calcination stage and fuses the calcined raw mix into hard nodules (again referred to as clinker) that resemble small gray pebbles. at temperatures between 1350 and 1450oC. which controls the rate of hydration of the cement in the cement-setting process. After a preheating step. Flow sheet of a typical. Lime is produced from limestone and dolomite in a very similar process. lime is produced through calcination within a kiln. state-of-the-art process for the manufacture of lime and cement. Gypsum (CaSO4).

which was operated at a lower temperature of 203-230oC. and NH3 is given in Figure 9. older H2 production plants (still in existence) required two steps for the water gas shift reaction to achieve maximum CO conversion into H2 using H2O and producing more CO2 as the byproduct. stems from the reforming of natural gas and other hydrocarbon feedstocks. with PSA units replacing the CO2 scrubbing step for the purification of H2. Hydrogen purification with the PSA option became less expensive because it eliminated the need for the low temperature shift reactor and a methanation step to fully eliminate CO from the hydrogen stream. based on a typical reforming process. is cooled down and sent to either one or two water gas shift reactors. At the present time the PSA tail gas is used as fuel. new avenues for CO2 removal came into practice.4% of those CO2 emissions (Tables 2 and 3 and Figure 3). In these reactors. 48 . the resulting syngas. autothermal reforming. CH4. The gas leaving this reactor. This reactor utilized a Cu-Zn catalyst to convert any remaining CO into H2 and CO2. H2O is utilized to convert most of the remaining CO into CO2 while more H2 is generated. A brief overview is provided below. The source of the hydrogen and carbon in these gases. These important gases are all produced in a similar fashion through a chain of reforming and shift reactions. The corresponding stream compositions are given in Table 14. and NH3 production technologies by reforming. was sent to a highpressure scrubbing process that removed nearly 100% of the CO2 in the stream. Syngas. syngas. Hydrogen. which is relatively rich in CO2. But the CO2 was not enriched as much as it was before. and hence the CO2 that is formed. being responsible for about 10. CO2 is produced as a by-product in the production of H2. and even CO. A detailed report on hydrogen. It was then sent to a methanator. This step was then followed by the second water gas shift reactor. A typical flow sheet for the manufacture of H2. which contained less than 0. and NH3. and NH3 Production [446] The manufacture of H2. syngas. The first water gas shift reactor was a high-temperature shift reaction that converted most of the remaining CO into H2 and CO2 using a Fe-Cr catalyst at 315-430oC. which reduced CO by converting it back to CH4. with the resulting CO2 typically being released to the atmosphere. and capacity and flow rate information is given in Table 15. After leaving the reformer reactor at temperatures of over 1000oC and pressures of up to 20 atm. With the introduction of new NH3 plants. Before the advent of pressure swing adsorption (PSA) for H2 purification in the early 1980s.5 vol% CO. and partial oxidation processes has been published recently by the authors [1]. typically at very high purity (> 98 vol%). syngas (H2 + CO). and NH3 constitutes the third largest industrial producer of nonenergy related CO2. The PSA tail gas does not contain more than 40 vol% CO2 and is balanced with significantly high concentrations of H2.sold as is or it may be mixed with water to produce a milky suspension and sold as lime slurry. syngas.

The tail gas from the PSA or membrane unit (streams 2 and 3. respectively) are used as fuel. Flow sheet of a typical. the permeate. Selexol.99% H2 10 . is purified into H2 using either CO2 scrubbing with physical absorbents. CO2.5% =75% H2O Condensate CO2 Scrubber 70-95 oC 20-50 atm Physycal Abs.50 ppm COx 3 Retentate H2+CO2+CO+CH4 HYDROGEN PURIFICATION 95-97% H2. CH4 10 .5% =19% = 0. or membranes. and CH4 currently is 49 . state-of-the-art H2 or NH3 production plant. which is rich in H2. Purisol etc CO2 4 Membrane 20-50 oC 10-50 atm PSA 2 Purge H2+CO2+CO+CH4 Permeate 20-50 oC 10-50 atm Methanation 300-350 oC 20 atm Ni Based 99 to 99. H2 selective membrane technology also is available commercially and is being used for H2 production. 20 atm WATER GAS SHIFT High Temperature Shift 315-430 oC 20 atm Fe3O4/Cr2O3 Low Temperature Shift 205-230 oC 20 atm CuO/ZnO CH4 CO2 CO H2 = 5.50 ppm COx To Ammonia Production Figure 9. which contains H2. A methanation step may be required to convert the remaining CO into CH4 when using scrubbing or membranes. CO2.Reforming Natural gas 1 Syngas+CO2+H2O+CH4 At 800 oC. This technology takes advantage of the relatively high H2 concentration (> 75 vol%) produced from the low temperature shift reactor. The high pressure-reject gas. which is mostly H2. CO. requires recompression and may contain significant amounts of CO2 that forces further H2 purification. Shifted syngas. However. PSA. The compositions of the numbered streams are shown in Table 14. and CH4 with traces of CO.

with a much smaller fraction (< 5 vol%) of ethane and propane. Further steps may be required for the removal of excess N2 or CO2 in super sour streams. Low-pressure wells may be assisted with CO2 injection. H2S. After a series of dehydration steps. Processed natural gas consists principally of methane. When natural gas contains H2S. and after removal of the C2-C5 fraction via absorption. it normally is referred to as sour gas. The CO2 emissions result from the so called natural gas sweetening steps that are associated with natural gas processing. In a raw state. and capacity and flow rate information is given in Table 15. the natural gas is then sweetened by scrubbing it with alkanolamines to remove the sulfur-bearing compounds and CO2. Traditionally. The corresponding stream compositions are given in Table 14. and it may contain considerable amounts of water vapor.459] A typical flow sheet for natural gas production is given in Figure 10. Natural Gas Production [446. Likewise.used for fuel. are used to treat the tail gas from the scrubbing step to convert all the sulfur-bearing compounds into solid sulfur. This category accounts for around 10. state-of-the-art process for the production of natural gas. other sulfur bearing compounds. it is normally extracted as an associated gas. or polyaramide) are used prior to scrubbing to reduce the large concentrations of both the CO2 and sulfur-bearing compounds. PSA systems with molecular sieves (titanosilicate molecular gates or zeolite molecular sieves) are located downstream of the scrubbing unit to remove the remaining CO2 and excess N2. natural gas in the raw state also contains some butanes and pentanes. polyimide. with the CO2 again being released to the atmosphere. the sour gas is sweetened through an absorption scrubbing process (typically. and other compounds such as Hg. CO2. an ethanol-amine based process) that is followed by a desulfurization step (Claus/SCOT process). where all sulfur 50 . a series of steps are carried out to remove water and C3+ vapors. N2. and CO2. Flow sheet of a typical. He. CO2 Natural Gas Well > 500 Psia Claus/SCOT CO2 + N2 CO2 +H2S Scrubber MEA/M DEA PSA Molecular Gate CH4 + CO2 + H2S+N2 Separator Hydrocarbon Condensates H2O 1 Membrane CH4 +N2 Figure 10. which is presented in Figure 7. The Claus/SCOT process (or similar processes). The composition of the numbered stream is shown in Table 14. and Figure 3). Membrane systems (with cellulose acetate. Natural gas production constitutes the fourth larger producer of CO2 as a result of natural purification. either with glycol absorption or adsorption with silica gel or activated alumina. when extracted from oil wells.1% of the non-energy related CO2 emissions (Tables 2 and 3. either free or dissolved. in addition to ethane and propane. After extraction from a well at elevated pressures. or as a non-associated gas when extracted from gas and condensate wells where there is little or no crude oil. Once separated from crude oil (if present).

In the case of natural gas streams that are rich in N2. The corresponding stream compositions are given in Table 14. In the first step. that in 1 of every 10 wells the content of CO2 is larger than 2 vol% and that in 1 of every 100 wells the CO2 content is larger than 20 vol%. It is known.454-456. and N2 in some natural gas wells can be so high that traditional steps for gas sweetening may be insufficient. alumina is produced out of bauxite using either the Bayer process or the Sinter process. and capacity and flow rate information is given in Table 15. only those streams containing more than 10 vol% N2 can be economically blended with more dilute streams after the sweetening step. The same is true with H2S and N2. where concentrations may vary between 2 and 98 vol% for the former and up to 20 vol% for the latter. The compositions of the numbered streams are shown in Table 14. Natural gas sweetening is responsible for more than 15% of the total sulfur production in the US.459. the CO2 concentration can even exceed 50 vol%. A typical flow sheet for the manufacture of aluminum is given in Figure 11. Bauxite NaOH Bayer Process Sinter Process Na2CO3 Residue Residue Alumina graphite CO2 graphite Hall-Heroult Smelting Process 1 atm + Cryolite (Na3AlF6) 1000 oC Carbothermic Advanced Reactor Process 2100 oC 1 CO2 Aluminum 2 CO Figure 11. the concentration of CO2. Flow sheet of typical. for example. Aluminum Manufacture [446. state-of-the-art processes for the manufacture of aluminum.6% of the total.compounds and CO2 are removed. 51 . CO2 is produced during the electrochemical decomposition of carbon made cathodes. sulfur. Alumina is then electrochemically converted into aluminum either by the Hall-Heroult process or the more recently developed carbothermic process. However. and Figure 3) or about 2. In the latter case.460] The manufacture of aluminum constitutes the sixth largest single source of non-energy related CO2 emissions (Tables 2 and 3.

respectively. Bauxite is a mineral rich in gibbsite (Al2O3•3H2O) and boehmite (Al2O3•3H2O). is the carbothermic advanced reactor process (CARP). Alumina is manufactured via the Bayer process. the Sinter process is of minor commercial significance compared to the Bayer process. An alternative electrochemical process to the Hall-Heroult process. The major component of the off gas is CO instead of CO2. which is when alumina starts to melt. the temperature of the reactor would need to be over 2000oC. Ti. Ti. or a combination of the two processes. Without cryolite. The process is based on the use of cryolite (Na3AlF3). recently developed for the production of aluminum out of alumina. and desilication. The temperature of the digestion process varies between 150 and 250oC depending on whether the bauxite is richer in gibbsite or boehmite. the Sinter process. This digestion process is followed by a sedimentation and filtration step. The sintered material is then converted into a very fine white alumina powder after realizing a series of steps that include water extraction. The overall reaction is given by: 2 Al2O3 + 3C → 4 Al + 3CO2 (4) Besides CO2. The Sinter process starts with a rotary kiln. where aluminum is produced electrochemically at about 1000oC. where oxides of Fe. The purified alumina is then fed into a Hall-Heroult smelting process. The electrochemical energy is provided in the form of graphite anodes and carbon cathodes placed in the upper and lower parts of the reactor.5% pure alumina. The precipitate is dried and filtered and finally undergoes a dry calcination step at 900-1100oC that leads to the formation of 99. which is considered economically suitable for bauxites containing 30-60% Al2O3 as aluminum hydroxides and less than 7% SiO2 as clay (kaolin) minerals. In the Bayer process. and Si are removed. It also contains significant concentrations of oxides and hydroxides of Fe.The manufacture of aluminum starts with the production of alumina from bauxite. and Si. Boehmite cannot be economically extracted below about 200oC. precipitation. the bauxite is reacted with a hot aqueous solution of NaOH (~ 200 g/L) to extract the aluminum in the form of an oxide (such as Na2O•Al2O3). the major emissions are perflurocarbons that result from the decomposition of cryolite and SO2 that derives from sulfur impurities in the graphite. However. The caustic aluminate liquor is then sent to a crystallizer (60-70oC) that forms precipitates of gibbsite. which can be flared to produce CO2 anyway. and it eliminates all perflourocarbon and carbon anode baking furnace emissions. It is able to dissolve alumina to the extent of 15 wt% at 1030oC. CO2 is evolved from the surface of the anodes and becomes the largest fraction of the off gas. 52 . wherein pellets of the bauxite and minerals of sodium carbonate and sodium hydroxide are converted into NaAlO2 at a relatively high temperature of 900-1100oC. because of its complexity and high energy consumption. This process has been shown to be more economically viable. but it eliminates the use of cryolite so that the reactor temperature must reach 2000oC. while alumina reduces into aluminum when in contact with the cathode surface. CARP also uses graphite as the anode. consisting of one or more (typically three) potlines of several ovens. which melts at temperatures a little under 1000oC.

In the Claus step. state-of-the-art Claus-SCOT process for the production of sulfur from a stream rich in sulfur-bearing compounds. CS2 and elemental sulfur).Sulfur Recovery Processes [446. which converts all sulfur compounds in the gas leaving the Claus unit (e. The corresponding stream compositions are given in Table 14. the CO2 emissions due to sulfur recovery processes are not included here in tables or figures. etc Oxidizer 1000-1400 oC 1 atm Air CLAUS PROCESS H2O 1 CO2+H2S+SO2+ COS/CS2 Figure 12. Flow sheet of a typical. SO2. the principal process that is used for sulfur recovery is based on the Claus and Shell-Claus offgas treating (SCOT) technologies.462] Sulfur recovery in the petroleum refineries. Today. The Claus/SCOT process removes species from sour streams that contain sulfur and converts them into elemental sulfur. The compositions of the numbered streams are shown in Table 14. which produces elemental sulfur. while the rest comes from oil refineries and a very minor fraction from coke manufacturing. The 53 . A typical flow sheet for these technologies is given in Figure 12. In the SCOT step. COS. 10% of which is in the form of sulfuric acid. which is then recycled back to the Claus step for further processing. Sulfur N2+ CO2+H2S+SO2 H2 Reactor 200-350 oC 1-2 atm Alumina 2 To injection or Incinerator SCOT PROCESS Sulfur Reactor 250-300 oC 1-2 atm CoMo Based N2+CO2 +H2S H2S+CO2+N2 3 CO2 Scrubbing 15-25 oC 1-2 atm MEA/MDEA. This process is followed by the SCOT process.g. into H2S. Around 17 % of the total sulfur produced in the U. Currently.. the gas is further polished by removing the remaining sulfur by first converting SO2 into H2S and then using a MEA/MDEA scrubbing step. the gross fraction of the sulfur is removed from the stream. Hence. with CO2 being the second largest species.S. The process starts with the Claus step. which constitute more than 80% of the total sulfur recovery plants in service in the U. and capacity and flow rate information is given in Table 15. coke production and natural gas sweetening is another important source of CO2 emissions. while leaving only H2S and SO2 in the processed gas as sulfur-bearing species. The process is designed to treat gas streams containing more than 50 vol% H2S.Sulfur recovery constitutes around 25% of the CO2 emissions produced in the natural gas industry.461. comes from natural gas sweetening.S. the tail of which is sent back to the Claus step. while at the same time it constitutes less than 2% of the total non-energy related CO2 emissions. the sulfur recovery industry produces about 9 millions tons of pure sulfur per year.

At this step. The corresponding stream compositions are given in Table 14. This reactor is then followed by an absorption process that removes more than 99% of the H2S from the processed gas. or it builds up pressure within the landfill (6) 54 . They consist of layers 50 to 100 ft thick of solid human-generated wastes that are entombed beneath 5 ft of inert material that plays the role of reducing both gas permeation and rainfall water infiltration.S. The first step. and the world. and all traces of organic compounds combust into H2O and CO2. CO2. The Claus process consists of two steps. relatively new sources. all traces of NH3 also react to form H2 and N2. Several improvements have been done to improve this process. The SCOT process also consists of two steps. Landfill and Coal Bed Methane Gases [463. Each one covers anywhere from 10 to 1500 acres of land. As a result. they are both sources of CO2 emissions. The gases produced during this step are mainly N2. albeit. CO2.remaining gas is sent to an incinerator prior to exhausting to the atmosphere. which is referred to as the thermal step. For example. but they may use as an option Co-Mo as the catalyst. where all the sulfur compounds react at about 250-300oC with H2 to form H2S. is basically an incineration step. Similar to the Cluas process. The reactors consist of packed beds containing alumina as the principal catalyst. where H2S and SO2 react (200-350oC) to produce elemental sulfur according to: 2 H 2 S + SO2 → S + 2 H 2O The elemental sulfur is removed in the liquid state through the condensers. These two gas streams are not included in any category in Table 2. Landfills are scattered all over the U. It is where the sour gas becomes combined with air at high temperatures (1000-1400oC) to oxidize at least one third of the H2S into SO2 according to: H 2 S + 1. This gas either slowly permeates the landfill cap into the environment. the gases produced during the SCOT process are mainly N2. it contains relatively high concentrations of CH4. the superclaus process converts H2S directly into elemental sulfur in one step. it is added upstream. and H2O. More than 95% of the sulfur compounds are removed in this step. and H2O. and capacity and flow rate information is given in Table 15. Nevertheless.464] Typical flow sheets for landfill and coal bed methane gas production are given in Figures 13a and 13b. The first step consists of a reactor containing CoMo catalyst. Otherwise.5O2 → SO2 + H 2O (5) This reacted gas then goes to the second step that consists of a series of reactors and condensers. Landfill gas (LFG) is produced naturally from the anaerobic decomposition of the waste material. where the H2S-rich gas is sent back to the Claus step. Hydrogen may already be present in the Claus tail gas.

as oxygen and nitrogen may be present in considerable amounts. This causes the infiltration of significant amounts of air into the landfill. which dilutes both the CH4 and CO2 constituents. however. but the amounts of these gases in each case are quite different. significant amounts of N2 become incorporated into the extracted gas mixture. Coal bed methane contains about the same amount of CH4. Coal bed methane gas represents not only a virtually untapped source of energy. the CO2 emissions are offset by the CO2 storage. the extraction lines are subjected to vacuum. The composition of coal bed methane gas can vary considerably.and chlorine-bearing compounds are also present in typical LFG.a) Flaring CH4 + CO2+N2+H2O b) CH4 + N2+O2+ CO2+H2O 1 1 Air Landfill Coal Bed Figure 13. but not necessarily all. For a typical LFG site. However. creating the potential for an explosion. but much more N2 and O2 and much less CO2 than landfill gas (Table 14). Some. CO2 and H2O. from coal mine to coal mine. N2 and some toxic non-methane organic compounds. Another 45 vol% is composed of CO2.5 million standard cubic feet of gas per day. Most of the permeating gas out of landfills consists of methane and carbon dioxide in an almost 1:1 split. and the storage of CO2 comes with energy benefits because the mine produces coal bed methane gas that can be recovered during the storage process. contains N2. The compositions of the numbered streams for flow sheets (a) and (b) are shown in Table 14. As a result. pipes have been installed in most capped landfills to facilitate bringing the LFG to the surface for flaring or recovery as an energy source. The remaining 10 vol% is composed of a small amount of water vapor (saturated). the flow rate is 2. state-of-the-art a) solid waste landfill gas recovery process and b) coal bed methane gas recovery process. of the oxygen is bioprocessed near the surface before reaching the suction lines. methane splits 1:1 with N2. 55 . Coal bed methane gas. much like landfill gas. the coal mine itself is being considered as a viable place to sequestor CO2. such as VOCs. which naturally vents to the atmosphere or is flared to convert methane into CO2. Potential mechanical extraction of methane by vacuum may lead to diffusion of air into the landfill and may require separation steps similar to those of natural gas production. In such a situation. Flow sheet of a typical. Over the past few decades. CH4. O2. In the forced extraction of LFG for energy recovery. and sulfur. In coal bed methane gas. but also another source of CO2 emissions if tapped for this energy. The same considerations are valid for coal bed methane gas. About 45 vol% of typical LFG is composed of CH4.

The ethanol produced worldwide by fermentation constitutes more than 90% of the manufactured ethanol destined for use as a motor fuel. odors. a nearly 21% increase from the 2. The composition of the numbered stream is shown in Table 14. a growth trend is apparent and likely to continue. During 2004. organics Figure 14. The ethanol fermentation process is carried out in a batch mode at a temperature of around 35oC. Water is mixed with baking yeast and milled corn that contains between 150 and 250 g/L of starch. organics CO2 water + starch Aqueous Fermentor 35-40 oC H2O Scrubbing PSA AC/SiO2 1 Ethanol (8-9 vol%) in water H2O . this juice is ready for distillation. H2S. ethanol manufacture from the fermentation of either cornstarch or ground whole corn is increasingly becoming a significant source of CO2 emissions. Mitigation Approaches to Combat CO2 Emissions One approach to address CO2 emissions worldwide is known as the Kyoto Protocol. 3. So far 120 countries. Nearly 4000 tons of CO2 are produced along with each million gallons of ethanol.S. The reactants are converted into a juice that contains between 7 and 9 vol% percent ethanol. The fermented juice produced contains about 8-9 wt% ethanol.4 billion gallons of ethanol were produced in the US. It is highly likely that the non-fuel related CO2 emissions in this area have already overcome those of the aluminum industry. Adsoption processes for trace contaminant and moisture removal. Flow sheet of a typical. Nevertheless. with H2O and ethanol being very minor components. After a series of purification steps. using nearly 2 billion gallons of fuel ethanol annually. The offgas is mostly CO2. CO2 is produced as result of a methabolic process by yeast.Fermentation to Produce Ethanol [465] A typical flow sheet for the manufacture of ethanol through fermentation is given in Figure 14.S.81 billion gallons produced the previous year. and capacity and flow rate information is given in Table 15. with its use on the rise. Ethanol manufacture is not included in any table or figure because it constitutes less than 2% of the non-energy related CO2 emissions. including odor removal and drying. which corresponds to the U. much (but not all) of the CO2 produced during ethanol manufacture is being sold for commercial use. responsible for 44% of the world's 56 . In recent years it has accounted for around 1% of the U. This is changing rapidly in the US. state-of-the-art fermentation process for the production of ethanol typically out of corn-starch. The corresponding stream compositions are given in Table 14. which was introduced in December 1997. In countries that promote the use of ethanol as a motor fuel. gasoline supply. odor. followed by condensation and liquefaction are the principal methods for the purification of the CO2 generated from ethanol production.

but only by a small margin [470]. A recent MIT report [470] presented a study on the impact of a CO2 emission tax on the cost of retrofitting existing PC or building new (e. mid distillates. an IGCC plant is more amenable to CO2 capture and sequestration as the CO2 can be removed before entering the turbine. It appears that the Kyoto Protocol will be challenged to meet its goals. storage.. Finally.S. Because IGCC technology is more amenable to CO2 capture. They also require about 30% less water than their coal fired counterparts because the turbines do not require cooling. Since it is anticipated that CO2 capture and storage technology may be considered as an essential part of any future power plant. these countries have agreed to reduce their anthropogenic CO2 equivalent emissions of greenhouse gases to levels that are at least 5% below their 1990 levels for the period of 2008 to 2012. ammonia.. which has cut emissions to four-fifths of their 1990 levels. and operational problems have plagued some units [471]. Their footprint is also considerably smaller. 57 . In general.g. are increasing [466]. including Germany. Also. and an IGCC plant does not contribute nearly as much waste to landfills because many of the wastes are saleable items. and sequestration technologies. Emissions from Canada and Japan. fuel and town gases. will likely need to be considered. There are a number of reported benefits of IGCC technologies compared to traditional PC-fired power plants [469]. it should also foster the continued development of CO2 recovery. and Canada has admitted that the required Kyoto protocol emissions levels are unachievable [467]. and or electricity from various fossil fuel feedstocks. the capitol and operating costs of an IGCC plant are not as favorable as initially anticipated [470]. the PC type power plant was found to be more economical than the IGCC type power plant. global CO2 emissions are still rising. A penalty or tax on CO2 emissions in the U.S.S. a number of countries had begun curbing emissions. requiring around 10 to 35% less fuel compared to traditional coal fired power plants. As an example. per ton of CO2 produced forced a natural gas producer to store CO2 in an undersea aquifer rather than release it into the air [468]. steam. has been the institution of a tax associated with the release of CO2 into the atmosphere.S.greenhouse gas emissions have ratified this agreement. whereas in traditional coal fired power plants it can only be removed after combustion. capture.g. when a tax of $10 to $30/t CO2 was factored into the analysis. the IGCC type plant became marginally more economical than a PC type power plant. synthesis gas. However. IGCC) fossil fuel power plants based on old and new technologies with the tax ranging from $1 to $35/t CO2. There has also been a drive to develop energy efficient and cost effective technologies to integrate the production of energy with the production of chemicals. especially on fossil fuel power plant operations. has not signed on. methanol. As of early 2006. However. IGCC technology should become the standard for the industry. a 1996 Norwegian carbon tax of $50 U. Fisher-Tropsch liquids. When a CO2 tax was not considered. numerous demonstration projects are under way worldwide and in the US. However. NGCC power plants) that are operating or under development as of January 2000 is provided in Table 16. two countries that ratified the Kyoto Protocol. A summary of the 29 largest commercial IGCC or related processes (e. The IGCC power plants that arose in the mid 1980s are designed to produce H2. An IGCC is currently the most efficient means to convert coal into electricity. the U. Another approach that has been quite effective outside the U.

ChevronTexaco. this would represent up to a 50% increase in the cost of electricity – thus. There are around five hundred 500 MW coal fired power plants in the U. This is a daunting volume of gas or liquid CO2 that must be stored underground at each power plant (improbable) or transported via a gas or liquid pipeline to a yet to be determined centralized CO2 sequestration site (probable. capture. With the density of cryogenic or compressed liquid CO2 (1.04/kWh.000 MW power plant using the GreenFuel system could produce 40 million gallons of biodiesel and 50 million gallons of ethanol per year on a 2. a “CO2 Capture Project” was initiated in 2000 by eight of the world's leading energy companies. including BP. It is worth putting the above numbers on the CO2 emissions from a typical 500 MW coal fired power plant into perspective. and MIT. transport. The approach is quite attractive as algae not only have the ability and capacity to effectively separate CO2 from gas streams. led by Isaac Berzin through GreenFuel Technologies Corp. For example.S. and Statoil. power generator are also poised to begin partnerships with them to build full-scale power 58 . Suncor. DOE has also shown that the separation of CO2 represents 75% of the overall cost associated with its separation. a 1. This R&D is being conducted together with governments and other stakeholders to deliver technology that is costeffective and meets the needs of society.g. utility company and a major U. amine scrubbers and cryogenic coolers)..025 to $0. with a 3 MW cogeneration demonstration plant at MIT having 50 to 80% of its CO2 emissions removed by the algae-based system.S. In recent years. Putting this into perspective.000 acre farm near the power plant. algae growth can be so prolific that biodiesel generated from algae can yield about 15. This cost could raise the price of electricity by $0. The U.S. and New York. the volume of liquid CO2 that must be processed per year from each one of these power plants fills two 100 story buildings the size of the twin towers. With electricity costs varying from around $0.org . To address the complex issues of CO2 emissions. Shell. Massachusetts. this team aims to develop new. but costly as noted above). The cost to recovery CO2 from fossil fuel power plant combustion processes is estimated to be $40/t of CO2 produced using currently available technology (e. have been developing a technology that uses algae to reduce CO2 emissions from power plants.S.08 to $0. a typical 500 MW PC fired power plant produces 11. More information can be found at http://www. the potential to remove 100% of the CO2 emissions from power plants certainly exists. DOE has estimated the cost of capturing CO2 from power plants and the impact on the cost of electricity [3]. The fuel produced from this one farm in a year corresponds with about 20% of the amount consumed daily in the U. and geologic storage from combustion sources.03 g/cm3) being essentially that of water (1.11/kWh.S. Columbia.00 g/cm3).. EnCana. A large U. This would have a significant impact on the cost of electricity. but its biomass can also be used for biodiesel production. Eni.co2captureproject. by transportation. Under the leadership of Linda Curran of BP. GreenFuel has launched small projects in Arizona. breakthrough technologies to reduce the cost of CO2 separation. like IGCC and other technologies. and sequestration operations. is clear. Hopefully these technologies will be widely used by many different industries. a group of scientists from Harvard. storage. This substantial. international effort addresses the issues to achieve an environmentally acceptable reduction of CO2 emissions with competitive pricing that is compatible with our global energy supply.The U.S.000 t CO2/day. Norsk Hydro. today that produce 11. Moreover. In fact. the need for improved technology.000 t CO2/day [2].000 gallons of biodiesel per acre per year compared to only 60 gallons of biodiesel per acre per year from soybean.

plants. The pre-combustion approach is unique to the IGCC and NGCC power plant technologies. Examples of these kinds of gas streams include those resulting from metabolic combustion (i. Examples of these kinds of gas streams are found during steel industry blast furnace operations that typically are rich in CO. the tail gas from a pressure swing adsorption unit of an ammonia production plant that are typically rich in H2. This methodology also eliminates the need for post combustion NOx removal. The post-combustion approach is the only economical approach to existing airfueled power plants based on pulverized carbon or natural gas fuel sources. Nevertheless. in IGCC and NGCC power plant technologies controlled amounts of pure oxygen are added to achieve partial oxidation of the fuel during the initial gasification step. This approach offers the possibility for improving the economics of CO2 production. CO2 is separated from the gas stream prior to its conversion into flue gas. and oxyfuel combustion concepts that can be applied to CO2 separations in non-energy related processes are presented conceptually in Figure 15. The post combustion approach involves the use of any CO2 capture step where the gas stream has no energetic value. Examples of where this approach can be used 59 . from a potentially CO2-producing source. The pre-combustion approach consists of the use of any CO2 capture step in a process where the gas stream has some value. or those in cement kilns and lime production. pre-combustion. Flue gas typically is low in both pressure and CO2 concentration (1 atm. Expanding the Definition of CO2 Capture Approaches used in Power Plants In this section. respectively). and 3 to 20 vol%. post-combustion. The oxyfuel combustion approach consists of using pure O2 or O2 enriched air as oxidants in reaction processes that produce CO2 as a by-product. In the pre-combustion approach. The post-combustion approach consists of the removal of CO2 from flue gas. such as autothermal reforming. energetic or otherwise.greenfuelonline. The oxyfuel combustion approach also could be applied to existing fossil fuel power plants. fermentation) or reactions facilitated by the direct contact of a combustion step. or even natural gas before sweetening. the gas to be treated consists typically of synthesis or shifted gas at relatively high partial pressures of CO2 (15 and 40 vol% at total pressures of over 20 atm).com. In the oxyfuel combustion approach.. such as CO and H2. but the design and materials of construction may not be compatible with the use of higher concentrations of oxygen. More broadly defined post-combustion.e. N2 is excluded from the combustion process to produce flue gas with elevated CO2 concentrations. This approach is applied to produce gases other than CO2. and oxyfuel combustion approaches that traditionally have been considered for the capture of CO2 from fossil fuel power plants are described in such a way as to make them general approaches that can be adopted for use with any CO2 producing process. Also. pre-combustion. A typical gas may consist primarily of flue gas produced during a combustion or flaring step. More information can be found in two patent applications by Berzin [472.473] and at the GreenFuel website: http://www.

The three conventional approaches for CO2 capture in the fossil fuel power plant industry are defined here in broader terms for use in any CO2 producing industrial process (Figures 16 to 23). and NH3.include in combustion processes and in the production of iron and steel. lime and cement. Postcombustion refers to a CO2 capture step from inert gas or one with no energetic value. POST COMBUSTION CO2 Process Inert Gas CO2 capture step Inert Gas PRE COMBUSTION CO2 Process Fuel Gas CO2 capture step Fuel Gas OXYFUEL COMBUSTION Air Air-Separation Unit O-rich Air Process Inert or Fuel Gas N2 CO2 CO2 capture step Inert or Fuel Gas Figure 15. such as a fuel. Oxyfuel combustion refers to those CO2 capture steps that exploit the use of oxygen or an oxygen enriched stream for fuel. 60 . Pre-combustion refers to a CO2 capture step from a gas that has some value.

# or CS#-#. H2O Post-combustion and oxyfuel-combustion approaches for the capture and concentration of CO2 in combustion processes for stream 1 in Figure 4. pre-combustion and/or oxyfuel combustion approaches. At the CO2 separation steps. CS1. VOC. pre-combustion and oxyfuel combustion approaches that have evolved over the years for the capture of CO2 from fossil fuel power plants [468]. They are given in Figures 16 to 23.2 refer to CO2 separation steps appropriate to boxed flow sheets I and II. The shorthand notation used here appears as CS#.1 and CS1. VOC. etc H2O Drying CS1. The first number (#) corresponds to a figure in the report (or figures in the report as indicated by #-#).producing processes were discussed at length in a preceeding section.#. respectively.2 N2. a new flow sheet has been drawn that includes the incorporation of post-combustion. CO. while boxed flow sheet II is lean in this gas species. Nox. CS stands for a CO2 separation step. Figure 24 provides alternative processes for the CO2 separation steps CS1. For each of the CO2 producing processes discussed in this report. and S refers to the final CO2 sequestration step. Depending on the CO2 concentration. O2 and H2. Nox.1 WG H2O CO2 S 1 G I N2 OXYFUEL COMBUSTION Air Separation O-rich Air N2 Sx. POST-COMBUSTION Sx. 61 . The second number (#) after the comma represents the proposed CO2 separation step that is indicated within the boxed region labeled with the corresponding Roman numeral.Conceptual Flow Sheets for Additional Guidance The flow sheets given in Figures 4 to 14 for the most intense CO2. WG refers to a guard step particular for water. This number (or numbers) corresponds to one (or more) of the CO2 producing flowsheets depicted in Figures 4 to 14. O2 CO2 S 1 G Flow I above Drying H2O II Figure 16. To further assist in this goal. etc Air N2 Boiler H2O WG CS1. This final CO2 stream is H2O free but may contain small amounts CH4. and that were just introduced in the last section. They should be used for guidance to foster ideas for near.2. Boxed flow sheet I is rich in N2.and long-term CO2 production plant modifications with adsorption and membrane technologies. WGS refers to a water gas shift step. boxed flow sheets I and II contain CO2 and N2 as main gas components.1 and CS1. new conceptual flow sheets have also been devised that are based on the post-combustion.

and far-term developments of new adsorption and membrane processes for CO2 separation or capture from industrial sources. where streams have been classified according to three main categories: 1) streams free of H2 and sulfur bearing compounds. Also.g. CS stands for a CO2 separation step. at high pressure. Within each classification and according to the quality of the stream. WG refers to a guard step particular for water. stream compositions and conditions differ widely. Pre-combustion approaches for the capture and concentration of CO2 in the coal gasification industry for stream 1 in Figures 5 and 6. the removal of CO2 from coal-fired power plants is very different from natural gas sweetening. CO. H2. boxed flow sheets I and II contain CO2. This final CO2 stream is H2O free but may contain small amounts CH4.1. The conditions of all the process streams are given in this report to ensure that these important design and development criteria are not overlooked.1 and CS3. In the latter.. and CH4 as main gas components.CS3. adsorption. and 3) streams containing significant concentrations of sulfur bearing compounds. PRE-COMBUSTION CO2 1 CS2. and S refers to the final CO2 sequestration step. The shorthand notation used here appears as CS#. 2) streams containing significant H2 and no sulfur bearing compounds. potential locations have been proposed where a CO2 separations unit may be able to augment the performance of the current CO2 producing plant. rather. This number (or numbers) corresponds to one (or more) of the CO2 producing flowsheets depicted in Figures 4 to 14. the differentiation between these locations is not based on the type of separation process that may be applicable (e. WGS refers to a water gas shift step.Within each of these new flow sheets. Hence. absorption. should be especially helpful to guide the near. At the CO2 separation steps. At this point.# or CS#-#. at low pressure.. CO and H2. The second number (#) after the comma represents the proposed CO2 separation step that is indicated within the boxed region labeled with the corresponding Roman numeral.e. 62 . the CO2 can be concentrated.1 and CS3. In the former. and potentially may have a high sulfur content. the proposed CO2 separation processes for each of the indicated locations shown in Figures 16 to 23 are identified in Figures 24 to 26. Depending on the CO2 concentration. The first number (#) corresponds to a figure in the report (or figures in the report as indicated by #-#). and corresponding stream differentiations. liquefaction. respectively.. the CO2 is dilute. or membrane) is suggested where they may be most advantageous.1 refer to a CO2 separation step appropriate for the process in Figures 5 and 6. Figure 22 provides detailed alternative processes for the CO2 separation steps CS2. one or more separation units (e.#. adsorption.1. CS2.g. For example.1 WG S H2O WGS or Process Fig 8 Figure 17. it is based on the quality of the stream (i. depending on the process. membrane). These conceptual flowsheets. and dirty. the composition and CO2 concentration in the stream).

Sx, Nox, VOC, etc

H2O 1 G



Process Fig. 8 Oxyfueled

H2O Drying

N2 CS4,1

H 2O G CO2 S

3 2 4 Process Fig. 8

RP Drying H2O CS4,2 N2 H2O WG CO2 S WG CO2 H2O S

Sx, Nox, VOC, etc


H2O Drying

H2 CS4,3 H2



3 2 4 G H2O Drying


CS4,4 N2





Sx, Nox, VOC, etc


Sx, Nox, VOC, etc

H2O Air Separation N2
Blast Furnace Electric Arc Furnace

2 4

Boxed Flows I, II, III or IV







Figure 18.

Post-combustion, pre-combustion, and oxyfuel combustion approaches for capture and concentration of CO2 in the stainless steel industry for the streams 1 through 4 defined in Figure 7. The shorthand notation used here appears as CS#,# or CS#-#,#. CS stands for a CO2 separation step. The first number (#) corresponds to a figure in the report (or figures in the report as indicated by #-#). This number (or numbers) corresponds to one (or more) of the CO2 producing flowsheets depicted in Figures 4 to 14. The second number (#) after the comma represents the proposed CO2 separation step that is indicated within the boxed region labeled with the corresponding Roman numeral. G refers to a guard step, WG refers to a guard step particular for water, HS refers to a hydrogen separation step, WGS refers to a water gas shift step, CS4,1 through CS4,4 refer to CO2 separation steps appropriate to boxed flow sheets I through IV, respectively, and S refers to the final CO2 sequestration step. A stream labelled with CO2 indicates that stream is ready for injection (i.e., sequestration). This stream is H2O free but may contain small amounts of N2, CH4, O2 and H2. At the CO2 separation steps, boxed flows I and II contain CO2 and N2 as main gas components, while boxed flows III and IV contain CO2, N2 and H2 as the main gas components. Boxed flow sheets I and III are lean in N2, while boxed flow sheets II and IV are rich in this gas species. Depending on the CO2 concentration, Figures 21 and 22 provide alternative processes for the CO2 separation steps CS4,1 through CS4,4.


Sx, Nox, VOC, etc






OXYFUEL COMBUSTION Air Separation O-rich Air N2

N2, O2


Sx, Nox, VOC, etc

N2, O2



Boxed Flow I

WG CS5,2 N2, O2





Figure 19.


Post-combustion and oxyfuel-combustion approaches for capture and concentration of CO2 in the cement and lime industry for stream 1 defined in Figure 8. The shorthand notation used here appears as CS#,# or CS#-#,#. CS stands for a CO2 separation step. The first number (#) corresponds to a figure in the report (or figures in the report as indicated by #-#). This number (or numbers) corresponds to one (or more) of the CO2 producing flowsheets depicted in Figures 4 to 14. The second number (#) after the comma represents the proposed CO2 separation step that is indicated within the boxed region labeled with the corresponding Roman numeral. G refers to a guard step, WG refers to a guard step particular for water, CS5,1 and CS5,2 refer to CO2 separation steps appropriate to boxed flow sheets I and II, respectively, and S refers to the final CO2 sequestration step. This final CO2 stream is H2O free but may contain small amounts of N2, CH4, H2S, O2, and SO2. At the CO2 separation steps, boxed flow sheets I and II contain CO2 and N2 as main gas components. Boxed flow sheet I is rich in N2, while boxed flow sheet II is lean in this gas species. Depending on the CO2 concentration, Figure 24 provides alternative processes for the CO2 separation steps CS5,1 and CS5,2.





H 2O CO2

2 3




H2O H2 recovery or Process Fig 8




Figure 20.

Pre-combustion and post-combustion approaches for capture and concentration of CO2 in the ammonia manufacture industry for streams 1 through 4 in Figure 9. The shorthand notation used here appears as CS#,# or CS#-#,#. CS stands for a CO2 separation step. The first number (#) corresponds to a figure in the report (or figures in the report as indicated by #-#). This number (or numbers) corresponds to one (or more) of the CO2 producing flowsheets depicted in Figures 4 to 14. The second number (#) after the comma represents the proposed CO2 separation step that is indicated within the boxed region labeled with the corresponding Roman numeral. WG refers to a guard step particular for water, WGS refers to a water gas shift step, CS6,1 and CS6,2 refer to CO2 separation steps appropriate to boxed flow sheets I and II, respectively, and S refers to the final CO2 sequestration step. This final CO2 stream is H2O free but may contain small amounts CH4, CO and H2. At the CO2 separation steps, boxed flow sheets I and II contain CO2, CO, H2, and CH4 as main gas components. Boxed flow sheet I is rich in CO and CH4, while boxed flow sheet II is very lean in these gas species. Depending on the CO2 concentration, Figure 22 provides detailed alternative processes for the CO2 separation steps CS6,1 and CS6,2. No particular action is taken over stream 4 other than a drying step.


coal. Figure 26 provides alternative processes for the CO2 separation step CS7. WG refers to a guard step particular for water. This number (or numbers) corresponds to one (or more) of the CO2 producing flowsheets depicted in Figures 4 to 14. Pre-combustion approach for capture and concentration of CO2 in the natural. VOC. The first number (#) corresponds to a figure in the report (or figures in the report as indicated by #-#). At the CO2 separation step.1 refer to a CO2 separation step appropriate for the processes in Figures 10 and 13. Depending on the CO2 and H2S concentrations.1. and H2S.1. N2 and H2S as main gas components. 66 .1 WG H2O CO2 S odors. and landfill gas industries for stream 1 defined in Figures 10 and 13.# or CS#-#. CH4. CS stands for a CO2 separation step. and S refers to the final CO2 sequestration step. Sx. The second number (#) after the comma represents the proposed CO2 separation step that is indicated within the boxed region labeled with the corresponding Roman numeral. G refers to a guard step.1 and CS10.#.1 and CS10.CS10. etc CH4. N2 Figure 21. respectively. the stream contains CO2. CS7. The shorthand notation used here appears as CS#.PRE-COMBUSTION S 1 G CS7. This final CO2 stream is H2O free but may contain small amounts of N2.

Nox.1 through CS9. The shorthand notation used here appears as CS#. No particular action is taken over stream 1 other than a drying step. and S refers to the final CO2 seqestration step. etc H2O 2 Process Figs. CS stands for a CO2 separation step. CS9. 8 Oxyfueled Drying N2 CS9.2 N2 H2O CO2 WG H2O S II PRE-COMBUSTION III 2 G Sx. This final CO2 stream is H2O free but may contain small amounts of N2. G refers to a guard step. respectively. etc H 2O WGS H2 H2O Drying CS9. The first number (#) corresponds to a figure in the report (or figures in the report as indicated by #-#). At the CO2 separation steps.# or CS#-#.3 WG H2O CO2 S Figure 22.#. Figures 24 and 25 provide alternative processes for the CO2 separation steps CS9. PFC. The second number (#) after the comma represents the proposed CO2 separation step that is indicated within the boxed region labeled with the corresponding Roman numeral.3 refer to CO2 separation steps appropriate to boxed flow sheets I through III. 8 Drying H2O CS9. Depending on the CO2 concentration.POST-COMBUSTION 1 G Drying H2O CO2 S VOC. N2 and H2 as the main gas components. Boxed flow sheets I and III are lean in N2. boxed flow sheets I and II contain CO2 and N2 as main gas components. WGS refers to a water gas shift step.3. WG refers to a guard step particular for water. while boxed flow sheets III and IV contain CO2. 67 . Post-combustion and pre-combustion approaches for capture and concentration of CO2 in the aluminum industry for the streams 1 and 2 defined in Figure 12. This number (or numbers) corresponds to one (or more) of the CO2 producing flowsheets depicted in Figures 4 to 14.1 through CS9.1 WG CO2 S I Process Figs. VOC. while boxed flow sheet II is rich in this gas species.

This final CO2 stream is H2O free but may contain small amounts of N2. O2.2. and adsorption (ADS). intermediate (I).2 D: (5-20% CO2) CS4. CS9. membrane (MEM). PG CO2 C I D LIQ MEM ABS ADS Vent (PGs) CO2. O2.1. CS4. etc Figure 23.1 I: (20-90% CO2) CS1.1. CS9. No particular action is taken over stream 1 other than a drying step.1. CS9. CS4. Post-combustion approach for capture and concentration of CO2 in the ethanol production industry for stream 1 defined in Figure 14. Sx.2. 18.1. CO or CH4 as permanent gases (PG) in addition to CO2. CS4. VOC. The separation step may consist of one or more separation processes that include liquefaction (LIQ).1. absorption (ABS). The step flow diagram allows different accesses depending on whether the CO2 content in the stream is concentrated (C). CS5. PG C: (>90% CO2) CS1. 68 . G refers to a guard step and S refers to the final CO2 sequestration step. 19 and 22 that contain N2. CO and CH4 Vent (PGs) CO2 CO2 CO2. Process I: CO2 and gases such as N2.2 Figure 24.2. CS5.2. Flow diagram representing a CO2 separation and concentration step for streams in Figures 16. CS9. or dilute (D).POST-COMBUSTION H2O. ethanol 1 G Drying CO2 S odors.

or dilute at room temperature (D1) or dilute at high temperatre (D2) 69 .1.1 Figure 25. CS9. gases such as N2. CH4 and significant H2 CO2 I D1 CO2.1. The step flow diagram allows different accesses for the stream depending on whether its CO2 content is intermediate (I).2. CS4. CO or CH4 as permanent gases (PG) as well as significant concentrations of H2 in addition to CO2. H2 + PG D2 PG.2. CO2 Vent or Process I MEM CO2 CO2 ABS ADS Vent (H2) I: (20-90% CO2) CS4. The separation step may consist of one or more separation processes that include membranes (MEM). Flow diagram representing a CO2 separation and concentration step for streams in Figures 17. absorption (ABS). CS6. O2. CS6.3. 20 and 22 that contain N2. and adsorption (ADS).2 D2: (5-20% CO2. CS9. HOT) CS2.4. O2. CS3. 18. CS6.3 D1: (5-20% CO2) CS4.Process II: CO2.4.

Flow diagram representing a CO2 separation and concentration step for streams in Figure 21 that contain N2. gases such as N2. and adsorption (ADS). PG CO2. H2S. H2S S Claus/SCO CO2 I D1 MEM CO2.1 D: (5-20% CO2) CS7. CS10.1. COS. H2S. CO2 Vent or Process I CH4 HS: (> 20% H2S) CS7. 70 . absorption (ABS). etc. or on whether its content of sulfur bearing compounds is elevated (HS).1.1 Figure 26. membranes (MEM). PG ABS ADS N2. O2. CH4 and H2S S HS Claus/SCO CO2.1 I: (20-90% CO2) CS7.1. CS10.Process III: CO2.g. H2S. CS10. The separation step may consist of one or more separation processes that include a Claus/SCOT step for sulfur removal. CO or CH4 as permanent gases (PG) as well as sulfur bearing compounds (e. The step flow diagram allows different accesses for the stream depending on whether its CO2 content is intermediate (I) or dilute (D).) in addition to CO2.

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912. CO2 in natural gas.013.70 105. Other sourcesd 4. CO2 Emissions [474] U. 1990 and 2004 Worldwide and U.309.20 U. CO2 emissions (MMt).736.30 5.70 a Sum of rows 1 to 4. Non-fuel use of fossil fuelsc 7.20 1.803.S.20 1. 97 .12 27. and waste combustion.426. Comercial 3.80 953.S.45 5. and includes natural gas flaring.57 Worldwide Emissions [474] 5.566.043. c Emissions in row 6 included in emissions in rows 1 to 4. CO2 Emissions [475]a 1.213. b Total emissions from electricity needed to power activities in rows 1 to 4.60 1.034.10 1. d Emissions in row 7 not included in emissions in rows 1 to 4. Industrial 5.70 1. Electricb 6.683.Table 1.939.S.80 1. Transportation 4.10 98. and includes total emissions from energy and non-energy related sources.923. other industries.90 1.984. cement production.00 2. 1990 2004 21.10 88.40 111.00 780. Residential 2.

00 0.00 68.00 4.00 0.60 1.60 Non-Energy Related Sources NonFossil Total [477]d Fossile [475] 177.20 0.70 305. Residential 2.00 1.40 1.20 --------1.40 7.00 8.20 48.00 106.80 0. This value includes all values reported in Tables 2 and 3 of [477].871.10 8.00 36.80 66.00 39.00 1.70 ----- Natural gas 263. Lime 12.80 87.00 0.60 0.70 1.00 190. Natural gas flaring CO2 Consumption [475] a b c d e f g 12.00 0.20 1. 98 .80 49.10 247.40 1.60 642.30 3.70 23.20 6.70 2.177.40 782.00 Sum of rows 1 to 4. but emissions expected to be negligible.00 0.30 0. Municipal combustion 15.30 --------0.10 --------0.00 Energy Related Fossil Fuels [476]c Total Manufacturing Industry [476]c 6.40 --------2.90 1.401. Data for municipal combustion and natural gas flaring and production obtained from [475].00 0. Natural gas 11.20 126.30g 1.10f 51. Ammonia and natural gas production not mentioned in this report.31 1.90 0.40 43.70 0. Cement manufacture 9.831.10 4.10 450. Other manufacturing Other industries and sources [475] 14.60 0.90 14.00 0.80 Natural Gas Petroleum 325. Transportation 4. Total CO2 Emissions [475.90 14. Industrial 5.40 77.00 12.10 6.00 0.752.476] 1.00 0.00 0. CO2 emissions (MMt). Iron and steel industry 8.40 Coal 1.70 459.00 17. including natural gas production reported in row 10 of this table.684.10 295.00 0.Table 2. Aluminum production 13.90 Electricity 540.00 6.20 0.00 --------6.60 27.853. This value includes natural gas production reported in row 10 of this table.009.00 12.20 Coal 202.50 0.00 18.00 6.30 257. Comercial 3.90 5.186.00 0. Total manufacturing 7.00 18. Difference between total non-energy related sources and non-fossil sources.90 Other 74.10 4.70 Other 0. Electricb a Electricity 821.20 1. Summary of 2002 U.70 35.60 20. Ammonia 10.00 6.00 400.70 89.00 0.20 0.70 170.00 6. Total emissions from electricity needed to power activities in rows 1 to 4.30 48.00 --------10. and and includes total emissions from energy and non-energy related sources. but excluding those for combustion and natural gas flaring.30 43.90 22.20 37.00 11.90 Petroleum 100.50 17.00 0.70 1.250.S.

39 0.3 3.50 0.2 4.6 16.9 16.a Industry Fossil fuel power plants: Coal Gas Petroleum Iron and steel industry Cement manufacture Ammonia Natural gas (absorption) Aluminum production Ethanol industry a Year Number of Plants Emissions Average Plant Emissions 1998 1998 1998 2004 2004 2004 1991 2006 2006 1198 3321 2148 95 116 32 460 400 101 1801.05 0.04 0.1 104.3 45.1 51.03 Except for fossil fuel plants. Average U.1 249.53 0.08 0. CO2 emissions per plant within several industries (MMt).54 0. emissions are non-energy related.01 0.5 1. 99 .S.Table 3.

Canada Nitto Denko Corporation. Japan U. USA Praxair Technology. USA Engelhard Corporation . Yong Ding Gilles P.. Inc. of Singapore. USA Membrane P 0(0) M 35(9) Membrane Process P M Adsorption P M Absorption P M P Other M 1(1) 37(29) 8(8) 42(22) 2(1) 1(0) 31(25) 3(0) 29(13) 1(0) 15(6) 0(0) 1(0) 26(6) 0(0) 8(1) 1(1) 23(16) 7(4) 14(4) 12(5) 9(9) 6(6) 2(2) 0(0) 43(11) 5(5) 2(2) 4(2) 2(1) 5(5) 0(0) 2(2) 1(1) 4(4) 2(0) 3(3) 0(0) 6(2) 1(1) 0(0) 0(0) 10(8) 5(0) 3(1) 1(1) 2(2) 3(3) 3(3) 0(0) 1(1) 0(0) 0(0) 8(6) 1(1) 6(4) 1(1) 9(6) 3(2) 2(1) 1(1) 12(7) 2(1) 2(2) 1(0) 2(1) 100 . Number of patents (P) and peer review manuscripts (M) per researcher or research group on CO2 related separation processes since 1995 and 2002 (in parentheses). Donald J. of Twente. Hasse. Robertson.. of Science and Tech. Baker. Deckman. Japan National U. Richard J. Inc.Table 4. the Netherlands Membrane Tech. Nanyang Technological U. Japan North Carolina State University. USA U. Dolan Raymond Clarke John W. France ExxonMobil. USA Landec Corporation. Main Investigator Katsuki Kusakabe. Guiver Hisao Hachisuka. USA National Institute of Advanced Industrial Science and Technology. Vu Benny D.. USA L’air Liquide. Freeman William D. France UOP LLC. and State U. Tomomi Ohara. Japan Tokyo Metropolitan University. Victory. Sudhir S. Chung and Rong Wang William J. USA Korea I. & Research. Miller. Hidetoshi Kita Richard D. Singapore Georgia Institute of Technology. Michael D. USA Institute for Chemical Process and Environmental Technology... USA Yamaguchi University. USA L’air Liquide. Momoji Kubo Matthias Wessling Richard W. Joice K. Nelson. USA Eltron Research Inc. Simmons Santi Kulprathipanja David J. Kang Shigeo T. Curtis L. Ken-Ichi Ikeda Nikunj P. USA Virginia Polytechnic I. Eugene R. and State U. USA Hampton University.. Munson. USA Chevron USA Inc. Falconer Kenji Haraya Hiroyoshi Kawakami Akira Miyamoto. Noble and John L. Ingo Pinnau Stephen J. Thomas Benjamin Bikson. South Korea Virginia Polytechnic I. Kulkarni Harry W. Japan University of Colorado.. Patel. Sammels Company or Institution Kyushu Sangyo University. Koros Ken-ichi Okamoto. De Q. Oyama Anthony M. Shigeharu Morooka Tai S. Japan Tohoku University. Spontak Liang Hu Eva Marand Yong S. of Texas.

of Michigan. Italy Institut Europeen des Membranes. degli Studi di Firenze. USA Instituto Nacional del Carbon. Monotobu Goto Kumamoto University. of South Carolina. Germany Sawas Vasileiadis Ivatech Corporation. the Netherlands U. of Science and Tech. South Korea U. Alexander Stern Shivaji Sircar. Ted Oyama Zhi Kang Xu Enrico Drioli. Japan Alirio E. USA Air Products and Chemicals. Machado Henk Verweij Daniele Fiaschi Jose Sanchez Kamalesh K. Toshihiro Tomita Paul A. H.S. Teknologi of Malaysia. Ritter U. Federal de Santa Catarina. Ismail Ho Bum Park. Yang U. Winston Ho Ravi Prasad. USA Aristotle Univ Thessaloniki. de Oporto. Frank Notaro George P. Rodrigues U. China U. Rao Charles L. Young Moo Lee S... Teresa A. F. Spain Isao Mochida Kyushu University. Spain U. Jeffrey R. Rios. Dongliang Wang Takeshi Matsuura Gilbert M.... Yong Soo Kang Ricardo A. of Southern California. Stephane Sarrade Tsutomu Nakagawa Theodore T. Lua Fudan University. Daus. Japan Chang Ha Lee Yonsei University. Singapore U. Hitoshi Sakai. South Korea Angel Linares. Inc. Diego Cazorla U. Italy Korea I. USA L’Air Liquide. Brazil U. Centeno A. Amelia Martinez. Tascon. Canada I. Charles R. of Ottawa. Greece National University of Singapore. of Calabria. France ExxonMobil. France New Jersey Institute of Technology. Teo. Japan U. China Juan M. Spain Silvia Villar Rodil 101 . Europeen des Membranes-UM2. USA Zhejiang University. Aik C. Inc. Pauley Gas Research Institute. of Twente. Sirkar Tomonori Takahashi. USA Tsutomu Hirose. South Korea Virginia Polytechnic Institute and State University. D. Portugal James A. Wah K. USA Ralph T. de Alicante. Hufton. Japan 0(0) 2(0) 8(0) 0(0) 3(0) 2(0) 7(0) 5(0) 9(0) 5(0) 2(2) 0(0) 4(0) 0(0) 1(1) 0(0) 1(0) 1(1) 1(0) 10(1) 1(0) 19(6) 0(0) 12(6) 0(0) 21(3) 0(0) 13(5) 0(0) 11(2) 0(0) 9(4) 0(0) 19(16) 2(1) 9(5) 0(0) 0(0) 5(4) 0(0) 0(0) 0(0) 0(0) 10(4) 20(12) 15(6) 6(5) 5(2) 5(4) 15(6) 0(0) 3(2) 4(1) 0(0) 0(0) 8(2) 0(0) 3(1) 0(0) 2(2)a 0(0) 4(0) 3(0) 2(1) 3(1) 2(2) 0(0) 2(0) 1(0) 19(6) 0(0) 18(4) 0(0) 19(8) 0(0) 29(14) 0(0) 12(2) 0(0) 16(9) 0(0) 5(1) 0(0) 12(6) 0(0) 30(21) 0(0) 1(1)a 3(1) 14(3)b Messer Griesheim Industries. USA NGK insulators. Inc. Madhukar B. Sakellaropoulos Kang Li. Malaysia Hanyang University. F. France Meiji University. USA Praxair Technology. Instituto Nacional del Carbon. Anderson W. Fuertes. USA Jia Guo. Tsotsis Antonio B.

Svendsen Takayuki Saito Masaki Iijima.. Switzerland Agency of Industrial Sci. Sandall Hallvard F. Khanmamedov Guido Sartori Bernt H. Kazuto Kobayashi. of Texas. Wegeng Alan Mather Sang Wook Park Gary T..& Tech. India Chung Yuan Christian University. Inc. Harald Linga. Canada Agency of Industrial Sci.. USA U. USA Air Products and Chemicals. Inc. Keefer Amitabh Gupta. Japan Instituto Mexicano de Petroleo. USA Battelle Memorial Institute. Malaysia U. Inc.. USA Matheson Tri-Gas. Inc. Martin Sigmundstad. USA The BOC Group. of Kaiserslautern. Lemcoff. Inc. Inc. of Chemical Engineers. Inc. Patrick Finn James E. Whitley. Argentina U. Lyon Omar M. Baksh Roger D.USA Den Norske Stats Oljieselskap A.. of Ottawa. USA The BOC Group. USA Air Products and Chemicals. USA General Electric Co. USA U. Taiwan U of Basel.. Inc. Yaghi Robert S. of Alberta. Canada Questair Technologies. Canada Praxair Technology. Mexico U. Germany U.. Bandyopadhyay Menghui Li Helmuth Sigel Fumio Kiyono Arturo Trejo Mohamed K Aroua Gerd Maurer Orville C. of Technology. Golden Hans H.USA Norwegian Inst.& Tech. of Malaya... Divyanshu R. Inc. Dan Fraenkel Richard K. Handan Tezel Kenzi Suzuki Martin Bulow Ravi Kumar Akhilesh Kapoor Ravi Jain Mohamed S. Robert L.. Canada Korean Inst. Inc. of California Santa Barbara. Norway Nat.. Korea U.. Rochelle Syamalendu S. Shrikar Chakravarti Timothy C.Jose Ortiga. Japan Texaco Development Corp. Kazuhiro Morita. Wallace Tofik K. USA The BOC Group. Shigeaki Mitsuoka Paul L. Funkel.... Japan Mitsubishi Heavy Industries. A. USA Indian I. Chiang Norberto O. of Michigan. Norway Hunstmann Petrochemical Corp. of Science and Tech.USA ExxonMobil. & Environ. USA 0(0) 5(2) 0(0) 10(4) 0(2) 7(0) 3(12) 7(5) 4(13) 2(1) 0(8) 0(0) 0(7) 0(0) 2(4) 0(0) 4(4) 0(0) 2(5) 3(1) 6(9) 1(1) 11(28) 6(7) 5(5) 4(5) 2(2) 0(0) 0(0) 1(0) 1(1) 4(0) 15(8) 0(0) 1(0) 0(0) 6(1) 0(0) 0(0) 18(2) 0(0) 16(16) 2(2) 15(10) 0(0) 14(13) 0(0) 13(6) 0(0) 13(6) 1(0) 5(5) 1(0) 9(5) 0(0) 7(4) 0(0) 8(5) 0(0) 8(0) 0(0) 8(7) 2(0) 8(1) 19(10) 8(1) 3(1) 3(1) 23(0) 7(0) 2(0) 0(0) 1(1) 1(0) 0(0) 1(0) 102 . USA TKK Company. Acharya Bowie G.S.. Cristina Volzone F. Institute for Res. Critchfield Centro de Tecnologia de Recursos Minerales y Ceramica. Japan The BOC Group. USA Praxair Technology. Torkildsen. USA The BOC Group. Inc.

Canada U. Canada Fluor Corporation. France Alberta Limited. Inc. USA Zoher M. Meratla Olav Falk-Pedersen Fawzy T. Japan U. Vishwas Y. Masaaki Teramoto Kew-Ho Lee. USA Kyoto Institute of Technology. Spencer Frederic Dutil Joan F. Abdelmalek a Membrane contactors b Immobilized liquid and facilitated transport membranes c Autorefrigeration and liquefaction d Cryogenic separation 103 .b 0(0) 15(9)b 2(1) 16(10)a 1(0) 2(0)d 2(0) 8(4)a 4(0) 1(0)c Institutt for Kjemisk Prosessteknologi. Canada Indian Institute of Technology. South Korea Tianjin University. Inc. Italy Toshiba Corporation. You-In park Zhi Wang Paul H..Jerry D. Bandyopadhyay Cheng Fang Zhang Dwain F. of Chemical Tech. China Electric Power Research Institute. USA Institut Francais du Petrole.. India Shanghai Jiaotong University. M. USA 3(1) 0(0) 3(3) 3(2) 2(2) 0(0) 7(7) 2(2) 0(0) 5(1) 0(0) 12(4) 0(0) 30(18) 0(0) 5(2) 0(0) 8(4) 7(1) 5(2) 7(7) 0(0) 0(0) 37(14) 1(1) 0(0)b 0(0) 1(1) 4(2) 0(0)c 1(1) 11(7) 0(0) 8(8)a 0(1) 6(1) 0(0) 6(1)b 0(0) 17(4)a. Norway Air Products and Chemicals. Brennecke Satish Reddy Geert F. Amornvadee Veawab. The Netherlands CDS Research Ltd.b 0(0) 18(11)a. Japan Korea Research Inst.. USA CO2 Solution. Inc. USA Politecnico di Milano. Blue Fabrice Lecomte Gary Palmer John Mak Paolo Chiesa Masahiro Kato Paitoon Tontiwachwuthikul. Dindore Robert Quinn Hideto Matsuyama.. of Notre Dame. Feron Alliance. China TNO Institute of Environmental Sciences. of Regina. Raphael Idem Syamalendus S.. USA Fluor Corporation. Versteeg. Norway Abdelmalek & Associates. USA Kvaerner ASA.

USA DSM N V. USA Hunstmann Petrochemical Corporation. France Chevron USA Inc.. Inc... USA Kvaerner ASA. Inc. UK-USA Union Carbide. USA Praxair Technology.USA Institut Francais du Petrole. USA Membrane Technology and Research. USA ExxonMobil. USA General Electric Co. Norway Matheson Tri-Gas. USA Texaco Development Corp. Inc. Japan Korea Institute of Science and Technology. USA Engelhard Corporation . USA Messer Griesheim Industries.I. Inc. USA Norsk Hydro ASA. Norway Questair Technologies. USA BP-Amoco. Du Pont de Nemours and Company. USA UOP LLC.. USA Shell Internationale Research. The Netherlands Battelle Memorial Institute. France Landec Corporation. Company Air Products and Chemicals. USA Membrane 11(3) 3(1) 23(7) 10(4) 7(3) 23(9) 1(1) 11(5) 9(9) 4(2) 4(3) 5(0) 6(6) 2(2) 6(1) 2(0) 2(2) 3(0) 4(1) 3(0) 1(0) 4(3) 2(2) 1(0) 4(2) Adsorption 51(18) 49(15) 24(9) 2(2) 17(5) 2(1) 7(3) 3(3) 3(2) 4(3) 4(3) 1(0) 4(4) 5(5) 9(6) 4(4) 7(6) 3(0) 1(0) 3(0) 2(1) 2(1) 3(2) 1(2) 1(1) Absorption 5(2) 5(2) 10(2) 28(1) 2(0) 19(10) 2(0) 5(5) 8(7) 4(3) 13(8) 8(7) 5(1) 3(2) 3(0) 7(0) 2(2) 4(1) 3(0) 4(0) 2(0) 2(0) 1(1) 0(2) 4(3) 4(1) 3(3) 3(2) 104 . USA Honeywell International Inc... Norway Hamilton Sundstrand Corporation.. Inc. USA E. Agency of Industrial Sci.. South Korea Conoco/Phillips. Japan L’Air Liquide. USA Mitsubishi Heavy Industries.Table 5.S.. Canada Den Norske Stats Oljieselskap A. USA DOW/Corning Corp. USA The BOC Group. The Netherlands Fluor Corporation. Inc. Inc.& Tech.. Number of patents per company on CO2 related separation processes since 1995 and 2002 (in parentheses).

V (ADIP-X) Prosernat-IFP Group Tech. As. H2O CO2 AG AG (P) (P) (P) (P) (P) (P) (P) (P) (P) (P) (P) (P) (P) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R) (R. (Improved Econamine ) Fluor Enterprises. HFMC = hollow fiber membrane contactor. (Fluor Solvent) Advantica Ltd. Inc. ABB Lummus Global Inc. type of process. (Econamine FG Plus) Fluor Enterprises. TBC. amine) Liquifaction Liquifaction Membrane Membrane Membrane HFMC Primary Goal H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 CO2.95 1-200 15-120 230-1350 500-1800 650-2050 -1850 2-10 0. Inc. Air Liquide (Medal) NATCO Group Inc.V (ADIP) Shell Global Solutions International B. GC= Gas contaminants (Hg.V (Sulfinol) Fluor (CO2LDSEP) Costain Oil. CEL = compression-expansion liquefaction. Licensor Linde AG Technip Uhde Haldor Topsøe A/S UOP LLC (Polybed) CB&I Howe-Baker Foster Wheeler Lurgi Oel-Gas-Chemie GmbH Air Products (PRISM) Linde AG Uhde Gmbh Haldor Topsøe Kellogg Brown & Root. Mem = membrane. and number of plants worldwide [478]. Inc. P = purification.Table 6.3-25. L = Liquefaction. Co.5-700 -500 -350 -500 2700 3-400 -300 547 -220 300 -15 5-1200 1-1000 5-750 1-1000 MMscfd MMscfd MMscfd MMscfd MMscfd MMscfd MMscfd MMscfd mtpd mtpd mtpd mtpd MMscfd Plants Worldwide 250 240 60 31 700 170 100 105 50 3 14 60 200 2 60 2 400 1 120 230 500 700 8 49 55 24 7 13 30 2 1 7 100 55 200 7 several 30 50 10 Nm3/d MMscfd MMscfd MMscfd MMscfd mtpd MMscfd mtpd MMscfd MMscfd MMscfd MMscfd mtpd MMscfd MMscfd MMscfd PSA = Pressure Swing Adsorption. H2O. (Molecular Gate) Axens ProPure As (CAP-compact) Shell Global Solutions International B. H2O GC+CO2 H2S AG AG AG AG AG AG AG AG AG CO2 CO2 CO2 CO2 CO2 AG AG AG AG AG AG CO2. Licensors of CO2 separation processes. Inc Engelhard Corp.280 1. NH and Sx) 105 ..e. Inc. P) (P) (R) (R) (R) (R) CO2 in Tailgas 30-60% 30-60% 30-60% 30-60% 30-60% 30-60% 30-60% 30-60% 30-60% 30-60% 30-60% 30-60% 30-60% 1-98% 1-98% 1-98% 1-98% 1-98% 1-98% 1-98% 1-98% 1-98% 1-98% 1-98% +99% +99% +99% +99% +99% 1-98% 1-98% 1-98% 1-98% 1-98% 1-98% +99% 100% 2-70% -95% 1-98% Capacity/unit 1-100 -110 -20 -200 1. Exxon Mobil Research & Eng. production rate. Gas & Process ltd. H2S. MDEA) Scrub (MDEA) Scrub (amine) Scrub (Methanol) Scrub (DEA-K2CO3) Scrub (MEA) Scrub (amine) Scrub (DGA) Scrub (MEA) Scrub (DGA) Scrub (fluor solvent+PC) Scrub (LRS10-K2CO3) Scrub (Morphysorb) Scrub (Morphysorb) Scrub (NMP) Scrub (Methanol) Scrub (DME. (LRS-10) Uhde Gmbh (Morphysorb) Lurgi Oel-Gas-Chemie GmbH (Omnisulf) Lurgi Oel-Gas-Chemie GmbH (Purisol) Lurgi Oel-Gas-Chemie GmbH (Rectisol) UOP LLC (Selexol) Shell Global Solutions International B. (CYNARA) UOP LLC (Separex) Merichem Chem & Refineries Services (AMINEX) System PSA-H2 PSA-H2 PSA-H2 PSA-H2 PSA-H2 PSA-H2 PSA-H2 PSA-H2 PSA H2 PSA-NH3 PSA-NH3 PSA-NH3 PSA-NH3 Adsorption Adsorption Scrub (MDEA) Scrub (MDEA. PC = propylene carbonate. PEG) Scrub (sulfolane. COS and CO2). DIPA) Scrub (MDEA) Scrub (DEA. (Advanced Amines) BASF AG (aMDEA) UOP LLC (Amine Guard FS) Prosernat IFP & Titan SNC Lavalin (ifpex-2) UOP LLC (Benfield) Randall Gas Tech. (FlEXSORB) Fluor Enterprises. AG = All acid gases (i.2 3. R = removal. (Econamine) Fluor Enterprises. H2 CO2 CO2.

0061 100 58 41 58 46 51 Hydroxyethanolamine DGA (Diglycolamine) Diisopropanolamine DIPA Methyldiethanolamine MDEA 106 .058 0. Molecular Name Chemical Formula Weight Vapor Pressure (mm Hg) Relative Acid Gas Capacity (%) Ethanolamine MEA (Monoethanolamine) Diethanolamine Triethanolamine DEA TEA HO-CH2CH2-NH2 (HO-CH2CH2)2-NH (HO-CH2CH2)3-N H-(OCH2CH2)2-NH2 (CH3CH(OH)CH2)2-NH (HO-CH2CH2)2-N-CH3 61 105 148 105 133 119 1.05 0.0160 0.Table 7.0063 0. Characteristics of key alkanolamines used in gas treating [479].010 0.

MDEA.33-55 Operating Problems Solution degradation. DIPA K2CO3. wt% MEA. but pressure principally May be selective for H2S Yes None 250-1000 Ambient temperature Steam or air* Flash. reboiler.Table 8. 107 . H2S Meets ppmv H2S Effect of O2 in Feed Insensitive to pressure 100-400 Steam Reboiled stripper Temperature principally Only MDEA selective for H2S Yes Amine degradation products > 200 200-250 Steam or air* Stripper Both. or steam stripper Pressure principally COS and CS2 Removal MEA – no removal and strong and degradation degradation.. Rectisol. foaming. DGA. Absorption of heavy hydrocarbons Low to medium Best for high pressure gases. DEA – slight removal and some degradation. dimethyl ether of polypropylene glycol (selexol). inhibitors used to control corrosive character of loaded alkanolamines. Physical dissolution Adsorbents CO2 & H2S absorption mechanism H2S: 2RNH2+H2S↔(RNH3)2S (RNH3)2S+H2S↔2RNH3HS H2S: Na2CO3+H2S↔NaHS+NaHCO3 Operating Pressure. DGA – removes both. DEA. strong degradation. psig Operating Temp. no H2S. 13-25. K2CO3-MEA. no degradation Solvent: solute H2O: concentration. Major types of acid gas absorbent processes [479-481]. DEA. corrosion.10-30. evaporation (MEA) Utility Cost High Other comments MEA limited to COS. Selexol. DIPA. no degradation degradation H2O: K2CO3 < 30 Column instability. CS2 free streams with low CO2 and H2S concentrations. methanol (rectisol). MDEA – Removes both. Chemical Absorption Alkanolamine Inorganic Carbonate MEA. oF Stripper Gas Absorbent Recovery Swing variables (Temp. or Pressure) Selectivity CO2 vs. erosion Medium Rate enhancers are used to improve low adsorption rates. performance improves: MEA< DEA< DIPA< MDEA * For streams free of sulfur compounds. good for high pressure gases N-methyl-2-pyrrolidone (purisol). DGA. MDEA. then removes both. Some selectivity for H2S Yes Sulfur (S8) precipitates at low temperatures Converts both into CO2 and Removes both.40-60. corrosion. K2CO3-DEA Chemical reaction Chemical reaction CO2: CO2: 2RNH2+CO2+H2O↔(RNH3)2CO3 (RNH3)2CO3+CO2+H2O↔2RNH3HCO3 Na2CO3+CO2+H2O↔2NaHCO3 Physical Solvent Absorption Purisol.

Table 9. Absorbent Methyldiethanolamine (MDEA) Monoethanolamine (MEA) Diethanolamine (DEA) Piperazine (PZ) Potassium Carbonate Aminomethylpropano (AMP) Triethanolamine (TEA) Diglycolamine (DGA) Sodium Glycinate Dyethylene triamine (DETA) Diisopropanolamine (DIPA) # 73 55 38 33 7 6 5 4 4 3 2 108 . Number of papers since 2000 containing in the title the indicated alkanolamine and other absorbents for CO2 removal.

2 ~ 3.4-0.5 4-8 7 0.0 0. Adsorbent Adsorbate T (oC) P (torr) Loading (mol/kg) Mode act. carbon 5A zeolite 5A zeolite titanosilicates titanosilicates titanosilicates solid amine (supported PEI) HTlc (K-promoted) double-layer hydroxides alumina (un-doped) alumina (doped w/Li2O) alumina (basic) Li zirconate CaO CaO Cu(I) (alumina) Cu(I) (alumina) 1 CO2 CO2 CO2 CO2 CO2 N2 CH4 25 250-300 25 250 25-200 25-200 25-200 75 500 500 500 500 760-6x105 760-6x105 760-6x10 760 200-700 230 500 500 500 760 150 76 760 760 5 1.52 0.06 0.Table 10.0 0.5 0.3 3.7 1.5 – 3.8 1 PSA PSA PSA PSA PSA PSA PSA PSA PSA PSA PSA PSA PSA TSA TSA TSA PSA PSA CO2 CO2 CO2 CO2 CO2 CO2 CO2 CO2 CO CO 300-400 375 400 400 300 500 500 700 25-30 30 Molecular Gate titanosilicates molecular sieves patented by Engelhard Coproration [10].0 0. 109 . carbon act.1-0.2 proprietary1 proprietary1 proprietary 1.2 0.8-1.5-2. Typical capacities of commercial and developmental CO2 and CO selective adsorbents.4-4.

LEE. FP. with the process performance judged primarily in terms of the CO2 purity in the heavy product (yCO2. CnD. ** All processes operated at ambient temperature except for HTlc (hydrotalcite like compound). LR HTlc 1. CnD.F (%) yCO2.1 17. HPP or HR-IP. CnD. F.4 12 15 83 17 14 [37] 5-bed 5-step LPP. CnD. ReC = recycle. F. F. F. LR 13X 1.5 30 20 63 70 273 [491] 4-bed 4-step LPP. CnD 13X 5. HPP.1 17. CnD.0 3. CnD.4 12 15 76 49 23 [37] 4-bed 4-step LPP. F.0 2. LEE 13X 1. F.2 10 82 57 477 [38] 2-bed 4-step HPP. HR.0 20 13 99 55 156 [487] 3-bed 8-step FP. HR (from CnD).4 98 908 [485] 3-bed 8-step FP. CnD HTlc 1. LEE AC 2.4 12 15 89 72 58 [61] 4-bed 4-step LPP. CnD. N. CnD. CoD = cocurrent depressurization. CnD.HP (%) RCO2 (%) θ (LSTP/hr/kg) Reference 2-bed 2-step FP. CoD. F.5 110 20 48 94 426 [491] 2-bed 5-step LPP.5 69 228 [488] 3-bed 8-step FP. CnD. LR 13X 1. with the CO2 recovery (RCO2) and the feed throughput (θ) being secondary but also important process performance indicators. F. CoD. LR 13X 3.9 15 24. CnD. CnD.5 15 17 99. LR HTlc 1. CnD AC 1. Performances of various PSA cycle configurations investigated for CO2 concentration from flue gas. F. FP = feed pressurization. which was done at 575 °K.1 17.8 34 331 [486] 3-bed 7-step FP. F.5 110 20 43 88 426 [491] 3-bed 4-step LPP. LR = light reflux. FP. F. LR HTlc 1. HR. LEE = light end equalization.9 15 56. F. LR HTlc 1. HR-IP. CnD 13X 5. CnD. F = high pressure feed. CnD. HPP = heavy product pressurization.1 16. 110 . LEE.4 9 17 [484] 2-bed 4-step FP. F. LEE 13X 1. LR 13X 1. CoD. N. CnD. F+ReC. HR (from CnD). HR.4 12 15 72 82 12 [37] 5-bed 5-step LPP. LR HTlc 1.4 12 15 65 87 12 [37] 5-bed 5-step LPP. N AC 1. F. CoD. LEE AC 1.4 12 15 63 75 22 [37] 4-bed 5-step LPP.2 12 17 99.6 16 99 50 610 [489] 4-bed 4-step LPP. LR. F. FP. CnD. LR 13X 1. CnD 13X 1.0 15 18 90 12.3 --15 [483] 1-bed 4-step LPP.Table 11. F.1 11 13 64 80 120 [491] 3-bed 5-step FP. F.2 10 68 50 507 [38] 1-bed 4-step FP. HR-IP. LR HTlc 1.7 1. CoD. CnD. HR (from LR). HR = heavy reflux. LR 13X 1.4 12 15 84 68 15 [37] 5-bed 5-step LPP. F.4 12 15 98 5 202 [61] * CnD = countercurrent depressurization. FR. F. HR (from CnD).9+ 68 33 [490] 4-bed 8-step LPP. F. N. FP.0 15. CnD HTlc 1. HR (from LR).2 10 83 54 338 [38] 2-bed 6-step LEE.5 30 20 58 75 273 [491] 3-bed 6-step LPP. CnD. LEE. HR. LR 13X 14. CnD Y 2. F. N = null or delay. LPP = light product pressurization. F.600 [482] 2-bed 4-step FP. N. N. HR-IP. LEE.5 30 13 99. IP = intermediate pressure. CoD. Cycle Configuration Cycle Step Sequence* Ads** PH (atm) PH/PL yCO2. LEE.0 8. CoD.F).

00 5.95 3. R' = n-C8H17 R = CH3. R' = n-C6H13 R = Cl.63 1. 'Poly(cis-isoprene) R = CH3. R' = CH(CH3)2 (PMP) R = CH3.20 1.15 1.51 8.71 6.49 3. R' = CH(n-C3H7)Si(CH3)2-n-C6H13 R = Ph. R' = SiMe3 (PTMSP) R = CH3.68 7. R' = n-C6H13 R = H.08 9. R' = n-C5H11 R = CH3. R' = n-C7H15 R = Cl.86 3.17 3.61 1.65 5. R' = n-C8H19 R = H.00 10.07 1.02 8. R' = t-Bu R = H.52 10.84 1. * ORGANIC MEMBRANES Polyacetylenes R groups R = H.64 3.9 21 24 21 23 29 29 14 16 11 10 8 6. R' = CH2CH(CH3)2 (P5M2H) R = CH3. R' = n-C6H13 R = CH3.07 3.5 7730 3000 130 91 75 78 57 60 74 71 35 47 32 35 27 19 14 9.00 11. R' = CH(n-C5H11)Si(CH3)3 R = H.65 1.60 2.71 4.3 5.5 2.71 3. R' = SiMe3 (PTMSP) R = CH3.12 3.82 18.69 3.05 2.42 6.93 2.59 3.70 3.48 [230] [230] [219] [219] [219] [231] [222] [116] [116] [116] [116] [116] [116] [218] [218] [218] [218] [116] [116] [116] [116] [116] [116] [116] [116] T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE M 23 S S S S S S S S S S S S S S S S S S 35 25 25 35 25 25 35 35 35 35 25 25 25 25 25 25 25 25 111 .89 7.21 1.72 1.80 1.47 6.28 1.43 7.5 13000 4300 85 150 45 38 51 64 84 83 40 46 33 30 21 17 14 7 130 2700 2460 245 130 11000 85 2900 2690 190 112 560 10700 9090 900 390 41000 18200 28000 19000 560 520 310 290 200 230 290 290 130 170 130 180 120 70 48 54 2.43 1.92 3.87 3.11 8.24 1.96 1.87 1.07 1.29 10.43 1. R' = n-C7H15 R = CH3.71 2.56 13.25 3. R' = SiMe3 (PTMSP) R = CH3.27 9.54 13. R' = n-C4H9 R = Cl.45 3.00 1. R' = CH3.63 10.60 2.74 3.02 14.76 12.16 5.00 15.15 4.86 3.11 5.19 5.00 1.59 3. R' = CH2CH2CH(CH3)2 (P6M2H) R = CH3.63 3.05 2.64 1.11 4.71 1. R' = CH(CH3)2 (PMP) R = CH3.00 10.67 1.48 14. R' = Si(CH3)2CH2Si(CH3)3 R = H. R' = o-C6H4Si(CH3)3 R = CH3.Table 12. R' = C(CH3)4 R = CH3.63 11. Permeabilities and permeances of membrane materials used for CO2 separations.38 4.97 1.05 7. R' = SiMe3 (PTMSP) R = H.59 3. R' = CH(n-C3H7)Si(CH3)2Ph S S S S S S 25 25 35 35 35 25 Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer 48 43 41 59 60 58 30 25 5080 2200 180 100 180 170 270 290 150 140 150 140 76 76 66 100 84 42 45 29 5200 300 180 2630 2650 460 240 300 5800 5640 750 370 18000 11800 43 1330 1250 93 51 7000 5700 4970 1800 43 35.20 1.00 9.73 21.94 6.33 1.

55 1. R' = Si(CH3)2CH2CH2Si(CH3)3 R = CH3.83 0.1 8.1 0.56 1.52 2. R' = Cl R = H.21 0.33 2.18 34.72 0.87 0.2 1.1 58 28 21 6.4 0.3 23.89 23.8 11 2.00 0.33 0.07 0.24 31.93 9.08 0.2 1.2 3.70 8.5 2.00 13.00 0. R' = Et R = Ph.6 6.7 0.3 12 5.00 5.00 1.25 0.67 1.0052 156 90 1 10.089 0.03 0.3 2.2 4.85 15.47 0.14 0.75 0.83 1.53 1.4 7.9 0.1 7.81 11.36 8.00 0.8 4.50 10.5 1 3 20 50 39 25 6.66 4. R' = n-C3H7 R = H.2 1.70 0.00 0.09 17.3 0.23 4.58 0.2 0.93 0.78 5.32 13.3 0.4 762 473 120 15 23 22.30 0. R' = Ph (PPP) S S S S S S S S 25 35 25 25 25 25 25 25 Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer 130 30 40 23 29 130 180 160 140 43 57 29 39 280 14 12 7.29 23. R' = o-C6H4(CH3) R = (CH3).4 200 1.6 0.00 5.40 0.9 0.15 0.1 23.8 1.93 10.79 0.9 10.50 1.7 11 0.3 0.4 7.92 0.95 0.00 [116] [218] [116] [116 [116 [116 [116 [231] Polyolefins Polystyrene Polytetrafluoroethylene (PTFE) Polyethylene Polystyrene Polybenzylmethacrylate Polymethylmethacrylate Polyvinylacetate Polyethylene:Polyvinylalcohol Polyvinylidenefluoride Polyvinyltrimethylsilane (PVTMS) Polyvinylacetate Poly(ethyl methacrylate) Poly(methyl methacrylate) PVTMS PVTMS (silicone coated) PVTMS (silicone coated & fluorinated) Poly(2-hydroxyethyl methacrylate)/alumina S 35 Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer GPU GPU GPU 15.26 17.3 14 0.2 1.8 17.3 2.44 0.7 17.) R = CH3.03 119.83 21.52 1.00 17.02 138 52 3.00 0.00 14.00 5.4 7.1 0.2 200 3.9 0.90 [116] [492] [249] [249] [249] [249] [249] [249] [249] [116] [359] [116] [116] [493] [493] [493] [248] M 25 S S S S S S S S S S S 30 30 30 30 30 30 30 25 35 35 35 S 20-25 S 20-25 S 20-25 S room Barrer 112 .9 0.71 18.69 5.01 0.00 5.35 0.38 0. R' = (CH3) (PPP) R = Ph.3 3 150 120 130 25 40 23 15 260 1.71 10.4 9.41 8.89 20.98 0.6 2.6 4.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE Polyacetylenes (Cont’d.64 1.71 19.29 0.36 5.78 12.4 44 0.62 746 450 110 7 0.19 1.6 13.4 11.4 15. R' = o-C6H4CF3 R = Ph.92 14.3 2.8 8.65 32.9 7.00 110.4 1.35 0.

6 42 25.96 3.37 11.5 26.24 23.3 7.00 22.50 23.46 38.44 10.92 6.29 [492] [492] Silicones Poly(dimethylsiloxane) Poly(dimethylsiloxane) PDMS Poly(dimethylsiloxane) (PDMS) Poly(methylpropylsiloxane) Poly(methyloctylsiloxane) Poly(trifluoropropylmethylsiloxane) Poly(benzilmethylsiloxane) [(CH3)2Si(CH2)6Si(CH3)2O]x [(CH3)2SiCH2]x [(CH3)2Si-p-C6H4Si(CH3)2O]x M 23 S S S S S S S S S S 30 23 35 35 35 35 35 35 35 35 Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer 590 950 375 890 380 299 400 351 540 800 781 850 600 1200 1430 531 314 201 36.5 17 100 80.90 3.23 3.8 138 1.86 2.36 29.71 70.71 18.54 28.3 395 130 10.45 22.47 4.4 3200 1300 3800 4550 1520 917 1210 226 1310 542 52.09 5.3 33.17 5.29 [177] [177] [254] [255] [255] [255] [255] [255] [255] [255] [255] S room Barrer S room Barrer S room Barrer S room Barrer S room Barrer S room Barrer S room Barrer S room Barrer 113 .24 2 3.57 4.92 9.42 139.27 8.8 10 0.22 24.13 24.55 17.59 3.03 4.32 4.17 3.62 5.03 [222] [249] [364] [116] [116] [116] [116] [116] [116] [116] [116] Polyethers Pol(ethylene oxide) PEO Pol(ethylene oxide) PEO PEO Poly (phenylene oxide) (PPO) PPO 20% brominated PPO 40% brominated PPO 60% brominated sulfonated PPO sulfonated PPO 20% brominated sulfonated PPO 40% brominated sulfonated PPO 60% brominated S S S 25 35 35 Barrer Barrer Barrer 0.42 4.83 50.83 4.40 51.52 3.7 0.37 3.7 9.53 0.96 0.79 2.71 3.26 0.1 88.8 27.53 59.88 16.07 0.35 9.53 3.76 2.01 34.69 118.18 2.81 1.00 135.28 22.00 24.1 1.44 50.22 112.19 0.67 0.6 39.17 15.76 24.68 0.73 9.33 5.17 3.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE Polydienes Polychloroprene Polybutadiene M 25 M 25 Barrer Barrer 13.50 12.98 5.02 6.

9 5.4-5. DHBP w/High KOH conc.33 2. BisA w/Low KOH conc.20 33.53 12.33 12.63 24.92 1.1-58.00 32.075 0.20 [494] [494] [494] [494] [494] [494] [494] [494] [494] [494] [494] 114 .60 17.00 7.18 1.545 0.061 0.00 27. TBBA w/High KOH conc.95-1.486 31.8-4.00 53.3 5.1 1. M room M room M room M room M room M room M room M room M room M room M room GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU 5.00 40.7 6.19 1.319 0.1 13.00 2.00 230.952 0.76 7.00 55.7-68.52 11.390 0.6 1.667 0.00 21.8 6.55 0.40 0.50 1.9 2.95 22.96 4.0-10.14 15.8 14 12.35 0.5 3.3 6.8 0.00 2.7-8.4 3.2 14.36-1.00 [254] [249] [116] [121] [121] [121] [121] [127] [127] [127] [127] [359] Polyaryleneethers 6FPT-6FBPA 6FPT-BPA 6FPPy-6FBPA 6FPPy-BPA S S S S 35 35 35 35 Barrer Barrer Barrer Barrer 41.37 2.0-51.40 8.81 5.56 5. supports S S S S S S S S S S S S 35 30 35 25 25 25 25 22 22 22 22 35 Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer 10.5 2 4.21 15.44 0.53-0.00-8.08-0.00 25.6-20.39 1. TCHFBA w/High KOH conc.78 25.37 30.8 32 2.034 17.50 4.00 1.25 25.9 28.480 10.01 13.4 0.1 41.8-43.2 0.04 [172] [172] [172] [172] Polyesters BisA w/High KOH conc.18 1.00 8.00 2.77 0.8 0.00 38.53 29.65 0.0 0. DHBP w/Low KOH conc. DHDPE w/Low KOH conc.00 3.7 38.7-35.7 20.8 50.6-8.2 2.80 21.64 0.00 35. TDP w/High KOH conc.9 5.19 0.4 0.6 23.8 2 22 0.23 0.91 4.00 35.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE Polysulfones Bisphenol-A polysulfone (PSf) PSf PSf PSf PSf PSf PSf PSf PSf aldehyde (PSFCHO) PSFCHO/3A zeolite PSFCHO/5A zeolite Polyvinylacetate/diverse inorg.18 5.7 1.43 0.6 6.71 0.29 18.41 1.46 21.1 4.60 0.20 1.20 12.8-23.06 0.60 13.7 11.4 0.500 12.58 1.3 3 69 4.2-136 32.34 12.6 0.00 2. TMBA w/High KOH conc.00 1. DHDPE w/High KOH conc.59 0.3-8.1 10.38-0. BisF w/Low KOH conc.61 16.00 1.90 0.00 21.1 0.

46 31. SDP w/Low KOH conc.34 0.50 19.5 3.059 0.1 0.5 0.43 0.64 0. TBBA w/Low KOH conc.5 37.12 0.15 0.06 11.95 0.00 41.2 11 0.00 35.67 22.82 0.5 47.33 0.7 4.78 24.75 0.82 0.9 2.25 0.) BHPF w/High KOH conc.2 4.6 4.18 0. TDP w/Low KOH conc.1 0.38 14.4 0.1 0.40 28.89 18.93 17.067 3.9 60.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE Polyesters (Cont’d.4 6.20 0.7 22.065 0.8 3.82 1.02 4.1 30.9 0.17 27.4 191 4.02 1.15 3.61 0.4 12.48 0.2 0.072 0.93 40.00 15.78 [495] [495] [495] [495] [143] [143] [143] [143] [143] [116] [116] [116] S 35 Barrer Barrer Barrer Barrer 16 39.16 0.8 0.5 4.9 12.6 2.91 0.2 2.03 [116] Cellulose based Ethyl cellulose Cellulose acetate Cellulose acetate Cellulose acetate Polyimides PI-1/PTMSP PI-1/PTMSP PI-2/PTMSP PI-3/PTMSP BDCDA-MPD BDCDA-DDSO HDCDA-6F PDCDA-6F BDCDA-6F PMDA-ODA PMDA-MDA PMDA-IPDA S S S S S S S S S S S S 25 25 25 25 30 30 30 30 30 35 35 35 GPU GPU GPU GPU Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer 8 9.3 5.30 29.03 26.46 30.98 7.70 [494] [494] [494] [494] [494] Polycarbonates Bisphenol-A polycarbonate S 35 Barrer 13 0.9 1.71 4.8 75 22.38 27.00 48.12 0.89 [116] Polysilmethylenes Poly(dimethyl silmethylene) S 35 Barrer 43.14 0.52 17.22 17.80 2.2 3.2 2.71 1. M room M room M room M room M room GPU GPU GPU GPU GPU 1.40 13. TMBA w/Low KOH conc.36 6.18 0.93 1.1 5 15.1 25 41.03 [116] [492] [492] [116] M 25 M -20 S 35 115 .81 25.28 0.8 0.296 1.80 1.25 39.64 0.8 0.00 31.84 1 0.00 34.27 0.88 6.00 31.6 0.13 0.00 2.9 23.39 15.67 31.17 4.4 37.76 2.72 2.49 6.038 0.38 1.45 0.30 1.1 7.95 0.4 12.1 11.24 0.00 8.10 37.00 45.1 0.9 4.4 14.00 1.06 1.35 3.

6 7.825 4.83 612 84 66 51 28.279 0.0099 0.92 0.41 0.85 5.72 44.5 50 71.3 0.937 0.733 47.00 93.89 27.06 0.2 2.11 10.54 16.28 42.28 1.189 0.86 0.50 [149] [132] [132] [132] [132] [132] [311] [493] [493] 94.) 6FDA-ODA 6FDA-MDA 6FDA-IPDA 6FDA-DAF PMDA-m'pODA PMDA-p'pODA PMDA-BAPHF PMDA-BATPHF BPDA-p'pODA BPDA-BAPHF BPDA-BATPHF BPDA-BAHF BTDA-p'pODA BTDA-BAPHF BTDA-BATPHF BTDA-BAHF 6FDA-m'pODA 6FDA-APAP 6FDA-p'pODA 6FDA-BAPHF 6FDA-BATPHF 6FDA-BAHF 6FDA-TADPO (polypyrrolone) 6FDA-HAB 6FDA-durene 6FDA-6FpDA-8%-DABA 6FDA-6FpDA-8%-DABA:Aluminophoshate(95:5) 6FDA-6FpDA-8%-DABA:Aluminophoshate(90:10).21 REFERENCE [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] [116] 4.88 49.21 32.3 3.47 17.7 19.48 18.4 67.6 0.80 35.99 24.37 0.52 0.85 34.43 0.34 0.6 30.33 SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 60.1 6 3.98 7.3 2.53 56.7 0.6 0.2 1.7 0.145 0.2 0.5 83.57 2.15 27.78 0.4 3.41 0.43 38.2 30 32.0258 0.2 23 7.13 0.89 3.1 0.1 6.259 38.48 22.195 24.00 18.45 0.31 0.6 1.1 0.2 77 S 35 Barrer M 20-25 GPU M 20-25 GPU 116 .145 34.57 0.58 31.17 2.33 39.51 0.71 50.2 0.57 14.42 0.40 10.3 0.981 55.42 0.125 0.1 6FDA-6FpDA-8%-DABA:Aluminophoshate(90:10).94 10.23 40.7 16.55 17.54 3.38 0.4 0.226 0.7 0.78 11.05 8.33 0.6 0.76 22.88 5.4 10 6.62 36.5 1.217 0.74 37.2 4.473 40.26 110.11 0.28 0.* Polyimides (Cont’d.8 51.5 0.39 1.34 4.44 23.47 20.7 0.32 186 36 24 18.66 16.14 2.65 24.943 50.341 0.51 57.5 18.59 26.45 0.53 7.97 36.5 PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 4.93 26.73 32.69 48.245 30.49 0.2 1.47 0.30 0.0109 0.62 22.40 0.071 490 178 148 786 55.11 7.5 9.31 48.2 98.18 3.703 1.25 19.024 16.17 0.638 0.2 Matrimid 5218 Matrimid 5218 Matrimid 5218 (Fluorinated) S S S S S S S S S S S S S S S S S S S S S S S S S S S S S T UNITS (OC) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 30 30 30 30 Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer He 51.79 0.34 41.33 0.20 0.48 0.7 CO2/He 0.045 10.1 1.68 17.78 19.642 4.25 13.46 25.563 59.45 23.24 0.27 0.12 45.1 1.25 0.41 18.34 CO2 23 24.625 4.105 0.26 0.3 0.37 6.96 9.29 23.34 0.8 0.29 0.24 16.28 0.6 24.25 64.59 22.191 1.7 0.13 6.4 108 89 1.5 14.0937 0.40 45.28 0.47 0.43 35.1 22.3 10 28.54 0.

5 23 75 1.1 30 110 39 32 72 68 19 221 113 120 2.6 7.33 2 7 5 15 1.9 16 19.56 20.00 10.33 72.47 9.2 13.64 10.00 5.2 4 1.4 3 3.7 5 4.50 6.24 11.27 18.98 10.40 [241] [241] [241] S S S S S S S 30 30 30 30 30 30 30 Barrer Barrer Barrer Barrer Barrer Barrer Barrer 4.2 5.54 2.00 3.6 1 0.2 1.1 13.81 11.20 27.24 0.9 1.35 14.6 21.71 2.2 11 1.64 0.07 42.56 17.9 107.9 17 4.1 Poly(3-(2-hydroxyethyl)thiophene) (P3AcET).42 53.73 0.8 18 7 1.42 6.84 2.8 3.8 7.1 1.25 27.71 53.01 5.2 7.5 59.40 15.00 23.96 22.4 3.7 250 1.1 16.5 0.00 31.2 14.3 2.7 10.7 15.3 1.4 3 2.53 3.36 56.3 8.44 2.00 [150] [150] [150] [150] S S S 30 30 30 Barrer Barrer Barrer 7.4 25.40 51.89 7.00 21.24 1 9.3 10.44 5.2 11 9.62 13.1 8.9 226.7 9.87 10.9 8.8 17 27 0.3 38.36 3.81 22.61 29.23 62.9 81.73 [264] [264] [264] [264] [264] [264] [264] S room Barrer S S S 35 35 35 Barrer Barrer Barrer 117 .08 9.8 1.7 28.69 7.7 4.2 Copolymers Ether-Olefin Poly(propylene glycol) diacrylate (PPGDA) 540 PPGDA900 Poly(ethylene glycol) diacrylate (PEGDA) 575 PEGDA575 + 10 wt% fumed silica PEGDA700 PEGDA700 + 10 wt% fumed silica PEGDMA/alumina poly(tetramethylene oxide) (PTMEO):nylon (PEA)12 (80:20) PTMEO:PEA12(53:47) PEO:PA6(55:45) S S S S S S 23 23 23 23 23 23 Barrer Barrer Barrer Barrer Barrer Barrer 6.98 4.29 12.21 2.7 15 33 7.8 25 0.20 67.82 30.21 4.80 19.5 7.04 8.33 5.74 0.00 75.70 3.6 23.90 4.7 115.40 20.4 19.8 16.00 15.42 6.22 4.8 2.50 9.27 [242] [242] [242] [242] [242] [242] [248] [252] [252] [252] S S S S 35 20 20 20 Barrer Barrer Barrer Barrer 1270 620 34 22 5 5 130 111 63 60 11 36 14 8 300 668 281 336 0.00 4.48 8.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE Polyphosphazenes Pendant groups: 2-(2-methoxyethoxy)ethanol : 4Methoxyphenol : 2-Allylphenol 6:75:19 23:72:5 25:59:16 38:46:16 48:48:4 74:24:2 100:0:0 R Group PPOP PTBP PBTBP:Cl (20:80) Other Polymers Cytop Poly(3-(2-acetoxyethyl)thiophene) (P3AcET) Poly(3-(2-hydroxyethyl)thiophene) (P3AcET).73 32.54 7.41 6.75 7.

36 7.70 5.42 0.00 34.2-bis(4-methacryloxy polyethoxy phenyl)propane (DB)30:MM9 (100:0) S DB30:MM9 (90:10) DB30:MM9 (70:30) DB30:MM9 (50:50) DB30:MM9 (30:70) DB10:MM9 (90:10) S S S S S 118 .53 3.59 6.73 2.00 41.61 2.55 0.00 49.87 6.00 47.60 30.00 51.658 0.159 0.00 53.684 1.15 2.00 50.00 53.00 41.239 0.65 5.81 6.17 0.4 5.40 9.70 52.00 48.50 11.00 51.10 6.570 2.45 6.57 2.25 66 6.00 48.180 0.00 50.04 9.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE Copolymers (Cont’d.80 33.00 32.174 0.00 48.40 32.) PEO:PA12(57:43) Methoxy PEG acrylate (MePEGA)0/Polyacrylonitrile (PAN) MePEGA2/PAN MePEGA4/PAN MePEGA6/PAN MePEGA8/PAN MePEGA10/PAN MePEGA12/PAN MePEGA14/PAN MePEGA16/PAN MePEGA18/PAN PEGDA/Poly(ethylene glycol) methyl ether acrylate (PEGMEA) (100:0) PEGDA/PEGMEA(80:20) PEGDA/PEGMEA(50:50) PEGDA/PEGMEA(30:70) PEGDA/PEGMEA(9:91) PEGDA/PEGMEA(1:99) PEG dimethacrylate(DM)14:PEG methyl ether methacrylate (MM)9 (100:0) DM14:MM9 (90:10) DM14:MM9 (70:30) DM14:MM9 (50:50) DM14:MM9 (30:70) DM9:MM9 (90:10) S S S S S S S S S S S S S S S S S S S S S S S 35 30 30 30 30 30 30 30 30 30 30 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 Barrer GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer 8.52 9.532 3.46 1.00 52.00 58.80 3.00 [252] [251] [251] [251] [251] [251] [251] [251] [251] [251] [251] [237] [237] [237] [237] [237] [237] [253] [253] [253] [253] [253] [253] [253] [253] [253] [253] [253] [253] [253] DM23:MM9 (90:10) S 2.68 13.90 29.64 112 150 250 320 520 570 65 85 129 185 260 28 194 128 140 185 231 308 12 7.23 1.81 12.00 47.14 5.00 5.53 3.00 54.00 41.80 56.90 1.63 4.186 0.90 2.206 0.06 7.

4 195-197 44.4-butanediol:DMT PEG-1500:1.26 7.0246 3900 0.1 5.88 9.14 1.00 41.94 2.6 34.8 58.6-6.50 40.24 [496] [134] M 35 M 35 Barrer Barrer 32.50 44.5 S S S S S 36 33 33 35 30 M 25 119 .33 66.86 10.50 7.00 11.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE Copolymers (Cont’d.5 [175] [175] S S 35 33 Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer 32.3 5.2 28.8 32.25 6.2-12.0-9.9 7.67 63.024 1600 0.8 5.00 41.00 70.7-5.6 DMN PEG-1500:1.67 9.6 10.59 16.33 8. 12.00 6.1 45.99 1.) Ether-Ether EO:2-(2-methoxyethoxy)ethyl glycidyl ether(EM-2):allyl glycidyl ether (AGE) (94:4:2) Ethylene oxide (EO):propylene oxide(PO):AGE (83:16:1) EO:epichlorohydrin(EP):AGE (56:39:5) PO:EP:3-glycidoxypropyltrimethoxysilane (GPTMS) (35:63:2) EO:AGE (92:8) EP:AGE (94:6) EO:GPTMS (95:5) EO:PO (90:10) EO:EM-2 (78:22) Ester-Ether PEG-1500:1.50 9.20 1.2 30.7-3.24 600 0.50 8.3 63.6 [175] [175] M 35 M 35 Barrer Barrer 8.5-55.11 10.7 2.4-butanediol:2.33 45.0-16.12 [176] [176] [176] [176] [176] [176] [116] [249] [492] S S S S S S S S S 35 35 35 35 35 35 35 35 35 Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer 20 30 30 30 30 20 40 45 38 4 5 6 6 5 6 6 6 7 250 220 260 270 350 250 380 400 610 12.67 87.50 9.9 25.50 5.9 0.0 15.2 5.7-50.60 8.1 77.15 5.5-34.2 4.2-ethyleneglycol:2.5 262 333 353 237 322 59.8 23.3 171 15.1-11.29 10.67 12.3-propanediol:DMCH PEG-1500:1.3-propanediol:SBMB PEG-1500:1.2 2.6 35.2 3400 780 0.05 62.00 43.08 0.14 [254] [254] [254] [254] [254] [254] [254] [254] [254] S 33.3-propanediol:DMBPD PEG-2000:1.89 16.8-62.6-DMN Diene-Olefin Poly(butadiene-styrene) Polyvinyl-butadiene Poly(acrylonitrile-butadiene) Ether-Urethane PU1 PU3 Ether-Urethane urea PU2 PU4 Copolyimides Teflon AF2400 (Hyflon AD87) BTDA-TDI/MDI (80:20) (P84) S S 25 25 Barrer Barrer 3600 7.3 1.

44 0.02 1.36 0.7 27.025 0.3 1.92 27.33-3.28 33.006 0.1-2.9 433 460 1620 40 40 24 16 51 40 28 8.6 27 125 0.#1 Poly(vyvilbenzyltrimethylammonium fluoride) PVBTAF.77 43.23 25.0:3) Polysulfone:poly(4-vnylpyridine):Silcon Rubber (23:0.5 0.n=4 PVBTAF-nCesiumFluoride-1cholineFluoride.22 28.65 54 0.8 16 0.0:3) Polysulfone:poly(4-vnylpyridine):Silcon Rubber (17:2.39 0.0751 0.20-0.2 1360 790 52 180 17.5:3) Polysulfone:poly(4-vnylpyridine):Silcon Rubber (21:1.109-0.1:3) Polysulfone:poly(4-vnylpyridine):Silcon Rubber (25:0.31-24.3 2.1 0.62 22.92 74 0.9 3.43 371-587 178-400 53-81 17-44 12-24 490-10000 42-64 629-835 6.21 47.30 30.3-3.065 0.42 [153] [153] [153] [126] [126] [126] [126] [126] [126] [126] [126] [126] 90 0.83 1.55 44.221 2.068 0.276 0.95 83.119 0.0:3) Polysulfone:poly(4-vnylpyridine):Silcon Rubber (21:2.32 0.044 25-800 7.087 0.011 0.293] [281] [281] [281] [277] [277] [279] [279] [279] [279] [280] [280] [288] [288] [288] [288] M 23 M 23 M 23 M 23 M 23 M 23 M 23 M 23 M 23 M 23 M 23 S S S S 25 25 25 25 0.42 0.112-0.0417 0.#2 Polyvinylamine (PVAm)/poly(ether sulfone) Polyvinylamine (PVAm)/polyacrylonitrile Polyvinylamine (PVAm)/celullose acetate Polyvinylamine (PVAm)/polysulfone S 26 GPU Barrer GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU 0.30 0.022 0.111 36.00586 0.1 6.0:3) S S S S S S S S S S S S 35 22 22 25 25 25 25 25 25 25 25 25 Barrer Barrer Barrer GPU GPU GPU GPU GPU GPU GPU GPU GPU 140 1.44 58.3 8.69 2.91 759.33 0.10 0.0128 0.51 3.50 5.023-0.375 2.1 5.007 0.2:3) Polysulfone:poly(4-vnylpyridine):Silcon Rubber (21:0.67 2.1 120 .4 3 FACILITATED TRANSPORT Solid-Polyelectrolyte Polyvinylpyrrolidone (hydrolyzed)/polysulfone PVBTAF:poly(diallyldimethylammonium fluoride) Poly(vinylbenzyltrimethylammonium fluoride) (PVBTAF) PVBTAF/poly(diallyldimethylammonium fluoride) PVBTAF-nCesiumFluoride.n=3 PDMS/poly(diallyl-dimethylammoniumfluoride) (PDADMAF)/PDMS PTMSP/PDADMAF/PTMSP PTMSP/PDADMAF/microporous polymer PTMSP/PVBTAF/microporous polymer Poly(vyvilbenzyltrimethylammonium fluoride) PVBTAF.007 0.10 17.437 12.016-0.96 51.02 7.39 0.12 39.8 0.87 1.0443 0.6 1.33 24.061 19.17-9.35 0.00636 0.44 0.31 36-778 120-239 150-380 78-118 43-87 4910-10270 [292.163 0.57 4.32 0.88-6.55 8.023 0.84 1.7 4.77 0.035-0.6 7.44 0.5:3) Polysulfone:poly(4-vnylpyridine):Silcon Rubber (25:1.29 0.48 36.60 17.10 278.87-1.00 5.) Hyflon AD60 Hyflon AD60 Hyflon AD80 Polysulfone:poly(4-vnylpyridine):Silcon Rubber (25:0.5 5.026-0.07-0.4 8.96-2.85 8.99 0.83 13-25.26 1.54 109.00 25.03 43-126 180.3 0.88-6.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE Copolymers (Cont’d.02 2.59 132 96 81 20 54 1.003-0.2:3) Polysulfone:poly(4-vnylpyridine):Silcon Rubber (25:0.45 22.33 54.04 12.48 0.

61 358.27 30.81 2.00 30.5 7.2 Fau-type.) Inmobilized liquid Glycerol-Na2CO3 in poly(vinylidine fluoride) (PVDF) (dry) Glycerol-Na2CO3 in PVDF (100 RH) Glycerol carbonate in PVDF (dry) Glycerol carbonate in PVDF (humid) Glycerol carbonate in Celgard 2500 (dry) Glycerol carbonate in Celgard 2500 (humid) 44% dendrimer (generation 0) in glycerol in PVDF (dry) 44% dendrimer (generation 0) in glycerol in PVDF (humid) 75% dendrimer (generation 0) in glycerol in PVDF (dry) 75% dendrimer (generation 0) in glycerol in PVDF (humid) Pure dendrimer in PVDF by impregnation (dry) Pure dendrimer in PVDF by impregnation (humid) INORGANIC MEMBRANES Zeolites Fau-type.44 777.08 9.72 233.25 1135 90.40 5380.75 46.13 448.24 1.19 930 0.6 Fau-type.09 45.79 1770 100 320 260 160 17 900 5800 3200 4700 3600 2.54 567.58 275.50 15.83 14.74 16842 5.79 0.00 100.1 Fau-type.63 1644.71 2.25 957 6.54 0.4 3.86 23.1 3.41 7.98 38.42 47.58 2.7 Fau-type.56 1.91 86.02 230.7 4.05 21176 [272] [272] [274] [274] [274] [274] [275] [275] [275] [275] [275] [275] M 30 M 40 M 180 121 .8 ZSM-5 ZSM-5 Na-Y K-Y Silicalite S S S S S S S S S S 50 50 50 50 50 50 50 50 25 25 GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU 717.30 20.92 19.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE FACILITATED TRANSPORT (Cont’d.18 104.17 116.45 4.00 54.49 59.48 177.94 860 0.00 [320] [320] [320] [320] [320] [320] [320] [320] [314] [314] [329] [327] [334] M 23 M 23 M 23 M 23 M 23 M 23 M 23 M 23 M 23 M 23 M 23 M 23 Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer 1.23 161.97 627.65 5.62 2.5 Fau-type.17 2.3 Fau-type.76 388.4 Fau-type.50 7.82 0.80 50.

83 418.6 Aminosilicate.8 Aminosilicate.88 63.93 32.88 61.9:9.8 4.38 0.40 3.26 45.33 2989 1494 120 2.50 2.95 298.88 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 5.97 7772.1 Silica.72 0.44 1.18 18.3 366 1.19 0.) Silicalite K-ZSM-5 B-ZSM-5 Na-ZSM-5 Sapo-34.60 212.64 2.23 83.27 37.1 100 77.62 3.10 Microporous Silica Microporous Silica Carbon Molecular Sieves (precursors) BTDA-TDI/MDI BTDA-TDI/MDI (80:20) (P84) BTDA-TDI/MDI (80:20) (P84):AgSPEEK (95:5) BTDA-TDI/MDI (80:20) (P84):AgSPEEK (90.78 15.58 CO2 209.76 0.51 418.53 25.5 161 465 14049 5380 1250 0.00 12.43 20 20 22 22 22 22 22 22 22 22 22 22 50 50 25 25 25 25 GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU Barrer Barrer Barrer 8968 5381 400 58.40 1.2 76.88 0.8 80 6.5 Aminosilicate.13 0.79 0.8 400 3 27.70 26.82 72.33 30.18 10164 2391 2000 3.51 17.23 2.00 87.75 1.83 56.11 35.37 225.12 [325] [325] M 22 M 22 S S S 27 25 25 22.3 62.2 Aminosilicate.72 50.49 0.2 52.32 12.60 17 7.05 67.36 158.9 3.52 0.3 419 50.25 134.00 REFERENCE M 30 M 50 M 27 M 27 S S S 24 24 24 [330] [333] [322] [322] [315] [315] [315] [316] [316] [321] 1.2 Aminosilicate.1 Sapo-34.12 0.3 83.9 70.1) S S S S S S S S S S S S S S S S S S T UNITS (OC) GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 38.67 1.2 Silicas Silica.00 17.4 Aminosilicate.70 70.51 573.2 Sapo-34.91 110.44 116.8 52.80 4.89 304.52 567.11 4.7 Aminosilicate.82 1.37 179.60 16.6 10.36 32.5 91.83 1.50 37.61 50.6 60.3 Aminosilicate.44 5.3 41 49.16 3.40 1.54 5.47 4.33 1.* Zeolites (Cont’d.1 Aminosilicate.00 [317] [317] [318] [318] [318] [318] [318] [318] [318] [318] [318] [318] [318] [497] [497] [308] [306] [306] [306] 122 .08 567.9 Aminosilicate.88 1.60 13.26 7.27 328.06 0.54 203.1 Sapo-34.82 179.3 Sapo-34 Sapo-34 Carbon-Silicalite composite Sapo-34.00 0.

3 24.74 200.49 200.91 38.39 0. BuOH pretreat P84 P84.2 Matrimid 5218 Matrimid 5218.2 Matrimid 5218.5 2 21 1068 84 1509 386 2526 1500 350 1800 400 1950 550 611 423 191 565 547 499 402 278 428 829 1674 2863 0.00 4.89 31.13 173.36 0.03 29.65 0.52 0.15 191 12.44 26.81 13.8 1.14 0.67 15.5 7.8 6.32 0.19 1.4 44 12 10 8.56 30.3 PMDA-ODA-PDM (Poly(imide-siloxane:PIS).61 31.9 0.53 0.8 13.81 13.14 0.4 40 8.22 0.2 PMDA-ODA-PDM (Poly(imide-siloxane:PIS).14 201.5 69 47 9 57 13 66 17 30.1 PMDA-ODA-PDM (Poly(imide-siloxane:PIS).17 26.20 0.22 0.3 Kapton PMDA-ODA-PDM (Poly(imide-siloxane:PIS).07 0.6 9 14.00 11.15 0.2 BTDA-ODA (PI)-(PVP) blend (10:10:5).7 7 5.6 BTDA-ODA (PI)-(PVP) blend (10:10:0).3 15.72 0.32 0.90 0.88 0.1 1.31 0.54 34.1 21 17.00 39. EtOH pretreat P84.77 30.07 48.00 88.7 3 22 4.16 34.4 204 186 158 132 101 144 256 501 707 10 4.33 70.15 8 326 30 399 111 595 500 140 550 160 640 230 227 138 75.30 0. PrOH pretreat BTDA-ODA-mPDA-DBA (10:8:2:0) BTDA-ODA-mPDA-DBA (10:8:0:2) BTDA-ODA-mPDA-DBA (10:8:0:5) S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S 25 25 35 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 35 35 35 35 35 35 35 35 35 25 25 25 Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer Barrer 2763 3208 4193 18 70 22 9 315 3416 610 4245 1258 7319 1700 1100 2000 1250 2200 1700 12598 9518 8216 361 169 3.67 0.77 29.9 0.68 0.16 0.35 0.6 24 49 83 52.64 84.72 0.97 65.8 2.) BTDA-TDI/MDI (80:20) (P84):AgSPEEK (83.33 [306] [306] [390] [148] [148] [148] [148] [304] [304] [304] [304] [304] [304] [302] [302] [302] [302] [302] [302] [309] [309] [309] [309] [309] [309] [309] [309] [309] [250] [250] [250] 123 .4 PMDA-ODA-PDM (Poly(imide-siloxane:PIS).* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE Carbon Molecular Sieves (precursors) (Cont’d.32 34. PrOH pretreat Matrimid 5218.1 6.35 20.3:16.56 60.00 37.2 BTDA-ODA (PI)-(PVP) blend (10:10:10).00 109.00 11.65 139.43 5.7 2 3.32 23.1 BTDA-ODA (PI)-(PVP) blend (10:10:0).5 0.00 108.32 0.7) BTDA-TDI/MDI (80:20) (P84):AgNO3 (94:6) Matrimid 5218 Matrimid 5218.1 BTDA-ODA (PI)-(PVP) blend (10:10:5).89 29.33 78.1 BTDA-ODA (PI)-(PVP) blend (10:10:10). MeOH pretreat Matrimid 5218. MeOH pretreat P84. EtOH pretreat Matrimid 5218.1 Matrimid 5218.55 32.05 28.73 45.5 3.13 0.31 0.58 30.3 27 1.26 26.5 PMDA-ODA-PDM (Poly(imide-siloxane:PIS).41 36.89 0.37 2 0.6 3.00 32.

89 119.29 703.71 113.1 Zeolite-T DDR-zeolite Sapo-34.1 SSZ-13 Zeolite.05 646.00 792.17 6.57 59.19 1.00 2.02 134.75 2.45 10.59 1.25 47.77 1.1 60 0.00 7.55 55.4 CMSM. MII Carbonized latex-graphite.76 702.25 72.01 0.56 89.74 3. MII Carbonized latex-graphite.59 1.20 25.82 5.67 8.33 97.80 1.05 70.18 3.72 2.80 89.43 10.77 2.50 7.17 0.34 11 0.99 151.79 38.53 486.04 216.62 124 .28 0. MI Carbonized latex-graphite.38 0.21 8.33 0.538 2.11 65.78 6.46 29.68 34.353] [355] [325] [357] [357] [357] S S S S S 20 20 20 20 20 GPU GPU GPU GPU GPU 2160.67 288.67 6.00 3.1 CMSM.49 8.284 0.87 0. MIIIB Carbonized latex-graphite.67 7.298] [297.68 239.53 [492] [492] [492] [492] [492] [492] [492] [356] [351] [358] [262] [262] [262] [262] [356] [356] [356] [356] [356] [352.42 0.40 478.3 SSZ-13 Zeolite.15 448.58 5.28 46.21 5.12 [297.80 12.77 403.88 1.70 1150.60 3.00 150.33 141.70 4.00 34.11 83.33 1130. n = 1 Novolak-phenolic resin-N-methyl-2-pyrrolidone.00 10.028 0.07 4.6 214.62 1.64 6.298] [297.73 311.57 8.93 322.) CMSM.88 335.31 5.03 1.09 2.58 4.40 65. n = 18 CnH2n+1(CH3)2SiCl in porous glass.86 39.75 5.298] 2093.43 3.051 0.81 1.90 68.86 1.3 M M M M S S S S S S S S S S S S S S S S S S S S S 25 -20 25 -15 22 22 22 25 20 20 25 25 25 25 25 25 25 25 25 35 18 25 25 25 25 Barrer Barrer Barrer Barrer Barrer Barrer Barrer GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU GPU 10.91 5.38 26.3 CMSM.00 530.38 22 31 28 239 1. MIIIA Carbonized latex-graphite.1 Novolak-phenolic resin-N-methyl-2-pyrrolidone.50 0.29 615. MI Carbonized latex-graphite.90 1.70 2.34 20.64 48.33 13.59 448 350 240 250 58 335 663 551 836 0.30 8.40 119. MIIIC Carbonized phenolic resin HDFS in Vycor ODS in g-Alumina CnH2n+1(CH3)2SiCl in porous glass.52 553.51 677.29 1.91 3.69 3.23 4.00 1. n = 8 CnH2n+1(CH3)2SiCl in porous glass.00 6.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE Carbon Molecular Sieves (precursors) (Cont’d.57 0.71 3. n = 3 CnH2n+1(CH3)2SiCl in porous glass.40 1680.29 627.70 8.70 11 16.60 1.37 21.75 0.56 17 1130 1080 1800 1500 631 1054 973 1195 2.84 80.57 14.95 248.2 SSZ-13 Zeolite.47 86.1 Novolak-phenolic resin-N-methyl-2-pyrrolidone.2 CMSM.93 44.33 4.52 38 150 129 145 329 0.61 134.13 4.12 5.1 Novolak-phenolic resin-N-methyl-2-pyrrolidone.75 5.10 248.358 3.67 317.298] [297.23 0.298] [297.27 63.53 4.33 58.89 405.03 107.5 Surface Flow (adsorption Selective membranes) Carbonized latex-graphite.98 23.00 1.299 2.68 388.67 16.1 Novolak-phenolic resin-N-methyl-2-pyrrolidone.33 1893.27 28.60 7.

84 6.* Surface Flow (adsorption Selective membranes) (Cont’d.52 89.3 94.13 1.16 2.68 5.30 75.1 13.14 25.2 4.50 41.28 8.19 1.52 4.52 1.22 6.32 0.00 42.1 3 0.80 15.48 3.52 5.35 134.64 110 132.2 1.69 2.70 150.41 6.97 6.50 125 .) SSZ-13 Zeolite.59 8.81 5 6.80 6.78 3.3 26.95 33.63 6.84 9.092 0.50 38.35 72.01 23.81 0.76 10.6 20.315 4.30 118.3 10.49-20.71 2.05 [364] [364] [364] [363] 30 30 30 Barrer Barrer Barrer 0.46 1.1 10.50 [206] [206] [206] [206] 0.4 25.06 20.03 702.60 [363] [363] [363] [363] 30 30 30 20 20 Barrer Barrer Barrer Barrer Barrer 3.406 7.51 2.69 [207] [207] [207] [207] [364] 23 23 23 Barrer Barrer Barrer 479 647 285 206 381 156 441 665 341 648 1246 466 1154 4511 1422 2.6 15.09 6.67 [363] [363] [363] [363] 30 30 30 Barrer Barrer Barrer 1.26 20.4-50.49 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 1.74 11.4 SSZ-13 Zeolite.60 71.92 49.73 3.56 7.50 78.6-34.54 3.00 237.18 83.6 21.07 19.3 122 154 205 277 6.17 9.264-0.68 74.26 37.11 5.098 0.73 9.162-0.91 48.40 REFERENCE [357] [357] [207] 25 25 25 25 Barrer Barrer Barrer Barrer 18.67 32.04 8.37 72.60 11.35 134.29 16.5 [363] [363] [363] [393] [393] [206] 25 25 25 25 Barrer Barrer Barrer Barrer 0.3 28.46 1.04 18.12 1.22 0.24 4.52 463.5 2 2.99 5.97 4.31-10.16 15.12 6.51 108.31 0.2 46.5 32.08 0.73 CO2 553.20 8.08 8.39 6.08 7.56 1.99 7.5 HYBRID ORGANIC-INORGANIC MEMBRANES Poly(amide-6-b ethylene oxide)(PEBAX)-Silica PEBAX:Silica(100:0) PEBAX:Silica(90:10) PEBAX:Silica(81:19) PEBAX:Silica(73:27) PDMS-pentaerythrithol triacrylate (PETA)-Silica PDMS:PETA:Silica (11:89:0) PDMS:PETA:Silica (10:85:5) PDMS:PETA:Silica (10:80:10) Poly(ethylene glycol)(PEG)-Silica PEG600:Silica PEG1000:Silica PEG2000:Silica Poly(propylene glycol)(PPG)-Silica PPG600:Silica PPG1000:Silica PPG2000:Silica (PEG-PPG-PEG) (PEPG)-Silica PEPG2000:Silica PEPG2700:Silica PEPG3300:Silica Acrylonitrile-butadiene-sturene (ABS)/Activated carbon 1(AC1) ABS/AC2 6FDA-TAPOB hyperbranched polyimide (HBPI)-Silica HBPI-Silica(100:0) HBPI-Silica(90:10) HBPI-Silica(80:20) HBPI-Silica(100:30) S S S S S S S S S S S S S S S S S S S S S S S S T UNITS (OC) 25 25 GPU GPU He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 463.82 8.62 3.4 10 12 19 26.56 26.

09 47.67 39.67 32. 126 .81 2.51 2. To convert values in GPU into mol m-2 s-1 Pa-1.19 43.24 0.38 1.3 10.391] [390.63 14.41 2.391] [390.52 30.32 0.22 10 10.391] [390.65 12.78 46.136 1.67 28.39 26.391] [390.71 1.08 2.21 12.6 11.22 1.391] [390.94 26.16 4.13 57.26 33.6 44 26.391] [390.56 0.65 2.35 24.30 24.00 [390.9 4.77 2.79 10. multiply the value by 5.12 76.058 0.25 68.35 0.29 0.00 [390.98 200.5 12.391] S S S S S S 35 35 35 35 35 35 Barrer Barrer Barrer Barrer Barrer Barrer 0.95 3.1 2.7 3 22 0.72 75.17 12.95 10-4.06 0.67 39.45 2.391] S S S S S S 25 25 25 25 25 25 GPU GPU GPU GPU GPU GPU 2.92 52.391] [390.391] [390.24 0.071 0.44 5.28 48.12 2.30 14.16 26.05 1.083 0.12 89.78 11.052 0.391] [390. GPU: 10-6 cm3 (STP) cm-2 s-1 cmHg-1.38 0.67 86.33 53.25 3.67 35.* T UNITS (OC) He PERMEANCES AND PERMEABILITIES H2 N2 O2 CH4 CO2 CO2/He SELECTIVITIES CO2/H2 CO2/N2 CO2/CH4 REFERENCE HYBRID ORGANIC-INORGANIC MEMBRANES (Cont’) Polysulfone (PSF)-Carbon Black(CB) PSF:CB (100:0) PSF:CB (98:2) PSF:CB (95:5) PSF:CB (90:10) PSF-Vapor grown carbon fibers (VGVF) PSF-Titania Matrimid® 5218-Carbon molecular sieve (CMS) Matrimid® 5218:CMS (100:0) Matrimid® 5218:CMS (83:17) Matrimid® 5218:CMS (81:19) Matrimid® 5218:CMS (67:33) Matrimid® 5218:CMS (64:36) Matrimid® 5218:CMS (0:100) Ultem® 1000-Carbon molecular sieve (CMS) Ultem® 1000:CMS (100:0) Ultem® 1000:CMS (84:16) Ultem® 1000:CMS (80:20) Ultem® 1000:CMS (65:35) Ultem® 1000:CMS (0:100) S S S S S 35 35 35 35 35 Barrer Barrer Barrer Barrer Barrer 0.01 35.88 35.037 0.09 0.46 33.52 3.67 35.41 30.50 200. M: Data based on mix-gas experiments.38 0.56 26.48 44 27. Cells in gray show materials with preference of CO2 over H2.40 [125] [125] [125] [125] [125] [125] * S: Data based on single gas experiments.28 0.89 12.65 0.94 2.35 26.23 0.7 2.71 44.23 0.25 41.09 22 0.29 30. Barrer: 10-10 cm3 (STP) cm cm-2 s-1 cmHg-1.

0* 1.000 NA 0.37 5. loadinga) Mat.180 NA 2.120 95 0. length and surface area of the fibers (i.125 0.47 20. di.60 30.0 0.83 52.400 0.212 4.6 144.212 14.68 1.044 1 NA 0.0 0.60 10.910 NA 3.750 88 0.580 99 +80 h 0.0 0.090 0.0* 1. The parameters reported include number.5 9.765 7 0.0 10.0 471 Pure water 20 20 22 22 22 22 PF (kPa) NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA 137.0 1.90 11.9 144. No di L a TF mm cm m2/m3 (oC) PTFE 28 3.47 20.5 116.017 0.e.0 416 MEA(30wt%) 40 40 MEA(30wt%. internal diameter.100 100 <2 h 0.50 FCO2 (SLPM) NAc NA NA NA NA NA NA NA 2.50 87.034 19 0. No.030 17 NA 0.60 2.354 8 1.20 70. 0.0 8. PF.230 35 0.5 8.070 0.5 115.0 0.360 NA 1.90 11.20 30.47 20.5* 1.0 2. (mmol/m2 s) (%) 1.68 9.255 20 0.080 0.0 924 Pure water 22 22 22 22 PP 400 0.300 2.0 1542 MEA(5wt%)+TEA(5wt%) 40 40 40 40 PVDF 130 0.417 0.68 11.180 NA 2.e. FCO2).47 20.0* 0.00 87.043) 25 55 PVDF 2050 0.68 5.010 0.5 6. TF.00 43.090 95 0. 0.417 CO2 Stabilityb Flux Eff.0* 3.760 100 +50 h 1..30 70.190 0.5* 1.47 30.68 7. concentration of absorbent (wt%). and feed temperature.0 0.133 27 [418] [444] [442] [429] 127 . 0.5 0.125 0.017 0.760 86 0..910 NA NA 3.450 NA 2.84 5.0 0.313 3 0. Authors Membrane Solvent (Conc.8 115. yCO2.00 30. concentration and flow (i.212 6 0.5 116.086 7 0.0 1391 Piperazine (PZ) (5wt%) 40 40 TEA(5wt%) 40 40 PZ(5wt%)+TEA(5wt%) 40 40 PP 4900 0.730 100 1.070 0.0 0.190 14.750 4.0 2.0* 1.5 119.0* 1. pressure. L.70 20..150) 40 40 MEA(30wt%.60 10.Table 13.70 11. Trans-membrane flux (mmol/m2s) for different capillary hollow fiber membrane contactors reported in the literature.670 100 0.8 137.120 4.0 1. a).83 23.068) 40 40 MEA(30wt%.6 119.0 0.68 5.270 NA 2.9 Conditions yCO2 VL (%)e (cm/s) 1.47 20.30 2.0 8.200 3.0 1.

0 3.000 NA 20.0 13.0 2.6 100.50 NA Propylene Carbonate PP 1 0.6 10.500 NA 0.000 NA 56.50 NA 25 1013.Membrane Solvent (Conc.000 NA 2.6 100.6 10.200 NA 17.500 NA 0.6 10.110 40 NA 25..7 100.000 NA 25.00 14.9 100.0 9.3 100.0 8.5 100.000 NA 0.920 NA 128 .00 NA 25 2026.90 24 101.00 19.450 66 NA 0.3 2.00 NA 25 810.0 0.640 NA 0.3 32.00 19.045 40 NA 25.540 NA NA 0.00 NA 25 405.00 NA Propylene Carbonate PP 1 0.0 2.950 100 0.00 NA Propylene Carbonate PP 1 0.3 100. loadinga) Conditions Mat.3 32. No di L a TF PF yCO2 VL FCO2 mm cm m2/m3 (%)e (cm/s) (SLPM) (oC) (kPa) [443] PVDF 139 0.00 NA 25 405.0 25 405.50 NA 25 810.000 NA 38.6 22.0 9.00 14.6 1.6 2.00 NA 25 405.0 0.045 20 172.680 100 Short 1.800 NA 1.6 1.00 NA 20 202.36 0.530 55 NA 0.760 NA 0.050 NA 0.00 NA 25 810.6 22.0 0.000 NA 11.0 9.50 NA Propylene Carbonate [422] PP 1 0.60 13.3 32.6 8.0 20 172.50 NA Propylene Carbonate PP 1 0. (mmol/m2 s) (%) 0.90 K2CO3 (0.0 1. b NA: not available or cannot be elucidated from data provided.0 0.6 8.0 14.76 0. Authors CO2 Stabilityb Flux Eff.0 3.7 100.00 NA 20 202.55 0.60 13.0 1340 MEA(5wt%) 40 NA 25.6 100.3 32.700 NA 4.6 10.6 100.00 NA 25 810.0 12.00 NA [422] PP 400 0.000 NA 2.0 4.6 10.50 NA 25 425.60 11.0 1488 MEA(5wt%) 40 NA 25.83 23.60 10.000 NA 24.3 100.5 2.3 10.5 8.3 100.0 25 425.5 25 1519.5 25 1013.9 100.200 NA 9.27 0.50 24 101.60 15.0 471 K2CO3 (0.00 NA 25 2026.110 PTFE 70 1.50 a Loading is shown in some results and is evaluated as mol of CO2 absorbed per mol of active absorbent (water excluded).50M) 24 101.700 NA 3.5 100.60 13.300 NA 9.00 23.200 NA 2.0 0.950 NA 1.00 NA 25 1519.25M) 24 101.

9 >0.5 38 <0. Sx.3 19 42 <10 <100 20-60 3 1 <0.05 20 COS.CS2.05 . Clx 20-40 1 10a 1 40 7 50 3 <1 <1 <5 10b 1 .VOC. 129 .VOC 1000 1 5 1 72 6 12 8 >70 1000 20-30 6 1 42 15 37 7 20-50 20-30 6 2 39 12 48 <1 20-50 20-30 6 3 >99 <100 1 6 4 4 91 <1* <1* 6 COS.05 <2 10 <100 1 9 3 <10 <1 45 40 <5 VOC.<0.05 8 NOX. Estimations based on dry basis.CS2 <100 <1 9 1 75 <3 23 <2 <1 <0. PAH: Polycyclic aromatic hydrocarbons. PAH 1000 1 4 1 51 <1 5 <1 20 22 ~ 7 NOX.CS2 1000 20-80 2 2 <0.<0.>99. Processa Stream N2 O2 H2 CH4 CO2 CO H2S SO2 C2+ H2O Other Emissions* Temp (oC) Press (atm) 76 5 16 <0.VOC 1000 1 8 1 99 ~ 1000 1 8 2 <0.3 19 42 <10 <100 20-60 2 1 <0. VOC: volatile organic compounds.0 <2 COS. Clx. NO.5 38 <0.1 30-40 11 1 a Figure number in the text.VOC 1000 1 4 4 70 9 22 <1 13 NOX. NOX: NO2.3 19 42 .Hg. HCl 1000 1 1 1 76 5 16 <100 1 1 2 <0.5 PFCs.: S.5 58 <0.5 36 60 <1.5 38 <0.HCN <100 >30 7 1 99 <0. Typical molar fraction concentrations in each of the streams listed in Figures 4 to 14. PFC: perfluorocarbons.5 <2 10 COS.CS2 <100 1 9 2 75 <3 23 <2 <0.3 40 <1 <10 <100 20-60 3 2 4 50 30 2 8 <1 2 55 VOC.Table 14.VOC 1000 1 4 2 10 2 15 70 VOC 1000 1 4 3 55 4 12 28 ~ <1 NOX. Sx.and Cl-bearing compounds.

000 scf gas/t cement or lime 1. -0.000 scf gas/t pig iron prod.8 kg CO2/gal ethanol -20 MGa-140 MGa ethanol/plant -50 scf/gal ethanol a Figure number in the text.5 t Coke/t of pig iron prod.000-80.00 -5. -0. Coal Bed Wells 2.000-85. Blast Furnace 3. -1. Pulverized Coal Power Plant -7.200 scf gas/t steel prod. MW: Megawatt.60 -0. -3.8 MMt. scfa: scf per annum.000-110. MGa: megagallons per annum. SBC: sulfur bearing compounds. Typical capacities and gas flows for processes in Figures 4 to 14.5 MMscf gas /t coal 0. Electric Arc Furnace -70.84 t Coal/MW power 1 -10-1000 MW plants Gas Production 0. -1. Hall Heroult Process 1-3 potlines of 50-200 pots each 1.0-1.85 MMtpa steel prod.0 t landfill/person/year -14-15 Ga ethanol/gal of batch fermenter -2.000-8. Hydrogen/Ammonia Plants 1. usually > 45 ovens -7. Ga: gallons per annum. Natural Gas Wells 1. Basic Oxygen Furnace 4.500-11.8 t coke/t coal -Coking time: 18-22 h -Battery capacities: 0. Acronyms: Mtpa: metric tons per annum. Fermenter Sizes 1.5 MMscfd 5 6 7 8 9 1.83 t CO2/t Al -33500 scf gas/t Al -5-50 mol% SBC in gas steam <1 mol% SBC in gas steam -0.065 MMscf CO2/t coal -9. IGCC 1. Capacities Processa 1.0 MMscfd 10 1.05-2.Table 15. MMscf: Million scf.Claus Process 2. scf: standard cubic feet. -3.500 scf gas/t coal 2-3 4 1.000 Mtpa per potline 3-4000 t Sulphur/day 0.90 MMtpa -2. Landfills 1.060-0.18-0.4-0.7-1. Scot Process -66.Coke Oven Battery: 10-105 ovens.50 MMtpa steel prod. Mtpd: metric tons per day. Kiln 1.0t -100MMt (average 3.5 t CO2/t NH3 -.52 t Coal/MW power -300-4000 MW plants -10-45 t coal/charge/oven -0.1-2.5-2. 50% 1-10 MMt) -220 scfa gas/t landfill -0. 11 130 .0 MMtpa per kiln 1-270 MMscfd H2 (7.000 Mtpd of pig iron prod.2 t CO2/t cement or lime -75. scfd: scf per day.800 scf gas/t steel prod.3-400 t Sulphur/day -1. MMtpa: million Mtpa. -0.5-2000 Mtpd NH3) 2.

130 4.S.654 1. Corp.S.032 984 982 911 895 637 636 621 615 591 588 588 558 496 492 466 455 451 439 436 410 405 364 328 1977 1982 2004a 1984 2000b 1993 1997 1999b 1955 2003a 1997 1996 1984 1978 1995 1973 1997 1999b 1999b 1971 1994 1996 1979 1995 2000b 1994 1982 2000 1984 Subbit.S. Italy Malaysia Germany Italy South Africa Netherlands Taiwan Germany U. coal Vac. SARLUX srl Shell MDS Linde AG ISAB Energy Sasol-1 Shell Nederland SUV/EGT Chinese Pet Corp Hydro Agri Brunsbutt Global Energy VEBA Chemie AG Elcogas SA Motiva Enterprises API Raffineria Chemopetrol NUON Tampa Electric Ultrafertil Shanghai Pacific Chem. Res Coal & pet coke Fluid petcoke Visbreaker res Vac. * MWth is a measure of syngas thermal energy. p. Owner Sasol-II Sasol-III Repsol/Iberdrola Dakota Gasification Co. Brazil China U.S.067 1. Res Products FT liquids FT liquids Electricity Syngas Electricity & H2 Mid-distallates H2 & methanol Electricity & H2 FT Electricity & H2 Electricity & H2 Elec. Gujarat National Fertilizer Esso Singapore Quimigal Adubos a Plant Location South Africa South Africa Spain U. Germany Spain U. 2000. Corp. b Plant was under construction at time of survey. Largest IGCC and NGCC plants in the world as of January 2000. Res Bit coal Coal Asphalt res Anthracite coal Petcoke Bit coal Ref residue Residual oil Vac.Table 16. Italy Netherlands U. Res Lignite & ref res Visbreaker res Natural gas Visbreaker res Asphalt Subbit. 7. coal Fuel oil Visbreaker res Coal Bitumen Hvy vac res Bit.S.130 1. coal/pet coke Vac. China India Singapore Portugal Technology Output Year Feedstock (MWth)* Online Lurgi Dry Ash Lurgi Dry Ash GE Energy Lurgi Dry Ash GE Energy Shell Shell GE Energy Lurgi Dry Ash GE Energy Shell GE Energy Shell E-gas Shell PRENFLO GE Energy GE Energy Shell GE Energy Shell GE Energy GE Energy IGT U-Gas GE Energy GE Energy Shell 4. Exxon USA Shanghai Pacific Chem.” Jan. Source: NETL/Gasification Technology Council. 131 .545 1. coal Subbit. & steam H2 & CO Ammonia Electricity Ammonia & methanol Electricity Electricity Electricity Methanol & Ammonia Electricity Electricity Ammonia Methanol & Town gas Electricity & Syngas Fuel gas & Town gas Methanol & Ammonia Electricity & H2 Ammonia Total France/edf/GE Energy France Czech Republic Lurgi Dry Ash Czech Republic Shell was in advanced engineering at time of survey. “Gasification: Worldwide Use and Acceptance.

Krish R. Pendergast. Inc. Frank Patrick H. Sharon Robinson – Vice Chair Oak Ridge National Laboratory Linda Curran BP Timothy C. Inc. Inc Brendan Murray Shell Greg Chambers GE 132 . Krishnamurthy Stevan Jovanovic BOC Charles G.Vision 2020 for the Chemical Industry Separations Committee Members Francis Via – Chair Fairfield Resources International. Santi Kulprathipanja UOP Dilip Kalthod Air Products and Chemicals. Dow Scott Barnicki Eastman Chemical Hans Wijmans Membranes Research & Technology. Au-Yeung John G. Jr. Scouten The Fusfeld Group Dante Bonaquist Neil Stephenson Praxair Inc.

Glossary Å BFLM BOF CARP DEA DGA DIPA EAF EOR FCM FTM HGCU HTlc IEM IGCC ILM MDEA MEA MMt NGCC PC PDMS PEI PSA Psig PTFE PTMSP SCOT SERP SMR SSF TEA TSA VOC WGS Angstrom unit Bulk flow liquid membrane Basic oxygen furnace Carbothermic advanced reactor process Diethanolamine Diglycolamine Diisopropanolamine Electric arc furnace Enhanced oil recovery Fixed carrier membrane Facilitated transport membrane Hot gas cleanup unit Hydrotalcite Ionic exchange membrane Integrated gasification combined cycle Immobilized liquid membrane Methyldiethanolamine Monoethanolamine Million metric tons Natural gas combined cycle Pulverized coal Poly(dimethylsiloxane) Polyethyleneimine Pressure swing adsorption Pounds per Square Inch Gauge Polytetrafluoroethylene Poly(1-trimethylsilyl-1-propyne) Shell-Claus offgas treating Sorption enhanced reaction processes Steam methane reforming Selective surface flow Triethanolamine Temperature swing adsorption Volatile organic compound Water gas shift reaction 133 .

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