CARBON CAPTURE

Carbon dioxide capture and storage in the nitrogen and syngas industries
Rick Strait and Manoj Nagvekar of KBR Technology look at the options for large-scale syngas producers for carbon capture and storage.

oncern over carbon dioxide emissions and its effect on the environment is peaking worldwide. Ammonia and synthesis gas-based chemical plants are significant generators of carbon dioxide, although not at the same levels as carbon dioxide emitted from power plants. Although there is a great deal of interest in carbon capture and storage (CCS), few in the industry are implementing large-scale CCS projects. KBR Technology discusses some of the obstacles faced when considering a CCS project and what is on the horizon for new and existing synthesis gas-based chemical plants, including ammonia plants.

Background
According to the 2008 International Energy Outlook1, total global CO2 emissions were about 28 Gigatonnesin 2005. The CO2 emissions are increasing at a rate of about 1.7% annually and are expected to more than double, reaching about 60 Gigatonnes/yr by 2050. CO2 emissions from large fixed sources, which theoretically could be captured, account for 15 Gigatonnes/yr2. An overwhelming majority (80%) of these emissions are from power plants. Total emissions from the industrial sector, including its share of power consumption, amount to about 11 Gigatonnes/yr. Within the chemical industry, the three largest sources of CO2 emissions are from the production of ethylene and other petrochemicals, ammo-

nia for nitrogen-based fertilizers, and chlorine. It is estimated3 that the fertilizer industry uses about 1.2% of world energy consumption and is responsible for about the same share of global CO2 emissions. It may therefore appear that, in the global picture, the fertilizer industry is a minor contributor to CO2 emissions. As a result of improvements in energy efficiency, the use of natural gas as the primary feedstock, and industry restructuring which drives less efficient producers out of the market, there is not a significant scope for additional reductions in energy consumption and associated CO2 emissions. (China is a major exception since two-thirds of its ammonia production is based on coal). Notwithstanding, all of the successes in reducing energy usage, the industry will be required to comply and take additional steps when global emissions reduction regulations are introduced.

Carbon capture and storage mandates

The Kyoto Protocol set binding targets for 37 industrialised countries and the European Union for reducing greenhouse gas (GHG) emissions. The post-Kyoto framework, focusing on issues such as the scale of future reductions, improvements to emissions trading and carbon offset mechanisms, was discussed at the UN Climate

Conference in December 2009, but the Copenhagen accord is not legally binding. Since 2005, the EU has had an annual cap on CO2 emissions from specific industrial sectors so that the EU and individual member countries can attain their Kyoto mandated targets by the year 2012. The EU has also established a goal of a 20% reduction in CO2 emissions by 2020 as compared to 1990 levels. The European Fertilizer Manufacturers Association (EFMA) has estimated4 that prices in the European nitrogen fertilizer industry will increase by 21-34% in order to compensate for an increase of 30-48% in the production cost due to an estimated CO2 price of 30-50 per tonne from 2013 to 2020. EFMA, while supporting the EUs goal to reduce emissions 20% by 2020, has concluded that unless granted free emission allowances, the European fertilizer industr y in general will be unable to maintain its competitiveness with non-regulated producers.

Ammonia plant emissions

Figure 1 shows the primary sources of CO2 emissions in the typical ammonia plant. In a recent 2,000 metric tonne per day ammonia plant design producing 660,000 t/a of ammonia, the CO2 stripper vent emits 812,000 t/a and the primary reformer stack emits 421,000 t/a. The combined total of the CO2 emissions from the strip-

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CARBON CAPTURE

Fig 1: CO2 Emission Sources in a Typical Ammonia Plant

CO2 in flue gas air primary reformer secondary reformer shift & CO2 removal methanation & dryers magnetite synthesis CO2

compression

NH3 product

feed & steam

to fuel

purge gas recovery

loop purge

per vent and primary reformer stack equals 1.23 million t/a or a ratio of 1.87 tonnes of CO2 per tonne of ammonia produced. Ammonia plants using coal produce the most CO2 emissions while those using natural gas produce the least. Heavier feedstocks containing ethane, propane, butane, pentane etc. produce more CO2 than the example used above. Alternative feedstocks such as oil, petcoke or coal result in even greater amounts of CO2. Even among plants using the same feedstock type there are differences in CO2 emissions. The natural gas used in the example above contains 98.23% methane and 0.16% CO2. Some natural gas contains very significant amounts of CO2 to start with such as one plant in China which uses natural gas containing 20.7% CO2.

Options for CCS

As shown in Figure 2, there are different types of CO2 capture systems: post-combustion, pre-combustion, and oxyfuel combustion. The concentration of CO2 in the gas stream, the pressure of the gas stream, and the fuel type (solid or gas) are important factors in selecting the capture system.

Post-combustion capture
Post-combustion capture of CO2 from the flue gas of power plants can be economically feasible under specific conditions. Despite many well planned national and international programs, and the existence of some pilot and demonstration plants, there is no full-scale demonstration plant yet for post-combustion CO2 capture from power plants. The two biggest hurdles for post-combustion capture are the significant energy requirements for solvent regeneration and large equipment sizes that are

both due to the relatively low concentrations and partial pressures of CO2 in the flue gas, which is essentially at atmospheric pressure. In the case of a power plant with post-combustion capture, the energy required for solvent regeneration and CO2 compression could represent anywhere from 25 to 35% of its output. Amines, or strictly speaking alkanolamines, are the most frequently used solvents for post-combustion CO2 capture with monoethanolamine (MEA) as the typical benchmark. Proprietary solvents, mostly based on MEA, have been developed by several solvent technology vendors. The goal of these efforts is to improve the solvent reactivity, reduce thermal degradation and, most importantly, reduce the energy consumed for solvent regeneration. For ammonia we refer to the reformer stack as being a difficult location for CO2 capture because it is a post-combustion stream. As mentioned earlier, post-combustion streams are difficult to deal with because the stream is generally at atmospheric pressure and diluted with about 80% nitrogen from the combustion air. This results in a very low partial pressure of CO2, large volumetric flow of solvents, and large absorbers, strippers, circulating pumps, and intercoolers. The net effect is expensive CO2 removal systems consuming large quantities of energy for solvent circulation and stripping steam. Of particular relevance to the fertilizer industry are the post-combustion CO2 capture projects executed by Mitsubishi Heavy Industries (MHI). The CO2 contained in the flue gas emitted from the primary reformer during the ammonia production process is absorbed into the KS-1 proprietary solvent, which MHI jointly developed with Kansai Electric Power Company, Inc (Kansai EP). The CO2 is then synthesized with ammonia

for use as feedstock for urea production. The projects have ranged in size from about 200 to 450 tonnes CO2/day which would still be regarded as about one-eighth the size of a large-scale (1 million tonnes/year) CO2 capture project.

Pre-combustion capture
The technology required for pre-combustion capture is widely applied in fertilizer manufacturing and in hydrogen production. For the power industry, the typical application for pre-combustion capture would be an Integrated Gasification Combined Cycle (IGCC) plant where some of the CO2 is removed from the fuel stream before combustion in a gas turbine. The process involves gasification or steam reforming followed by shifting the syngas to produce H2 and CO2. The feedstock could be from a variety of fuels including coal, natural gas, biomass, etc. Depending upon the conditions, the CO2 concentration in the syngas could range from 15-60% and a physical solvent could be used for separation. The syngas processing steps are those that one would employ for H2 production or conversion to Fischer-Tropsch (FT) fuels. Following CO2 capture, the hydrogen-rich syngas is combusted in the gas turbine and the exhaust is now mostly water vapour. Although the initial fuel conversion steps of pre-combustion are more elaborate and costly, the higher concentrations of CO2 in the gas stream and the higher pressure make the separation and the subsequent compression of CO2 easier than post-combustion. The typical solvents used for pre-combustion capture are either physical (i.e. Selexol and Rectisol) or chemical (i.e. methyldiethanolamine). Unlike the solvents for post-combustion capture, these

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technologies are mature and proven on a large commercial scale. IGCC and CO2 Capture are proven independently but have not operated in an integrated manner. There is no gasificationbased IGCC power plant that recovers CO2. Currently in the US, there are three nonpower gasification facilities that recover and compress CO2. There are, of course, many gasification plants for ammonia which recover CO2 for urea production.

Fig 2: Schematic of CO2 Capture Systems [2]

N2 O2 coal gas biomass air air/O2 stream reformer H2 +CO2 sep air power & heat air separation CO2 N2 power & heat CO2 separation CO2 CO2 N2O2 power & heat CO2 compression & dehydration

coal biomass

gasification gas, oil coal gas biomass

Oxyfuel combustion capture

Oxyfuel combustion is still in the demonstration phase and uses high purity oxygen. This results in relatively higher CO2 concentrations in the gas stream and, hence, in easier separation of CO2 but at the cost of increased energy requirements in the separation of oxygen from air.

air air/O2 coal gas biomass

process+CO2 sep

CO2

Industrial processes
In Figure 2, the ammonia process falls under Industrial Processes. The largest difference between industrial processes and others is that others are generating a fuel, while industrial processes are generating a synthesis gas, which for the most part winds up in the product instead of a vent or stack. The processes for capturing CO2 from industrial applications are well known; in fact, most have been developed in ammonia plants.

raw material

gas, ammonia, steel

Applications to ammonia plants

Urea production from an ammonia plant is a great way to capture CO2 but it is argued that this is merely relocating the emission from the plant vent to the farmers field. Also, if ammonia is produced from coal or a heavy feedstock, the CO2 is typically more than what is needed for urea. Co-location of ammonia facilities with methanol facilities is another way to use CO2 in a merchant product. As with urea, this scheme has the disadvantage that CO2 can end up in the atmosphere when the methanol is used for transportation fuels. But if the methanol is used for polymers and plastics, the CO2 may become captured in the finish product such as with polyolefins. If, however, the CO2 from the ammonia plant has to be captured and stored, the CO2 stripper is a convenient location to collect the CO2. This is commonly done when urea is manufactured. The CO2 is compressed to about 2000 psig and sent to the

urea plant for processing. In a scheme for CO2 capture and sequestration, the same system is used to dry and compress it before sending it to a pipeline. From there, it is stored underground to recover oil and gas from depleted reserves or into aquifers or geological formations that will hold the CO2 for many years into the future. The greater challenge is capturing the CO2 from the primary reformer stack. This is classic post-combustion capture with the associated issues outlined in the previous section. In the power industry, where extensive studies have been performed, it has been determined that the capital cost of capturing a metric tonne of CO2 in a postcombustion retrofit is about $40/tonne per CO2 avoided5. These same studies also conclude there is an operating cost for steam, cooling water, and electric power amounting to another $30/tonne of CO2 avoided for a total cost of about $70/tonne of CO2 avoided. Experience with post-combustion is limited and no one is capturing all the CO2 emitted from stack gases. A very significant parameter is the stripping energy per tonne of CO2 captured from the stack (postcombustion) which is very high in comparison to the energy to capture CO2 from the synthesis gas (pre-combustion) in an ammonia plant. A technology breakthrough needs to occur to reduce the energy of post-combustion capture of CO2. Research is underway to find better solvents, includ-

ing enzymes and other capture methods such as algae, but none of these have been tested at any sizable scale.

Summary
The ammonia industry is in a better position than most, as so much of the ammonia is produced from natural gas and is quite efficient. Typically, CO2 is captured from the syngas and compressed for urea production. Clearly, the industry is also watching developments in biomass, alternate fuels, etc. as part of the shift to nontraditional feedstocks to produce the syngas. If there is legislation requiring further cuts in CO2 emissions, the industry will, however, have to look at the primary reformer stack and this would have a significant impact as the CO2 is difficult to capture and will substantially increase the I cost of production.

References
1. International Energy Outlook 2008, Energy Information Administration, U.S. Department of Energy, Washington, D.C. (2008). 2. Carbon Dioxide Capture and Storage, Intergovernmental Panel on Climate Change (IPCC) Special Report (2004). 3. Industry in Climate Change 2007: Mitigation, Fourth Assessment Report of the Intergovernmental Panel on Climate Change (2007). 4. European Fertilizer Manufacturers Association (EFMA) Press Release (2008). 5. CO2 Retrofit from Existing Plants, US DOENETL Report 401/110907 (2007).

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CO2 Capture and Storage in the Ammonia Industry What the Future Holds
Concern over carbon dioxide emissions and its effect on the environment is peaking worldwide. Ammonia and synthesis gas-based chemical plants are significant generators of carbon dioxide although not at the same levels as carbon dioxide emitted from power plants. There is a requirement for some new hydrocarbon and energy plants to capture CO2 emissions and inject it for enhanced oil recovery (EOR) or store it in underground formations a mile below the surface. Even though there is a great deal of interest in carbon capture and storage (CCS), few in the industry are implementing largescale CCS projects. One such project is the In Salah project in Algeria, which captures and stores one million metric tons of carbon dioxide each year. This paper discusses some of the obstacles faced when considering a CCS project and what is on the horizon for new and existing synthesis gas-based chemical plants including ammonia plants. Rick Strait KBR Manoj Nagvekar KBR

Introduction

population, and are expected to more than double reaching about 60 Gigatons/yr by 2050. At the start of the industrial revolution, CO2 levels in the atmosphere were at 280 ppm and have increased to 380 ppm today. If emissions continue at the rate mentioned above, the CO2 level in the atmosphere would reach 510 ppm by 2050 and 720 ppm by the end of this century. At these levels, global warming is expected to be irreversible and would lead to a temperature increase in the range of 4-7 C with a significant impact on the environment and human activity [2]. It is widely agreed that in order to limit the expected temperature increase to less than 3 C, the CO2 levels in the atmosphere would need to be stabilized at about 550 ppm. This would require the expected emissions to be reduced by at least 50%

arbon emissions are being regulated in many European countries and before long they will be regulated worldwide. Ammonia producers in the US and abroad have managed to bypass carbon emissions regulation and taxation but that too is about to change.

Background
According to the 2008 International Energy Outlook [1], the total global CO2 emissions were about 28 Gigatons in 2005 (the latest year for which data are available). The CO2 emissions are increasing at a rate of about 1.7% annually, largely as a result of the rising use of fossil fuels for an increasing

by 2050 and followed by even further cuts to below todays levels by the end of the century. While energy conservation, improving efficiency, alternate fuels, and renewable energy are all options for lowering CO2 emissions, fossil fuels will continue to be the dominant energy source for our global economy. In this fossil fuel-dominated economy, Carbon Capture and Storage (CCS) technologies have the potential to allow the use of fossil fuels with reduced CO2 emissions. CO2 emissions from large fixed sources, which theoretically could be captured, account for 15 Gigatons/yr [3]. These represent just over 53% of the total worldwide emissions. An overwhelming majority (80%) of these emissions are from power plants. Total emissions from the industrial sector, including its share of power consumption, amounts to about 11 Gigatons/yr. Approximately 85% of the industrial sectors energy use is in the energyintensive industries: iron and steel, non-ferrous metals, chemicals and fertilizers, petroleum refining, minerals and pulp and paper. Within the chemical industry, the largest sources of CO2 emissions are from the production of ethylene and other petrochemicals, ammonia for nitrogenbased fertilizers and chlorine. It is estimated [4] that the fertilizer industry uses about 1.2% of world energy consumption and is responsible for about the same share of global CO2 emissions. It may therefore appear that, in the global picture, the fertilizer industry is a minor contributor to CO2 emissions. Furthermore, as a result of improvements in energy efficiency, the use of natural gas as the primary feedstock, and industry restructuring, which drives less efficient producers out of the market, there is not a significant scope for additional reduction of energy consumption and associated CO2 emissions. (China is a major exception since two-thirds of its ammonia production is based on coal). Notwithstanding, all of the successes in reducing energy usage, the industry will be required to comply and take additional steps when global emissions reduction regulations are introduced.

Carbon Capture and Storage Mandates

The Kyoto Protocol set binding targets for 37 industrialized countries and the European community for reducing greenhouse gas (GHG) emissions. These correspond to an average of five per cent reductions against 1990 levels between 2008 2012. Under the Treaty, countries must meet their targets primarily through national measures. However, the Kyoto Protocol offers additional means of meeting their targets by way of the following three marketbased mechanisms: Emissions trading or a carbon market", Clean Development Mechanism (CDM) projects, and Joint Implementation (JI) projects. These mechanisms stimulate green investment and help the signatories meet their emission targets in a cost-effective way. The Kyoto Protocol is generally seen as an important first step towards a truly global emission reduction regime that will stabilize GHG emissions, and provide essential architecture for any future international agreement on climate change. It is expected that the first outline of a post-Kyoto framework will emerge in Copenhagen in December 2009, where discussions will focus on issues such as the scale of future reductions, improvements to emissions trading and the Kyoto Protocols carbon offset mechanisms. Clearly, the European Union is at the forefront in terms of a climate policy and other nations are taking note of their efforts. Since 2005, the EU has had an annual cap on CO2 emissions from specific industrial sectors. The first three-year phase was essentially a learning period and an attempt to establish an Emissions Trading System (EU-ETS). In the second phase, the emissions caps have been lowered so that the EU and individual member countries can attain their Kyoto mandated targets by the year 2012. Although there is not yet a successor to the Kyoto agreement, the EU has decided to establish a third phase (2013 - 2020) based on a

goal of 20% reduction in CO2 emissions by 2020 as compared to 1990 levels. The ETS is a cap-and-trade scheme, which has led to a market for CO2 allowances and a price for these allowances based on supply and demand. In general, the price of an EU allowance, which is the right to emit one ton of CO2 is in the range of 1525. Companies that manage to keep their emissions below their level of allowances can sell their excess allowances. On the other hand, companies facing difficulties in meeting their allowances have a choice between taking measures to reduce their emissions, which could be investing in using less carbon intensive energy sources, using CCS or buying excess market allowances. The European Fertilizer Manufacturers Association (EFMA) has estimated [5] that prices in the European nitrogen fertilizer industry will increase by 21 - 34% in order to compensate for the increase of 30 - 48% in the production cost due to an estimated CO2 price of 30-50 per ton in 2013 - 2020. The EFMA, while supporting the EUs goal to reduce emissions 20% by 2020, has concluded that unless granted free emission allowances, the European fertilizer industry will be unable to maintain its competitiveness with non-regulated producers. In North America, with the establishment of three regional agreements (the Western Climate Initiative, the Northeast's Regional Greenhouse Gas Initiative, and the Midwestern Climate Accord), as many as 20 states and three Canadian provinces have adopted cap-and-trade strategies for reducing their greenhouse gas emissions. Legislation, which includes a cap-and-trade plan to control CO2 emissions, has been introduced in the US Congress. The new US administration has also advocated cap-and-trade climate solutions.

Ammonia Plant Emissions

Figure 1. CO2 Emission Sources in an Ammonia Plant Carbon dioxide (CO2) is emitted from two sources in a typical ammonia plant: the CO2 stripper vent and the primary reformer stack. In a recent 2000 metric ton per day ammonia plant design producing 660 ktpa of ammonia, the CO2 stripper vent emits 812 ktpa and the primary reformer stack emits 421 ktpa. The combined total of the CO2 emissions from the stripper vent and primary reformer stack equals 1,233 ktpa or a ratio of 1.87 ton of CO2 per ton of ammonia produced. Not all ammonia plants are equal when it comes to CO2 emissions. Coal to ammonia plants produce the most with natural gas to ammonia plants producing the least. Even among plants using the same feed stock type there are differences in CO2 emissions. The amount of carbon and carbon dioxide varies widely in natural gas around the world. The natural gas used in the example contains 98.23% methane and 0.16% CO2. Heavier feed stocks containing ethane, propane, butane, pentane etc. produce more CO2 than the example plant. Also some natural gas contains very significant amounts of CO2 to start with such as one plant in China, which uses natural gas containing 20.7% CO2. Alternative feed stocks such as oil, petcoke or coal result in even greater amounts of CO2. It is interesting to note however that the oil and coal facilities that use partial oxidation funnel CO2 into the pressurized process gas stream allowing for much simpler CO2 capture. As we will discuss later, the price of recovery of CO2 from a reformer stack is much more costly than from the pressurized process stream.

Moving CO2 from the reformer stack to the process stream is an advantage of KBRs KRES technology. Unlike conventional processes using primary and secondary reformers, KRES technology produces reformed gas with 13% higher CO2 content while reducing the fuel burned in the primary reformer and reducing the reformer stack CO2 emissions.

Options for CCS

As shown below in Figure 2, there are different types of CO2 capture systems: post-combustion, pre-combustion, and oxyfuel combustion. The concentration of CO2 in the gas stream, the pressure of the gas stream, and the fuel type (solid or gas) are important factors in selecting the capture system.

Figure 2. Schematic of CO2 Capture Systems [3]

Post-Combustion Capture Post-combustion capture of CO2 in power plants can be economically feasible under specific conditions. It is used to capture CO2 from part of the flue gas stream from a power plant. The process involves separation of CO2 in the natural gas processing industry, which uses quite similar technology and operates in a mature market. Despite many well planned national and international programs,

and the existence of some pilot and demonstration plants, there is no full-scale demonstration plant yet for post-combustion CO2 capture from power plants. The two biggest hurdles for post-combustion capture are the significant energy requirements for solvent regeneration and large equipment sizes that are both due to the relatively low concentrations and partial pressures of CO2 in the flue gas, which

is essentially at atmospheric pressure. In the case of a power plant with post-combustion capture, the energy required for solvent regeneration and CO2 compression could represent anywhere from 25 to 35% of its output. Amines, or strictly speaking alkanolamines, are the most frequently used solvents for post-combustion CO2 capture with monoethanolamine (MEA) as the typical benchmark. Proprietary solvents, mostly based on MEA, have been developed by several solvent technology vendors. The goal of these efforts is to improve the solvent reactivity, reduce thermal degradation and, most importantly, reduce the energy consumed for solvent regeneration. Of particular relevance to the fertilizer industry are the post-combustion CO2 capture projects executed by Mitsubishi Heavy Industries (MHI). The CO2 contained in the flue gas emitted from the primary reformer during the ammonia production process is absorbed into the KS-1 proprietary solvent, which MHI jointly developed with Kansai Electric Power Company, Inc (Kansai EP). The CO2 is then synthesized with ammonia for use as feedstock for urea production. The projects have ranged in size from about 200 to 450 tons CO2/day which would still be regarded as about one-eighth the size of a large-scale (1 million tons/year) CO2 capture project. For ammonia we refer to the reformer stack as being a difficult location for CO2 capture because it is a post-combustion stream. As mentioned earlier, post-combustion streams are difficult to deal with because the stream is generally at atmospheric pressure and diluted with about 80% nitrogen from the combustion air. This leaves a very low partial pressure of CO2 and large volumetric flow of solvents and large absorbers, strippers and circulating pumps and intercoolers. The net result is expensive CO2 removal systems consuming large quantities of energy for solvent circulation and stripping steam. The power industry in the US and abroad is looking for a low capital and operating cost solvent or

system to remove the CO2 from the coal fired boilers that generate so much of our electrical power. For example 50% of Americas power comes from Pulverized Coal (PC) boilers generating steam that is then used in a steam generator set to generate electricity. All greenhouse gas (GHG) reduction programs are working hard on finding a way to reduce emissions from these existing sources as shutting down 50% of our electrical power generation is not an option. Pre-Combustion Capture The technology required for pre-combustion capture is widely applied in fertilizer manufacturing and in hydrogen production. For the power industry, the typical application for pre-combustion capture would be an Integrated Gasification Combined Cycle (IGCC) plant where some of the CO2 is removed from the fuel stream before it enters the gas turbine (GT). The process involves gasification or steam reforming followed by shifting the syngas to produce H2 and CO2. The feedstock could be from a variety of fuels including coal, natural gas, biomass, etc. Depending upon the conditions, the CO2 concentration in the syngas could range from 15-60% and a physical solvent could be used for separation. The syngas processing steps are those that one would employ for H2 production or conversion to FischerTropsch (FT) fuels. With CO2 capture, the gasifier would normally operate in an oxygen-blown mode. Following CO2 capture, the hydrogen-rich syngas is combusted in the gas turbine and the exhaust is now mostly water vapor. The CO2 stream can be compressed and used for sequestration or enhanced oil recovery. Although the initial fuel conversion steps of pre-combustion are more elaborate and costly, the higher concentrations of CO2 in the gas stream and the higher pressure make the separation and the subsequent compression of CO2 easier than post-combustion. The typical solvents used for pre-combustion capture are both physical (Selexol, Rectisol, etc.) or chemical (Methyldiethanolamine or MDEA, etc.).

Unlike the solvents for post-combustion capture, these technologies are mature and proven on a large commercial scale. IGCC and CO2 Capture are proven independently but have not operated in an integrated manner. There is no gasification based IGCC power plant that recovers CO2. Currently in the US, there are three non-power gasification facilities that recover and compress CO2. There are, of course, several gasification plants for ammonia which recover CO2 for urea production. Oxyfuel Combustion Capture Oxyfuel combustion is still in the demonstration phase and uses high purity oxygen. This results in relatively higher CO2 concentrations in the gas stream and, hence, in easier separation of CO2 but at the cost of increased energy requirements in the separation of oxygen from air. Industrial Processes In Figure 2 the ammonia process falls under Industrial Processes. The largest difference between industrial processes and others is that others are generating a fuel, while industrial processes are generating a synthesis gas, which for the most part winds up in the product instead of a vent or stack. The processes for capturing CO2 from industrial applications are well known; in fact, most have been developed in ammonia plants. Regardless of whether we use chemical or physical solvents and amines or hot potassium carbonate with and without additives, we have tried them all.

Collocation of ammonia facilities with methanol facilities is another way to use CO2 in a merchant product. With collocation, the excess CO2 from the ammonia production can be used in methanol production and in this way can turn a waste stream CO2 into methanol. This scheme as with that of urea production has the disadvantage that CO2 can wind up in the atmosphere when the methanol is used for transportation fuels. But if the methanol is used for polymers and plastics, the CO2 may become captured in the finish product such as with polyolefins. If however the CO2 from an ammonia plant needs to be captured and stored, the CO2 stripper is a convenient location to collect the CO2. This is commonly done when urea is manufactured. The CO2 is piped to a CO2 compressor that compresses it to about 2000 psig and sends the CO2 to the urea plant for processing. In a scheme for CO2 capture and sequestration, the same system is used with CO2 to dry and compress it before sending it to a pipeline. From there, it is stored underground to recover oil and gas from depleted reserves or into aquifers or geological formations that will hold the CO2 for many years into the future. The greatest challenge is capturing the CO2 from the primary reformer stack. This is classic postcombustion CO2 capture. As this stream is a high volume stream, and the CO2 is diluted with about 80% nitrogen, the CO2 is expensive to collect. The issues with post-combustion capture are: High capital cost of the facilities High operating cost of the facilities Large plot space required CAPEX: In the power industry, where extensive studies have been performed, it has been determined that the capital cost of capturing a metric ton of CO2 in a post-combustion retrofit is about $39/ton per CO2 avoided. OPEX: These same studies also conclude there is an operating cost for steam, cooling water and electric power amounting to another $29/ton of

Applications to Ammonia Plants

Urea production from an ammonia plant is a great way to capture CO2 but it is argued that this is merely relocating the emission to the farmers field from the plant vent. Also if you are producing ammonia from coal or a heavy feed stock, you are generating more CO2 that you need for urea.

CO2 avoided for a total cost of about $68/ton of CO2 avoided. Experience with post-combustion is limited and no one is capturing all the CO2 emitted from stack gases. The most important parameter is the stripping energy per ton of CO2 captured from the stack.
Steam Consumption, GJ/ton CO2 2.96 2.84 2.70 2.50

HTC Fluor MHI Cansolv

The ammonia industry is in a better position as so much of the ammonia is produced from natural gas and is relatively efficient. Also, the synthesis gas stream already captures CO2 and compresses it for enhanced oil recovery or to upgrade products or even for storage. The primary reformer stack poses another problem as this CO2 is very difficult to capture and will add greatly to the cost of producing ammonia if it must be captured. One option for improving the recoverability of carbon dioxide is KRES technology which produces reformed gas with 13% higher CO2 content while reducing the fuel burned in the primary reformer and reducing the reformer stack CO2 emissions It is interesting to note that partial oxidation of coal or pet coke or other heavy feed stock may have an advantage over natural gas based plants. These heavy hydrocarbon feed stocks will generate more CO2, but it is in a form that is much more readily available for capture, and if it can be stored, it may result in a solution to the problem of emitting CO2 into the atmosphere.

Table 1. Steam Consumption for Post-Combustion CO2 Capture with Proprietary Solvents As can be seen from Table 1, the energy to capture CO2 is very high compared to the energy to capture CO2 from the synthesis gas in an ammonia plant. A technology breakthrough needs to occur to reduce this energy in half and make it more like that of ammonia CO2 recovery. Post-combustion commercial solvents are all amines as they work better in the conditions found in boiler and reformer stacks. Research is underway to find better solvents, including enzymes and other capture methods such as algae, but none of these have been tested at any sizable scale.

References
1. International Energy Outlook 2008, Energy Information Administration, U.S. Department of Energy, Washington, D.C. (2008). 2. Climate Change 2007: Synthesis Report, Intergovernmental Panel on Climate Change (2007). 3. Carbon Dioxide Capture and Storage, Intergovernmental Panel on Climate Change (IPCC) Special Report (2004). 4. Industry in Climate Change 2007: Mitigation, Fourth Assessment Report of the Intergovernmental Panel on Climate Change (2007). 5. European Fertilizer Manufacturers Association (EFMA) Press Release (2008).

Summary
The European Union (EU) has given us a glimpse of what a CO2 capture world will look like. With cap-and-trade the cost of being an emitter of CO2 goes up, but it remains an economic decision. Today, the utilities are looking at a cost of postcombustion capture of CO2 of about $60-80/ton of CO2, and unless the tax on CO2 emissions exceeds this value it will be cheaper to pay it than to modify the existing coal fired power plants.