Natural Gas Chemical Looping

CHEM. LOOPING INTERNATIONAL

Final Report

CHE-4080

Dr. Holles

Spring 2014

Nasser Aiyd AlhajriDaniel DebroyEsjae E. Eiden

Valeriya LitvinovaMoises Vazquez

Management Summary

The combustion of fossil fuels for energy is a human activity that leads to a large amount of

carbon dioxide emission. The carbon dioxide levels in the atmosphere increased due to the use of

fossil fuels. According to the Environmental Protection Agency, before the industrial revolution

the atmospheric concentration of carbon dioxide was 35% less than today’s levels [Yeh, 2009].

Energy is significant factor for a modern society. Electricity is a primary source of energy

in the United States [Carbon Dioxide Emissions, 2013]. However, the combustion of fuel for the

electricity generation is the main cause and attribute of CO2 emissions. In the United States,

statistical data shows that electricity generation radiates massive amounts of carbon dioxide

annually.

Many advanced technological processes and practices have been developed to capture

CO2, Chemical Looping Combustion is a significant one. Chemical looping combustion is a

significant process in which one has to separate the combustion fuels into oxidation and

reduction reactions. Proceeding with the process the reactions are swept out into two independent

reactors (air and fuel reactors). The required oxygen is provided to the fuel by a suitable metal

oxide in this process known as oxygen carrier. The fuel reacts with the metal oxide in the fuel

reactor and reduces it. The reduced metal oxide circulates to the air reactor where it is oxidized

with air. The metal oxide keeps circulation between the fuel and air reactors to make a chemical

reaction going. Therefore, this process is named as Chemical Looping Combustion. The product

of the fuel reactor consists of H2O and pure CO2 in which both products can be separated and

CO2 can be captured, moreover the air reactor produces N2 and O2.

A fixed capital investment of $1.8 billion and a total capital investment of $2.2 billion

will be required for the total project. The variable costs are $5.2 million. The NPV0 is $11.9

billion and after 10 years the NPV10 is $4.3 billion. The IRR is 36.0% and the payback period is

about 2.1 years. This process is using a new technology, so having an IRR of 36.0% is

reasonable but has a high risk [Peters, 2006]. As a conclusion, this project can be profitable even

if the cost of the chemical looping combustion is high.

Contents

1. Project Definition.............................................................................................................................1

1.1 Business Opportunities..............................................................................................................1

1.2 Key assumptions.......................................................................................................................1

1.3 Key issues..................................................................................................................................2

1.4 Project Goals.............................................................................................................................2

2. Process Information..........................................................................................................................3

2.1 Chemical Looping Combustion.................................................................................................4

2.2 Carbon Dioxide Separation.......................................................................................................7

2.3 Electricity Generation System...................................................................................................8

3. Reactions and Properties................................................................................................................11

3.1 Oxygen Carrier............................................................................................................................11

3.2 Reactions.................................................................................................................................12

3.3 Properties.................................................................................................................................13

4. Material Data..................................................................................................................................14

4.1 Text Flowsheet........................................................................................................................14

4.2 Overall Material Balance.........................................................................................................15

4.3 Key Recycles............................................................................................................................17

5. CO2 sequestration..............................................................................................................................17

5.1 Storage and transportation of CO2...............................................................................................17

5.2 Economics for CO2 storage and transportation............................................................................19

5.3 CO2 storage regulations...............................................................................................................20

6. Nitrogen Sales...................................................................................................................................20

7. Economics.........................................................................................................................................21

7.1 Overall Economics.......................................................................................................................21

8. Government Regulations...................................................................................................................24

8.1 Permits.........................................................................................................................................25

8.2 OSHA Law & Regulations..........................................................................................................25

9. Conclusion........................................................................................................................................26

Appendix...............................................................................................................................................27

A1. Flowsheets (detailed)..................................................................................................................27

A2. Detailed Material Balance...........................................................................................................30

A3. Physical Properties details..........................................................................................................33

A4. Economics/Production Cost Statement.......................................................................................35

A5. Equipment List w/sizes, Sizing Bases, Costing Bases................................................................38

A6. Piping and Instrumentation Diagram..........................................................................................43

Symposium Presentation...........................................................................................................................43

Database\Progress Reports\Symposium\CHE4070_Final Presentation_Chemical Looping.pptx......43

References.............................................................................................................................................44

1. Project Definition

A 500 MW power plant is designed and fueled by natural gas. Chemical Looping technology

will be used to produce CO2. This project consists of three parts: a Chemical Looping

Combustion, Carbon Dioxide capturing and electricity generation. Electricity and CO2 will be

sold as products and H2O will be re-engaged in the process. Electricity is generated from steam

turbines. To be a beneficial supplier to Wyoming, Colorado and Utah this plant will be located

between Green River and Rock Springs because it is near by several natural gas pipelines and the

Green River as a source of water while CO2 is captured and stored.

1.1 Business Opportunities

To have a sustainable economy that is environmentally friendly, it is necessary to find a

clean, cheap, and abundant energy supply. Chemical looping is an environmentally friendly

process, and if the efficiency is high enough, it can be a competitor for other electricity

production processes. The projected energy supply through year 2030 will be drawn from oil,

coal, natural gas; renewable forms of energy; and nuclear energy, in that order. Competition for

the chemical looping process includes traditional combustion processes. Among these, fossil

fuels account for more than 86% of the world’s energy supply. For primarily economic reasons,

fossil fuels will continue to play a dominant role in the world’s energy supply for the foreseeable

future. Natural gas has been a common energy source for heating, electricity generation, and

hydrogen production. The price of natural gas varies significantly with locations and source. It is

projected that the natural gas price will decrease from $4.44/MMBtu in 2014 to $4.11/MMBtu in

2015 [U.S. Energy Information Administration, 2014]. Despite the projected price decrease, the

share of natural gas in world energy consumption is expected to remain at 24% from year 2005

up to 2030 [ Fan,NJ,2010].

1.2 Key assumptions

The effective performance of the chemical looping particles or oxygen carrier particles is

important to have a successful operation of chemical looping process. Metal oxide, support, and

agent are effective particles of the chemical looping. These particles have to have desired

properties in order to be effective ones [Fan, 2010].

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To have a successful operation process, the list below contains the assumptions that were made:

1. The oxygen carrier has a good oxygen carrying capacity, long-term recyclability, and

good mechanical strength [Fan, 2010].

2. Both in the Air reactor (oxidation) and the fuel reactor (reduction) have a good gas

conversion with the oxygen carrier. That is, a fully conversion of the fuel into CO2 and

H2O and is achieved when reacting with the oxygen carrier. Also, the reduced oxygen

carrier that is circulating to the air reactor is assumed to be able to fully oxidize through

reaction with air [Fan, 2010].

3. The oxygen carrier remains environmental friendly and not harmfully [Fan, 2010].

4. Pure CO2 will be captured and to be sold, CO2 will be sent directly to pipeline [Fan,

2010].

1.3 Key issues

Compared to other normal power plants, this project is costly because it is using a new

technology and capturing CO2. Currently, a lot of reaches is studying how to improve the oxygen

carrier circulation between the two reactors. A catalyst is mostly needed to improve some

properties of the oxygen carrier. To be mentioned, the chemical looping process is not existed in

any commercial power plants. So, the scaling of this project was based on pilot power plant

references.

1.4 Project Goals

Selecting the appropriate oxygen carrier and reactors type was achieved. An Aspen+

simulation file was developed and the plant location was decided. A process optimization was

considered including a final economic analysis, and also reliability and safety analysis.

2

2. Process Information

The process designed has two main parts: chemical looping combustion (with carbon dioxide

separation), and electricity generation (or boiler). These two steps can be seen in Figure 1.

Figure 1. Flowsheet of the overall Chemical Looping Combustion System: a) Combustion

section, b) Boiler section

2.1 Chemical Looping Combustion

The Combustion system consists of two interconnected fluidized bed reactors, in which a

metal oxide circulates in order to achieve a reversible reaction that produces two separate

3

product streams. Chemical Looping Process can be seen in Figure 2. Because of the amount of

electricity produced, there will be three identical lines, each with the same design specifications.

This part is subdivided in three sections.

Figure 2. Chemical Looping Process

2.1.1 Oxidizing Section

A detailed scheme of the oxidizing section is detailed in Figure 4 in the appendix. The

inlet air is at room temperature and atmospheric pressure (77⁰F, 14.7 psia). The total air flow

required is 23.21 MMft3/hr, equivalent to 1.710 Mlb/hr. The air is only slightly compressed to

compensate for the pressure drop in the process, due to heat exchangers and the reactor itself.

The pressure drop in the process is calculated to be around 1.6 psi, so the compressor

(AIRCOMP) has to elevate the pressure of the air to 16.3 psia, resulting in a slight temperature

increase. The total power used by this compression is 1.76 MW. This air has a composition of

79% N2 and 21% O2 by volume. Traces of other components are ignored for the calculations.

The air is then preheated, using a tube and shell heat exchanger and the product from the

oxidizing reactor (HE01). The total area of heat exchange for this step is 40,500 ft2, equivalent to

13,500 ft2 for each heat exchanger. The flow of preheated air is at 705⁰F. This air then enters the

oxidizer. This process will be detailed in section 2.1.3. The product of this reactor has a

composition of 96% N2 and 4% O2 by volume [Sharma, 2011]. Due to the nature of the reaction,

this gaseous mixture is at a high temperature (1832⁰F), so heat can be further extracted from it to

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produce steam. Using a heat exchanger (HE02), which is part of the boiler system detailed in 2.3,

about 111 MW are extracted from this stream, reducing the its temperature to around 842⁰F. The

product stream is then used to preheat the incoming air as mentioned before. The final product is

at 98⁰F and 15 psia, and has the same composition as stated previously. The amount leaving the

system is around 1.376 Mlb/hr, which is a considerable amount. It can be sold to a Nitrogen

consuming plant; however, because of the rather large flow, using a compressor to send it to a

pipeline, which would require a compression to about 400 psia (compression ratio of 27), would

be extremely expensive as well as energy consuming, so this alternative is not recommended.

2.1.2 Reducing Section

A detailed scheme of the oxidizing section is detailed in Figure 5. The fuel we are using

is natural gas, which we assumed to be pure methane for this process. The inlet flow is at 77⁰F

and 350 psig, and we use a flow of 83,591 lb/hr of methane, equivalent to 78.06 Mft3/hr. This

flow is passed through a turbine to reduce the pressure. For this reason, we use the turbine

(FUETURB), which reduces the pressure to 16 psia. The power produced by this expansion is

2.42 MW. The fuel then proceeds to enter the Reduction reactor, further explained in 2.1.3. The

product flow of this reactor is 66.7% H2O and 33.3% CO2. Due to the nature of the reactor

operation, the flow is also at high temperature, 1787⁰F. Part of this heat is used to produce steam

in the boiler section, detailed in 2.3. We can extract 67 MW from this process, resulting in a

stream of Carbon Dioxide and Water at 392⁰F. This stream is taken to the Carbon Dioxide

Separation Unit detailed in section 2.2.

2.1.3 Reactor Section (Chemical Looping)

This is the main section of this process, and it is where most of the heat is extracted for

steam generation, and the basis of the process itself. Due to its nature, it produces two separate

streams: one of Nitrogen and Oxygen, and another one of Carbon Dioxide and Water. This

allows easy separation of the Carbon Dioxide produced, and it is why it is considered a clean

technology when compared to traditional combustion processes. The details of the reaction used

are in section 4.1.

The detailed scheme of the Looping process can be seen in figure 6 in the Appendix. The

information used to build this cycle was extracted from the article by Sharma, R [Sharma,2011].

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Some of the parameters used for the design were the fluidizing velocities in the reactors,

temperatures, conversion rates and densities. The following table details the values used.

The system used has a circulating metal oxide, with two interconnected fluidized bed

reactors. The air reactor has a higher speed (9.6 m/s), compared to the fuel reactor (0.16 m/s),

due to the reduction/oxidation rates found in literature. This influences the design of the reactors,

further detailed in Appendix A5, because it makes the air reactor have a smaller diameter (almost

half), compared to the fuel reactor. The residence time for the fuel reactor (30 s) is also higher

than that of the air reactor (which is around 9.2 s), because the endothermic reaction taking place

in the fuel reactor is slower. However, because of size limitations, the reactors used will be

smaller than those specified in the article. Because of this, for each air reactor, there must be five

fuel reactors to ensure the fuel speed and residence time in the reactors’ stays the same.

This system operates at a very high temperature (1832⁰F for the air reactor, 1787⁰F for

the fuel reactor). The fuel reactor is at a lower temperature because it is endothermic, so it uses

some of the sensible heat (around 33 MW) of the hot metal oxide to complete the reaction. The

reaction taking place in the air reactor is highly exothermic, so heat can be extracted from it

while maintaining an extremely high temperature. A piping system to produce steam is installed

in the reactor itself, and is used to extract 333 MW. This is the part of the whole process that

produces the most energy.

The flow is a type of recycle, in which the iron oxide (Fe2O3/Fe3O4) circulates between

the reactors, being oxidized and then reduced, and then repeating the process. The metal oxide’s

6

reactivity and durability is enhanced by doping with Al2O3, in a 60:40 mass ratio of iron oxide

and aluminum oxide. The stream ME is the reduced stream, and it has a mass flow of 31,233

Mlb/hr Fe2O3, 9,648 Mlb/hr Fe3O4, and 27,010 lb/hr Al2O3. As it enters the oxidizer, the Fe3O4 is

oxidized, and produces a stream with 41,214 Mlb/hr Fe2O3 and 27,010 Mlb/hr Al2O3. The

amount of oxygen carried is then 342 Klb/hr O. The reaction rates account for the relatively low

amount of Oxygen transferred.

2.2 Carbon Dioxide Separation

The detailed scheme for the carbon dioxide separation unit can be seen in Figure 7 in the

Appendix. The flow coming from the reducing section, which contains 66.7% H2O and 33.3%

CO2, has to go to a separation unit. This is one of the most important steps of the process,

because it differentiates it from conventional combustion processes. These generally have a

product flow of Nitrogen, Water, and Carbon Dioxide. The separation of Nitrogen and Carbon

Dioxide is expensive and require specific equipment. The separation of Carbon Dioxide and

Water, on the other hand, is pretty straight forward, and it can be done in a simple flash tower

that takes advantage of the vapor-liquid equilibrium of the system. The system is still expensive,

because it requires cooling down and compressing high amounts of flow gas.

The cooler lowers the gas temperature from 392 ⁰F to 72⁰F, using cooling water at 55⁰F

that heats up to 95⁰F. This requires a very large cooler: 168,000 ft2. This is one of the constraints

of the process, and requires multiple heat exchangers in parallel to accomplish. The temperature

of the outlet flow of gas was specified to obtain a high purity carbon dioxide stream out of the

flash tower. After the mixture is cooled, it passes through a flash tower, which produces two

streams. The liquid phase, which has a flow of 185,579 lb/hr, is composed of mainly water

(99.98% Water) and traces of Carbon Dioxide. Though slightly acidic (due to solubility of

Carbon Dioxide in water), it can be used for other purposes in the process or discarded easily.

The vapor phase, with a flow of 231,364 lb/hr, is mainly Carbon Dioxide (99%) and a small

amount of water, carbon monoxide, and hydrogen. This stream is at atmospheric pressure, so it

has to be compressed in order to send it to a pipeline. The specification used was 365 psia, so the

compression ratio is high (about 25). However, the flow isn’t too high, so it can be compressed

using compressors that use 10.4 MW.

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2.3 Electricity Generation System

For the design of the electricity generation system, an article by Zhou, S. and Turnbull,

A. was used. Figure 3 is a diagram of a steam cycle in a conventional fossil fuel electricity

generation plant. The system consists of an acuotubular boiler, which heats the incoming water

using pipes and a superheater to produce superheated steam. This steam passes through a high-

pressure turbine, and the outlet steam is reheated. The steam then passes through two lower

pressure turbines, which are connected to a generator. The system is closed so all the water is

recycled.

Figure 3. Simplified steam cycle in a power plant

Also, conditions of inlets and outlets of turbines were found and used for the model of the

chemical looping plant, as described in Table 2.

Table 2. Typical inlet and outlet temperatures and pressures of steam for a fossil-fired steam

turbine with a rated output of 500 MW.

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Turbine Inlet Outlet

Temperature

(⁰F)

Pressure

(psia)

Steam

wetness

Temperature

(⁰F)

Pressure

(psia)

Steam

wetness

HP 1047 2199 / 685 609 /

IP 1047 545 / 446 45 /

LP 444 44 / 86 9 8%

Adapting the values and cycle found to the Chemical Looping Plant, a suitable electricity

generation section was designed. A detailed scheme of the boiler section is detailed in Figure 7

in Appendix. Though the boiler appears to be a single block of operation, it is actually comprised

of piping that passes through the Oxidizing Reactor (OXIDIZER) and the two heat exchangers

found in the reducing and oxidizing sections of the plant (HE02 and HE03). So although we are

using a model similar to the one in Figure 3, the actual plant would not have a boiler per se, but a

complex piping system that goes through the equipment mentioned, through which water/steam

will be transported to have heat transferred to it. The total energy that can be extracted from the

reactor and heat exchangers is 510 MW. This energy will be distributed between the main

heating section (which uses 325 MW) and the reheating section (which uses the remaining 185

MW).

The flow of water was determined to be 3,473,000 lb/hr. This amount was determined

assuming the power loss of the heating system was 100% efficient, meaning that all the energy

extracted from the reactor and heat exchangers would be effectively transferred to the water. The

turbines used for the process have an isentropic efficiency of around 0.8, which is on the higher

side of the steam turbines found for commercial processes. For the efficiency of the steam

generation however, Aspen+ has included calculations regarding the use of energy extracted

from the process and used to heat up the water. The efficiency is set around 0.6, which means the

efficiency of the whole electricity generation process is around 48%.

The water is first heated by the main heating section, elevating its temperature to 1047⁰F

and 2200 psia. This steam is superheated, and has the highest amount of energy in the loop. The

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water then passes through a high pressure turbine (HPTURB), which produces 138 MW. The

steam that comes out of the turbine is at 706⁰F and 610 psia. This steam is then reheated, passing

through the piping system, to 1047⁰F and 545 psia. This steam then goes to the intermediate

pressure turbine (IPTURB), which produces 254 MW, and releases steam at 521⁰F and 45 psia.

Finally, the steam passes through the low pressure turbine (LPTURB), which produces 119 MW,

and releases water at 266⁰F and 9 psia. This water is recycled and directly sent to the main

heating system again in a closed loop. This reduces water use and maximizes the efficiency of

the process.

The work done by the turbine is transferred to a generator, which produces the electricity

which can then be sold. The total energy generated is 511 MW, plus the 2.42 MW produced by

the fuel turbine. Of those, 1.71 MW are used for the air compressor, and 10.4 MW are used for

the carbon dioxide compressor. This means that the plant is self-sufficient in terms of electricity,

and supplies a total of 500 MW which will be the main product of the power plant.

2.3.1 Power line

Existing power line infrastructure is widespread throughout Wyoming. We will not have a

problem with transmission of our power to other places around Wyoming. In the summer of the

2014, work is to begin on a new power transmission line that has the potential to carry over 1500

Megawatts across 990 miles of power lines through southern Wyoming into the state of Nevada.

With this power line access, we will be able to expand our range not just from Wyoming, but

from Wyoming through Idaho, Utah, and Nevada.

3. Reactions and Properties

3.1 Oxygen Carrier

The oxygen carrier is an essential part for the chemical looping process since it is in

charge of transferring the oxygen from the air to the fuel reactor. The oxygen carrier will be

10

oxidized in the air reactor and then it will transfer the oxygen to the fuel reactor. The reduction

will occur in the fuel reactor and the oxygen carrier will cycle back to the air reactor to repeat the

cycle. The oxygen carrier selection decision was an important aspect to our project. The best

two oxygen carrier options were a nickel based oxygen carrier and an iron based oxygen carrier.

Consequently, the Iron based oxygen carrier was selected because it was chap, safe, possessed

high reduction and oxidation numbers, a high oxygen capacity and it is also widely available.

However, recyclability is still an issue for this iron based oxygen carrier [Li, 2009]. There is a

lot of interest to develop better oxygen carriers so there is a lot of research being done in this

area. Table 3 below shows the advantages and disadvantages for Nickel and Iron based oxygen

carriers. Table 3 shows that the iron based oxygen carrier is cheaper, it has a higher oxygen

capacity, it also has high oxidation/reduction numbers, is safe to use and widely available. The

only disadvantage that the iron based oxygen carrier has is that it has a low recyclability. To

address this problem it was decided to use an aluminum oxide inert that improves the mechanical

strength and recyclability of the oxygen carrier.

Table 3. Nickel vs. iron based oxygen carrier comparison

Nickel Based Iron Based

Cost Expensive Inexpensive

Oxygen Capacity (wt %) 21 30

Recyclability Normal Low

Environmental Hazards Poisonous Safe

Oxidation/Reduction Numbers Low High

Availability Low Wide

In conclusion, this table shows that the iron based oxygen carrier is a better option for the Chemical Looping Process.

3.1.1 Other Oxygen Carriers

The chemical looping process requires an oxygen carrier that can withstand the

conditions required for the looping process. The oxygen carrier must provide high

11

oxidation/reduction numbers, high mechanical strength to ensure a reasonable recyclability and a

high reactivity. Other factors such as cost and availability are considered to guarantee the

economic feasibility of the project. Although many oxygen carriers have been created to be part

of the chemical looping process, very few possess the desired qualities. Here are some of the

oxygen carriers that are not suitable:

Copper and Manganese Based Oxygen Carriers

The synthesis of copper and manganese oxygen carriers has been proven to be

challenging due to the decomposition or melting of the implicated compounds. Therefore this

type of oxygen carriers is not desirable because “as it is known, MnO2 decomposes to Mn2O3 at

about 500°C, and to Mn3O4at about 950°C” [Adanez, 2003]. By decomposing or melting at

high temperatures, copper and manganese based oxygen carriers are not suitable for the chemical

looping process. On the other hand, iron based oxygen carriers possess high crushing strength

values, especially those sintered with Al2O3 at temperatures higher to 1100°C. This makes iron

based oxygen carriers more suitable for the chemical looping process in comparison to copper

and manganese based oxygen carriers.

Calcium Based Oxygen Carriers

Another possible alternative for the oxygen carrier concern are calcium based oxygen

carriers. Calcium based oxygen carriers provide many advantages. Two of them are: the fact that

calcium is cheaper and more abundant in comparison to other oxygen carriers. Calcium based

oxygen carriers also provide high oxidation/reduction numbers. However, calcium based oxygen

carriers have fundamental disadvantages. The main disadvantage that calcium based oxygen

carriers have is that they have low reaction rates. This limits their use for the CLC process.

Another disadvantage is that the activity of calcium based oxygen carriers at high temperatures is

compromised due to sintering. This also makes calcium based oxygen carriers not appropriate for

the CLC process. Research in the future might provide solutions to the problems that calcium

based oxygen carriers have but currently they are not the best option for the CLC process.

3.2 Reactions

The two chemical equations that are used in this process are both carried out in two reactors.

The air reactor deals with oxidizing the oxygen carrier that reduces in the fuel reactor.

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3.2.1 Fuel Reactor (Reduction)

The Fuel Reactor uses an Endothermic, Non-electrical generating reactor. Methane is put

in contact with Hematite which then converts to carbon dioxide, water and Magnetite. Methane

flows in at the rate of 86,000 lb/hr and is in contact with the catalyst. The catalyst which also

includes Hematite mixed in with a little aluminum oxide, flows at a rate of 70.1 MMlb/hr.

Together they produce Carbon dioxide at a rate of 236,000 lb/hr.

CH 4+12 Fe2O3 →C O2+2 H2O+8 Fe3 O4

3.2.2 Air Reactor (Oxidation)

The air reactor uses an exothermic energy reactor. This reaction generates steam which is

then used to make electricity. Air enters into the reactor at a rate of 1.7 MMlb/hr. Break that

down into base components, and we get O2 at 67,000 lb/hr and N2 at 1.3 MMlb/hr. This process

does not use Nitrogen, so it is vented straight to the atmosphere. The equation is:

O2+4 Fe3O4 →6 Fe2O3

3.3 Properties

Table 4 below shows the molecular weight, melting point, boiling point, and enthalpy formation

for the main components (CH4, Fe2O3, CO2, H2O, Fe3O4, and O2) of the Chemical Looping

process.

Table 4. Properties for the process chemical components

Properties:

MW Melting Temp

C

Boiling

Temp C

enthalpy of

formation

Methan

e

16.043 -182.5 -161.6 -74.852

Fe2O3 159.69 1566 ------------ -822.2

13

CO2 44.01 -56.6 -78.6 -393.505

H2O 18.015 0 100 -241.835

Fe3O4 231.533 1538 --------- -1120.9

O2 31.999 -218.8 -183 0

The operating conditions for these components are very specific in the Chemical looping

process, so their physical and thermodynamic properties have to be considered. The components

must be able to withstand high pressures and temperatures. That is why the properties above in

Table 4 have to be extensively considered for the design of the power plant.

∆ Hf = 96.877 (endothermic)

∆ Hf =-449.6 (exothermic)

For the simulation, the property packages used were Peng Robinson for the Reactor systems,

while the steam and boiler system used NBS steam package to provide more accurate data on

both systems, which differ based on the components used.

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4. Material Data

4.1 Text Flowsheet

Figure 3. Block Flow Diagram for the Chemical Looping Combustion Process

Figure 3 above shows the block flow diagram for the chemical looping combustion

process. The process starts by the feedstock, natural gas, entering the fuel reactor and air going

into the air reactor. The oxygen carrier transfers oxygen from the air to the fuel reactor.

Following the reduction of the oxygen carrier in the fuel reactor, the oxygen carrier cycles back

to the air reactor. The oxygen carrier gets oxidized again and continues supplying the fuel reactor

with oxygen. The flue gas obtained from the chemical looping process is then transferred to the

heat exchanger system. The first stream out of the heat exchanger system is the carbon

dioxide/water stream. The separation of carbon dioxide and water is achieved through the

condensation of water. This produces a stream that contains pure carbon dioxide. The separated

carbon dioxide must be over 95% pure to be commercially acceptable. The main market for

carbon dioxide is the enhanced oil recovery industry; however, the pure carbon dioxide can also

be sold to some food industries. Figure 1 also illustrates a stream for the production of nitrogen;

however, the demand for nitrogen is not enormous and its production nearly doubles the

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compressor electricity consumption for the entire process. Consequently, it was decided that the

production of nitrogen was non-profitable and therefore it was decided not to produce it. The last

section of the process is the electricity generation system. This part of the process utilizes

conventional boiler and turbines technology to produce electricity. The goal to produce 500MW

for this process was accomplished

4.2 Overall Material Balance

The overall material balance for the entire process is shown in the following table, table 5.

The data was collected from the Aspen+ simulation file.

Table 5. Overall Material balance

In/Out

Stream

Reference Component Flow Rate (x1000 lb/hr)

In FUELIN CH4 83.4

In AIRIN N2 1,311

In AIRIN O2 398

Out HEO1CO N2 1,311

Out HEO1CO O2 65

Out HEO1CO NO TRACE

Out WATERO CO TRACE

Out WATERO CO2 TRACE

Out WATERO H2 TRACE

Out WATERO H2O 186

Out WATERO O2 TRACE

Out CO2PROD CO TRACE

Out CO2PROD CO2 229

Out CO2PROD H2 TRACE

Out CO2PROD H2O 2

Out CO2PROD O2 TRACE

TOTAL 0

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As shown above in Table 5, the feed components are changed into the desired products.

Carbon dioxide comes out with purity over 99% and the byproducts (carbon monoxide,

hydrogen, water and oxygen) are not a threat to the environment or people at low levels. The

water stream out (WATERO) also illustrates the high efficiency of the separation of carbon

dioxide and water. Water is the main component for this stream of water out (WATERO).

The material balance for the recycle streams is shown below in Table 6.

Table 6. Material balance for recycles

Recycled

Stream

Reference Component

Flow Rate

(x1000lb/hr)

Recycled WATEREC H2O 3,473

Recycled MEO FE2O3 41,214

Recycled MEO AL2O3 27,010

Recycled ME FE203 31,233

Recycled ME FE304 9,648

Recycled ME AL2O3 27,010

The recycle flow rates seem to be reasonable since the oxygen carrier has to transfer the

oxygen from the air and the fuel reactor. This transfer requires relatively high flow rates. Water

will also be recycled in the electricity generation system.

4.3 Key Recycles

The oxygen carrier recycle is an essential characteristic for the chemical looping

combustion system. The recycle of the oxygen carrier provides the fuel reactor with the

necessary oxygen. The importance of the oxygen carrier requires a high performance. That is

why AL2O3 was added as a catalyst to provide greater mechanical strength and improve the

recyclability. The conversion for the oxygen carrier in the air reactor is 98% and the fuel reactor

has a conversion of 96% [Sharma, 2011]

Another key recycle for this process, is the water recycle for the electricity generation

system. The water comes out after the electricity is produced in the turbines and is recycled back

17

to the boiler. After the water goes through the boiler it enters the turbines once again to produce

more electricity.

5. CO2 sequestration

5.1 Storage and transportation of CO2

In recent years CO2 storage and different methods for storing CO2 have been discussed.

CO2 can be stored in three main ways: in deep geological formations, ocean storage, and in the

form of mineral carbonates. The storage in the deep geological formations is considered more

realistic and promising. In 2004, The International Energy Agency (IEA) organized a meeting

with the Carbon Sequestration Leadership Forum (CSLF) to discuss the legal rights of CO2

storage. The method our group chose for storing CO2 is by injection and monitoring it

underground in different geological formations. The CO2 must be stored under a formation

where it will be trapped and not allowed to be released into the atmosphere. The formation has to

prevent the CO2 leakage risk. The formations which are sufficiently permeable to take large

quantities of CO2 are depicted in Figure 1.

Figure 1. Possible geological formations to store CO2.

According to Figure 1 there are layers of sandstone trapped between layers of shale. The

sandstone has a high permeability which allows for the injection of CO2. The shale, having a low

permeability, acts as a seal to prevent the escape of the CO2.

18

CO2 must be pressurized to around 100 bar or more where in our process it is 25 bar for

transportation and storage. CO2 can be stored in the geological formations at depths more than

600 meters. At depths below 800-1000 meters the CO2 will become a liquid, the result of

ambient pressures and temperatures. The liquid occupies a much smaller volume than the

gaseous state which will help to store CO2 more efficiently and secure [Kerr, Thomas 2007]. So

to keep the CO2 relatively dense and in the supercritical phase, injection underground will be at

least 1 km depth. It will not be more than 2 km because of the economic reasons and safety

issues. The location of the plant is between Green River and Rock Springs. The geological

formation of this location has great opportunities for CO2 sequestration (storage). Potential

reservoir for CO2 injection in the plant location is Sandstone with seal formed by the Gypsum.

The injection of CO2 in deep geological formations involves the same technology as in the oil

and gas industry. There are well drilling, computer simulation, fluid injection, and monitoring

technologies used to store CO2 underground.

5.2 Economics for CO2 storage and transportation The cost of carbon capture from power plants is between $40 to $90 per tonne of CO 2

captured and stored. The price for the most expensive technologies of CO2 capture can be varied

from $20 to $40 per tonne of CO2 stored. It is projected that the cost for CO2 capture for coal-

fired plants will be around $25 per tonne of CO2 by 2030 (IEA, 2004). We assume that the cost

for our power plant with natural gas as a feed would be around the same price. On the contrary,

the natural gas power plants with CO2 capture and storage would increase the electricity price by

$0.02 to $0.03 per kilowatt hour (kWh). As for the transportation of CO2 by pipelines the cost

would be varied on the volume which is transported and the distance we would choose. The large

scale pipeline transportation costs range from $1 to $5 per tonne of CO2 per 100 kilometers

(IEA, 2004). Also there are other costs of CO2 storage depending on the location and methods of

injection chosen and monitoring. It can be around $1 to $2 per tonne of CO2 stored. To store CO2

underground can be economically positive as well. CO2 is largely used for enhanced oil recovery

(EOR). The level of EOR can range from 0.1 to 0.5 tonne oil per tonne of CO2 used. The

majority of CO2 EOR sites are in North America and there is approximately 40 million metric

tonnes of CO2 injected annually. Compared to the oil price nowadays being already $100.44 per

barrel and it is projected to be $115 per barrel in a year. In conclusion, at higher oil prices the

project of capturing and storing CO2 can be very promising for EOR [Kerr, Thomas 2007].

19

The challenges associated with CO2 storage can be technology, costs, regulation issues,

and public acceptance. The financial issues include insurance and liabilities. The CO2 storage

projects have been going on in Norway, Canada, Algeria, and Australia. The researchers were

working on injection of different amounts of CO2 into a variety of geological formations which

are sufficiently permeable to store CO2. Another challenge is that the large scale of CO2 injected

underground need to be approved by the public. The potential problem which can arise from CO2

injection between Green River and Rock Springs area is the fear of oil and gas companies

because of possible contamination. There could be problems associated with undiscovered

hydrocarbon resources.

5.3 CO2 storage regulations Governments are interested in promoting CO2 storage but also need to introduce regulations to

protect the public safety and the environment. There should be an agency that will be in charge

of certain actions to ensure the risk assessment, and monitoring of CO2 storage. In 2010 United

States Environmental Protection Agency (EPA) adopted regulations governing carbon dioxide

storage under the Safe Drinking Water Act’s Underground Injection Control (UIC) Program. It is

designed to protect underground sources of drinking water. The regulations are directed towards

CO2 injection through the well and long term storage. The wells need to be appropriately

suitable, constructed, tested, and monitored. The EPA introduced another requirement under the

Greenhouse Gas Reporting Program for facilities that inject CO2 underground. The EPA is able

to track the amount of CO2 being injected into the formations and to ensure safe long term CO2

storage [Kerr, Thomas 2007]. There is still concerns regarding CO2 storage method by injection

it into the geological formations. One of them is that the technology is still not as effective and

need a lot of improvement; another one is that there can be a possibility of leakage of CO2 from

transportation or from the storage itself. There must be certain concepts and regulations made.

The public acceptance to store the CO2, the regulating agencies and non-government

organizations need to be organized to ensure the CO2 has been properly stored and etc [White,

2003].

6. Nitrogen SalesAt the beginning of the project, the probability to commercially produce nitrogen was

given. The simulation of the process to produce nitrogen was done using Aspen+. The resulting

nitrogen production was not economically feasible due to the fact that the compressor input

20

doubled. The electricity cost to compress nitrogen made the nitrogen production non-profitable.

If the nitrogen could have been sold somewhere near where compression was not necessary, its

production would have been lucrative. That is why at the end nitrogen was not produced

because it was not economically feasible.

7. Economics

7.1 Overall Economics

Designing a chemical plant is a complex process. It involves knowledge of multiple

engineering disciplines as well as knowledge of economics. Economic evaluation is important

part in chemical plant design as engineering studies and theoretical calculations.

The overall economics for our process included consideration of selling CO2 for $15 per ton,

which is the projection price in 2020 according to the “2013 Carbon Dioxide Price Forecast

[Wilson, 2013]”. Electricity is sold for 11 cents per Kilowatt-hour according to Rocky Mountain

Power [Residential Price Comparison]. Our key assumption was a constant price for natural gas.

However, the sensitivity analysis on CO2, natural gas feed and electricity price was performed to

analyze any fluctuation in price that may happen. The natural gas price according to the state of

Wyoming is $6.69 per 1000 ft3 [U.S. Energy Information Administration - EIA - Independent

Statistics and Analysis, 2013]. Table 7 below indicates the total price we will spend on natural

gas and the earnings procured by selling CO2 and electricity.

Table 7. Feed and product total price

Feeds Base Units Basis Units Total Price per

21

Price year

Natural Gas

Feed

78,065 ft3/hr 0.0069 $/ft3 $4,632,402.02

Products

Electricity

Generation

510.723414 MW 11 Cents/KW-hr $471,712,575.36

Pure Carbon

Dioxide

29.1055104 kg/sec 15 $/ton $13,516,599.03

According to Table 7 there will be 78,065 ft3/hour of natural gas at a price of $0.0069 per

ft3. This leads to a total price of $4,632,402.02. Products from this include roughly 511

megawatts and 29 kilograms of CO2 per second. These can be sold at 11 cents per kilowatt hour

and $15 a ton. This gives total revenue of $471,712,575.36 for the electricity and $13,516,599.03

for the CO2.

The total capital investment for the process is about $2.2 billion with a two year building

period. The working capital is about $324 million. The total variable cost is $5.2 million per year

which includes the price of natural gas and catalyst. Electricity will be provided by our power

plant to operate equipment. The 12.1 MW will be used to run the compressors, and heat

exchangers. The total fixed cost which includes labor, maintenance, laboratory, plant overhead,

taxes and insurance is around $190 million. The revenue of the plant considering selling CO2 and

electricity at the prices indicated above would be around $485 million per year. After running the

process simulation a 20 year cash flow analysis was completed. Table 8 below indicates the

overall costing for the entire chemical looping power plant with 500 MW and CO2 capture.

Table 8. Overall costing for the chemical looping power plant with 500 MW and CO2 capture.

Fixed Capital investment $1.8 Billion

Total Capital Investment $2.2 Billion

22

NPV0 $11.9 Billion

NPV10 $ 4.3 Billion

IRR 36.0 %

Pay Back Period 2.1 years

According to Table 8 the Net Present Value at zero years is $11.9 billion, while at 10 years, it is

at $4.3 billion. This gives an internal rate of return of 36%, which is more than enough for

covering costs of this project, but has high risk as this is a new technology. This high IRR gives

this project a fairly short payback period of just over 2 years.

The fixed capital investment includes all the capital necessary for equipment and its

installation for complete process operation. Piping, instrumentation, insulation, site expenses

preparation, and etc. were included to calculate fixed capital investment. This equipment

includes the chemical looping process with CO2 capture and the power plant itself. Steam turbine

with boiler installation cost is between $800-$1000 per Kilowatt [Gas-Fired Power, 2010]. The

500 MW of electricity is produced by the power plant and the installation of turbines with boilers

cost around $460 million. The price of the power plant itself with installation seems pretty high

comparing to the installed equipment of chemical looping process which is around $28.5 million.

Sensitivity analysis was performed by varying the electricity, natural gas, carbon dioxide prices,

and fixed capital investment. The effect of payback period was investigated and recorded in

Table 9.

Table 9. The sensitivity analysis on IRR NPV10 and PBP by varying prices of natural gas,

electricity, CO2 and FCI

Sensitivity Analysis CalculationsNatural Gas Base

23

Natural Gas Varying Prices [dollars/ft3]

4 5 6.69 8 9IRR 36.1% 36.1% 36.0% 35.9% 35.9%NPV10 4,348,845,79

6 4,337,201,742 4,315,078,041 4,291,789,934 4,290,625,528PBP 2.07 2.07 2.07 2.08 2.08

Electricity BaseElectricity Varying Price [cents/Kwh]

9 10 11 12 13IRR 28.8% 32.5% 36.0% 39.3% 42.5%NPV10 2,854,730,74

3 3,584,904,392 4,315,078,041 5,045,251,689 5,775,425,338PBP 2.48 2.26 2.07 1.92 1.78

Carbon Dioxide

Base

Carbon Dioxide Varying Price [$/ton] 8 10 15 30 50IRR 35.5% 35.6% 36.0% 37.0% 38.4%NPV10 4,207,675,24

2 4,238,361,756 4,315,078,041 4,545,226,895 4,852,092,034PBP 2.10 2.09 2.07 2.02 1.96

BaseCapitalFCI Increase -10% -5% 0 5% 10%IRR 40.0% 37.9% 36.0% 34.2% 32.5%NPV10 4,683,423,20

5 4,499,314,636 4,315,078,041 4,130,940,908 3,946,695,879PBP 1.89 1.98 2.07 2.17 2.26

According to Table 9 the analysis for CO2 and natural gas showed that a change in price

will not make much of an impact on the IRR, NPV10, or PBP. These price numbers were chosen

because there is a possibility that the price of our raw materials can change, according to

24

suppliers. However, the PBP decreases by varying the price for the electricity and fixed capital

investment.

8. Government RegulationsNatural gas chemical looping is a new process that does not exist in power plant

commercial plants. So it is a costly process due to the new technology been used and to the many

modifications and units necessary. However, Natural gas chemical looping is an environmentally

friendly process and it can be competitor for other electricity generation processes.

The combustion of fossil fuels for energy is a human activity that leads to a large amount

of CO2 emission. The Environmental Protection Agency stated that the atmospheric

concentration of carbon dioxide was 35% less than todays present time [Yeh, 2009]. In the

United States, the combustion of fuel for the electricity generation is one of the main causes of

CO2 emission and radiates massive amounts of carbon dioxide annually. So the public demand

that power plants have lower emissions. Also the public is asking for a punishment for such of

companies that emits above a certain level.

Electricity generation utilities are regulated by state, federal and local agencies. Some

agencies control the prices they charge, the terms of the service those utilities do for the

consumers, the construction plans and their budgets. Also other agencies are responsible for the

utility impacts on the environment.

In 2012, the current administration proposed new EPA legislation that would stop building new

traditional power plants in order to reduce the amount of CO2 emission. It seems chemical

looping technology will be a favorable options for power plants. To be mentioned, chemical

looping technology can be integrated into any existing power plant and that will help reducing

the amount of CO2 emissions.

Environmental Protection Agency (EPA ) established regulations for air pollution. Those

regulations are enforces by state agencies. For building a new industrial facility or applying

changes to an existing facility that would change the emission of air pollutants, a construction

permit is required. An estimation of the emissions with no pollution control equipment is one of

the requirements for this permit. Also, the permit asks for an estimation of the emissions with

25

pollution control technique. Also, EPA is suggesting a maximum limit of 1,000 lbs. of CO2

emissions per MW-hr of electricity generation.

8.1 PermitsBeing located outside of the Flaming Gorge reservoir, we will not be distracting the

natural wildlife and recreational activities that coexist within the boundaries that exist in the

reservoir. Permits will have to be issued from the Department of Environmental Quality. A pre-

application meeting will have to be requested. This is to make sure that the permits that are

issued will be true to form and not fabricated. This will be followed by application completeness

reviews. This will take a while, so the application requester is asked to allow time to complete

the reviews.

8.2 OSHA Law & RegulationsThere are three major types of risks involved with a natural gas power plant; mechanical,

chemical and electrical. Mechanical risks can be reduced by following specific guidelines

outlined by OSHA requirements. The safety of mechanical aspects of the plant can be achieved

by following these four guidelines.

1. “When boilers are manually operated in lieu of automated combustion/safety

controls, additional emphasis must be placed on work practices. Necessary elements

for emphasis include written operating procedures, job briefings, verification

checklists, training, proficiency testing, and maintenance of training records.

2. When equipment nears the end of its useful life, the employer must be particularly

diligent, as well as vigilant, with respect to maintenance. Boiler safety controls (e.g.,

flame monitors) must be operational and well maintained.

3. Safety has the upmost importance in this process. In order to be safe, there has to be

clear lines of communication between each individual including maintenance,

operations, management, health and safety representatives, and the safety department.

These are simply guidelines, they are not a new standard or regulation, and therefore,

there are no legal obligations.

26

Chemical risks can be reduced by careful maintenance and containment. There also is the

added element of a terrorist attack or a faulty crack in an existing pipeline. Currently there are

three pipelines in the area that we are looking at to put our power plant. This is to create a

redundancy in case one pipeline is complete, there will be two other pipelines to siphon off from.

If this is the case, then people will not be worried about not receiving any power.

High pressure is also a probability risk of danger. In the case of extreme pressure, caution

will be used and have safety valves put into practice. These valves will ensure that if a case such

as this arose, then they will open and release the pressure so that no harm or injury will occur to

an observer. This will help to reduce lawsuits and malpractice issues from such incident.

9. Conclusion

Carbon Dioxide is the primary greenhouse gas that emits by human activities. The impact

of the fossil fuels in the environment allowed several technologies that decrease the amount

of CO2 emissions. Chemical looping combustion is one of these technologies, and can be

applied to power plants with the benefit of capturing pure CO2. This is a new technology that

does not exist in a commercial power plant yet, so it is a costly process. As a conclusion, this

project can be profitable even if the cost of the chemical looping combustion is high.

27

Appendix

A1. Flowsheets (detailed)

Figure 4. Detail of the Oxidizing Section of the Chemical Looping Combustion Step

28

Figure 5. Detail of the Reducing Section of the Chemical Looping Combustion Step

Figure 6. Detail of the Reactor System of the Chemical Looping Combustion Step

29

Figure 7. Detail of the Carbon Dioxide Separation Unit

Figure 8. Detail of the Electricity Generation Section of the Plant

30

Simulation\Chem_Looping_Simulation.bkp

A2. Detailed Material BalanceTable 10. Material Balance (Part 1)

Equipment Stream Reference In/Out Temperature

(F)Pressure (psia) Component Mass flow

(x1000 lb/hr)

AIRCOMPAIRIN IN 77 14.7 N2 1,311.4

O2 398.2

AIRCOMPO OUT 91.2 15.7 N2 1,311.4O2 398.2

HE01

AIRCOMPO IN 91.2 15.7 N2 1,311.4O2 398.2

HE01HI IN 842 15.7N2 1,311.4O2 64.7NO 0.3

HE01CO OUT 704.5 15.7 N2 1,311.4O2 398.2

HE01HO OUT 98.5 14.7N2 1,311.4O2 64.7NO 0.3

OXIDIZER

HE01CO IN 704.5 15.7 N2 1,311.4O2 398.2

ME IN 1787.1 15.7Fe2O3 31,232.7Fe3O4 9,648.3Al2O3 27,009.6

OXIAIRO OUT 1832 16.3N2 1,311.3O2 64.7NO 0.3

MEO OUT 1832 16.3 Fe2O3 41,214.4Al2O3 27,009.6

HE02

OXIAIRO IN 1832 16.3N2 1,311.3O2 64.7NO 0.3

HE01HI OUT 842 15.7N2 1,311.3O2 64.7NO 0.3

FUETURB FUELIN IN 77 364.7 CH4 83.6FUETURBO OUT 89.1 15.7 CH4 83.6

31

Table 11. Material Balance (Part 2)

Equipment Stream Reference In/Out Temperature

(F)Pressure (psia) Component Mass flow

(x1000 lb/hr)

REDUCER

FUETURBO IN 89.1 15.7 CH4 83.6

MEO IN 1832 16.3 Fe2O3 41,214.4Al2O3 27,009.6

ME OUT 1787.1 15.7Fe2O3 31,232.7Fe3O4 9,648.3Al2O3 27,009.6

REDFLUEO OUT 1787.1 15.7

CO traceCO2 229.2H2 TraceH2O 187.7O2 traceCH4 trace

HE03

REDFLUEO IN 1787.1 15.7

CO traceCO2 229.2H2 TraceH2O 187.7O2 traceCH4 trace

COOLIN OUT 482 14.7

CO traceCO2 229.2H2 TraceH2O 187.7O2 traceCH4 trace

COOLER

COOLIN IN 482 14.7

CO traceCO2 229.2H2 TraceH2O 187.7O2 traceCH4 trace

COOLOUT OUT 71.6 14.7

CO traceCO2 229.2H2 TraceH2O 187.7O2 traceCH4 trace

32

Table 12. Material Balance (Part 3)

Equipment Stream Reference

In/Out

Temperature (F)

Pressure (psia) Component

Mass flow (x1000 lb/hr)

FLASH

COOLOUT IN 71.6 14.7

CO TraceCO2 229.2H2 TraceH2O 187.7O2 TraceCH4 Trace

WATERO OUT 71.6 14.7

CO TraceCO2 0.1H2 TraceH2O 185.5O2 Trace

CO2O OUT 71.6 14.7

CO TraceCO2 229.1H2 TraceH2O 2.2O2 Trace

CO2COMP

CO2O IN 71.6 14.7

CO TraceCO2 229.1H2 TraceH2O 2.2O2 Trace

CO2PROD OUT 721.4 364.7

CO TraceCO2 229.1H2 TraceH2O 2.2O2 Trace

BOILER WATEREC IN 265.9 8.7 H2O 3,472.9HPTURBIN OUT 1047.2 2199.8 H2O 3,472.9

HPTURB HPTURBIN IN 1047.2 2199.8 H2O 3,472.9HPTURBO OUT 705.7 609.9 H2O 3,472.9

REHEAT HPTURBO IN 705.7 609.9 H2O 3,472.9IPTURBIN OUT 1047.2 544.9 H2O 3,472.9

IPTURB IPTURBIN IN 1047.2 544.9 H2O 3,472.9IPTURBO OUT 521.4 45 H2O 3,472.9

LPTURB IPTURBO IN 521.4 45 H2O 3,472.9WATEREC OUT 265.9 8.7 H2O 3,472.9

33

A3. Physical Properties details

Methane

Table 13. Methane physical Properties [Physical Properties for Methane, 2013]

Name  MethaneFormula CH4Molecular Weight (lb/mol) 16.04Critical Temp. (°F) -116.2Critical Pressure (psia) 673Boiling Point (°F) -258.7Melting Point (°F) -296.5Psat @ 70°F (psia) (note 1)Liquid Density @ 70°F (lb/ft3) (note 1)Gas Density @ 70°F 1 atm (lb/ft3) 0.0416Specific Volume @ 70°F 1 atm (ft3/lb) 24.06Specific Gravity 0.565Specific Heat @ 70°F (Btu/lbmol-°F) 8.53

Carbon Dioxide Table 14. Carbon Dioxide physical properties [Physical Properties for Carbon Dioxide, 2013]

Carbon DioxideFormula CO2Molecular Weight (lb/mol) 44.01Critical Temp. (°F) 87.9Critical Pressure (psia) 1071Boiling Point (°F) -109.2Melting Point (°F) -69.9Psat @ 70°F (psia) 852.8Liquid Density @ 70°F (lb/ft3) 47.64Gas Density @ 70°F 1 atm (lb/ft3) 0.1144Specific Volume @ 70°F 1 atm (ft3/lb) 8.74Specific Gravity 1.555Specific Heat @ 70°F (Btu/lbmol-°F) 8.92

34

Water

Table 15. Water physical properties [Physical Properties,2013]

molar mass 18.0151 grams per molemelting point 0.00 °Cboiling point 100.00 °Cmaximum density (at 3.98 °C) 1.0000 grams per cubic

centimetredensity (25 °C) 0.99701 grams per cubic

centimetrevapour pressure (25 °C) 23.75 torrheat of fusion (0 °C) 6.010 kilojoules per moleheat of vaporization (100 °C) 40.65 kilojoules per moleheat of formation (25 °C) –285.85 kilojoules per moleentropy of vaporization (25 °C) 118.8 joules per °C moleviscosity 0.8903 centipoisesurface tension (25 °C) 71.97 dynes per centimeter

Iron Oxide

Table 16 Iron Oxide physical properties

Name: Iron OxideFormula as often written: FeO

Hill system formula: Fe1O1CAS registry number: [1345-25-1]Formula weight: 71.844Class: oxideColor: blackAppearance: crystalline solidMelting point: 1370°CBoiling point: decomposes at 3414Density: 6000 kg m-3

35

A4. Economics/Production Cost Statement

Feed and Product MaterialsFeeds Base Basis Price Total PriceNatural Gas Feed 78,065 ft3/hr 0.0069 Dollars/ft3 538.65$ Dollars/hrProductsElectricity Generation 510.723414 MW 11 Cents/KW-hr 56,179.58$ Dollars/hrPure Carbon Dioxide 29.1055104 Kg/sec 15 Dollars/ton 1,571.70$ Dollars/hr

Electicity usageAIRCOMP 1.71497391 MWCO2COMP 10.369354 MWTotal 12.08432791 MW

Revenue Power generated MW 510.723414Power used for utilities MW 12.08432791Power used for sale MW 498.6390861Power used for sale in KW 498639.086Power generated KW-h per year 4288296140eelctricity price $/KW-h $0.11Electricity Sale Revenue $/yr $471,712,575.36

By Product RevenueCO2 $/yr 13,516,599.03$

Table 6-9 fluid processing plant p. 251 P&TDirect Costs

$19,421,093.64$9,127,914.01

$313,239,183.67$460,461,600.00$147,222,416.33

$332,660,277.31$119,757,699.83$226,208,988.57

$36,592,630.50$59,878,849.92$33,266,027.73

$349,293,291.18Land cost (1% of TCI) $21,593,782.92CO2 storage equipment $985,321.42

$1,336,587,199.72

Service facilities (installed), 1.05*TE

Total direct plant cost, D

Total Purchased equipment, TEInstrumentation and controls (installed), 0.36*TEPiping (installed), 0.68*TEElectrical systems (installed), 0.11*TEBuildings (including services), 0.18*TEYard improvements , 0.1*TE

Purchased equipment for chemical looping process , EPurchased equipment chemical looping installation, 0.47EPurchased equipment for electricity generationPurchased equipment and installation for electricity generationPurchased equipment electricity generation installation

36

Indirect costsEngineering and supervision, 0.33*TE $109,777,891.51Construction expenses, 0.41*TE $136,390,713.70Legal expenses, 0.04*TE $13,306,411.09Total indirect cost, I $259,475,016.30

Total direct and indicrect cost (D+I) $1,596,062,216.02

Contractor's fee, 0.05*(D+I) $79,803,110.80Contigency, 0.1*(D+I) $159,606,221.60

Fixed-Capital Investment (FCI) $1,835,471,548.43

Table 3-11 p. 114 P&TTotal product cost estimate $/yrDirect production costsRaw materials

Natural gas $4,718,586.25Catalyst $540,822.73

Operating Labor8 men/shift @ 15$/hr *1.6*8760hr/yr $4,204,800.00Operators 20 permanent positions

Operating supervision (15% operating labor) $630,720.00Maintenance (labor and materials, 4% FCI) $73,418,861.94Utilities $0.00Operating supplies (15% maintenance) $11,012,829.29Laboratory charges (20% operating labor) $840,960.00

Indirect production costsDepreciation (10% FCI) $183,547,154.84Insurance and taxes (2% FCI) $36,709,430.97

Plant overhead costs (80% total labor costs) $63,276,273.55

Total Fixed Cost $/yr $190,093,875.75

37

Summary

Table 6-9 p. 251 P&TFixed-Capital Investment (FCI) $1,835,471,548.43Working capital (WC) $323,906,743.84Total Capital Investment (TCI) $2,159,378,292.27

Revenue $/yr $485,229,174.39

Total Variable cost $/yr $5,259,408.97

Start up $ $183,547,154.84

Cash Flow analysisTax Rate 35.00%Year (for discounting)(year end) -1 0 1 2 3 4 5 6MACRS5 Factors 20.00% 32.00% 19.20% 11.52% 11.52% 5.76%

CASE: 85% Recovery, TraysYear (for discounting)(year end) -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20FCI -1,835,471,548 -917,735,774 -917,735,774WC -323,906,744 -323,906,744 323,906,744StartUp -183,547,155

Depr Amount 367,094,310 587,350,895 352,410,537 211,446,322 211,446,322 105,723,161Depr Tax Credit 128,483,008 205,572,813 123,343,688 74,006,213 74,006,213 37,003,106

Revenue 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174 485,229,174

Variable Costs -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409 -5,259,409Fixed Costs -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876 -190,093,876Total Expenses (including SU) -378,900,440 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285 -195,353,285

Sales-Total Expenses 106,328,735 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890 289,875,890

Cash Flow -917,735,774 -1,241,642,518 708,234,788 1,372,675,488 1,055,506,005 865,204,315 865,204,315 722,478,047 579,751,779 579,751,779 579,751,779 579,751,779 579,751,779 579,751,779 579,751,779 579,751,779 579,751,779 579,751,779 579,751,779 579,751,779 579,751,779 903,658,523CumCF (PV0) -917,735,774 -2,159,378,292 -1,451,143,505 -78,468,016 977,037,988 1,842,242,303 2,707,446,617 3,429,924,664 4,009,676,444 4,589,428,223 5,169,180,002 5,748,931,782 6,328,683,561 6,908,435,340 7,488,187,120 8,067,938,899 8,647,690,678 9,227,442,458 9,807,194,237 10,386,946,016 10,966,697,796 11,870,356,319

DF10 1.10 1.00 0.91 0.83 0.75 0.68 0.62 0.56 0.51 0.47 0.42 0.39 0.35 0.32 0.29 0.26 0.24 0.22 0.20 0.18 0.16 0.15PV10 -1,009,509,352 -1,241,642,518 643,849,807 1,134,442,552 793,017,284 590,946,188 537,223,808 407,820,023 297,504,332 270,458,484 245,871,349 223,519,408 203,199,462 184,726,784 167,933,440 152,666,763 138,787,967 126,170,879 114,700,799 104,273,453 94,794,049 134,323,081CumPV10 -1,009,509,352 -2,251,151,870 -1,607,302,063 -472,859,510 320,157,773 911,103,962 1,448,327,770 1,856,147,792 2,153,652,124 2,424,110,608 2,669,981,957 2,893,501,365 3,096,700,827 3,281,427,610 3,449,361,050 3,602,027,813 3,740,815,780 3,866,986,658 3,981,687,457 4,085,960,911 4,180,754,959 4,315,078,041

NPV0 11,870,356,319 $ IRR 36.0% Everything new, high R&D and marketing effort Level of risk Very High Table 8-1 P&TNPV10 4,315,078,041 $ PBP 2.1 2.074341611NPV10 4315.08 MM$

Sensitivity analysis

Electricity BaseElectricity Varying Price [cents/Kwh] 9 10 11 12 13IRR 28.8% 32.5% 36.0% 39.3% 42.5%NPV10 2,854,730,743 3,584,904,392 4,315,078,041 5,045,251,689 5,775,425,338PBP 2.48 2.26 2.07 1.92 1.78

Carbon DioxideCarbon Dioxide Varying Price [$/ton] 8 10 15 30 50 60 70IRR 35.5% 35.6% 36.0% 37.0% 38.4% 39.10% 39.78%NPV10 4,207,675,242 4,238,361,756 4,315,078,041 4,545,226,895 4,852,092,034 5,005,524,603.35 5,158,957,172.83 PBP 2.10 2.09 2.07 2.02 1.96 1.93 1.90

CapitalFCI Increase -10% -5% 0 5% 10% 15%IRR 40.0% 37.9% 36.0% 34.2% 32.5% 0.30955756NPV10 4,683,423,205 4,499,314,636 4,315,078,041 4,130,940,908 3,946,695,879 3762482867PBP 1.89 1.98 2.07 2.17 2.26 2.35

38

Appendix\Chem_Looping_Project_Calculations.xlsx

A5. Equipment List w/sizes, Sizing Bases, Costing Bases

Fuel ReactorsBecause of the linear speed requirements of the air and fuel through the reactors, which is directly correlated to the reaction rate of the oxygen carrier in both reactors, we require very specific reactor sizes. These reactors will be designed according to the specifications in several articles found, which enlist several aspects that must be considered while sizing. The diameter of the reactors was set to 20 ft, according to the maximum diameter found in Peters, Timmerhaus, and West. Using the maximum linear velocity, it is possible to find the amount of reactors required for optimum operation. According to the calculations, the total number of air reactors required is 3, while we require 9 fuel reactors to complete the reduction reactions. However, the air reactor requires a height of 68 ft, while each fuel reactor requires 4 feet in height to complete the task. However, it is possible to build a multiple feed reactor for the fuel, which will reduce the number of fuel reactors to three by stacking them in sets of 3. By doing this, energy loss is decreased, as well as space requirements.

The final dimensions for the reactors are as follows:

39

Figure 9: Air Reactor Design (Oxidation Reaction)

40

Figure 10: Fuel Reactor Design (Reduction Reaction)

Table 17: Reactor Specifications

Fuel Reactor Air ReactorFluidizing Speed (ft/s) 0.78 47Height (ft) 12, with 2.5 feet below and

above each section for distribution

68

Diameter (ft) 20 20Gas distributors Bubble Cap Bubble CapΔP (psi) 1 1Flow Rate (MMft3/h) 1.11 47.17Conversion (%) 99 85

41

Oxygen Carrier/CatalystFe2O3 was chosen as the oxygen carrier and Al2O3 is the catalyst. The price for Fe2O3 is 1.03$/Kg

and 1.5$/Kg for Al2O3 [Alpha Chemicals, 2013].

Air CompressorThe type of air compressor is centrifugal and the price for it was based on the heat duty that it

requires. The heat duty for the air compressor was 2365hp.

Fuel CompressorThe type of the fuel compressor is centrifugal and the heat duty needed for it was 207hp.

Carbon Dioxide CompressorThe type of the fuel compressor is centrifugal and the heat duty needed for it was 14300hp. This

compressor requires the most heat duty since it has to compress the large amount of carbon

dioxide produced.

Heat ExchangersFive heat exchangers will be needed for the chemical looping process. Their pricing was based

on the required area, which was 40487.09ft2.

Coolers14 coolers will be needed for the chemical looping process. Their pricing was based on their area

11991 ft2.

Flash One flash is required to separate the carbon dioxide and water. The pricing for the flash was

based on the diameter, which was 6.32ft.

Electricity Generation System The electricity generation system pricing was based on the Megawatts produced by the power

plant. The price is 800$/KW[Gas-Fired Power, 2010]

The following table summarizes the information above.

42

Table 13 Equipment list w/sizes, Sizing Bases, Costing Bases

Qty Sizing Bases Costing Basis Cost Reference

Fuel Reactor (Reducer) 15

[Sharma, 2011] 20.93 ft Diameter

792,000

Figure 12-54 (Multiplied by 3)

Air Reactor (Oxidizer) 3

[Sharma, 2011] 20.57 ft Diameter

742,500

Figure 12-54 (Multiplied by 3)

Catalyst (FE2O3/Al2O3)

266022 kg/1773

48 kg[Sharma,

2011] 1.03$/Kg Price

540,823

Alpha Chemicals

Air Compressor 1

[Sharma, 2011] 2364.58 hp

Heat duty

800,000

Figure 12-28

Fuel Compressor 1

[Sharma, 2011] 207.13 hp

Heat duty

90,000

Figure 12-28

Carbon Dioxide Compressor 1

[Sharma, 2011] 14297.13 hp

Heat duty

4,200,000

Figure 12-28

Heat Exchanger 5

[Sharma, 2011] 40487.09 ft2 Area

215,000

Figure 14-18

Cooler 14[Sharma,

2011] 11991.04 ft2 Area 980,000

Figure 14-18

Flash 1[Sharma,

2011] 6.32 ft Diameter 11,550

Figure 12-54

Electricity Generation System 1

[ Gas-Fired Power, 2010] 512.00

MW Price

409,299,200

[Gas-Fired Power, 2010]

43

A6. Piping and Instrumentation Diagram

Symposium Presentation

Database\Progress Reports\Symposium\CHE4070_Final Presentation_Chemical Looping.pptx

44

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