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Group Synergy:

In general the group worked effectively as a team. Most members attended the group meetings. However, the group was faced with an unforeseen challenge. Indeed, James Finlayson was not present for the majority of the project for personal reasons. In addition, he insisted on taking on work with the promise to deliver. Nevertheless, after a few weeks no work was sent back to the group and communication was difficult and mainly one-sided. This sequence of events was repeated several times as James reappeared periodically (every few months) for 1-3 days. A lot of group effort went into redistributing his work to other group members which led to major delays.

This information was added as per Dr. Ahns request as it largely influenced the group dynamics over the course of the project. We were unaware of the severity of Jamesconditions. However, we are sympathetic and wish him a speedy recovery.

We were unaware of the severity of James ’ conditions. However, we are sympathetic and wish

Production of High Purity Hydrogen with CO 2 Capture

Volume 1

of High Purity Hydrogen with CO 2 Capture Volume 1 Group 1: Jennifer Coyle - s1227207

Group 1:

Jennifer Coyle - s1227207 Jack Mercer - s1240259 Elissa Mui s1219617 Qi-Shaun Wong s1302249 Aidan Cairnie - s1102723 Yongjun (John) Chen - s1105812 Astrid Stroobants - s1202301 James Finlayson

Table of Contents

1 INTRODUCTION AND DESIGN

2

2 PROCESS SELECTION

6

2.1

DESULPHURISATION OF THE FEED

6

2.1.1 Initial Considerations

6

2.1.2 Options for Desulphurisation of the Feed

6

2.2 WET BASED PROCESSES

6

2.3 DRY BASED PROCESSES

7

2.4 CONCLUSION

8

2.5 HYDROGEN PRODUCTION

8

2.5.1 Steam Methane Reforming (SMR)

8

2.5.2 Partial Oxidation (Pox)

8

2.5.3 Autothermal Reforming (ATR)

9

2.5.4 Conclusion

9

2.6

CARBON CAPTURE (CC)

10

2.6.1 Pressure/Vacuum Swing Adsorption

10

2.6.2 Chemical Absorption

10

2.6.3 Membrane Reactors

11

2.6.4 Sorption Enhanced Reaction Process

11

2.6.5 Chemical Looping

12

2.6.6 Cryogenic Capture

12

2.6.7 Conclusion

13

2.7 HYDROGEN PURIFICATION

14

2.8 CONCLUSION

14

3 PROCESS FLOW DIAGRAM AND PROCESS DESCRIPTION

15

3.1 PROCESS FLOW DIAGRAM FOR DESIGN 1

15

3.2 DESIGN 1

16

3.2.1 Process Description

16

3.2.2 Process Control

17

3.2.3 Heat Integration Design 1

18

4 PROCESS FLOW DIAGRAM FOR DESIGN 2

20

4.1

DESIGN 2

21

4.1.1 Process Description

21

4.1.2 Process Control

21

4.1.3 Heat Integration Design 2

22

5 ENERGY AND MATERIAL BALANCES

23

5.1 ASSUMPTIONS MADE

23

5.2 DESIGN 1

23

5.2.1 Overall Mass Balance

23

5.2.2 Overall Energy Balance

23

5.3

DESIGN 2

24

5.3.1

Overall Mass Balance

24

 

5.3.2

Overall Energy Balance

25

6

THERMODYNAMICS AND CHEMISTRY

26

6.1

DESIGN 1

26

6.1.1 Reactions

26

6.1.2 Separations

28

6.2

DESIGN 2

32

6.2.1 Reactions

32

6.2.2 Separations

33

7

HAZARDS AND SAFETY

34

7.1 CHEMICAL HAZARDS

34

7.2 PROCESS HAZARDS

36

7.2.1 General Plant Hazard

36

7.2.2 Desulphurisation Unit

36

7.2.3 Furnace

36

7.2.4 Pre-Reformer, Steam Methane Reformer (SMR)

36

7.2.5 Water Gas Shifters

36

7.2.6 PSA Unit

36

7.2.7 MEA Carbon Capture Unit

37

7.2.8 Chemical Looping Combustion Reactors

37

7.3

HAZARDS RANKING

37

8

ENVIRONMENTAL IMPACT

39

 

8.1 GENERAL

42

 

8.2 FLUE GAS TREATMENT AND DISPOSAL

42

8.3 SOLID WASTE DISPOSAL

43

8.4 LIQUID WASTE DISPOSAL

43

9

ECONOMIC ANALYSIS OF THE TWO DESIGNS

44

9.1 INTRODUCTION AND ASSUMPTIONS

44

9.2 ESTIMATING THE TOTAL CAPITAL COST

44

9.3 ESTIMATING THE TOTAL VARIABLE COSTS

45

9.4 ESTIMATING THE HYDROGEN AND CO 2 REVENUES, AND NATURAL GAS ANNUALISED COST

45

9.4.1 Hydrogen Revenues

46

9.4.2 CO 2 Revenues

46

9.4.3 Natural Gas Costs

46

9.5 ESTIMATING THE TOTAL COST OF PRODUCTION

47

9.6 ESTIMATING THE ANNUAL NET PROFIT

47

9.7 CALCULATING THE ANNUAL DEPRECIATION OF THE PLANT

47

9.8 DISCOUNTED CUMULATIVE CASH FLOW, NPV AND UNCERTAINITY OF THE TWO DESIGNS

47

10

START UP AND SHUT DOWN

49

11

RECOMMENDATIONS AND CONCLUSIONS

54

List of Figures

Figure 1-1: Hydrogen Market Distribution [2] Figure 2-1: Process flow diagram for chemical absorption[42] Figure 2-2: Process flow diagram of CLC[48] Figure 2-3: Process flow diagram of cryogenic CC[53] Figure 3-1: Process Flow Diagram for Design 1 Figure 4-1: Process Flow diagram for design 2 Figure 6-1: PSA Adsorption Isotherm [63] Figure 6-2: PSA Adsorption Isotherm [63] Figure 6-3: CO2 loading as a function of its partial pressure [65] Figure 11-1: Proposed designs

3

10

12

13

15

20

29

29

31

54

List of Tables

Table 1-1: Product specifications Table 2-1: SWOT of the two proposed Desulphurisation Techniques Table 2-2: SWOT for Hydrogen production techniques Table 2-3: SWOT analysis for Carbon Capture techniques Table 2-4: Proposed Designs Table 3-1: Design 1 HEN Table 4-1: Design 2 HEN Table 5-1: Overall Mass Balance for Design 1 Table 5-2: Overall Energy Balance for Design 1, Part 1 Table 5-3: Overall Energy Balance for Design 1, Part 2 Table 5-4: Overall Mass Balance for Design 2 Table 5-5: Overall Energy Balance for Design 2 Table 6-1: Reactions in Design 1 Table 6-2: Rates of Reaction in Design 1 Table 6-3: Pre-exponential factors and Equilibrium Constants in Design 1 Table 6-4: Adsorption Constants in Design 1 Table 6-5: PSA cycles Table 6-6: Reactions in Design 2

2

8

9

13

14

19

22

23

23

24

24

25

26

27

27

28

29

32

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Table 6-7: Kinetic data for CLC

32

Table 7-1: Hazardous information process chemicals

34

Table 7-2: Hazard ranking

37

Table 7-3: Hazard and Risk Safety Sheet

38

Table 8-1: Design 1 Material inventory list

39

Table 8-2: Design 2 Material inventory list

41

Table 9-1: Calculated steps involved in the estimate of the Total Capital Investment

45

Table 9-2: Calculated annual operating cost for each design

45

Table 9-3: Expected prices for the products and feedstock

46

Table 9-4: Revenues and Feed Costs

47

Table 9-5: Total Cost of Production of both Designs

47

Table 9-6: Annual Net Profit of both designs

47

Table 9-7: Expected price of H 2

48

Table 11-1: Summary table for both designs

54

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1 Introduction and Design

Design Brief The design brief stated that a high purity hydrogen production plant with integrated Carbon Dioxide Capture must be designed. The plant was required to have a capacity of 5 tonnes/h of product hydrogen and was to be situated near a chemical production site in the United Kingdom. All utilities were readily available including our natural gas feed supply, which was available by pipeline at 33 bar(a). The final requirement was the pressurisation of the carbon dioxide product to 150 bar(a) for transportation. Carbon dioxide and hydrogen had specific product composition requirements, detailed below.

Table 1-1: Product specifications

Component

Carbon Dioxide Product

Hydrogen Product

Carbon dioxide, CO 2

Minimum 97%

 

-

Carbon monoxide, CO

Maximum 3%

 

-

Methane, CH 4

2%

 

-

Oxygen, O 2

0.01%

<

5vpm

Nitrogen, N 2

3%

< 100vpm

Hydrogen, H 2

3%

 

>99.98%

Moisture

-

<

8vpm

Total Carbons

-

 

< 10vpm

Discussion of Design Remit in a Chemical Engineering Context Process Background: Hydrogen can be produced using various processes, which can be defined according to four different categories. The first of which, thermochemical processes, which release hydrogen from organic material such as fossil fuels and biomass using heat and reforming reactions. Next, electrolytic processes use electricity to split water into hydrogen and oxygen. Then, solar processes also operate through the splitting of water. Finally, the fourth type of hydrogen production centers on Biological processes, where micro-organisms such as bacteria and algae produce hydrogen.[1] Biological and solar processes are currently still at an early stage of research, while electrolytic and thermochemical processes contain well-developed technologies. However, as electrolytic processes incur large capital costs and energy inefficiencies, thermochemical processes are prevalent in industrial applications. The design options for hydrogen production via thermochemical processes were limited with the awareness of our natural gas feed. Three options were identified; Steam Methane Reforming (SMR), Partial Oxidation and Auto- thermal Reforming. SMR technology is by far the most advanced with many industrial scale operations and is also the best performing in terms of energy efficiency for hydrogen production. First introduced in 1930, SMR is preferential compared with other methods due to its high yield of hydrogen. Several hydrogen production facilities operate with SMR technology, for example Linde has a plant located in Texas producing approximately 10 t/hr of

H 2 .[2]

With respect to Carbon Capture technologies, this aspect of the plant has a vibrant process background with multiple innovative processes emerging in recent years. Various carbon capture techniques can be implemented in fossil fuel based plants with three categories identified; post-combustion capture, pre-combustion capture and oxy- fuel combustion. Post-combustion captures carbon dioxide from the flue gas, while pre-combustion captures the carbon dioxide after a syngas stream passes through a Water Gas Shift reactor. Oxy-combustion capture uses oxygen to replace air in combustion, creating a stream of concentrated CO 2 and water. For comparison and innovation, Design 1 utilises a post-combustion capture technology whilst Design 2 integrates an oxy-combustion capture

approach. The most common technique currently used in industry is the Chemical Absorption technique with Monoethanolamine (MEA). As Carbon Capture is a relatively new technology, level of maturity was a considerable aspect when selecting a method.

Historical Developments: The hydrogen production part of the plant is well established as opposed to the carbon capture section which relies on techniques that are still being developed and improved. In recent years various processes have progressed from the laboratory to a pilot plant: Pressure Swing Adsorption of flue gas in Port Arthur by Air Products[3], Membrane separation in the flue gas in Wilsonville by the National Energy Technology Laboratory[4] and finally Chemical Looping Combustion in Germany at the Technical University of Darmstadt.[5]

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Chemical Engineering Design: Projects 4 Amine absorption is also being used in industry at the Boundary Dam project by Saskpower[6]. These ground- breaking projects are key to the development and improvement of Carbon Capture techniques.

Alternative Technologies: For both hydrogen production and carbon capture there are numerous technologies available. Coal gasification is a popular production method of hydrogen when coal is used as a feedstock. Partial Oxidation and Autothermal Reforming are alternatives to SMR with respect to hydrogen production. For carbon capture, there are many alternatives to Chemical Looping Combustion (Design 2) and MEA Absorption (Design 1). Technologies for capturing carbon dioxide include Cryogenic capture, Membranes, Pressure Swing Adsorption and Sorption Enhanced Reaction. Please refer to Process Selection in Section 2 for a full analysis of the different processes feasible for natural gas feed.

Market Studies: The market research undertaken provides important information to identify and analyse the market need, market trends and commodities pricing. It encompasses both qualitative and quantitative information to assess the current situation surrounding hydrogen production and CCS both in the U.K. and worldwide. Furthermore a hypothetical plant location is discussed.

Commodities Pricing Carbon Dioxide: The EU emissions trading system (EU ETS) is currently in practice to combat climate change and effectively reduce greenhouse gas emissions. It is the biggest international trading scheme for greenhouse gas emission allowances and covers power stations, airlines and many more areas of pollution. With a Carbon Capture facility integrated into the process carbon taxing would be avoided and income generated through selling CO 2 emission allowances. Currently the allowance price is EUR 4.85 /tonne CO 2 [7] while the market price for CO 2 ranges between £3.50-13/ tonne depending on logistic costs.[8]

Natural Gas: Natural gas currently sells for £28.5 p/therm, which converts to £160/t, as of March 2016. Natural gas prices have not been this low for twenty years, [9] but due to the market trend discussed on page 4, it is expected for the price to remain at or close to this figure. As a result, £160/t was used for the economic analysis in Section 9. Figure 1-1: Hydrogen Market

Hydrogen:

form of delivery, consumed volume, location and contract length; in the past, prices have ranged from £715 to £3170/tonne [10] in today’s money. The most common (mode) value for hydrogen was found to be $3/kg, which converts to £2250/t H 2 in today’s money. An expected value of £2360/tonne was calculated using Swanson’s Rule (Refer to Appendix C). Please refer to Section 9: Economics for more information.

Supply and Demand Carbon dioxide is heavily valued in many industries, and has a number of purposes; precursor to chemicals, foods, beverages & wine making, inert gas for pressurised systems, agricultural and biological applications, enhanced oil recovery and as a refrigerant.

As the plant is producing significant amounts of carbon dioxide, it is realistic to suggest the carbon dioxide will be sold locally, within the UK via truck. The main area of focus for selling would be the food and drink industry as there are several potential companies to sell to located all over the UK.

Due to the food and drink industry requiring a specific quality of carbon dioxide in their products by law, our product may need to be pre-treated first. Ultimately this would affect the market selling price. If unsuitable for the food and drinks industry applications carbon dioxide can also be piped off-shore for enhanced oil recovery in the oil and gas sector.

Natural gas production has spiked in the past two years due to the dramatic increase of U.S. shale gas extraction. Supply therefore is abundant, with Argentina and China both drilling numerous shale gas wells for a stake in the market. However with growth in China the weakest since the global financial crisis, worldwide demand for natural gas is declining. These global effects will increase the global supply and hence the availability of natural gas in the UK.

Hydrogen market prices show great variation depending on the

Distribution [2]
Distribution [2]

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Chemical Engineering Design: Projects 4 Hydrogen can be utilised in the production of soap in the chemical industry, and can therefore be sold to nearby soap manufacturing businesses such as 'Soapworks' located outside Glasgow. Since the purity of the hydrogen product is specified to be 99.98 %, there is potential to sell to ammonia plants within the UK, such as Billingham plant in Teeside. The demand of hydrogen in the global market can be seen in Figure 1-1.

Market Trends It is expected that natural gas will continue to increase its share of the global energy mix, growing at 2% per year until 2020[11] due to its clean combustion advantage. This increase in supply suggests a future reduction in natural gas purchase price. Consequently, the feedstock expense for the plant would decrease.

World consumption of hydrogen is expected to increase annually by 3.5% through to 2018 to 300 billion cubic metres.[12] The primary reason being the increase of hydrogen usage in refinery hydro-processing in developing countries in Asia. Any surge in demand will increase profitability of the plant, with plant product expansion possible within flexibility limits.

Carbon dioxide is a key component in Enhanced Oil Recovery.

output whilst reducing operating costs, EOR techniques are becoming ever popular with a substantial demand for

CO 2 .

Location The plant must be situated in an area away from local population but close enough for a reliable of supply of feedstock to reach. The National Grid can provide electricity, while transportation links and storage must also be considered. The central belt in Scotland is one candidate for a location for the hydrogen production facility. It is also close to Glasgow where Soapworks could be a potential buyer of the hydrogen product. Similarly, the heavily industrialised area of Teeside in North-East England will also have utility connections available and Billingham ammonia plant is nearby to buy hydrogen.

Necessary Constraints and Implications on Design Options There were a number of constraints imposed on the design; which were limiting factors on design options. The main constraints surrounded the final products, as discussed in Design Brief, on page 1.

The high purity of hydrogen requirement influenced the choice of purification process. Pressure Swing Adsorption (PSA) is selected due to its ability to produce a hydrogen purity of 99.9%. PSA however has the drawback of reduced recovery rates, with 10.4% of hydrogen in Design 1 sent back to the Furnace post-PSA for combustion. This loss of hydrogen will impact the overall efficiency of the plant, and hence affect profitability.

The natural gas feed was specified to contain 5.1 ppm(wt) sulphur. A desulphurisation unit was therefore necessary to remove the sulphur, preventing catalyst poisoning downstream. Two design options were explored in depth for desulphurisation; Iron Oxide/Sulfatreat and Amine Absorption. After comparing preliminary calculations, the Sulfatreat method was selected due to its superior performance. Please refer to Process Selection, Section 2, for a full review of each method.

Carbon dioxide is required to be compressed to 150 bar(a) for transportation needs.

Global Assumptions and Implications on Design Options For simplification and short cut design it was necessary to include some comprehensive assumptions. In terms of feed, we assumed that supply is reliable and stored in a hold up tank on-site. Furthermore, no product storage facilities are included as it is assumed that products are instantly transported to buyers.

With a focus on combustion, both designs assume complete combustion of fuel when providing a heat generation for the endothermic SMR reaction. As a result, the total production of carbon dioxide may be overly optimistic and provide a degree of inaccuracy in the economics. Concerning plant emissions NOx formation, and hence discharge, is assumed to be zero. This assumption is valid regarding thermal NOx formation as the furnace does not operate above 1700K the temperature where significant formation occurs[13]. The assumption also holds for fuel NOx, as neither combustive fuel in design 1 or 2 contains pre-ionized nitrogen.[14] Lastly, NOx formation can occur through molecular nitrogen in the air combining with fuel during combustion. This creation is called Prompt NOx and the amount formed is often debated, but presumed negligible at high temperatures. [14] However, low NOx burners are implemented in Design 1 and accounted for in the process economics. For Chemical Looping Combustion in design 2,

As the Oil and Gas industry seeks to increase oil

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Chemical Engineering Design: Projects 4 one of the advantages surrounds the fact that no NOx form due to the fuel and air streams never directly mixing. Therefore the assumption for short cut design is credible.

In both designs, perfect separation was assumed for each water knock-out drum. In reality this assumption is invalid, however it was deemed acceptable for short cut purposes. The presence of carbonic acids may induce corrosive issues, and so the materials of construction would need to be thoroughly assessed.

The cyclone, C-201, flue gas (stream 21) in Design 2 is assumed to be dispersed to atmosphere (after heat recovery) without incurring dangerous toxicity levels of nitrogen for personnel.

Regarding the sulphur feed specification, it is assumed that H 2 S is the only sulphur based component present in the feed, and therefore the only sulphur based component that requires removal. This focused the research of desulphurisation methods towards H 2 S removal, in preference to COS (carbonyl sulphide), organic sulphur compounds and mercaptans removal.

Design Objectives and Priorities Profitability: The primary economic objective is to design a profitable hydrogen production plant with integrated carbon capture. The economics of Design 1 and 2 are compared to provide an indication of where maximum profitability can be achieved. Heat integration is paramount in order to find the minimum energy requirement in each design, and hence minimise the energy costs. Please refer to Economics, Section 9, for a further information and analysis.

Safety: The main priority is to ensure the plant is safe for personnel to operate within, and for the general public to live around. Careful consideration is given to control schemes and hazardous materials, such as MEA and Nickel Oxide. Please refer to Safety and Hazards, Section 7, for further details. Equipment is designed with safety factors in mind in terms of material of construction, operating conditions and size.

Emissions: Emission limits were sought for the hazardous materials and discharges in the plant. The objective to never exceed these limits - this is achieved except for an uncertainty regarding our MEA emissions. However, an improvement to the process is suggested to reduce MEA emission limits to trace levels. Section 8 details our environmental impact and the Critical Review, Section 10, goes into process modifications in more detail.

Literature Survey (and extended limitations) The sources used to construct these designs were taken from a wide variety of literature for enhanced credibility. Reference was made to scientific journals, reputable news and industry websites, conference papers, textbooks, and Edinburgh University lecture material. The majority of scientific papers sought for design methods and verification were highly peer reviewed, aiding to the reliability of the report.

Due to the nature of this preliminary design and short cut procedures, the designs carry certain limitations which are discussed further in Critical Review, Section 10. However, two designs are presented with justifications and fulfill all pre-requisites and design objectives.

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2 Process Selection

The plant was divided into four main sections: desulphurisation, hydrogen production, carbon capture and hydrogen

purification. For each of these different sections different techniques were considered and compared to each other

in order to choose the best options for the design phase. The evaluation of each of these techniques consisted of an

environmental, safety, economical and maturity analysis which was complimented by a SWOT (strength weaknesses, opportunities and threats) analysis and a scoring system (Appendix F).

2.1

Desulphurisation of the Feed

2.1.1

Initial Considerations

It was decided that a desulphurising unit was required in both designs due to the presence of sulphur in the natural

gas feed (5.1 ppm wt).[15], [16], and [17] suggest that hydrogen sulphide (H 2 S) is usually the most prevalent sulphur

compound present followed by mercaptans and organic sulphur compounds. As the sulphur compound in the feed was never explicitly specified, it was assumed that only hydrogen sulphide (H 2 S) was present. In addition, it was

found from [18] that H 2 S concentrations in the order of 5 ppm poisons the (nickel) catalyst used in the SMR process. While the provided natural gas feed is only slightly above the suggested poisoning concentration, it was decided that

a desulphurising unit would be used to remove the H 2 S completely or down until extremely trace amounts.

Desulphurisation would therefore be the first process in both designs as its goal is to ensure that there is no H 2 S in all

of the downstream processes. In addition, this section of the plant would also treat the fuel gas used in H 2 production.

2.1.2 Options for Desulphurisation of the Feed

Desulphurisation processes are usually split into two distinct categories which are wet or dry based processes. Only a select few desulphurisation processes were considered for use in the plant.

2.2 Wet based processes

Description: The operating principle is that the H 2 S in the feed gas stream will be absorbed using basic solution of

most commonly monoethanolamine (MEA), Diethanolamine (DEA), or hot potassium carbonate. In addition, MEA process derivatives like the Sulfiban process are modern variations of the basic MEA system where a few other chemicals are added to minimise degradation of the amine sorbent. Almost all absorption based desulphurisation processes are scalable with great flexibility toward the concentration of H 2 S in the feed.

Maturity: The basic MEA process was developed in the 1920’s; the Sulfiban process has been commercially used since 1954. As of 1978, around 100 units had been constructed, treating a combined gas volume of 4.7 x 10 7 m 3 per day[19]. In essence, MEA based processes are considered the ‘standard’ way to treat sour gas in the chemical industry.

Technical: The sour feed gas enters the bottom of an absorber while the lean amine solution (often 12-30 wt% MEA) enters the top. The purified product gas leaves the top of the absorber and should be clean enough to continue to the SMR reactor. The sulphur-rich amine solution is pumped to the stripping column where it is heated and reverse chemical reaction occurs, stripping the acid gases into the vapour phase, where they are treated for sulphur recovery. The sulphur-lean amine solution is returned to the absorber.

The reactions occurring in the absorber are as follows:

2

+ → ( )

Eq. 1

( ) + → 2

Eq. 2

Reactions in the stripper are the exact reverse of these. A process flow diagram (figure G-2) can be found in Appendix G.

Environmental: In general, amine based desulphurisation processes release very little to the surroundings due to regeneration of the sorbent. However, MEA, DEA, Caustic Soda or other absorbents are usually highly soluble in water and present a serious threat to aquatic environments. Safe disposal will incur additional taxes due to the ‘active’ nature of the absorbents.

Economic: Regenerative absorbent based processes for desulphurisation like MEA are considered economical for treating high H 2 S concentrations (2% mole fraction+) in the feed. The ability to scale the process with H 2 S

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Chemical Engineering Design: Projects 4 concentration gives it an edge when it comes to treating variable or very sour feed gas streams. However, absorption based processes are not known for use in ultra-purification and may not be the best choice for this plant.

Safety: Amines do cause mild chemical burns if exposed to the skin or ingested. At temperatures above 250 °C MEA can spontaneously combust in self-sufficient exothermic reaction. Pressures are low in the absorber and around 2 bar (g) in the stripper. Temperatures range from around 32 °C in the feed to 115 °C in the stripper. With proper control, it appears that the MEA absorption option is inherently the safest option of the wet processes.

2.3 Dry based processes

Description: Dry based desulphurisation processes are almost always adsorption based and very similar in terms of operation. They only differ in the type adsorbent used. Examples of adsorbents used in dry based desulphurisation methods are iron, zinc or metal oxides, activated carbon and molecular sieves (zeolites). Additionally, modern variants like Sulfatreat (iron oxide) improve on the physical properties of the adsorbent as well as reduce the operating requirements and considerations. References such as[15], [17], [19] and[16] provide a satisfactory range of dry based desulphurization methods but only the iron oxide variant Sulfatreat and zinc oxide method will be discussed here.

Maturity: Sulfatreat takes it roots from the iron oxide desulphurisation process which is a very mature process and has been in use since the 1850s. It was generally one of the more favoured methods for desulphurising low H 2 S concentrations in feed streams but had an inherent safety problem due to its exothermic nature when reacting with air[20] which would ignite the support material (wood). Sulfatreat solves this problem by using non-pyrophoric support material. Similarly, zinc oxide guard beds have been in use throughout the 1900s and is the preferred method for ultra-purification.

Economic: Sulfatreat and Zinc oxide based desulphurisation methods are cheap when compared to MEA or absorptive based processes. However, this is only true for low H 2 S concentrations in the feed. Above a certain threshold (1200 ppm for iron oxide and much lower for zinc oxide[19]), this method of desulphurisation becomes uneconomical due to the large volume of adsorbents required. Additionally, this also means that large variations in the feed H 2 S concentrations will cause problems for these processes.

Technical: Dry based desulphurisation processes all operate on the same principle which is to feed sour gas through a fixed (or fluidised) bed of adsorbent material in a lead/lag design. This means that it is essentially a batch process which continues to sweeten the feed gas until the sulphur loading point is reached and the bed has to either be regenerated or dumped. An example of the iron oxide process with the relevant chemical equations from [20] is provided below.

1 1

() + 3 () →

3

() + ()

Eq. 3

Δ = −22 25° 1 The PFD (figure G-3) in Appendix G represents a typical flow sheet for the iron oxide desulphurisation process but can be applied to almost all other dry based desulphurisation processes. In this two-column design, one column will undergo gas sweetening via adsorption and the other will either be on standby, regenerating or dumped and replaced with fresh adsorbent. In some cases, water is added to saturate the feed stream, which enhances the adsorptive capabilities of the adsorbent (iron oxide). However, zinc oxide based processes must operate dry otherwise the adsorbent material will be ruined.

Environmental: In terms of environmental impact, most dry based desulphurisation processes are material heavy and require change-outs every year or quarter year depending on the estimated breakthrough time. However, the spent adsorbents are usually inert in nature and require no special disposal considerations. For example, spent Sulfatreat is essentially pyrite which is both safe, inert and reusable as supplement material in bricks, roads and sand stabilisers[21]. Zinc oxide on the other hand is not as environmentally friendly and is indeed toxic to aquatic bodies but present no problems otherwise[22].

Safety: Almost all dry based adsorbents are safe to handle and present no safety risk to the staff or the plant. Iron oxide was an example of a fire hazard earlier but the modern variant of it completely solves the problem. Table F-2 shows the SWOT of the Desulphurisation Section; the resulting scoring matrix is in Appendix F, Table F-1.

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2.4 Conclusion

Table 2-1: SWOT of the two proposed Desulphurisation Techniques

Amine absorption or similar wet based processes (Sulfiban process) Dry based desulphurisation processes (Sulfatreat, Zinc

Amine absorption or similar wet based processes (Sulfiban process)

Amine absorption or similar wet based processes (Sulfiban process)

Dry based desulphurisation processes (Sulfatreat, Zinc oxide)

Dry based desulphurisation processes (Sulfatreat, Zinc oxide)

Strengths

Flexibility in

sulphur removal

Good removal efficiency for low H 2 S applications

Good removal efficiency for low H 2 S applications

Weaknesses

May incur large operating and capital expenses that far outweigh low sulphur removal applications

May incur large operating and capital expenses that far outweigh low sulphur removal applications

limited H 2 S concentration operating range with significant waste material footprint

limited H 2 S concentration operating range with significant waste material footprint

Opportunities

Possibility to save on material costs due to regeneration Low release to environment

Possibility to save on material costs due to regeneration Low release to environment

Economical for

current plant

Threats

Additional costs due to tail gas treatment unit to separate H 2 S and CO 2 waste gas stream

Additional costs due to tail gas treatment unit to separate H 2 S and CO 2

Not able to cope with high H 2 S feed streams

Not able to cope with high H 2 S feed streams

Dry based desulphurisation via Sulfatreat (Iron oxide) is our primary choice for desulphurisation as it is able to reliably remove the trace H 2 S concentration in the feed from 5.1 ppm (wt%) down to < 0.1 ppm (wt%) whilst still being very economical when compared to the wet based amine absorption desulphurisation method. The scoring matrix for the proposed desulphurisation techniques are presented in Appendix F, Table F-2.

2.5 Hydrogen Production

There are three main processes used for producing H 2 from natural gas.

2.5.1 Steam Methane Reforming (SMR)

Description: Steam methane reforming is a traditional method used to convert natural gas to syngas, it requires an external heat source due to the endothermic reactions that occur. This method for producing reformate can therefore only achieve its potential when effective heat integration in the plant can be conducted. Subsequently, in what is called the "water-gas shift reaction," the carbon monoxide are converted to carbon dioxide and increasing the concentration of hydrogen at the same time. Finally, a process step called "pressure-swing adsorption” (PSA) is used, which will be covered in a later section. [23-26]

Maturity: SMR has been around for more than 80 years. It was first introduced in 1930 and has been the leading method for producing hydrogen at large scale. Examples of SMR plant would be the one located in Texas from Linde with a capacity of 10 tonnes/hr and Air product have major hydrogen pipelines in places such as Lousiana USA and Rotterdam in the Nether. [2, 24, 27]

Technical: In steam-methane reforming, methane reacts with steam (700 °C -1000 °C) under high pressure in the presence of a nickel catalyst to produce hydrogen, carbon monoxide, and a relatively small amount of carbon dioxide. The main processes involved are[28]:

: + + 3

Eq. 4

: + +

Eq. 5

Safety: Safety hazard of dealing with flammable gases like methane and hydrogen under a high temperature is considerable, however with the maturity of this production method, appropriate control techniques and procedures exist.

Economic: The cost of conventional steam reforming catalysts is relatively low although they tend to be vulnerable to the sulphur-based catalyst poisons. According to a survey conducted by Petroleum energy centre in 1999 [29] SMR has the highest relative cost out of the three technologies, it was used as a based case and has been given 100 as the value.[30]

2.5.2 Partial Oxidation (Pox)

Description: In partial oxidation, hydrocarbons in natural gas react with a rich air-fuel ratio. The reaction products contain primarily hydrogen and carbon monoxide (and nitrogen, if the reaction is carried out with air rather than pure oxygen), and a relatively small amount of carbon dioxide and other compounds. Subsequently, in a water-gas shift reaction, the carbon monoxide are converted to carbon dioxide and increasing the concentration of hydrogen at the same time.[25, 26]

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Chemical Engineering Design: Projects 4 Maturity: Partial oxidation is a relatively new process compared to SMR. It has been around for about 30 years, an example plant in industrial scale would be the located one in Texas by Eastman Group. [31]

Technical: Methane reacts with air (1000 °C - 1400 °C) under 125 bar pressure in the presence of a microlith-based catalyst to produce hydrogen and carbon monoxide. It is an exothermic process and is typically much faster than steam reforming and requires a smaller reactor vessel. As seen in the reaction equations below, the process initially produces less hydrogen per unit of the input fuel than that of steam reforming.[28] [32]

The main processes involved equation 5 and 6 [28, 32]:

+

1

2

+ 2

Eq. 6

Safety: The control of the oxygen/air flowrate must be strictly accurate, otherwise the reaction instead of being

partial oxidation, will become complete combustion, the volume of the end products are much larger than the original expected ones, the gas expansion could lead to an explosion of the reactor in the worst case scenario.

Economic: According to a survey conducted by Petroleum energy centre in 1999 [29] Pox is slightly cheaper in terms of relative cost compared to SMR, it was given a value of 95 compared to 100 given to SMR. This can be interpreted as 5% cheaper than the SMR method. However it was stated in the Petroleum energy centre in 1999 [29] that the economy evaluated for Pox is just an estimation. [30]

2.5.3 Autothermal Reforming (ATR)

Description: ATR combines the exothermic nature of partial oxidation and the endothermic steam reforming reaction to balance the heat requirements, giving an advantage of a thermally neutral system, while providing reasonable hydrogen yield. The reactor tends to be relatively moderate in cost and size. Reactions occur over steam reforming catalysts located in close proximity to the partial oxidation catalysts. The quality of the ATR reformate, defined in terms of hydrogen mole fraction, is thus superior to the CPO X reformate but not as good as the SMR reformate. [26, 33]

Maturity: ATR is a relatively new technology and is still under continuous development. There are only a few example plants; one of them would be the plant located in South Africa by SASOL. [33]

Technical: In Autothermal Reforming, methane reacts with steam (1000-1400 °C) under 125 bar pressure in the presence of either nickel or microlith-based catalyst to produce hydrogen and carbon monoxide.[28]

The main process involved is [28]:

+ (1 − ) + + (3 − )

2

ℎ 0 < < 1

Eq. 7

Safety: On the downside, a more extensive control system is needed for ATRs to ensure a safe and robust operation of the fuel processing system.

Economic: According to a survey conducted by Petroleum energy centre in 1999 [29] ATR was given a value of ranging from 85 - 95 compared to 100 given to SMR. This can be interpreted as 5 - 15% cheaper than the SMR method. [30]

2.5.4 Conclusion

Table 2-2: SWOT for Hydrogen production techniques

 

Strengths

Weaknesses

Opportunities

Threats

SMR

High level of maturity High purity of hydrogen

Require external heat from the furnace

Most conventional method: reliable

Many recent developments on newer technologies

CPOx

An exothermic process

Relatively new process

Mainly used for smaller scale (less than 1 tonne/h of H 2 )

Very limited information

ATR

Thermally neutral system

Very precise control system to integrate the process heat

More suitable for very large scale (greater than 20 tonne/h of H 2 )

Very limited information

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Chemical Engineering Design: Projects 4 SMR is our primary choice for hydrogen production as it achieves the highest yield of H 2 and it is the most mature and leading technology in producing large scale of hydrogen. The scoring matrix for the proposed hydrogen

production techniques are in Appendix F, Table F-3.[34]

2.6 Carbon Capture (CC)

In a Hydrogen Production Plant, there are various streams that contain CO 2 . The figure G-1 in Appendix F indicates a simplified block flow diagram of the Hydrogen Production Plant in which the streams containing a significant amount of CO 2 are identified. It can be seen that CC systems can be located in three different places. From a first look CC at position 3 seems the best option as CO 2 from the hydrogen production line and from combustion could be captured while CC at position 1 and 2 do not enable the capture of CO 2 formed during the combustion process. However, the pressure in stream 3 is lower therefore the volume and equipment will be bigger. There are various CC techniques at various stages of maturity. The main techniques that were considered in this project are as follows: (1) Pressure or

Vacuum Swing Adsorption (P/VSA), (2) Chemical Absorption, (3) Membrane Reactors, (4) Sorption Enhanced Reaction Process (SERP), (5) Chemical Looping (CL) and (6) Cryogenic Capture.

2.6.1 Pressure/Vacuum Swing Adsorption

Description: This technology is based on the physical binding of gas molecules onto an adsorbent. The process operates at relatively constant temperatures and relies on alternating pressure to perform adsorption and desorption. It is estimated that high purity CO 2 (97%) could be obtained using PSA at position 3 and that the CO 2 emissions can be reduced by 90%[35].

Maturity: P/VSA has been used for many years for hydrogen purification. However, the application of P/VSA for CC is still being tested. Indeed, in Port Arthur a VSA project by Air Products is in operation since 2013[3] to test the application of VSA for CC in position 3 of figure 7. The project consists of a large scale DEMO that eventually will capture one million tons of CO 2 annually. This CO 2 would then be purified to 97%[3]. The project cost $431million[3]. In 2015, VPSA post-combustion carbon capture reached a Technology readiness level of 5[36].

Technical: this CC technique would come at an efficiency penalty of 15% for an IGCC[37]. Zeolites are the most common adsorbents. In order to provide a continuous supply of CO 2 , a minimum of four adsorption vessels are

required[38].

Environmental/Safety: Zeolites are safe adsorbents. They do not have flammable or explosive properties[39]. In addition to that they are not considered to be toxic, carcinogenic or irritating to the skin and no accumulation in organism is to be expected[39]. If the adsorbent is ingested or inhaled repeatedly or in high doses the substance may cause kidney damage[39].

Economic: In recent studies, the capital cost of the PSA CC was estimated to be 800 10 3 US$/MW[36] and the fixed O&M was estimated to be 23.41 10 3 US$/MW[40].

2.6.2 Chemical Absorption

Description: CO 2 is separated from the flue gas by passing the flue gas through a continuous scrubbing system. This system is composed of an absorber and a desorber. The absorption process is based on the reversible chemical reaction of CO 2

with an aqueous alkaline solvent, usually an amine. In the desorber, CO 2 is stripped from the alkaline solution and the regenerated solvent is sent back to the absorber.[41]

Maturity: Chemical absorption systems have been in use since the 1930s for the capture of CO 2 from

e c a p t u r e o f C O 2 f r o

Figure 2-1: Process flow diagram for chemical absorption[42]

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ammonia plants and hence, are a commercially realized technology in various sectors (power plants, food

industry,

SaskPower[6].

Technical: MEA can reduce CO 2 emissions by 75% at an efficiency penalty of 11%[37].

Safety: MEA can cause burns to the eyes and skin. It is also harmful if inhaled, swallowed or absorbed through the skin. It can cause lung damage if aspirated, and repeated exposure may cause liver and kidney damage. MEA is highly corrosive. [43] Contact with iron or steel MEA can form an unstable crystalline complex: tris(ethanolamino)-iron. This compound can ignite when heated to 5471°C in the presence of air[43]. Due to its water solubility and reactivity with other compounds, MEA biodegrades rapidly and is not likely to bioaccumulate in the aquatic food chain. Studies on a wide variety of freshwater fish show that MEA has very low toxicity to fish. [43] MEA exhibits good temperature stability. Nevertheless, at temperatures above 250°C, it can undergo a self-sustaining exothermic reaction, causing rapid decomposition. [43]

This technology has been used in the first CC project for power plants: Boundary Dam project by

)[41].

Economic: Studies have been conducted using Aspen to predict how post-combustion carbon capture would affect the operation of a natural gas powered power plant. A natural gas flowrate of 167.3 Ib/hr was used as a basis and a 90% carbon capture requirement was set. The efficiency drops from 50.2% to 42.2%. The total as spent capital cost increases from 771$/kW to 1637$/kW. The cost of electricity also increases from 58.9$/kWh to 87.2$/kWh. The first year CO 2 avoided cost is 87.3$/tonne. [44, 45]. MEA has also been tested in industry and recent studies estimated that the capital cost of MEA was 613 10 3 US$/MW while the fixed O&M was estimated to be 24.52 10 3 US$/MW[37].

2.6.3 Membrane Reactors

Description: Membrane reactors combine reaction with separation to increase conversion. One of the products of a given reaction is removed from the reactor through the membrane, which shifts the equilibrium of the reaction to the products (according to Le Chatelier's Principle).

Maturity: More research needs to be conducted to enable the production of a membrane that combines a thin layer, high flux, and stability in all operating conditions. Membrane materials other than Palladium could provide an inexpensive alternative and could be explored.

Environmental/Safety: Palladium has no adverse effects on humans. In terms of the environment, palladium metal has relatively low toxicity. It is however harmful to some plants in salt form.

Economic: Higher CO conversions are attainable with lower temperatures, meaning potential gains can be made with prolonged catalyst life, enabling lower production and material costs. Furthermore, the simultaneous CO2 capture and generation of extra pure H 2 , eliminates traditional WGS reactors and PSA. However, the expensive nature of Palladium could be of concern. The incremental total capital requirement (TCR) for capture was estimated to be 334US$/kW and the incremental Cost of Electricity (COE) was estimated to be 9.0US$/MWh[46].

2.6.4 Sorption Enhanced Reaction Process

Description: This technique involves combining CC with the Steam Methane Reforming (SMR) process. During the reforming CO 2 is adsorbed onto a sorbent which is generally calcium oxide following the following reaction.

+

Eq. 8

The CO 2 can then be desorbed in-situ using pressure swing adsorption leading to solvent regeneration and pure CO 2 capture. By removing one of the products of the reforming process, the equilibrium is shifted to the product side, which leads to an increased production of hydrogen. Also, reformation takes place at a significantly lower temperature (300-500°C) than conventional SMR process (800-1000°C) while achieving the same conversion of methane to hydrogen. There is a minimization of side reactions such as coking. Therefore, hydrogen is produced at relatively high purity directly from the reactor.

Maturity: The concept of a combined reaction and separation in hydrogen production is not new. Indeed, Rostrup- Nielsen reports that the first description of addition of a CO 2 -acceptor to a hydrocarbon steam reforming reactor was published in 1868 (by Tessiedu Motay and Marechal). More recently, the SEPR and the use of calcium-based CO 2 sorbents has been demonstrated and intensively studied by a group at Louisiana State University (USA).

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Chemical Engineering Design: Projects 4 Environmental/Safety: Calcium Oxide is not combustible but contact with water or moisture may generate sufficient heat to ignite combustible materials. It is also not considered to be an explosion risk. However, it is toxic and when inhaled it can severely irritate the upper respiratory tract and ulceration and perforation of the nasal septum may occur from extended exposure. As a corrosive substance, when ingested it may attack the oesophagus resulting in abdominal pain, nausea and vomiting and it may cause serious alkali burns in the mouth and throat. It is also a skin irritant and it may damage eye tissues causing redness, tearing, blurred vision and pain. In addition to that, it is toxic to aquatic life.

Economic: Initially it seems the cost would be reduced, as there is no need for WGS reactors. However, a study estimated that by including a sorption enhanced water gas shift in a hydrogen production and power plant in order to capture 96% of the CO 2 led to an additional cost of 75.9€/t CO 2 . [47] The incremental total capital requirement (TCR) for capture was estimated to be 365US$/kW and the incremental Cost of Electricity (COE) was estimated to be 11.2 US$/MWh[46].

2.6.5 Chemical Looping

Description: Chemical looping can be included in a hydrogen production plant in two different ways: Chemical Looping Combustion and Chemical Looping Steam Reforming. The Chemical Looping Combustion process is similar to conventional steam reforming but the furnace is replaced with a CLC system. This is an indirect combustion system that avoids the direct contact of fuel with the oxidant. The system is split into two reactors: a reduction reactor (fuel reactor) and an oxidation reactor (air reactor). The oxygen is brought to the fuel via a solid carrier constituted of a metal oxide material. In the fuel reactor the fuel reduces the solid oxide material. It is then transported to the air reactor where the reduced metal oxide is oxidized again with air. Also, CL can be included in the steam methane reforming process. It can produce highly concentrated H 2 and CO 2 as the reaction products. The CL-SMR system consists of fuel reactor (FR) for CH 4 oxidation and steam reactor (SR) for steam reduction, where oxygen carriers (metal oxides) circulate between the two reactors. Chemical

Looping reactors are fluidised beds.

two reactors. Chemical Looping reactors are fluidised beds. Figure 2-2: Process flow diagram of CLC[48] Maturity:

Figure 2-2: Process flow diagram of

CLC[48]

Maturity: Chemical looping combustion (CLC) dates from the early 1980’s when it was proposed as a system for augmenting power station efficiency[49]. A number of CL concepts are being researched around the globe to test the system design and to estimate capital and operating costs for commercial-scale systems. Currently, NETL supports several CL projects in collaboration with industry, academia, and NETL’s Office of Research and Development (ORD) ranging from lab and bench scale testing to evaluation of pilot-scale prototypes. [50, 51] Nowadays, Chemical looping for oxy-combustion has reached a TRL of 6 as it has been demonstrated at 1MW th pilot plant using hard coal and ilmenite as oxygen carrier where the total time of operational experience exceeds 7000h[36]. Presently, more than a thousand materials have been tested in the laboratory. Also, from testing, it was established that >99% conversion of the fuel can be obtained and that 100% CO 2 capture is possible using gaseous fuels[36]. Chemical looping reforming however has been tested in a pilot plant.

Environmental/Safety: There should be no formation of thermal NOx since the regeneration of the carrier is achieved at moderate temperatures. The exit streams are relatively clean. The exit stream of the fuel reactor is mainly composed of water and CO 2 while the exit stream from the air reactor is mainly composed of nitrogen and oxygen. Most metal oxides are toxic to aquatic life. Dust is irritating to the eyes, skin and respiratory system. Eye contact may cause corneal damage. In addition it may cause dermatitis.

Economic: A study estimated that by including CLC in a hydrogen production and power plant in order to capture 93.5% of the CO2 led to an additional cost of 81.5€/t CO 2 . [47] The incremental total capital requirement (TCR) for capture was estimated to be 413US$/kW and the incremental Cost of Electricity (COE) was estimated to be 13.1

US$/MWh[46].

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2.6.6 Cryogenic Capture

Description: CCC (Cryogenic Carbon Capture) uses phase change to separate CO 2 and other pollutants from exhaust or process gases. In CCC the CO 2 is cooled to such a low temperature (about -140 °C) that it desublimates - changes from a gas to a solid. The solid CO 2 is separated from the remaining gas, pressurized, melted, and delivered at pipeline pressure. Cryogenic Carbon Capture (CCC) is a post-combustion technology that has the potential to reduce carbon emissions from fossil-fuelled power plants by 9599%, at half the cost and energy of current state-of-the-art carbon capture processes. In addition, CCC also removes other pollutants, such as SOX, NOX, and mercury. [52]

Maturity: Cryogenic separation is widely used commercially for high CO2 concentration streams - typically above 90% - but it is not used for more dilute streams.

Environmental/Safety: The heat integration aspect provides a certain amount of safety as no external heat sources are required. This also improves the environmental aspect as no energy is wasted for heating purposes.

Economic: Cryogenic carbon capture is estimated to cost less than $30 per ton of captured CO2, this could make cryogenic capture a favourable option. Water may have to be removed before the gas stream is cooled to avoid

For dilute streams the energy associated with cooling can increase operating

blockages, incurring further costs. costs. [52]

operating blockages, incurring further costs. costs. [52] Figure 2-3: Process flow diagram of cryogenic CC[53] 2.6.7

Figure 2-3: Process flow diagram of cryogenic CC[53]

2.6.7 Conclusion

Table 2-3: SWOT analysis for Carbon Capture techniques

 

Strengths

Weaknesses

Opportunities

Threats

PSA

Safe adsorbent

Low maturity

High purity CO 2

High cost

MEA

Low temperatures and pressures

Corrosive

Small flexibility in flue gas composition

Energy intensive

SERP

Low temperatures

Harmful sorbent

Sorbent regeneration No water-gas shift Higher purity H 2 Higher conversion

Not mature enough

CLC

No formation of thermal NOx

Harmful sorbent

Carrier can be regenerated Less harmful exit stream

Durability

Membranes

High SMR conversions

Surface poisoning

Increased H 2 production

Durability

Cryogenic

Energy efficient

Removal of water - additional step

Reduced cost

Not mature enough

GROUP 1 The University of Edinburgh School Of Engineering Volume 1 Chemical Engineering Design: Projects 4 Even though cryogenic capture, chemical looping reforming and Sorption enhanced reaction process seem like very promising technique they were not chosen as the maturity level is very low which would impact the reliability of the design. Amine absorption was on the other hand chosen because it has been tested in industry. Out of the remaining techniques PSA and CL, CLC seemed to me more promising from an economical viewpoint. Membranes were also chosen as it can lead to higher conversions of methane.

2.7 Hydrogen Purification

Many hydrogen plants that were designed and built 20 or more years ago rely on a hot potassium carbonate or MEA chemical absorber (as explained in section 1.3.2) to remove CO2 and a methanator to convert the remaining CO 2 and

CO to methane and water. Methanation is the catalytic hydrogenation of CO 2 to methane also called the Sabatier

reaction[54]:

+ 4 + 2 = −252.9/

Eq. 9

The final product however only achieves a purity of 95-97%[55]. This purity does not satisfy the product requirements for this plant, therefore this option was not considered in further detail. More recently hydrogen plants rely on a PSA unit (as explained in section 1.3.1) to purify the reactor effluent. The use of PSA enables a 99.9% product purity[55]. The off-stream of the PSA can be used as a fuel source to supply the required energy to the SMR.

2.8 Overall process selection conclusion

The two final proposed designs are summarised in table 2-4. Sulfatreat was chosen as the feed natural gas desulphurisation technique for both designs due to it being very economical for treating low quantities of sulphur in

the feed; additionally the bed is safe to dispose and poses little risk to the environment. For design 1, the more traditional design, it was decided to go with the more mature technologies of conventional SMR with Amine Absorption Carbon Capture of the flue gases, whereas design 2 utilises the more modern technology of membrane SMR with integrated Chemical Looping Combustion to capture the CO 2 . Finally, design 1 utilises pressure-swing adsorption to purify the hydrogen to product specification, whilst in Design 2 a simple two-phase separator is used to purify the hydrogen from water.

Table 2-4: Proposed Designs

 

Design 1

Design 2

Desulphurisation

Sulfatreat

Sulfatreat

Reaction

SMR

Membrane SMR

CC

MEA

CLC

H 2 purification

PSA

Water knock-out

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3 Process Flow Diagram and Process Description for Design 1

3.1 Process flow diagram for Design 1

Process Description for Design 1 3.1 Process flow diagram for Design 1 Figure 3-1: Process Flow

Figure 3-1: Process Flow Diagram for Design 1

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3.2

Design 1

3.2.1

Process Description

Desulphurisation: The natural gas feed (stream 1) enters the plant at 33 bar(a) and ambient conditions.

functions as a back-up compressor in case the inlet feed is at a lower than expected pressure (maximum 9% deviation to feed pressure). Stream 1a is then heated in E-101 to 30 o C, as slightly elevated temperatures enhance the adsorption process. To further enhance adsorption, stream 1b can be water saturated via stream U1 but this is dependent on the adsorbent employed. Stream 2 then enters the desulphurisation section, which is comprised of two adsorption columns, T-101 A/B, each filled with an iron oxide (Sulfatreat) bed. The desulphurisation columns operate at 30 o C and 33 bar(a). While one column is operational, the second column is emptied. This process achieves total sulphur removal so as to avoid catalyst poisoning downstream. The adsorbed sulphur and spent bed (stream U2) are sent to landfill.

P-101

Pre-reformer: The desulphurisation outlet (stream 3) splits into two streams: stream 4 and stream U6. U6 is sent to the furnace through compressor P-201 for subsequent combustion. Stream 4 is sent through the furnace and is additionally heated through E-204 to 400 o C. Make-up steam (stream U3) combines with stream 4 to achieve the required 0.3 steam to carbon ratio in stream 5. Stream 5a then enters the pre-reformer, R-201.

In the pre-reformer cracking occurs when the stream reacts with a bed of nickel catalyst on an aluminium oxide support. This reduces all of the higher hydrocarbons down to methane. Due to side reactions, partial conversion of methane to hydrogen occurs. All reactions are exothermic and the temperature of the outlet stream (stream 6) reaches 415 o C. The pre-reformer operates at 400 o C and 32.9 bar(a).

SMR: Stream 6 mixes with a further steam input, utility stream U4 to increase the steam to carbon ratio. Stream U4 flowrate is three times as large as the flowrate of methane in stream 6 in order to reach this ratio. The combined stream (stream 7) is heated to 950 o C in the furnace, E-204. Afterwards stream 7a flows through the SMR tubes in reactor R-202, located in the radiant section of E-204.

The SMR reactor, operating at 30 bar(a) and 950 o C, is composed of multiple parallel tubes containing a nickel alumina catalyst. This environment causes the methane to react with steam, producing hydrogen and carbon

monoxide. A side reaction occurs between the steam and the carbon monoxide to produce carbon dioxide and hydrogen. The net heat of reaction is endothermic (H r,298K = 206.kJ/mol). The outlet of R-202 (stream 8) is cooled in E-

201 to 450 o C before entering the high temperature WGS, R-203.

WGS: In the high temperature WGS, R-203, carbon monoxide reacts with steam to produce the two desired products hydrogen and carbon dioxide. This reaction is exothermic (H r,298K =-41.2kJ/mol), with the reactor operating at 30 bar(a) and 450°C. Following on from this, stream 9 is cooled to 250 o C in E-202 before entering the low temperature WGS, R-204. The same exothermic reaction occurs only at this lower temperature and over a different catalyst (copper/zinc based). The outlet of the low temperature WGS (stream 10) is cooled in E-203 to condense and hence remove the water. Stream 10 then enters vessel V-202 where the water (stream U5) separates. The vapour products including H2, CO, CO2 and N2, (stream 11) is sent to the Pressure Swing Adsorption unit.

PSA: Pressure Swing Adsorption involves a number of columns, operating at various pressure stages to produce high purity (99.9%) hydrogen. The designed PSA unit cycle schedule contains several steps; Feed (F), Equalisation 1 (EQ1), Equalisation 2 (EQ2), Equalisation 3 (EQ3), Purge Preparation (PP), Blowdown (BD), Purge (PU) and Feed Recovery (FR). There are also corresponding Equalisation Receiving steps, (EQR1, EQR2 and EQR3). For simplification stream 11 is assumed to be a binary mixture of CO2 (20%) and H2 (80%) in design methods.

Operation of the PSA unit starts with an explanation of the cycle schedule for a single column (T-306) from start to end. Starting with the feed step, the binary gas mixture is passed through T-306 at 30°C and 25 bar(a). Hydrogen is the least likely to be adsorbed and so passes through to the outlet at (>99.99%) purity via stream 12 while the 20%

mixture of CO 2 , N 2 and hydrocarbons are adsorbed onto the activated carbon/zeolite adsorbents. After the feed step (250 seconds est.), T-306 undergoes pressure equalization with T-304, followed by T-303 and T-302 to save on re- pressurising the vessel upon purging. After that, T-306 undergoes purge preparation with T-301, which is a similar step to pressure equalisation but with T-301 undergoing purge. Blowdown then proceeds which sends the now CO 2 , N 2 and hydrocarbons rich stream along with some of the unrecovered H 2 to the furnace via stream 13. After that, T-

301 now undergoes purge which also sends the off-gas to the furnace followed by receiving equalisation and finally

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Chemical Engineering Design: Projects 4 re-pressurisation by feed. The cycle then starts again from the feed step. As the cycle schedule for a single column is now known, the other columns T-302 through T-306 will undergo similar steps in a sequence defined by the PSA

cycle schedule table which is presented in Section 6: Thermochemistry, Table 6-5.

Furnace: From the PSA unit, stream 13 is combined with air utility streams; U6 and U7. U6 provides a 1.1 air to fuel ratio entering the furnace, E-204, undergoing combustion. The furnace provides the necessary heat for the SMR reaction, and to pre-heat streams 4 (pre-reformer inlet) and 7 (SMR inlet) convectively. The flue gas (stream 16) is then cooled to 40 o C through E-401 and stream 16a then enters the MEA unit. The furnace operates at ambient pressure and 950 o C, producing 119MW of power.

Monoethanolamine (MEA) Absorption: Flue gas, stream 16, is cooled in E-401 to 40 o C before entering water knock- out drum V-401 to remove the condensed water. The vapour outlet, stream 17, is then compressed to 3.1 bar(a) to promote the transfer of mass from the vapour phase into the liquid phase. It is assumed pressurising to 3.1 bar(a) creates a pressure drop sufficient enough to propel the outlet gases up through the absorber to the stack. The gas is then cooled again to the optimum temperature for absorption, 40 °C, while further condensed water is removed by knock-out drum V-402. The vapour outlet (stream 18) containing N2, CO2, water vapour and excess O2, is then fed into the bottom of the trayed absorption unit, T-401, for absorption of CO 2 using MEA into the liquid phase.

An exothermic chemical reaction occurs in T-401, which binds the MEA and CO 2 together into the liquid phase with the water. The liquid outlet (stream 19) is called the rich amine since there is a high molar loading of CO 2 per mole of MEA in the solution. The rich amine is heated by E-404 to 70 °C prior to entering the stripping column, T-402.

The stripping column attains high recovery rates of CO 2 into the vapour phase. The reaction is endothermic and so heat is provided by reboiler E-403, heating the column to 120 °C. The liquid outlet from the reboiler (stream 24) contains very little CO 2 and therefore is called the lean amine stream. This is combined with the MEA-water recycle stream R6 (itself a combination of two water-MEA recycles R1a and R2) to form an aqueous solution which is slightly under 30 wt% MEA. This is then pumped into surge drum V-403 to allow for a constant lean amine flowrate to enter the top of the absorber T-401 as stream 25c. Thus ends the amine circulation at steady state, any MEA lost out the top of the absorber is recovered in MEA-water recycle stream R3, and likewise before CO 2 compression in recycle stream R4. It is assumed for simplicity of the design that MEA does not degrade over time.

CO 2 Compression: The vapour outlet of the reflux drum (stream 28) is cooled to ambient conditions in order to condense out MEA and water for separation in V-501, leaving 99.98% pure CO 2 with 0.02 % Nitrogen (stream 29). It must be noted that this assumption of 100 % separation of liquid water from gaseous CO 2 was a design simplification which significantly reduces the amount and cost of separation equipment. This high-purity CO 2 stream is compressed in a series of three centrifugal compressors, P-501, P-502 and P-503. Intercoolers E-503, E-504 and E-505 reduce the temperature of the CO 2 to 25 °C before each subsequent compression. After the final stage of compression and cooling, the CO 2 by-product is at 70 bar(a) and 25 °C which means it is in liquid state. It is then routed to hold-up tank V-502 before being pumped to 150 bar(a), ready for distribution and sale.

3.2.2 Process Control

Desulphurisation: Control is paramount on the desulphurisation unit to prevent sulphurous feed entering the process downstream and damaging catalysts. Should breakthrough point be close, the composition control (CC- 103/105) sends a signal to send the remaining gas into the standby column (T-101B). Temperature indicators (TI- 104/106) are also placed on the columns across stream 2 linked to E-101 to ensure feed is at 30 °C. Pressure indicator (PI-109) ensures downstream pressure requirements are met by linking to back up compressor P-101. A sample point has been provided to ensure sufficient sulphur removal has occurred. Pressure safety valves to flare

prevent the column from over-pressurization.

Pre-reformer: A pressure relief valve to be used in the case of an emergency is situated on the pre-reformer. Multiple temperature indicators (represented by TI-204) along the side of the reactor at regular intervals measure temperature changes and indicate the completion of the reaction.

SMR: A high-high temperature level alarm and trip system is attached to the SMR (not shown on PFD) to stop fuel flowing into the furnace and generating more heat. The SMR outlet temperature is controlled through TIC-208 which regulates the fuel inlet stream. Composition control (CIC-218) attaches to a steam make-up utility stream to ensure the optimum ratio enters the furnace.

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Chemical Engineering Design: Projects 4 WGS: A high-high temperature level alarm and trip system (not shown on PFD) activates a cooling jacket on both HWGS (R-203) and LWGS (R-204).

PSA: Composition indicator CIC-310 changes the step cycle times, with composition control usually being a PI controller or variant. Differential pressure indicators are linked to the CIC for the pressure equalization step. Pressure indicator PI-303 in the feed must show 25 bar pressure as inlet pressure has to be kept high to ensure higher partial pressure of adsorbate. Temperature indicators must show a bed temperature around 30C to ensure high levels of adsorption. Flow valves are located at feed inlet for protection in case of composition control failure. A pressure safety valve fitted to the vessels transport vapour to flare due to avoid a potential H 2 rich release.

Furnace: A composition indictor controller, CIC-218, is placed on stream 14 to measure the composition of hydrocarbons in the fuel gas line. Air utility stream U3 is then adjusted accordingly to ensure complete combustion in the furnace. A temperature indicator, TI-301, is fixed at the end of the convection section of the furnace to monitor the flue gas temperature. Fuel input should be reduced if the temperature is too high. Sample point, SP- 219, is located at the furnace outlet (stream 15). Analysis is then carried out to check for concentrations of carbon monoxide, hydrocarbons and carbon. Presence of these components indicates incomplete combustion and that more air is needed.

Monoethanolamine (MEA) Absorption: For the stripping column, T-402, temperature indicator TIC-404 is placed on the outlet reboiler stream to ensure the column will not exceed 125°C. The temperature for the reboiler is set to be 120°C so that there is a safety margin for operation fluctuations. Temperature control reduces MEA thermal degradation and the generation of other undesired corrosive products.

For the absorption column, T-401, composition control (CI-408) of the CO 2 flowing to the stack is controlled by manipulation of the lean amine inlet (stream 25c). The flowrate of flue gas from the furnace (stream 18) must be measured since it will likely fluctuate. The flowrate of the lean amine (stream 25c) will therefore be manipulated to allow for both the changing flowrate of the furnace gas and also the composition of CO 2 emitted above the absorber. Temperature of absorber gas inlet (stream 18) is maintained at 40 °C by manipulating the flowrate of coolant to E- 402. The level of lean amine solution in surge drum V-403 must be maintained at a safe level by manipulation of the flowrate of stream 25a into the drum. High and low level trips are installed (not shown on PFD) on surge drum V-403 to help prevent the surge drum from filling or running dry.

CO 2 Compression: Level control is achieved in liquid CO 2 hold-up tank V-502 by manipulating the inlet flowrate of stream 29f. Temperature control is incorporated on all heat exchanger outlets by manipulating the flowrate of coolant to the relevant heat exchanger.

3.2.3 Heat Integration Design 1

Figure A-3 in Appendix A summarizes the suggested heat exchanger network with data support from Table 3-1 for design 1. Following this, it was evident that there was no pinch temperature in design 1 due to the very large amounts of cooling required with not enough complementing process streams to use the heat. HINT calculated the pinch temperature to be 1290 [K] (no pinch) with 189 [MW] of cooling utility required using a minimum temperature difference of 10 [K]. The actual cooling required will be greater (~250 [MW]) since not all hot streams were taken into account even though all cold streams were tabulated. The most likely cause for this “no pinch” case is due to an overdesigned furnace. Currently, the furnace pre-heats two important energy intensive streams which are the pre- reformer and SMR pre-heating streams. Each of these streams require ~30 MW of energy each in order to preheat. Therefore, by reducing the size of the furnace and allocating these streams to the HEN, the amount of heating utility may be reduced and a pinch can be obtained.

However, the current unaltered design more than manages to meet the heating energy required which means that no additional hot utility will need to be purchased other than for start-up purposes. To ease reading, Table 3-1 is provided below to walk the reader through streams in the HEN. Finally, it is important to note that E-6XX series heat exchangers (required for full heat integration) were not shown on the PFD so as to keep it concise but will mean that additional heat exchangers will be designed specifically for process heating. Where possible, PFD heat exchangers were included and directly referenced.

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Volume 1

Stream

 

Stream description

 

Description

9-9a

Cooling of the gas stream after high temperature water gas shift reactor

Used to heat utility stream U4 (liquid) then cooled via E-202

8-8a

Cooling of the gas stream after main SMR reactor

Used to heat utility stream U4 during its phase change then cooled via E-201

16-16a

Cooling of the post furnace flue gas stream and condensing the water present

Used to superheat U4 to 688 [K] then fully superheat U3 from liquid to 673 [K] and finally cooled using E-401

17a-17b

Cooling and condensing the water present following compression via P-401

Used to heat E-403 utility until it becomes a saturated vapour at 406.5 [K] before being cooled by E-402

 

Cooling

of

the

compressed

CO 2

product

Used to supply heat to the natural gas feed so that it can enter the desulphurization section at 303 [K] before being cooled by E-

505

29e-29f

stream

before

condensing

at

its

critical

temperature

 

1a-1b

gas desulphurization section at 303 [K]

Natural

feed

that

enters

the

Heated completely using 29e-29f

 

Reboiler

water

that

is

pre-heated

to

 

E-403 Utility

saturated

steam

before

entering

E-403

Heated completely using 17a-17b

(reboiler)

U4

Make up steam that is required for SMR reaction

Heated completely using streams 9-9a, 8-8a and 16-16a before being sent to the furnace for further heating

U3

Make up steam that is required for the pre- reformer

Heated completely using stream 16-16a before being sent to the pre-reformer

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4 Process Flow Diagram and Process Description for Design 2

4.1 Process flow diagram for Design 2

Process Description for Design 2 4.1 Process flow diagram for Design 2 Figure 4-1: Process Flow

Figure 4-1: Process Flow diagram for design 2

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4.2

Design 2

4.2.1

Process Description

The desulphurisation

product (stream 3) is split into U5 and 4, to be a source of fuel for CLC and pre-reforming respectively.

Pre-reformer: Stream 4 is heated to 400 °C by E-201 and is injected with steam to achieve the require 0.3 steam to carbon ratio in the pre-reformer. The flow enters the pre-reformer, operating at 415 °C and 30bar(a), to begins the cracking process. The reactions and conditions within pre-reforming for this design are the same as those which occur in design 1.

Membrane SMR: The pre-reformer outlet (stream 6) is expanded to 25 bar(a), before being heated to 500 o C in E- 201. Make up steam (U4) provides a steam to carbon ratio of 2.5:1 before, the stream is sent to the SMR membrane reactor where it is split between the multiple tubes mounted horizontally in the reactor.

Inside of each tube is a smaller tube. The space between the two tubes is filled with a nickel alumina catalyst while steam (U10) flows through the inner tube. The inner tube is comprised of a palladium membrane, which allows the hydrogen to pass from the SMR to the steam but keeps other gasses in the catalyst layer. Water and hydrogen flow out from the reactor at 2bar(a) and 497 o C (stream 8) and are cooled to 25 o C in E-205 before entering water knock- out vessel, V-301. Hydrogen is then recovered at the required product purity.

The SMR Membrane outer tube exits the reactor at 25 bar(a) and 497 o C (stream 11) and is cooled through E-206 to 25°C before passing through a water knock-out vessel (V-202) to separate the water. The vapour stream (stream 12) then combines with the desulphurisation split (stream U6) before being pre-heated to 500°C in E-203 for the fuel reactor of the chemical looping system, R-202.

Chemical Looping Combustion: Compressor, P-202 provides air to the Air Reactor, R-203, which is filled with Nickel particles supported on alumina and operates at 500°C and 25bar(a). Through fluidisation the nickel particles are fully oxidised and passed to three cyclones (stream 20) working in parallel, C-201 A/B/C. The remaining nitrogen gas is separated from the particles and dispersed to atmosphere.

Stream 14a enters the fuel reactor, R-202, and combusts with Nickel Oxide particles from the cyclones (stream 22). The fuel reactor operates at 500°C and 25bar(a), and provides 800 kJ/mol of energy through the combustion reaction. This energy is transferred to the SMR Membrane reaction which is highly endothermic. After reduction, the nickel particles are transported back to the air reactor (stream 19) by gravity to re-start the cyclic process. The fuel reactor outlet (stream 15) is comprised of carbon dioxide and water, and is cooled through E-204 before being sent to water knock-out drum V-201 for water separation.

CO 2 Compression: The carbon dioxide vapour (stream 16) exits the knock-out drum and is sent to compressor P-301 to begin pressurisation to 70 bar(a). Cooler E-301 cools the gaseous CO 2 stream to the liquid, and it is subsequently pressurised to 150 bar(a) using pump P-304.

Desulphurisation: The desulphurisation section for Design 2 is exactly similar to Design 1.

4.2.2 Process Control

Desulphurisation: The control in Design 2 for the desulphurisation unit is the same as for Design 1. Please refer to

Section 3.2.2 for further details.

Pre-reformer: The control in Design 2 for the pre-reformer is the same as for Design 1. Please refer to Section 3.2.2 for further details.

Membrane SMR: Due to the severe consequence of high temperatures regarding the Palladium membranes, a temperature trip system (not shown on PFD) is installed to cut inlet flow to both the CLC system and the SMR membrane tubes. This prevents any further reaction and heat generation.

Chemical Looping Combustion: Flow indicators, FIC 210/212, are located onto the inlet streams of both reactors to adjust the flowrate of either/both feeds to ensure sufficient combustion and heat release. A Pressure Relief Valve is implemented onto the Air Reactor (R-203) to relieve the pressure and dispel harmless oxygen and nitrogen into the atmosphere in the case of an emergency. To avoid the particles also leaving with the hot air in this case, a fine mesh has been inserted into the pressure valve. A temperature indicator on the Fuel Reactor (R-202) provides a monitor in the control room in the case of the reactor overheating. The SMR Membranes can only withstand a temperature of

GROUP 1 The University of Edinburgh School Of Engineering Volume 1 Chemical Engineering Design: Projects 4 500°C, and so it is imperative for a trip system so in the case of any temperature spike, the system is shut down to prevent irreversible membrane damage. A temperature indicator on the Air Reactor also monitors performance over time. A Gas Analyser, CI-216, on the outlet Fuel Reactor stream, allows full operation of CLC system once sufficient combustion has been achieved.

CO 2 Compression: The control in Design 2 for the CO 2 Compression is the same as for Design 1. Please refer to Section 3.2.2 for further details.

4.2.3 Heat Integration Design 2

Figure A-6 in Appendix A summarizes the suggested heat exchanger network with data support from Table 4-1 for design 2. HINT calculated a pinch temperature of 507 [K] with a required heating duty of 8.36 [MW] and cooling duty of 145 [MW] using a minimum temperature difference of 10 [K]. This takes into account almost all hot and cold streams in the process besides stream 4-4a which was overlooked during the HEN design. In the interest of time, the HEN was not redesigned as this problem was noticed after the HEN was completed. Further analysis will be provided in the critical review section but a summary of the results will be presented here.

For the most part, design 2 has arguably better heat management. A key result is the heating of stream U10 which supplies steam to the SMR-membrane reactor and stream U4 which is the SMR-membrane steam make up. Taking this streams out of the HEN will result in a similar situation to design 1 where the pinch was at the highest available temperature. However, doing so will result in a 22 [MW] requirement to heat stream U10 and 24 [MW] to heat stream U4 whereas the HEN only requires 8.36 [MW] total heat utility, indicating an 80% reduction in heating utility required. Should stream 4-4a be added during a redesign, a similar conclusion will be found. Overall however, the cooling duty required by the HEN is still substantial and this will be further discussed in the critical review subsection.

Similar to design 1, Table 4-1 is provided below to walk the reader through streams in the HEN for design 2.

Table 4-1: Design 2 HEN

Stream

Stream description

Description

11-11a

Cooling of product gas exiting the SMR-membrane via outer membrane (not in the membrane tube)

Used to heat U4 (sensible) and U4 (sensible and latent) before being cooled via E-206

8-8a

Cooling of product gas exiting the SMR-membrane via inner membrane (membrane tube)

Used to heat U10 (sensible), U4 (latent) and U10 (sensible) before being cooled via E-205

21-21a

Cooling of cyclone flue gas before release

Used to heat U10 (sensible), U3 (sensible) before being cooled by E-208

15-15a

Cooling of the CO 2 rich chemical looping flue gas and condensing the water before removal

Used to heat 14-14a (sensible), 6-6a (sensible), U3 (sensible and latent), cooled via E-204 (sensible) before final heating of U4 (sensible)

U9

Cooling of hyper-compressed make up air for the chemical looping air reactor

Used to heat U4 (latent)

16a-16b

Cooling and condensing of compressed CO 2 product gas before pumping

Used to completely heat 1a-1b (sensible) before being cooled by E-301

1a-1b

Heating of natural gas feed to 303 [K] before entering the desulphuriser

Completely heated by 16a-16b

U3

Heating of the utility steam make up for the pre-reformer

Completely heated by 21-21a, E-606 (latent) and 15-15a

U4

Heating of the utility steam make up for the SMR- membrane

Completely heated by 15-15a, 11-11a, U9, E-612 (latent), 8-8a, and E-609 (sensible)

U10

Heating of the utility steam make up for the SMR- membrane (not combined with feed gas)

Completely heated by 8-8a, 21-21a

14-14a

Heating of the feed gas to be used as fuel in the chemical looping fuel reactor

Completely heated by 15-15a

6a-6b

Heating of the post expanded pre-reformer product gas to ensure that it reaches the SMR-membrane reactor at 688K

Completely heated by 6a-6b

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5 Energy and Material Balances

5.1

Assumptions made

 

20% of the heat produced by the furnace is lost to the surroundings

Less than 5% of the heat produced by the CLC system is lost to surroundings

5.2

Design 1

5.2.1 Overall Mass Balance

Table 5-1: Overall Mass Balance for Design 1

Streams In

kg/h

Streams Out

kg/h

1

2.02

x10 4

12

5.23

x10 3

U1

[-]

27

127x10 5

U3

5.37

x10 3

30

5.15x10 4

U4

4.02

x10 4

U2

1.00

x10 -1

U7

1.55

x10 5

U5

1.89

x10 4

 

U8

1.75

x10 4

U9

5.52

x10 3

Total

2.21

x10 5

Total

2.26

x10 5

Difference (kg/h)

 

4.82 x10 3

 

Overall percentage difference

 

2.19%

The table above shows the inlet and outlet streams of the plant. The values were obtained following the calculation method described in Section 3.1 and 3.2 in Appendix D. The basis of calculation followed the standard procedure for mass balances, with an analysis on the mass flowrates in and out of the process. The error in the overall mass balance was found to be 2.19%. This error was considered acceptable and likely due to just rounding errors.

5.2.2 Overall Energy Balance

The overall energy balance was separated into two sections; Part one being the Desulphurisation unit to the Furnace outlet, and part two being the MEA process to the CO2 compression train. The reason for this being the two different methods of energy balance calculations used. The conventional energy balance equation was used for

calculations in part one, while Unisim was implemented using the amine package for energy calculations in the MEA process. Please refer to section 3.1 and 3.2 in Appendix D for further clarification on equations utilised.

Part 1: Desulphurisation to Furnace Outlet The energy balance is illustrated by Table 5-2. It shows the energies of the streams, energy provided by heaters and coolers, and finally the energy of the various reactions.

Table 5-2: Overall Energy Balance for Design 1, Part 1

 

Stream Energy Balance

 

Energy In

MW

Energy Out

 

MW

1

-1.66 x10 -1

 

12

 

1.04

x10 -1

U1

0.00

 

16

 

3.30

x10 1

U3

1.16

 

U2

 

1.44

x10 -7

U4

9.04

 

U5

 

4.90

x10 -2

U7

-6.52 x10 -1

   

Total

9.37

Total

 

-6.88 x10 1

 

Heaters and Coolers Energy Balance

 

Energy In

MW

Energy Out

 

MW

E-101

2.23

x10 -1

E-201

 

-3.34 x10 1

E-205

0.00

E-202

 

-1.15 x10 1

 

E-203

 

-1.13 x10 1

Total

2.12

x10 1

Total

 

-5.60 x10 1

 

Heat Generated by Reactions

 
 

Reaction Location

   

MW

 
 

Furnace

 

1.19

x10 2

 

SMR

 

4.43

x10 1

 

Pre reformer

 

-2.67 x10 -1

 
 

HWGS

 

-3.74

 

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LWGS

-1.97

Other Sources

Heat loss to surrounding

-2.38 x10 1 MW

Overall Balance

Overall difference

2.29 x10 1 MW

Overall percentage error

14.5 %

The error in all process sections were considered to be acceptable, except for the energy balance surrounding the furnace. This is due to the inconsistency in the method used for calculating the enthalpy of the stream. Please refer to section 3.1 and 3.2 in Appendix D for further explanation.

Part 2: MEA Process and CO2 Compression Train Table 5-3: Overall Energy Balance for Design 1, Part 2

 

Stream Energy Balance

 

Energy In

MW

 

Energy Out

MW

16

6.28

x10 2

 

27

1.41

x10 2

   

30

-1.70 x10 3

 

U8

-8.07 x10 1

 

U9

-3.64 x10 1

Total

6.28

x10 2

 

Total

-1.68 x10 3

 

Equipment Energy Balance

 

Energy in

MW

 

Energy out

MW

E-403

5.26

x10 3

 

E-401

-5.08 x10 2

E-502

0.00

 

E-402

-1.46 x10 2

P-401

9.78

x10 1

 

E-405

-2.00 x10 2

P-502

-3.29 x10 3

 

E-501

-3.45 x10 3

P-503

2.60

x10 1

 

E-503

-2.72 x10 1

P-504

1.56

x10 1

 

E-504

-2.96 x10 1

     

E-505

-5.78 x10 1

Total

2.10

x10 3

 

Total

-4.41 x10 3

 

Heat generated by Reactions

 

Absorption column

   

-9.20 MW

Stripping column

   

-10.5 MW

 

Overall Balance

Overall difference

   

21.7 MW

Overall percentage error

   

0.8 %

As can be seen from the table above an error of 0.8% was obtained which was considered to be insignificant. This result was calculated following the method in section 3.1 and 3.2 in Appendix D.

5.3 Design 2

5.3.1 Overall Mass Balance

Table 5-4: Overall Mass Balance for Design 2

Streams In

kg/h

Streams Out

kg/h

1

1.59

x10 4

U2

8.00

x10 -2

U1

0.00

9

5.24

x10 3

U3

5.37

x10 3

10

1.07

x10 5

U4

3.01

x10 4

13

1.05

x10 4

U7

4.00

x10 4

17

3.73

x10 4

U9

1.07

x10 5

18

5.78

x10 3

 

21

3.77

x10 4

Total

1.99

x10 5

Total

1.97

x10 5

 

Difference

-1.92 x10 3

 

Overall percentage difference

   

-0.97%

The table above shows the inlet and outlet streams of the plant. The values in the table were obtained following the calculation method described in section 3.1 and 3.2 in Appendix D. The basis of calculation followed the standard procedure for mass balances, with an analysis on the mass flowrates in and out of the process. The error in the overall mass balance was found to be -0.97%. This error was considered acceptable and was likely to be caused by rounding errors.

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5.3.2 Overall Energy Balance

Table 5-5: Overall Energy Balance for Design 2

 

Stream Energy Balance

 

Energy In

 

MW

Energy Out

MW

1

-1.20 x10 -1

 

U2

1.04x10 -7

U1

 

0.00

9

0.00

U3

 

1.04

10

-6.55 x10 1

U4

 

8.47

13

-5.38

U7

-1.69 x10 -1

 

17

4.9x10 -1

U9

3.01

x10 1

18

-2.97

 

21

4.52

Total

3.93

x10 1

Total

-6.88 x10 1

 

Equipment Energy Balance

 

Energy in

 

MW

Energy out

MW

E-101

1.60

x10 -1

E-204

-1.03 x10 1

E-201

4.01

 

E-205

-1.06 x10 2

E-202

 

1.86

E-206

-1.33 x10 1

E-203

 

6.32

E-207

-1.05

P-101

 

0.00

E-301

-1.31

P-202

 

7.03

P-201

-2.40 x10 -2

P-304

4.90

x10 -1

P-203

-2.72 x10 -1

P-301

 

1.31

   

Total

2.12

x10 1

Total

-1.32 x10 2

 

Heat Generated by Reactions

 

Reaction

   

MW

 

CLC

 

-3.24 x10 1

 

Membrane SMR

   

-3.33 x10 1

 

Pre Reformer

   

-2.41 x10 -1

 
 

Other Sources

 

Heat loss to surrounding

   

1.29

MW

 

Overall Balance

 

Overall difference

   

1.23

MW

Overall percentage error

   

2.03 %

 

As can be seen from the table above an error of 0.25% was obtained which was considered to be insignificant. This result was calculated following the method in section 3.1 and 3.2 in Appendix D.

Excel online was used for overall flowsheets in Design 1 and 2. This allowed all group members to keep up-to-date with flowsheet and design changes.

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6 Thermodynamics and Chemistry

This section will focus on the thermodynamics behind the design of reactors and separators. This section is divided into two parts: Design 1 and Design 2. These are divided further to discuss reactions and separations.

6.1 Design 1

6.1.1 Reactions All reactions taking place is reactors in Design 1 are summarised in the table below:

Table 6-1: Reactions in Design 1

No.

 

Reaction

 

ΔHrx (298K)

Location

Basis for Reactor Design/ Kinetic Data

 

(J/mol)

1

+

6

13 +

6

79600

Pre-reformer

100% conversion

2

5 11 +

+

5

59210

Pre-reformer

100% conversion

3

+ 4 → 9 + 4

38370

Pre-reformer

100% conversion

4

+

3

7 +

3

19530

Pre-reformer

100% conversion

5

+

2 → 5 +

2

-2440

Pre-reformer

100% conversion

6

+

3 +