Red Planet Recycle

Red Planet Recycle

An Investigation Into Advanced Life Support system for Mars

Tuesday 24th January, 2 PM

Chemical EngineeringDesign Projects 4

Outline

1. Design objectives

2. Stages 1 & 2 outline

3. Criteria & Constraints

4. Water treatment

5. Air treatment

6. Discussion

Outline1. Design objectives

Design BriefYour consulting company has been hired by the Mars Exploration Consortium, represented by Drs. Sarkisov and Valluri. The objective of the consortium is to build a space station on Mars, capable of a continuous support of a 10 member crew.

It has been planned that a re-supply mission should return to Mars every 18 months, with the main resources re-supplied being water, oxygen and food. With the current cost of the re-supplement estimated at £1 M/kg, there is a clear need for intensive onsite recycling of the resources, including water, air and waste. Your company has been hired to develop an integrated recycling solution, with an objective to minimize the weight of the re-supplement cargo.

Other technologies that should be explored along with the recycling, include collection and purification of water on Mars and local production of food stock (high protein vegetables etc).

The primary source of energy for the Martial station will be provided by a nuclear reactor with up to 50 MWe capacity.


Design Outline

We have identified 3 key stages of the design:

1. Resource requirements assuming no recycling or utilisation of local sources

2. Resource requirements with recycling introduced

3. Resource requirements with recycling introduced and utilisation of local resources. Investigation into unconventional technologies


Using previous isolated systems as examples the essential resources that must be controlled in a life support system are:

• Water• Air• Food• Waste• Thermal energy• Biomass

The last three require control but no resupply on the Mars space station, therefore these are not considered at this stage of design.

2. Stages 1&2 Outline

Stage 1 – Design basis


Stage 1 – Resource requirements

Total Water Requirement

Drinking Hygiene* Safety Total

[kg] [kg] [kg] [kg]

17472 92345 27454.25 137271.25

Total Air Requirement

N2 O2 CO2 Safety Total

[kg] [kg] [kg] [kg] [kg]

0 4599 0 1149.75 5748.75

Calorific requirement

Standard Safety Total

[MJ] [MJ] [MJ]

57.3 14.325 71.625

Total Oxygen

Total Water

Total Resupply Weight

Total Resupply Cost

[kg] [kg] [kg] [£Million]

5748.75 137271.25 143020 143020



Design Outlook

Stage 1 Stage 2 Stage 3



Stage 2 – Design basis

Stage2: Introducing recycling processes to the Mars space station in order to minimise the resupply requirements

Of the three focus resources identified in stage one, only two can effectively be recycled. These are:

• Water

• Air



Water Recycling

Assumptions:

1. All consumed water requires recycling

2. Assuming NASA standard water composition



Water Recycling Design Basis

Stage 1Water

Waste water (ppm)

Treated water (ppm)

Ammonia 55 calcium 0.9chlorine 229 phosphate 134 sulphate 80 Nitrate <100 sodium 150 potassium 133 magnesium 1.5 TOC >11

Ammonia 0.05 calcium 30chlorine 200 phosphate N/A sulphate 250 Nitrate 10 sodium N/A potassium 340 magnesium 50 TOC <0.5

Flowrate 200.6 kg/day


M.Flynn (1998)

?Outline


Air Recycling

Assumptions:

1. The air treatment is split into three distinct processes: CO2 separation, CO2 consumption and O2 production

2. Assuming same composition of air as on Earth

3. Assume N2 is a buffer


?Outline


Air Recycling Design Basis

Stage 1Air

Pre-treatment

10 kg/day CO2Stage 1

AirAir treatment

8.4 kg/day O2

Air

Air



Criteria & Constraints

1. Applicability

2. Reliability

3. Modularity

4. Resupply

But in general we look for the technology to be;

Lightweight and economical, able to recover a high percentage of waste water and operate with minimal consumables


3. Criteria &Constraints

?Outline


Criteria & Constraints- Water treatment

2. Criteria & constraints

Technology Applicability Reliability Modularity Resupply

VPCAR

DOC

Electrocoagulation ?

Microorganism based - - -ISS

Membrane

Advanced oxidation - - -Ecocyclet - - -UV treatment - - -

4. Watertreatment



?Outline


Criteria & Constraints- Water treatmentsTechnology Applicability Reliability Modularity Resupply

VPCAR

DOC

Electrocoagulation ?

Microorganism based - - -ISS

Membrane

Advanced oxidation - - -Ecocyclet - - -UV treatment - - -

4. Watertreatment



?Outline


Water treatment- Final 5


DOC EC ISS Membranes

Resupply (kg/18 months)

50 Unknown 1032 0

No. of independentunits

3 1* 4 3*

Feed streams 2 1 2 1

Recovery rate (%)

92 - 99 90

Maintanence Unknown - 50 days >18 months

4. Watertreatment


?Outline


Water treatment- Final 5


DOC EC ISS Membranes


50 Unknown 1032 0


3 1* 4 3*

Feed streams 2 1 2 1

Recovery rate (%)

92 - 99 90

Maintanence Unknown - 50 days >18 months

4. Watertreatment


?Outline


DOC VS ISS WATER RECOVERY SYSTEM


4. Watertreatment


• DOC requires a Re-supply of 4393 kg every 18 months• ISS Water Recovery System requires a Re-supply of 1032 kg

every 18 months• Due to the difference in weight per Re-supply mission we

have decided to choose to design the ISS Water Recovery System. However this is based on the 2007 paper where the recovery rate of the DOC system was 96%. If a more recent paper is able to determine a greater recovery rate the DOC system should be reconsidered for design.

?Outline


Gas/Liquid Separator


4. Watertreatment


• The PFD shows that the stream exiting the Reactor enters the Gas/Liquid Separator before moving on to the Ion-Exchange bed.

• The Stream Leaving the Reactor contains oxidized organics which need to be removed from the system.

• The Separator needs to be designed to remove the excess Oxygen before the Stream continues to the IX Bed.

• Excess Oxygen can be damaging and so its removal is also important for protecting expensive equipment.

?Outline


Methods of Removal


4. Watertreatment


• In order to determine the Method of Removal the phase and composition of the stream exiting the Reactor needs to be determined

• From the PFD it is known excess oxygen needs to be removed. If the oxygen is dissolved in a liquid stream, membrane degasification is an option as it is able to remove the dissolved gas by allowing it to pass through the Gas-Liquid Separation membrane.

?Outline


Schematic of ISS Technology


4. Watertreatment


?Outline


ISS Urine Purification


4. Watertreatment


?Outline


List of Assumptions


4. Watertreatment


• The Water Safety factor of 27454.3 kg is taken up but kept in storage rather than used and put through recycling process.

• It is assumed that all water used is 100% conserved and there is no loss as all vapours end up contributing to the cabin humidity which is condensed before going through the recycling process.

• The required amount of water per day for the crew will be used up per day, thus the water is recycled on a daily basis.

• How is water consumed on board?

?Outline


Multifiltration Beds


4. Watertreatment


• MF consists of a particulate filter upstream of six unibeds in series. Each unibed is composed of an adsorption bed (activated carbon) and ion exchange resin bed.– Particulates are removed by filtration– Suspended organics are removed by adsorption beds– Inorganic salts are removed by ion exchange resin beds.

Source: Mark Kliss, NASA ARC

• The MF canisters are designed for a 30 day life, and hence will be replaced on a monthly basis.

?Outline


Schematic of a MF Bed


4. Watertreatment


?Outline



4. Watertreatment


Media Function Media DescriptionMCV-77 Disinfection iodinated strong base anion, SBA, exchange resin

IRN-150 Removal of anions and cations

mixture of gel types strong acid cation, SAC, (IRN-77, H+ form) and SBA (IRN 78,OH- form)

IRN-77 Removal of cations SAC gel exchange resin in the H+ form

IRA-68 Removal of strong and weak acids

weak base anion, WBA, gel exchange resin in the free base form

580-26 Removal of nonpolar organics

coconut-shell based activated carbon

APA Removal of nonpolar organics

bituminous-coal based activated carbon

XAD-4 Removal of nonpolar organics

polymeric adsorbent

IRN-150 Removal of anions and cations

mixture of gel types SAC (IRN-77 , H+ form) and SBA (IRN-78, OH- form)

IRN-77 Removal of cations SAC gel exchange resin in the H+ form

Ref. David Robert Hokanson, MICHIGAN TECHNOLOGICAL UNIVERSITY

?Outline


Water Storage


4. Watertreatment


• The water prior to Recycling must be stored. Based on daily recycling of 200.4 kg/day the tank would need to contain that volume plus a safety factor of 10%.

• Thus the Water Tank before the process must store 220.5 kg, which corresponds to a volume of approximately 220.5 Litres. This volume includes the 20 kg/ day that will come from the urea treatment process that will join the water recovery process at the start.

• Post Water Treatment • At 99 % Recovery Rate the amount of water obtained is 198.5 kg/day. Including a

safety factor of 10% the total tank should accommodate 218.3 kg/day,

corresponding to a volume of 218.3 litres.

?Outline



4. Watertreatment


Tank Storage Volume (Litres)

Water Pre-Treatment 9.2

Water Post-Treatment 9.1

Tank Storage Volume (Litres)

Water Pre-Treatment 110.3

Water Post-Treatment 109.2

Alternative Rate of Recycling Storage

• Hourly Basis

• Twice a day

?Outline



4. Watertreatment


Urine Processer Storage• The Urine Tank for the Urine Processor should be collected

and recycled once daily

• Materials?• Does this storage provide an acceptable hold up time?• Long term storage can occur in Teflon bags• Ultimately decided water should be recycled on a daily basis.

?Outline



4. Watertreatment


Gas-Liquid Separator

• The PFD shows that the stream exiting the Reactor enters the Gas/Liquid Separator before moving on to the Ion-Exchange bed.

• The Stream Leaving the Reactor contains excess carbon dioxide and oxygen which need to be removed from the system.

• The Separator needs to be designed to remove the excess Oxygen before the Stream continues to the IX Bed.

• Excess Oxygen can be damaging and so its removal is also important for protecting expensive equipment

?Outline



4. Watertreatment


Gas-Liquid Separator• Methods of Removal

• In order to determine the Method of Removal the phase and composition of the stream exiting the Reactor needs to be determined

• From the PFD it is known excess oxygen needs to be removed. If the oxygen is dissolved in a liquid stream, membrane degasification is an option as it is able to remove the dissolved gas by allowing it to pass through the Gas-Liquid Separation membrane whilst containing the liquid.

• If the stream contains separated gas and liquid a vertical gas-liquid separator can be used due to low holding time

• The reactor by products will remain in the liquid and thus require the ion exchange bed to remove them.

• If the stream is completely in gaseous form it will require a gas separator and vice versa is the stream is completely in the liquid form.

?Outline



4. Watertreatment


Assumptions to be Determined?

• Batch process of water? I.e. wastewater collected in a tank and when a level indicator determined the correct volume of wastewater has been reached the process can begin?

• What will the level indicator be? I.e. What is the decided flow-rate for the process?

• This flow rate will be based on the rate at which waste water will collect? And the rate at which recovered water is needed?

• If clean water from initial mission is in storage the latter will not be an issue

• How will the water from the initial supply mission be stored? Teflon bags?

?Outline



4. Watertreatment


Schematic of Urine Processing Assembly (UPA)

Ref. Development of an Advanced Recycle Filter Tank Assembly for the ISS Urine Processor Assembly

?Outline



4. Watertreatment


UPA System

• Urine is pretreated before enters the system with sulphuric acid and Chromium Trioxide.

• The total amount of urine that will be processed for a 10 man crew is 20 kg/day.

?Outline



4. Watertreatment


Fluid Pump Assembly

• The pump assembly consists of 4 Peristaltic pumps:– 1 supplies wastewater– 2 remove excess

wastewater and sends it to the recycle filter tank

– 1 removes water product water from the product side of the distillation unit (DU).

Motion of the peristaltic pumps

Ref. Final Report on Life Testing of the Vapor Compression Distillation/Urine Processing Assembly (VCD/UPA) at the Marshall Space Flight Center (1993 to 1997)

?Outline



4. Watertreatment


Distillation Assembly

• Incoming wastewater is spread in a thin film on the rotating drum centrifuge.

• From here it is evaporated at ambient temperature and reduced pressure

• Water vapour is transferred to outside the drum through a compressor, where it condenses as clean water.

• Demister ensures only clean water is removed with the compressor, leaving waste water droplets behind.

• Passes through 100 micron filter before going to WPA

?Outline



4. Watertreatment


Distillation Assembly

Ref. Final Report on Life Testing of the Vapor Compression Distillation/Urine Processing Assembly (VCD/UPA) at the Marshall Space Flight Center (1993 to 1997)

?Outline



4. Watertreatment


• Filters solids from the wastewater before it is recirculated through the distillation unit.

• Consists of bellows to draw waste water into the tank, and force it out as a concentrate.

• Then passes through a 10μ brine filter, which has an estimated life of 60 days.

• This filter has a 100μ filter incase of failure of the 10μ filter.

Advanced Recycle Filter Tank Assembly (ARFTA)

?Outline



4. Watertreatment


Bellows Tank Brine Filter

ARFTA

Ref. Development of an Advanced Recycle Filter Tank Assembly for the ISS Urine Processor Assembly

?Outline



4. Watertreatment


ARFTA Unit

?Outline



4. Watertreatment


• Removes gas from the condenser side of DU when the pressure gets to high.

• Similar to fluid pumps, except operate at a higher RPM therefore require a cooling jacket

• Pump system compresses the non-condensable gas & water vapour to condense the water vapour.

Purge Pump Assembly

?Outline



4. Watertreatment


Purge Stream Filtration

• Water that leaves these pumps is filtered using 20μ filter.

• Stream then passed through water separator. This sends product water to WPA, expelling any non-condensable gases to the atmosphere.

?Outline


Aqueous Catalytic Oxidation Reactor


4. Watertreatment


• Used as an effective post-treatment technology for the removal of low molecular weight polar (but non-ionic) organics which are not removed by sorption in the multifiltration (MF) train.

• Typical contaminants of this kind are ethanol, methanol, isopropanol, acetone, and urea

?Outline


Aqueous Catalytic Oxidation Reactor


4. Watertreatment


Design:• The reactor operating pressure is determined primarily by the requirement to

maintain water in the liquid phase• The ISS uses a VRA which is co-current bubble column which uses gas phase

oxygen as the oxidant over a catalyst• Catalyst consists of a noble metal on an alumina substrate• For design assume plug flow reactor

?Outline


Ion Exchange Bed


4. Watertreatment


• Removes dissolved products of oxidation exiting the reactor • Including both organic & inorganic compounds• Organic Anion exchanged bed contains a synthetic resin, often

styrene based with a capacity of 10-12 kg/ft3*

(*Nalco Chemical Company, 1998)

?Outline


New Proposed System


4. Watertreatment


• Aim to remove volatile organic compounds (VOC) from the cabin air via catalytic oxidation prior to absorption in the aqueous phase

• This reduces the load on the Ion exchange bed. Oxidation kinetics indicate this is more efficient.

• Second, vapour compression distillation (VCD) technology processes the condensate and hygiene waste streams in addition to the urine waste stream

?Outline


New Proposed System


4. Watertreatment


• Experimental evidence (Carter et al.,2008) shows this system can effectively reduce the Total Organic Compounds (TOC) to ‘safe levels’:

TOC removal by organic reactorCarter, et al., 2008)

?Outline


Questions


4. Watertreatment


• The composition and Phases of the Reactor Exit Steam?• Confirmation of what needs removed from the Reactor Exit

Stream prior to it entering the Ion Exchange bed?• If a Gas-Liquid Separation Membrane is the most appropriate

method of Removing Oxygen?

?Outline



4. Watertreatment


Membrane Bioreactor – Forward Osmosis• Originally eliminated due to reliability concerns over microorganisms survival.

• However after conversations with the NASA team responsible for designing waste water treatment for Mars, decision was taken to reconsider.

• NASA cited this technology as their current focus, moving away from DOC & ISS

• Microorganisms spores were taken to low orbit earth in 1984 with 70% survival and with developments in UV radiation protection, experts believe the technology is plausible (Benardini et al., 2005)

• Membrane bioreactor has the potential for excellent treatment of waste water with removal of contaminants in excess of >95 % (Atasoy et al., 2007)

• However significant challenges remain and will be investigated

?Outline



4. Watertreatment


Membrane Bioreactor Continued

FEED

Aeration zoneImmersed membrane

Activated sludge

Material balances of substrate:

Rsu = Q(Si-Se)/Va = …?

Q Si Xi

Q, Se, Xe

?Outline



4. Watertreatment


Membrane Bioreactor Continued

• First we need a volume: 200 l/day requirement

• Process will operate in a continuous mode

• For our capacity assume preliminary volume of 50 l

• rsu= Q(Si-Se)/Va = 42 mg/l/day (substrate utilisation rate)

• Primary Flux?

• J= (1/A) x (dv/dt)

• A = Membrane surface area* = 0.83 m2

• Therefore J= 10 l/hr/m2

• Permeate flux? :

• Material balance of permeate in reactor?: rg=dXv/dt

*(Kraume, 2010)

?CO2 Separation

1. CDRA - Carbon Dioxide Removal Assembly (ISS)

2. PSA – Pressure Swing Adsorption

3. MEA CO2 Absorption

4. Activated Carbon Absorption

5. Scrubbers



4. Watertreatment


5. Airtreatment

?1. CDRA – Process Description

• Utilises regenerative molecular sieve technology to remove carbon dioxide.

• In the CDRA, there are four beds of two different zeolites.

• Zeolite 13x absorbs water, while zeolite 5A absorbs carbon dioxide.

• Each side of the CDRA contains a zeolite 13X connected to a zeolite 5A bed.

• As the air passes through the zeolite 13X bed, water gets trapped and removed from the air.

• The dried air goes into the zeolite 5A bed where carbon dioxide gets trapped and removed.

• The outgoing air is then dry and free from carbon dioxide.



4. Watertreatment


5. Airtreatment

?1. CDRA – Simplified PFD



4. Watertreatment


5. Airtreatment

?2. PSA – Process Description

• Similar process to the CDRA with the exception that pressure is used instead of heat.

• Beds are operated at 150kPa or higher.

• Higher the pressure, the more CO2 is adsorbed.

• When bed becomes saturated it is depressurised to atmospheric levels.

• CO2 is released from the bed and the regeneration is complete.



4. Watertreatment


5. Airtreatment

?3. MEA CO2 Absorption

• This is a regenerative method of removing CO2 from air.

• Uses an aqueous solution of 25-30 wt.% (4-5 M) monoethanolamine (MEA), NH2CH2CH2OH to absorb the CO2 from the air.

• The aqueous solution is then regenerated by passing it through a column of packed glass rings and by heating it to drive off the CO2 under pressure. As shown below.

• H-O-CH2-CH2-NH-CO-OH H-O-CH2-CH2–NH2 +O=C=O



4. Watertreatment


5. Airtreatment

?4. Activated Carbon Adsorption

• A form of carbon that has been processed to make it highly porous so as to have a very large surface area available for adsorption or chemical reactions.

• CO2 saturated air is passed over the activated carbon and the CO2 is adsorbed onto the surface.

• Can be regenerated by blowing air with a low CO2 concentration through the bed.

• Only useful to us if we have a waste stream of air from another process that can be used to clean it.

• There is no way of gaining a pure CO2 stream, which may cause problems in later processes when converting the CO2 to O2. Therefore this technology is not applicable to the space station.



4. Watertreatment


5. Airtreatment

?5. Scrubbers

I. Soda Lime – used on submarines • Constant air circulation through a scrubber system filled with 75% calcium hydroxide. CO2 is

removed via the following reaction.

CO2 + Ca(OH)2 → CaCO3 + H2O

• Non regenerative, Ca(OH)2 must be resupplied.

II. Lithium Hydroxide – used in spacesuits• Used to remove CO2 from exhaled air by one of two reactions.

2 LiOH·H2O + CO2 → Li2CO3 + 3 H2O2LiOH + CO2 → Li2CO3 + H2O

• Second is lighter and produces less water.• Neither systems are regenerable and LiOH must be resupplied.



4. Watertreatment


5. Airtreatment

?Criteria & Constraints- CO2 Separation


CRDA

MEA Absorption

Activated Carbon - - -

PSA

Sorbents



4. Watertreatment


5. Airtreatment

?Criteria & Constraints- CO2 Separation


CRDA

MEA Absorption

Activated Carbon - - -

PSA

Sorbents



4. Watertreatment


5. Airtreatment

?CO2 Separation - Final 3

CDRA MEA Absorption

PSA


0 0* 0

No. of independent

units

2 2 2*

Feed streams 1 1 1

Recovery rate (%)

- 70-90 95*

Maintenance (years)

3-5 - 3-5



4. Watertreatment


5. Airtreatment

?CO2 Separation - Final 3

CDRA MEA Absorption

PSA


0 0* 0

No. of independent

units

2 2 2*

Feed streams 1 1 1

Recovery rate (%)

- 70-90 95*

Maintenance (years)

3-5 - 3-5



4. Watertreatment


5. Airtreatment

?Outline



4. Watertreatment


5. Airtreatment

CO2 Separation

• Temperature swing adsorption with molecular sieves.– Temperature swing versus pressure swing.– Zeolites preferred to activated carbon for the

adsorbent.– How the ISS system operates– Differences between the ISS system and that which

we will design– Mass balance– Design requirements

?Outline



4. Watertreatment


5. Airtreatment

TSA

• Advantages:– Can achieve higher product purities than PSA in low CO2

environments– Cheaper than PSA

• Indirect heating– Direct heating requires large volumes of adsorbent and high

heating requirements.– Use of an indirect heat exchanger can solve this problem

• Water circulation to provide a heat sink during adsorption• Steam condensation to provide heat for desorption

?Outline



4. Watertreatment


5. Airtreatment

Choice of Adsorbent

• Activated Carbon or Molecular Sieves?• A comparison of activated carbon to two molecular sieves (13X and 4A)

showed preferential adsorption of CO2 over nitrogen or hydrogen at all pressures up to 250 psia.

• 13X and 4A performed better than activated carbon at low pressures, but activated carbon was preferential at high pressures.

• Our system will operate at a low (atmospheric) pressure – indicates molecular sieves are a preferential choice.

• No data could be found on how activated carbon and molecular sieves act at different temperatures but all examples of TSA systems used molecular sieves – it is a proven and preferred technology.

?Outline



4. Watertreatment


5. Airtreatment

CDRA - ISS

?Outline



4. Watertreatment


5. Airtreatment

CDRA - ISS

There are a few main differences between that system and ours that should be considered.

• Larger crew – capacity of system should be higher.

• CO2 must be recycled– On the ISS the space vacuum is utilised to remove the CO2

and vent it to space.

?Outline



4. Watertreatment


5. Airtreatment

Mass Balance

• 0.416667 kg/hr CO2 produced by crew members.

• Assuming composition of air inside the station is 20.95% O2,

0.03% CO2, and the remainder (79.02%) N2.

• Due to the 95% CO2 removal rate 161.95 kg/hr of cabin air needs to be treated.

?Outline



4. Watertreatment


5. Airtreatment

Mass Balance

Air Intake (kg/hr)

Air Return (kg/hr)

Air Removed

(kg/hr)Oxygen 33.917 33.917 0Nitrogen 127.594 127.594 0Carbon Dioxide 0.439 0.022 0.4167Total 161.95 153.436 0.4167

?Outline



4. Watertreatment


5. Airtreatment

Design Requirements

• 2 Parallel desiccant beds for water removal

• 2 Parallel adsorbent beds for CO2 adsorption

• Vacuum system to remove the desorbed CO2

• Indirect HE for regeneration of CO2 adsorbent bed.

• Humidity control system (Plate heat exchanger)

?Outline



4. Watertreatment


5. Airtreatment

Desiccant Bed

• To remove remaining water vapour from air. • Desiccant subsystem consists of two beds, one adsorbs while the

other desorbs. • Process gas flow drawn from cabin into adsorbing desiccant bed. • Gas is dried to its dew point (around -62˚C) using an in bed heat

exchanger. • Desiccant beds desorbed by cycling CO2 free air back through

the bed to replace the water.• At an inlet temperature of 10 ˚C (and an outlet of (-62˚C) silica

gel has a capacity for holding water of 7% by weight (saturated).

?Outline



4. Watertreatment


5. Airtreatment

Desiccant Bed• The desiccant bed consists

of alternating layers of zeolite 13X and silica gel in order to protect the silica gel from entrained water droplets which may cause the silica gel to swell and fracture.

• Perforated metal screens and fibre filters in place at each end to stop desiccant particles and dust entering the gas stream.

?Outline



4. Watertreatment


5. Airtreatment

Desiccant Bed

• Before design takes place we need:– Water content of air on cabin. – Dew point of air– Cycle time of air streams

• Heat exchanger within bed occupies a relatively small volume (compared to overall volume) .– Packing of desiccant around tubes will be looser so calculated

dimensions need to be increased slightly.

?Outline



4. Watertreatment


5. Airtreatment

CO2 Adsorbent Bed

• Design decisions:– Cycle time– Flow direction (Down-flow preferable) – Mode of re-generation (creation of a vacuum to draw the

CO2 into a holding chamber)– Operating conditions (Temp, flow rates, etc)– Vessel dimensions

?Outline



4. Watertreatment


5. Airtreatment

Indirect Heating of CO2 Adsorbent Bed

• Current ISS System has separate heating and cooling units on the air streams passing through the bed.

• Proposed idea, to create one heat exchanger within the bed for both cooling and heating.

• Bed would be cooled whilst adsorbing CO2, this increases the column capacity.

• The bed would then be heated to desorb the bed.• This reduces cycle time – however induces higher energy cost.

?Outline



4. Watertreatment


5. Airtreatment

Indirect Heating – Simplified PFD

?Outline



4. Watertreatment


5. Airtreatment

CO2 Treatment

1. RWGS

2. Sabatier

3. Bosch

4. Bosch-Boudouard

?Outline



4. Watertreatment


5. Airtreatment

Criteria & Constraints- CO2 treatment


RWGS

Sabatier

Bosch

Bosch-Boudouard n/a

?Outline



4. Watertreatment


5. Airtreatment

Criteria & Constraints- CO2 treatment


RWGS

Sabatier

Bosch

Bosch-Boudouard n/a

?Outline



4. Watertreatment


5. Airtreatment

Sabatier RWGS


2343.5 1334.2


1 1

Feed streams 2 2

Maintanence Unknown Unknown

CO2 treatment – Final Two

?Outline



4. Watertreatment


5. Airtreatment

CO2 treatment

Feasibility studies for CO2 treatment methods indicate that the Sabatier reaction is the best choice for “stage 2”.

Possibility of improving the process in “stage 3” by recovering hydrogen from the methane, as opposed to venting it to Mars. This would create a closed loop for both H2 and O2, meaning neither would need to be resupplied.

?Outline



4. Watertreatment


5. Airtreatment

CO2 treatment

?Outline



4. Watertreatment


5. Airtreatment

Sabatier reactor operating in isothermal mode

• Simple model assuming that temperature stays constant.

?Outline



4. Watertreatment


5. Airtreatment

Sabatier reactor operating in non-isothermal mode

?Outline



4. Watertreatment


5. Airtreatment

ComparisonRun 1 Run 2 Run 3 Run 4

Tin(K) 423 500 423 500Tout (K) 423 500 500 518.6P(atm) 0.9 0.9 0.9 0.9Mode Isothermal Isothermal Non-isothermal Non-isothermal

Reactor volume(m3) 16.09 0.93 1.87 1.06Residence time (days) 0.37 0.02 0.04 0.02Residence time (hours) 8.83 0.43 1.03 0.49Mass flows in (kg/day) CO2 10.00 10.00 10.00 10.00H2 1.82 1.82 1.82 1.82H2O 0.00 0.00 0.00 0.00CH4 0.00 0.00 0.00 0.00Mass flows out (kg/day) CO2 0.64 0.62 0.24 0.23H2 0.13 0.12 0.05 0.04H2O 7.65 7.68 7.99 7.99CH4 3.40 3.40 3.55 3.56Conversion of CO2 (mass basis) 93.6 93.8 97.6 97.7

?Outline



4. Watertreatment


5. Airtreatment

Key Points• Operating temperatures above 550 K have

been disregarded due to material properties such as susceptibility to creep

• Can we assume that the reactor is isobaric even with temperature change? Pressure affects rate of reaction and density of gas stream (can make things much more complex). ΔP for 500K would be 0.036 atm and for 423K =0.106 atm.

• Assuming that we would want to be able to generate oxygen at a fast rate (in case of emergencies), a non-isothermal reactor operating at 500K inlet and 0.9 atm would be the best choice (relatively compact and lowest residence time (plus highest conversion).

• Reason for pressure selection – Station will be at 1 atm pressure, if a leak in the reactor casing occurs then we would prefer that air is sucked into the reactor rather than a mixture of gases passed straight into the habitat.

• The lower the pressure used, the greater the reactor volume becomes and therefore only a slight vacuum is needed (i.e. just below station pressure) so 0.9 atm was selected.

?Outline



4. Watertreatment


5. Airtreatment

PFD

?Outline



4. Watertreatment


5. Airtreatment

Other Units to be Designed

1. Gas Storage Vessels (for CO2, H2, O2, CH4)

2. Liquid Storage Vessel (for H2O)

3. Water separation HX (to remove water from reactor exit stream – simple)

4. Gas separation (can separation group offer any advice?)

5. Electrolysis unit (continuous or cyclic?)

6. Pumps, valves etc (last)

?Outline



4. Watertreatment


5. Airtreatment

CO2 Storage VesselInformation required for design:

• CO2 flowrate (including recycle if appropriate)

• Need to choose a “hold-up” time – depends on mode of operation of

Sabatier (and if cyclic operation then depends on time to heat up)

• Need to choose a safety factor (Trelfa’s lecture?)

• Need to choose T&P

?Outline



4. Watertreatment


5. Airtreatment

H2 Storage Vessel

Information required for design:

• Full amount of hydrogen which must initially be delivered (flowrates and

hold-up are unnecessary as the H2 volume will never increase)

• As before, safety factor, T&P

?Outline



4. Watertreatment


5. Airtreatment


• Inlet flowrate of O2 from electrolysis (need conversion from reactor and

electrolysis unit)

• Outlet flowrate of O2 to station atmosphere

• As before, safety factor, T&P, Hold-up

• Will electrolysis use continuous or cyclic operation?

O2 Storage Vessel

?Outline



4. Watertreatment


5. Airtreatment

CH4 Storage Vessel

Is this vessel necessary? If all the methane is going to be purged then can it

simply be purged as it is produced (simple no-return valve on CH4 stream

from gas separations)?

?Outline



4. Watertreatment


5. Airtreatment

Additional Questions on Gas Storage

• Will any CO2 or H2 be purged?

• Is it necessary to include a hydrogen recycle stream (in addition to the

hydrogen recycled from electrolysis)?

?Outline



4. Watertreatment


5. Airtreatment

Liquid Storage Vessel


• Inlet flowrate of H2O (need conversion from reactor)

• Will electrolysis use continuous or cyclic operation?

• As for gases, safety factor, T&P, Hold-up

?Outline



4. Watertreatment


5. Airtreatment

Gas Separation

Is this necessary or are outlet flowrates of reactants (CO2 and H2) low

enough to allow them to be purged?

Need advice from CO2 separation group!

- Need to separate a mixture of CO2, CH4 and H2.

?Outline



4. Watertreatment


5. Airtreatment

Electrolysis Unit

• Need to check we’re not overlapping with the electrolysis group – who

will design the storage for water, oxygen and hydrogen?

• Any recycle streams around electrolysis unit?

?Outline



4. Watertreatment


5. Airtreatment

Alternatives to Electrolysis

1. Photocatalytic splitting

2. Thermolysis

3. Thermochemical cycles

4. Catalysis

?Outline



4. Watertreatment


5. Airtreatment

Alternatives to Electrolysis Cont…

1. Photocatalytic splitting

• Advantages – simplicity (use catalyst suspended in water to electrolyse solution in the presence of sunlight)

• Disadvantages – Critical system would depend on the availability of sufficient insolation

2. Thermolysis

• Advantages - Can use methane as a fuel (if Sabatier is used)

• Disadvantages – Extremely high temperatures (2000°C) required to split water which means high rate of component failure.

?Outline



4. Watertreatment


5. Airtreatment

Alternatives to Electrolysis Cont…

3. Thermochemical Cycles

• Advantages – Relatively low temperature (530°C for Cu-Cl cycle).

• Disadvantages – Requires several different reactors and chlorine gas may be produced which is a potential problem.

4. Catalysis (Milstein 3 stage process).

• Advantages – Low temperature (100°C) and fairly simple system, can be scaled up.

• Disadvantages – Relatively new technology, may require more research before it is a viable alternative to electrolysis.

?Outline



4. Watertreatment


5. Airtreatment

Alternatives to Electrolysis Cont…Alternatives to Electrolysis Cont…

5. Bipolar Electrolysis

• Advantages – Developed from monopolar electrolyzer. Low energy consumption and high efficiency make it suitable to scale up.

• Disadvantages – Compact conformation of this system lead to difficulty of initial design.

6. Laser

• Advantages – Similar to photocatalystic splitting, use laser instead of sunlight, simplicity structure, can be used on Mars.

• Disadvantages – Sensitive plant, low reliability and difficult to repair by astronauts. High Energy consumption.

?Outline



4. Watertreatment


5. Airtreatment

Alternatives to Electrolysis Cont…Alternatives to Electrolysis Cont…

7. PEM Electrolyzer

• Advantages – no electrolyte required in this system, high efficiency and reliability

• Disadvantages – The materials of the anode and cathode are very expensive and cannot be scaled up

8. Solid Oxide Electrolyzer

• Advantages - High efficiency, exhaust heat can be recycled to save energy.

• Disadvantages –High operating temperatures (Over 1000°C) lead to low system reliability. Strong limitation on cell material

?Outline



4. Watertreatment


5. Airtreatment

Criteria & Constraints- Alternatives to ElectrolysisTechnology Applicability Reliability Modularity Resupply

Photocatalytic - - -Thermolysis - - -Thermochemical Cycles

?

Catalysis ? Laser - - -Bipolar Electrolysis

PEM Electrolyzer - - -Solid Oxide Electrolyzer

- - -

?Outline



4. Watertreatment


5. Airtreatment

Oxygen Generation using Electrolysis

Design Basis

Stage 1Air

Pre-treatment

10 kg/day CO2Stage 2

AirAir treatment

8.4 kg/day O2

Air

Air

?Outline



4. Watertreatment


5. Airtreatment

Process Description

PRE-INVESTIGATION OF WATER ELECTROLYSIS

http://www.futureenergies.com/pictures/fuelcellpower.jpg

?Outline



4. Watertreatment


5. Airtreatment

Process Description

•OH- (aq) anions are oxidised at the anode, producing O2(g), H2O (l) and electrons.

•The electrons flow through the diaphragm to the cathode.

•At the cathode, water is reduced producing H2(g) and OH- anions (aq).

•These hydroxide anions flow to the anode, where the cycle is repeated.

Modelling of advanced alkaline electrolyzers: a systemsimulation approach

?Outline



4. Watertreatment


5. Airtreatment

Process BFD

?Outline



4. Watertreatment


5. Airtreatment

Overall Mass Balance

Assumptions

• All electrolyte is recycled• All un-reacted water is separated and recycled• No deterioration of electrodes

?Outline



4. Watertreatment


5. Airtreatment

Overall Mass Balance

Recycle2.36 kg/day

Electrolysis Unit

H2H20 1.05 kg/day9.45 kg/day

O2 8.4 kg/day

?Outline



4. Watertreatment


5. Airtreatment

Key Process Parameters

• Voltage and Current Levels• Electrode Surface Area• System Temperature• Diaphragm Material• Electrolyte Choice• Electrode Choice

?Outline



4. Watertreatment


5. Airtreatment

Voltage and Current Levels

Using an electrochemical basis the rate of oxygen production is related to voltage and current levels by;

With F in mol/sec

?Outline



4. Watertreatment


5. Airtreatment

Electrode Surface Area

• Faradays Efficiency is dependant upon the electrode surface area

• The equation for faradays efficiency is;

This model uses non-temperature dependant coefficients

?Outline



4. Watertreatment


5. Airtreatment

System Temperature

• Typically operated at 70-90˚C• Higher temperatures beneficial as they reduce the ohmic

resistance of the electrolyte solution and that of the electrodes.

Hydrogen and Fuel Cells: Fundamentals, Technologies and Applications

?Outline



4. Watertreatment


5. Airtreatment

Diaphragm Choice – Inorganic and Organic Materials

Important properties for choice:• Reliability / overall lifespan• Efficiency• Low electrolyte resistance• Health hazard

?Outline



4. Watertreatment


5. Airtreatment

Inorganic - Asbestos

• Being phased out of use in industries (<20% in EU)

• Not suitable at higher temperatures

• Corrodes/deteriorates when used alone.

• Possible health problems – rule out

?Outline



4. Watertreatment


5. Airtreatment

Refractory-Type Materials

• Inorganic material combined with binder or alone.• e.g. Ceria (CeO) or zirconia E fibre.

– Both exhibit high stability.• Made into membranes by NASA.• Combined and alone yielded poor results.

– Fragile, brittle, poor strength…

?Outline



4. Watertreatment


5. Airtreatment

Polyantimonic Acid (PAM)

• Extremely stable at high temp (up to 150oC)• Stable in highly concentrated KOH• Best option: Polyarylethersulfone-PAM

– Membrane resistance 0.2cm2 at 90oC– Reasonably easy to reproduce

• Needs further testing

?Outline



4. Watertreatment


5. Airtreatment

Sintered Nickel

• Highly resistant to corrosion• Tested at 30% KOH, 50 bar and temp >150• Gives good ionic conductivity • High electronic conductivity – problem• High cost - $1000 per m2. Not a problem.• Possibly coat with oxide.

?Outline



4. Watertreatment


5. Airtreatment

Comparison of Inorganic MaterialsMaterial Reliability/

LifespanHealthHazard

Efficiency Low Electrolytic Resistance

Asbestos - -

Refractory Type - - -

PolyantimonicAcid

(PAM)-

Sintered Nickel -

?Outline



4. Watertreatment


5. Airtreatment

Polybenzimidazole fibres

• They are not readily attacked by oxidizing agents and have high melting points and excellent stabilities at high temperatures

• It lose 80% of its tensile-strength after one month's exposure to 30 % KOH at 80 °C

Teflon

• It has excellent chemical and heat resistance to alkaline media.

• It is lack of wettability, bubble will occur on the surface of membrane, lead to the conductivity decreasing. Grafting techniques seem more difficult to use and have yet to be proven for the electrolyser application.

?Outline



4. Watertreatment


5. Airtreatment

Polysulphones

• It was tested at 150 °C in KOH/O2 and KOH/H2 environments, no loss of tensile strength when KOH occupy more than 70% of the solution

• Maximum service temperatures in water electrolyzers are smaller than expected. Hydrophobicity lead to low conductivity

Ryton

• Excellent thermal and oxidative stability, it is stable in alkaline environments even at high temperatures and high concentration of alkaline

• Ryton is not widely used due to production problems

?Outline



4. Watertreatment


5. Airtreatment

Ion-exchange membranes

• Only certain ions can pass the membrane due to its high selectivity. Simplify the separation process

• More instable than other materials even in low temperature. Nafion is more stable but limited to low alkaline concentration

?Material Reliability/

LifespanHealthHazard

Efficiency LowElectrolytic Resistance

Polybenzimidazole fibres - -

Teflon -Polysulphones -

Ryton -

Ion-exchange membranes -



4. Watertreatment


5. Airtreatment

Comparison of Organic Materials

?Outline



4. Watertreatment


5. Airtreatment

Conclusion

• The choice is between Sintered Nickel and Ryton. • Sintered Nickel (or other porous metal diaphragms) is the

preferred choice.

• This is because organic materials are generally used for electrical insulation.

• We desire a low resistance to the electrolyte to avoid prohibiting the ion pathway.

?Outline



4. Watertreatment


5. Airtreatment

Electrolyte Solution

• Products of Anode

1. If the anode is active electrode (metal which is more active than Ag), anode will be dissolved.

2. If the anode is non-active electrode (Pt or Au) According to priority of positive ions discharge: S2- > I- > Br- > Cl- >OH-

• Products of Cathode

According to priority of negative ions discharge: K+ < Ca2+ < Na+ < Mg2+ < Al3+ < H+ < Zn2+ < Fe2+

?Outline



4. Watertreatment


5. Airtreatment


Ions in the solution

Positive Ions: K+, H+

Negative Ion: OH-

Anode：Cathode：

?Outline



4. Watertreatment


5. Airtreatment


• The number of electrons lost from anode is equal to the number of electrons of cathode obtained

• Ideally, the concentration of KOH is a constant or accumulated as new KOH comes in.

• In practice, a small part of KOH will be carried out of system by oxygen and hydrogen

?Outline



4. Watertreatment


5. Airtreatment

Electrolyte Choice for Electrolysis

Considerations:

• High resistance to corrosion, erosion, wear.• Electrical conductivity.• Suitability to situation.• Physical Properties (mass, strength).• Cost- relatively low.

?Outline



4. Watertreatment


5. Airtreatment

Materials Considered

Material Resistances Electrical Conductivity

Suitability Notables

Copper Oxides readily.

Brass <Resistant than Cu.

Graphite All round usage.

Titanium Lightweight.

Silver Soft. Need Alloy.

Platinum Doesn’t oxidse.

?Outline



4. Watertreatment


5. Airtreatment

Gas-liquid Separation

1. Gravity settling separator

• Advantages: • *Simple structure• *Low operating and capital cost• *Excellent operating flexibility• • Disadvantages:• *Long residence time• *Separator is too big and heavy• *Poor separation results, only works on gas • with large liquid drop (over 100 )m

Gas Exit

Gas ExitFeed

Feed

Liquid Exit

Liquid Exit

?Outline



4. Watertreatment


5. Airtreatment


2. Inertial separator

Advantages: *Simple in structure*Convenient in operation*Large in capacity Disadvantages:*Large in residence*Re-entrainment occurs on gas exit*Poor separation results on those liquid drop which size is smaller than 25

Different Configurations of Baffles

m

?Outline



4. Watertreatment


5. Airtreatment


m

3. Filtration Separation

Advantages: *Excellent separation results on liquid drops with small size from 0.1 - 10 Disadvantages:*System has limit on feed flowrate, fast flowrate lead to poor separation.*High operating cost*Inconvenient in resupply and cleaning of filter

Filter

?Outline



4. Watertreatment


5. Airtreatment


4. Centrifugal separator

Advantages: *Short residence time*Small in vessel size, easy to install*High reliability in continuous operation Disadvantages:*System requires extremely high flowrate, not suitable to separate a small amount of feed*High energy consumption

Entrance

Gas Exit

Liquid

Exit

Bubble Zone

Swirl Zoneg/l Splitting Zone

GLCC Separator

?Outline



4. Watertreatment


5. Airtreatment

Condensing Heat Exchanger (CHX)

• H2/H2O and O2/H2O enter heat exchanger

-may be aided by fans

• Cooling water used to condense water vapour.

• Water condenses on hydrophilic fins.

• Sucked between capillary plates.

• Possible Centrifugal separation.

?Outline



4. Watertreatment


5. Airtreatment

CHX Advantages/ Disadvantages

• Already used in Space.• Easily designed.• Lifespan of 10 years.• LCOS downstream of CHX.• Problems due to microgravity.• Possibility of microbial growth.

Documents

Red Planet Recycle