Senior Design IISpring 2013

Mentor: Dan RusinakGroup Presentation #1

Team FoxtrotAli, Mudassir

Drake, StephenMeaux, Kevin (Team Leader)

Sieve, Brandon 1

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FT was designed in 1920 by Franz Fischer and Hanz Tropsch in Germany.

The Fischer-Tropsch (FT) synthesis is a commercially proven method for converting synthesis gas (a mixture of hydrogen and carbon monoxide) to a broad range of hydrocarbon

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The feed stock is Syngas (CO +H2) The sources of syngas are

BiomassCoal

Natural Gas

CO + H2

Fisher Tropsch4

FTL are neat fuels with no sulfur content and no aromatics.Can be used in various fuel blends with conventional diesel.FTL can power today's engines at dramatically reduced emission levels without sacrificing performance.Actually FTL improvises the engines efficiency and a cetane rating of 72 can be attained.They can also be transported with todays infrastructure

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Temp: 220-250 C Feed Stock: CO+H2 Targeted intermediates and products: Wax; Diesel and

Jet oil Reactor: Slurry Bubble Column Reactor Catalyst: Precipitated Fe promoted with K

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Most important FTL plants

Geboren te Stellenbosch, Zuid-Afrika 7

ASTM D 975 will be the target product of the FTL plant. It has a cetane rating of 40 and no specific gravity specification since we are in the US.

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Our mission

Increasing trend

http://online.wsj.com/article/SB122660972377725619.htmlhttp://www.eia.gov/dnav/pet/hist/LeafHandler.ashx?n=pet&s=emd_epd2d_pte_nus_dpg&f=a

Producing transportation liquids such as Diesel and Jet fuel.

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http://www.airlines.org/Pages/Aviation-Fuels---Needs,-Challenges-and-Alternatives.aspxhttp://www.eia.gov/dnav/pet/hist/LeafHandler.ashx?n=PET&s=EER_EPJK_PF4_RGC_DPG&f=D

Increasing trend

Commercial FTL Production

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Environmental Review

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Competing Processes Fe catalyst

http://crtc.caer.uky.edu/ft6/ft_6.htmhttp://ir.sxicc.ac.cn/bitstream/0/2142/1/1358-1364.pdf

Increasing trend

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Competing Processes

Cobalt catalyst

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Co Catalyst Fe Catalyst

Longer deactivation time and longer life time due to greater resistance to re-oxidation by water

Provides a good and limited distribution of desirable hydrocarbons.

Promotes water formation and also methane formation which is what we don’t want.

Used at low operation temperatures.

Cost is expensive. Works best on a 2:1 ratio.

Longer life time when compared to Co and better selectivity when promoted with K.

Provides a wide distribution of desirable; 58.3% diesel yield and is better for wax production.

Promotes the formation of CO2 and reduces methane formation by 30% therefore the water gas shift reaction.

Promotes up to 80% CO conversion. Used at high and low operation

temperatures. Costs is much cheaper than Co. Typical ratio of 3:1 but a ratio of 2:1

can be used.

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Why Fe catalyst?To reduce the CH4 production

Cheaper than Cobalt

Better life

Catalysis Research Unit, Department of Chemical Engineering, University of Cape Town, Private Bag, Rondebosch 7701, South Africa

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Fischer–Tropsch Refining, First Edition. Arno de Klerk

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HTFT LTFT

The distillate and residue fractions from HTFT syncrude can be hydroprocessed to produce an on-specification diesel fuel that meets both the minimum density and cetane number requirements[3], but since we are in the US we don’t need to meet the minimum density requirements.

There is a high carbon cost associated with the HTFT light hydrocarbons and the HTFT aqueous product[3].

Gives a relatively lower cetane number of 47

All of the scenarios highlighted the constrained nature of diesel fuel production, as well as the negative impact that it has on the blending flexibility of other fuel types.

No minimum density specification to be met which serves our criteria fully as we are in the US.

An acceptable cetane rating of 72 can be met. Clearly LTFT is the way to go

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Competing Processes

http://alfin2300.blogspot.com/2010/05/award-winning-microchannel-fischer.htmlhttp://www.axens.net/document/19/conversion-of-syngas-to-diesel---article-ptq/english.html

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Micro Channel Reactor (The future)

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Ebullating Bed reactor/ H-star reactor

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Bed Column reactors Micro-Channel ReactorSlurry Bed Column reactor:PROSEasy Isothermal operation in the reactorFlexible when regenerating (oxidizing environment) / rejuvenating catalyst (reducing environment)Lower modeling cost

CONSCauses to produce more light ends and lighter hydrocarbons because of short circuiting of the reactionSolution:Have 2 SBCR is series or increase the size of the reactor, so the production of light ends is reduced.

Ebullating Bed reactor/ hydrotreator:2 or more cstrs in seriesLarger catalysts are used Catalyst can therefor withstand more agitationPrimarily used to obtain methanol from syngasEliminates the pressure drop problem

Fixed Bed Column reactor:This technology requires heavy work up for raw materials and provides a limited selectivity of transportation fuels and specialty chemicalsFluidized Bed Column reactor:Simple scale up, provides easy separation of solids and liquids but almost impossible for easy catalyst rejuvenation and regeneration.

PROSMicro channel reactors are compact reactors that have channels with diameters in the millimeter

range[2].they greatly intensify chemical reactions, enabling them to occur at rates 10 to 1000 times faster than in conventional systems.[2]Excellent tool for small scale distribution.Achieved a 70% conversion per single pass as compared to 50 % conversion pass of the conventional units.CONSThe tubes can get easily clogged Catalyst and reactor costs are highLoading and unloading the catalyst is a hassle

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Catalyst Rejuvenation/Regeneratio

n

Aqueous

Oligomerization

Distillation unit

Exhaustive Hydrocracker

Waste water

C3-C10

C5-C10

C22+

> C23

Syngas (2:1)

5000bpdLPG

Jet fueldiesel Motor

Gasoline

SBCRwithFe/k

Catalyst

C11-C22

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Diesel Gas Jet LPGProduct Weight Fraction (1) 0.6 0.138 0.137 0.1Density 0.832 0.717 0.817 0.533Weighted Density 0.4992 0.098946 0.111929 0.0533Average Density (kg/L) 0.763375Volume of a barrel (L) 158.99Mass per barrel (kg) 121.3689913bbl/day 5000kg/day 606844.9563Product average Carbon number 17 8 13 3Atomic Mass C (Kg/kmol) 12Atomic Mass H 1molar mass cnH2n+2 242 116 186 46Weighted Molar Mass 145.2 16.008 25.482 4.6Average Molar Mass 191.29Weighted Average Carbon number 10.2 1.104 1.781 0.3Overall Average Carbon number 13.385Mass of 13.385 C atoms 160.62

Mass Fraction C in overall Products 0.839667521Kg Carbon/day 509547.9998Kg Moles Carbon/day 42462.33331Kg Moles of CO 42462.33331ratio CO:H2 2Kg Moles of H2/day 84924.66663lb moles of CO/day 93417.13329lb moles of H2 186834.2666lb/lbmol CO 28lb/lbmol H2 2lb of CO/day 2615679.732lb of H2/day 373668.5332lb methane per day used 1494674.133

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Relevant Stoichiometry

Syngas production : CH4 + H2O CO + 3H2 -Delta_Hrx @298K = 206 kJ/mol

Alpha: Wn/n = (1 − α)2αn−1 ;-Wn is the weight fraction of hydrocarbon molecules containing n carbon atoms. α is the chain growth probability or the probability that a molecule will continue reacting to form a longer chain. -Alpha numbers above about 0.9 are, in general, representation of wax producing processes

Riedels number :

Alpha distributionLPG --C2-C4; Naptha-- C5-C8; Jet-- C9-C14; Diesel-- C14-C20;Wax-- C19 and so on

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The Riedels or the SN number helps in manipulation of the H2: CO ratio. Since we need a 2:1 internal ratio, we can still accept a greater ratio and still

correct the ratio through the RWGS CO2 produced.

CO2 consumed H2 and produces CO and the ratio comes down to 2.

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The wastewater will be pretreated with caustic soda to lower the pH before being sent to the water treatment plant.

We can use the CO2 produced by other groups and produce CO The Naptha produced may be sell/transferred to the gas treatment plant The Methane build up (Tail gas) produced is going to be syngas plant as a feed stock or

the CHP plant to produce energy thus can be used as fuel gas. Upgrade the crude olefins and transfer to the MTO plant Left over H2 and CO will be internally recycled to obtain high superficial velocity in the

SBCR or can be sent back to the syngas plant LPG would be transferred to the plant that is processing Natural Gas as NGL is Naptha

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Department of Chemical Engineering, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, Netherlands

Faculty of Chemical Technology and Materials Science, Delft University of Technology, Julianalaan 136, 2628 BL Delft, Netherlands

Velocys, Inc., 7950 Corporate Blvd, Plain City, Ohio 43064, USA (Registered in the State of Delaware, USA). Velocys, Inc. is a subsidiary of Oxford Catalysts Group PLC

ExxonMobil Research and Engineering Company Journal of Chemical technology and Biotechnology ,2001 society of chemical industry Axens,2011 Chevron Products Company, 2007 Rentech Inc, 2013 Stoichiometry, B I Bhatt Applied Catalysis,Vol 186, oct 1999 Fischer–Tropsch Refining, First Edition. Arno de Klerk. FUNDAMENTALS OF INDUSTRIAL CATALYTIC PROCESSES, second edition Fuel Processing Technology, Vol 64, May 2000

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Thank you kindly! , Questions please?

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