CHL 794 - PETROLEUM REFINERY

ENGINEERING

CONVERSION OF BIOMASS TO LIQUID

FUELS

Submitted by Aman Agrawal(2009ch10058) Rituraj (2009CH10094) Harshit Agrawal(2009CH70136)

OUTLINE
Feed Composition Biomass Gasification Syngas Production Water Gas Shift Reaction Syngas Up gradation Methanol Synthesis Methanol to Gasoline conversion

BIOMASS
Biomass is plant matter that includes forest residues (such as dead trees, branches and tree stumps), yard clippings, wood chips and even municipal solid waste. It is a mixture of carbonaceous, phosphorus and nitrogenous compounds, with heavy metals and micro-organisms.

WHY BIOMASS ???

Biomass is: bundant A enewable R otentially carbon-neutral P he only sustainable source of hydrocarbons. T Biomass can: ill the gap between energy demand and petroleum F availability in the near to mid term. e a renewable source of hydrogen in the long B term.

ULTIMATE ANALYSIS OF BIOMASS FEED

BIOMASS CONVERSION

GASIFICATION
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Biomass gasification means incomplete combustion of biomass resulting in production of combustible gases consisting of Carbon monoxide (CO), Hydrogen (H2) and traces of Methane (CH4). This mixture is called producer gas.

The production of these gases is by reaction of water vapour and oxygen through a glowing layer of charcoal. Thus the key to gasifier design is to create conditions such that a) biomass is reduced to charcoal and, b) charcoal is converted at suitable temperature to produce CO and H2.
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REACTIONS DURING GASIFICATION

GASIFICATION REACTOR

Circulating Fluid Bed Gasifier

REACTOR PROPERTIES

This system has two chambers a gasifier and a combustor Biomass is fed into the CFB / BFB gasification chamber, and converted to nitrogen-free syngas and char using steam The char is burnt in air in the CFB / BFB combustion chamber, heating the accompanying bed particles This hot bed material is then fed back into the gasification chamber, providing the indirect reaction heat Cyclones remove any CFB chamber syngas or flue gas Operates at temperatures below 900C to avoid ash melting and sticking. Could be pressurised.

TABLE: GASIFIER OPERATING PARAMETERS, GAS COMPOSITIONS, AND EFFICIENCIES

FUELS FROM SYNGAS

WATER GAS SHIFT REACTION

The H2/CO ratio obtained is 0.59 after the gasification but the desired ratio is about 4.5. CO+H2O CO2 +H2 H= -41.1 kj/mol

Operating Conditions:

Temperature 400-500 C Pressure 1 Bar Peng-Robinson Fluid Package

Mass Flow Rate 18 x 104 kg/hr

Ref: Sorin et al.,2011, Process simulation to obtain a synthesis gas with high concentration of hydrogen

SIMULATION STAGES IN WATER-GAS SHIFT

RXN

PROCESS STAGES

Reformer: A conversion reactor in which most of the methane is reacted with steam and it is produced hydrogen, carbon monoxide and carbon dioxide.
Combustor: A second conversion reactor which has as a feeds stream the product of the reformer, air stream and combustion steam. Shift Reactors: A series of equilibrium reactors in which the water gas shift reaction occurs.

INITIAL CONDITIONS

SIMULATION RESULTS

INFERENCE OF SIMULATION AT DIFFERENT O2

PERCENTAGE If the content of O2 in the air used in the second reactor, the combustor, is increased, the content of hydrogen in the produced synthesis gas is higher. Also the content of nitrogen which is an inert gas is decreased (7.99%). The 50 % O2 content in the air stream ensure the highest content of hydrogen (63.49%). The synthesis gas obtained in these conditions has a better value of calorific power, higher than in the cases in which the content of O2 in the combustion air is smaller.

SYNGAS TO METHANOL
Methanol Synthesis The cleaned and conditioned syngas is converted to methanol in a fixed bed reactor containing a copper/zinc oxide/alumina catalyst. The mixture of methanol and unconverted syngas is cooled through heat exchange with the steam cycle and other process streams. The methanol is separated by condensing it away from the unconverted syngas. Unconverted syngas is recycled back to the entrance of the methanol synthesis reactor.

PROCESS CONDITIONS FOR METHANOL

SYNTHESIS

The composition of this methanol product is shown in Table below. After this step, the product is nearly 96% methanol, with the remainder being mainly CO2 and water and small amounts of various components.

METHANOL TO GASOLINE: SALIENT FEATURES

Reaction in MTG Reactor : 2CH3OH CH3-O-CH3 + H2O H=55.68KJ/mole

Methanol is first dehydrated to dimethyl ether (DME). Then an equilibrium mixture of methanol, DME and water is converted to light olefins (C2-C4). A final reaction step leads to the synthesis of higher olefins, n/iso-paraffins, aromatics and naphthenes. The shape selective MTG catalyst limits the hydrocarbon synthesis to C10 and lighter.

METHANOL TO GASOLINE CONVERSION

REACTOR PARAMETERS

PROCESS SPECIFICATIONS

High-quality gasoline is synthesized by catalytic reaction of methanol over zeolite ZSM-5 between 330-400 C at a liquid methanol volumetric space time of 0.6-1 hour Prior to conversion , the crude methanol from the intermediate storage tank is pumped into the MTG process to raise the liquid pressure to 200 psia (1.4 MPa). The methanol is then passed over the ZSM-5 zeolite catalyst in a fluidized bed reactor . The overall stoichiometric equation in the conversion of methanol to hydrocarbons is shown below: n (CH3OH) (CH2) n + n (H20)

OUTLET RESULTS
Products production (on daily basis)
Products CH4 C2-C4 olefins C2-C4 paraffins Gasoline (C5-C9) Distillates / diesel Oils and waxes Oxygenates % Composition 1.9 2 17 79 0.1

MTG PROCESS VS FT PROCESS

MTG process selectively converts methanol to high quality gasoline with virtually no sulfur and low benzene which can be sold as is or blended in the refinery gasoline pool. About 90% of the hydrocarbon in methanol is converted to gasoline as the single liquid product, with the remainder primarily LPG. The Fisher-Tropsch process produces a broad spectrum of straight-chain paraffinic hydrocarbon which requires upgrading to produce finished products such as gasoline, jet fuel, diesel fuel, and lube base stocks. MTG process uses fixed bed reactor where as FT process uses slurry bed reactors which are more complex