ROLAND ESQUIVEL

C OA L T O M E T H A N O L D E S I G N R E P O RT
GASIFICATION

UNIVERSITY OF C A L I F O R N I A , S A N D I E G O, 9500 GILMAN DR., LA JOLLA, CA 92093

1. Executive Summary The gasification of coal to methanol process and benefits was discussed as a means to developing a preliminary design report. Gasification process and technology were the focus to understand how syn gas is produced. Syn gas is later converted to methanol. Safety and Technical considerations are highlighted when choosing a reactor. Several real world comparisons aided in determining an gasifiers is the best reactor. It is still to be determined if one or several in parallel will be need to meet demand. 2. Introduction to Gasification The design scope will investigate the processing capabilities and the economic feasibility to create a chemical plant for the gasification of coal to methanol as an alternate energy source.
Coal gasification has been used for many years. Primitive coal gasification provided town gas worldwide more than 100 years ago, and a gasification industry produced coal-based transportation fuels for Germany in World War II. In the U.S., a Texaco gasifier is utilized in commercial operation at the Tennessee Eastman chemical plant in Kingsport, Tennessee to produce synthesis gas for production of methanol. The Dakota Gasification plant in North Dakota

produces substitute natural gas and chemicals based on an advanced World War II gasification technology. Technologies being demonstrated in the Department of Energies Clean Coal Technology program is Integrated Gasification Combined-Cycle (IGCC).IGCC is an innovative electric power generation process that combines modern coal gasification with gas turbine and steam power generation technologies. Attractive features of technology include: The ability to produce a consistent product that can be used for the generation of electricity or as primary building blocks for manufacturers of chemicals and transportation fuels.1 The ability to process a wide range of feedstock including coal, heavy oils, petroleum coke, heavy refinery residuals, refinery wastes, hydrocarbon contaminated soils, biomass, and agricultural wastes.1 The ability to remove contaminants in the feedstock and to produce a clean syngas product.1 The ability to convert wastes or low-value products to higher value products. The ability to minimize the amount of solid waste requiring landfill disposal. Solid by-products have a market value can be used as fuel or construction material, and are non-hazardous.1 Over 90% of gasification-based methanol production operates with LURGI isothermal reactors.7 Several

reaction involved in gasification. The syn gas product ratio of H2:CO has a target of 2:1 for direct synthesis to methanol. However, there are several different gasification operators that produce a variety of products

3. Gasification Process Description Gasification is a process for converting carbonaceous materials to a combustible or synthetic gas (e.g., H2, CO, CO2, CH4).In general, gasification involves the reaction of carbon with air, oxygen, steam, carbon dioxide, or a mixture of these gases at 1,300F or higher to produce a gaseous product that can be used to provide electric power and heat or as a raw material for the synthesis of chemicals, liquid fuels, or other gaseous fuels such as hydrogen. Figure 3.2 list the chemical

from syn gas. The aim for methanol synthesis is to use the operation that will minimize an extra processing step, namely the down stream water gas shift reactor to adjust the levels of CO to meat the 2:1 ratio with methanol. Figure 3.2 illustrates the different syn gas profiles of 6 production plants.
Syn Gas Profile by Gasification Operator
CO2 CO2 CO2 CO2 CO2 CO2

CO

Component vol%

CO

CO CO

CO

CO

H2 H2 H2 H2 H2

H2

LURGI-Oxy

Texaco-Oxy

BG/L-Oxy

KRW-Air

KRW-Oxy

Figure 3.1 Syngas profile produced by gasification plants in the world

Chemical Reactions in Coal Gasification4 Reaction Reaction heat, kJ/(kgmol) Process Solid-gas reactions +393, 790 C + O 2 CO 2 Combustion +74, 900 C + 2 H 2 CH 4 Hydrogasification 175, 440 C + H 2O CO + H 2 Steam carbon 172,580 C + CO 2 2CO Boudouard Gas-Phase reaction +2,853 CO + H 2O H 2 + CO 2 Water gas Shift +250,340 CO + 3H 2 CH 4 + H 2O Methanation Figure 3.2 Table of major chemical reactions involved in carbon gasification. A great deal depends on the gasifier system, coal reactivity and particle size, and method of contacting coal with gaseous reactants (steam and air or oxygen). It is generally believed that oxygen reacts completely in a very short distance from the point at which it is mixed or comes in contact with coal or char. The heat evolved acts to pyrolysis the coal, and the char formed then reacts with carbon dioxide, steam, or other gases formed by combustion and pyrolysis Entrained Bed The two primary examples of oxygen-blown, dry feed, entrained-flow gasifiers are Shell and PRENFLO. These two gasifiers share common roots and are very similar. An advantage

of Shell coal gasification technology is the lack of feed coal limitations. Such the ability to take in dry coal versus slurry. The penalty for this small efficiency improvement is a more complex coalfeeding system. Like the Shell, the PRENFLO gasification process uses pressurized, dry-feed, entrained-flow technology with water-cooled gasifier vessels. The primary difference between the two processes is in the design of the syngas cooler. While the Shell process uses cooled recycle gas to partially cool the hot syngas before heat recovery, the PRENFLO process uses a radiant water-wall boiler with fins (to increase the surface area for heat transfer) that is connected directly to the gasifier. The PRENFLO gasifier was selected for a 300-MW IGCC project in Puertollano, Spain, to begin operation in 1996. The project is funded by power companies from several European countries and by the European Community.4

BURN SEPARAT E AIR PRODUCT S GASES SOLIDS

Q-DECOMP

EXHAUST DRY-FLSH

DRY-REAC NIT ROGEN IN-DRIER WET-COAL INBURNER

DECOMP DRY-COAL

4. Design Basis, Principle and Limitations Aspen Plus software was used to run a simulation on coal gasification for an estimate of process capability. The syn gas profile and balances for heat and material are located in Appendices. A coal feed rate based on the Montana Sub-Bituminous coal analysis was set to 5032 lb/hr with a sulfur content translating to a 97.5 lb/hr feed rate. An air mixture, rather than the pure oxygen feed, was used to estimate a worst case scenario for the gasification and heating of coal in the reactor. Steam was feed into the reactor at 833 lb/hr. Heat duty out of the reactor was calculated by Aspen at -5.5x105 Btu/hr. The syn gas flow rate is 18392 lb/hr for CO2, 30.3 lb/hr for CO. The particle size distribution was set to 10% on a 120 mesh screen (149 m), 20% on 140 mesh screen (125 m), 30% on a 160 mesh screen (105 m) and 40% on a 180 mesh screen (88 m). One limitation of the particle is to have finely ground dust to maximize surface area of reaction and

minimize residence time. The fine particle sizes will also reduce caking or agglomerating of the slag, and possible causing a plug up or corrosion. A scale will need to be done to feed the next reactor, the water shift. The water shift reactor will be used to balance the syn gas profile to a 2:1 hydrogen to carbon monoxide for methanol synthesis. Calculated feed rates for Montana sub bituminous coal for full scale production will be 75,000 kg per hour. Reactor size and materials of construction may limit the reactor size, creating the need produce syn gas with 2-3 gasifier reactors. Current reactors have a variety of steam and oxygen feed stock depending on the final product. Figure 4.1 is a table listing of operational gasification plants through out the world.
Developer Type of Bed Coal feed form Coal type Oxidant Pressure, Mpa (psia) Ash form composition, vol% H2 CO CO2 CH4 Other hydrocarbons H2S COS N2+Ar H20 NH3+HCN HCL H2S:COS Lurgi Texaco BG/L KRW KRW Moving Entrained Moving Fluid Fluid Dry Coal Coal Slurry Dry coal Dry Coal Dry Coal Illinois #6 Illinois#6 Illinois #6 Illinois#6 Illinois#6 Oxygen Oxygen Oxygen Air Oxygen 0.101 4.22 2.82 2.82 2.82 Slag Slag Slag Agglomerate Agglomerate 52.2 29.5 5.6 4.4 0.3 0.9 0.04 1.5 5.1 0.5 20:1 30.3 39.6 10.8 0.1 1 0.02 1.6 16.5 0.1 0.02 42:1 26.4 45.8 2.9 3.8 0.2 1 0.1 3.3 16.3 0.2 0.03 11:1 15.7 24.9 5.3 0.8 <0.01 47 6.2 0.02 8:1 27.7 54.6 4.7 5.8 <0.01 1.3 0.1 1.7 4.4 0.08 9:1 Shell Entrained Dry Coal Illinois#6 Oxygen 2.46 Slag 26.7 63.1 1.5 0.03 1.3 0.1 5.2 2 0.02 0.03 9:1

Figure 4.1 lists of current gasification producers and feed stock analysis for comparison.4 Gasification reactor configurations for synthetic fuel production will have the goal of maximizing the product yield at the lowest cost. Other factors that are considered when choosing a reactor can be stability, control, reliability downstream processing requirements, environmental effects and safety. Heat and mass transfer will transform the material brought into the reactor. The extent and rate of the reaction characterize the reactor kinetics. In the case of gasification three distinct phases will be involved: solid, liquid and gas. Estimates of coal and raw material requirements needed to meet 5000MTper day of demand were calculated to be 855.1 MT per hour of coal based on the 48.72% fixed carbon analysis. Oxygen requirement at feed are 208.3 MT per hour and 117.2 MT per hour of steam are required, basis is preliminary in that 100% carbon conversion is expected.

5. Technology Selection Criteria and Conclusion Over 90% of gasification-based methanol production operates with Lurgi Isothermal reactors.7 This includes all the large capacity ones. Residence time of coal particles inside reactor is a critical factor and a accepted form of characterizing the reactor is to use the residence time9. Shipping restrictions limit size gasifier to 4.25 m2,7. Units with these restrictions will generally have flow rates that range up to 50scfm (106,000 standard cfm) Typical settling chamber waste gas flow capacity is 15 to 30 scfm per cubic foot of chamber volume.5 Figure 5.1 is a illustration of the Texaco gasifier Inlet gas temperatures are only limited by the materials of construction of the settling chamber and have been operated as high as 1000F. Gas pollutants loading can range from 20 to 4500 grams per standard cubic meter. Leakage of cold air into the chamber can cause local gas quenching and condensation which can lead to corrosion and plugging up of the hopper 1. The efficiency of the settling chamber increases with residence time of the waste gas in the chamber. Because of this, settling chambers are often operated at the lowest possible gas velocity. Advantages include low capital cost Very low energy cost Reliability Lowe pressure drop.

Figure 5.1Texaco gasifier

Figure 5.2 Process flow diagram of the coal to methanol gasification. Listed values are the Aspen process calculations. An entrained gasifier similar to the Texaco of Shell gasification plant is recommended.

Figure 5.2 PFD of gasifier with material balance results from Aspen.

7. Health, Safety, Toxicity and Environmental Impact There are various technologies that can be used to remove unwanted components, including particulates, alkali, tars, sulfur, and ammonia, from the producer gas stream after gasification. The gas cleanup and conditioning technologies for gasification systems are addressed. In practice, the gasifier and the gas conditioning technologies must be considered as integrated systems to maintain operational. The primary types of systems include cyclonic filters, barrier filters, electrostatic filters, and wet scrubbers. Cyclones remove bulk and solid contaminates and often are set up in series. The most common wet scrubbers use a venturi design to create a pressure drop that allows solutions to be easily sprayed into the gas stream. Gas velocities are typically 60 to 125 m/sec in this throat area. Particulate removal efficiency is proportional to the pressure drop across the Venturi. Entrained Flow Gasifiers do not suffer from corrosive slags, because a protective film of water or steam protects the wall lining from the slag. Recoveries of sulfur species in the fuel are in the form of solid sulfur or sulfuric acid to be removed in a acid bath and desulfurization process.

Low temperature processes produce a char that can be sold as fuel. High temperature processes produce a slag, a non-leachable, on-hazardous material suitable for use as construction materials. In contrast, coal gasification produces a relatively clean fuel. Further environmental credits can be gained by augmenting coal with opportunity fuels that contain fewer toxic components, such as biomaterials, municipal solid wastes, and some petroleum refinery wastes.7 Reference: 1) C. Higman and M. Van der Burgt, Gasification, Elesevier, Amsterdam, 2003. 2) J.M. Moe, Design of water-gas shift reactors, Chemical Engineering Progress 58 (1962) 33-36. 3) WWW.Worldcoal.org 4) R. Perry, Perrys Chemical Engineering Handbook, ed. D.W. Green and J.O. Maloney, McGraw-Hill, New York, 7th edn, 1997, ch. 27, pp. 17 5) R. Reubroycharoen, and N. Tsubaki, in Methanol Synthesis in Inert or Catalytic Supercritical Fluid, ed. B.H. Davis and M.L. Occelli, Elservier, Amsterdam, 1st edn., 2007. pp. 367-378. 6) R. Probstein, in Synthetic Fuels, McGraw-Hill, New York, 1976, pp. 31-140. 7) C. Higman, Methanol Production by Gasification of Heavy Residues, Elesevier, Amsterdam, 2003