UNIVERSITY OF CALIFORNIA SAN DIEGO

Coal-to-Methanol Conversion
Gasification
Group 5
Jennifer Inouye Aerang Kim Wilson Wong Angelica Zabala April 24, 2008

ASPEN Simulation: J. Inouye, A. Kim, W. Wong, A. Zabala; EH&S: J. Inouye; Costing, Gasify Simulation, BFD: A. Zabala; Gasification Selection, PFD: W. Wong; Hand Calculation, Appendix, PFD: A. Kim

Abstract The overall goal of this study is to provide a preliminary design for the conversion of coal to methanol with a desired production rate of 5000 MT/day of AA Grade alcohol, and to determine its economic feasibility. Previously, the Montana sub-bituminous was chosen as the coal type with the entrained flow gasification as the suitable technology. Specifically, the Shell Coal Gasification Process (SCGP) is selected and is discussed in detail on this report. Using ASPEN Plus to simulate the SCGP, it is found that 3000 MT/day of coal with 1750 MT/day of oxygen and 437 MT/day of water is estimated to produce 4000 MT/day of syngas, with a 3 to 2 CO to H2 molar ratio. The capital and annual operating costs were determined to be $84M and $104M respectively. Introduction The rapid increase in prices of crude oil and the continuous rise in demand for chemical feedstocks among the developing Asia-Pacific countries have fueled the need to search for alternative sources of energy. In the United States, a significant percentage of the primary energy source comes from imported crude oil, despite the enormous energy reserves in the form of coal available. In fact, the US is considered as one of the top world leaders in coal reserves, bearing about 26.7% of the worlds total coal resource.1 With the growing environmental concerns, the immediate utilization of coal as a fuel may not be the right direction to follow. One of the more sound alternatives is the production of methanol from these coal deposits, which offers a feasible method for storing energy, as well as a convenient intermediate for the chemical industry. This method, if successfully designed and implemented, has the potential of being a staple and reliable energy source in the years to come.2 The main objective of this study is to devise a preliminary design for this coalto-methanol technology, and to assess the technical and economic viability of constructing and operating a new-world scale methanol facility on the Texas Gulf Coast. This study would follow the proposed methodology in the problem statement but would primarily focus on selecting, evaluating and simulating the technologies in the reviewed literature. Preliminary costing would be accomplished by considering the capital and operating costs, and the Internal Rate of Return (IRR) would be calculated to evaluate the economic potential of the proposed design. For this report, emphasis is given on the gasification process that produces synthesis gas from coal. Specifically, the SCGP design specifications are outlined, along with simulation results and initial costing analysis. Project Description The general scheme for the coal-to-methanol conversion is given in the block flow diagram that appears on Figure 1. The block enclosed in the dotted line represents the gasification process, which is the main focus of this discussion. The flow rates shown are generated from the preliminary simulation with ASPEN and are further explained in the report. 2

Coal Gasification

Acid Gas Removal

Water Gas Shift

Methanol Synthesis

Methanol Refining

O2 + steam
1750 MT/day

H2O

Pre-processed coal
3000 MT/day

1500 C 30 bar

Raw Syngas
4000 MT/day

Pure Syngas
< 0.1 ppmv S

2H2:1CO Syngas
63 mol% H2 37 mol% CO

Unrefined Methanol

AA Grade Methanol
> 99.85 wt% Methanol < 0.1 wt% Water < 50ppm Ethanol

Slag 300 MT/day

H2S + CO2

Impurities

Figure 1. Block Flow Diagram of the Coal-to-Methanol synthesis.

Background on Coal Gasification Coal gasification is utilized as the main conversion technology in producing syngas for methanol synthesis from coal. This process occurs at extremely high temperatures (1500oC or higher) and therefore could be modeled as a thermodynamic equilibrium since the reaction rates are considerably high. The simplified reaction is as follows: CxHy + x/2 O2 x CO + y/2 H2 , where x and y are dependent on the actual coal compositions. Under assumptions of equilibrium, several reactions are expected to occur and could be used to determine the composition of the outlet gas by means of their equilibrium constants, Kp. The reactions include, but are not limited to: a) CO shift reaction CO + H2O CO2 + H2 Kp =

PCO2 PH 2 Pco PH 2O

yCO2 yH 2 yco y H 2O

b) Boudouard reaction C + CO2 Kp = c) Water gas reaction C + H 2O Kp =

2 CO

2 2 PCO yCO P = Pco2 yco2

CO + H2 =

PCO PH 2 PH 2O

yCO yH 2 y H 2O

d) Steam methane reforming reaction CH4 + H2O Kp =

CO + 3 H2.
3 yCO yH 2

P P

3 CO H 2

PCH 4 PH 2O

yCH 4 y H 2O

P2 .

In addition to these, other reactions involving sulfur and nitrogen compounds also occur. Some of the important products formed are H 2S, COS, NH3 and HCN. Progress Update Gasification Technology Selection Entrained flow gasifiers have several distinct advantages over fluid and moving bed gasifiers. For instance, they produce a cleaner, tar-free gas since the operating temperature is well above the melting point of ash (~1500C). The high temperature is advantageous because it breaks down the tar and oils into their components so that they do not contaminate the syngas, and in the process, it ensures a high carbon conversion. Unfortunately, because entrained-flow gasifiers are of the slagging type, one major drawback is that they consume a relatively large portion of oxygen. Since the quality of the syngas is of great importance, entrained 4

flow gasifiers are still most suitable for the syngas production using the subbituminous coal. With regards to the selection of coal-loading technique, dry coalloading is deemed more beneficial. It offers a 20-25% lower oxygen consumption when compared to wet/slurries, which leads to a lower operating cost of the overall process. It also provides an extra degree of freedom since the amount of water could be regulated, leaving more room for optimization. There are several dry-loading, entrained-flow gasifying technologies available, including Koppers Totzek, Shell, Noell and CCP. Several similarities exist among them and the determining criterion in choosing one over the other is on how established the technology is. As such, SCGP was chosen because there are enough base cases that could aid in better planning of the plant design. Figure 2 shows the process flow diagram for a typical Shell Coal Gasifier. It features a co-current oxygen and water blast, with an operating temperature of 1500oC and pressure of 30 bar. Higmans Gasifier and ASPEN Plus Simulations In order to obtain an approximate proportion of coal, oxygen and water for use in the ASPEN simulation, Higmans Gasify program was used. The complete data appears in Appendix A while a summary of the relevant information is provided in Table 1. The composition of the effluent gas is also shown. Table 1. Summary of feed and product properties and composition from Higmans Gasify program.
Temperature (oC) Pressure (bar) Mol/mol ratio Components (mol fraction) CO2 CO H2 O2 H2S H2O Coal (MAF) Ash Others Feed 1 Coal 50 30 1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.3944 0.5298 0.0758 0.0000 Feed 2 Oxygen 100 30 1.0947 0.0000 0.0000 0.0000 1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 Feed 3 Water 300 30 0.2925 0.0000 0.0000 0.0000 0.0000 0.0000 1.0000 0.0000 0.0000 0.0000 Product 1 Syngas 1500 30 5.4932 0.0013 0.6077 0.3722 0.0000 0.0038 0.0029 0.0000 0.0000 0.0121 Product 2 Slag 1500 30 0.0758 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 1.0000 0.0000

For the ASPEN simulation, a coal feed rate of 3000 MT/day is used (neglecting losses from material transfer and assuming 100% carbon conversion, with coal as the sole carbon source), from where the amount of oxygen and water would be determined. Some Shell gasifiers that were reviewed operate with this maximum capacity; hence, one gasifier would be sufficient to carry out the process. Peng Robinson is used as the thermodynamic method due to its suitability on the high

temperatures and pressures that the gasification process operates on. The complete ASPEN simulation flow sheet appears on Appendix B. The pressurizing of coal before entering the gasifier is simulated using an RYIELD reactor at 30 bar and 50oC. Coal is assumed to be broken down completely into its components, namely H2O, N2, O2, H2, S and ash. Since the Shell gasifier does not exist as a single unit in ASPEN, it is broken down into several parts. The reaction chamber is modeled as two reactors in series with both operating at 1500 oC and 30 bar. The first reactor is modeled as an RSTOICH, which is used to ensure complete consumption of the O2 that is fed. This is added in order to determine exactly how much oxygen is required to completely oxidize the coal that is present. This is then followed by an RGIBBS reactor that completes the gasification process by determining the probable products based on minimization of the Gibbs free energy. Oxygen and water at 30 bar and 150oC are added to the pressurized coal just before it enters the gasifier. From the Gasify data, the oxygen-to-water ratio is determined to be about 1:3 (by mole). The coal-to-oxidizer ratio, unfortunately, could not be calculated since the molar mass of the coal is unknown. As such, different amounts of O2/H2O feed ranging from 1300 MT/day to 1800 MT/day were inputted into the RSTOICH block and evaluated on the basis of the quality of the syngas produced (See Appendix C for the syngas composition derived from the different feed values). Relative to others, a feed of 1750 MT/day (1313 MT/day of O 2 and 437 MT/day of H2O) yields syngas with a 3:2 molar ratio of CO:H 2, which is expected of most gasification products 3 and which is also similar to the values generated from the gasify program. In addition, H2S produced is at a minimal 3.0 mol% and CO2 production is almost negligible. The table below summarizes the ASPEN simulation results for the gasification process, including the feed and syngas characteristics. Table 2. Summary of feed and product properties and composition using ASPEN Plus simulation.
Feed 1 Coal Temperature (oC) Pressure (bar) Flow Rates (MT/day) Components (mole fraction) Coal O2 H2O CO H2 H2S Ash Others 50 30 3000 Feed 2 Oxygen+Wat er 150 30 1750 Product 1 Syngas 1500 30 4000 Product 2 Slag 1500 30 300

1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.7500 0.2500 0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.0000 0.0029 0.5823 0.3948 0.0041 0.0000 0.0188

0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 1.0000 0.0000

The gasification products, syngas and slag, are separated using an idealized SSPLIT, which assumes that all the solids exit out to the bottom. This is not the actual case on most gasifiers since fly slag is typically present in the syngas, but the correct proportion of fly to bottom slag is not known. This exiting slag is rapidly cooled down from 1500oC to 500oC using a heat exchanger with 1500 MT/day of H2O. Meanwhile, the syngas moves to the top section of the gasifier, where it is quenched to 900oC by a cooled syngas at 280oC. This syngas is recycled from gas exiting the syngas cooler, which is modeled as a simple cooler in ASPEN. This cooled raw syngas is passed on to a candle filter that takes out the remaining solid from the gas. For the simulation, this was not included since all the solids were designed to be discharged on the bottom of the gasifier. After the solid removal, the syngas stream is split into two equal streams, with one half going back as the recycled gas quench in the gasifier and the other half proceeding to the next processing step for the methanol synthesis. Preliminary Costing In estimating the capital cost for the gasification process, the 2000 Shell Gasifier IGCC Base Cases was used as the basis. The plant that was referenced in the report operates with a nominal case of 3000 MT/day of coal, 4 which is similar to the estimated amount of coal required in this project; hence, the same equipment costing could be utilized to approximate the startup cost. Using their values, the capital cost that includes the Shell gasifier, contingency fees and royalties amount to $84M. With regards to the operating cost, the costs of buying, transporting and processing coal were considered, along with the costs of some of the consumable materials used in the process. The coal costs comprise the bulk of the annual operating cost, totaling to $65M. The remaining of the annual cost comes from the consumable materials that include HP steam, oxygen and process water. The cost of these materials amounts to $37M. A maintenance cost was also allocated to be 2.20% of the total equipment cost and was found to be about $2M. As a preliminary value, $188M is required for the startup and one-year operation of the Shell Gasifier. The table below summarizes the costing information. Table 3. Capital and Annual operating cost for SCGP. Capital Operating (annual) Equipment Cost* $78M Coal $65M Contingency Fee* $4M Consumable $37M Materials Prepaid Royalties* $2M Maintenance $2M Total $84M Total $104M Safety and Environmental Considerations The gasification process entails guidelines to be considered for safe operation. During start-up, the ignition of coal is one of the most dangerous processes due to the pressure changes that occur within the reactor because of the cooling down of the membrane walls. To compensate for these pressure changes, 7

burners are used. In this situation, a mixture of combustible gas and oxygen must be avoided from entering at all times. Precautions must also be considered during the shutdown of the gasifier such as during repairs. Often, the gasifier is nitrogen blanketed to avoid corrosion. Only air is allowed to be present within the gasifier, which can be ensured with the use of a good vacuum and breaking this with air. This process should be repeated several times to completely remove any noxious gases present in insulating materials, bricks, and dead ends in the plant. It is recommended that air masks be worn under certain conditions. Inevitably, toxic gases are present in a gasification complex such as H 2S, which can be handled and disposed of properly by following the information available on the material safety data sheets. In addition, concentrated CO 2 that is produced poses a problem. Danger can be avoided by ensuring the CO 2 that is vented have sufficient buoyancy by keeping temperatures elevated. Purity of the air entering the air separation unit is also an important aspect to consider. In previous cases, concentration of hydrocarbons in the atmosphere increased to such a vast amount that it overloaded an internal hydrocarbon filter. Effects have shown hazardous results of an explosion in one case. Therefore, the specifications of feed air quality are highly recommended.

Figure 2. Process Flow Diagram for the Shell Coal

Gasification Process.

Recommendation In conclusion, the Shell Coal Gasification Process is the suggested gasification technology method for syngas production. Barring all the carbon losses in the process and assuming coal as the only source of carbon, 3000 MT/day would be sufficient to meet the methanol production requirement. For this amount of coal, a 3:1 molar ratio of O2:H2O with a flow rate of 1750 MT/day is required to produce enough syngas to act as both a quench gas and as the synthesis gas required for the eventual synthesis. In the next few weeks, the sour gas removal technology and water gas shift will be studied extensively. References 1 W. Shepherd and D.W. Shepherd, Energy Studies 2 nd edition, 2005, 103-104. 2 S. Lee, Methanol Synthesis Technology, 1989, 1-2. 3 C. Higman and M. Burgt, Gasification, 2003, 120-121. 4 W. Shelton and J. Lyons, Shell Gasifier IGCC Base Cases, 2000. 2008 AICHE Design Competition Problem Statement

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