Chemical Engineering XXX Design Project:

Texas Lignite Coal Gasification and Methanol Production

Final Report Submitted: XX/XX/XXXX

Team X

Table of Contents
Executive Summary ......................................................................................................................... 1 I. Introduction .................................................................................................................................. 2 II. Process Description ..................................................................................................................... 2 III. Process Flow Description ............................................................................................................ 2 i. Gasifier (Gasification Unit) ....................................................................................................... 2 ii. Gas Treatment Units (Pre-Rectisol, Rectisol and Claus Processes) ......................................... 3 iii. Water Gas Shift (WGS System) ............................................................................................... 5 iv. Methanol Production (MeOH Production Loop) .................................................................... 5 IV. Safety and Controls .................................................................................................................... 6 V. Sizing Calculations ....................................................................................................................... 7 VI. Utility Requirements .................................................................................................................. 8 VII. Economic Analysis ..................................................................................................................... 9 i. Fixed Capital Investment and Working Capital ........................................................................ 9 ii. Annual Operating Expenses ................................................................................................... 11 iii. Revenues............................................................................................................................... 11 iv. Discounted Cash Flow ........................................................................................................... 11 v. Profibility Analysis.................................................................................................................. 12 vi. Sensitivity Analysis ................................................................................................................ 12 VIII. Conclusions ............................................................................................................................ 13

Executive Summary

I. Introduction
This paper outlines a basic comprehensive design for a methanol synthesis plant using syngas produced from Texas Lignite, a low quality, but highly reactive coal. In order to produce commercial grade methanol, the coal must pass through several process stages to produce syngas, remove undesirables from the process stream, optimize syngas composition, and synthesize methanol. These processes were modeled in Aspen Plus, and the proposed design has been subsequently characterized with respect to technical and economic considerations as well as safety concerns.

II. Process Description

Traditional methanol synthesis involves the use of: X) a gasification unit, X) a series of gas treatment units, X) a water-gas shift reactor, and X) a methanol production loop, which optimizes the production of pure methanol and includes a recycle for unreacted gases. In the gasifier, a fraction of the coal is combusted to provide the energy required for the concurrent endothermic gasification reaction, C(s) + HXO --> CO + HX. The combustion, gasification, and accompanying reactions in the gasifier generates raw syngas from the coal. Ash, ammonia, and water are removed from the raw syngas prior to the Rectisol process unit (which removes HXS and COX via physical absorption) followed by a Claus process (which converts HXS to solid sulfur). After passing through the gas treatment units, the clean syngas consists primarily of HX, HXO, CO, and COX. In preparation for the methanol production reaction, a water gas shift (WGS) reactor is used to generate a X.X:X mol ratio of HX:CO. This slightly-above stoichiometric ratio of the reactants ensures an excess of HX, preventing the precipitation of solid carbon on the catalyst. The process stream then enters the methanol production loop, where the syngas is used to produce commercial grade methanol by the reaction XHX + CO --> CHXOH. The methanol is distilled from the rest of the product stream, and the gas stream is recycled back into the clean syngas stream to increase reaction conversion.

III. Process Flow Description

(See Appendix A.X for the Process Flow Diagram)

i. Gasifier (Gasification Unit)

The gasifier is modeled in Aspen by four reactors in series. The reactions that occur in the gasifier, as well as all other reactions, are tabulated in Appendix A.X. The reactors are modeled at XX atm under adiabatic conditions, since running the reactors at an elevated pressure 2

decreases the size of the gasifier, the number of filtration units needed to remove impurities in the syngas, and the need for compressors later on in the production process . In the first stoichiometric reactor (INTRXNS) the hydrogen, nitrogen and sulfur compounds present in coal are transformed into HXO, HXS and NHX. A heat correction of XXX kcal per kg of coal is applied to the unit in order to account for the difference in the enthalpies between a mixture of pure elements present in coal and the actual compounds present in coals complex chemical structure. The second stoichiometric reactor (COMBUST) models the complete combustion of hydrogen into HXO and the fractional combustion, approximately XX%, of carbon into COX. This design currently operates under slagging conditions, and uses a feed of pure OX. The target syngas temperature of XXXXXC is achieved using a design specification varying the feed of OX. Compression of OX for the gasifier occurs in multiple stages (with cooling steps in between) in order to maintain reasonable pressure ratios. The third stoichiometric reactor (GASIF) uses a stoichiometric reactor to model gasification of the remaining carbon. XXXXX kmol/hr of steam is fed into the gasifier as a reactant, and the carbon is assumed to react completely. The final reactor in the series, an equilibrium reactor (WGSGASIF) represents the WGS reaction that naturally occurs within the gasification unit.

ii. Gas Treatment Units (Pre-Rectisol, Rectisol and Claus Processes)

At this stage in the process, the exit stream contains HX, CO, COX, HXO, and small amounts of HXS, OX, and NHX. The process stream must be cooled to a low temperature in order to remove the undesirable acid gases present. A combination of two heat exchangers (one producing steam, one using cooling water) and a chiller is used to decrease the syngas temperature to XoC before entering the acid gas removal process.

Pre-Rectisol Scrubber It is imperative to remove the ammonia and water from the syngas prior to treatment with Rectisol, because ammonia builds up as ammonium carbamate in methanol, while water is a solid at the low temperatures required for the Rectisol process. To separate the ammonia and water from the process stream, the syngas is sent through a water scrubber (AMMSCRUBB), modeled as a RadFrac column with XX stages. Rectisol Process Prior to entering the Rectisol process, the dry syngas is cooled to -XX oC by means of a multistream heat exchanger, which transfers heat between the room temperature makeup methanol and dry syngas streams and the cold acid gas and clean syngas streams. This is done in order to obtain the low-temperature, high-pressure operating conditions necessary for optimal absorption of HXS and COX in methanol in the absorption column (RECTSOLX), modeled as a RadFrac column with XX stages. Recycle and makeup streams of methanol are fed into RECTSOLX as the liquid solvent stream, countercurrent to the dry syngas. HXS and COX are physically absorbed into the liquid methanol stream in RECTSOLX at lower temperature and higher pressure (-XXoC and XX atm), and are then removed in the stripping column (RECTSOLX), also modeled as a RadFrac column (but with XX stages), at higher temperature and lower pressure (XXoC and X atm). Through the use of a reboiler and partial condenser in RECTSOLX, methanol functions as both the liquid and vapor streams, so that no separate inert carrier gas is needed to strip HXS and COX from the liquid methanol. Because there is no accumulation of inert species in the methanol, no purge is used in this design. EPA regulations cap SOX emissions, and assuming a X:X conversion ratio of HXS to SOX, the two major limitations are: X) less than X.X% sulfur in the fuel by weight, and X) less than X.X lbs SOX per MMBtu of energy generated from the fuel. Therefore, the clean syngas leaving the Rectisol process must fulfill these two requirements. The first requirement is easily fulfilled, since there is only approximately X.XXXX% sulfur present in the clean syngas stream. The second requirement is also fulfilled, since modeling a simple turbine that generates power from the syngas shows that only X.XXX lbs SOX would be generated per MMBtu of theoretical energy produced (using a XX:X pressure ratio in the turbine). 4

Claus Process The Claus process is modeled using a stoichiometric reactor (CLBURNER) and a Gibbs reactor (CLSRCT) in series. Much of the modeling is accomplished with rough approximations, since in reality the entire Claus process unit will be purchased externally according to the amount of sulfur it is expected to produce. In CLBURNER, one third of the HXS from the Rectisol process is combusted with a stoichiometric amount of OX to form HXO and SOX. HX, CO, and methanol present in the syngas will also combust to form HXO and COX. After removing excess water by means of a flash tank (CLFLASH) to increase conversion, the remaining HXS is reacted in CLSRCT with the SOX generated in CLBURNER to form HXO and sulfur. To be more accurate, as a Gibbs reactor, CLSRCT determines the most energetically favorable compositions of all species present at equilibrium under the operating conditions, which are XXXoC and X atm. Sulfur, which is primarily present in the liquid phase as SX, can then be separated (modeled as an ideal separator, SULFSEP) from the tailgas. The expected sulfur production rate of this design is X.X tonnes/day.

iii. Water Gas Shift (WGS System)

A splitter sends a fraction of the clean syngas exiting the Rectisol process into the jacketed plug flow water gas shift reactor, WGSINDEP, along with XXXX kmol/hr of input steam. The split ratio was adjusted using a design specification that held the composition of the exiting syngas stream to be the X.X:X HX:CO ratio desired for methanol production. The simulated reaction kinetics can be found in Appendix A.X. The WGS reaction is run at high pressure, so in order to obtain a reasonable reactor volume (see Appendix A.X.X), the catalyst should be diluted by a factor of XXXX times to keep superficial gas velocity manageable. This was modeled in Aspen by proportionally decreasing the pre-exponential factor. Because the WGS reaction is exothermic, this design uses a heat exchange jacket with cocurrent coolant. Most of the conversion occurs near the beginning of the reactor, so a cocurrent heat exchange causes the lowest temperature coolant to contact the hottest part of the reactor, thus maintaining a steadier temperature profile within the reactor.

iv. Methanol Production (MeOH Production Loop)

The reaction kinetics used in the methanol synthesis reactor are shown in Appendix A.X. Methanol production occurs within a recycle loop to increase conversion. The methanol synthesis heat-jacketed plug flow reactor, METHRXN, is operated at XX atm (a small pressure 5

drop in the process has been accounted for) and an inlet temperature of XXX oC, which is higher than the rest of the recycle loop. In order to minimize the outside heating and cooling necessary, the reactor inlet and outlet streams exchange heat, before the reaction product stream is further cooled with cooling water, and chilled to XoC. The synthesized methanol product is then separated through a series of two flash drums with a final yield of XXXX tonne/day of methanol predicted.

IV. Safety and Controls

Safety precautions and protocols are critical to a comprehensive plant design. Plant safety should be integrated at all levels within a plant, from the engineering controls to the administrative procedures. All potential hazards should be carefully evaluated and, if possible, preemptively addressed at the design and engineering stage. However, it is still imperative that the plant workers are aware of the risks around them, and follow all safety procedures and protocols set in place. Process units should be interlocked so that upon detection of the failure of one unit, other processes will automatically be paused or shut off. Hazards should be isolated as much as possible, so that in the case of a fire or explosion in one part of the plant, the collateral damage can be minimized. One example of this is the installation of firebreaks, especially in the gasification and methanol production units. One simple precaution that should be taken is establishing adequate checkpoints throughout the entire process for temperature, pressure, flow rate, etc. The more information that is monitored, or at least available, the more likely it is to locate a failure when it occurs. For example, in this design, the WGS catalyst is diluted by XXXX times, which constitutes a potential hot spots risk in the reactor because the dilute catalyst may become unevenly distributed along the reactor length. Closely monitoring the temperature profile along the reactor would decrease the severity of this risk, since quick action can be taken if the temperatures fluctuate too severely. As another example, because the coal gasification is run under slagging conditions, it is important to maintain a consistently high reactor temperature to ensure full slagging. Incomplete slagging may end up damaging downstream equipment and cause unexpected equipment failure. 6

This particular process runs at high pressures throughout, and thus runs the risk of pressure buildup. Safety measures to minimize this risk include constant monitoring of pressure at all points in the system, and the installation of safety valves, pressure relief valves, and explosion panels. Danger to personnel can be reduced by overseeing the workfloor with cameras in place of direct observation, although safety glass can be used when remote observation is infeasible. Regular plant maintenance and housekeeping is also very important in reducing safety risks. Through regular equipment checks and replacement of old seals and gaskets, the potential of flammable syngas or methanol leaking can be minimized. Processes involving volatile hazardous compounds such as methanol should be carried out in areas with good ventilation, in case of leaks, and in a cool location. Easily ignitable materials such as coal and methanol should be properly stored away from any potential sources of ignition. Long-term or large-quantity storage of hazardous materials should be kept to a minimum. Solid inerts accumulation is also a consideration. Deionized water can be used in heat exchanger cooling water pipes to prevent calcification buildup, which decreases heat transfer between the water and the hot stream while increasing the pressure in the pipe, potentially resulting in pipe rupture. Additionally, ammonia reacts with methanol in the Rectisol process to produce ammonium carbamates, and though the ammonia is removed beforehand, there may still be non-negligible accumulation of inerts; the same concept applies to ice buildup in Rectisol.

V. Sizing Calculations
(All equipment dimensions and sample calculations can be found in Appendix A.X.) An initial estimate of gasifier size can be performed based on previous empirical values for a similar unit [X], with the approximation that the space velocity remains the same. Given the coal feed rate and gasifier dimensions of the empirical case, and the coal feed rate of this design, the gasifier volume for this design was determined to be XX mX. The water gas shift reactor size scale is approximated by assuming a gas hourly space velocity (GHSV) found in a previous study [X]. With a reasonable GHSV, and the volumetric flow rate entering the WGS reactor, a preliminary reactor volume estimate was determined to be X.X mX. Because the dimensions of the WGS reactor strongly affect the reactor temperature and 7

conversion, the modeled reactor dimensions were then tuned to obtain optimal profiles, resulting in a final reactor volume of X mX. The methanol reactor dimensions were chosen in Aspen to obtain a desirable conversion profile. The number of tubes in the reactor was selected in order to obtain a desirable temperature profile. The reactor is composed of XX tubes, each with a diameter of XX cm and a length of XXXX m. Absorption, stripping and distillation columns are sized using a correlation relating the flooding limit to tray spacing, shown in Appendix A.X.X. [X] Since the flooding limit is the maximum superficial gas velocity allowable in the column, the volumetric flow rate of gas determines the diameter of the column. Column height is then calculated using tray spacing and number of stages. Size dimensions of all columns can be found in Appendix A.X.X. Heat transfer area is calculated by setting the heat gained by the cold stream (or the heat lost by the hot stream) equivalent to the heat transferred across the hot and cold streams. The temperature gradient in each of the single streams is the difference between inlet and outlet temperatures, while the temperature gradient across the streams was taken to be a log mean average of the single stream temperature gradients. The same calculation is used for multi-heat exchangers, for which heat from each stream may be transferred across multiple streams. Area requirements for all heat exchangers can be found in Appendix A.X.X.

VI. Utility Requirements

To deal with most of the plants heating and cooling requirements, steam and cooling water heat exchangers are used, respectively. In this way, the need for refrigeration systems can be greatly reduced, and the need for electric heaters is fully eliminated. Most of the high-pressure steam in this design is generated at the gasifier outlet, where pressurized water at XX atm and XX C exchanges heat with the hot process stream at XXXX C, generating over XXXX tonnes/day of steam at XX atm. This steam is then used to feed the gasifier and WGS reactions, as well as to heat the Rectisol methanol stream (RICHMETH) and the pre-WGS process stream (WGSX). Additionally, low pressure steam at X atm is also produced from the reactor cooling-jackets, some of which is used to heat the methanol leaving the Methanol Production Loop (METHCOND). For cooling purposes, water at X atm and XX C exchanges heat with hot process 8

streams. As a result, the water is heated to approximately XX C and then cycled to a cooling tower, where it is cooled back to room temperature via evaporation at a rate of XXXX tonne/day.

VII. Economic Analysis

The fixed capital investment and working capital are calculated; the sum of these expenses represent the costs needed to build the plant and bring it to an operational state. Yearly expenses and revenues were estimated be extrapolating current market values for utilities, coal, and sulfur. The potential profitability of this design is then considered in the discounted cash flow analysis. Note that costs are estimates and the overall analysis accuracy is within XX%. The majority of costing is based on Towler, a XXXX edition with a comprehensive approach to overall plant costing. [XX]

i. Fixed Capital Investment and Working Capital

Fixed Capital Investment Fixed capital investment represents the total cost of designing, constructing, purchasing all materials, and installing a plant. The economic analysis of this project predicts a $X,XXX million ($XXXXM) fixed capital investment, which is obtained by adding the costs of its four components: ISBL investment, OSBL investment, engineering and construction costs, and contingency charges. Inside Battery Limits (ISBL) Investment ISBL investment represents the cost of the plant itself, and includes (i) the major process equipment, (ii) bulk items such as piping, valves, wiring, instruments, insulation, catalysts, etc, (iii) civil works such as roads, foundations, buildings, sewers, etc, and (iv) installation labor and supervision. It also includes indirect costs such as construction costs, field expenses, construction insurance, labor benefits and burdens, and other miscellaneous costs. The individual equipment costs can be estimated by correlations in Towler. Hand factors are then be used to approximate the total cost including costs associated with installation. The total ISBL costs sum to $XXXM (the depreciable portion of which is $XXXM) and the details of the calculations appear in Appendix B.X.X.

Outside Battery Limits (OSBL) Investment OSBL costs include all offsite expenditures such as electrical support, cooling towers, circulation pumps, water treatment, sewers, feed and product pipelines, loading facilities, warehouse, railroads, laboratories and analytical equipment, offices, workshops and maintenance facilities, site security, fencing, landscaping, etc. These costs are estimated as a XX% of ISBL costs for this initial economic analysis, as is consistent in Towler. The resultant estimate is $XXXM, as detailed in Appendix B.X.X. Engineering and Construction Costs Engineering and construction costs include design of process equipment, piping systems, control systems, plant layout, civil engineering, procurement of plant items, construction and supervision services, administration, contractors profit, etc. Engineering costs are estimated as XX% for small projects and XX% of ISBL plus OSBL costs in accordance of Towlers estimate for larger projects; we chose XX% due to the large scale design of this plant. This works out to $XXM as detailed in Appendix B.X.X. Contingency Changes Contingency charges account for extra costs added to the project budget to allow for variation from the cost estimate. They account for changes in prices, project scope, currency fluctuations, and other unexpected events. This analysis estimates the contingency charges to be XX% of ISBL plus OSBL costs - a value reasonable for a process using established technologies. Appendix B.X.X shows that the total for this category is $XXXM. Working Capital In addition to the fixed capital investment charges above, working capital - additional money needed to start up the plant and run it until it begins earning income -- is also considered. This includes the following:

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Item Cash on hand

Costing Criteria estimated as X weeks worth of production -

Value $XX.XM

Two weeks worth of raw materials spare parts inventory TOTAL

$X.XM

estimated as X% of ISBL + OSBL costs

$X.XM $XX.XM

It can be seen that the total total, the fixed capital and working capital sum to $X,XXXM.

ii. Annual Operating Expenses

In addition to the initial money needed to start a plant, there are two categories of annual operating expenses: (i) variable costs of production and (ii) fixed production costs. Variable costs of production scale with plant output. They include raw materials, utilities, consumables, and waste disposal. As Appendix B.X shows, the costs total to $XX.XM/year. Fixed production costs do not scale with plant output. These costs include operating labor, supervision, direct salary overhead, maintenance, property taxes, land rent, general plant overhead, etc. These costs are detailed in appendix B.X, and sum to $XX.XM.

iii. Revenues
Sales of methanol and sulfur provide revenues for the plant. The Aspen simulation modeling the plant predicts plant outputs of XXXX tonnes/day of methanol and X.X tonnes/day of solid sulfur. As Appendix B.X outlines, the selling price of these commodities are $XXX/ton and $XXX/ton, respectively. Methanol and sulfur annual profits total to $XXXM/year and $XXX,XXX/year, respectively, resulting in total revenues of $XXXM/year.

iv. Discounted Cash Flow

Discounted cash flow diagrams are calculated to illustrate the rate of return on an initial investment. The relevant equations used are:

11

Most years, this sums to $XXX.XM, however, every Xth year (starting year X) catalyst is purchased and an additional $XXXM is added to the operating costs. Gross Profit compares these operating costs to the income and depreciation:

Depreciation is calculated with double declining balance until the linear depreciation values are greater. The tax rate is then applied and the net product is calculated:

Where the overall tax rate is estimated to be XX% -- this includes federal, state, and local taxes. The addition to cash flow (the desired annual number) is simply the sum of the depreciation and the net profit. There is the option of multiplying this number by a discounting factor, where the discount rate is fractional (eg: XX% discount rate = X.XX) and n is the number of years passed since year X. For a X% discount rate, the profit over XX years is $X,XXXM. Note that this is not corrected for the time value of money. By solving for the discount rate that gives X net cash flow at year XX, the annual rate of return is identified. Applying this method, the rate of return is determined to be XX.X%. The cash flow diagrams and plots are shown on the proceeding pages.

v. Profibility Analysis
A large initial capital investment ($X,XXXM) is required to cover the costs of building the plant outlined in the design. The economic analysis, although only accurate within XX% suggests that over a period of thirty years, this investment will generate substantial returns.

vi. Sensitivity Analysis

As electricity is a major cost in operating this plant, one of the primary considerations in optimizing the economic viability of this design is the number and type of electricity-consuming equipment utilized. The three operations that require electricity are: heating and cooling, pressurization, and distillation. Through the strategic implementation of heat exchangers, the number of electrically-powered heaters and coolers needed was reduced. Additionally, the 12

process flow was modified (when possible) to pressurize liquids instead of gases, since liquids are relatively incompressible, and thus require less energy. Finally, addition of a flash tank before the Methanol Production Loop eliminated the need for an energy-intensive distillation column at the end of the process. By making these changes, the total consumption of electric power was reduced by more than XX%, from over XXX MW to fewer than XX MW. Another aspect of the process design that is extremely susceptible to changes is the temperature profile along the reactor in the methanol production loop, as shown in Appendix A.X. With minor changes in the heat jacket coolant flow rate (around X.X%), the equilibrium conversion temperature and length shift much more significantly (around XX%). Changes in the inlet temperature rate (around X.X%, or XXoC) lead to a surprisingly large shift in equilibrium conversion and length (around XX-XX%). Because the methanol reactor conversion equilibrium has a direct effect on revenue, it is important to note that minor changes in operating conditions may have a significant effect on profitability.

VIII. Conclusions
This project is an introductory survey into the feasibility of constructing a proposed methanol plant. This plant design provides an estimated XX% return on investment for the production of methanol from Texas Lignite coal. The process makes use of coal gasification, rectisol, water-gas shift, and methanol synthesis technology to yield a reasonable conversion of coal to methanol. Many factors have been taken into account and assessed in this report, including technical considerations, science and engineering fundamentals, safety and controls, and economic principles. This introductory investigation provides the groundwork for future analyses.

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References:
[1] Bockelie, M.J. et al. CFD Modeling For Entrained Flow Gasfiers. Neville Holt, Electric Power Research Institute, Palo Alto, CA.

[2] Catalyst information. UC Berkeley Chemical Engineering XXX Resource, Spring XXXX, Microsoft Word Document (accessed Apr. XX, XXXX).

[3] Choi, Y.; Stenger, H.G. Water gas shift reaction kinetics and reactor modeling for fuel cell grade hydrogen. Journal of Power Sources. [Online] XXXX, XXX, XXX-XXX. http://www.sciencedirect.com. (accessed Apr. XX, XXXX).

[4] Crawford, J.; Ellifritz, B.; Root, B. Process Design of an Anhydrous Ammonia Production Facility for Dyno Nobel. UC Berkeley Chemical Engineering XXX Resource, Spring XXXX, PDF Document (accessed Apr. XX, XXXX).

[5] Economics cheat sheet. UC Berkeley Chemical Engineering XXX Resource, Spring XXXX, Microsoft Word Document (accessed Apr. XX, XXXX).

[6] Gasification Plant Cost and Performance Optimization; Vol. X.; DE-ACXX-XXFTXXXXX; Bechtel, Global Energy, and Nexant: XXXX.

[7] GKT Project. Methanol Synthesis Reactor/Kinetic Information. XXXX. UC Berkeley Chemical Engineering XXX Resource, Spring XXXX, PDF Document (accessed Apr. XX, XXXX).

[8] Methanex. Methanol Price. http://www.methanex.com/products/methanolprice.html (accessed Apr. XX, XXXX).

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[9] Perry, R.H.; Green, D.W. Process Safety. In Perrys Chemical Engineers Handbook; Xth Ed. McGraw-Hill: XXXX.

[10] Peters, M.S.; Timmerhaus, K.D.; West, R.E. Plant Design and Economics for Chemical Engineers, Xth Ed.; McGraw-Hill: New York, XXXX.

[11] Towler, G.; Sinnott, R. Chemical Engineering Design. Elsevier, Inc.: XXXX.

[12] U.S. Energy Information Administration. Coal Explained: Coal Prices and Outlook. http://tonto.eia.doe.gov/energyexplained/index.cfm?page=coal_prices (accessed Apr. XX, XXXX).

[13] U.S. Energy Information Administration. Electricity: U.S. Data. http://www.eia.doe.gov/ fuelelectric.html (accessed Apr. XX, XXXX).

[14] Usual Weekly Earnings of Wage and Salary Workers First Quarter XXXX. Bureau of Labor Statistics, U.S. Department of Labor; USDL-XX-XXXX; April XX, XXXX (accessed Apr. XX, XXXX).

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Appendix A: Table of Contents

A.X Process Flow Diagram A.X Materials Flow Information A.X.X Overall Balance Key Summary A.X.X and A.X.X Mass and Molar Flow Sheets A.X Reactor Specifications A.X Reaction Kinetics A.X Equipment Sizing Summaries and Calculations A.X.X Reactor Sizing A.X.X.X Gasifier (INTRXNS, COMBUST, GASIF, WGSGASIF) A.X.X.X WGS Reactor (WGSINDEP) A.X.X.X Methanol Reactor (METHRXNX) A.X.X Column Sizing A.X.X Heat Exchanger Sizing A.X Power Consumption A.X.X Compressors, Pumps, Columns A.X.X Coolers A.X Water and Steam Balance A.X Power Consumption Sensitivity Analysis 17 17 17 17 17 18 18 18 18 19 19 19 20 21 21 22 22 22

16

A.X Process Flow Diagram (see attached pages) A.X Materials Flow Information
A.X.X Overall Balance Key Summary

Key Overall Materials

Input (tonne/day) Output (tonne/day) XXXX XXXX XXXX XXXX X.XX XXXX X.X

Coal Steam OX CHXOH Sulfur

A.X.X and A.X.X Mass and Molar Flow Sheets (see attached pages)

A.X Reactor Specifications

Reactor INTRXNS Reactions specified .X OX + HX HXO S(Cisolid) + HX HXS NX + X HX X NHX HX + .X OX HXO C(Cisolid) + OX COX C(Cisolid) + HXO CO + HX CO + HXO HX + COX X HXS + X OX X HXO + X SOX X HX + OX X HXO X CO + OX X COX X CHXOH + X OX X COX + X HXO (specified by thermodynamics) CLSRCT WGSINDEP CO + HXO HX + COX HX + COX CO + HXO METHRXNX CHXOH CO + X HX CO + X HX CHXOH Extent of Reaction XXX% Frac. Conv. of OX XXX% Frac. Conv. of S XXX% Frac. Conv. of NX XXX% Frac. Conv. of HX XXX% Frac. Conv. of OX XXX% Frac. Conv. of C Equilibrium conditions XX% Frac. Conv. of HXS XXX% Frac. Conv. of HX XXX% Frac. Conv. of CO XXX% Frac. Conv. of CHXOH Operating conditions @ XXXoC, X atm Kinetics-based Kinetics-based Kinetics-based Kinetics-based SRK SR-POLAR SRK Property Method SRK

COMBUST GASIFER WGSGASIF CLBURNER

SRK SRK SRK SRK

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A.X Reaction Kinetics WGS (WGSINDEP) [X,X]

Forward: CO + HXO HX + COX Af = X.Xe-XX Ef = XXXXX Reverse: HX + COX CO + HXO AbX = X.XXe-XX
1

Methanol (METHRXNX) [X]

Forward: CO + X HX CHXOH Af= X.XXXE-XX Ef= XX,XXX Reverse: CHXOH --> X HX + CO Ab= X.XXXXXEX Eb= XXX,XXX

Eb = XXXXX

A.X Equipment Sizing Summaries and Calculations

A.X.X Reactor Sizing
Reactors GASIFIER2 WGSHIFT METHRXNX Diameter (m) X.X X.XX XX Length (m) X.X XX XXXX # of tubes N/A XX XX Sizing Method Holt Neville Choi & Stenger [X] -

A.X.X.X Gasifier (INTRXNS, COMBUST, GASIF, WGSGASIF)

and are constant for reactors of a similar type (slagging entrained bed) and scale (a few thousand tonnes of coal per day), it is evident that reactor volume scales with feed rate of coal. Also, the height-to-diameter ratio is assumed to be constant.
Since

Thus, given certain values for reactor dimensions and flow rate in the Holt Neville study [X], the following values are obtained:
1

Pre-exponential factor scaled down by XXXXx because of catalyst dilution

encompasses INTRXNS, COMBUST, GASIFIER, WGS 18

Diameter (m) Length (m) Volume (mX) Flow (tonne/day)

Holt Neville This design X.X X.X X.X XX.X XX.X XX.X XXXX XXXX

A.X.X.X WGS Reactor (WGSINDEP) Reasonable WGS reactor gas hourly space velocities (GHSV) noted in a previous study were in the range of XXXX to XXXXX hr-X. A GHSV of XXXX hr-X was chosen for the sizing purposes of this process.

Exact diameter and length values were obtained by optimizing the temperature and conversion profiles in Aspen. A.X.X.X Methanol Reactor (METHRXNX) The methanol reactor was sized solely in Aspen in order to provide the optimal temperature and conversion profile.

A.X.X Column Sizing

AMMSCRUB RECTSOLX RECTSOLX Length (m) Diameter (m) # of trays Tray spacing (in) XXX.X X.X XX XX.X XX.X X.X XX XX XXX.X X.X XX XX

The columns in this design are sized by correlating tray spacing, number of trays, and flooding velocity with column diameter: ( ) ( )

19

where

is the gas velocity (in ) at the flooding limit, is the surface tension (in

is a capacity parameter (in ) , are densities (in

correcting for surface tension (value obtained from a chart, and is dependent on flow parameter and tray spacing), ) of the liquid phase, and

) of the liquid and gas phases. A numerical example of sizing is shown below for RECTSOLX: ( ) ( ( ) )

A.X.X Heat Exchanger Sizing

HTX Unit
HTXCMPX HTXCMPX HTXSYNGX HTXSYNGX HTXR (MHTX) HTXR - X HTXR - X HTXR - X HTXRECT HTXWGS HTXWGSX HTXM
3

Heat Duty (MW)

X.X X.X XXX.X XX.X X.X X.X X.X X.X XX.X X.X XX.X XXX.X
th

Area (mX)
XX.X XX.X XXXX.X XXX.X X.X X.X XXXX.X XX.X XX.X XXXX.X XXXX.X

From chart, Perrys Handbook X ed. Fig. XX-XX

20

HTXMETHX HTXMETHX

XX.X X.X

XXXX.X XX.X

Sizing of a heat exchanger involves determining the area of heat transfer. The equations required are shown below:

Sizing of a heat exchanger, HTXCMPX, is shown below as a numerical example:

A.X Power Consumption

A.X.X Compressors, Pumps, Columns

Compressors, Pumps and Columns

Type Unit OXCOMPX Compressor OXCOMPX OXCOMPX WATPUMPX AMMPUMP Pump MEPUMP RECPUMP Distillation RECTSOLX Net Work 21 Work Required (MW) X.X X.X X.X X.XX X.XX Xe-X X.XX XX.X XX.X

A.X.X Coolers

Coolers
Heat Duty Work Required Unit (MW) (MW) X.XX GASCHILL -XX.X X.XX AMMCOOL -X.XX XX.X RECTCOOL -XX.X XX.X METHREFR -XX.X XX.X Net Work

A.X Water and Steam Balance (see attached pages) A.X Power Consumption Sensitivity Analysis (see attached pages)
HIGH PRESSURE STEAM (XXX C, XX ATM) Stream Phase Substream: MIXED Mass Flow tonne/day HXO Temperature C Pressure atm Vapor Frac Liquid Frac Total prod. @ XXX C (tonne/day) Total used @ XXX C Total prod. @ XXX C (tonne/day) Total used @ XXX C LOW PRESSURE STEAM (X ATM) Stream Phase Substream: MIXED Mass Flow tonne/day HXO Temperature C Pressure atm Vapor Frac Liquid Frac Total prod. @ XXX C (tonne/day) Total used @ XXX C Total prod. @ XXX C Total used @ XXX HOT WATER (XX C, X ATM) PRODUCED LPSTMX LPSTMX VAPOR VAPOR USED LPSTMINX VAPOR PRODUCED HPSTMX HPSTMX VAPOR VAPOR HPSTMINX VAPOR USED HPSTMINX HPSTMINX VAPOR VAPOR HPSTMINX VAPOR

XXXX.X XXX.X XX.X X.X X.X XXXX.X XXXX.X XXX.X X.X

XXX.X XXX.X XX.X X.X X.X

XXX.X XXX.X XX.X X.X X.X

XXX.X XXX.X XX.X X.X X.X

XXXX.X XXX.X XX.X X.X X.X

XXX.X XXX.X XX.X X.X X.X

XXX.X XXX.X X.X X.X X.X XXX.X X.X XXXX.X XXXX.X

XXXX.X XXX.X X.X X.X X.X

XXXX.X XXX.X X.X X.X X.X

22

Stream Phase Substream: MIXED Mass Flow tonne/day HXO Temperature C Pressure atm Vapor Frac Liquid Frac Total prod. @ XX C (tonne/day) Total used @ XX C COOLING WATER Stream Phase Substream: MIXED Mass Flow tonne/day HXO Temperature C Pressure atm Vapor Frac Liquid Frac Total used (tonne/day)

HOTWATX LIQUID

HOTWATX LIQUID

PRODUCED HOTWATX LIQUID

HOTWATX LIQUID

HOTWATX LIQUID

XXXX.X XX.X X.X X.X X.X XXXXXX.X X.X

XXXX.X XX.X X.X X.X X.X

XXXXX.X XX.X X.X X.X X.X

XXXXX.X XX.X X.X X.X X.X

XXXXX.X XX.X X.X X.X X.X

COOLWATX LIQUID

COOLWATX LIQUID

COOLWATX LIQUID

USED COOLWATX COOLWATX LIQUID LIQUID

COOLWATX LIQUID

COOLWATX LIQUID

COOLWATX LIQUID

XXXX.X XX.X X.X X.X X.X XXXXXX.X

XXXX.X XX.X X.X X.X X.X

XXXX.X XX.X X.X X.X X.X

XXXXX.X XX.X X.X X.X X.X

XXX.X XX.X X.X X.X X.X

XXXXX.X XX.X X.X X.X X.X

XXXX.X XX.X X.X X.X X.X

XXXXX.X XX.X X.X X.X X.X

23

Appendix B: Table of Contents

B.X General Notes B.X Fixed Capital Costs B.X.X ISBL Costs B.X.X OSBL Costs B.X.X Engineering Costs B.X.X Contingencies B.X Working Capital B.X Variable Costs of Production B.X.X Utilities B.X.X Consumables B.X Fixed Costs of Production B.X Revenues 25 25 25 28 29 29 29 30 30 31 32 33

24

B.X General Notes

Costing is based on XXX days/year of production, where the operational days run XX/X. Costing estimates have an overall accuracy within XX%.

B.X Fixed Capital Costs

B.X.X ISBL Costs
Equipment Costs4 To calculate the gasifier cost, the hypothetical power output of this Texas Lignite coal at the specified flow rate is calculated. This power is multiplied by XX%. This coal contains X.XX Btu/lb; by multiplying by the mass flow rate and X.X, the energy output is determined to be XXXMW. This is very close to the XXX MW gasifier listed in Bechtel [X]; hence, we approximate the design gasifier to have the cost cited in the paper, namely $XXXM. Other major pieces of equipment were sized according to the correlations in Towler [XX]. This method uses a sizing parameter S and the constants a, b, and n in the following function:

Item

Sizing Parameter, S area, mX

Acceptable Range for S XX-XX,XXX

heat exchanger (U-tube shell and tube) jacketed reactor, agitated compressor (centrifugal)

XX,XXX

XX

XX,XXX X,XXX

XX,XXX X.X volume, mX XXXX X.X driver power, kW X.X flow, Liters/s

X.X-XXX XXX-XX,XXX

pump (single stage centrifugal) pump driver (electric motor, explosion

4

X,XXX

XX

X.X-XXX

XXX

XXX

X.X power, kW

X-X,XXX

Because the book used was a XXXX edition, adjusting the cost to XXXX values using cost indices was deemed unnecessary

25

proof) distillation column (stainless steel, XXXss) sieve trays cooling tower XX,XXX XXX XX,XXX XXX X.X shell mass, kg XX-XXX,XXX

XXX XXX

diameter, m

X.X-X XXX-XX,XXX

X.X flow, Liters/s

ISBL COSTS The total ISBL cost is estimated by the Hand method, which proposes that the total ISBL cost is given by where Fi and Ci are the Hand factor and delivered cost of the given piece of equipment. The Hand factor used for each type of equipment is tabulated below and a sample calculation is provided. Equipment Type Hand Factor X.X X X X.X

compressors distillation columns fired heaters heat exchangers

miscellaneous equipment X.X pressure vessels X

The following are the equipment costs and installation costs:

ISBL COSTS:
GASIFIER
$XXX,XXX,XXX $ installation costs

JACKETED REACTOR
$XX,XXX WGS $X,XXX,XXX Methanol $XX,XXX,XXX 26

Columns & Trays

$XXX,XXX RECTSOLX column $XX,XXX all trays $XX,XXX column RECTSOLX $X,XXX all trays $XXX,XXX column AMMSCRUB $XX,XXX all trays $X,XXX,XXX installation costs (for all columns and trays)

COMPRESSORS
$XX,XXX $XX,XXX $XX,XXX $XX,XXX OXCOMPX OXCOMPX OXCOMPX installation costs (for all columns and trays) Heat Exchanger HTXCMPX HTXCMPX HTXSYNGX HTXSYNGX HTXR - X HTXR - X HTXR - X HTXRECT HTXWGS HTXWGSX HTXM HTXMETHX HTXMETHX installation costs (for all heat exchangers) Pump Name WATPUMPX AMMPUMP MEPUMP RECPUMP installation costs (for all)

HEAT EXCHANGERS
Cost: $XX,XXX.XX $XX,XXX.XX $XXX,XXX $XX,XXX $XX,XXX $XX,XXX $XXX,XXX $XX,XXX.XX $XX,XXX.XX $XXX,XXX.XX $XXX,XXX.XX $XXX,XXX.XX $XX,XXX.XX X.XXE+XX

PUMPS
Cost: $XXX,XXX $XX,XXX $X,XXX $XXX,XXX $X,XXX,XXX

Cooling Tower
$XXX,XXX XXXXXX.XXXX installation costs 27

PUMP DRIVERS (electric motors)

$XX,XXX.XX $X,XXX.XX $XXX.XX $XX,XXX.XX $XXX,XXX WATPUMPX AMMPUMP MEPUMP RECPUMP installation costs (for all)

CLAUS PROCESS
$XXX,XXX

Land
$XX,XXX,XXX Subtotal: ISBL COSTS: includes: equipment erection, piping, instrumentation, control, electrical, civil, structures & buildings, lagging and paint $XXX,XXX,XXX depreciation amount: $XXX,XXX,XXX doesnt include installations

In addition to the costs listed above, land costs and Claus System costs were added. Investigations of land cost suggested a reasonable purchase price of $XXM5. The Claus system cost was based on [X]. This reference states that a XXX tons/day sulfur treatment plant costs X million Euros. Using a linear extrapolation with an intercept of zero, and a conversion rate of $X.X per Euro, the cost is determined to be $XXX,XXX. The adjustment from the XXXX value listed in the paper to the XXXX value desired was adjusted by the Chemical Engineering Magazine cost indices; the ratio of XXXX to XXXX was X.XX resulting in the adjusted Claus unit cost of:

The total ISBL costs are used in subsequent calculations, so we note here that it sums to $X,XXXM

B.X.X OSBL Costs

Towler suggests the OSBL costs generally range from XX to XX% of the ISBL costs, with XX% being a good estimate for processes where nothing is known. Because our primary OSBL cost is the cooling tower, which is accounted for in ISBL in this case, we selected a relatively low value of XX%. Thus, the OSBL costs are estimated at $XXXM.

For approximately XX acres outside of Austin, Texas

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B.X.X Engineering Costs

Towler suggests that engineering costs can be estimated as XX% of ISBL costs for larger products. We accept this value, and estimate engineering costs to total $XXM

B.X.X Contingencies
The minimum estimation for contingencies proposed by Towler is XX% of ISBL + OSBL costs. Thus, we calculate:

B.X Working Capital

Working capital costs are estimated by combining cash on hand, two weeks worth of raw materials, and the spare parts inventory. Again, we used the values suggested by Towler. The values for each are tabulated below along with the method used to calculate them.

29

Item Cash on hand Two weeks worth of raw materials spare parts inventory TOTAL

Costing Criteria estimated as X weeks worth of production estimated as X% of ISBL + OSBL costs

Value $XX.XM $X.XM $X.XM $XX.XM

B.X Variable Costs of Production

B.X.X Utilities
Coal costs are estimated based on the US Energy Information Administration, which notes that the cost of lignite coal is $XXXX per ton [XX]. Using our simulated coal input, we find that our coal costs are: ( ) ( )

The average wholesale electricity cost in Texas is $XX.XX/MW*hr ($X.XXX/kW) as of XXXX [XX]. Our design uses XX.XX MW of electricity ( ) ( )

Oxygens price was estimated using Towler, which suggests $X.X/lb of OX ($XX.X/tonne). This process uses XXXX tonnes/day of OX for combustion, and the cost is given by: ( )( )

Water is used to replenish water that evaporates in the cooling tower and water that is discarded from the process as low pressure steam. The price of water is suggested by Towler to be X.X/Mlb ($X.XXXE-XX/tonne) and this design uses XXXX tonnes/day resulting in a cost of: 30

)(

B.X.X Consumables
The lifetime of the catalyst is finite; this analysis predicts the need to replace the catalyst (and inert catalyst support/diluents) every five years. The value of each replacement is a product of the catalyst bulk volume, bulk density, and cost per weight. In the water gas shift reactor, the catalyst is diluted to X/XXXX to keep the reaction rate under control. Catalyst cost = $X.XX/lb=$XX.XX/kg [X] and catalyst density is X.X X.X kg/L so we use X.XX kg/L. Ex: water gas shift, active catalyst only (diluents calculation cost is separate), ( ( ) )

( diameter cm X XX

) ( length cm XXXX X*XXX

)( # of tubes XX XX

) volume (cmX) XXXX X.XX*XXX volume (L) X.XX X.XX*XXX active catalyst fraction X/XXXX X

Item methanol reactor methanol reactor:

Item

Volume (L)

catalyst bulk density (kg/L)

mass (kg)

Catalyst Cost ($/kg)

Total Cost

methanol reactor: active catalyst

X.XX*XXX

X.XX

X.XX*XXX

$XX.XX

$XXXM

31

WGS active catalyst WGS inert support

X.XX

X.XX

X.XX

$XX.XX

$XX.XX

XXXX

X.XX

XXXX

$X.XX

$X,XXX

B.X Fixed Costs of Production

Operator Salary is calculated by (X) estimating operator hours/week (X) multiplying by operator hourly salary. For (X), figure X-X of Peters [XX] was used to estimate the need of XX operator hours per day per processing step. The number of processing steps was determined to be X, which gives XXX operator hours/day. The salary of such operators was estimated at $XXX; this value is given by the US Bureau of Labor Statistics [XX] by the median national weekly salary of individuals with some college or associates degree. In X day: ( )

There are X days in a week, but an operator only does X shifts a week so we multiply by X/X to get the number of operators we need on weekly salary: we must pay about XX operators per week. ( ) ) . Thus

Cost Item Operator Salary Supervision Maintenance

Method of Costing

Source Textbook and Bureau of Labor Statistics PDF [XX]

Cost ($/year) $X.XXM $XXX,XXX $X.XXM

XX% of operator labor

X% of ISBL investment

PDF [XX]

32

Property Taxes and Insurance Plant Overhead Total

$X.XXM X% of ISBL fixed capital PDF [XX]

XX% of total labor (including supervision) --

PDF [XX] --

$X.XM $XX.XM

B.X Revenues
The selling price of methanol was taken from methane, the largest methanol producer in the world. The most recent price was methanol price from Methanex [X], whose XXXX prices were approximately $XXX.X/tonne. This design produces XXXX tonnes/day of methanol, yielding $XXXM/year. Sulfur currently sells at $XXX/tonne. With the current plant output of X.XX tonne/day, the plant is predicted to produce $X,XXX/day or $X,XXX,XXX per year.

33