Chapter VIII Process and Economic Overview PDF

CHAPTER VIII
PROCESS AND ECONOMICS

OVERVIEW
Chapter VIII - Process and Economics Overview
PROCESS AND ECONOMICS OVERVIEW

This portion of the study is intended to provide a general overview of commercially
viable methanol, formaldehyde, acetic acid, MMA, MTBE, methylchloride, mixed
methylamines, and DME production technologies.
For methanol, natural gas and coal based processes are discussed and diagrammed,
and general economic models of the natural gas process is provided.
For acetic acid, formaldehyde, MMA, and MTBE a simple process diagram is
provided, and a general economic model of a methanol carbonylation technology is
provided.
For mixed methylamines and DME, a brief process description is provided along
with an economic model summarizing production costs.
For methylchloride, a brief process description is provided.
While quite a bit of information is presented on the difference between coal and
natural gas based methanol production capabilities in this section, if the reader is
looking for a comparative analysis of the outlook for the use of the two feedstocks,
they are referred to the Methanol Supply Feedstock Dynamics section of the
study.
These descriptions are meant for reference and are meant to be utilized mainly for
discussion. Application of these towards a particular model or design should be
done only after consultation with MMSA staff. MMSA is available to provide more
detailed economics and forecasts of the costs of these processes, including detailed
capital and replacement cost estimates (among other valuation methods), under
separate arrangement.
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METHANOL
Methanol is made from synthesis gas (syngas), which itself is the product of
hydrocarbon-rich material that has been heated in the presence of metal catalysts.
Almost exclusively, that hydrocarbon is natural gas (methane). However in China, a
large amount of production capacity uses coal as the source of hydrocarbons.
Therefore, a discussion of natural gas based and coal based methanol production
processes is merited. The diagrams in this section are for reference only, and the
reader is cautioned that they are not applicable for design of production processes.
Natural Gas Based Methanol Production
Methanol production from syngas takes place in three major steps: reforming, the
catalyzed production of syngas from saturated, de-sulphurized natural gas
(reformation); second, methanol synthesis with a Cu/Zn/Alumina catalyst, and
finally, crude methanol (water containing) purification via distillation.
There are four major established process licensors of methanol process technology.
There are relatively minor differences between these technologies, most of these
being optimization of the reforming thermodynamics and kinetics. Changes are
focused on enabling larger and larger processes, and todays largest plants (currently
under construction) will allow the manufacture of 5,000 tons per day of methanol
(1.75 million tons per year). Methanol synthesis and crude methanol distillation
technologies are similar (there are 2 and three stage distillation processes) between
suppliers, although catalyst technology in the methanol synthesis step varies.
Again, most of the differences in methanol production technology can be found in

the reforming portion of the process, the most complex of the sections, and where
the bulk of cost resides. For natural gas feed, there are two broad commercial
reformer designs used today; the first is the original, conventional low pressure
reformer, which uses natural gas, water, and air as intake, with the other the
combined reforming process, which usually incorporates an air separation unit to
isolate oxygen sent to a secondary reactor (autothermal oxidation). A major
advantage of the combined process is its efficiency in generating methanol grade
syngas. A third technology, basically an optimized ATR process, which is still being
commercialized, offers a more compact reforming section by using heat from the
secondary reactor to warm incoming feedstock (rather than imported fuel), further
improving efficiency.
The low pressure process has been the workhorse of methanol production. However,
most new world scale facilities are employing the combined reforming process, and
several mega facilities are considering the use of the optimized ATR process.
Major technology providers include Davy Process Technology (a division of catalyst
manufacturer Johnson Matthey), Lurgi, Haldor Topsoe, and Mitsubishi Gas
Chemical. These technology suppliers have licensed contractors, who are mostly
engineering and construction companies, and currently include Mitsubishi Heavy
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Industry, Chiyoda, Jacobs, Linde, Krupp, Toyo, Technip, and others (including
increasing presence of Chinese EPC firms even in the USGC). For the purposes of
this study, comparisons of individual technology providers will be avoided. More
details behind each reforming section are provided below.
Conventional Reforming
Shown below is a generic process schematic for a conventional low-pressure

methanol reforming process. Natural gas feedstock, saturated with steam, is heated,
and then passed over catalyst, and the resulting syngas is then cooled in a steam heat
exchanger, after which it is sent to the methanol synthesis reactors. The steam is used
subsequently in other portions of the process.
Fuel
Feed
200C 1000C
Steam
880C
Steam
Air
Syn Gas
(400C)
Conventional Low Pressure Reforming
Combined Reforming
In the combined reforming process, a secondary autothermal reformer (ATR) is

added in series with the conventional reformer. The ATR uses oxygen in this
secondary reforming to optimize methanol synthesis feedstock stoichiometry, as
oxygen helps the combustion of excess hydrogen in the natural gas based syngas.
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Like the conventional reforming step, gas exiting the ATR is cooled and generates
HP steam. A depiction of the combined reforming step is shown on the next page.
Fuel
Oxygen
Feed
900C
Air Steam
1000C
Syn Gas
(400C)
Combined Reforming
Optimized ATR Process
The optimized ATR process involves a two-staged combined cycle reformer that
uses syngas secondary reformer (autothermal) off gas to heat saturated natural gas
feedstock. This eliminates the need for fuel to preheat the feedstock, and also
maximizes heat transfer (avoids the use of steam). A diagram is offered below.
Natural Gas
+ Steam
Oxygen
Syn Gas
(400C) 1000C
Optimized ATR Reforming
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This process configuration requires specialized metallurgy, as the extremely hot

carbon monoxide issuing from the ATR is corrosive to conventional tubes, but cost
savings per unit throughput are possible due to the relatively smaller reformer size.
Methanol Synthesis
For methanol synthesis portion of the process, most commercial methanol plants use
gas-phase heterogeneous catalytic reactors. Two main methanol synthesis processes
account for the majority of methanol produced; the Lurgi process, which uses a
water-cooled, tubular, fixed-bed reactor, and the DPT process, which employs larger
fixed-bed reactors with interstage cooling. Copper-zinc oxide alumina catalysts are
now the standard for methanol plants, but they are subject to sulfur poisoning if
sulfur species in the feed gas are not removed to less than 1 ppm.
Crude Methanol Distillation
Crude methanol (which comes from the synthesis section) contains water and other
impurities that must be removed to meet commercial specifications. The amount of
distillation is dependent upon the type and quantity of by-product formation from
the methanol synthesis catalyst employed. The quantity of by-products typically
increases with catalyst age, with ethanol typically being the most troublesome
impurity. The first column is a topping column, which removes light ends in the
crude methanol. Most processes then use one or two more columns (two and three
column finishing) to refine the product to specification grade methanol. The two
column system uses an atmospheric refining column to separate out remaining gases
and heavier components (including organic contaminated water, which is then
treated). A three column system places a pressurized column after the topping
column, reducing the amount of heat required for distillation, and can provide
relative cost savings when energy prices are high.
Coal Based Methanol Production
Coal is another significant commercial feedstock for methanol production, and its
use is concentrated in coal-rich China. [Please refer to Chapter VI, Methanol
Feedstock Dynamics, for more discussion about coal use and types in China.] Coal
comes in thousands of varieties around the world, varying significantly in chemical
composition and energy content. There are coal types which are almost purely
hydrocarbon at one extreme (high energy content per ton), and coal types which
have high ash and high sulphur content at the other (low energy content per ton).
Often, coal is separated into grades according to energy, ash, and sulphur content.
Coal is mostly used in heating, but can also be used in the manufacture of steel
(coking coal). The production of syngas from coal, which has been a commercial
reality since the 1920s, can be considered in two major subsets in China. The first is
where residual gases from the steel production process, which contain large
amounts of hydrogen, carbon monoxide, and natural gas (among other components)
are reformed to synthesis gas, and then converted to methanol via conventional
means. These facilities tend to be limited in sizes not larger than 350,000 metric tons
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per year, and are driven by investments in steel manufacturing. These coke oven
gas based methanol facilities can be considered as highly competitive when their
associated steel making operations are up, as they essentially receive feedstock
free. Coke-oven methanol is mostly limited to steel mills in China, where it is
thought that Chinese towns historically had little other use for the waste gas streams.
The second subset of coal based syngas production, and the focus of this section, is
coal gasification. This process also follows the three main steps of the natural gas
process (reforming, synthesis, and distillation), and are described in greater detail
below.
Reforming
Coal-based syngas processes are significantly more complex than natural gas based
systems, and yield a slightly different type of syngas, as the carbon to hydrogen ratio
of coal is higher than that of natural gas (therefore coal based syngas has excess
carbon dioxide). Without elaboration, the following steps are required in most coal
based syngas operations, which are clearly more involved, as they may include
feedstock preparation, solids handling (sulphur, slag fines, and ash), and carbon
dioxide removal, steps not needed in the natural gas operations:
Steps in Coal-based Synthesis Gas Production

Feed Preparation
Milling. Drying, Pressurizing
and/or Slurrification
Air Separation (O2)
Gasification
Syngas Prep
Cooling
Desulphurization (COS Hydrolysis)
CO2 Removal
Converter/Pressurization
Sulphur Recovery
Water Treatment
To Conventional Methanol Synthesis
In making methanol from coal, there are 9 different suppliers of commercial

technology for coal gasification, with 4 more under development (one of the
commercial suppliers is the Institute of Clean Coal Technology, which has
borrowed heavily from a leading technology provider, offering a slight
modification at more than half of the licensing fee).
The main differences technologies differ in the form of the feedstock utilized (dry
coal or water slurry), and the type of gasifier reactor (entrained bed, fluid bed,
moving bed). MMSA has more information on the various types of gasification,
available on request.
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The following schematic shows a generic commercial coal gasification process,

which highlights the differences between coal and natural gas reformers.
The largest proven single line units process 2500 tpd coal (approx 600,000 methanol
at 100 percent availability), with larger scale envisioned.
This process is also used as the front end of other processes, including IGCC
(combined cycle), ammonia production (in China), among others.
Methanol Synthesis and Distillation
The process diagram for methanol production is very similar to that of the natural
gas based systems. However, syngas from the coal based process must be heated
and pressurized before being sent to the synthesis unit, as coal based syngas contains
sulphur and excess carbon dioxide (lower carbon to hydrogen ratio in the feed), and
must be treated before synthesis.
Distillation technology is not significantly different compared to natural gas systems.
On the following page, an overall conventional methanol process schematic for

natural gas is provided. The coal process schematic, which is not included, would
mostly differ only in the reforming end.
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Simplified Methanol Flow Diagram
Process Heat Fuel Water

Steam Recovery
Natural Gas (Desulphurized)
Reformer Reactor Refining MeOH
Steam
Low Pressure Remove Two or

Condensate Three
Combined (ATR)
Column
Compress
Optimized ATR
Syngas Separate
out water,
Contact
gases, fusel
with
oil
Catalyst
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Methanol Process Capital and Operating Costs
Natural Gas Based Production
In the table below, costs to manufacture and deliver methanol from a typical
Middle East Gulf supplier to a coastal China location are provided, using
representative pricing placeholders (as with all of these snapshots, they are easily
updated please contact MMSA). There is a comparison between conventional low
pressure and combined reformer economics, which show a slight operational cost
advantage. However, it should be noted that the capital costs of the combined
reformer are slightly higher, owing to additional equipment required to separate
oxygen for the secondary (ATR) reformer in that process.
Methanol Production Costs

900,000 tpy unit, 100 percent utilization, MeOH Middle East Delivered China
Unit Production Requirements Costs, US $ per metric ton
Low Pressure Combined Reformer Low Pressure Combined Reformer
Variable Costs
Feedstock MMBtu/t 32.0 28.0
Net Fuel (incl O2 for CR) MMBtu/t 3.0 5.5
Total MMBtu/t 35.0 33.5 52.5 50.3
Electricity kWh/t 70 70 4.2 4.2

Cooling Water Makeup m3/t 8.05 8.05 0.5 0.5
Boiler Feedwater Makeup m3/t 0.75 0.75 0.1 0.1
Catalyst per ton 1.75 1.75 1.8 1.8
Total Variable 59.0 56.7
Fixed Costs
Labor per ton 4 4 4.0 4.0
Others (SGA, IOWC, Maint.) per ton 12 12 12.0 12.0
Frieght to Market per ton 50 50 50.0 50.0
Total Fixed 66.0 66.0
Total Delivered Cost (China) 125.0 122.7
Assumptions
Natural Gas Price 1.50 USD/MMBtu
Electricity Cost 0.06 USD/kWh
Cooling Water 0.06 USD/m3
Boiler Water 0.07 USD/m3
Freight PG - China 50.00
Capital costs for todays world scale natural gas based methanol facilities (between
1.6 and 1.9 million metric tons per year) vary significantly depending upon location,
existing infrastructure, civil works required for site preparation, and numerous other
variables. The range of costs for such facilities has skyrocketed in recent years,
owning mostly to labor and raw material price escalation. The range of costs for a
new facility (world scale, greenfield) in the recent years could vary between 550 and
900 USD per metric ton of installed capacity, accordingly. For more information on
specific costs, please contact MMSA.
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Coal Based Production
Given the large amount of materials needed (especially large scale refractory and the
associated structural support required), plus more complex process and handling
equipment on the reforming side versus natural gas based production, much larger
capital investment is required for a coal based reformer than for a natural gas
reformer. The costs are quoted in a range estimated to be 2.8 to 3.1 times higher. The
largest single trains on coal based plants are limited by reformer size, which allow
methanol production facilities no greater than 600,000 metric tons per year. Like
natural gas based production, costs depend upon location, existing infrastructure,
and site preparation costs, among others.
In general, coal based synthesis gas requires 1.5 to 2.0 tons of coal per ton of
methanol production, with the variation depending on coal type. Water costs can
vary significantly, depending on local resource availability and the amount of water
recycling designed into the process. Fixed costs of operating facilities are also up to
twice as high, with more operations (solids, dust handling as described above), and
higher maintenance costs.
In the table below, costs to manufacture and deliver methanol from a typical Inner
Mongolia (China) location are provided, using representative pricing figures.
Methanol Production Cost

Coal-Fed Slurry Gasifier, 600,000 tpy unit, Inner Mongolia Delivered East China
Based on GE Process
Variable Costs
Coal mt/mt 1.60 131.2
Raw Water (net after recycle) m3/mt 0.75 5.2
Catalyst per ton 2.64 2.6
Total Variable 139.1
Fixed Costs
Labor per ton 18.9 18.9
Others (SGA, IOWC, Maint.) per ton 44.0 44.0
Frieght to Market per ton 81.0 81.0
Total Fixed 143.9
Total Delivered Cost 282.9
Assumptions
Coal Price 82.00 USD/mt
Raw Water 7.0 USD/m3
Employees 105 Per Shift
Average Wage 36.0 MUSD/year
Total Fixed Investment 480.00 MMUSD/installed ton capacity
% Other Fixed Cost of TFI 5.5%
Freight 81.00 Rail to Port (Northeast China)
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As stated earlier, the amount of coal required per ton of methanol production can
vary widely, and the number chosen is at the low end of the range. Additionally,
many of the other assumptions used are highly site variable (especially water costs,
labor cost, and freight to market). Further information can be found in the
Methanol Supply Feedstock Dynamics section of this study, or by contacting
MMSA.
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FORMALDEHYDE
Most of the world's commercial formaldehyde is manufactured from methanol and

air either by a process using a silver catalyst or one using a metal oxide catalyst
(Formox process). Essentially all formaldehyde is produced as aqueous solutions
containing 25-56 wt % HCHO and 0.5-15 wt % CH3OH. Yields from both processes
are around 90% to 92% but the oxidation route has a lower reaction temperature and
the metal catalyst is cheaper than silver. While there is still a significant quantity of
silver based systems in operation, the vast majority of new facilities incorporate the
metal oxide process.
Silver Catalyst
In the silver catalyst route, vaporized methanol with air and steam is passed over a
thin bed of silver-crystal catalyst at about 650C. Formaldehyde is formed by the
dehydrogenation of methanol. The heat required for the endothermic reaction is
obtained by burning hydrogen contained in the off-gas produced from the
dehydrogenation reaction. Today there are two main routes: oxidation-
dehydrogenation using a silver catalyst involving both the complete or incomplete
conversion of methanol and the direct oxidation of methanol to formaldehyde using
metal oxide catalysts.
Metal Oxide Catalyst
The other route involves the oxidation of methanol over a catalyst of molybdenum
and iron oxide. A mixture of air and methanol is vaporized and passed into catalyst-
packed reactor tubes. The reaction which takes place at 350oC is highly exothermic
and generates heat to provide steam for turbines and process heating.
A simple process flow diagram depicting the DB Western process is provided on the
following page:
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REACTION ABSORPTION CATALYTIC

INCINERATION
WATER
UREA WATER
E-108 VENT
EXPORT STEAM
E-109
M
E-110
E-100
BOILER FEED WATER E-101
E-107
E-103
E-104 E-106
E-102 UFC-85
E-105
AIR
E-111
37-52% HCHO
METHANOL
In this process, note the optional incorporation of urea-water mixtures to the

absorption column to yield urea-formaldehye concentrates (UFC).
Perstorp offers a high pressure version of the Formox process which can be
retrofitted to existing plants to boost capacity. The high conversion rate of the
Perstorp process eliminates the need for methanol recovery via distillation and it can
produce formaldehyde at concentrations up to 57%.
Other Processes
A wide range of alternative feedstocks can be used, but are generally not economic.
The ancient process of non-catalytic oxidation of propane-butane mixtures is no
longer in use. Formaldehyde can be produced from methane but a mixture of
products needs to be separated. It is also a byproduct of the oxidation of naphtha to
acetic acid. Finally, while no commercial processes using the technology are known,
much effort has been spent on making formaldehyde directly from methane by
partial oxidation. The incentive for such a process is reduction of raw material costs
by avoiding the capital and expense of producing the methanol from methane.
Formaldehyde Process Capital and Operating Costs
In the table on the next page, costs to manufacture formaldehyde from a

hypothetical manufacturing location are provided, using representative pricing
figures. Assumptions for feedstock, utilities, catalyst, and fixed costs used are listed.
The process assumed is a commercially available Uhde system.
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Formaldehyde Production Costs

150,000 tpy unit, 100 percent utilization, Ex-Works (37 wt% aq. soln.)
Udhe Inventa-Fischer Process
Variable Costs
Feedstock - Methanol mt/mt 0.45 155.8
Feedstock - Water mt/mt 0.39 42.9
Electricity kWh/mt 38 2.3
Cooling Water m3/mt 40 2.4
Fixed Costs
Total Fixed 14.5
Total Cost 220.3
Assumptions
Methanol Price 350.00 USD/mt
Process Water 110.00 USD/mt
Steam @ 100 psig 15.00 USD/mt
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ACETIC ACID
Capital and Operating Costs Carbonylation
Acetic acid technology is perhaps the most diverse of all major industrial organic
chemicals. No other large volume chemical can claim the varied feedstocks and
production approaches that acetic acid can. However, methanol carbonylation has
become the dominant acetic acid production technology, accounting for over 65% of
global capacity, with the majority of the balance from acetaldehyde and butane-
naphtha oxidation. Acetic acid is also a by-product of xylene oxidation to
terephthalic acid, although that process overall requires net addition of acetic acid.
Discussion below will focus on the most commercial routes.
World-scale acetic acid plant size using methanol carbonylation technology has also
grown significantly from less than 50 thousand metric tons per year in the 1960s to
as much as 600,000 metric tons per year per line.
Methanol Carbonylation
Patented processes for adding carbon monoxide to methanol to produce acetic acid
go back to the 1920s, and commercialization efforts were undertaken by BASF in the
1960s. In 1970, Monsanto commercialized a rhodium carbonyl iodide catalyst that is
included in what is commonly called the Monsanto Acetic Acid Process.
The process transformed the market because of lower cost raw materials, gentler,
lower cost operating conditions, and higher yields. In the early 1980s, Celanese
developed a major improvement over the Monsanto technology (AO Plus), also
based on rhodium (with lithium iodide/CH3I co-catalyst), that allowed considerably
higher throughput and efficiency in the catalysis and reduced side reactions caused
in the Monsanto process.
In 1986, Monsanto sold its acetic acid plant and technology to BP. Since then, BP has
further advanced the technology using a proprietary Cativa (iridium with CH3I
co-catalyst) catalyst. Each improvement has lowered the unit cost of producing acetic
acid.
Chiyoda has recently developed its own process (ACETICA), which employs
rhodium catalyst and a CH3I immobilized co-catalyst complex. A process schematic
for the ACETICA process is provided on the following page.
A very closely related process to methanol carbonylation is the Eastman Chemical

carbonylation of methyl acetate to produce acetic anhydride (essentially the same as
the rhodium based processes, only the initial reactant has changed). Methyl acetate
carbonylation yields both anhydride and acetic acid, controllable in part by the
conditions. A plant based on this process was put in operation in 1983.
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Simplified Acetic Acid Flow Diagram

(Based on Chiyodas ACETICA Process)
BFW Steam
Cooler
Flasher Dehydration Finishing Acetic Acid

Bubble Remove Remove Water,
Column Heavy Light Gases Heavy Ends
Ends for
Reactor Recycle Air,
Incinerator Flue Gas
Rhodium complex catalyst Fuel
Absorbers
Methanol CO CH3I
Makeup
In this process, methanol is split into two absorbers, and eventually charged to a
bubble-column reactor (sparged carbon monoxide provides the bubbles). Reactor
product is flashed and dehydrated to remove heavy ends and water/light gases,
respectively. The finishing column separates heavy byproducts, and trace iodide
components are removed. An incinerator processes unconverted CO, methane, and
other light byproducts off the absorbers, as well as heavy ends from the finishing
column. Flue gases are scrubbed.
Acetaldehyde Oxidation
In this process, ethanol is dehydrogenated oxidatively to acetaldehyde using silver,

brass, or bronze catalysts. Acetaldehyde can then be oxidized in the liquid phase in
the presence of cobalt or manganese salts to yield acetic acid. This route to acetic acid
is reliable, but requires higher cost ethanol as well as extra purification steps, and
therefore cannot compete on a cost basis with methanol carbonylation (and is
becoming less prevalent).
Butane-Naphtha Liquid-Phase Catalytic Oxidation
Direct liquid-phase oxidation of butane and/or naphtha was once the most favored
worldwide route to acetic acid, but the costs of these hydrocarbons has become
prohibitive in recent years and the process is increasingly used less. Butane, in the
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presence of cobalt, chromium, or manganese, undergoes simple air oxidation in

acetic acid solvent. Ethyl acetate and butanone are produced, and the process can be
altered to provide larger quantities of these valuable materials. Formic acid,
propionic acid, and minor quantities of butyric acid are also formed. Some safety
concerns also exist for this process, as two explosions, in 1987, at the then-largest
butane liquid-phase oxidation plant resulted in fatalities.
Direct Oxidation of Ethane
SABIC has developed a new process for producing acetic acid via catalytic gas phase
oxidation of ethane. According to SABIC's patents, ethane is oxidized with either
pure oxygen (i.e., ethane rich) or air (i.e., ethane lean), at temperatures ranging from
150C to 450C and at pressures ranging from 1 to 50 bar, to form acetic acid and
water. Undesired by-products of CO, CO2, and ethylene (largely lost on recycle) can
also be formed.
The new SABIC catalyst system is a calcined mixture of oxides of Mo, V, Nb, and Pd.
Little is known about the costs of such a process. Currently, this process is not
expected to materialize on any significant commercial scale through the study
period.
Acetic Acid Process Capital and Operating Costs
Methanol Carbonylation Based Production
In the table on the next page, costs to manufacture and deliver acetic acid from a
hypothetical integrated Southeast Asian manufacturing location are provided, using
representative pricing figures, and estimates of feedstock, utilities, catalyst, and fixed
costs, with assumptions used listed. Producers can optimize costs by integrating
near petrochemical and refining areas that have readily available CO or CO
feedstock.
Capital costs for todays world scale methanol carbonylation facilities (between 0.5
and 0.6 million metric tons per year) vary significantly depending upon location,
variables. While costs of construction are typically not detailed in most project
announcements, the range of costs for greenfield facilities are estimated to vary
between 450 and 700 USD per metric ton of installed capacity. For more information
on specific costs, please contact MMSA.
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Acetic Acid Production Costs

200,000 tpy unit, 100 percent utilization, SEA Delivered China (CFR)
(Based on Chiyoda ACETICA Process)
ACETICA Process (Chiyoda Corp.)
Variable Costs
Feedstock - Carbon Monoxide mt/mt 0.52 165.4
Steam mt/mt 1.7 25.5
Fixed Costs
Total Fixed 70.0
Total Delivered Cost (China) 472.1
Assumptions
Carbon Monoxide Price 320.0 USD/mt
Freight SEA - China 40.00
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MMA
Methyl methacrylate (MMA) has three basic categories of production, all of which
use methanol. Most of the worlds supply of MMA is produced by C3 routes,
starting with propylene. These are more commonly known as acetone cyanohydrin
(ACH) processes. These have been practiced commercially since 1937, based on
technology patented by ICI in 1934. There have been significant improvements in
catalysts and resulting yields for key transformations in many routes since the 1980s.
ACH is prepared via a base-catalyzed reaction of acetone and hydrogen cyanide.
Acetone and hydrogen cyanide are obtained as by-products from the commercial
production of phenol and acrylonitrile, respectively. Phenol and acrylonitrile are
made from propylene. Mitsubishi Gas Chemical Co. has developed and patented a
modified acetone cyanohydrin-based route that does not use sulfuric acid and
therefore presents the opportunity for reduced waste costs, but is not commercially
used.
A rough schematic of the steps involved in the various commercial routes to MMA is
provided below:
Simplified MMA Flow Diagram

(Generic Processes)
Hydrogen Cyanide meOH
C3 Route Propylene Acetone Acetone Methacrylamide

(ex phenol) Cyanohydrin Sulfate
Esterification MMA
C4 Route MTBE or TBA Isobutylene Oxidation Methacrolein
- meOH
(Raff-1)
O2 Proprionaldehyde
C4 Route
Ethylene
C2 Route
Several C4 processes are commercially viable and growing in commercial

significance, particularly in Asia as more C4 streams come available from
investments in refinery and heavy feed olefins complexes. In 1982, Japanese
researchers introduced an isobutylene-based process, and by 1984 commercial
production via isobutylene was underway in Japan. Isobutylene or tert-butyl alcohol
(TBA) can be converted to methacrylic acid in a two-stage, gas-phase oxidation
process via methacrolein as an intermediate. Depending on technology, the
methacrylic acid is either isolated and the remaining methacrolein is fed to the
second stage or product gas from the first-stage reactor is directly introduced into
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the second-stage reactor without isolating methacrolein. TBA and isobutylene may
be used interchangeably in the processes since tert-butyl alcohol readily dehydrates
to yield isobutylene under the reaction conditions in the initial oxidation. MTBE can
also be backcracked to yield isobutylene and methanol (which can be utilized in
the later esterification to MMA). Variations of the C4 process have been
commercialized by Mitsubishi Rayon and by what is now Sumitomo.
Finally, C2 MMA processes utilize ethylene as a feedstock via propanol, propionic

acid, or methyl propionate as intermediates. Propanal may be prepared by
hydroformylation of ethylene over cobalt or rhodium catalysts. The propanal then
reacts in the liquid phase with formaldehyde in the presence of a secondary amine
and, optionally, a carboxylic acid. BASF began operation of an ethylene-based plant
in Ludwigshafen, Germany, in 1990, based on propanal, which is available at that
site. However, propanal is typically not available in significant quantities, and
favorable economics appear to be limited to conditions unique to that site. Lucite has
built an ethylene based facility (using their proprietary Alpha technology) in
Singapore, which was commissioned in late 2008.
MMA Process Capital and Operating Costs
Isobutylene (Raffinate-1) Based Production
In the table on the next page, costs to manufacture and deliver MMA from a
hypothetical integrated Southeast Asian manufacturing location to China are
provided, using representative pricing figures, and estimates of feedstock, utilities,
catalyst, and fixed costs, with assumptions used listed. Producers can optimize costs
by integrating near petrochemical and refining areas that have readily feedstocks
and utilities.
Capital costs for todays world scale C4 based (between 80,000 to 100,000 metric tons
per year) vary significantly depending upon location, existing infrastructure, civil
works required for site preparation, and numerous other variables. While costs of
construction are typically not detailed in most project announcements, the range of
costs for greenfield facilities are estimated to vary between 1200 and 1600 USD per
metric ton of installed capacity. For more information on specific costs, please
contact MMSA.
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Methyl Methacrylate Production Costs

90,000 tpy Raffinate-1 unit, 100 percent utilization,
SEA Delivered China (CFR)
Combined Reformer
Variable Costs
Feedstock - Raffinate-1 mt/mt 1.56 1794.0
Steam @ 5bar mt/mt 7.4 185.0
Oxygen mt/mt 0.48 57.6
Process Water m3/mt 0.22 0.0
Credits
Raffinate-2 mt/mt 0.86 -946.0
Water mt/mt 0.04 0.0
Fuel Oil (net) mmbtu/mt 2.60 -31.2
Total (Net) Variable 1297.9
Fixed Costs
Total Fixed 195.0
Total Delivered Cost (China) 1492.9
Assumptions
Methanol Price 370 USD/mt
Raffinate-1 Price 1150 USD/mt
Fuel Oil Price 12.00 USD/mmBtu
Steam @ 5bar 25.0 USD/mt
Oxygen 120 USD/mt
Process Water 0.05 USD/m3
Water 0.03 USD/m3
Freight SEA - China 40.00
383
MTBE
MTBE is produced using methanol and isobutylene. Isobutylene used in MTBE

operations is sourced from three major upstream locations:
Refinery/Petrochemical plants: Dilute isobutylene (contained in a stream

called raffinate-1) is produced as a byproduct in refinery catalytic crackers
and in olefin crackers, and is reacted with methanol to produce MTBE after a
further butadiene recovery step (in most cases). The C4s from the refinery can
also be referred to as B/Bs (butylenes/butadienes), whereas the C4s from
the crackers are often called Crude C4s. The olefins based raff-1 stream is
usually higher in isobutylene than the refinery based one. A byproduct of
these processes is a stream of residual C4 isomers (raffinate-2). These are the
smallest and the least expensive MTBE plants to build, and the use of readily
available streams generally improves their competitiveness.
Butane Dehydrogenation (Merchant) plants: These facilities isomerize
normal butane to isobutane, dehydrogenate isobutane to isobutylene, and
then react the isobutylene with methanol to produce MTBE. Most of these
on-purpose (as opposed to using byproduct streams) plants were built in
North America, South America and the Middle East from the early 1990s.
TBA plants: Tertiary butyl alcohol (TBA) is a byproduct of the styrene
monomer/propylene oxide (SM/PO) production process. TBA is converted to
isobutylene, then reacted with methanol to produce MTBE. Only a few
facilities globally use this process.
A simple schematic summary of these various routes is provided in the chart below.
Simplified MTBE Flow Diagram

(Comparing 4 Major iso-C4= Sources)
C4 ex Gas Plant
Isobutane H2
C4 ex Refinery Dehydrogenation
(B/Bs)
C4 MTBE MTBE
Purification,
Isobutylene
Recovery (Raff-1) Operations Recycle Residual C4
Isomers
(Raff-2)
C4 ex Olefins Unit
(Crude C4s)
Dehydration MeOH
Butadiene
H2O
TBA ex
PO/SM
385
Technology providers historically include Snamprogetti/ANIC, ARCO, C.W. Huels,

Phillips, Texaco, Shell, CDTECH (a JV between CR&L and ABB Lummus Crest),
UOP, Davy-McKee, Suntech, Gulf and Erdoelchemie. The CDTECH, Gulf and
Erdoelchemie processes cover the production of tertiary amyl methyl ether (TAME)
in addition to MTBE.
MTBE Process Capital and Operating Costs
Refinery/Petrochemical (Raffinate-1) Based MTBE Production
In the table below, estimates of costs to manufacture MTBE at a hypothetical

integrated China manufacturing location are provided, using representative pricing
figures, and estimates of feedstock, utilities, catalyst, and fixed costs. The scale of this
facility is 100,000 metric tons per year (2,300-barrel per day), utilizing a standard
raffinate-1 based process. Producers can optimize costs (capital and operational) by
integrating near petrochemical and refining areas.
Methyl tert-Butyl Ether Production Costs

100,000 tpy Raffinate-1 unit, 100 percent utilization, China, ex-works
Combined Reformer
Variable Costs
Feedstock - Raffinate-1 mt/mt 1.45 1116.5
Electricity kWh/mt 14.20 0.9
Steam, LP (5bar) mt/mt 0.72 11.5
Cooling Water m3/mt 40.30 2.0
Fuel mmBtu/mt 0.48 0.6
Catalyst per mt 3.20 3.2
Credits
Raffinate-2 mt/mt 0.82 -622.4
Fixed Costs
Frieght to Market per ton n/a
Total Fixed 26.0
Total Cost (ex-works) 674.3
Assumptions
Natural Gas Price 1.25 USD/mmBtu
Hydrogen Price 596 USD/mt
Steam, LP (5 bar) 16.00 USD/mt
386
Capital costs for this scale of facilities vary significantly d epending upon location,
announcements, the range of costs for greenfield facilities of this size are estimated
to vary between 250 and 300 USD per metric ton of installed capacity. For more
information on specific costs, please contact MMSA
n-Butane Based MTBE Production
The table below summarizes estimates of costs to manufacture MTBE at a

hypothetical Middle East n-Butane based manufacturing operation, using
representative price figures, and estimates of feedstock, utilities, catalyst, and fixed
costs, with assumptions used listed. The scale of this facility is 650,000 metric tons
per year (approx 15,000-barrel per day). As with the previous example, producers
Methyl tert-Butyl Ether Production Costs

650,000 tpy n-Butane Dehydro unit, 100 percent utilization, Middle East,
CFR Singapore Basis
Combined Reformer
Variable Costs
Feedstock - Butane mt/mt 0.69 659.3
Feedstock - Hydrogen mt/mt 0.01 5.0
Electricity kWh/mt 47.50 2.4
Steam, LP (5bar) mt/mt 1.31 15.7
Cooling Water m3/mt 42.70 2.1
Fuel mmBtu/mt 0.48 0.6
Catalyst per mt 43.70 43.7
Credits
Hydrogen mt/mt 0.02 -13.8
Fuel mt/mt 0.04 -20.5
Fixed Costs
Total Fixed 79.8
Total Delivered Cost (Singapore) 890.8
Assumptions
Butane Price 950 USD/mt
Natural Gas Price 1.25 USD/mmBtu
Hydrogen Price 626 USD/mt
Steam, LP (5 bar) 12.00 USD/mt
Freight ME Gulf - Singapore 42.00 USD/mt
387
can optimize costs (capital and operational) by integrating near petrochemical and
refining areas.
Capital costs for this scale of facilities vary significantly depending upon location,
announcements, the range of costs for greenfield facilities of this size are estimated
to vary between 450 and 525 USD per metric ton of installed capacity. For more
information on specific costs, please contact MMSA.
388
METHYL CHLORIDE
Making methyl chloride is the first step in the manufacture of chloromethanes.

Methyl chloride is the product of a substitution reaction between hydrogen chloride
and methanol. In this process, different levels of chlorine addition to the carbon
molecule are achieved, resulting in methyl chloride, methylene chloride, chloroform,
and carbon tetrachloride.
Chlorine can be mixed with excess methyl chloride to increase the yields of the three
other chloromethanes. Products are separated after reaction. This reaction is usually
carried out in the gas phase thermally but can also be done catalytically or
photolytically.
389
MIXED METHYLAMINES
Commercial production of mixed methylamines requires ammonia and methanol.

These are reacted in the presence of a catalyst, along with recycled amines. The
reaction is exothermic and heat is recovered in feed preheating. Reactor products are
sent to a separation system where the ammonia is taken out and recycled. Further
processing removes the various amine types. Methanol recovery is possible.
Mixed Methylamine Process Capital and Operating Costs
Recent manufacturing costs for mixed methylamines are estimated below.

Assumptions for feedstock, utilities, catalyst, and fixed costs are listed. Equal parts of
mono, di, and tri methylamines are manufactured in this model. In practice, a larger
percentage of dimethylamine is manufactured. The process assumed is a
commercially proven Davy Process Technology system.
Mixed Methylamines Production Cost Estimates

40,000 tpy unit, 100 percent utilization, FOB USGC
Based on Davy Process Technology (Leonard) Process
DPT Process 3 x 1/3 mono, di, tri
Variable Costs
Feedstock - Ammonia mt/mt 0.40 220.0
Fixed Costs
Total Fixed 226.6
Total Delivered Cost 1162.4
Assumptions
Ammonia Price 550.00 USD/mt
Total Fixed Investment 140.00 MMUSD
Freight 0.00
391
DIMETHYL ETHER (DME)
Commercially, most DME is made via the methanol dehydration route, where crude
(containing water) or refined methanol is reacted in the presence of a catalyst.
Reactor effluents DME with byproduct water and unconverted methanol are fed
to a DME separation column. DME is cooled and stored. Methanol is recovered and
recycled with feedstock.
DME Process Capital and Operating Costs
In the table below, costs to manufacture DME from a hypothetical manufacturing

location are provided, using representative price figures. Assumptions for feedstock,
utilities, catalyst, and fixed costs are listed. The process assumed is a commercially
proven system.
Dimethyl Ether Production Cost Estimates

50,000 tpy unit, 100 percent utilization, FOB China
Methanol Dehydration Process
DPT Process
Variable Costs
(0.35MPa, 32)
Catalyst kg/mt 0.80 4.0
Fixed Costs
Total Fixed 29.8
Total Cost 636.5
Assumptions
Catalyst Cost 5.00 USD/kg
Total Fixed Investment 17.50 MMUSD
Freight 0.00
393

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CHAPTER VIII

PROCESS AND ECONOMICS

PROCESS AND ECONOMICS OVERVIEW

For methylchloride, a brief process description is provided.

Natural Gas Based Methanol Production

Again, most of the differences in methanol production technology can be found in

Shown below is a generic process schematic for a conventional low-pressure

Conventional Low Pressure Reforming

In the combined reforming process, a secondary autothermal reformer (ATR) is

Optimized ATR Reforming

This process configuration requires specialized metallurgy, as the extremely hot

Crude Methanol Distillation

Coal Based Methanol Production

Steps in Coal-based Synthesis Gas Production

In making methanol from coal, there are 9 different suppliers of commercial

The following schematic shows a generic commercial coal gasification process,

Methanol Synthesis and Distillation

Distillation technology is not significantly different compared to natural gas systems.

On the following page, an overall conventional methanol process schematic for

Simplified Methanol Flow Diagram

Process Heat Fuel Water

Reformer Reactor Refining MeOH

Low Pressure Remove Two or

Methanol Process Capital and Operating Costs

Natural Gas Based Production

Methanol Production Costs

Electricity kWh/t 70 70 4.2 4.2

Catalyst per ton 1.75 1.75 1.8 1.8

Total Variable 59.0 56.7

Total Fixed 66.0 66.0

Total Delivered Cost (China) 125.0 122.7

Coal Based Production

Methanol Production Cost

Catalyst per ton 2.64 2.6

Total Variable 139.1

Total Fixed 143.9

Total Delivered Cost 282.9

Most of the world's commercial formaldehyde is manufactured from methanol and

Metal Oxide Catalyst

REACTION ABSORPTION CATALYTIC

In this process, note the optional incorporation of urea-water mixtures to the

Formaldehyde Process Capital and Operating Costs

In the table on the next page, costs to manufacture formaldehyde from a

Formaldehyde Production Costs

Catalyst per ton 2.50 2.5

Total Variable 205.8

Total Fixed 14.5

Total Cost 220.3

Capital and Operating Costs Carbonylation

A very closely related process to methanol carbonylation is the Eastman Chemical

Simplified Acetic Acid Flow Diagram

Flasher Dehydration Finishing Acetic Acid

In this process, ethanol is dehydrogenated oxidatively to acetaldehyde using silver,

Butane-Naphtha Liquid-Phase Catalytic Oxidation

presence of cobalt, chromium, or manganese, undergoes simple air oxidation in

Direct Oxidation of Ethane

Acetic Acid Process Capital and Operating Costs

Methanol Carbonylation Based Production

Acetic Acid Production Costs

Catalyst per ton 2.50 2.5

Total Variable 402.1

Total Fixed 70.0

Total Delivered Cost (China) 472.1