Become a member Login Contact Partners Solutions Providers Contributors Connect to us

Upgrading Methanol plants for Increase in Capacity an

Energy Efficiency

Author: Harshad P Pandya, Independent Consultant

Methanol manufacturing has been one of the most energy intensive chemical productions. High energy consumption and associated costs, high demand
and requirement for minimizing emission of GHG gas and other pollutants have led to major technological changes in the last 30-40 years. Methanol is
produced largely from Natural Gas with Steam reforming and resultant raw synthesis gas is treated differently to produce synthesis gas as per need of
technology employed. Broad comparison of synthesis gas quality required for ammonia and methanol is presented This study paper highlights benefits
and ways of revamping vintage methanol plants for capacity increase and efficiency improvement. The paper also brings out various innovative modules
available for potential increase in methanol production capacity through use of technological innovations such as addition of carbon dioxide, energy
efficiency improvement in methanol distillation, revamping of methanol synthesis. It also presents the case study for converting old ammonia plant to
methanol plants and producing ammonia from purge gas of conventional methanol plant.

Methanol: Methanol (methyl alcohol СН3ОН) is one of the major organic synthesis products and feedstock for production of
formaldehyde, acetic acid, dimethyl terephthalate, methyl methacrylate, methyl amine, methyl tetra butyl amine and other
chemical products.

Methanol production process includes synthesis gas preparation, methanol synthesis and distillation stages. At synthesis gas
preparation stage different feedstocks are used to produce hydrogen and carbon oxides mixture. At distillation stage methanol is
separated from water and purified from organic micro-impurities. The methanol industry spans the entire globe, with productions
in Asia, North and South America, Europe, Africa and the Middle East. Worldwide, over 90 methanol plants have a combined
production capacity of about 110 million metric tons. According to IHS, global methanol demand reached 70 million metric tons in
2015 driven in large part by emerging energy applications for methanol which now account for 40% of methanol consumption.
Each day, nearly 200,000 tons of methanol is used as a chemical feedstock or as a transportation. Capacity of methanol plants
range from less than 100 MTPD (old generation plants) to more than 5000 MTPD (modern design plants). 82% of the actual
production capacity is based on natural gas technology. Coal based methanol units account for 15% of the installed capacity.
Further portions are represented by fuel oil and stranded natural gas based methanol units. Diagram 1 shows conventional
process for producing methanol from natural gas.

Diagram 1

Methanol from Natural gas by conventional process

Comparison of Ammonia and Methanol Processing scheme

Raw Synthesis gas required for both ammonia and methanol can be produced from different hydrocarbon feedstock. Synthesis gas
purification and quality requirements are quite different (refer to Table 1).

Table 1

Comparison of process schemes

Ammonia Methanol

Feedstock NG, Naphtha, coal, fuel oil, petcock NG, Naphtha, coal, fuel oil, pet coke

NG, naphtha Reforming (primary and/or secondary with

NG, naphtha Reforming (primary and/or secondary with
Synthesis gas generation /oxygen). ATR+HER. Gasification of coal, fuel oil or pet
air/oxygen). Gasification of coal, fuel oil or petcoke
coke

Crude synthesis gas mixture of CO, CO2 and H2 with

Synthesis gas purification Removal of CO, CO2, CH4 H2S, Argon as per technology
complete removal of H2S

Synthesis gas quality Stoichiometric ratio of H2/N2 3.0 free from all impurities Mixture of CO+CO2+H2

Synthesis Gas for Methanol Production

Following reactions are involved in Methanol Synthesis

CO + 2H2 = ͍ CH3OH ΔH -90.77 kj/mol

CO + 3H2 = ͍ CH3OH + H2O ΔH -49.58 kj/mol

CO2 + H2 = ͍ CO + H20 ΔH +49.19 kj/mol

As both CO and CO2 are linked by shift reaction, synthesis gas composition for methanol is defined by Stoichiometric Number

SN = (H2 – CO2) / (CO + CO2).

Table 2 provides interpretation and suggested corrective actions.

Table 2

Stoichiometric Number and corrective action

Corrections suggested

SN VALUE Interpretation

SN less than 2 Excess carbon dioxide relative to hydrogen Bypass around shift reactor in gasification plant

Addition of carbon dioxide

Use of PSA for removing excess hydrogen

Surplus hydrogen and carbon deficiency result in large
before methanol synthesis
SN more than 2 recycle of unconverted hydrogen giving low efficiency and
higher cost of plant
Use of hydrogen rich purge gas for ammonia
production

SN nearer to 2.05 Optimum value (slight excess hydrogen )

Energy consumption in methanol plants

Methanol production process is highly energy intensive. Several improvements are carried out for reducing utilities consumption to
minimum and development of optimal process equipment implementation. Several improvements are common with Ammonia
technology due to process similarity. Diagram 2 describes the technological efforts to optimize energy consumption.

Diagram 2

The largest plants are operated in South America (particularly in Trinidad and Tobago and Chile) and in the Middle East (in Iran and
in Saudi Arabia). These two regions accounted for more than half of the global capacity in 2006. On average, Europe and some new
plants installed in these developing countries are the most energy efficient regions in methanol production with an estimated
average SEC, including feedstocks, of approximately 33 GJ per ton of methanol. The plants with the highest energy usage are
operated in developing Asia, including India, and in transition economies. The energy efficiency improvement potentials compared
to the international benchmark are approximately 10% to 15% in Europe and as high as 25% in economies in transition and in India
(reference 2). Furthermore, many small to medium size methanol plants (specifically in the USA) were shut down due to high cost
of gas. With availability of cheap natural gas, there is a good opportunity for restart of these plants with revamp/modernization for
higher capacity and energy efficiency.

Methanol plant limitations to be considered during revamp

Like ammonia plant, Methanol plant also faces similar plant limitations while attempting revamping to increase production and
reduce energy consumption. These limitations are of following nature:
 Reformer pressure drop
Maximum tube wall temperature, coil design temperature, fan capacity etc. not allowing to increase feedstock rates
Compressor / circulator limitations
Higher purge rates compared to design plant due to excess hydrogen in loop
Product quality
Low carbon efficiency around methanol synthesis reactor
Limitations and high energy consumption in Methanol Distillation

This paper describes a few case studies for increasing capacity and energy efficiency of conventional methanol plants:

Case Study 1: Addition of carbon dioxide to increase Methanol production

The chemistry indicates that adding CO2 to the synthesis gas mixture can increase the capacity of the methanol plant due to excess
hydrogen available in the synthesis loop. If H2 and CO are synthesized by the natural gas steam-reforming, then the H2 : CO ratio is
3:1. On the other hand, for methanol synthesis the best H2 : CO ratio is 2:1. Such condition can be corrected either by skimming
extra hydrogen, generally by Pressure Swing Adsorption or by addition of carbon dioxide, to obtain desired ratio. To increase
methanol production, judicious addition of CO2 is required to the process gas either upstream or downstream of the steam
methane reformer. Injection of CO2 upstream of reformer requires extensive control modifications, heat transfer and hydraulic
limitation checks, and produces a more reactive synthesis gas which would require modification in synthesis reactor. Therefore,
CO2 is mostly added to the reformer in new designed methanol plants. In the existing plants it can be added either in the suction of
synthesis gas compressor or directly into the methanol synthesis loop. CO2 addition results in higher production of methanol
where the existing synthesis gas has unbalanced carbon oxides. CO2 addition reduces purge rate so NG fuel requirement in
reformer will increase proportionally. It will also introduce more water to crude methanol which must be removed in distillation.
CO2 could be sourced from nearby ammonia plant that does not consume all recovered CO2, or from the methanol plant itself
where CO2 can be recovered from reformer flue gases. There are a few successful installations, like Qatar Fuel Additives Company
(QAFAC), where CDR units are set up to reuse the carbon dioxide emitted from their methanol plant. It is estimated that 500
ton/day of CO2 is recovered from its methanol reformer stack and injected into the Methanol Synthesis unit to enhance the
production capacity. The Recovery Unit has been constructed under license of MHI (Mitsubishi Heavy Industries, Japan). CO2 from
CDR Unit is compressed and sent back to the Methanol plant to mix with the synthesis gas (1). Gulf Petrochemical Industries has
installed 450 mtpd CO2 recovery plant to supply CO2 to urea and methanol plants. They reported increase in methanol production
by 120 mtpd and urea by 80 mtpd(1). The key result of the above successful projects and other study lies in not only the capacity of
the Methanol Plant increase, the atmospheric CO2 emission reduction by about 40 % and a small reduction in specific energy
consumption by about 0.5 mmbtu/mt. It is pertinent to note that many ammonia plants operating with lean natural gas are not
able to convert all ammonia to urea because of shortage of Carbon dioxide. To overcome this limitation many Indian Fertilizer
plants like IFFCO, NFCL, INDOGULF have installed CO2 Recovery unit for recovering CO2 from flue gases. Such technology is
available from MHI Japan (3) and LINDE-BASF.

Case Study 2: Revamping of Methanol Distillation to reduce energy consumption

Crude methanol contains about 15 % of water by weight and other impurity. Steam requirement is set primarily by absolute
amount of Me OH. Being lighter it is evaporated and energy requirement is 3 to 4 % of total heat rate depending on Me OH product
purity and configuration of distillation system.

Various distillation concepts have been developed to match energy requirement of distillation section with energy available from
front end. These are:

1. Typical 2 column methanol distillation system with first stage being for light ends removal and it is carried out in Topping column. This column acts as a
reflux stripper. In the second column, known as methanol refining stage, the pure methanol is recovered as the overhead product. This is
demonstrated on diagram 3.

Diagram 3

Two stage Methanol Distillation System

 2. Standard 3 column scheme with a topping column followed by high pressure refining column which provides pre-rectified feed to the 3rd column .This
is shown on Diagram 4.

Diagram 4

Three stage Methanol Distillation System

Based on realized energy consumption in operating plants of comparable capacity and purity requirement (AA+ Grade), specific
energy required in 2 stage distillation is 1.1 Gal per MT as compared to 0.4 Gcal per MT Methanol in 3 stage distillation. For typical
1000 MTPD methanol plant, improvement from 2 stage to 3 stage distillation represent potential of 4.5 million USD (United States
dollar) per year at a gas price of 5 USD per mmbtu. Actual energy savings shall be dependent on extent of additional steam
consumption after utilizing low level energy source available from front end of the plant. (4, 5, 6)

Case Study 3: Revamping of methanol synthesis unit

Methanol synthesis is highly exothermic reaction with lower conversion per pass, therefore in typical methanol synthesis process
the fresh synthesis gas will be combined with recycle stream before sending to methanol reactor. Methanol conversion is favored
at low temperature (low reaction rate!) and high pressure (higher energy consumption!). Several improvements such as better
catalyst, design of methanol reactor, integrated heat recovery have taken place. Methanol synthesis reactors have been developed
from adiabatic reactor, multiple beds with quenching to single bed reactors with continuous removal of heat. Typically, all such
reactors raise steam and try to achieve almost isothermal situation to keep temperature close to path of maximum reaction rates.
For example, Linde isothermal reactor has helically coiled tubes embedded in the catalyst bed. Lurgi, Topsoe and others offer
methanol reactors that have vertical shell and tube heat exchangers with catalyst in tubes and BFW on the shell side. Casale offers
Isothermal Methanol Convertor IMC which is a pseudo-isothermal reactor in which heat transfer surfaces are plates and catalyst is
loaded outside the cooling plates. It provides perfect temperature profile and other benefits of easy loading and unloading of
catalyst, axial radial configuration and other mechanical benefits. Another important aspect of methanol synthesis section lies in
proper utilization of removed exothermic heat which is obtained by heat optimization of the entire methanol plant. (7, 8)

The following revamp opportunities for capacity increase and energy efficiency can be examined for old methanol plants:

Adopt the new design of methanol convertor from reputed technology suppliers for capacity increase and product quality improvement;
 Adopt installation of once–through reactor OTR or purge gas reactor as modular modification in the plant (7)
Review present heat recovery and integrate the same one within entire plant for energy efficiency

The following examples illustrate the benefits of such revamp in old methanol plants:

Methanol plant capacity enhancement at GNFC Bharuch India

GNFC had a small methanol plant of 60 MTPD capacity. Well-planned modifications such as methanol chiller in gas cooling circuit,
additional synthesis gas generation unit, revamping of reefing column with high capacity Superfrac trays and replacement of
quench adiabatic convertor to Linde Isothermal reactor helped in increasing plant capacity to 160 MTPD .The plant witnessed
improved yield of methanol due to high conversion rate and stable reaction condition and less by product formation (9) .

Case Study 4: Conversion of Ammonia plant for methanol production

Considering the process similarity in generating reformed gas from Natural gas/naphtha, conversion of ammonia plant to
methanol production is possible with addition of methanol synthesis and methanol distillation steps. It is estimated that with same
quantity of Natural gas as a feedstock capacity ratio of a methanol plant to ammonia plant will be 0.82 by weight. For example,
1000 mtpd ammonia plant with conventional process will produce on conversion about 820 mtpd of methanol. It is observed that
cost of a converted methanol plant will be approx. one third less expensive than building a new methanol plant. Besides lower
cost, the economics of producing methanol vs. ammonia, local requirement, use of otherwise idle facility etc. are several long term
factors for approving the conversion (10).

GSFC Vadodara, India, has revamped their 450 mtpd Ammonia –I plant into Topsoe technology Methanol plant with a name
plate capacity of 525 MTPD. This was a brownfield project utilizing idle assets of Ammonia –I plant and preventing gas venting, i.e.
oxygen and carbon dioxide, from their 1350 MTPD Ammonia plant (Reference 13). Under normal conversion this would have
capacity of about 470 MTPD, however, use of excess oxygen and carbon dioxide (both raw materials) for methanol production has
helped in getting capacity of 525 mtpd. This shows innovative way of utilizing idle capital resources and available raw materials in
the complex (11).

Case Study 5: Substantial ammonia production from Purge Gas from Methanol plant

Conventional methanol plant designed with steam methane reformer generates synthesis gas with stoichiometric ratio in the
range of 2.8 to 3.0 dependent upon the feedstock composition, recycle of CO2, steam to carbon ratio and other design factors. This
would mean the excess hydrogen can then react with available CO and CO2. Such excess hydrogen is purged from the synthesis
loop and generally used as a fuel in the reformer of methanol plant. As such, quantity of hydrogen in purge gas is quite large and
recovery of pure hydrogen can be done through use of Pressure Swing Adsorption or by cryogenic recovery. Such hydrogen
recovered from 3000 mtpd methanol plant with conventional design can support around 1000 mtpd ammonia production.
Typically such ammonia facility will have pre-treatment for removal of wax etc., PSA for hydrogen recovery or CO2 removal +
nitrogen wash for removing all methane, carbon monoxide / dioxide, Air Separation Unit for nitrogen production and ammonia
synthesis loop. (21) Major pros and cons of such ammonia production are:

Lower fixed and operating cost for ammonia production as compared to stand-alone ammonia production plant
Meet local ammonia demand. However for export, the cost of ammonia loading facility would be quite high
If methanol demand is high , economics of additional methanol production with additional cost of installing Carbon dioxide recovery unit and cost of
revamping methanol synthesis ammonia production should be carefully examined
Such combination of methanol and ammonia production provides large flexibility in adjusting product mix

As per recent announcement, Salalah Methanol Company SMC Oman has announced 1000 mtpd ammonia plant based on purge
gas from their 3000 mtpd methanol plant. (22) This project will have PSA for hydrogen recovery, Air Separation for pure nitrogen
both of Linde Design and inert free ammonia synthesis loop from Haldor Topsoe Design.

Concluding Observations

High cost of natural gas, need of additional production and environmental issues are prompting methanol operators to
continuously strive for newer improvements in the process. Various add-on concepts like addition of carbon dioxide, revamping of
methanol distillation and modernization of methanol synthesis can improve capacity and energy efficiency of old methanol plants.
Conversion of old ammonia plant to methanol and ammonia production from methanol purge gas is now technologically quite
established and the same can be implemented after careful economic analysis. This can be achieved by better understanding of
the process by owners themselves and process intervention with suppliers of such process modules to develop integrated
revamp.
References and literature cited

1 Al-Hitmi KMR. QAFAC: Carbon dioxide recovery plant, Sustainable Technologies, Systems and Policies 2012 Carbon Capture and
Storage Workshop:22 https://dx.doi.org/10.5339/stsp.2012.ccs.22

2 www.gpic.com

3 Masaki Iijima et al., “CO2 Recovery/Effective Utilization/Fixation and Commercialization,” MHI Technical Journal, 39 (5), 286, 2002

4 A process integration approach to the design of two and three column methanol distillation schemes: A P Doughlas, A F A Haadly
. Applied Thermal Engineering 26 (2006) 338-349

5 Reduction of energy use in methanol distillation: Ashok Rao,Valerie Francuz.OTC Annual meeting 5-8 October 2008

6 A review of cleaner production methods for manufacture of methanol

Amjad Riaz et all, Journal of cleaner production 57 (2013) 19-37

7 Teaching old plant new tricks: The rise of methanol plant Revamp Stanbridge S .Hydrocarbon processing July 2016

8 Distinctive Technologies for Methanol plants Casale

9 Methanol Plant Capacity Enhancement C D Bhakta, A J Shaikh, Y N Patel, S J Darjee https://technicaltextile.net/articles/methanol-

plant-capacity-enhancement-3006

10 Technical reports –Conversion of Ammonia plant to Methanol. Daniel P Heiser EPA –AA-SDSB-82-3, February 1982

11 Compliance of EC conditions for revamping of Ammonia I to methanol plant (EC No. – F No. : J-11011/901/2007-IA (II)
dated31/07/08)

https://www.gsfclimited.com/ECComplaince report for Methanol Plant.

12 Purge Gas Recovery –An attractive scheme for methanol-ammonia coproduction: John Pach, John Brightling,Terry Fitzpatrick .
16th IMPCA 2013 Asian Methanol Conference

13 www.smc.co.om on announcement of ammonia project

About the author:

Mr. H P Pandya is independent consultant for technology and Energy Management and Advisor Project
Management to Zeppelin System India Ltd. Prior to this ,he has 39 years’ experience in operation, technology
selection, project development and execution , Energy management in fertilizers, Petrochemicals and
renewable energy at Gujarat State Fertilizers and Chemicals Ltd GSFC Vadodara India ,After retiring from
GSFC as Executive Director/Advisor Projects, he was with Linde Engineering India as Senior Consultant
Fertilizer for 3 years. He holds BE in chemical engineering from Gujarat University, ME in Petrochemical
Engineering from MS University Baroda, MBA Finance from IGNOU .He is also certified Energy Auditor. He can be reached at
harshadppandya@gmail.com, hppandya251250@gmail.com and Mobile 919979853515

Share this on:

 LinkedIn  Twitter
 AMMONIAKNOWHOW and its partners
provide solutions for various ammonia READ MORE

plants sections

Latest news Recent Publications Latest forum discussions

Habonim Ammonia Isolation Valves Applications Habonim Ammonia Isolation Valves Applications Floating off npk
June 25, 2022 June 25, 2022 2 weeks ago

Navigance Whitepaper Optimizing with Intelligence Navigance Whitepaper Optimizing with Intelligence Process Air introduction
June 25, 2022 June 25, 2022 4 weeks, 1 day ago

2005-2015 The first decade of OMIFCO fertilizer 2005-2015 The first decade of OMIFCO fertilizer Waste heat boiler tube side fouling removal w
complex complex shutting down plant
June 13, 2022 June 13, 2022 3 weeks, 5 days ago

Annual Turn-arounds in an Ammonia-Urea Annual Turn-arounds in an Ammonia-Urea Cryogenic operating temperature

Complex–Experience at Tata Chemicals Fertilizer Complex–Experience at Tata Chemicals Fertilizer 2 months, 1 week ago
Division, Babrala Division, Babrala
June 13, 2022 June 13, 2022 HB Ammonia Capacity Factor/Variation of effi
by loads
Physico-chemical properties lime-ammonium Physico-chemical properties lime-ammonium 5 months, 1 week ago
nitrate based on chalk, nitrate and ammonium nitrate based on chalk, nitrate and ammonium
sulphate sulphate New techno-economic report on Ammonia
February 21, 2022 February 21, 2022 technology
5 months, 3 weeks ago

2021 – 2023 © Fertilizer Industrial Services – United Kingdom. All rights reserved | Terms and conditions | Privacy Policy | A website designed by conceptie.ro