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Petrochemical Developments

Use new economics for purification on a small scale

For smaller methanol units, new designs balance energy cost against capital cost for long-term profitability
K. Patwardhan, G. Satishbabu, S. Rajyalashmi and P. Balaramkrishna, Larsen and Toubro, Powai, Mumbai, India

rude methanol (MeOH) distillation is an energy intensive separation process and contributes significantly to the total production cost of this alcohol. It is very important to choose the right distillation configuration columns for MeOH purification. In the presented study, a two-column configuration is compared with three-column configuration with forward- and backward-heat integration schemes. Reduction of approximately 64% in lowpressure (LP) steam consumption is observed in a three-column configuration case as compared to the base case of two-column case for a small capacity plant (about 23,000 metric tpy). Further reduction in specific energy consumption for a three-column configuration is possible with a backward-heat integration scheme.
KEY PETROCHEMICAL

summarizes a typical composition of the crude MeOH obtained through commercial processes. US federal-grade specification OM-232e identifies three grades of MeOH. Grade C is for wood alcohol used in denaturing. Grade A covers methanol generally used as a solvent. Federal-grade AA is the purest product and it is used for petrochemical/chemical applications in which high-purity and low-ethanol content are required, such as for MTBE, methyl amines manufacture, etc. The general standard observed by the chemical industry for MeOH product purity is US federal-grade AA. Another known methanol grade is the fuel-grade; it is used as a blending component for gasoline.
Purification schemes. Crude MeOH is purified by distillation with one- or two- or three- or four-column configuration. Fuel-grade methanol is normally produced with a single distillation tower. But to produce federal-grade AA methanol, two-, three-, and sometimes, even four -tower distillation systems are used. The amount of distillation required depends on the byproduct formation of the MeOH synthesis catalyst and plant capacity. The economics of the purification scheme involves the complex relationship of plant capacity, heat available in the plant, the energy export requirement and customer requirements, etc. For example, the four-column configuration is justified only at large capacities such as 5,000 metric tpd of MeOH production where as choice of two- or three-column configuration depends very much on customers requirements and energy availability in the front end.

Methanol is one of the most important petrochemicals produced globally. It is extensively used as feedstock in the production of chemicals such as formaldehyde, methyl tertiary-butyl ether (MTBE), tertiary amyl methyl ether (TAME) and acetic acid, and also as a hydrogen source in the fuel cells used in automobiles. The majority of MEOH is produced via natural gas through steam reforming; other processing methods include use of petroleum fraction and process offgas. The MeOH-manufacturing process can be divided into three major sections: feedstock purification and syngas generation, compression and MeOH synthesis, and MeOH purification. Fig. 1 is a general flow diagram of a MeOH facility using natural gas as the feedstock. In this design, three process sections may be considered independently, and the technology may be selected and optimized Single-column configuration. For fuel-grade MeOH as a separately for each section. The normal criteria for technology blending component (for gasoline), the major demands regardselection are capital cost and plant efficiency. ing quality are the water content and dissolved gases. Fuel-grade In a conventional natural gas-based MeOH plant with a capacity of 2,500 + Natural MeOH metric tpd, syngas generation accounts for gas MeOH MeOH Syngas Compression Desulfurization synthesis distillation production 55%, distillation accounts for 12%, compression and MeOH synthesis accounts for 12% and utilities and other services Reactor Distillation Reforming account for 24% of the total capital cost. technologies technologies technologies
Methanol purification. Crude

MeOH, as removed from the MeOH synthesis section, contains water, higher alcohols, impurities and light ends. Table 1

1. Steam 2. Combined 3. Autothermal

1. Isothermal 2. Adiabatic

1. Single column 2. Multicolumn

Fig. 1

General flow diagram for a natural-gas based MeOH facility.

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MeOH should be dissolved-gas free and preferably should not contain more than 500 wt-ppm of water. The limitation on water content is due to its immiscibility with gasoline (Fig. 2).
Multi-column configuration. The condensate from the syn-

thesis loop is generally purified in two stages using conventional distillation columns operating at pressures slightly above atmospheric pressure. The first distillation stage is for light ends removal, and is carried out in a single-distillation column known as the topping column. This column acts as a refluxed stripper. The liquid feed enters near the top stage and MeOH vapor generated in the reboiler strips the light endssuch as di-methyl ether (DME), methyl formate and acetoneand residual dissolved gases from the crude MeOH. The main area of investigation is the second stage of MeOH purification. This is the MeOH refining stage, where MeOH is recovered as the overhead product from one or more distillation columns. Water is withdrawn as the bottoms product. Middle boiling impurities (principally ethanol, but also higher alcohols, ketones and esters), referred to as fusel oil are withdrawn as a side stream below the feed stage. Provision of this side stream enables the MeOH production to US federal specification O-M- 232K Grade AA. In typical two-column MeOH purification scheme, as shown in Fig. 3, about 20% of the total heat for purification is associated with the topping column. The remainder is required to separate methanol from ethanol and water. This basic arrangement is widely reported in the literature.1,2 With the sharp rise in energy costs, MeOH technology licensors and operators have focused considerable attention on alternaTable 1. Typical crude MeOH composition to MeOH purification section
Component Wt% CO, CO2, H2, CH4, N2, DME, aldehydes, ketones Ethanol, higher alcohols (propanol, butanol, etc.) 0.50.8 0.10.6 Methanol 8890 Water 911

tives to this standard two-column arrangement.28 A double-effect three-column scheme was developed and it is widely applied in industry.4 A number of these alternative schemes involve splitting the refining column into two separate columns operating at different pressures, such that the overheads of the higher pressure column can be used to reboil the lower pressure column. Several novel energy-saving three-column distillation configurations have been explored in the literature.9 The capital cost of the three-column schemes is significantly greater than the standard two-column arrangement. The threecolumn distillation unit consists of a topping column and two refining columns. Refining column II operates at normal pressure. Refining column I operates at a higher pressure, thus utilizing the condensation duty of this column as the reboiler duty of refining column II. This substantially reduces the LP steam consumption of the distillation section. Another configuration of three-column systems is operating refining column I at atmospheric pressure and refining column II at high pressure (HP). Federal-grade AA MeOH is withdrawn close to the top of both refining columns. Although the three-column system is more costly, it can reduce the required distillation heat input by 30%40%. Multi-column systems (three or more columns) can generally only be justified when energy costs are prohibitively high. The design of the MeOH distillation unit primarily depends on the energy situation in the front end. The two-column distillation unit represents the low-cost unit, and the three-column distillation unit is the low-energy system. Multi-column design maximizes the yield and minimizes LP steam consumption. The four-column design (Fig. 4) includes the three columns described previously as well as an additional recovery column. The fusel oil purge from refining column II is processed in the recovery column to minimize MeOH losses even further. The distillation unit can be designed to limit the MeOH content in the process water to a maximum of 10 wt-ppm. Furthermore, the heat available from the front end (syngas generation) at a low temperature is efficiently used to minimize steam consumption. As we go higher up in the column configuration, MeOH recovery increases but specific steam consumption decreases. In
Condenser 1 Stripped gas Liquid off steam Product MeOH Condenser 2

Tail gas

Fuel-grade product

Reux drum 1 Crude MeOH Stabilizer column

Reux drum 2

Raw MeOH

Higher alcohols Concentration column

Process gas LP steam Fig. 2 Single-column configuration for an MeOH plant. Fig. 3

Process gas

LP steam Recycle water

Stabilizer MeoH pump Two-column configuration for an MeOH plant.

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Petrochemical Developments
four-column configurations, as high as 60% savings in the steam consumption can be achieved when compared to the base case of a two-column configuration.
Simulation study

An analysis was conducted for purifying AA grade MeOH from crude MeOH through a two-column and three-column configuration using a commercially available process simulator. The results were validated with the reference data available for the two-column scheme. The simulations were extended for the three-column configuration. As in three-column configuration, due to higher degree of freedom, one extra case is generated for the reboiler coupling. In forward heat integration, out of the three columns, the first column is the topping column, as in the twocolumn case; the second is a HP refining column; and the third is LP refining column. Total heat required for the HP-column reboilers is provided by LP steam. Instead of using a cooling water heat exchanger to chill overheads of the HP column, heat is used to run the LP column reboiler. This is called the forward-heat integration because heat integration is in the direction of material flow. The HP column is operated at a pressure of 7 to 10 atmospheres depending on the feed composition. The LP column is operated near to atmospheric pressure. Table 2. Simulation results for column schemes
Two-column scheme No. of stages Reboiler duty, Gcal/hr Condenser duty, Gcal/hr Diameter, m Reflux ratio Boil-up ratio Stabilizer column 38 5.20 6.26 1.84 132 0.64 Concentration column 80 25.53 25.22 4.10 2.21 13.27

In backward-heat integration, the second and third columns are exchanged. In this scheme, the overheads from third column (HP) supply heat for the second-column reboiler. The material and heat flows in the opposite direction. The basic assumptions made are: All trays behave ideally (tray efficiency is 100%). Liquid reflux from the condenser is saturated at calculated conditions. Pressure drop/ tray is 0.01 kg/cm2. Negligible pressure drop in reboiler and condenser. Reductions or increases in the pressure between the columns are achieved by the reduction valve and pump respectively. A 15C approach ( temperature difference) is maintained between LP column reboiling liquid and HP column overheads. Table 2 summarizes the simulation results for the base case of two-column, three-column schemes with forward- and backwardheat integration configuration. The LP steam consumption in the two-column configuration is much greater than the three-column configuration. This is because
Condenser 1 Stripped gas Condenser 2 Product MeOH Reux drum 2 Reux drum 3

Reux drum 1

Crude MeOH Topping column Process gas

Liquid off steam HP column LP steam Reboiler 2

Higher alcohols LP column

Reboiler 1 Stabilizer MeOH pump

Reboiler 3 Recycle water

LP steam consumption 1.3384 (metric ton/metric ton of MeOH) Three-column (forward integration) scheme No. of stages Reboiler duty, Gcal/hr Condenser duty, Gcal/hr Diameter, m Reflux ratio Boil-up ratio LP steam consumption (metric ton/metric ton of MeOH) Stabilizer column 38 5.20 6.26 HP column 58 19.47 17.98 LP column 53 17.98 19.09

Fig. 4A Three-column configuration (forward integration) for an MeOH plant.

Condenser 1 Stripped gas

Condenser 2

Product MeOH Reux drum 3

1.84 2.61 3.51 132 5.64 2.96 0.64 3.45 9.44 0.934 Crude MeOH HP column 55 17.46 17.67 LP column 58 17.85 17.46 Topping column Reux drum 1

Reux drum 2

Liquid off steam HP column LP steam Reboiler 2

Three-column (backward integration) scheme No. of stages Reboiler duty, Gcal/hr Condenser duty, Gcal/hr Diameter, m Reflux ratio Boil-up ratio Stabilizer column 38 5.20 6.26

Process gas Reboiler 1

Higher alcohols LP column Reboiler 3 Recycle water

1.84 3.36 2.62 132 2.70 5.00 0.64 3.83 9.92

LP steam consumption 0.8265 (metric ton/metric ton of MeOH)

Fig. 4B Three-column configuration (forward integration) for an MeOH plant.

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Petrochemical Developments
the heat required for the concentration column is supplied by LP steam. In a three-column configuration, there is a possibility to couple the reboiler of one column with the condenser of another. Temperature differences between utility (LP steam) and reboiler temperature decrease with increasing column pressure. Thus, the reboiler requires a higher area for the same duty when compared to base two-column configuration. In the backward-heat integration scheme, due to altered column sequencing (i.e., LP column preceding the HP column), around 60% of MeOH product is recovered in the first stage. This offers advantages in two ways: 1) Ease of separation (characterized by the relative volatilities) increases with decreasing operating pressure for a constant feed composition 2) Altered composition as compared to a forward-heat integrated scheme distillation can be done at lower pressure in HP column. This reduces the heat duty on the HP column reboiler. The reverse heat integration results in more energy savings.
Economics of methanol distillation

lation setup under consideration. The cost contribution is higher for instrumentation in three-column backward configuration than for a forward design due to the complex control system. The capital cost in the case of the three-column configuration is more (12%17%) than that of two-column configuration due to the additional column and associated equipment. It is very important that before adopting any of the listed schemes, a balance between the fixed and operating cost is done.
Operating cost. The operating cost for the distillation column scheme under consideration includes cost for cooling water in the overhead condenser and steam in the reboiler. The operating cost of cooling water is governed by various factors such as ambient conditions, electrical consumption in fans and cooling water pumps, water cost and chemical treatment. The cost of cooling water is taken as $0.2/m3. The three-column configuration saves energy consumption in terms of LP steam supplying heat to the reboiler. The steam required is the operating cost, and it can be expressed in terms of natural gas consumption. The steam costs can be determined assuming water at available temperature is heated in boiler by burning natural gas, and it can be expressed by:

For capital cost, an MeOH distillation complex involves distillation column, reboiler, condenser, reflux tank, pump and associated column controls. The cost for each units depends on various operating and design parameters. Fig. 5 summarizes the contribution of the individual costs to the total cost for the distil2.56% 5.61% (a) 0.34% 2.58% 4.23% 84.69%

M Cp T T + w( B ref ) Cost of steam, $ = ( LHV NG )Boiler

) (NG unit price)

3B-column conguration Operating cost Capital cost

3F-column conguration

3.15% 7.04%

0.28% 4.27%

7.75%

77.52%

2-column conguration 0 20 40 60 80 Relative cost 100 120 140

(b)
Fig. 6

Relative capital/operating cost for column configuration.

7.18% 2.93%

0.27%

3.36%

9.58%

76.68%
3B-column conguration LP steam CW

(c)
3F-column conguration

Column Reboiler Condenser drum

Fig. 5

Condenser Pump Instrumentation

2-column conguration 0 Fig. 7 20 40 60 80 Relative cost 100 120

Cost contribution to the capital cost of equipments for various configurationA: two-column configuration, B: three-column forward integration configuration and C: three-column forward integration configuration.

Operating cost contributions.

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Petrochemical Developments
The three-column configuration saves energy. Thus, less natural gas is consumed via lesser steam demand by the reboiler. Almost 30%40% savings can be realized by adopting either three-column forward configuration or three-column backward configuration. But a higher coolant flowrate is required in the additional condenser in the three-column configuration; accordingly operating costs increased. Fig. 6 illustrates the combined effect, where it can be seen that operating cost is high for a threecolumn configuration with forward integration, while, in others, marginal savings can be seen. Fig. 7 shows the split.
New thinking. A techno-commercial comparison of the
IMTOF, London, 1993. T. P. and W. L. Luyben, Comparison of energy consumption in five integrated distillation column configurations, Industrial Engineering Chemical Process Des. Dev., No. 22, 1983, pp. 175179. 6 Wu, J. and L. Chen, Simulation of novel process of distillation with heat integration and water integration for purification of synthetic methanol, Journal Chemical Industrial Engineering, China, No. 58, 2007, pp. 32103214. 7 Liu, B. Z., Y. C. Zhang, P. Chen, and K. J. Yao, Research on energy saving process of methanol distillation, Chemical Industry Engineering Progress, China, Vol. 27, 2008, pp. 16591662. 8 Douglas, A. P. and A. F. A. Hoadley, A process integration approach to the design of the two- and three- column methanol distillation schemes, Applied Thermodynamics Engineering 26, 2006, pp. 338349.
5 Chiang,

two-column and three-column schemes for medium capacity MeOH plant is presented here. The three-column scheme with backward-heat integration offers approximately 60% saving in LP steam as compared to two-column scheme. It can provide as an option where LP steam costs are higher compared to cooling water. Although, in the three-column scheme, backward integration offers higher savings as compared to forward integration scheme the column control will be complicated, and it needs to be provided more attention during operation. HP

LITERATURE CITED Methanol distillation process, US patent 4,210,495, 1980. 2 Fiedler, E., G. Grossmann, D. B. Kersebohm, G. Weiss, and C. White, Ullmanns Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag/ GMbH & Co., Weinheim, 2002. 3 Meyers, R. A., Handbook of SynfuelsTechnology, McGraw Hill, New York, 1984. 4 M. Harvey, Methanol Distillation-Two and Three Column Schemes,
1 Pinto,

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