Improved Benfield Process for Ammonia Plants

by

S.K. Furukawa and R.K. Bartoo

UOP
Des Plaines, Illinois, U.S.A.

Abstract
Several process improvements have recently been incorporated into this Hot
Potassium Carbonate process for CO2 removal. Of interest to ammonia plant
operators are an improved activator to replace DEA, new packing evaluations for
high-efficiency packings, and changes in process flow sheets to reduce energy
consumption. The result is a process design for CO2 removal that is competitive
in today’s new plants in all aspects: capital costs, operating costs, and ease of
operation. Comparative cost and energy values are included.

Introduction
The BenfieldSM process is well known around the world for CO2 removal. Operating
Benfield units in India include some 25 units installed in ammonia plants plus 10 in
other industries. Because the majority of the Indian units were designed prior to 1985,
the casual observer may think that this process is fully mature and not capable of further
improvements. As this paper shows, continuing improvements have been made in several
areas for both proposed newly designed units and for revamping older units.

These improvements have been fully proven in units operating elsewhere, such as China,
Indonesia, Malaysia, and the United States. The specific Benfield improvements to be
discussed that are of interest to the ammonia industry include the following.

• New highly effective ACT-1TM activator, which shows substantial benefits over DEA
• Newly evaluated high-efficiency random packings for process designs
• Proven energy integration in the Benfield Hybrid LoHeat design to further reduce
regeneration steam compared with designs of 10 years ago

The New Activator

The Benfield process uses a chemical absorbing solvent based on 30% potassium
carbonate (K2CO3) in water plus an activator and corrosion inhibitor. An activator is a
low-concentration additive put into the carbonate solution to improve the absorption rate
of CO2. For many years, DEA (diethanolamine) has been the standard activator and is
still used today in many operating plants.

1
However, like most other organic chemicals, DEA is subject to degradation.
• DEA will break down from overheating (thermal degradation).
• DEA reacts with oxygen from air contact or from over use of reoxidation agents such
as potassium nitrite (KNO2), used to regenerate the corrosion inhibitor (vanadium).
• By absorbing CO2, a secondary amine activator such as DEA forms a carbamate
chemical that normally is easily regenerated. However, because further reactions can
occur, some by-products are formed that are not regenerable, and thus a degradation
compound is formed. Typically, these compounds are large-molecular-weight
polymer-type chemicals.

Evidence of the degradation of DEA can be seen in solutions from operating potassium
carbonate plants. Visually, the solution samples appear black and opaque as liquid coal.
Interference occurs with analytical procedures such as carbonate titrations and vanadium
valence determinations. Foaming upsets are frequent and the constant addition of
antifoam may be required. Often there is a rapid reduction of valence state of the
corrosion inhibitor (vanadium) from the active V +5 to passive V+4 material.

Potassium formate and a few other carboxylic acid salts are one result of the breakdown
of the DEA molecule, and these can be analyzed for. These salts are benign at low
concentrations. However, when they are found at concentrations of 5% or more, they
interfere with operations by altering the physical properties of the carbonate solution.
However, most of the other known and unknown DEA degradation compounds are
notoriously difficult to analyze for because they are large polymer-type compounds that
are still reactive and only a few have been identified chemically. Some amine
degradation compounds are even considered to be corrosion accelerators in that they
may solubilize iron, keeping it in solution and preventing it from reprecipitating as in
formation of the passivation coating.

UOP has found an alternative to DEA in its recently commercialized new activator called
ACT-1 activator. This material, a proprietary chemical from UOP, is also an amine but
with a more-stable molecule that is considerably more resistant to degradation. Side-by-
side accelerated laboratory degradation tests were performed to compare a carbonate
solution with DEA and with ACT-1 activator. The first test was to heat samples of both
solutions to 75o C (167o F) and expose them to oxygen by continuously injecting air. The
DEA was 15% destroyed (degraded) within 45 days, but the ACT-1 activator was still
100% available. See Table 1.

In another test, both solutions were heated to 121o to 132o C (250o to 270o F) and
saturated with CO2 at autoclave pressures of 9 to 14 bar (135 to 200 psi). After 15
days, only 25% of the DEA remained; 100% of the ACT-1 activator remained and was
reactive after 50 days. See Table 2.

The ACT-1 activator is currently in use in at least 15 units worldwide, including several
ammonia plants, and is being tested in a few units in India. It has been used in new units

2
where no DEA was present and in existing units that have used DEA for more than 20
years. Concentrations most effectively used in plant solutions are 0.3 to 1.0 wt.% ACT-1
Table 1
Effect of Oxygen on Benfield Activators

% of Starting Material *

Days of Test ACT-1 DEA

0 100 100
3 100 -
8 100 -
10 - 97
14 100 -
18 - 93
21 100 -
37 - 87
43 100 -
46 - 86
67 100 -
___________
* Lab test conditions: CO2 saturated,
constant air injection, temperature at 75o C

Table 2
Effect of Temperature and CO2 on Benfield Activators

% of Starting Material *

Days of Test ACT-1 DEA MMEA

0 100 100 100

3 100 75 70
8 100 50 50
10 100 42 46
15 100 26 40
18 100 - 33
20 100 - 30
30 100 - -
50 100 - -
__________
* Lab test conditions: 250 to 270o F and continuously
exposed to 135 to 200 psi CO2 in vapor.

3
activator compared to about 3% for DEA. When an ammonia plant operator or process
designer considers the quantities of replacement chemicals for losses of DEA by
degradation plus the higher concentrations needed, the overall costs for using ACT-1
activator can be equal or lower than for DEA.

When further cost savings are included for a considerably lower antifoam consumption, a
typically much reduced consumption of reoxidizing agent, and the improved smoother
process operation (less foaming upsets), ACT-1 activator appears attractive for
operations of new and old Benfield units.

Even more important, the CO2 absorption rate or activation with ACT-1 activator is far
superior to that of DEA. In all comparisons, the ACT-1 activator in Benfield solutions
substantially reduces the CO2 slippage to methanation typically to about 50% of the
levels achieved by DEA activation. This improved absorption of CO2 is at no added costs
for energy to regenerate the solvent and at no added pumping rates; in fact, plants
frequently find slight reductions in regeneration heat or solution pumping are achievable
compared with the requirements for the same units operating with DEA additive.

Table 3 compares the features of a Benfield unit designed for activation with DEA or
with ACT-1 activator. Table 3 also compares designs using high-efficiency packings, as
discussed below.

In summary, UOP believe the most important benefits of the ACT-1 activator are a
reduction in the CO2 slip to about half of that achieved with DEA; plus either
• Potential for capacity increases of up to 10% in the CO2 removal unit; or
• Potential reduction in regeneration heat by up to 10%, or
• Potential reduced solution pumping requirements by up to 10%
Much improved operations with better solution condition is another important benefit.

These benefits are fully achievable in new green-field units, and the same benefits can be
achieved in units fully converted from DEA to ACT-1 activator. A UOP technical paper
that covers additional information specific to the ACT-1 activator was presented at the
AIChE annual ammonia symposium, September 1994, by T.M. Gemborys.

High-Efficiency Packings
Designs for the Benfield process using random packings have always been based on
experimental data generated in-house by Benfield and UOP. Over the years, this data has
required extensive experimental work using the same carbonate-plus-activator solution
composition as used in operating Benfield plants: 30% carbonate plus up to 3%
activator. The original testing was with DEA; some testing has now been done with the
ACT-1 activator. Packing efficiency is a measure of the degree of gas and liquid contact,
and so any comparison of the hydraulic efficiency remains the same regardless of which
activator is used.

5
 Table 3
Process Design Comparisons

Case 1 Case 2 Case 3

Packing Pall Ring IMTP IMTP

Activator DEA DEA ACT-1

Major Equipment Sizes

Absorber Tower Top
Diameter 8.75 ft 7.75 ft 7.75 ft
Packed Height 2 x 27 ft 3 x 22 ft 2 x 24 ft
Packing Volume 3247 ft3 3113 ft3 2264
3
ft
Packing Type 2 in Metal Pall #50 Metal IMTP #50 Metal
IMTP

Absorber Tower Bottom

Diameter 14.00 ft 12.50 ft 12.50 ft
Packed Height 2 x 21 ft 2 x 26 ft 2 x 22 ft
Packing Volume 6465 ft3 6381 ft3 5400 ft3
Packing Type 2 in Metal Pall #50 Metal IMTP #50 Metal
IMTP

Regenerator Tower
Diameter 17.75 ft 15.75 ft 15.50 ft
Packed Height 3 x 27 ft 4 x 25 ft 3 x 26 ft
Packing Volume 20,043 ft3 19,483 ft3 14,718 ft3
Packing Type 2 in Metal Pall #50 Metal IMTP #50 Metal
IMTP

Utilities
Net Heating Duty:
MM Btu/hr 130.3 130.6 123.6
Btu/lb mol CO2 33400 33500 31,700
Lean Pump, U.S. gpm 5935 5935 5890
Electricity, kWh 1920 1920 1830
Cooling Water, U.S. gpm 12180 12180 11640

Capital Investment (± 30%)

Purchased Equip. Cost, U.S. $ 4.1 MM 4.0 MM 3.6
MM
Installed Equip. Cost, U.S. $ 8.3 MM 8.2 MM 7.3
MM

6
UOP’s standard for many years has been the steel Pall Ring or equivalent-type random
packing. This type of packing was widely available from several manufacturers, the
efficiency was fully adequate for industrial use, and it came in several sizes and
materials. Typically, 1.5 inch, 2 inch, and 3.5 inch ring sizes in stainless and mild steels
were used for Benfield ammonia plant designs.

As a result of the latest evaluations, UOP has identified several newly commercialized
packings available that are super-efficient for CO2 absorption in hot carbonate service.
In particular, UOP now has a new standard for designs proposed for new and revamped
units based on UOP laboratory data and confirmed in the first new units using these
packings. Evaluation has shown that the following packings have higher efficiency than
Pall Rings for Benfield service.

• Norton Co. IMTP packings

• Glitsch Co. Mini-Ring packings
• Nutter Engineering Co. Nutter Ring packings
• Koch Engineering Co. Fleximax packing

UOP is also looking at designing with structured packings, and three Benfield units are
already operating using a Sulzer Flexipac brand of structured packings.

By combining the use of the new ACT-1 activator with the high-efficiency packings,
UOP is able to design for reduced tower diameters for new units by 0.2 to 0.5 meters (1/2
to 1.0 ft) and reduce the packed heights by 3 to 4 meters per column for some designs.
Table 3 compares a unit designed for Pall Ring packings or for IMTP Packing, with DEA
or with ACT-1 activator. This comparison is for CO2 removal designs for a 1,500 MTD
ammonia plant. Comparing Case 1, Pall Rings, vs. Case 2, IMTP, the absorber diameter
is reduced with IMTP by 1.0 ft in the top section and by 1.5 ft in the bottom, and the
regenerator tower is reduced by 2.0 ft with DEA activator. Even more reduction in
diameter and packed height is found when both the new activator and high-efficiency
packings are used. In comparing Case 1 with Case 3 (ACT-1 in combination with IMTP)
in Table 3, the packed volume is reduced by 26.7% in the absorber and 36% in the
regenerator tower. Conservatively, this result translates to at least a 10% reduction in
capital cost for building a new unit.

Reference lists of installed units using these new packings and for units using ACT-1
activator are available from UOP.

Benfield Hybrid LoHeat Process

The UOP Benfield low-energy CO2 removal process integrates well into the newest
designs for high-energy-efficient ammonia plants. When optimized, this newly
commercialized process can achieve a net thermal energy consumption of only 650
kcal/Nm3 of CO2 removed or less. Four ammonia plants of 1,350 MTD capacity were
constructed in China using this low-energy hybrid concept; three were designed by CF

8
Braun and one by Uhde. All are operating now for 1 to 3 years. Figure 1 shows the
principal features of this process design.

The Benfield Hybrid LoHeat process, as it is called, is similar in design to the standard
4-stage ejector, lean solution flash tank design of the Benfield LoHeat process, which is
used in several Indian ammonia plants today. The conventional LoHeat process reduces
energy consumption from about 1,200 kcal/Nm3 for Benfield units without LoHeat,
down to about 800 kcal/Nm3 of CO2 removed for conventional Loheat units. A form of
internal energy recovery and recycling, this energy recovery is accomplished by flashing
the reboiled solution to generate steam, and then using steam ejectors to compress the
flashed steam for injection back to the regenerator column.

To make further improvements on the LoHeat process, UOP has added a fifth stage of
solution flashing, with mechanical vapor recompression (MVR) to boost the fifth-stage
flashed steam back to the pressure of the regenerator column. The combination of
ejectors plus MVR for multistage heat recovery is referred to as the Benfield Hybrid
LoHeat process. This improvement by itself allows energy consumption to be reduced to
650 kcal/Nm3, and can be combined with benefits of the ACT-1 activator to further
reduce to as low as 600 kcal/Nm3 of CO2 removed.

Figure 1 illustrates the overall Hybrid LoHeat process flow scheme with synthesis gas
heat integration for the internal generation of motive steam and for heating boiler feed
water. Data from a recent design of a 1,500 MTD ammonia plant show the following.

• Purified gas would contain not more than 500 ppm CO2.
• The removed by-product of 1,650 kg/hr CO2 is fully recovered at a purity expected to
be 99.3% CO2 (dry basis).
• Net thermal energy is calculated at 23.9 MM kcal/hr.
• Net electrical power for the Benfield Hybrid LoHeat unit is 1,826 kWh distributed as
follows:
- 1,635 kWh for process pumps
- 730 kWh for the MVR compressor
- 539 kWh reduction by incorporating hydraulic power recovery from the let-
down of enriched solution.

Net thermal energy consumption is 647 kcal/Nm3 of CO2 removed, and net electrical
power is 1,826 kWh. Converting electrical energy to thermal energy, this electrical
consumption is equivalent to 6.23 MM kcal/hr so that the net total energy consumed is
only 30.1 MM kcal/hr, or 815 kcal/Nm3 of CO2 removed.

Table 4 shows UOP’s estimates of installed costs for this Benfield Hybrid LoHeat flow
sheet.

9
Comparison of Energy Consumption
Table 5 compares the energy consumption for the Benfield Hybrid LoHeat process with
the conventional Benfield Loheat process and with older Benfield units not using the
Loheat process. The Hybrid LoHeat process was designed to achieve a thermal
regeneration energy consumption of less than 650 kcal/Nm3 of CO2 removed, compared
with typically about 1,200 kcal/Nm3 for units without LoHeat and about 850 kcal/Nm3
for the conventional ejector LoHeat process.

Table 4
Installed Costs for Benfield Hybrid Process

Equipment Cost, MM U.S. $ (*)

Towers & Vessels 2.820
Tower Packings 0.343
Flashtank 0.455
Pumps 1.037
Compressor 0.618
Turbine 0.462
Exchangers 2.428
Total Installed Costs $ 8.163
___________
* Cost based on 1,500 MTD ammonia plant

Table 5.
Comparison of Energy Consumption

________ Benfield Process *_________

Energy Consumption __ Not LoHeat LoHeat Hybrid Loheat

Thermal Energy,
MM kcal/hr 47.91 34.01 23.90
kcal / Nm3 of CO2 1297 920 647
Electrical Power,
kWh 1826 1826 2365
MM kcal/hr equivalent 6.23 6.23 8.07
Net Total Energy,
MM kcal/hr 54.14 40.24 31.97
kcal/Nm3 of CO2 1465 1089 865
__________
* Energy consumption based on 1,500 MTD ammonia plant

10
Adding a Mechanical Compressor
In the past, several potential objections have been raised to the use of a mechanical
compressor in the CO2 removal unit of a typical ammonia plant:

• What do you do when the compressor is down? Do you have to shut down the
ammonia plant?
• How reliable are these compressors? How frequently are they out of service? How big
are the motors, relative to other motors in the plant?
• Using electricity to operate a compressor increases the required generation of
electricity by more than just the pure energy equivalent. For units that generate their
own electric power, for example, what is the true energy consumption, including the
inefficiencies of generating electricity?

Although these concerns are valid, actual experience gained over several years of
operating time with MVRs in some 10 to 15 Benfield units show that the compressor
size is really smaller than expected, the reliability is much better than expected (well over
98% on-stream time for most units), and for the few hours per year when the compressor
is out of service for routine maintenance, the unit can run satisfactory with a temporarily
higher energy consumption by using extra steam from increased reboiling or by using
plant steam injected directly into the base of the Benfield regenerator.

For the 1,500 MTD ammonia plant Benfield Hybrid LoHeat example discussed
previously, the motor for the compressor requires only 730 kWh, less than half that of the
lean Benfield solution pumps (which consume 1,630 kWh electricity). The compressor
cost is estimated at U.S. $618,000 installed. The estimated cost for lean solution pumps
is U.S. $975,000. Finally, as shown in Table 5, the electricity to operate the compressor
adds only 1.84 MM kcal/hr to the net total equivalent energy consumption, and the
Hybrid system saves 10.11 MM kcal thermal energy compared with the ejector LoHeat
system. So the net savings is 8.27 MM kcal/hr over a conventional LoHeat process unit.

Hybrid LoHeat and MVR Experience

The Arcadian ammonia plant in Memphis, Tennessee, was constructed more than 20
years ago with a one-stage lean solution flashtank using ejector Loheat in their Benfield
CO2 removal unit. In about 1985, they added a stage 2 of lean solution flash using MVR
and thus became a Hybrid LoHeat unit. Operating for 10 years now, the plant operators
comment that the reliability of their compressor has been excellent: typically, they had
only one or two shutdowns per year in the first few years, usually because their operators
would accidentally surge the machine. On-stream time has been better than 98%, and
during the few times that the MVR was out of operation, the ammonia plant still
operated at full capacity but with added steam for regeneration. The steam-to-carbon
ratio normally is 3.52, the CO2 slippage to methanation was 800 ppm (designed for
1,000), and capacities of 102 to 105% of design were achieved with the ammonia loop
being the limitation to further capacity.

11
Similar comments have been received from the operators of Hybrid LoHeat units in
China. One stated they have achieved an on-stream time of more than 8000 hours per
annum. The four units there have run for a cumulative total of about 9 years. Some 12 to
15 other Benfield units use mechanical compression, either MVR alone or in
combination with ejector LoHeat flash.

Summary
These three basic improvements to the Benfield process have each been fully proven by
several years of operating experience in ammonia plants and are now available for
designing into newly proposed units. Further, UOP can retrofit most existing units for
achieving many of the same features and benefits. The IFFCO plant at Phulphur, India,
has just added a four-stage ejector LoHeat to improve their energy efficiency. The RCF
Thal units have recently changed packings to gain the benefit of added capacity of the
higher efficiency. At least three units in India have begun testing the ACT-1 activator.
The Hybrid LoHeat system has been demonstrated in China, but not yet in India.

The net energy consumption of the Hybrid LoHeat process is extremely competitive
when compared with any other CO2 removal process. The excellent energy efficiency
plus a lower solution circulation than used by many competing processes makes this
process the choice for modern ammonia plant operators who want the lowest net
operating costs for CO2 removal. Also, the UOP standard design uses two towers
compared with three for some other processes, and the Benfield columns are smaller by
design because they use high-efficiency commercial packings and the new ACT-1
activator. Thus, the Benfield process also has the lowest capital costs. The new,
improved Benfield process is still the number-one choice worldwide for CO2 removal in
new ammonia plants.

RKB, 1 / 97

UOP’s Benfield process and other gas processing technology is represented in India by
Mr. Youg Ganju and Mr. J.P. Roy. They can be contacted at offices of UOP Asia Limited.

UOP Asia Limited

3rd Floor, Vaitaklik Building, USO Road
A-8 Qutab Institutional Area
New Delhi 110 067 INDIA

Telephone: 011-65-18919
Telefax: 011-65-17814
Telex: 031-65167 UOPA IN

12