HC Processing April 1995 PDF
HC Processing April 1995 PDF
HC Processing April 1995 PDF
INEOS LLC
As part of a Federal Trade Commission mandated remedy to the merger of The Dow Chemical Company and the Union Carbide Corporation,
INEOS plc was able to purchase both Dows Ethanolamines and GAS/SPEC MDEA-based specialty amine businesses. This purchase became effective on
February 12, 2001.
INEOS LLC was set up as the newly acquired company, which includes the GAS/SPEC Technology Group. All the key Ethanolamines and GAS/SPEC personnel
were retained by INEOS LLC. All GAS/SPEC products, technology and know-how became the exclusive property of INEOS on a global basis.
8 psig stripper
Reflux ratio, mol H2O/mol acid gas
chart (Fig. 10). To calculate the central line, the raw data
3
is averaged. The upper and lower control limits are then
calculated in two steps.
2
First, the estimated standard deviation is calculated
by dividing the moving range average value by 2.128.
1
This standard deviation estimate is then multiplied by 3.
The resulting product is added to and subtracted from
0
5:00 9:00 13:00 17:00 21:00 1:00 5:00 9:00 the central line value to become the X-chart upper control
7:00 11:00 15:00 19:00 23:00 3:00 7:00 limit (UCLx) and X-chart lower control limit (LCLx).
Actual time, hr
Again, 99.7% of the data points will fall between these
Fig. 7. Raw data run chart. limits if the data is in control.
The Rules of Seven are then applied to the X-chart.
Furthermore, the data points must fall between the two
2.5 control limits to be considered in control. Fig. 10 satis-
2.4
fies all these criteria, so the data are in control. An exam-
ple of what the overall X-MR control chart would look
2.3 like for this data set is in Fig. 11.
2.2
Since these data represent stable plant operation, con-
trol limits and center lines will be used as new data is
2.1 collected. This way the new data will be compared with a
ppm H2S
Moving range
the center line. Also, there are seven data points trend-
0.15
ing upwards after 18:30. Either of these violations would
trigger an operator response.
By recognizing a potential problem early enough,
0.10
the operator has time to collect and review other data.
The operator would look at all the run and control
charts and check for positive or negative correlations.
0.05
Fig. 15 shows a combined run chart of six critical oper-
ating parameters. There is a positive correlation
between outlet H2S content and differential pressure 0.00
across the contactor. By a careful data review, the usual 5:00 7:00 9:00 11:00 13:00 15:00 17:00
6:00 8:00 10:00 12:00 14:00 16:00
solution of increasing the reboiler temperature can be Actual time, hr
avoided. This is because the run chart data indicates the
problem is in the systems front end and not the sys- Fig. 9. Moving range control chart (MR-chart).
tems regeneration section. Increasing heat to the
reboiler may appear to temporarily solve the problem by
giving a leaner solution entering the contactor and, Table 3. Troubleshooting guide for foaming
hence, a lower outlet H2S content. But this will only
Symptoms
delay proper response to the true problemfoaming Fluctuating absorber or stripper P
in the contactor. Amine carryover from absorber, stripper or flash tank
Even though this example is simplistic, it does point Swinging liquid levels in any vessel
out the power of control charts combined with a little Decrease in H2S removal with increase in CO2 removal
Off-specification treated gas
process know-how. Positive results from foam test
Step 4: implementing control charts. This Poorly stripped solvent
methodology is not difficult to put into place. However, Causes
it takes a commitment by all members associated with Hydrocarbons + organic acids = > amine soaps
a particular gas treating facility. The process can be Poor inlet gas separation
Lean amine temperature too low
implemented only with some graph paper, a pencil and Well-treating fluids and corrosion inhibitors
a calculator. If fancy output is desired, there are various Inadequate inlet gas separation
programs that will collect data and create elegant pro- Oil, inhibitors and welding fluxes
cess control charts. Improperly cleaned equipment
Suspended solids* (FeS, carbon fines, colloidal iron oxide)
The key is to first have the people that are directly Poor inlet gas separation
involved with the process decide which data are critical. Inadequate solution filtration
Next, this same group of people will be given responsi- Raw cotton filters
bility for constructing and maintaining the control charts. Improper selection of filter material
Makeup water
It does no good to have the data go into head office, have Corrosion inhibitors from steam condensate system
it manipulated by office professionals and sent back out. Bacteria
The time delay is too great and the person who sees imme- Preventionmaintaining a clean system is the key!
diate changes in the process is not at the plant and may Maintain lean amine temperature 10F above inlet gas temperature to min-
not appreciate the significance of the change. imize hydrocarbon condensation
Adequate inlet gas separation to minimize liquid hydrocarbons, iron sul-
As more data is collected, it is most likely the facility fide/suspended particles and well-treating chemicals from entering the
will move away from X-MR charts and advance to Mbar- amine system
R charts and then to Xs charts. The major difference Proper cleanout of new equipment prior to startup
between these chart types is the amount of data the Adequate carbon and mechanical filtration
Foam test with proposed makeup or initial fill water
charts are based on, as well as how the data is manipu- Proper mechanical filter material selection
lated. We will not go into these control charts. Their pro- Temporary use of antifoams
cedures are clearly outlined in other references.16 Either silicone, polyglycol or high molecular-weight alcohols
We strongly recommend that personnel involved in Antifoam usage in most cases should be considered a temporary treat-
ment while the root cause(s) is identified and corrected
the implementation and maintenance of control charts
*Suspended solids do not cause foaming, but rather stabilize the foam.
be given the proper tools to efficiently handle chart devel-
opment. This can be through a team leader reading the
appropriate background material and summarizing the
critical issues during a couple of training sessions. Or it Benefits of using control charts will soon be seen in
can be as simple as an operator doing some background the daily operation of a facility as well as during opti-
reading and trying the charting. mization activities.
X-chart
2.2
2.1
2.1 1.9
ppm H2S
1.7
2.0 1.5
0.35
1.9
0.30 Moving range values
AVGmr
1.8 0.25 UCLmr
MR-chart
0.20
1.7 0.15
0.10
1.6
0.05
1.5 0.00
5:00 7:00 9:00 11:00 13:00 15:00 17:00 5:00 7:00 9:00 11:00 13:00 15:00 17:00
6:00 8:00 10:00 12:00 14:00 16:00 6:00 8:00 10:00 12:00 14:00 16:00
Actual time, hr Actual time, hr
Fig. 10. Variables control chart (X-chart). Fig. 11. Control charts for variables data.
0.30
Moving range
3.0
0.15
2.5
0.10
2.0
0.05
1.5 0.00
5:00 9:00 13:00 17:00 21:00 1:00 5:00 9:00 5:00 9:00 13:00 17:00 21:00 1:00 5:00 9:00
7:00 11:00 15:00 19:00 23:00 3:00 7:00 7:00 11:00 15:00 19:00 23:00 3:00 7:00
Actual time, hr Actual time, hr
Fig. 12. Extended X-chart with new data. Fig. 13. Moving range control chart (MR-chart).
Foaming. Table 3 lists some common symptoms of treating plants can, however, be controlled and mini-
foaming along with likely causes. Foaming is the most mized with proper plant design and operating param-
common cause of upsets in an amine plant, usually eters. The key is to minimize acid-gas flashing and to
resulting in excessive amine losses, off-specification understand other contributing factors that can enhance
treated gas and a reduction in treating capacity. All corrosivity of amine solutions. Like the three previ-
of these affect operating costs and revenue. Monitor- ous categories, monitoring and an understanding of
ing key parameters such as absorber or stripper pres- key process parameters can help minimize corrosion in
sure drop, vessel liquid levels and treated gas outlet amine units. Listed in Table 5 is a troubleshooting
composition can alert the operators to potential foam- guide for corrosion based on a method from DuPart,
ing problems. Bacon and Edwards.8
Fig. 14 shows the use of a combination of run charts
to alert the operator to a foaming problem by moni- OPTIMIZATION
toring absorber P as well as outlet H 2 S content. It is almost imperative that amine plant operations
Again, not only is it important to monitor key process be optimized to the maximum. It is no longer acceptable
parameters, but to understand what they are indi- to operate plants with huge safety margins on circula-
cating so appropriate corrective or preventative action tion rate and energy input. Plants are required to func-
can be taken. tion closer to the edge of the operating envelope. This
Operating philosophy when dealing with foaming new operating discipline can only be achieved with an
should be to address the root cause as opposed to con- understanding of the operating envelope and penalties
tinually treating symptoms. Using antifoams for tempo- associated with huge safety margins.
rary relief is acceptable. But for long-term, more reliable To successfully optimize an amine unit and main-
operation, identifying and correcting the root cause(s) tain an optimum process, a good baseline data set and
should be the norm. an understanding of, and commitment to, optimized
target conditions is required. If one or the other is
Amine losses. Every amine plant can expect to have missing, the optimization will be haphazard or will
some amine losses associated with its operation. Accept- not occur. Again, continuous gathering of plant data,
able losses vary with different applications. However, graphical representation and an understanding of the
excessive amine losses can have a negative economic cause-and-effect relationship between different pro-
impact on total plant operating cost, and it is important cess parameters is a key aspect of successful plant
to understand how losses can occur and the appropriate optimization.
corrective action to take. Losses usually fall into five Optimization of a plant entails the correct balance
major categories: mechanical, entrainment, solubility, between capacity, energy and corrosion. Ideally, acid gas
vaporization and degradation. Listed in Table 4 is a trou- in the treated-gas stream should be slightly less than
bleshooting guide for amine losses based on Stewart and the maximum specified limit, heat input to the reboiler
Lannings method.7 should be at a minimum and corrosion should be within
tolerable and accepted limits.
Corrosion. This can result in unscheduled downtime, An important, but frequently overlooked, aspect of
loss of production, reduction in equipment life and plant optimization is to get everybody involved in the
even injury or death. Corrosion in alkanolamine gas process. Teamwork and buy-in are very important and
Stagnant areas with high halide ion content accelerate this condition
2.0
Intergranular corrosion
Most often found in stainless steels in heat affected zones
Selective leaching corrosion
Removal of one element from a metallic alloy
1.8
Erosion corrosion
High flowrates and turbulence can accelerate attack on a metal
Aggravated by the presence of solid particles or entrained gas bubbles
Stress corrosion cracking
1.6 Simultaneous presence of tensile stress and corrosive media
Presence of chloride ion can induce this phenomenon
Hydrogen damage corrosion
14:00 15:30 17:00 18:30 20:00 21:30 23:00 Mechanical damage caused by the presence of, or the interaction of the
Actual time, hr metal with, hydrogen
Symptoms
Fig. 14. Detailed look at extended X-chart. High solution metals (Fe, Cr, Ni, etc.) content Vessel failure
Wall thinning using ultrasonic monitoring High rates on coupons
6
or probes
Physical leaks Positive solution corro-
ppm H2S sivity test
5 Lean gpm/100 Process considerations
Lean temp/100
Lean load 1,000 Rich acid gas loading too high due to low amine concentrations or under-
Reflux ratio circulation of amine
4 Delta pressure There is potential for corrosion at total acid gas loadings greater than:
0.35 mols acid gas/mol MEA
Parameter
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GSMR002-8/01