Catalytic Reforming Improved by Moisture Metering

Process Control:
Catalytic Reforming Improved by Moisture Metering

A critical process variable in refinery catalytic reformers is the moisture level in the reactors. Absolute measurement of this variable insures improved unit efficiencies.
M.G.Bloch and P.P.Lifland, Mobile Research and Development Corp., Paulsboro, NJ. One very big effect on refining operations brought about by the ecology challenge has been the ever-increasing severity of catalytic reformer operation. This high-severity operation could cause excessive yield loss and catalyst deterioration, thereby increasing consumption of valuable natural resources. However, close control of operating variables has enabled refiners to continually increase the output of reformers, both in quality and quantity, while keeping losses and costs at a minimum. One of the most critical process variables is the moisture level in the reactors. High moisture content removes chloride from reforming catalyst, thereby accelerating activity loss to the point where high octane levels can no longer be attained. Along with this activity loss, sizeable losses of liquid product yield are also encountered. The performance of reforming catalyst depends greatly on the degree of hydration of the catalyst support. If the moisture level in the reactors is too low, the catalyst will deteriorate. The optimum moisture level for a specific operation depends on the charge stock hydrocarbon types, boiling range and chloride content and on reformer operating variables such as pressure, temperature and product octane number. Figure 1 shows the effects of variations in moisture level in a particular reforming operation (1). Although the exact numbers for moisture levels, yield loss, and cycle life will be different for different reformers, this general picture applies to all reformers. Generally, the magnitude of the yield and cycle life losses is higher at higher octane number severities. In Figure 1, the optimum moisture level is 10 to 15 parts/million by volume in the recycle gas. Increasing the moisture level to 50 parts/million results in a 12 % reduction of cycle life and a decrease in liquid yield equal to 1% of reformer charge. Attempts to avoid these losses caused by wet operation sometimes lead to overly dry operation. In this range the losses are often more drastic. At 3.5 parts/million of water, this reformer showed a 40% loss in cycle life and more than 2 % loss in liquid product.
Accuracy and reliability needed in measurements

Therefore, it is not sufficient merely to operate a reformer as dry as possible. The moisture must be controlled within a narrow range to get the best results from the process unit. In order to control the moisture, it is necessary to have accurate, reliable measurements of the moisture level. Since Mobil's first catalytic reformer went on stream 20 years ago, we have tried a wide variety of instruments for this purpose.
Fig. 1
Effect of Moisture on Reformer Yields
MOISTURE LEVEL
PPM OZ. PPM
VARIATION FROM OPTIMUM

OUNCES 14 oz. GLASSFULS
LOST YIELD (*)
%
2 1 0.6 0.5 0.2 0.1
$ /HOUR
$ /DAY
$ /YEAR
3.5 5.0 6.0 6.5 8.0 12 16 19 20 25 27 30 32 33 38 50 52 85 140
-19 -15 -13 -12 - 9 0 8 14 17 28 32 38 42 44 56 80 84 155
-8.5 -7.0 -6.0 -5.5 -4.0 0 +4 7 8 13 15 18 20 21 26 38 40 73 128
7 11 13 14 17 26 34 40 42 53 58 64 68 70 82 106 110 181 300
1.36 1.07 .93 .86
333 167 100 83 33 17
8000 4000 2400 2000 800 400
2,400,000 1,200,000 720,000 600,000 240,000 120,000 240,000 420,000 480,000 600,000 660,000 720,000 840,000 1,200,000 1,800,000 2,400,000
1 2 3 4 5 13 21.4 0.2 0.3 0.4 0.5 0.57 0.6 0.7 1.0 1.5 2.0
33 800 58 1400 67 1600 83 2000 2200 100 2400 117 2800 167 4000 250 6000 333 8000
*Assumptions: Plant capacity: 1-0,000 bbl/day (400,000 gal/day) (51,200,000 oz/day)
300 stream-days of operation. Value of gasoline: $1.00/gallon at the refinery. Optimum moisture level: 12 ppm (26 ounces)
TRACE MOISTURE MEASURMENT APPLICATION for ANALYZERS using QMB-DETECTORS IN REFINING and HYDROCARBONPROCESSING: REFINERY saves $ 291,048 in one year on a PLATFORMER with MOISTURE ANALYZER using QMB Detector Techniques. Pays for itself in a week by boosting yield 2% & decreasing fuel !
By R. T. TUCKER, Sunray DX Oil Company, Tulsa, Oklahoma with GORDON H. WEYERMULLER, Executive Editor CHEMICAL PROCESSING Example:
Inadequate control of moisture on a Platforming unit at Sunray DX Oil Company reduced yield. Efficiency of the catalytic reforming operation is tied directly to the moisture content of the hydrogen system. The stream contains C1 and C2 compounds and traces of olefins, in addition to hydrogen. If the moisture is too high, the water will wash the chloride coating off the catalyst and kill the process. If it is too low, the activity of the catalyst is reduced. Platformer input is 15,000 bpd of naphtha with an output of about 13,000 bpd of reformate gasoline. In order to obtain the maximum yield of gasoline, moisture content needed to be maintained between 25 and 100 ppm and average about 40 ppm. Close enough control could not be maintained with spot laboratory tests.
Solution:
An analyzer which utilizes a pair of quartz crystals for continuously measuring and recording the moisture was placed in operation in February 1967. The polymer coated quartz crystals serves as the sensing element of the instrument. The crystals vibrate at 9 million cycles / sec. This frequency of vibration is affected by the amount of moisture absorbed by the coating on the surface of the measuring crystal. Each crystal is housed in a separate compartment. A dry reference gas flows over one crystal while the monitored stream flows over the second crystal. The absorption of water in the wet stream by the coating on the crystal results in a decrease in frequency for this crystal. Measurement of the frequency difference between the 2 crystals is then a measure of the water absorbed and thus of the water content of the monitored stream. The gas streams are automatically reversed from one crystal to the other every 30 seconds the water on each crystal being rapidly and reversibly absorbed and desorbed. While one crystal is absorbing moisture the other is drying. A change in the frequency of the crystals is created by temperature variations outside the range of 70-85 F (*). When the atmospheric temperature falls below 70F, a means has been provided at Sunray DX for heating the crystals. However, no cooling is available. The plant has found that switching between the 2 crystals and averaging the 2 readings gives acceptable results. Based on the analysis water content of hydrogen stream is adjusted with an-off proportioning pump. One of the principal advantages of the analyzer its ability to measure moisture in hydrogen streams and in hydrocarbon streams containing olefins. It also has a rapid response to changes in moisture levels and has a lack of hysteresis. Another advantage is the ability of the instrument to detect low levels of moisture down to only a few parts per million.
Results:
Measurement of moisture on a continuous basis with the QMB - analyzer has enabled the unit to obtain a 2 % greater yield. This improves the value of output obtained from each barrel of feed processed by 5.3 Cent. This results in an increased product value of about $23,850 per month. Closer control of moisture has also decreased the amount of furnace heat needed to create proper reaction conditions,
thus saving fuel. Furnace heat has been reduced 3,026,000 Btu/hr, which amounts to 2800 cfh of natural gas. This is worth $404 per month. The 2 amounts total up to $24,254 per month or $291,048 per year. The moisture analyzer has been found to be within 1 or 2 ppm of lab tests in the range of 40-250 ppm. Outside this range, the 2 methods are not as close, but it is not certain which method is more correct, especially in the lower range. ((*)) Instrument manufacturer points out that the detector cell is thcrmostated at 130F and normally will operate at an ambient temperature range of 10-100F
Reprinted from February 1969 CHEMICAL PROCESSING For E. I. Du PONT de NEMOURS & COMPANY, INC. INSTRUMENT PRODUCTS DIVISION Wilmington, Delaware 19898
A SAVING Of $404 / MONTH only in fuel costs has been achieved by more efficient utilization of fuel, made possible by a QMB Moisture Analyzer Model 510 from DuPONT. In this photo cover has been removed from sensing portion of analyser as a check is made on it. Model 510 moisture analyzer is a product of Instrument Products Division, DuPont Company, Wilmington, Del. 19S98. Remarks by Triple A: Those where the days: Models 510 and 560 are no longer available. A novel optimized QMB analyser is the TRIPLE A Quality Moisture Analyzer Model QMA 2020. But we also repair and service DuPONT / AMETEK moisture analyzers worldwide

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Process Control:

Catalytic Reforming Improved by Moisture Metering

Accuracy and reliability needed in measurements

Effect of Moisture on Reformer Yields

VARIATION FROM OPTIMUM

LOST YIELD (*)

3.5 5.0 6.0 6.5 8.0 12 16 19 20 25 27 30 32 33 38 50 52 85 140

-19 -15 -13 -12 - 9 0 8 14 17 28 32 38 42 44 56 80 84 155

-8.5 -7.0 -6.0 -5.5 -4.0 0 +4 7 8 13 15 18 20 21 26 38 40 73 128

7 11 13 14 17 26 34 40 42 53 58 64 68 70 82 106 110 181 300

1.36 1.07 .93 .86

333 167 100 83 33 17

8000 4000 2400 2000 800 400

*Assumptions: Plant capacity: 1-0,000 bbl/day (400,000 gal/day) (51,200,000 oz/day)

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