1) During normal operation of a nitrogen wash system, a section of carbon steel piping suddenly ruptured due to extremely low temperatures caused by liquid nitrogen. The rupture caused fragments to launch in all directions but no injuries occurred.
2) Just before the rupture, the nitrogen wash system was experiencing unstable temperatures and gas compositions. Operators attempted to manually control instruments to break this cycle but temperatures continued dropping rapidly.
3) It is believed the rupture occurred when liquid nitrogen rapidly vaporized in the carbon steel piping, subjecting it to both rapidly increasing pressure and heavy thermal shock, causing the violent rupture. Once the liquid nitrogen entered the steel lines, the situation was uncontrollable.
1) During normal operation of a nitrogen wash system, a section of carbon steel piping suddenly ruptured due to extremely low temperatures caused by liquid nitrogen. The rupture caused fragments to launch in all directions but no injuries occurred.
2) Just before the rupture, the nitrogen wash system was experiencing unstable temperatures and gas compositions. Operators attempted to manually control instruments to break this cycle but temperatures continued dropping rapidly.
3) It is believed the rupture occurred when liquid nitrogen rapidly vaporized in the carbon steel piping, subjecting it to both rapidly increasing pressure and heavy thermal shock, causing the violent rupture. Once the liquid nitrogen entered the steel lines, the situation was uncontrollable.
1) During normal operation of a nitrogen wash system, a section of carbon steel piping suddenly ruptured due to extremely low temperatures caused by liquid nitrogen. The rupture caused fragments to launch in all directions but no injuries occurred.
2) Just before the rupture, the nitrogen wash system was experiencing unstable temperatures and gas compositions. Operators attempted to manually control instruments to break this cycle but temperatures continued dropping rapidly.
3) It is believed the rupture occurred when liquid nitrogen rapidly vaporized in the carbon steel piping, subjecting it to both rapidly increasing pressure and heavy thermal shock, causing the violent rupture. Once the liquid nitrogen entered the steel lines, the situation was uncontrollable.
1) During normal operation of a nitrogen wash system, a section of carbon steel piping suddenly ruptured due to extremely low temperatures caused by liquid nitrogen. The rupture caused fragments to launch in all directions but no injuries occurred.
2) Just before the rupture, the nitrogen wash system was experiencing unstable temperatures and gas compositions. Operators attempted to manually control instruments to break this cycle but temperatures continued dropping rapidly.
3) It is believed the rupture occurred when liquid nitrogen rapidly vaporized in the carbon steel piping, subjecting it to both rapidly increasing pressure and heavy thermal shock, causing the violent rupture. Once the liquid nitrogen entered the steel lines, the situation was uncontrollable.
sating photoelectric setting to reg- dienes in empty reactors before the ing.
If such a thing does happen, NO
ister minor extinction differences. coke oven gas plant itself (i.e., the obviously has to be removed, and I For the future, the possibility is exchanger system). They do that by think low temperature absorption may being studied of removing the NO permitting the feed gas to go through be practical. and, if possible, also the unsaturated an empty tower right after the com- In Europe most of the hydrocarbon hydrocarbons and N,O from the gas pressor. After a period of time the separation units use the front exchang- at low temperatures by means of an empty reactor is washed down with ers to remove water, in other words, adsorbent. Molecular sieves and acti- caustic, and these gums are removed. as driers in terms of sequence or vated carbon are being considered The percentage of NO encountered switch changes. We prefer to use driers for this purpose. in coke oven gas operation is extreme- ahead of them. While driers are cer- Behavior of NO resins ly low (0.1 is very high, while 0.05 tainly no cure-all insofar as absorption is more acceptable). Obviously you of contaminants, we feel that they It is possible to make a comparison can not afford to shut a plant down may absorb some of the dienes that of the behavior of NO resins in coke- every several months just to wash it cause trouble. This is no solution if oven gas splitters and in units for down. With respect to treatment of the NO goes beyond 0.01%. washing converted gas with N, since other hydrocarbon gases, engineers Acetylene is another problem that we have operating experience with want to know the quantities of NO, has been looked at for a good many both types. The conditions in the plant heavy hydrocarbons, and C,H,. In years. If the C,H, content is serious are shown in Table 2. most cases, the NO, very fortunately, enough, we always recommend that It is apparent from this table that is extremely low. As far as we are the feed gas be hydrogenated unless, the gas for the coke-oven gas splitters concerned, we can only afford to ig- of course, there is sufficient C,H, in contained more NO and much more nore NO if it's magnitude is about the feed gas. In that case, we normal- unsaturated hydrocarbons than the 0.01%. With concentrations beyond ly put in a special exchanger which converted gas. Nevertheless, there that, steps have to be taken to treat is nothing more than an C,H, reflw were no particular difEculties under NO and to remove it. NO can come condenser. We use C,H, to wash out these conditions in the coke-oven gas into a feed gas which has been pre- C,H, since the two form an azeo- units, whereas in the nitrogen wash pared by partial oxidation not neces- trope. However, you must have a unit, a spontaneous explosion occurred sarily through combustion, but through quantity of C,H,, in the order of 20- during normal operation. external means such as water wash- 25 times the C,H, content. Without going into details on the many differences between the two units, it can be stated that one differ- ence must be considered fundamental, namely that in the coke-oven gas splitters any NO resins formed will J. H. CONKLIN always be amply moistened by the DuPont Co. large excess of condensing hydrocar- bons. In view of the uncommonly low vapor pressure of the hydrocarbons in the unit for converted gas, the resins formed there will actually remain dry. We now think it probable that this Nitrogen wash incident difference is the cause of the greater unstability of the resins in our nitro- Process safety modifications include replacement gen-wash unit. For this reason we believe that for of carbon steel pipe subjected to low temperatures, gases with a low hydrocarbon content still more stringent requirements better instrumentation and control systems. should be made as regards NO content and accumulation than in the case of O N THE AFTERNOON OF MARCH 12, After the cold warm-ends had re- coke-oven gas units. # 1960, approximately 70 ft. of a sched- covered, feed gas was reintroduced ule 40 carbon steel line containing and shortly thereafter trouble began. LITERATURE CITED H, at a pressure of 325 lb. was sud- The first symptoms of trouble were 1. Wyier, Delwiche. Plant and Soil, V, NO.2. denly subjected to liquid N, ternpera- cycling temperatures and gas composi- tures causing the line to rupture with tions from the wash column. As had Questions and answers explosive violence. Despite the fact that fragments were thrown in all di- been done many times in the past, control instruments were placed in KERRY-American Air Liquide, N. Y., rections with sufficient force to embed manual in an effort to break this N. Y.: The problem of contaminants themselves into the lagging of adjacent vicious temperature and composition in N2 scrubbing units dates back over equipment, no one was injured and cycle that was obviously becoming thirty years. Although considered only little damage was done to nearby lines more extreme as time went on. Final- recently in this country, a great deal or equipment. ly, the temperature alarm in the of published information is available Just prior to the line rupture, the carbon steel piping sounded, which in Europe where intensive study has operation of the N, wash system had indicated that the temperature had been done on the reactions of NO or not been stable or satisfactory. In fallen to -20°C. NTO with dienes. The way they solve fact, only 4 hr. earlier it had been The operator pressed the toggle them in coke oven gases is to actually necessary to back feed gas out of the switch in the 60 point potentiometer induce the formation or the chemical boxes because of cold warm-ends on to read the temperature, and found it reaction of NO or NTO with the the heat exchangers. to be -120°C and falling rapidly. He
CHEMICAL ENGINEERING PROGRESS, (Vol. 57, No. 4)
' LOW TEMPERATURE ' box and entering the carbon steel lines. An instant before the line ruptured, a sudden pressure rise was noted in the carbon steel line. This pressure rise was caused by liquid N, vapori- zing rapidly in the relatively warm piping. Thus, the carbon steel was simultaneously subjected to a rapidly increasing pressure and a very heavy thermal shock. It is not at all sur- prising that the rupture was a violent one. It was the conclusion of all investi- gating parties that the operator took the proper action; but once liquid N, had entered the carbon steel lines, all control was out of his hands and there was nothing he could do to pre- vent the inexorable progression of events. Process modifications The plant was shut down for a number of weeks while the damage was cleaned up and extensive modi- fications made to the warm-end piping as well as the instrumentation associ- ated with the cold boxes. All of the carbon steel piping that Upper level operating platform after the line rupture at DuPont's nitrogen could be subjected to low tempera- wash unit. tures, that is, the purified H,, the recycle N,, and the waste gas lines immediately took emergency correc- umn was at a level greater than 100%. leaving the boxes were replaced with tive action by diverting the flow During the 2 to 2% hours in which type 304 stainless steel piping. The through another parallel heat exchang- feed gas was not in the boxes, the carbon steel lines leading to the er, but it was too late. The tempera- liquid N, reflux to the scrubbing col- compressors joined the stainless steel ture continued to fall and in 15 to umn was not reduced since the level lines 6 ft. downstream of a stainless 20 sec, had reached -140°C at which did not appear to rise abnormally. steel automatic block valve. A stain- time the line ruptured. The field Undoubtedly, the column was nearly less steel back-pressure control valve operators responded well to the erner- full- of liquid when feed gas was rein- was installed some distance upstream - of each block valve to maintain the gency and had the boxes valved off troduced. with purge N, flowing into the feed- The initial warm feed gas that desired pressure on the system and gas lines before the head count was entered the base of the column caused vent the excess gas to a stainless steel completed. heavy boiling and entrainment of stack. Each of the stainless steel auto- liquid in the overheads line. The first matic block valves was tied to the What happened and why? low temperature alarm that the opera- signal of the proper thermocouple in The rather exhaustive investigation tor observed was caused by the cold the warm ends of the final exchangers on the part of DuPont and Air Prod- gas preceding the liquid. By the in the boxes. ucts revealed that the trouble prob- time he had selected the proper tog- The instrumentation was so ar- ably started at the time the feed gas gle switch and read out the tempera- ranged that at -lO°C a panel alarm was first withdrawn from the boxes. ture, liquid was already leaving the would sound to indicate not only that At that time, the N, scrubbing column a low temperature was imminent at ( a sieve-plate column) dumped, and the exit of a heat exchanger, but also a 100%liquid level existed in the base in which exchanger the trouble ex- of the column. Shortly after the col- J. H. Conklin has isted. If the temperature continued umn had dumped, the level fell to been with the Ex- to fall, a low temperature trip set at 60%and the operator assumed that the plosives D e p a r t - -20°C would automaticallv dose the automatic level control valve had dis- ment of the DuPont proper block valve to prevent cold Co. since receiving gases from passing from the exterior posed of the excess liquid. a B.S. in Ch.E. However, what actually happened from Drexel Insti- stainless steel piping into the carbon when the level exceeded 100% was tute of Technology. steel piping leading to the compres- that liquid N, backed up into the He is presently sors. Of course, when this automatic Superintendent of block valve closed, the stainless steel upper impulse line to the level con- the anhvdrous am- troller. This impulse line was not back monia plant at the ~ e ~ a hWorks, o back-pressure control valve would bubbled with purge N2. The liquid Gibbstown, N.J., which is the Explo- then vent the cold gases up the proper in the impulse line gave the false level sives Department's largest installation. stainless steel stack to the atmosphere. signal that indicated a somewhat Other job assignments ranged from manufacture of explosives to work in A so called "panic" button also was normal level when actually the col- the Research Department. installed in the control room so that
CHEMICAL ENGINEERING PROGRESS, (Vol. 57, No. 4)
April 1961 17 the operator would not have to rely of the five warm ends leaving the fact, this automatic diversion system upon the automatic interlocks if he boxes were fed to a high.speed re- has literally saved our equipment a saw the temperatures getting out of corder which monitored and printed number of times. The ability to take hand. out each temperature every 5 sec. low temperatures exterior of the boxes In an effort to obtain earlier know- The liquid level impulse lines on and still keep iunning has enabled us ledge of impending temperature up- the scrub column and the liquid N, to uncover a number of shortcomings sets on the warm ends, alarms were phase separator, as well as the column and make the proper modifications to installed on the thermocouples in the pressure tap, were back bubbled with the cold equipment. lines leading to the final heat ex- purge N,. As an additional means of I seriously doubt that by now, even changers within the cold boxes. Also, detecting column flooding, a properly at the expense of more ruptured lines, all of the points on the 60-point back-bubbled recording differential we would be operating the cold boxes potentiometer were duplicated with pressure instrument was installed safely and in a controlled manner if new recording thermocouples. Thus, across the wash column. we did not have this ability to work the operator would have before him through the temperature upsets, de- a visual record of all critical AT Modifications satisfactory velop new operating techniques to pull values within the cold equipment. All of these modifications have ourselves out of the difficulty, and Likewise, the five new thermocouples proved very satisfactory during sub- then keep going regardless of exterior that were installed on the manifolds sequent operation. As a matter of cold lines. #
uestions and answers
WALTON-Rohm & Haas Co., Pasa- your procedure for bringing these ex- which has a poor thermal conductiv- dena, Texas: After the dump valve changers back in service after a nor- ity. We figure we can get quite a AT to the flare opens, what means do you mal defrost. across the thickness of the material use to stop the compressor? Is a com- SVOBODA, Dow Chemical Co., Plaq- and then contractual forces occurring pressor shutdown device tied in with uemine, La.: Did you purge your dif- in the length of the line. Several com- this system, or does the compressor ferential pressure or delta p indicator panies mentioned they have dumped kick off on low suction pressure? on the N, scrubbing tower with N, liquid N, into a brass line and into a CONKLIN: No, actually our compres- also? stainless steel tank. How often have sors then go on automatic recycle ANONYMOUS: Yes, we did. I, for they done this and what was their from, for instance, a 4th stage back one, am in Mr. Conklin's category of experience with thermal fatigue in to 3rd, 2nd back to 1st. Should these those who have experienced ruptures such a line? recycle valves be slow, or any other of carbon steel lines at low tempera- KRYZER-Standard Oil (Ind.), Whit- thing happen, we do have low pres- tures on both the air separation plants ing, Ind.: The line that we use is gen- sure suction trips on the machines. and the N, wash box. We have had erally cooled all the time. Because it ANDRIES-Spencer Chemical Co., numerous occasions where the defrost- also carries the continuous purge from Vicksburg, Miss.: I was wondering if ing lines or safety valve lines cracked, our auxiliary vaporizer, we do not you have ever had any trouble with usually at welds, when they got ex- shock it with a large dump. It's chilled channeling in your exchanger which tremely cold because of process upsets. continuously. would result in the same condition? LAWRENCE, U. S. Industrial Chem- WALTON-SunOlin Chem. Co., Clay- CONKLIN: No, we have had no indi- ical Co., Tuscola, Ill.: I wonder what mont, Del.: We have two blow-down cation that we have had channeling in your basis was for the statement that systems, one is a schedule 10 alumi- any of our heat exchangers. 6 degrees below was dangerous. It num 2-inch line which runs about a ANONYMOUS: What type of level actually is, of course, about 14 de- thousand feet to the aluminum vapor- indicating instrument or level sensing grees warmer than the code for car- izer. We have used this many times, instrument was on this tower? bon steel, and most low pressure am- dropping liquid N, out there and rich CONKLIN: The one that was on it monia systems operate lower than that. liquid bottoms from the air plant. was a DP cell. ELLIS-Du Pont: Du Pont has never There have been no failures in this HEPP-Sun Oil Co., Marcus Hook, agreed with this minus 20' because of line. It does contain expansion loops. Pa.: We cracked one low pressure line some experiences that we've had on We also have a blow-down system for and although the crack was minor the carbon steel equipment. We generally the hydrogen wash box made of a manner in which we cracked it might divide the materials into carbon steel stainless steel type 304. It goes to a be of some help for everyone. We be- down to 32°F. When we go from tank (about 2%-ft. in diameter by lieve this was cracked when the opera- 32°F to O°F, we consider all the car- about 4-ft, high) made of stainless tor was putting the unit back on bon steels with respect to their use steel, and is vented to a stainless steel stream, after regenerating the ex- and the consequence of their use in stack. We have dumped cold liquid in changer. Our procedure is as follows. this temperature range. Below 0°F we here many times. The coldest material To put an exchanger back on, you put go into specified materials with im- has been the bottoms of the nitrogen a crack of cold product gas through pact tests, special heat treatment, wash tower which is about -310°F. without any exchange until it cools special fabrication considerations with We have had no sign of failure in this down to a point where a thermal the equipment. system for over seven years. bump is avoided in the process when ANONYMOUS: You mentioned that LAWRENCE-U. S. I.: On your specs vou put it in service. The operator in you dumped the liquid N, into the on carbon steel, do you also disagree this case cracked this valve and, we stainless steel line several times. We with the code on shapely tested steel believe, allowed it to go too long. Of have always had a great concern for going down to minus 30 or minus 50 course, in time, the outlet line will go the thermal fatigue that might occur if it's A-300 or special type steels? on down to the inlet temperature. because of the rapid application of ELLIS-Du Pont: We do carry the Thus, you might wish to review the cold gases to the stainless steel A-300 material down to minus 50.
Room Temperature Synthesis of Copper Oxide Nanoparticles Morphological Evaluation and Their Catalytic Applications For Degradation of Dyes and C-N Bond Formation Reaction PDF