US3835930A

US3835930A - Storage and transport system

Info

Publication number: US3835930A
Application number: US00365136A
Authority: US
Inventors: E Denigan; D Ballard
Original assignee: Oxirane Corp
Current assignee: Lyondell Chemical Technology LP; Oxirane Corp
Priority date: 1973-05-30
Filing date: 1973-05-30
Publication date: 1974-09-17
Anticipated expiration: 1991-09-17
Also published as: BE807688A

Abstract

System for reducing hazards in storing and transporting hazardous material. Container for material includes a chamber containing a phlegmatizer for the material. Chamber has a seal melting, rupturing or releasing at a temperature substantially below the self-accelerating decomposition temperature of the hazardous material, to release the phlegmatizer into the material.

Description

United States Patent [191 Denigan, Jr. et al.

1 Sept. 17, 1974 STORAGE AND TRANSPORT SYSTEM [75] Inventors: Edward P. Denigan, Jr., Hopewell;

Donnell A. Ballard, Princeton, both of NJ.

[73] Assignee: Oxirane Corporation, Princeton,

[22] Filed: May 30, 1973 [21] Appl. No.: 365,136

[52] US. Cl 169/66, 169/57, 169/26,

220/88 R [51] Int. Cl A62c 35/54 [58] Field of Search 169/2 A, 4, 2 R, 26, 57,

[56] References Cited UNITED STATES PATENTS Bugg 169/2 A 3,614,987 10/1971 Bonne et al 169/2 A 3,698,597 10/1972 Burke 3,738,428 6/1973 lngro 169/2 A Primary ExaminerRobert S. Ward, Jr. Assistant ExaminerMichael Mar Attorney, Agent, or FirmFlynn & Frishauf [5 7 ABSTRACT System for reducing hazards in storing and transporting hazardous material. Container for material includes a chamber containing a phlegmatizer for the material. Chamber has a seal melting, rupturing or releasing at a temperature substantially below the selfaccelerating decomposition temperature of the hazardous material, to release the phlegmatizer into the material.

18 Claims, 4 Drawing Figures STORAGE AND TRANSPORT SYSTEM FIELD OF INVENTION This invention has to do with the storage and transporting of hazardous materials, and to reducing hazards associated therewith. More specifically, it has to do with reducing such hazards in the storage and transportation of peroxides, particularly tertiary butyl hydroperoxide (TBHP).

BACKGROUND OF INVENTION In view of the nature of a variety of industrial accidents that have occurred in storage depots and in facilities used to transport diverse materials, regulations have been enacted to avoid or lessen the number of such accidents. Governmental agencies have placed strictures on the type and character of storage tanks, tank cars, tank trucks and the like. This is the case with a liquid organic peroxide solution such as aqueous TBHP which, until recently, has been given proper clearances only for relatively small quantity containers for solutions of up to 70 percent (weight), and for bulk solutions of only up to 65 percent (weight). Obviously, it is an economic disadvantage to accommodate a relatively large amount of water in storing or transporting the solutions. Therefore, as more concentrated solutions can be controlled, storage and transportation expenses are reduced. To date, however this economic problem remains because of overriding safety requisites.

SUMMARY OF THE INVENTION In accordance with this invention, there is provided a system for storing a hazardous material contained in a container. The container has associated therewith a chamber containing a phlegmatizer for the hazardous material, the chamber having a discharge means in communication with the hazardous material and adapted to discharge the phlegmatizer into the hazardous material in the container. The discharge means includes a seal which melts, ruptures or releases at a temperature substantially below the self-accelerating decomposition temperature of the hazardous material, whereby the phlegmatizer is released from the chamber into the container.

As used herein, the term phlegmatizer denotes a material capable of desensitizing or reducing the decomposition susceptibilities of a hazardous material.

Thus, a phlegmatizer slows or makes stolid the hazardous material.

DRAWINGS FIG. 1 is a sectional side view of a tank having a plurality of drums therein.

FIG. 2 is a sectional side view of a tank having chambers secured to the ends thereof.

FIG. 3 is a sectional side view of a compartmented tank.

FIG. 4 is a sectional side view of a tank having an inner compartment to contain a hazardous material and an outer and adjacent compartment adapted to hold a phlegmatizer.

SPECIFIC EMBODIMENTS OF INVENTION As illustrated in FIG. 1, tank includes charging and discharging means 11 and 12, respectively, and has drums 13 disposed therein. Durms 13 are preferably polyethylene containers of about 0.040 inch wall thickness. Drums 13 are fitted with metal seals 14, which can be in the form of discs or other suitable form. Tank 10 contains an aqueous solution of percent (weight) TBHP, and drums 13 contain water. Drums 13 can be filled with water and a seal or seals 14 secured, before the drums are placed within tank 10. Drums 13 can be allowed to rest at the bottom of tank 10, due to a greater density than the TBHP solution, or can be secured by chains, cables, etc. (not shown).

Seals 14 are eutectic or non-eutectic alloys having a yield temperature or melting range substantially below the temperature at which an aqueous solution of TBHP decomposes rapidly. A particularly preferred eutectic alloy for seals 14 is Cerrobend which has a yield temperature of 70C. (158F.) and comprises the following metals (in weight percent):

Bi 50 Pb 26.7 Sn 13.3 Cd 10 Bi Pb Sn Cd Cerrobend and Cerrosafe are marketed by the Cerro Sales Corporation.

Other typical eutectic alloys and non-eutectic alloys suitable for use in the systems of this invention with a variety of hazardous materials, are shown at page 437 of The Condensed Chemical Dictionary; A.E. Rose; Reinhold Publishing Company, New York; 1966. It will be understood that an alloy selected will have a yield temperature or melting range substantially below the self-accelerating decomposition of a given hazardous material.

Thus, when the temperature of the system reaches the yield temperature or the melting range of metal seals 14, the seals no longer keep water within drums 13. The water is discharged into the TBHP solution and is sufficient to dilute the 70 percent TBHP solution to 65 percent in an emergency. A typical tank 10 would contain 40,000 pounds of a 70 percent aqueous TBHP solution and 3200 pounds of water in seven 55 gallon drums 13.

As indicated above, Cerrobend seals yield at 70C. (158F.) which is well below the temperature, 90.6C. (IF.), at which the 70 percent TBHP boils. Similarly, the Cerrosafe seals start to melt at 70C. (158F.) and have a melting range of 7090C. peroxide l58-l94F.).

FIG. 2 shows tank 10 with charging and discharging means 11 and 12, respectively. However, instead of drums l3, chambers 15 are secured to ends or side walls of the tank. Seals 16 are of the same character as seals 14 of FIG. 1, and are located in the common walls of tank 10 and chambers 15. Tank 10 contains a 70 percent TBHP solution and chambers 15 contain water. Chambers 15 have suitable inlet and outlet means water therefrom.

;-1n r1o. s-, mnk l is'shown-in modified form,;1with chargingand dischargingmeans 11 and 12, respectively andwith end compartments l7 separated from the main body. of tank 10 by walls 18. Seals 19 (similar I to seals 14 and l6,above are located in walls 18. The 70 percent TBHP solution is contained in the main fcompartmentof tank 10,- and water is contained in compartments 17. lt'willbe understood that tank 10 can include a plurality of compartments rather than one compartment. Compartments 17 have' suitable charging and discharging means (not shown) similar to i In FIG. 4, tank is shown with charging means 11 and 12, respectively, and with outer water compartment 20. Wall 21 separates the'main body of tank 10' from compartment and has seals 22 located therein. Here again, the 70 percent TBHP solution is contained in the main tank body and water is in compartment 20. Seals 22 are similar to seals l4, l6 and 19 above. Compartment 20 has charging and discharging means (not shown) similar to 11 and 12.

L (not shown) forgchar ging water thereto and'removing- Analysis of -the -70 percent aqueous TBHP solution after contact withaCerrosafe seal at 21C. (70F.) for various periodsofrtime is given in TABLE 1 below in weight percent.

7 TABLE 1" COMPONENT l r'o'Av 'j ,7 AYS ,14 DAYS TBHP 1" 69.85 Iii-68.66 69.10 METHANOL I 0.014-

0.020- 0.0!8 ACETONE g 0.14, 0.13; 0.12 'TERTIARY j 040 0,42 0.4 "BUTANOL UNKNOWN Fire tests were conducted on a 70 percentaqueous TBHPsolut'ion. Testing has shown that when containremains) avery rapid alm ost explo sive. decomposi-f tion'occurs. Sixty-five percent TBHR in water does not in connection with FIGS. 1-4 wherein tank 10 is part i ofa tank truck, discharge means 12 can be located conveniently at a lower portion of tank 10.

The effect ofa 70 percent aqueous TBHP solution o Cerrosafe seals is illustrated by the following.

tainingvessels which contain sufficieht'water to" dilute One- Cerrosafe disc, 2 inches in diameter by 01125 a inch thick and weighing 54.5710 grams, was placed-in 5 gallons of 70 percent TBHP contained in a 5 gallon polyethylene pail which was tightly covered The ssytem was allowed tostand at ambient temperatures for 1 week.

At the end of this period, the disc has turned black in several places and had lost 0.0630, grams in weight. There was no discoloration' or any other signs of decomposition of the peroxide.

The five gallon quantity was then transferred to a 5 gallon steel pail. The disc was placedin the liquid and the pail covered with a steel cover withfour 0.25 inch I holes in it. This container was placed on cinder blocks on the testing grounds and a wood-kerosene.firebuilt.

Five minutes after the fire was started the peroxide 4 was noted burning through the holes in the cover and a short time later from under the edges of the cover.

beneath it. I

The rate of burning was moderate such as would be observed with a flammable solvent such as toluene, benzene or ethyl ether.

Burning at this rate continued for'one' hour. The rate a of burning then increased and, after a total elapsed' 'ers of 70 percent TBHP aqueous) are exposed to. open fires thatthe chemical product burns away quietly during most ofthe test. Avery short time before'allofthe l peroxideis consumed(less than5 percent of material show this rapid decomposition-at any time "during fire exposure. A 70 percent aqueous TBHPQsolution conthe 70 percent solution to about-'65 percent-gage, doesnot exhibit this rapid-decomposition. a v

The water vessels used in the fire tests;

ing at the top'of'thepaill Theburning-continued for 1 hour and 40 minutes" at whichtime both the peroxide and the wood fire were out Examination of the' pail showed that .it was still about one-third full of liquid. A larger fire was then built under itgTen minutes later the i-peroxidejyf irfeincreased considerably in volume and time from start of fire of one hour'and'9 minutes, thenflame was very large and rate of burning greatly accelerated. There was then a mild report, the top of the pail was bent very appreciably and blown off and the pailwas blown off the cinder blocks. The fire ceased'immediately Examination of the pail showed that neither the" bottom nor the sidewalk were distorted No'tr'ace of the metal of the disc could be found in the pail or on the ground around the fire.

This sequence of events is typical of this product under these conditions. It is considered that the presence of the fusible metal alloy did not increase or decrease the rate of burning and/or decomposition of the peroxide to any degree which could be detected by visible observation.

then went out. At no time was there any sign of sudden or violenfdecomposition.

. Th e'same set-uip was used in a second test except that the bottleswere h'eld inan inverted, verticalposition in the peroxide ina stainless steel-frame. The tops ofthe bottles (which were, of course, nearest thejbottom of the pail) were 4 inches-from the bottom of the 5 gallon drum- The wood-kerosene fire was larger than that in the first test and the peroxide was noted burning at the top {ofthe vessel 4 minutes after start of fire. Thirteen minutes after the fire was started the liwuid boiled over and increased the intensity of'the fire, but did not dislodge fl""* the cover. Forty-three minutes after start o'f-' 'fi're the flame from the burning perioxide enlarged greatly,

reaching a maximum heightof l0 -"l2 feet, b irned'this I way for about 30 seconds and then went out. Once again there was 'nosudden or violent decomposition. A These tests demonstrate that aisystem such as that described above ca'nbe used to reduce the hazard'of a e b r ounce polyethylene bottles with screw capsITwo-inch diameter holes were-cut in" the bottoms of the b'0ttl5- v and 1.25 inch holes in'th'e tops. These'were'fill'ed with- 70 percent TBHP to that of one containing 65 percent by weight when it is exposed to fire conditions.

Although the invention has been illustrated above by discussion of aqueous TBHP solutions, it is to be understood that the invention is useful also for storage and transport of solutions of other peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthene hydroperoxide and tertiary butyl isopropyl hydroperoxide.

Other phlegmatizers which can be used include glycols (e.g. dipropylene glycol), phthalates (e.g. diisopropyl phthalate), mineral oil and mineral spirits. It will be understood that the phlegmatizer selected is one which is substantially compatible with a particular peroxide or peroxides.

Included by the term seal," in addition to the alloys mentioned above, are membranes formed of plastics. Suitable plastics include polyvinyl chloride, polyvinyl chloride-polyvinylidene chloride and polyethylene glycols.

Numerous modifications and variations of the invention may be made without departing from the spirit and scope thereof. Accordingly, it is to be understood that the invention is not to be limited, but is to be construed in the light of the language of the appended claims.

We claim:

1. System for reducing hazards in storing and transporting a hazardous material contained in a container, comprising:

a chamber having therein a phlegmatizer for said hazardous material and having discharge means in communication with said hazardous material and said phlegmatizer, separating said hazardous material and said phlegmatizer, and adapted to discharge said phlegmatizer into said hazardous material in said container, said discharge means including a metallic seal inthermal communication with at least said hazardous material and which seal melts, ruptures or releases at a temperature substantially below the self-accelerating decomposition temperature of said hazardous material, whereby said phlegmatizer is released from said chamber into the container.

2. System adapted for storage or transportation of a hazardous material comprising:

a. a container having charging and discharging means,

b. a hazardous material contained in said container,

c. a chamber having charging and discharging means,

the latter discharging means being in communication with said container, separating said hazardous material and a phlegmatizer for said hazardous material, and adapted to discharge contents thereof into said container, and including therein a metallic seal in thermal communication with at least said hazardous material and which seal melts, ruptures or releases at a temperature substantially below the self-accelerating decomposition temperature of said hazardous material, said chamber containing said phlegmatizer which is released from said chamber into said container as said seal is melted, ruptured or released.

3. System adapted for storage or transportation of an aqueous solution of tertiary butyl hydroperoxide 6 (TBHP) comprising:

a. a container having charging and discharging means, b. an aqueous solution of TBHP having a concentration of from about 65 to about percent by weight of TBHP, contained in said first container,

c. a chamber having charging and discharging means,

the latter discharging means being in communication with and adapted to discharge contents thereof into said container and including therein a metallic seal which melts at a temperature substantially below the temperature at which said aqueous solution of TBHP boils, said chamber containing water in an amount sufficient to reduce said concentration of said TBHP substantially when said seal is melted and said water is released from said chamber into said container.

4. System of claim 3, wherein said aqueous solution ofTBHP in (b) has a concentration of about 70 percent by weight, and wherein the amount of water in (c) in said chamber is sufficient to reduce said concentration to 65 percent by weight or less.

5. System of claim 3, wherein said metallic seal in (c) is an eutectic alloy.

6. System of claim 3, wherein said metallic seal in (c) is an eutectic alloy melting at about 70C. and having the following approximate concentration, by weight Bi 50 Pb 26.7 Sn 13.3 Cd l0 7. System of claim 3, wherein said container of (a) is a steel tank and said chamber is a polyethylene drum.

8. System of claim 3, including a plurality of said chambers.

9. System of claim 3, wherein said chamber is immersed in said aqueous solution of TBHP in (b).

10. System of claim 3, wherein said chamber is affixed to said container.

11. System of claim 3, wherein said chamber is a partitioned section of said container.

12. System of claim 11, wherein said discharge means is in the partition.

13. System of claim 3, wherein said chamber surrounds said container.

14. System of claim 13, wherein said discharge means is in a wall between said chamber and said container.

17. System of claim 2, wherein said seal is also in thermal communication with said phlegmatizer.

18. System of claim 2, including a wall between said chamber and said container, said discharge means being in said wall between said chamber and container. l

Claims

1. System for reducing hazards in storing and transporting a hazardous material contained in a container, comprising: a chamber having therein a phlegmatizer for said hazardous material and having discharge means in communication with said hazardous material and said phlegmatizer, separating said hazardous material and said phlegmatizer, and adapted to discharge said phlegmatizer into said hazardous material in said container, said discharge means including a metallic seal in thermal communication with at least said hazardous material and which seal melts, ruptures or releases at a temperature substantially below the self-accelerating decomposition temperature of said hazardous material, whereby said phlegmatizer is released from said chamber into the container.

2. System adapted for storage or transportation of a hazardous material comPrising: a. a container having charging and discharging means, b. a hazardous material contained in said container, c. a chamber having charging and discharging means, the latter discharging means being in communication with said container, separating said hazardous material and a phlegmatizer for said hazardous material, and adapted to discharge contents thereof into said container, and including therein a metallic seal in thermal communication with at least said hazardous material and which seal melts, ruptures or releases at a temperature substantially below the self-accelerating decomposition temperature of said hazardous material, said chamber containing said phlegmatizer which is released from said chamber into said container as said seal is melted, ruptured or released.

3. System adapted for storage or transportation of an aqueous solution of tertiary butyl hydroperoxide (TBHP) comprising: a. a container having charging and discharging means, b. an aqueous solution of TBHP having a concentration of from about 65 to about 70 percent by weight of TBHP, contained in said first container, c. a chamber having charging and discharging means, the latter discharging means being in communication with and adapted to discharge contents thereof into said container and including therein a metallic seal which melts at a temperature substantially below the temperature at which said aqueous solution of TBHP boils, said chamber containing water in an amount sufficient to reduce said concentration of said TBHP substantially when said seal is melted and said water is released from said chamber into said container.

4. System of claim 3, wherein said aqueous solution of TBHP in (b) has a concentration of about 70 percent by weight, and wherein the amount of water in (c) in said chamber is sufficient to reduce said concentration to 65 percent by weight or less.

5. System of claim 3, wherein said metallic seal in (c) is an eutectic alloy.

6. System of claim 3, wherein said metallic seal in (c) is an eutectic alloy melting at about 70*C. and having the following approximate concentration, by weight

7. System of claim 3, wherein said container of (a) is a steel tank and said chamber is a polyethylene drum.

8. System of claim 3, including a plurality of said chambers.

10. System of claim 3, wherein said chamber is affixed to said container.

12. System of claim 11, wherein said discharge means is in the partition.

13. System of claim 3, wherein said chamber surrounds said container.

15. System of claim 1, wherein said seal is also in thermal communication with said phlegmatizer.

16. System of claim 1, including a wall between said chamber and said container, said discharge means being in said wall between said chamber and container.

18. System of claim 2, including a wall between said chamber and said container, said discharge means being in said wall between said chamber and container.