DANGEROUS GOODS CLASSIFICATION TESTING ON OOT STIM PRODUCT FAMILY.

Transcription

1 DANGEROUS GOODS CLASSIFICATION TESTING ON OOT STIM PRODUCT FAMILY. R.A. Bowes CANADIAN EXPLOSIVES RESEARCH LABORATORY, DIVISION REPORT EXP (CF) January, Work performed for: Owen Oil tools, Inc. c/o Owen Compliance Services, Inc. P.O. Box Fort Worth, TX Phone (817) , fax (817) Page 1 of 14

2 EXECUTIVE SUMMARY OCS contends that STIM charges are not Class 1 in the form proposed for transport. Tests, including those prescribed by the United Nations were performed to determine the hazardous properties of the charges. The results of the tests were consistent with exclusion from Class 1 or classification as Division 1.4, Compatibility Group S depending on the interpretation of the UN definitions. Depending on the interpretation, the family of products defined by OOT- APRV-037 is recommended for exclusion (Division Potassium perchlorate, mixture, UN 1489, packing group II proposed by OCS) or authorization and classification as Division 1.4, Compatibility Group S. NOTE The results in this report relate only to the samples supplied. This report shall not be reproduced except in full, without the written approval of Owen Oil Tools Inc., or Owen Compliance Services, Inc. and the Manager of the Canadian Explosives Research Laboratory. Reproduction by Owen Oil Tools, Inc. and/or Owen Compliance Services, Inc. in the pursuit of its business related to the products described herein is expressly authorized without further written authorization. The samples were received from OOT on Tests were carried out between and Page 2 of 14

3 CONTENTS INTRODUCTION...4 SAMPLE DESCRIPTION...5 TESTS APPLIED TO THE PRODUCTS...6 TESTS AND RESULTS...6 UN Gap Test - UN 1(a) / 2(a)...6 Koenen Test - UN 1(b) / 2(b)...7 Time/pressure Test - UN 1(c)(i) / 2(c)(i)...8 Thermal Stability Test at 75LC - UN 3(c)...9 Twelve Metre Drop Test - UN 4(b)(ii)...9 Single Package Test - UN 6(a)...9 Stack Test - UN 6(b)...10 External Fire Test - UN 6(c)...10 Unconfined package test - non-un test...11 CONCLUSION...13 REFERENCES...14 Page 3 of 14

4 INTRODUCTION Owen Compliance Services, Inc. (OCS) prepared and submitted an application [1] on behalf of Owen Oil Tools, Inc. (OOT) to the Explosives Regulatory Division (ERD) for the purposes of having a family of oil well stimulation products classified and added to the List of Authorized Explosives. Explosives Regulatory Division reviewed the application and referred it to the Canadian Explosives Research Laboratory (CERL) for testing. CERL prepared a test plan and OOT accordingly prepared and sent samples to CERL. OCS contends that the product is not Class 1 as presented for transport. The pressure and confinement present in an oil well are required for the product to react and function as desinged. The test plan therefore included, not only tests to determine suitability for transport (Series 4 tests) and tests to determine the type of hazard presented in transport (Series 6 tests), but also tests to determine the Class 1 status of the products (Series 1 and 2 tests). The only energetic ingredient of all the products in the family was a propellant - a cast mixture of potassium perchlorate and epoxy resin. The family has three configurations:- - StimGun Sleeve (SGS) - a hollow cylinder of the composition; - StimTube Tool (STS) - a steel tube with the composition cast on the outside: and - Well Stimulation Tool (WST) - A cylindrical casing of the composition with steel stubs at each end. The products are described in detail in the application [1]. The family is offered in five packaging configurations [1]. The configurations include fibre board boxes and fibreboard drums. At the time of examination, the family consisted of 76 products. The most dangerous configuration was not apparent from the supplied data, it was therefore decided to conduct the article tests on a combination of the three configurations. The following articles were selected as being representative of the family:- SGS-T337-27A STS-2000-T06A WST-2000-L06A Page 4 of 14

5 SAMPLE DESCRIPTION Specially formed samples were provided for the Series 1 and 2 tests. The samples were defined to represent those proposed for transport. The substance for the Gap Test was in the form of cylinders designed to match the internal diameter of the test setup. Similarly the substance for the Koenen Test was formed in cylinders to match the internal dimensions of the steel test tube. This was considered to be in accordance with the normally substances are tested as received requirement in the test prescription. Substance for the Time/pressure Test was provided in small lumps or granules less than 5 mm in size. These lumps were considered to be the largest size that would fit into the apparatus. Twenty four packaged articles (one article per package) were received. The articles included sample from the three types of charge proposed for transport. See Table 1. Table 1 - Dimensions and masses of articles received and properties of their packagings. Article Diameter. / inch Length. / inch Net charge mass / kg (pound) Packaging designation. Packaging description. SGS-T337-27A (6) BOX GR1 STS-2000-T06A (21) BOX G fibreboard drum, 45 inch by 6 inch dia., m3. 1G fibreboard drum, 88 inch by 5 inch dia., m3. WST-2000-L06A (8) BOX G fibreboard drum, 88 inch by 5 inch dia., m3. Page 5 of 14

6 TESTS APPLIED TO THE PRODUCTS CERL conducted the following tests on the substance:- UN Gap Test - UN 1(a) /2 (a); Koenen Test - UN 1(b) / 2(b); Time/pressure Test - UN 1(c)(i) / 2(c)(i); and Thermal Stability - UN 3(c). And the following tests on the packaged articles:- Twelve Metre Drop Test - UN 4(b)(ii); Single Package Test - UN 6(a); External Fire Test - UN 6(c); and an Unconfined Package Test. All of the above were UN prescribed tests [2, 3] apart from the Unconfined Package Test. The Unconfined Package Test was performed to further assess the hazardous properties of the products. UN Gap Test - UN 1(a) / 2(a): Test description: TESTS AND RESULTS The test was conducted on the cast propellant formed into cylinders, in accordance with the UN Manual prescription. The results are given in Table 2. Page 6 of 14

7 Table 2 - UN Gap Test Results. Trial number PMMA spacer length /mm Effect on steel tube. Effect on witness plate. 1 0 The steel tube was not fragmented. 2 0 The steel tube was not fragmented. The witness plate was not perforated or fragmented. The witness plate was not perforated or fragmented. The result was - by the Series 1 criteria. Koenen Test - UN 1(b) / 2(b): Test description: The test was conducted in accordance with the Manual. It was conducted on cylinders formed from the propellant and on the granular propellant. The results are given in Table 3. Table 3 - Koenen Test Results. Trial number Orifice size /mm Sample form. Sample mass. Time to explosion. / s Fragmentation Cylinder Type C - bottom of tube split. 2 1 Cylinder Type C - bottom of tube split. 3 1 Cylinder Type C - bottom of tube split. 4 1 Cylinder Type C - bottom of tube split. Page 7 of 14

8 Types A to E are no explosion by the test criteria. It appears that the sample ignited in the tube pressurizing the tube until it ruptured, releasing the pressure resulting in the quenching of the ignition. The result of the test on the cylinder shaped sample was - by the UN criteria. Time/pressure Test - UN 1(c)(i) / 2(c)(i): Test description: The test was performed in accordance with the Manual on granulated composition. It was not practical to perform the test on the product in the form in which it is transported. Three trials were conducted. The results are given in Table 4. Table 4 - Time/pressure Test Results. Trial number Maximum pressure reached /kpa Time for pressure to rise from 690 kpa to 2070 kpa. /ms Result rise time <30 ms rise time <30 ms rise time <30 ms The result on the granular propellant was + by the Series 2 criteria (rise time <30 ms). It should noted that the burning properties of the propellant in granular form would be expected to be different from the solid form (in which it is intended to be transported). Page 8 of 14

9 Thermal Stability Test at 75LC - UN 3(c): Test description: The test was performed on 50 g of the propellant and then on 100 g of the propellant in accordance with the instrumented UN method. The substance was exposed to 75L for 48 h. This test was done as the practical alternative to the UN 4(a) test. There was no explosion or ignition in any of the trials. There was no evidence of self heating as shown by an increase of temperature of the sample. Mass losses were 0.8% and 0.5% mass basis. The result of the test was "-" (negative) by the UN criteria (suitable for transport). Twelve Metre Drop Test - UN 4(b)(ii): Test Description: Three trials were conducted using one configuration for each trial. In each trial the packaged article was dropped through 12 m onto a 75 mm thick steel plate backed by concrete. There was no ignition or explosion in any of the three trials. Assessment: The result was - (negative) by the UN criteria (suitable for transport). Single Package Test - UN 6(a): Test description: Three trials were conducted. One trial was applied to the SGS-T337-27A, one to the STS T06A and one to the WST-2000-L06A These articles are not fitted with a means of initiation during transport. From previous tests, it was known that they would not respond to a detonator. For these tests, the articles were therefore fitted with 30 g black powder igniters placed against the surface of the propellant Page 9 of 14

10 and re-packaged as for transport. The packages were placed on 3 mm thick steel witness plates and confined with sand to a thickness of 0.5 m in all directions. In all three trials the black powder ignited, the propellant did not ignite, but the closure of the package blew out as a result of the reaction of the black powder ignition charge. There was no observable explosion, no scattering of the confinement, no effect on the witness plate and no formation of a crater. The result of the test was no mass explosion by the UN criteria. Stack Test - UN 6(b): The Stack Test was waived basis of the results of the Single Package Test. External Fire Test - UN 6(c): The test was performed on nine packages, clustered together, the total volume being m 3, (47.4 kg of propellant). This exceeded the UN requirement both in number and volume. The nine packages consisted of three SGS-T337-27A, three STS-2000-T06A and three WST-2000-L06A. The product was placed on a grid 1 m above the ground. Wood doused with kerosene was place under the grid and to a distance of 1 m outward from the packages. Witness panels (2000 mm by 2000 mm by 2 mm Al) were placed at 4 m from the packages in three quadrants around the grid. The wood was ignited remotely. The product began to burn at 2 min 30 s after the fire was ignited. Its burning was evident by white smoke. The white smoke stopped at 9 min 30 s and the fire continued to burn for another 30 min consuming the packages and their contents. There was one small fiery projection to 2-3 m. There were no other pyrotechnic or explosive effects beyond the flames of the fire. Observation relative to the test criteria are as follows:- - there was no mass explosion; - there were no perforations or dents in the witness panels; - there were no projectiles (metallic, fiery or otherwise, other than one described above); - there were no fireballs or jets of flame; and - the effects at 5 m were limited to smoke and heat as would be produced by the bonfire Page 10 of 14

11 without the packages. The heat flux was not measured. Approximately 50 kg of the propellant burned over 420 s. The UN criterion for 1.4S is >266 s for 50 kg, or >261 s protracted for 47.4 kg. Assessment: The results of the test are consistent with Division 1.4 Compatibility Group S or a not Class 1 determination. Unconfined package test - non-un test: Test description: Trials were conducted with detonator/detonating cord initiators or by applying igniters (30 g thermite) to the surface of the propellant. The articles were repackaged as for transport. The packages were placed on 3 mm thick witness plates inside an explosion containment tank and the igniters were fired remotely. The results are presented in Table 5. Page 11 of 14

12 Table 5 - Results of Unconfined Package Tests. Article. Initiator. Effect. STS-2000-T06A Detonator plus full length of 80 gr RDX detonating cord down centre. Steel core split, propellant and packaging scattered. SGS-T337-27A (article previously exposed to 12 m drop test). SGS-T337-27A (article previously exposed to Single Package Test.). STS-2000-T06A (article previously exposed to 12 m drop test). STS-2000-T06A (article previously exposed to Single Package Test.). WST-2000-L06A previously exposed to 12 m drop test). WST-2000-L06A previously exposed to Single Package Test.). 30 g thermite The article ignited and burned over 5 min with audible venting from the package. The fibreboard packaging was scorched but remained largely intact. 30 g thermite The article ignited and burned over 5 min with audible venting from the package. The fibreboard packaging was scorched but remained largely intact. 30 g thermite The article ignited and burned furtively over 15 min self extinguishing leaving 33% of the propellant unburned. About 50% of the packaging burned. 30 g thermite The article ignited and burned quietly leaving the packaging scorched but largely intact. 30 g thermite The article ignited but failed to support burning beyond the area that was in contact with the igniter. 30 g thermite The article ignited and burned slowly leaving the packaging scorched but largely intact. Assessment: The results of the test are consistent with Division 1.4 Compatibility Group S or a not Class 1 determination. Page 12 of 14

13 CONCLUSION The results of the UN Gap Test indicate the STIM propellant is not sensitive to the shock stimulus defined by the test. The propellant ignited in the Koenen test and the rate of combustion resulted in the rupture of the tube, but reaction was not defined as an explosion by the test criteria. The solid propellant would therefore be considered as being insensitive with respect to the UN criteria by these two tests. The Time-pressure Test does not prescribe how rigid solids should be prepared for the test. In order to perform the test, it was performed on the granulated propellant which may not truly represent the solid as presented for transport. The test showed that the granulated propellant burned rapidly in the pressurized environment of the test. The increased surface area of the granular form would account for the vigorous combustion in the test. The Thermal Stability Test and the Twelve Drop Test results indicate that the products are suitable for transport. The products were designed to ignite and burn in a propellant mode when initiated with detonating cord or a shaped charge jet in the confinement of an oil well. The products are not known to react to detonative stimuli outside of the an oil well. In the Single Package Test, although the products were not defined as a substance, it was felt the guideline given for the ignition of a substance was reasonable. The products failed to react with this defined igniter in the Single Package Test. In the External Fire Test, the products burned slowly without exploding or producing projectiles, and without thermal effects greater than the fire. Its burning time exceeded the UN criterion for 1.4S. By the criteria for the test, the products would be Division 1.4, Compatibility Group S or exclusion from Class 1. The External Fire Test and subsequent unconfined package tests indicate that the products can ignite when subjected to sufficiently intense heat, but the burning was not self sustained. In summary, the products are not susceptible to initiation to substantial stimuli (i.e. that in the Gap Test and that defined in the Single Package Test [2]). If burning is initiated it is relatively innocuous compared to the stimulus. If it is interpreted that the products are not transported in the form which it is intended for use (refer to the definition of Class 1 [3]), the product could be considered for exclusion from Class 1, in which case, OCS has recommended the assignment to Division 5.1 (Potassium perchlorate, mixture, UN 1489, packing group II. ). If the product is accepted as Class 1, the following classification is recommended:- Page 13 of 14

14 Proper shipping name: Articles, explosive, n.o.s. (Potassium perchlorate / epoxy) Product identification number: UN 0349 Division / compatibility group: 1.4S Packing group: Packing instruction: II P101 Note regarding packaging: The packaging instruction requires that the competent authority specifies the packaging. It is the opinion of the tester that wooden or fibreboard packagings similar to those specified in the application [1] should be specified as part of the authorization / approval. REFERENCES 1. Application for Examination, Testing, Classification, and Approval of Owen Oil Tools, Inc. STIM Product Family, Owen Compliance Services, Inc. Document dated Recommendations on the Transport of Dangerous Goods - Tests and Criteria, Third Edition, United Nations, New York 1999 ST/SG/AC.10/11/Rev Recommendations on the Transport of Dangerous Goods, Model Regulations, 11 th Edition, United Nations, New York 1999 ST/SG/AC.10/1/Rev.11. Page 14 of 14