Document om2gwNeQL7KQwqmR6b3nxJDgr

interoffice iliciiiorciiidiiiii O (Nime and Location) 0. G. Bremer ROM (Name and Location) J. L. White GEN 55 (REV.6/74) OATE April 12, 1977 REFERENCE NO. JLW-14-77 SUBJECT: Loading of the Prehydroqenation Catalyst In Frank Girolamo's letter, FJG-307-76 (attached), the Bay City Plant was cautioned about the possibility of getting platinosis from working with the .prehydrogenation catalyst. Employees working with Engelhard experienced symptoms of platinosis from being exposed to the prehydrogenation catalyst. Engelhard recommended that persons loading the catalyst wear dust protectors over their mouth and nose and wear protective clothing. The symptoms of platinosis are wheezing, coughing, running of the nose, tightness in the chest, shortness of breath, a bluish discoloration of the skin and mucous membranes, and skin irritation. Personal air samples were taken to determine the dust concentration while the catalyst was being loaded into the catalyst baskets. The catalyst loading procedure is described in Bill Seeliger's letter, WJS-13-77. There are six baskets; three baskets have six 10" sections of packing. These three baskets were loaded dry to insure proper catalyst distribution throughout the packing. After the catalyst was evenly distributed through the packing, the baskets were then submerged in demineralized water and the remaining catalyst was loaded while the basket was submerged. The other three baskets were loaded; while submerged in demineralized water. The catalyst is shipped in plastic bags placed in drums. When loading the catalyst between the packings, one operator fills a bucket with the catalyst. By means of a rope, another operator hauls the bucket of catalyst to the top of the basket, another operator lowers the bucket into the basket, and the fourth operator evenly distributes the catalyst with his hand. The person filling the bucket is exposed to black puffs of dust when she dips into the catalyst and empties her cup into the bucket. There was a slight breeze to give her some natural ventilation. The two people lifting and lowering the buckets received little dust exposure or skin contact. The person in the basket had no natural ventilation except for the updraft which blew more catalyst into his breathing zone and on his clothing and skin. The total operation took about three hours. There were four people doing the dry loading. The people loading the catalyst wore dust masks for protection, but no one wore any protective clothing. It is estimated that the prehydrogenation catalyst will last over six months before a new charge will be required. OSHA has set PEL's for inert dust at (1) 5 mg/m^ respirable dust and (2) 15 mg/m3 total dust. There is a PEL for soluble salts of platinum of .002 mg/m3, but Bay City's catalyst is platinum metal on carbon. There is no standard for exposure to platinum metal which is not known to cause any ill effects. UNITERMS: OSHA Catalyst CHOX 004905 JLW-14-77 April 12, 1977 Page 2 The catalyst dust was collected with a MSA Gravimetric Pump, with a cyclone assembly and 0.5 micron filter paper. The result from the catalyst loaded wet was 0.0018 mg/m3 for total dust. The result from the catalyst loaded dry was 1.16 mg/m3 for total dust, 0.011 mg/nr* for respirable dust, and 0.0001 mg/m3 platinum dust. This sample was taken on the man in the basket who got the greatest exposure. I watched both the dry and wet loading of the catalyst. The wet loading showed very small quantities of dust. The dry loading met 0SHA standards; however, people coming in direct contact with the catalyst were covered with the dust. Their clothing was shades darker from dust, and the man in the basket had to change his dust mask four times. The man in the basket has no natural ventilati except for the updraft which blows more catalyst into his face. I talked with him several days later and again a week later. He developed no skin rash or any other symptoms of platinosis from working with the catalyst. No other employee has reported any discomforts suffered because of the catalyst dust. According to the PEL'S established in the Federal Register for inert dust, there was not enough catalyst dust present to be harmful. I feel, however, that employees working with the platinum catalyst should continue to use dust masks. I would also recommend that employees working in the dustier jobs be supplied coveralls and be required to shower before leaving the plant. This precaution will protect them and others from being exposed to the dust away from the job. JLW/jg Attachment cc: D. H. Miller K. A. Dunn W. F. Soward J. N. Gann C. J. Duey W. 0. Seeliger J. M. Ramey, NY0 C. D. Barrett, CCCTC W. T. McNair, CCCTC Central Files, CCCTC (2) Tech. Obj. X. File: 71-1 (ft. L. White 004906 *=h Interoffice AVcmoniiuhidi yJLP 'fbx* GEN SS (REV.6/7 .!i& 1(-3 TO (yame and Location) FRC^M (Name and location) F. J. Girolamo - HPO rTM/'-' \ r-C / OATE Dec. 20. 1976 Rfenno. ;FJG/307/76~ J --------- i>. 0 ^u*'v-'Subject: Platinum Catalyst Safety Precautions or -r' Engelhard has advised me that some of their employees involved in loading and . sampling our platinum on carbon COP acids prehydrogenation catalyst have ex- Mh----- V ^^Jerienced platinoaij prolH'&ms. They have had to remove some persons from this work area for a period of time to allow them to get over the effects of this illness. It is my understanding that this is not uncommon when working with 3^ platinum group metal catalysts, especially on carbon support. There is a very small amount of dust produced at the point where the catalyst loads into the drums. This is where the material is sampled. Tha symptoms of-platinoow' are hroa-Hvrng diff'inulf-y tithI ilnn irritation These are reportedly reversed when the person is removed to fresh air. Engelhard is making us aware of this so that we can take precautions to protect our personnel who will be close to the catalyst during loading into the reactor. They recommend that these persons wear dust protectors over their mouth and nose and wear protective clothing. I think you should become familiar with this condition before we receive the catalyst and be prepared to handle it in the appropriate manner. Engelhard has offered to have one of their people talk to us about this. Please contact me if more detailed information is desired and I will get you in touch with Engelhard. t FJG/es cc: K. A. Dunn - Bay City W. F. Soward - Bay City J. S. Alder - Bay City L. E. Hackfeld - Bay City J. C. Bird - HPO S. H. Warren - HPO J. M. Ramey - NYO B. L. Pritchard - NYO Frank J. Girolamo 004907 uferoffffcc AlemoramUih. O (Name and Location) J. M. Ramey, NY0 ROM (Name and Location) J. L. White, BCP GeN SS <REV.6/7<) DATE April 12, 1977 REFERENCE NO. JLW-15-77 SUBJECT: Monthly Report of Bay City Employee Monitoring I have attached a summary of the monitoring done at the Bay City Plant for the month of March. The CHOX prehydrogenation catalyst was loaded the first of March. The catalyst is loaded into six baskets. Three baskets were loaded while submerged in demineralized water and the remaining baskets were loaded without water. Both loading procedures were below the action level for inert or nuisance dust and below the action level for soluble platinum. The Bay City Plant catalyst should be platinum metal on carbon instead of the soluble salt. A report is being prepared. A method for collecting and analyzing for nitrogen dioxide was given to us by David Barrett. The area samples collected were below the PEL for NO2. Additional samples will be taken. The Nylon Salt Unit had a shutdown March 20th and methanol samples were taken. Both the inside and outside operators were monitored. Also, the Century Organic Analyzer was used for spot sampling. The inside operator had an exposure of 25 mg/m3 and the outside operator had exposure of 379 mg/m3-. The Century Organic Analyzer registered spot samples exceeding 10,000 ppm. There have been two samples of benzene taken in the lab that exceeded the recommended PEL. The problem has been corrected by enclosing the pyridine, methanol and benzene solvent. A Drager Tube sample was taken as the employee used the new system. No exposure was registered. JLW/jg Attachments (3) cc: D. H. Miller J. N. Gann C. 0. Duey D. G. Bremer J. M. Jackson, Bishop M, P. Neff, Bishop J. W. Coe, CLP R. E. Green, CLP J. E. Sanborn, Bayport M. R. Stenzel, Pampa H. A. Thomas, Pampa C. Do Barrett, CCCTC B. J. Bland, CCCTC J. P. Hawthorne, CCCTC E. S. Ramey, CCCTC W. T. McNair, CCCTC Central Files, CCCTC (2) n i /j.L. White 004908 S}U3UliiO0 . cW/6M p3}03}3(] UOl}BJ}U3DUO0 IsaqfiiH CO u(tii')u(cossiaqqemjnuaw) (3A3qf;W6/61W111133 Ctf < s s ZD W/6W {[} VM1 3iqe4d3Do\/ CO o o o to CM W/6W OZ O 3ansodX3 -VftL unoH-8 r4--D CO V o4/1 </) Z XX #-H 32C C poqqaw 6ut4oqiuow I-- * tCoO - *os c -V- o E-r-J= 3T3 P r-- O CSS pauoqiuow queuiuiequoo o c C tu ar i 1 <H cc </> ZD Q uotqdiaosaa ' qor (aaqatfiq ^qj.jno3S leioos) 3UIC(t 33^0 [dug 1O4CV3r-3~tl O-o<i0QP-13. CfNO *o o ost_ <4- C*13MA" nun c O 44 >) 40 z co c co o a% oo o ps~ ;s oi- oZi to*-o coe Z O- 0ocO*l *0014S4- Xo ZQ "O 01 O c/1 40 S~ I *** >> o Q.OP*-- t_ 40 40 01*0 C 44 04= >>01 40 HP-C CTO 40 c*r01 o 43 U a3: a40 CO ro*i>. CM coo 01 43 (A P> 01 S0-1 S. 4-- 44 40 -O r-- 01 40 40u01 < Cocl C 40 r** CT 40 01 S +> a 0u*0 *co co aq.BQ (r~flfaIc o) -=J> a<d. (aiqcDtlddv ajaqn) *on aouanbas NNt r- t CO 44- oCO o--UJi E *T E01 a. cn 43 40 3 CM r-- </) O O 40 O CO 4= tn 2Or<so-- 4tA- r- C 3 Q. O E -x 40 40 (/) P CO o CO CM N 4iOr4---) > 44 40 <rt cSo- a3 <A COO 43 *--t --3 Z -a CttnoD 40 tCH-*4r*-*-T4O3Z C--3 S*O S4-> r-- C r-- ^ t40 44 | 40 44 44 44 <rt </1 - (/I to 3 C# f- 3f H- QQZ 0.0 O. o 40 C 44 T3 O A O40 UaO< *4*- r>-, r-- t- 40 40 *3 C 44 O 4= > 40 H+J= 0)0 *o I6---- mcQJ CD CO CtoIO CM to to 4i4- c 4- 44 " T- CO ro-- u w c -O )r-- 04= 3 > A C >>-- T3" CM CD <D t CO r^. I u0c1 fC- c40 40 a fc<- c 40 rr^-. N oi t CO 004909 JLW-15-77 Page 2 s^uauiuoo, eW/6W p3l03}3(] uopea}u33uoo }saq6jH to t>. <t)(ssa^nuiw uIi'uuoctqeana) eM/6w 13A31 6U11133 o *r o CC C c/6w o JUST CO r daoov CM VO CW/6W 3unsodX3 VMI O oc o unoH-8 poq}3W 6uiao*iiuon V) CO at o jo -- 3 as ot h to *o co o - r-- O 05 <EE -j sc pauo^Laow ^ucutun^aoQ i'i-- e . -C XJ S' 45 rc *o o *-4 cn tfl 45 o e ceo o at o-t jcatu H t-CL i -a JO o o JC P4J 40 O <0 -r- id O u o t- 4) .e -C 50 CJ | - o 45 4-> r-- <0 >,4J C 4) T" O s> < i. uoiqdtjossa 45 O -a 4-> * ,qp *- <o </) u Ui 4-> 45 3 a. cr o o to (jaqmnN Ok Ok < rs. t icioos) 4-5 45 U coo Of suiett C 45 C r-- H 33jto[dug 45 >i ^ H- to kiun C O 4 z> cido 45 O *C 4-> -r- id to *- o43-> oa45. i- Id 45 45 -Q Z cOc "o CO CoM CO I CM H. CO CO 45 4-> t-- 40 >k*P 45 r <J > C N. N o f^. (aiqeoilddv 3J3qH) on aaaanbas cm ^r o o> "O o 4-5 CO df o res: to <t oo -<8 zo. c 45 45 cn-a O -ruX H o ZQ -a c to -r- Ci U S 45 45 C+r+ 5: Xi -- 04- Jf O O-MM- 40 45 cU o 0.-0 IS r^. r>. o CO o o OO to co CM CM V) CO ao XJ - 3 Z Ok H in TJ to <a d> C *r- -a 1ii= *7 4J r- O flj CSS o c KJ x: 4^ Ok r^. co to to . CM I CM Ok | rtO ^ <. 45 C *3 4- id Vk t4-5 45 3 Q. OO TJ S_ >k <d H <+S- 4- 40 O -12 O I CO o' 4 CM CO c O 4- > 40 Z CO tN. N I CO c O 4 >> co Z CO 004910 r 04 ' 004!311 -- '______ --J 1 (aiqcDt [dd\/ ajaqM) *ou aouanba$ 34*0 oo> a 3--t:j toI cn fs nun o V) => aaKoidiig IBtDOS) aiuBfi c < Xq.unoas (jaquinu a: uoi4<k.ns3Q < qp LlI a: -3 2 0 -7 7 3-22-77 3-24-77 Nylon Salt Mary Crawford 450-70-1203 Inside Operator Methanol Alumina Tubes Modified NIOSF Method S59 Lab | Area oratory Near the K. Fisher methanol, pyridine, benzene solvent Lab oratory Carl Rhymes -4 5 2 6 0 -7 2 6 1 Finished Product Analysis Benzene Benzene Drager Tubes Charcoal Tubes GC 3-31-77 Lab oratory Area K. Fisher methanol, pyridine, benzene solvent * Benzene Drager Tubes pajo^Luow o ^UBUtuiejuoo ss o poqqaw 6uiuo^tuovj JnoH-8 ac o 04 m to <3 CW/6W aunsodX3 i/% tCooSJ W/6W (i )VMJL aiqeidaoov /.x(sa^nuiw ui'uot^eana) W/6W 13A31 6u 11.133 >- oc < rW/fiW pa:p3}a0 uot^cu^uaouoo ^saqCtH 3 .2 6 1 3 .2 6 3 .2 6 Found 2 4 .5 mg/m3 for 140 min.; this was averaged for 8-hr. TWA None Detected S^USUUIOO . Interoffice Alciiior;iii<luiii TO (Nam* and Location) D. W. Steele FROM (Nam* and Location) C. J. Duey qEN SS (REV.6/7 DATE July 18, 1977 reference no. CJD-218-77 SUBJECT: Safe Handling of Oxalic Acid I understand that the Lube Acids process will use oxalic acid to precipitate manganese and copper from the SO reactor product. The oxalic acid will be purchased in bags. It will be added to a mix vessel for solutioning before use. It is important that we plan now for the safe handling of oxalic acid to prevent creating an employee health problem. Oxalic acid can cause severe burns of the skin, eye, or mucous membranes either as a dust or in solution.1 Exposure of teeth to oxalic acid dust could cause dental erosion. OSHA has set a PEL for oxalic acid dust of 1 mg/m3 of air for an 8 hour TWA exposure. ACGIH has recommended a 15 minute STEL (short term exposure limit) of 2 mg/m3. There will be potential for brief employee exposure to oxalic acid dust when the employee dumps the bags into the mix vessel. The amount of exposure would depend a great deal on how much fine powder is present in commercial oxalic acid. (Laboratory reagent oxalic acid is not very dusty). The following suggestions are made for the safe handling of oxalic acid: 1. The employee dumping the oxalic acid should wear a full face mask to protect the eyes, teeth, and lungs from dust exposure. 2. Gloves and possibly other protective clothing should be worn to prevent skin contact. A safety shower and/or eye wash facility should be located nearby. 3. Local exhaust ventilation may be necessary if the commercial material is very dusty. Ci-'J. Duey .CJD/jg cc: D. H. Miller J. N. Gann D. G. Bremer C. D. Barrett, CCCTC W. T. McNair, CCCTC Central Files, CCCTC (2) File: 71-1 Tech. Obj. X. 1-Patty, Frank A., "Industrial Hygiene and Toxocology," Volume II, Interscience Publishers, New York, 1963. UNITERMS: Lube Acid, Oxalic Acid, OSHA, Safety 004912 '( t;u3owoo cH/6' P3J3S590 Li0}3f.qu9tt03 ***<6lH n J L t~ 2 i- ft O -f *> a U; 9u1 O 0 n to *<![ V-* to co o-- 91 -3 _J t- VO. !> * e vt OI 2e (.){;nun< of'uonsjna) rW/6H tl 6Uf3 <OC ac en/6 ax {i}m iqtidaasy v> c/ jntodX3 Ml jnoH-8 POLISH 6ujjo3|uoh 1CAM l WOJ) t g* CM o to CM - VI ^ vt -2^2. s *3** C o ** Wf-O M<C 40 CM * *TJ 41 41 ci ii C4J , n *> 9 *vto--t *-o v>- o Um kU (OUO CM CO *o 41/ -Si CO O41/ * .p9J<njU0H O X u 41 *0 S'* o c 2 41 O c X 4 %a c 3 c *c4 V *3 '4 ><** W. uo})d(jnsaa *>c N ll &. O *o- W m ^vt u BB t"O 4o1 "vt S 41 CJ 5<- O utside O perttor 41 Vt > 40 C x; 1{50S) . <W*N M/Coidaj 1 1 TJ JC > to l ao to vr nt N r*n vr 1. XJ u 5 c cnjz &a c Oto ^c >Xv4*3" oo ccoc CtoM 2 to to tot to r H CT ti L ti'S CLCC to to stot CO to vr i .1 . a - o- Jn" M-'-- - 4i 41 41 m *-4 V) V) n <1 oc c o 4o1 u40 * .8 Mt ui to Cn. to ->*) o# aouanoas . 00* __________________1 i fK/SH' J0J5-qU30U03 >sw)6t 4 is o1<2*? * <x a u O* M w*4,,1o- l*_4* 4J Cl 7: C^*" E -k 4 E Va14J>4c4 m<0 Of'uOnsJIQ) r/6H lA1 6uiu*9 to /E (ijwa l^id333V ae H/H sjnsodX3 YH1 4D0H-8 Ik Sff _J r* IA P09H eujJojtttOH V-- -- >, om Vc a4 nuu |jo;{UOH c c a U0Hdf43Ia ui W ac fJ9qn .. l*30S) . 93*016*3 V r - . wi t 1 u * r* a * 3 d4 tno o cSl f> CO IS 4- 1. 2 r> S in 3 .2 3 .2 *i- n A i t in -4^- s d c M C GO 4** > m < 1 g '- wj J= to w *. ci to <mli 4U*3 .2 mJ **. ti to otCoM O CO iSS oM r-a V)<tf o c 4i X **4C*>- 4oiV4. 8S > 5t && in oC%l t CM N S 44 M C X fs 2 CM iA e S^e 44N. i1 Gf-J 40 t" * sS o L< ub vxo tn oo C4 c N c CO -O 4o-* 44t *G- So t tC.J 44-04 *"3 COr tOot 03 5 tIOo > 44 4-- to co N CM to g. 0. 0 M X* <Ol a 0u 0 *ty*-o^ cc si t- s cn d * < t-s I CM to *0# 9303009$ . 00 * __ !_______ 1 ` iifceroffice A\eiiioraii<hiin o (Nama and Location) J. M. Ramey, NYO 'ROM (Nam and Location) J. L. White, BCP GEN SS (REV.6/7 DATE July 20, 1977 REFERENCE NO. JLW-20-77 SUBJECT: Monthly Report of Bay City Employee Monitoring Attached is a summary of the monitoring of various airborne substances throughout the Bay City Plant. This table contains information beginning May 1, 1977 and continuing to June 29, 1977. Note that a mechanic was highly over exposed to methanol vapor on June 29th. A permit system for maintenance in the Nylon Salt Unit will be implemented to insure that this does not happen again. -- U Aite JLW/jg Attachments (6) cc: 0. H. Miller J. N. Gann C. J. Duey D. G. Bremer J. M. Jackson, Bishop i.M. P. Neff, Bishop J. W. Coe, CLP R. E. Green, CLP J. E. Sanborn, Bayport M. R. Stenzel, Pampa H. A. Thomas, Pampa C. 0. Barrett, CCCTC B. J. Bland, CCCTC J. P. Hawthorne, CCCTC E. S. Ramey, CCCTC W. T. McNair, CCCTC Central Files, CCCTC (2) File: 71-1 - 004913 < "*v*t* srsasrirrrror: t^uauiooo u 4 C > 32 jou.4 ie rH/EKjont^quaauoo S4i 41 D /M(s;nuiH uf'uoHJna) rH/6 ISASl 6U|ij#3 x 9x ' H/ . {i)VHl tiq()<faV tOn ' M/6W ansodx3 i ee !o vni jnoH-8 po>0#K 6U(40}|U0H PM09|uoh ^U9t4(nU03 X X 1w uondj-ntsfl qoc M 43 i.1 m h 11 3 e si- - PsqwN Alarms * m*>s) . .* Mrtt<V3 ti - ?in 4404 Jc N t cm tn (iq3Hdd OH 3uanb9S .* 5 jc cv woo6 Xho1 wJ QE| <ao yCou o S 40 L t4440 O0u 41 i. O 40 Ik si ^ 40 rt 43t 1-**O- r34-0S if5 So V)OU s3 cm 4Mi >> 2 T3 U4*a0rs) *? osxu. s 4o4>0 Xo_4J0 frss. nCM tn Ok i&t L. 44-1* OC44* It C II ti o 0 u o *k- 4L0 sl t otU4fae44-t* tn to ectoio to tn XoX_> fs. . IS. tCoM tn too CM k 4) 3-vS'-5. s O3 ,_ C 24-* to. M- 410. <35- O x XUu no CM O 5 ^tn 44 5 c o X tfss. rCsM tn 260 CO ICsO. s c O c 55 T3 4 > S" So tn os to t CM tnr 44 t4n0 o. >t X rs i <n 40 - 004 .1 **.* *"* -~vC ' * * - / IN D U S T R IA L HEALTH MONTHLY. M O N ITO R IN G SUMMARY m \;u3un>33 ----- zU-C------cMJ cCl *u 4410 OO 1U7V. at l/l C3L. 1 J44c410i*-4so4--0-14oOlC1 nL<5 ICL. 0.4* 4J > 1400 4e- vo %3- J0j)jqu93UO3 5SM6jh (.)(s9;num Ufuoptjna) rH/6 l*Al 6mo H/6h ' tiUdM3y jCmHs/o6dxa . YfU jnoH-8 os in N poq}n 6lJKaiUOH 4oOiO<C7r* p paao^juoH )U9U|KV3U03 cU *n* o ra i. cs W *5? hu!o (jsqanN . X%\M09$ WM*tK*) . 93^0ld3 CsinM wc 3 3 s * - si<m . nta 5 co * n1 4 (iqU<Wy jaqI oh wanws rs c JTj fve; *XJ r*- O am *- M>% s E5 n oo ccr *c4 o e otij O in Sl CAO oaoo i*nr X r-* t IO os 6.5 tiguV 23C&*h v SI- 2X zb rc>UMU 4LO7 qTo ** 8 oo3>-kf*r zoo N*soi^n<ir "S3 < 3 .IKS CM J) * 279 O CM M X3 M 5e9^C2-.* o5 vs<o | x: <0 *a. xs_: vos 4 41 i4n0 oc fCs-.. CC4MM0 2369 260 oC 2 2*5- 41 V4S0 o. 5 CM CO ---- OOs j t}Ujuuo3 t. OX IN D U S T R IA L HEALTH HOHTHLT M O N ITO R IN G SUMMARY cm/Eh LiopWiJS^uaaWDUJoa R*R6lH IPSU,sOaJ?^wtJIiT}HQ) (1U&/f4yU*0 eH/6w daaay CH/6H unsodxj vm JOOH-8 6up|joam;(UaOn M 2*~Z }upatujMiUrj)iiuOoHo s i* uon^IJMsa W (qtanH " itu-Jinas > in**N) a/Oldaj IS. IS fc *R*G n 4. (tg*3Hddy SJ9RH) *0# 3tiano9S s? ii N O *f XUI^ s? o**=& ? CA-'" ofuOe*<c0 3 auc-US UK ^O <4i3V# 33 S3 o u *Vt3 o * S? k X a o u< Wi3 S 5 4i;.M? Ok CA s oo 8 004918 Pag* S *)U3UUK>3 eh/6h' W3l0 ifopvjt^ua^uoo - fi)(ss?nu{H Qf'uonsjnQ) rH/6 ll 6ufU*3 4 JC X" *. l^dwy * 3 .2 3 .2 H/6H unsodxj vm i ce o. . ` JnoH-8 iI *= poms 6<jjjo;iuoh ?* " 1 i-l* paj<muoH 3UVU}Cf3U03 ' * ft. ti II c fl 4i O SCO j. -i*mi . traudiussad r1 :; V." ..w rt. cs f-4* L g-g. 1^0.0 . -. (?' r AlMn^S : ,1*130S) . *** aa^Q(da3 ^8 ao e .C u oi ' c r* c SCO .\ n -o o . 8J o ^U VI uo c f as 4i > g cn 8 * t <o c o E ft. i o o tn o a u 2 _J N t CO CM li ifl Or- <0 *1 " U r2Tfe0 *- *- CM O 4 ft. C j Oft O ft. r- xv (O *f u. Ol t> IV (003- 02 -S.8 o eo vi'-' .t < ft. o n >i ft 0 A < J3 . r CoMi (iqrjuddy "<{*) *oh 3Unw$ *. * cn 03 M S mv ft. = s* * 2S.S KfCO M ft. Vo. c oC oo no as-- o o r-- O 40 CM M X) *1 3-- -8*- |Jg uS* S C ft C B "W f --n wi ^riz c >n Uttiu o M1 *r u a Vj fs. OCMl 40 * 00 :________________! BASF Wyandotte Corporation Wyandotte. Michigan 48192 313 282-3300 August 29, 1977 Mr. David Barrett Celanese Chemical Company Technical Center P.0. Box 9077 Corpus Christ!, Texas 78408 Dear Mr. Barrett: Enclosed is a summary of the toxicity information on tri- phenylphosphine that we discussed in our telephone conversa tion last week. These studies were conducted in the BASF AG toxicology laboratories in Ludwigshafen, West Germany; and we translated the summary into English. The study is con- fidential (BASF AG) and should be treated as such." Please lV <" Peontaict^e^.r_Sandi_BeTss~~irf~yb'u~Kave' any questions concern- '/ ing this information. " ' .......... " "" " Yours very truly mk enc Peter L. Lubs Industrial Toxicologist 004920 REPORT ON BIOLOGICAL TEST OF TRIPHENYLPHOSPHINE Irritant action on skin and mucosa: dorsal skin, ear and eye of rabbits. Acute and subacute toxicity: mice (s.c. and p.o.}, rats (i.m. and p.o.), rabbits (i.m. and p.o.), cats (i.m. and p.o.), dogs (p.o.). Inhalation of volatiles in mice, rats, rabbits, and cats. Evaluation: As mentioned in a preliminary report, the product proved to be of little activity in the acute experiment with rodents. Its irritant action is very slight: evan a 50% suspension on the extremely sensitive dorsal skin of white rabbits is com- . pletely non-irritating. A 10% solution produces only minor inflammation symptoms in the rabbit eye. After i.m. injection, some animals (rats) tolerate 2 g/kg, while even 3 g/kg is tolerated without intoxication symptoms after s.c. injection (mouse). Surprisingly, triphenylphosphine has a more potent action after .oral application (dissolved in oil) than after injection, which may be explainable by a poorer absorption of triphenylphosphine from the oil depot based on the postmortem findings in rabbits. Thus, while a. single dose of triphenylphosphine seems to be relatively nontoxic, repeated applications produced pronounced damaging effects in the nervous system? in rabbits, even fractions of one gram applied repeatedly led to increasingly complete"atonia of the entire body and characteristic paralysis signs of the hind legs up~t:o""death. The nerve damaging action of triphenylphosphine is still more evident in the experiments with cats and dogs: a single oral or i.m. dose of 300 mg/kg leads to grave and often lethal convulsions. Repeated oral doses first produce a certain degree of habituation, particularly with regard to the strychnine-like stimulant action of triphenylphosphine, so that somewhat higher doses are tolerated without marked symptoms. However, later, these doses lead to' pro nounced paralysis which are very similar to that produced by tri-ocresyl phosphate, and like the latter, appear to be hardly reversible of perhaps irreversible (observation period of 3 months). . 004921 Thus, like tr~ -o-cresyl phosphate, triph^nylphosphine must be considered a potent nerve poison and it is entirely possible that even small quantities would lead to nerve damage also in man, particularly after repeated application. Since the product can probably also be readily absorbed from the skin because of its oil solubility, prolonged--contact--with--the--skin7~-particu-larly--in-- \ dissoTved"fbrm7nTidSt*TDe~civoided-as--far--as-possible-during"handling\ of""ttphenylphosphine7--even though it practically has no local irritant action on the skin. Afteif^hy~contactr'wirth--the-product> the--most~careftr2r_crleaning-of--skin"and~c l'othe s -must-be_urged. " NatufaTlyr--contact-of---triphenylphosphine- with~mucous -'membranes, for-example-r--through--the-hands-r"raust-be^prevented'~xn"anyr"'case (washi3 ofhrands--before--eatingl_.__ / Ther~risk''of~damage-due~to~inhalation..of triphenylphosphine -vapo: I is slight according to our preliminary experiments, since^-the-produc 1 is-of~"l'ow"vbIatTrity-even--at"elevated-temperature (vapor-pressure 5 \mm Hg at 210) . Translated from Summaries' of German Reports. Testing performed at BASF AG, Ludwigshafen, West Germany. 004922 Interoffice A\eniaraii4lnn TO (Ntm nil Location) Mr. M. P. Neff - Bishop FROM (NamVafld Lilian) " " -------- _________C. D. Barrett - CCCTC___________________________________________ UN 55 (RV.6/? OATE 9/14/77 REFERENCE NO. CDB-80-77 Subject: BASF Wyandotte Report on Biological Test of Triphenylphoaphine I have attached summaries of the West German studies on triphenylphosphine. As the BASF Wyandotte cover letter indicates, this information is confidential. Based on the West German studies, TPP appears to be a potent chronic nerve poison. Since the information in the summary is so limited, it is difficult to assess the inhalation hazard (refer to CDB-76-77). However, I think we must conclude that TPP is potentially toxic by all routes of entry. --' Our use of TPP should be reviewed and exposure reduced to an absolute minimum. I would like to review the job and discuss control procedures with you and Jim Jacks on. I'll be sending this information along with the other study to Judy Tins for review and comments. Hopefully, we can find some additional research studies that can clarify the toxicity of TPP. Ang - Attachment cc: Mr. J. M. Jackson - Bishop Mr. J. M. Ramey - NYO Ms. J. A. Tins - NYO C. D. Barrett, Industrial Hygienist 004923 BASF Wyandotte Corporation Wyandotte, Michigan 48192 313 282-3300 August 29, 1977 Mr. David Barrett Celanese Chemical Company Technical Center P.0. Box 9077 Corpus Christi, Texas 78408 Dear Mr. Barrett: Enclosed is a summary of the toxicity information on triphenylphosphine that we discussed in our telephone conversa tion last week. These studies were conducted in the BASF AG toxicology laboratories in Ludwigshafen, West Germany; and we translated the summary into English. The study is con^ ^fidential (BASF AG) and should be treated as such. Please \ contact me'or SandT'Reiss if you have any questions concern ing this information. Yours very truly. mk enc Peter L. Lubs Industrial Toxicologist 004924 ONFIDENTIAL 1 V: REPORT ON BIOLOGICAL TEST OFTRIPHENYLPHOS PHINE Irritant action on skin and mucosa: dorsal skin, ear and eye of rabbits. Acute and subacute toxicity: mice (s.c. and p.o.), rats (i.m. and p.o.), rabbits (i.m. and p.o.), cats (i.m. and p.o.), dogs (p.o.). Inhalation of volatiles in mice, rats, rabbits, and cats. Evaluation: As mentioned in a preliminary report, the product proved to be of little activity in the acute experiment with rodents. Its irritant action is very slight: evan a 50% suspension on the extremely sensitive dorsal skin of white rabbits is com pletely non-irritating. A 10% solution produces only minor inflammation symptoms in the rabbit eye. After i.m. injection, some animals (rats) tolerate 2 g/kg, while even 3 g/kg is tolerated without intoxication symptoms after s.c. injection (mouse). Surprisingly, triphenylphosphine has a more potent action after joral application (dissolved in oil) than after injection, which may be explainable by a poorer absorption of triphenylphosphine from the oil depot based on the postmortem findings in rabbits. Thus, while a single.dose of triphenylphosphine seems to be relatively nontoxic, repeated, applications produced pronounced damaging effects in the nervous system; in rabbits, even fractions of one gram applied repeatedly led to increasingly complete atonia of the entire body and characteristic paralysis signs of the hind legs up to death. The nerve damaging action of triphenylphosphine is still more evident in the experiments with cats and dogs: a single oral or i.m. dose of 300 mg/kg leads to grave and often lethal convulsions. Repeated oral doses first produce a certain degree of habituation, particularly with regard to the strychnine-like stimulant action of triphenylphosphine, so that somewhat higher doses are tolerated without marked symptoms. However, later, these doses lead to pro nounced paralysis which are very similar to that produced by tri-ocresyl phosphate, and like the latter, appear to be hardly reversible of perhaps irreversible (observation period of 3 months) 2 Thus, like tri-o-cresyl phosphate, triphenylphosphine must be considered a potent nerve poison and it is entirely possible that even small quantities would lead to nerve damage also in man, particularly after repeated application. Since the product can probably also be readily absorbed from the skin because of its oil solubility, prelonged-contact with the skinr--particularly indissolved form, must be avoided as far- as poeeibie^-during-- handling of' triphenylphosphine, even though it practically has no local irritant action on the skin. AftST,,,ahy' cunLaeL wiih~the~ product, the- most careful cleaning of skin ~ and "Clothes* must-be., urged. Naturally,-contact -of triphenyiphosphine- witfrr mucous -membranes, for- example,--through-the hands-,- must be"prevent"ed'in~Sh'y case (washinc of' hands- before eating} . The'risk-of''damage- due to inhalatjjan^.Qf^tripheftylphoaphinQ^aporg is slight according to our preliminary experiments, ainse the preduetof-'low volatility-even-at-elevated--feepea?atere~4vapor-pressure 5 mm Hg at 210). Translated from Summaries of German Reports. Testing performed at BASF AG, Ludwigshafen, West Germany. 004926 Interoffice lWeinoniiHliiiii TO (Nam* and Location) * As Listed FROM (Nam and Location) M. P. Neff GEN 55 (REV.6 OATE 9-21-77 REFERENCE NO. MPN-225-77 * Messrs. John Hodges Bill Meyer Danny Walker Buddy Cloud Subject: Triphenylphosphine Attached for your review are the Material Safety Data Sheets and the summary of the German Study on TPP. I have also summarized the use of TPP as I understand it from our meeting. If there are any corrections or addi tions to the summary please point them out at the meeting on Wednesday. MPN/ks cc: Messrs. C. W. Lee C. W. Harrison P. J. Volpe M. A. John R. W. Swanbeck J. M. Sawyer N. J. Sternadel R. N. Updike M. P. Neff 004927 TPP MEETING SEPTEMBER 20, 1977 MPN-226-77 TPP is received in flake or powder form from either BASF-Wyandotte or M & T Chemical Company for use in the 0X0 Unit. The dry product is stored in the Shipping Services area, transported by Maintenance, added to the system by both Operations and Maintenance Department Personnel and sometimes has sample work performed on it by Laboratory Personnel. Maintenance Department Personnel are exposed to the product during routine repairs to equipment and when the catalyst is drummed for shipment to an outside vendor for recovery operations. On an annual basis the reactor system is dumped and then recharged with approximately 14,500 pounds of fresh TPP. This changing operation is usually handled by the Maintenance Department. The next meeting will be held on Wednesday, September 28, at which time we will review draft procedures for the handling of TPP by each of the areas that have exposure opportunities. Plans are to: 1. Have the Company Hygienist research for additional literature on toxicological testing of'TPP. 2. Have Corporate Medical ascertain if there are medical tests available that can determine any medical problems associated with exposure to TPP and to recommend the proper medical surveillance program for the future. 3. Notify the Chemical Company Product Safety Committee and the Houston S & D group of the problems associated with TPP. 4. Determine what will be necessary to legally dispose of containers, coveralls, etc. that have been exposed to TPP. Mr. Jack Sawyer will handle this area. 5. Inform employees that have an opportunity for exposure to TPP of the possible hazards of the product and the steps necessary to protect themselves from contamination. This will not be started until written S.O.P.'s have been established and approved. 004928 fasni-tfice (Name and Location) Mr. H. W. Head, TrT^^. if.-. (Name and Location) J. M. Sawyer :/JL FT ,\j&- ~A /1 / 'lO CJ 'Jii ^ %4~- 771/r/i //-/- DATE September 23, "ftEFERENCE NO. JMS-1000- 197 O x.o Triphenyl Phosphine We use Triphenyl Phosphine (TPP) in our OXO Unit reactor here, and Bay City will use it when the recently approved OXO Unit is constructed there. We charge about 14, 500 pounds of TPP to the reactor, axid~gdgorlJ jlll 220 poundc-pcr day to-malte up for losses in the liquid heavy ends stream burned-- f^n-eur-borier^: We have received information from Germany this week (see attach ment) which tends to show that TPP is an accumulative nerve poison, If true, and we are using this assumption, our Industrial Hygiene-Safety Department is in the process of re-defining guidelines for handling TPP. One of the proposed guidelines is to provide workers with coveralls, gloves, and other protective equipment. We need to dispose of these used clothes. The OXO reactor is emptied each year, and the contents are drummed, and shipped to Englehard in New Jersey for rhodium catalyst recovery. They recover the catalyst via a combustion process. I'm sure you have anticipated my next questions: How do we dispose of the coveralls? How do we dispose of the 1000 50# plastics-lined bags we use? If we use drums (plastic lined), can we sell the drums? What responsibilities do we have in the Englehard catalyst recover}' operation? I would appreciate your comments. kf Attachment cc: Messrs. Joe'Schaeferi R. H. Maurer M. P. Neff (w/o attach) 004929 iferoffice iUciuonindimi (N*m vocation) * As Listed Dn' (Mm ana t.oct<on) M. P. Neff luATc 9-21-77 REFERENCE NC. MPN-225-77 * Messrs. John Hodges 3iil Meyer Danny Walker 3'jqcv Cloud Subject: Triphenvlphosphine Attached for your review are the Material Safety Data Sheets and the summary of the German Study on T?P. I have also summarized the use of TPP as I understand it from our meeting. If there are any corrections or addi tions to the summary please point them out at the meeting on Wednesday. MPN/ks cc: Messrs. C. W. Lee C. W. Harrison P. J. Volpe M. A. John R. W. Swanbeck J. M. Sawyer N. J. Sternadel R. N. Updike M. P. Neff 004930 T?P MEETING SEPTEMBER 20, 1977 MPN-226-77 TP? is received in flake or powder form from either 3hSF-Wyandotte or M & T Chemical Company for use in the OXO Unit. The dry product is stored in the Shipping Services area, transported by Maintenance, added to the system by both Operations and Maintenance Department Personnel and sometimes has sample work performed on it by Laboratory Personnel. Maintenance Department Personnel are exposed to the product during routine repairs to equipment and when the catalyst is drummed for shipment to an outside vendor for recovery operations. On an annual basis the reactor system is dumped and then recharged with approximately 14,500 pounds of fresh TPP. This changing operation is usually handled by the Maintenance Department. The next meeting will be held on Wednesday, September 28, at which time we will review draft procedures for the handling of TPP by each of the areas that have exposure opportunities. Plans are to: 1. Have the Company Hygienist research for additional literature on toxicological testing of TPP. \ 2. Have Corporate Medical ascertain if there are medical tests available that can determine any medical problems associated with exposure to TPP and to recommend the proper medical surveillance program for the future. 3. Notify the Chemical Company Product Safety Committee and the Houston S & D group of the problems associated with TPP. 4. Determine' what will be necessary to legally dispose of containers, coveralls, etc. that have been exposed to TPP. Mr. Jack Sawyer will handle this area. 5. Inform employees that have an opportunity for exposure to TPP of the possible hazards of the product and the steps necessary to protect themselves from contamination. This will not be started until written S.O.P.'s have been established and approved. 004931 ;*erof?tce Meiuoramliim (N4r> ane >_ocJ*on) Mr. M. P. ON* (Nim Neff - Bishoo C. D. Barrett - CCCTC IOATE 9/14/77 REFERENCE NO. CD3-S0-77 Subject: BASF Wyandotte Report or. Biological Test of Trinhenylphosphine I have attached summaries of the West German studies on triphenylpnosphine. As the BASF Wyandotte cover letter indicates, this information is confidential. Based on the West German studies, appaarc ter~bc a-pcter.t chror-ie-acrve- poin-ea-. Since the information in the summary is so limited, it is difficult to assess the inhalation hazard (refer to CDB-76-77). Hamn7f>rl T -mo P| that TPP ic potenai*By by all routes of Our use of TPP should be reviewed and exposure reduced to an absolute minimum. I would like to review the job and discuss control procedures with you and Jim Jackson. I'll be sending this information along with the other study to Judy Tins for review and comments. Hopefully, we can find some additional research studies that can clarify the toxicity of TPP. &cr Attachment cc: Mr. J. M. Jackson - Bishop Mr. J. M. Ramey - NYO Ms. J. A. Tins - NYO C. D. Barrett, Industrial Hygienist 004932 BASF Wyandotte Corporation Vwanocrte. Michigan ^Si2 313 282-3300 August 29, 1977 Mr. David Barrett Celanese Chemical Company Technical Center P.C. 3ox 9077 Corpus Christ!, Texas 78408 Dear Mr. Barrett: Enclosed is a summary of the toxicity information on triphenylphosphine that we discussed in our telephone conversa tion last week. These studies were conducted in the BAS? AG toxicology laboratories in Ludwigshafen, West Germany; and we translated the summary into English. The study is con fidential (BASF AG) and should be treated as such. Please contact me or Sandi Reiss if you have any questions concern ing this information. Yours very truly. mk enc Peter L. Lubs Industrial Toxicologist 004933 CCS DEN X Irritant action on skin anc r.ucosa: dorsal skin, ear and eye of rabbits. Acute and subacute toxicity: mice (s.c. and p.o.), rats (i.m. and p.o.), rabbits (i.m. and p.o.), cats (i.in. and p.o.), dogs (p.o.). Inhalation of volatiles in mice, rats, rabbits, and cats. Evaluation: As mentioned in a preliminary report, the product proved to be of little activity in the acute experiment with rodents. Its irritant action is very slight: evan a 50% suspension on the extremely sensitive dorsal skin of white rabbits is com pletely non-irritating. A 10% solution produces only minor inflammation symptoms in the rabbit eye. .After i.m. injection, some animals (rats) tolerate 2 a/kc, while even 3 g/kc is tolerated without intoxication symptoms after s.c. injection (mouse). Surprisingly, triphenylp'nosphine has a more potent action after.oral application (dissolved in oil) than after injection, which may be explainable by a poorer absorption of triphenylp'nosphine from the oil depot based on the postmortem findings in rabbits. i*> r---,gin rnryp--o--- 1 r --tC -bp ^pip^hrslv nn^'n^rj--r-Qoea-ted--aps44ea-tiOTiS piuducfaG -^renounced ^n . -- ng1'Cf-feot-s-in the systre*.., .in--rabbits,--even fractions- nnc 1 .-Lor vcnc:-r^Ur 1 p- + ^ .-i-ru-- p-c i nc1 y nnmp~Lc2.t:r --n-'.v "-h1- 1-lr 1 r, pp>- = ` ye--: <- e-i<jng inr fb-g-s--up--to--dearth. The nerve damaging action of triphenylphosphine is still more evident in the exoeriments with cats and docs CL sincle oral or i.m. dose of 300 mg/kg leads to grave and often lethal convulsions. Repeated oral doses first produce a certain degree of habituation. triphenylphosphine, so that somewhat higher doses are tolerated without marked sympuoms. However, later, these doses lead to prono o- 2 -- 3 ,--2.1*: c =~e-cr.&gr?. yhooe-ha-te^--LrlphcJiyiphosphfne ~';;iJSz--------be--ognE-j-cs-re-d- -xi pc-U-.T nerve purst/;;--anc it. is on ti^ ci_>--p-n-g-sibi <=> ^T,= - pyc" ',aa~ -- - 1 r, r, --~-nf-ri . ' cu-lar 1-y cfter--app I ircationi x~ro ts? p^nrrrt^rgj------3 j>roh?KjV also be read-? 1 v-Jhs^v-ip^__from. t-he--skin. bocuu-se--&= its oil--------Solubility,--p^lnncifl^-rnr-^^rr ^-ith the ska a.,.--p-->-t 1 r-ri ts^ry Vr.----^ dissolved form,--mv.st be--es f?r ?<; pncep^-i<= t - ri^1 <X. triohg^v1.Taho^Tiy-nq^_ even though it practically fca^-- .wr-tnryT-----J irritant--action on--the skior" After any contact with the product, the most careful cleaning of skin and clothes must be urged. Naturally, contact of triphenylpnosphine with mucous membranes, for example, through the hands, must be prevented in any case (washing of hands before eating). The risk of damage due to inhalation of triphenylphosphine vapors is slight according to our preliminary experiments, since the product is of low volatility even at elevated temperature (vapor pressure 5 mm Hg at 210). Translated from Summaries of German Reports* Testing performed at BASF AG, Luawigsnafen, West Germany. 004935 Safety `Data Sheet f r j ^ iwuc; _____ ________ SECTION I < CMS. ".1C 2-3300 / \. C21S2 TRADE NAME SYNONYMS FORMULA 'riohenvl Phosnhire Triohenvl (c6h5)3p CHEMICAL NAME Trlohenvl ?hosohi r>e CHEMICAL FAMILY Phosohines MOLECULAR WEIGHT i -Err.-: . S ,^.SECTIONJL--HAZARDOUSjngredients NAME * I TLV I % ! UNITS j TOXICOLOGICAL DATA l Triohenvlohosshine 100 Rat Oral LD_^ 0.8-1.6 c/Kc r SECTION ill -- PHYSICAL DATA Boiiinc Point - 760mm Hg 36 0 C)[ 711 i Vapor Pressure, mm Hg O 20 C. (210^0 5 Soedfic Gravity (H^O = 1) 25 C 1.132 Solubility in Water Appearance and Odor Insol. sol. in ale. ber.zee. White crystalline solid aceto ne C CL. Tl ' SECTION IV -- FIRE AND EXPLOSION HAZARD DATA FLASH 0IN7 (TEST METHOD) AUT013NITI0N I TEM=ERATURS FLAMMABILITY LIMITS IN AIR - % EY VOLUME LOWER UPPER . EXTINGUISHING MEDIA S WATER FOG S FOAM ;TyJ g COj DRY CHEMICAL OTHER SPECIAL FIRE-- FIGHTir.G PROCEDURES UNUSUAL CIRE AND SXPLOSON hazards Explosion hazard slight, if vapor exposed to flame can react vicourouslv with oxidizing agents. EMERGENCY TELEPHONE NUMBER (201) 263-0200 This nucnbe' is available days, rights, wesxends. and holidays. 004936 SECTlOf r~. no"2AED DA threshold limit value ^ot establ.Ls~j3___________________ Er.-trC.S Of GVE'-.cXPCoUns mucous membranes . mucous membrane or oara1vsis . ?0S lb^ S c *5 "CT b~ ~ to g \*g s Repeated slight incesticn or absop skin lead to nervous system damage skin and ion through Possible EYES FLUSH with FLOWING WATER AT LEAST MINUTES FIRST AID PROCEDURES Wash affected areas throughly with detergent and water. Consult a physician. Strict personal hygiene after each exposure greatly reduce possibility cf harmful effects.- NEVER GIVE FLUIDS OR INDUCE VOMITING IF PATIENT IS UNCONSCIOUS OR HAVING CONVULSIONS SECTION VI -- REACTIVITY DATA STABILITY UNSTABLE STABLE CONDITIONS TO AVOID INCOMPATIBILITY Oxidizinc materi als HAZARDOUS decomposition PROOUCtS hazardous POLYMERIZATION MAY OCCUR JOOES NOT OCCUR Pnoschine : PO_. at hich temceratures CONDITIONS TO AVOID - STEPS TO BE TAKEN IN CASE OF SPILLS s ..WASTE DISPOSAL METHOD CONSUL T L OCA L AND STA TE LA WS RESPIRATORY PROTECTION VENTILATION LOCAL eXHAUST MECHANICAL IGeoerall Accec^ab1 PRC i EC :V clothing Rubber cloves. Cove: alls SPECIAL OTHER - EYE PROTECTION 004937 OTHER remove contaminated clothinc and launder afte~ exoosure / SEC ON IX -- S?EC!AL PP.ECA-,, IONS PRECAUTIONARY LABELING Tripenyl Phosphine Kay cause irritation of skin eyes, nose and throat. Repeated absorption harmful. Shipping regulation ICC, cg~ iata. Poison Label <=:--' .t HANOLING AND STORAGE CONDITIONS Avoid breathing dust. Wash thoroughly before eatinc or smoking Avoid contact with skin, eyes, and clothing. 004938 /v\ f / /-vceitiun j'.eac'cior^s Addition to aliphatic diazo compounds to form phosphazines (CeH4)3P ~ R,C:N\--------------3. R;C:XX:P(CtKj3 Phosphanines arc readily hydrolyzed into hydrazonei- P-C:NN:?(C,H4)a -f HjO----- -> H-C :XXK. -i- <C,Hs),PO K Sloudinjer oni J. k\cyc% Heir. Acta. 2, 6124 09t9i. iMT Triphsnv1phosphine adds one molecule of chlorine (or other halogen) to form triphenylphosphine dichlorice (or other dihalide) (CtE^P-J-Cl,. mcsiis>,pci; Ai<S:T T. .phenylpnosphine can be heated with sulfur to form triphenylphosphine sulfide ^C4H4)j? -- S -9- (CeKt)3?h TOXICOLOGY; Although M&T Triphenylphosphine is onlv slichtly toxic by ingestion and slightly irritating to the skin, care should be taken to avoid accidental swallowing and contact with the skin and eyes. Because triphenylphosphine oust may be irritating, care should be taken to avoid breathing it. SUGGESTED FIRST AID: Persons exposed to an excessive amount of triphenylphosphine dust should be removed to a non- contaminuted area. A prysiclan should then be consulted. In the event of skin contact, the exposed areas should be mashed thoroughly with soap and water. 3ontam:nated clothing should be removed and laundered before reuse. In case of eye contact, flush eyes with copious amounts of mater for 10 to 15 minutes. Then consult i physician. For Industrial Use Only MIT Chemlcslt Inc. <}vei e?o warranty, cor<it c imotito, ond fiti 0<oavcti ctt sold condition thot 0urcl*?ieM wiJi tnce o~n tClU to determine (he c;woltfr ond juitaoihty of tot pfOduch A*4 Chm<ol\ lt tholl be Jn no way eeiparub<e to* <hc prcse< wu one tervlee o( tne pfoowet. Any imorenotion pf grjctlcnt given off wjinoui warranty o? ony *ne one pufchsien o*t *o*ety ectpon$ib< for ony lou otitinp f/om fh? ** of such inforrnoion or 5nc*ian. No reformation o* by wt tnoM be ceeftied to be o rfCpmmimdstioA to ony ptoodd in (AamcI wm any ctiinv potent fights. % 004939 CELANESE CHEMICAL COMPANY TECHNICAL CENTER Corpus Christi, Texas To: As Listed* From: C. D. Barrett CDB-96-77 September 28, 1977 Subject: BASF Wyandotte Report on the Toxicology of Triphenylphosphine Recently, Mr. M. P. Neff received a material safety data sheet on triphenylphosphine from BASF Wyandotte, the supplier. Triphenylphosphine is used along with rhodium as a catalyst in the Bishop OXO Unit. According to the data sheet, BASF Wyandotte had .classified the compound as being a potentially toxic chronic nerve poison. Mr. Neff requested that I obtain additional toxicological information on TPP both from the supplier and from other sources. The following information on TPP has been obtained and forwarded to Corporate Medical and to Mr. Neff: - 1. The BASF Wyandotte classification of TPP as a chronic nerve poison is based on a series of sub-acute animal toxicity studies conducted in Germany by BASF AG toxicology laboratories. A confidential summary of these studies has been obtained for our review. According to the summary, the German group has conducted a series of acute and subacute toxicity studies by various routes of administration to mice, rats, rabbits, cats and dogs. Based oh these studies several conclusions have been drawn: a. TPP is generally non-toxic in short-term experi ments with rodents. The compound has a higher order of acute toxicity in rabbits, cats and dogs. b. Repeated applications of TPP to test animals, especially among non-rodents, results in paralysis and various other damaging effects to the nervous system. The mode of action is believed to be cholinesterase inhibition. Furthermore, the effects of chronic TPP exposure are considered by BASF Wyandotte to be comparable to that of tri-o-cresyl phosphate, a well documented nerve poison. They have concluded that TPP should be handled as a "potent nerve poison" and that human exposure by any route should be controlled to a very low level. 2. M. & T. Chemical Company, our other supplier of TPP, has con ducted only short-term animal toxicity studies and has concluded that the compound has a very low order of toxicity. Similar findings are published in Industrial Hygiene and Toxicology by Frank A. Patty, 1967. In addition, M. & T. is not aware of any occupational health problems among their employees who have worked in TPP manufacturing areas since the 1960's. However, chloinesterase testing has not been conducted. 004940 CDB-96-77 -2- September 28, 1977 3. Du Font's Haskell Laboratories conducted TPP acute and sub acute inhalation toxicity studies in rats in 1975. There was no indication of nerve damage or any other cumulative toxic effect. CONCLUSIONS The BASF German studies raise serious questions concerning the toxicity of TPP. BASF Laboratories is the only research group that we are aware of which has used non-rodents as experimental animals. We are in the process of obtaining a complete translation of these studies. In the meantime, our Company position should be to handle TPP as a hazardous material. We have no indication at the present time that our handling of TPP has resulted in any health problems. Bishop is presently reviewing work procedures and personal protective equipment requirements to further assure employee protection. Employees handling TPP will be informed in a low-key manner of the potential hazard. Furthermore, we will be reviewing along with Corporate Medical the complete translation of the German studies. We will keep you well informed of any new information or safe handling recommendations concerning TPP. The information in this report should be treated as confidential, pending release from BASF. C. D. Barrett, Industrial Hygienist 004941 MATERIAL SAFETY DATA SHEET SECTION 1 MANUFACTURER'S NAME BASF AG Ludwigshafen, West Germany ADDRESS (Number, Street, City, State, and ZIP Code) EMERGENCY TELEPHONE NO. CHEMICAL FAM.LYTr.arylphosphin TRADE NAME ANO SYNONYMS FORMULA C18H15P SECTION II HAZARDOUS INGREDIENTS PAINTS, PRESERVATIVES, & SOLVENTS % TLV (Units! ALLOYS ANO METALLIC COATINGS PIGMENTS BASE METAL CATALYST ALLOYS VEHICLE ' SOLVENTS AODITIVES METALLIC COATINGS FILLER METAL PLUS COATING OR CORE FLUX OTHERS OTHERS HAZARDOUS MIXTURES OF OTHER LIQUIOS. SOLIOS, OR GASES TLV % (Units) % TLV (Units) SECTION III PHYSICAL DATA BOILING POINT tF.) 0 c 377 SPECIFIC GRAVITY (HjO - 11 VAPOR PRESSURE (mm Hg.) VAPOR DENSITY (AIR ll SOLUBILITY IN WATER 4- 1 unsolul >le PERCENT VOLATILE BY VOLUME (%) VAPORATION RATE ( = 1) appearanceanoooor coiorless crystals, inherent odor SECTION IV FIRE AND EXPLOSION HAZARD DATA FLASH POINT (Mollvxl usctll 180UC. ASTM open cup FLAMMABLE LIMITS EXTINGUISHING MEOIA q - and powder extinguisher * SPECIAL FIRE FIGHTING PROCEDURES UNUSUAL FIRE ANO EXPLOSION HAZARDS L.194 ^1 Ld Uel 004942 ' THRESHOLD LIMIT VALUE ate 1 ION V HEALTH HAZARO DAT q effects^f^ve^p^fi^ that Tpp s injurious to human health, also in acu :e animal fHals nparlv untoxi colocrical. Injuries onlv if reoeatedl ? emergency ano firstaio procedures consumed in higher quantiti as 1 / I i t SECTION VI REACTIVITY DATA STABILITY UNSTABLE CONDITIONS TO AVOIO 1 STABLE t t INCOMPATA8ILITY (Materials to avoid) i X oxidation materials, like chlorine i HAZARDOUS DECOMPOSITION PROOUCTS none l HAZARDOUS tt414 . POLYMERIZATION MAY OCCUR WILL NOT OCCUR CONDITIONS TO AVOID X ________________________________SECTION VU SPILL OR LEAK PROCEDURES I STEPS TO 8E TAKEN IN CASE MATERIAL IS RELEASEO OR SPILLED 1I WAST DISPOSAL METHOD SECTION VIII SPECIAL PROTECTION INFORMATION RESPIRATORY PROTECTION (Specify type! VENTILATION LOCAL EXHAUST MECHANICAL (General) SPECIAL OTHER PROTECTIVE GLOVES omen protective eouipment EYE PROTECTION no spec. ia,l pro.tecJtive clothing ____________________________________SECTION tX SPECIAL PRECAUTIONS______________ PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING please avoid Contact With Skin for a longer period of time OTHER PRECAUTIONS keep working - clothing clean 004943 Interoffice AlciiioraiMlif**! TO (Nam* and Location) J.A. BOUSQUET F ROM (Mama and Location) JAMES M. RAMEY OATE October 13, 1977 REFERENCE NO. jmr/57V77 CONFIDENTIAL SUBJECT; TR1PHSNYLPHOSPH1NE (TPP) TOXICITY A summary of a phone call with Oave Bouchard of^BASF is attached which confirms the information given us previously. In essence, Mr. Bouchard stated that TPP must be considered a potent nerve poison, based on animal test data. Exposure by any route must be minimized. After any contact with the product, the affected area should be thoroughly washed. Contaminated clothing should be either discarded or lapndered. BASF also lifted the "confidentiality" from the toxicity summary and recommended we discuss the report with customers and/or suppliers. BASF also recommended that triphenyl phosphine oxide (TPPO) be considered a nerve toxin, even though they have very limited data on this chemical.' " As you know, TPP and TPPO are present in the oxo-Butanol process at 8ishop and will be present in the Bay City process coming on stream In mid-78. We have had limited useage of .TPP at CCCTC but none at the present time l am told. There are several actions which should or have been taken: 1. Bishop should immediately impose work practice controls to include compulsory use of protective equipment to reduce employee exposure to TPP to an absolute minimum. Mike Neff has outlined appropriate procedures in a letter which will issue this week. These procedures have been reviewed and approved by the Division Industrial Hygienist. 2. Bishop should immediately initiate an industrial hygiene survey to determine airborne concentrations of TPP and TPPO. If the measurements show a significant potential for exposure, engineering controls should be implemented.. ' 3. Dr. Dixon should make a recommendation on medical surveillance for employees potentially exposed to TPP and TPPO i.e. should we set up a program to monitor for cholinesterase inhibition? 4. I have~dTscussed reporting requirements under Section 8(e) of TOSCA (Substantial Risk), with the Law Department. They agreed we can wait until BASF makes a decision on whether or not TPP qualifies under the present definition of Substantial Risk. If they report, then we are relieved of the responsibility. If they do not, then we have a decision to make. 004944 J.A. Bousquet G. ELAN EI CONFIDENTIAL -2- October 13, 1977 JMR/57V77 5. We should pass on toxicity information on TPP to Engelhard Industries immediately. This should be handled by F.J. Girolamo or someone in Division Central Purchasing. After Engelhard has had a chance to review the data, we probably need to schedule a meeting with them several weeks in advance of the next scheduled catalyst recovery operation. 6. Bishop should determine if the Butanol Heavy Ends stream which we are now selling contains significant levels of TPP or TPPO. 7. We will receive the complete toxicity report on TPP from BASF in about 2 weeks. This should be reviewed by the Corporate Director of Toxicology and the appropriateness of our action reassessed. "" JMR/to enc. C.D. Barrett W.M. Brown E.M. Dixon R.D. Damron W. Harrison P.E. Hlme J.C. Martin B.R. Miller M. Neff J L. Starr R.E. Suggs P.J. Volpe F.J. Girolamo E.N. Wheeler Corpus Christ! Bishop Bishop Bishop Bishop Houston SSD 004945 Summary of Phone Call - October 12, \311 From: Dave Bouchar - 8ASF Received a phone call from Dave Bouchard of B.A.S.F. on 10/11/77 relative to the toxicity of triphenylphosphine (TPP). The substance of his call was: 1. He released us from the "confidentiality" assigned to the toxicity summary on TPP provided previously by BASF. After reviewing the toxicity test data with the West German laboratory which performed the study, BASF reaffirmed its position that TPP "must be considered a potent nerve poisorf* based on the animal test data. Ex posure by any route must be minimized. After any contact with the product, the affected area should be washed thoroughly and contaminated clothing either discarded or laundered 2. Triphenylphosphine oxide (TPPO) should also be considered to be a nerve toxin, even though toxicity data on TPPO is very 1imited. 3. BASF has provided M&T Chemical Company (our major supplier of TPP) with complete toxicity information. 1 assume this relieves us of any responsibility of discussing with M&T. k. BASF has not observed any medical problems in employees exposed to TPP in the manufacturing process. (They have been manufacturing TPP for over 10 years.) Mr. Bouchard did not have specific data on exposure levels. BASF has not run cholinesterase inhibition tests on employees exposed to TPP. 5. BASF lawyers have not reached a decision on whether or not the neurotoxic properties of TPP should be reported to EPA under the "substantial risk" clause in Section 8(e) of The Toxic Substances Control Act. 004946 Interoffice AVeiiioniuiliiiii <2N 55 (REV.6 TO (Niith md Location) DATE Mr. B. R. Miller - NYO FROM (Nim ao<S Location) October 14. 1971 REFERENCE NO. C. D. Barrett - CCCTC; M. P. Neff - Bishop _CDB-109-77 MFN- 244-77 Subject: Informing .Employees of the Toxicity of Triphenylphosphine Baaed on the toxicity information recently supplied by BASF Wyandotte, Bishop employees will be informed (per Policy-Hazardous Chemicals, April 15, of the possible toxicity of triphenylphosphine. The attached information will be appropriately communicated to employees. Comments should be submitted to M.F. Neff. 1977] /mg Attachment cc: E. M- Dixon, M. D. - NYO J. A*. Bousquet - NYO Dr. E. N. Wheeler - NYO Dr. L. Starr - CCCTC Mr. J. M. Ramey - NYO C. D. Barrett, Industrial Hygienist M. P. Neff, 4t CM Supervisor 004947 ATTACHMENT A1 TOXICITY INFORMATION As a Company, we are not aware of any related health problems among employees handling triphenylphosphine (TPP) as a catalyst in the OXO Unit. Similarly, our two suppliers of TPP (M. & T. Chemical Company and BASF Wyandotte Corporation) are not aware of any health problems among their employees handling TPP. Despite this seemingly good experience with the material, we have recently received the results of some animal toxicity tests conducted in West Germany that raise serious questions about the toxicity of TPP. When animals were exposed to TPP under laboratory conditions, the compound proved to be highly toxic by affecting the nervous system. After studying these animal test results, we have concluded that TPP and triphenyl phosphine oxide (TPPO) may be potentially toxic in humans. The compound may act as a nerve poison and thus affect the nervous system. Even though the dust or vapor is nonirritating to the skin or eyes, the TPP~can be rea.4i.lyabsorbed through the skin. The compound- can also enter~thc body through-----the lunge Therefore, we need to eliminate both skin contact and exposure to the dust as well as practice good personal hygiene. MATERIAL. SAFETY DATA SHEET (Attachment A2) MEDICAL SURVEILLANCE (Dr. E. M. Dixon will provide medical procedures.) ' Employees who have been exposed to TPP in the past will be requested to undergo a simple medical exam consisting of a series of blood tests. The tests will indicate if the TPP has had any detectable effect on the nervous system. INDUSTRIAL HYGIENE MONITORING An air sampling study will be conducted to determine the amount of dust or TPP vapor in the work areas. . Test results will be used to determine the need for control procedures. ,<r STANDARD OPERATING PROCEDURES FOR HANDLING TPP ( & TPPO) (S.O.P*s will be reviewed) .QUESTIONS & ANSWERS 004948 ^Safsty - Data Sheet dAor vvyanuuue ourpurauun /.; ------- -* { V. ^Xvaodatte. Mich. 43192 ` 313 282-3300 . SECTION I TRADE NAME Triphenvl Phosphine CHEMICAL NAME Triphenvl Phosphine SYNONYMS Triphenyl CHEMICAL FAMILY Phosphines FORMULA (c6h5)3p MOLECULAR WEIGHT K T. t'\K :/-f>-/V.SECTIQN 11 ~..HAZARDPUSiNGREDENTS * Tt \f I NAME TOXICOLOGICAL OATA Triphenylphos phine Rat Oral LD5Q 0.8-1.6 g/Kg jj ; *.. .. - *-1 s -e ECTION IH ~ PH YSICAL DATA . / : Boiling Point -760mm Hg ~?{36QaC) 711 .*. ** Vapor Pressure, mm Hg 4? 20 C. (210 flC] 5 Specific Gravity (H2O * 1) 25 1.132 Solubility in Water Insol. sol. ir ale. benzee, aceto ne C CL. Appearance and Odor White crystalline solid rSM^^ECfidNJV ^FIRE AN D %XPLOSl6tT HAZARDEDATA* FLASH POINT (TESTMSTHQOI | T FLAMMA8IL1TY UMITS IN AIR - % BY VOLUME TEMFSHATUHE LOWER UPPER . --1 EXTINGUISHING MEDIA 63 WATER FOG 0 FOAM ITyul 0 CO* O DRY CHEMICAL OTHER SPECIAL FIRE FIGHTING PROCEDURES UNUSUAL FIRE ANO EXPLOSION hazaros Explosion hazard slight# i__v-apor_exposed_to flame can react vigourously with-oxidizing agents. EMERGENCY TELEPHONE NUMBER-"" aa 4 a a (201) 263-0200 004949 This number is available djys.'higfus. weekends, and holidays. ~........................SECTi''N"V -- HEAL *h"HAZARD ' \TA THRESHOLD LIMIT VALUE______Not established______________________ __________________~ _______ EFFECTS OF OVEREXPOSURE Possible slicht irritation to eves, skin and mucous membranes. Repeated slicht ingestion or absoprtion through mucous membrane or skin lead to nervous'system damage- Possible paralysis. FIRST AIO PROCEDURES EYES flush' WITH FLOWING WATER AT LEAST MINUTES Wash affected areas throughly with detergent and water. Consult a physician. Strict personal hygiene after each exposure greatly reduce possibility of harmful effects. : NEVER GIVE FLUIDS OR INOUCE VOMITING IF PATIENT IS UNCONSCIOUS OR HAVING CONVULSIONS i- STABILITY .. V! --'REACTIVITY DATA * UNSTABLE. CONDITIONS TO AVOIO STABLE . INCOMPATIBILITY __ Oxidizing materials_______________________________'_______________ ____ HAZARDOUS DECOMPOSITION PRODUCTS HAZARDOUS POLYMERIZATION MAY OCCUR OOES NOT OCCUR Ph-o----s--o----h---i-n---e----:-----P---O-- 7.5.----a----t--- --h---i--g---h-------t--e---m-----p---e---r--a---t--u-- "r--es 1 - 11 CONDITIONS TO AVOIO STEPS TO 86 TAKEN IN CASE OF SPILLS .-WASTE DISPOSAL METHOO CONSULT LOCAL AND STATE LAWS l /Section .yin SPECIAL PROTECTION. INFORMATION RESPIRATORY PROTECTION t VENTILATION LOCAL EXHAUST PlTSf G3TiT6Cl MECHANICAL (Generali Acceotable SPECIAL othgh 004950 PROTECTIVE CLOTHING Rubber gloves. Coveralls EYE PROTECTION OTHER remove contaminated clothing and launder after exposure. * z.~. _ SECTION IX -- SPECIAL PRECAUTIONS 3 PRECAUTIONARY LAQEUNG Tripehyl Phosphine May cause irritation of skin eyes, nose and throat. Repeated absorption harmful. Shipping regulation ICC, CG, IATA. Poison Label HAN0L1NG AND 3 STORAGE CONDITIONS Avoid breathing dust. Wash thoroughly before eating or smoking' Avoid contact with skin, eyes, and clothing D 004951