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WORKS LEAD DROSSES By? J. Jackson 2/69 - 12/69 E. [. DU PONT DE NEMOURS & COMPANY 256 VANDERPOOL STREET NEWARK, NEW JERSEY Soria! No. KN-70-1 Copy No. I NEWARK PLANT ft A PIGMENT COLOR RESEARCH REPORT \ UTILIZATION OF LOW COST CHAMBERS WORKS LEAD DROSSES Period Covered February, 1969 - December, 1969 {Part Time) FILE: 211 DATE-. 1/30/70 NJ 14071 DUP050081 835 KN-70-1 1. Numerical Pile 2. Research Office Pile, Newark 211 3. Newark Library Pile 211 4. M. Hunt/E. Gonick, Pigments, Wilmington 5- W. S. Struve 6. F.F.Ehrich/E.F.Klenke/B.H.Perkins/Newark Library 7. A.R.Hanke/.E.S.Jaffe/Newark Library 8. p.J.Monahan, Newark (vital Records) 9. R.H.Wetzel, J.F.Maurer, J.W.Minnich, W.A. West 10. M.C.Crossan, Newport Research Pile 11* N.G.Fisher, Central Research, Wilmington 12. J, Jackson 13. Extra 14. Extra 15. Extra ' 16. Extra NEWARK PLANT PIGMENT COLORS RESEARCH REPORT SUBJECT: UTILISATION OP LOW COST CHAMBERS WORKS LEAD DROSSES PERIOD COVERED:/j February, 1969 - December, 1969 (Part Time) '/, Mi*? SUBMITTED BY v'' J. fi|C^N ^ DATE SUBMITTED: 12/15/69 APPROVED BY: wSs^J ATE RELEASED: 1/30/70 ABSTRACT This report summarizes a brief review of the suitability of Reverbatory Furnace Fume Scrubber Solids available from Chambers Works operations for the manufacture of chrome yellows. In the opinion of the writer, the lead nitrate made from this material offers very considerable promise as a lower cost route to a substantial portion of our N-41 requirements. Maximum savings per year would be $78,750 assuming a 7//lb. spread between Orchem and purchased lead price. Investment and operating costs would alter this figure. DUP050081 836 TABLE OF CONTENTS I.. INTRODUCTION II* SUMMARY AND CONCLUSIONS III. RECOMMENDATIONS IV. PATENT STATUS V. EXPERIMENTAL VI. REFERENCES Page 1 X 2 2 2 4 DUP050081837 X. INTRODUCTION * The availability of 2 to 3,000,000 lbs./yr. lead of low cost, by product, lead residues from tetraethyl lead manufacture at the Chambers Works has repeatedly given rise to inquiries as to its potential use in the manufacture of chrome yellows. The presence of large amounts of Cl (PbOCl2; Pbels? NaCl) has complicated the utilization of this material as a raw material for lead pigment manufacture, and its use has never been adopted. A more complete discussion of the properties of the bulk of this material is given in my memo "Chambers Works Lead Dross", 3/17/69 (Ref. #3 - copy attached). In this memorandum, I summarized my thoughts on possible means of converting this material to a more suitable form. Further chemical description of one source of this lead dross, "Accelator Concentrate" is given in J. r . Day's letter to me of 3/25/69 (Ref. #4 - copy attached). A review of the situation with j. R. Day of Orchero led to the conclusion that a cleaner source of lead (lower insoluble ClTM, Carbon residues, etc.) might be of more interest to the Pigments Department. The Orchero material known as "Reverberatory Furnace Fume Scrubber Solids" was considered to be of such a character. Approximately 1.26 million lbs./year lead basis are available from this source (Ref. #5, 6 - copies attached). The basic value of these residues to Orchero is that of the lead content equivalent, less toll charges for smelting the material. At the time of this report, this represented about 5 to 6//1b. During this period, Pigments Department was paying approximately 13-14//lb. of lead. The spread between these values would determine the maximum allowable costs to cover Orchem's and Pigments' required investment and manufacturing costs to recover and convert this material to a suitable alternative to Pigments (Pb(N03)2 solution (n-41). Orchem has supplied us a transfer price of $.06/lb. Pb in their letter of 7/31/69 (Ref. #6 - copy attached). XI. SUMMARY AND CONCLUSIONS 1. A possible source of 1-1/4 million pounds of lead equivalent (substantially in the form of 2PbC03.Pb(0H)2 is available from Orchem's Reverberatory Furnace Fume Scrubber Solids at $.06/lb. Pb. 2. This material has been converted to Pb(N03)2 by solution in hot concentrated nitric acid, adjustment of pH and filtration to remove excessive amount of Fe++, Fe*3. 3. This lead nitrate was converted in a 100% form and in 50% dilution with regular Pigments Department Pb(N03)2 (-41) to a Y-758-D type primrose yellow. 4. The pigments obtained were satisfactory in yield, very close in masstone, skindown, tinting strength, and Fadeometer lightfastness. *Ref. #7 - Received after report written indicates a potential of 4-6 million lbs./yr. DUP050081838 -2 - III. RECOMMENDATIONS In the writer's opinion, this work should he extended in cooper ation with Orchem to determine (1) the suitability of additional samples of these solids, (2) the quantitative conversion of the samples to soluble lead nitrate, and (3) the economics versus Pigments' routine manufacture of N-41 solution. IV. PATENT STATUS in the writer's opinion, nothing of a patentable nature was developed during these studies. Orchem*s considerations may be different from ours. V. EXPERIMENTAL A. Conversions to Pb(NO)a J. R. Day of Orchem supplied two samples of "C" Furnace Fume Scrubber Solids (Ref. #5)s 1, Dry sample CWNB 2794-178 440.5 grs. 5/26/69 .33 % Cl" 70 % Pb dry basis 2. Wet sample CWNB 2794-1791073,8 grs. 5/28/69 44 % Hj.0 1.7 % Cl" 70% Pb Dry basis These samples had been collected and washed to remove the bulk of water soluble cl**. Orchem x-ray data suggested they are essen tially 2PbC03.Pb(OH)2 plus SiOs. work Up of Samples Sample A. The samples were attacked with HNOs on the following basis s Celc. # Pb in 2PbC03.Pb(0H)2 - 621 80% Pb 775.67 Assume 6 mols HNO3 will dissolve 1 mol 2PbC03.Pb(0H)2 Weight of sample 440.5 * .567 mol basic lead carbonate - 775.7 assuming all sample is 2PbC03.Pb(QH)a Calc. HNO3 m Use .567 x 6 x 63.02 * 214.5 grs. 100% HN03 214.5 x 70% Pb * 268 gr. 70% HNO3 .7 80% Pb Calc, yield pb(N03)2 would be: 440.5 x 70% Pb x 331^ 492 grs. 207 DUP050081 839 Procedure: To 1250 cc H20 Add 268 gr. 70% HN03 Heat to 140F. - Add Sample A slowly Temp, rose to 165F. pH a .6 Heat to 195-200F. - Held 1 hr. Dilute with 250 cc HsQ Filter - Wash 300 cc H20 Save solids 129 grs. Dry WtJ (Very high - does not fit analysis) Save filtrate and wash water Total filtrate <= 2169 grs. Be* s* 23.9 Sp.gr. * 1.1973 gr/cc .2297 Assume Reg. N-41 sp. gr. = 416 gr. (Pb(N03)2 vs Calc. 492 gr. Actual analysis - solution ex sample A contained 18.34% Pb(N03)a 397 gr. vs calc. 492 Conclusion: Amount HN03 used inadequate for complete solution of Pb in this dry sample. Sample B 1073.8 gr. x 5.6% solids = .775 mols 2pbC03. 775.67 Pb(OH)2 Calc. HN03 .776 x 6 x 63.02 x 70% Pb a 366 gr HN03 (70%) _________ 80% Pb ,7 Calc. Pb(1103)2 1073.8 x .56 x .7 x 331 a 674 gr (Pb(N03)a 207 Procedure: To 1300 cc Ha0 Add 366 gr 70% HN03 Add presscahe slowly at 130f - little temp, rise Heat to 200F. - Hold 1 hr. pH 3.85 after 1 hr. Add additional 20 cc 70% HN0S - pH 3.5 Add additional 10 cc 70% h n o 3 - pH 1.6 Dilute with 200 cc H20 Filtered -- washed Save total filtrate - 3159 gr. Weight of dry residue = 190 gri (Highi) Assume N-41 Be* sp.gr. = 1.2447 gr./cc Yield as calc. = 718 gr. Chemical Determination Pb(N03)2 * 23.05% Yield = 730 grs. versus calc, yield on assumption of 70% Pb at 56% solids * 674 grs. Purification of Sample "B11 To filtrate of B add 82 cc 1% NaOH pH changed from 1.6 - 2.9 Fe(OH)3 formed - Supernatant liquid showed no test for Fe'*''* with NH* SCN Filtered - recovered1' 305C^,gr. solution Chemical analysis 22.47% and iron free. DUP050081840 -4 - Discussion; it is obvious that the composition is not quite that assumed 2Pbcc>3.Pb(OH)2 since HNO3 requirements were not as calcu lated. Moreover/ soluble lead nitrate recovered was very high since there was considerable insolubles remaining. TESTING OF B - PURIFIED LEAD NITRATE 50% Orchem B A-Control Purified 100% Orchem B 100% N41 50% N41 Purified Pb(N03)a equiv. 165.5 gr. 165.5 165.5 N41 537 gr.soln 263.5 Orchem (B) Purified 367.5 740.0 In Total 1345 cc H2O/80F X X Adjust to pH 4.1 X X Add - stir 1 min. Na2C03 25 gr/100ccH20 X X Add in 40 seconds solution Na2Cra07.2H20 (N-0) 54 gr. X X Na2S03 (N108) 5.54 gr. X X H2SO4 (100% N-27) 3.31 gr. X X Na2F2 (N--518) 1.45 gr. X X Al2(SO4)3I8H2O (N-15) 4.76 gr. X X Dissolved in Total 1345 cc/80 X X pH 1.85 X X Stir 8 minutes pH 4.35 4.2 4.2 Add-stir 1 minute betw/een additions Na2S04 5 gr/20cc X X Na2C03 4 gr/12cc X X Na4P207 (N-479) 2 gr/lOOcc X X PH 6.7 6,5 6.( Heat to 180CF. - Hold 20 minutes, Add - Stir 1 minute bestween MnS04.H20 (N-336) 1 gr/50cc X X Ala (S04) 3.18H2C) 17 gr/68cc X X Na4P20~* 2 gr/lOOcc X X Na2C03 1 gr/4cc to pH 5.1 Filter - wash to 2500 ohm/cm2 Dry 180 16 hrs. Bake 265 2 hrs. Pigment Yield 164.9 gr 164,1 166.1 Tested colors by rubout and found all to be similar in color and Fadeometer lightfastness, vi. REFERENCES - copies Attached 1. Utilization Low Cost Chambers Works Lead JJ 2/28/69 2. BAH - RJL Utilization of Low Cost Chambers Works Lead 3/5/69 3. chambers works Lead Dross j j 3/17/69 4. J.R.Day - Jj Composition-Accelerator Concentrate 3/25/69 5. J.R.Day - JJ Chambers Works Reverberatory Furnace Fume Scrubber Solids 6/9/69 6. J.R.Day - JJ Transfer Price of Reverberatory Furnace Fume Scrubber Solids 7/31/69 ?4 J.R.Day - JJ Accelator Concentrate as a Lead Source 1/19/70 dc DUP050081841 CC: M.Hunt/E.Gonick, Pigts.,Wilm, W.S.Struve/A.A.Brizzolara R.H.Zabel, Pigts., Wilm. W. J.McClure/R.A.Hageman R.E.Roberts, Engr., Louviers /JS.Jackson / NNeewark, New Jersey / FFeebruary 28, 1969 UTILIZATION OF LOW COST CHAMBERS WORKS LEAD 0 The availability of 30 - 40,000 lbs. of low cost lead per day at the chambers Works has repeatedly sparked inquiries as to its potential use in the manufacture of chrome yellows. It is my understanding that this material is valued at approximately $ cents/lb. lead versus our approximate cost of 13-14 cents/lb. (R.E.Roberts). In the past, consideration has been given to the conversion of this type material and other Cl~containing lead sources to satisfactory N-41 (lead nitrate solution) which can be utilized to make our standard lead containing colors. The presence of considerable quantities of Cl" (PbCla ?) makes this procedure difficult,and relatively costly,and it has never been adopted. I propose that thought be given to utilization of this raw material as a source of lead nitrate for low cost high volume medium yellow to be used in traffic paint and,possibly, comic strip inks. These outlets are presently not available to us because of the competitive pricing situation. I believe that there is a good chance that chloride impurities could be tolerated in pigment for traffic paint since its effect on particle size and color would be less difficult to overcome than in the case of our standard pigments. (Halogens are utilized in the chrome solutions to make these pigments.) I have assumed, in this suggestion, the absence of metals Other than lead,and the availability of suitable equipment for manufacture. The latter point may present problems, but I believe that the idea is worthy of consideration by all concerned. RESEARCH ASSOCIATE dc t. DUP050081842 W* J, Me Clure W. S, Struve.. ** Newark, Mew Jersey March 5, 1969 PR. R. J. LOMBARDO Pigments - Wilm. UTILIZATION OF LOW COST CHAMBERS WORKS LEAP * Utilization of Orchem's low cost lead residue for making traffic paint Chrome Yellows Is not economically attractive because (1) the Newark plant will have no excess inorganic capacity until at least 1972, (2) these products will be less profitable than our current Chrome yellow line. 1 Traffic paint yellows sell for approximately 129 less than market price. The use of this scrap lead would lower our ingredient cost about 39 per pound* It is therefore more profit able to make the high quality yellows. RAH:mkb ORIGINAL SIGNED BY R. A. HAGp;maN R. A. HAGEMAN ASSISTANT PLANT MANAGER Reference J. Jackson's suggestion 2/28/69*' # {&* Ok. U+ Cfjf* DUP050081843 CONFIDENTIAL CCj W.S. Murray, Orchem, Chambers Works C.E.Dailey, H.Day, " " "" "" J.Day, " "" R. E.Roberts,,Engr., Louviers w. j. McClure/R. A. Hageman, Newark M. Hunt/E.Gonick, Pigts., Wilm. W.S.Struve/A.A.Brizzolara, Newark J. Jackson /Newark, New Jersey March 17, 1969 CHAMBERS WORKS LEAD DROSS Ref: JJ - Utilization Low Cost Chambers Works Lead - 2/28/69 RAH-RJL " " " " " " - 3/5/69 On 3/12/69, H. Day and J. Day of Orchem-Chambers Works called * me to discuss possible utilization of a lead containing residue from the manufacture of tetraethyl lead. Hie following facts were ascertained. Supply 1. 2-3,000,000 lbs. Pb content per year available on a continuing basis. This represents a minimum of 14% and a maximum of 21% of Newark's 1968 lead requirements. Chemical and Physical Characteristics 1, Highly particulate material in the form of a sludge containing approximately 50% water. Solids contain silver lead carbonaceous material lead monoxide lead sulfide and sulfate equivalent to .5% $ basic lead carbonate lead oxychloride lead alkyls Cu compounds .3% Cu Bi " .3% Bi Fe " .3% Fe Magnesium hydroxide 3-4% Aluminum " 1-2% The presence of lead alkyls would necessitate some processing on the part of Orchem in order to insure safety in handling this mater ial . I outlined, in a general manner,, our manufacturing scheme for conversion of lead to lead nitrate, and spelled Out present purifi- ^ cation schemes. In addition, I suggested that a review of my KN report (51-44 - "Examination of Lead Bearing Residues for Conversion to Lead Nitrate") might be of some use. i DUP050081 844 In reviewing this situation, it appears to me that a possible approach to utilize this material would involve a scheme as follows* Filtration 1, Slurry (a) filter with filter aid if necessa (b) wash to remove bullc of halogen (c) dry. 2. Treat in Furnace - Feed to melting furnace under oxidizing conditions * (a) to slag off Mg and A1 possibly as silicates, (b) to oxidize lead alkyls, ('c') t'o 'oxi"di.z....e........l..e....a....d........s....u....l..f...i.d.....e.........to PbSO*' ri* Gr* Under reducing conditions; (a) Might be needed to convert PbSO* to Pb if .suffeih amount formed. Wr 3. Dissolve in Nitric Acid This impure Pb/Pbo/PbS04 could then be dissolved in nitric acid, treated with scrap iron to reduce Ag, Cu, Bi to metallic state (for recovery of metallic values) and filtered. 4, Subsequent Pb(^o3)2 solution could probably be purified of iron, by oxidation to Fe 3, adjustment of Ph and filtration. Such a Pb(N03)2 even if it contained small amounts of(1% Cl / Pb(n o 3)z) might be convertible to satisfactory medium yellow. The major question would appear to be one of economics. If the value to Pigments Department of pure Pb is $.13/lb. and recovery value of sludge to Orchem is $,05/lb. of lead* only $.08/lb. is available for these operations. This represents $240,000 per year for additional cost of processing and return on needed investment. JULIUS JACKSON RESEARCH DIVISION These approximate figures are based on a high spot value for lead content supplied by R. E, Roberts, Other considerations involving Orchem*s processing might lower this figure. JJsdc DUP050081845 fi. X. <3u Font tie Nemours & Co.* Inc. Ch inhere Works Da'-'jpvn.terv New Jersey OG023 vh-onu, h'lm, JB.idg li'-r >V3m. Bldg. . .Tectr-on its" Droartirrent Kotfjertrcy 7`2>o possibility of your plant using our Accolator concentrate F:s p. t?ureo of lead for load chromate manufacture is being explored. Daring cur recent phone conversation on this subject* yen revert tod the attached composition data. We have already ' started to loo?; more closely at the chloride content and the offsctiwneea of reslurrying to remove it. DUP050081846 COMPOSITION ACCFLRTOR CONCENTRATE % kverace Nol of Samples TrCu-a Lor.'3 43.3-81.5 2.6-28.2 30.B-56.1 64.4 19.3 39.8 25 10 10 Cl at JEa^r-blc Sb) S0]t, m 5 8 t C *Kg ia KgSOH).} hi BI 0.6-37.2 3.5-- 3.8 (e) 0.3 m 22.4 0.55 0.11 3.6 1.6 0.026 1 4 1 1 2 1 1 '1 (a) it -ic 'vi forms Include lead aulfato, lead sulfide, lead oxide, lead c::ychlord, basic' lead carbonate, and lead alkyls the latter are about 10% by weight of the total solids. SbJ Kostly graphite. Sc5 `bill bo determined. i (dj Unknown but small - estimate <0.1%." \7. JR. Day Easch 25, 1869 erne DUP050081847 I, du Pont de Nemours & Co., Inc Chambers Works Deepwater, New Jersey 08023 T. J, R. Stephens, Adm. Bldg. W. S. Murray, "Freon" Office 7nne P, 1059 Ju 1 ivi & Jr.eh son Pigmr.nts Department Research Division ITewa::k, Naw Jersey CHAMBERS WORKS REVERBERATORY FURNACE FUME SCRUB OF,R SOLIDS _ ________________ As nuv.sr 7 in our phone conversation on May 19 we are sending und r separate cover two samples of our reverberatory furnace fuvi ? scrubber solids. Both samples have been filtered, ros.iv.rriocl in distilled water, filtered and given three u.iiv illed water rinses. One sample has been dried and the other is as removed from the filter. Analyses are as follows: % HaO % Cl Wfc., g. Dry Sample Wet Sample 44* 0.33 1.7* 440 1073 *On dry basis. A ,vi JR. Dayf Pi.--.k ':3& Department Tatra Ethyl Lead Area : cmc DUP050081848 E. i. du Pont da Nemours ft Co. r Inc. chambers Works Deepwater, New Jersey 08023 V. R,, Hnrka, Orchem, Wilm. G. N. Ross, Orchem, WiXlti. w,, ,f- McClure, Pigments, Newark J n, oom;>v. Pigments, Wilm. w. ; ?, Cogdill, t '.E.I,. office C, E, Dellay, T.E.L, Office W. S. Murray, "Freon" Office H. L. Smith, Adm. Bldg. T. j. P, Stephens, Adm. Bldg. T. W. Torokowit, Adm. Bldg, tn/ss July 31, 1969 J. Jackson Pigments Department Research Division Newark, New Jersey TRANSFER p r ic e o f s e v e r b e r r t o k y f u r n a c e HXim SCRUBBER SOI,IDSh _____________________ This letter is in answer to your verbal request for a transfer price on our reverberatory furnace fume scrubber solids. We understand that this material may be suitable as a lead source for certain grades of lead chromate pigments and that in order to determine if an additional laboratory program on your part is justified, some idea of the cost of our material is required. After consulting our Control Department, we propose the follow ing method for determining a transfer price based on the best course of action for DuPont. Orchem will establish the cost of collecting and preparing the material in a suitable form for your use. Pigments would determine the additional costs incurred by handling our solids. The cost of shipping from Chambers to Newark would be added to these two numbers. If the total is .loss than the cost of new lead, and the likelihood off this being the case seems probable, then the savings could be split equally between the two departments. As a starting point, we have developed a rough figure off $0.06/ lb. lead for preparing the shipment of fume scrubber solids in a wet cake form. This figure considers the present recovery method and purchase of new lead to be a "stand-off", i.e, the recovery costs are equivalent tq the value of the lead in these solids. Therefore, our cost cf preparing the material DUP050081849 Pag? P ffuly 3.1, 1963 J. .Inch son Transfer i;.v| co of Reverberatory Furnace Ftrme Scrubber Solids for you ineludes only the operating cost of the new equipment needed for collecting and concentrating the solids (see attach'd calculation). Freight costs are estimated at $0.01/ lb. I d. The ':ho-/e two figures, along with the additional figure which you b elopr should indicate whether or not you might be inter' : ted in pursuing this work further. When you have deter, vlnod this, we would appreciate knowing your thoughts so that ? enn further refine our estimated cost or seek another or. - of notion.* Proco v. Department Tetxv Hithyi Lead Area ii, g. havener! Control Division Orchetn f Wi Xmington ) .-.D i 1 '.'u attachment DUP050081850 Attachment COLLECTION OF FUME SCRUBBER SOLIDS T.E.I.. Area ~ C.N. Operating Cost Basisi Investment $350,000 Amount of Lead ~ 1.26MM Ib./yx. Materials Operating Labor Repair Labor Direct Overhead Repairs Material Depreciation Operating Cost ' $ 10,000 14,000 6,000 10,500 35,000 Y5',BOO Operating Cdst/Xb. Pb 75,500/1,26xl06 ca. $0.06/lb. Pb 1RD sc 8/1/69 DUP050081851 0R.49II MU-210 -1 rsTAiusKEoiso? E. I. d u Po n t d e Ne mo u r s 61 Co mp a n y .INCORPORATED CHAMBERS WORKS DEEPWATER, NEW JERSEY 06023 D. F. McVaugh, Qrchem, Wilm. . W. W, Cogdill, T.E.L, Office G. E, Dailey, T.E.L. office W. S. Murray, "Freon" Office E * J Roszko, T.E.L. Office H. L, Smith, Adm. Bldg. T. W. Tomkowit, Adm. Bldg, T. J. R. Stephens, Adm, Bldg. January 19, 1970 J. Jackson Pigments Department Research Division Newark, New Jersey ACCELATOR CONCENTRATE AS A LEAD SOURCE FOR CHROMATE PIGMENTS______________ This letter records the sense of our recent telephone conver sation, It is understood that the major reason for the Pigments Department's lack of interest in our reverberatory furnace fume scrubber solids, which are Cl-free, is that this source (estimated at 1.25MM lb, lead/year) would provide too small a portion of the total requirement (around 12MM lb./yr.) to bother with. You indicated, however, that Accelator concentrate which is available in larger quantities (4-6MM lb. lead/yr.) would be of interest if it could be made Cl-free (previous_analytiCal data have indicated about 4% Cl). In recent high spot tests one of our chemists, R. Moore, has found that the Cl can be removed from Accelator concentrate by dissolving in HNO3 and refluxing to remove the HCl formed. Since your comments were encouraging, we propose to continue work with this material and will send you a Pb(N03)2 solution for end-use testing. J. R. Da Process Department Tetra Ethyl Lead Area JRD j emc BETTER THINGS FOR BETTER LIVING . . . THROUGH CHEMISTRY DUP050081852 o U o* a ca ss 1 C/3 2 8 a 8` r I ' & C/J < e go ?s e- ^ i 0> ^ 13 PH o 0 1 | DUP050081853