Document 6wxOEmmrLx2pM09aQ1qbbGgv4

MIC/D&P/R&D/N3A (CO./DIV./DEPTJ'LOCATlON) MONTHLY REPORT (TYPE OF REPORT! REPORT REPORT NO.: JOB/PROJECTNO.: DATE: JULY, 1979 TITLE: D&P R&D MONTHLY SUMMARY PRECEIVED J AUG 2 0 1979 M O riSA N T O CO*-ANY CtTRa L POSTS R-229 S T . LO UIS AUTHORS: H. W. Kilbourne, E. A. Matzner, G. J. McEwan, and J. D. Wilson ABSTRACT: D&P RM) MONTHLY SUMMARY - JULY, 1979 A U TH O R S: H- W. KJ.I b m u 'w * , oL fU TITLE: DESTROY WITHIN TWO MONTHS* TIME. TECHNICAL REPORTS LIBRARY, R2C, MAINTAINS A PERMANENT COPY FOR REFERENCE. C 02013 COMPANY CONFIDENTIAL z >a. This document is the property of Monsanto Company and the recipient is O o responsible for its safekeeping and disposition. It contains CONFIDENTIAL INFORMATION which must not be reproduced, revealed to unauthorized COPY NUMBER ABSTRACT ONLY D ETERGENTS & PHOSPHATES DISTRIBUTION Standard C. F. Callis M. W. Farrar H. C. Godt W. C. Hammann S. A. Heininger W. K. Johnson F. P. LaBelle J. T. Marvel F. E. Reese W. R. Richard C. W. Roos F. D. Shearin M. C. Throdahl R. L. Wasson R. W. Wise F. P. Zientv B2SA R2E T3B T3A G5EA G4NB G2WD TAB G4NH R2E RIB E2NB DID T3B 1010 T3A Other H. L. Epstein T. L. Gossage J. N. Haggart E. L. Head M. Hocking R. E. Keller I. Klaus R. C. Lebrett V. T. Matteucci J. P. Mieure M. E. Miller A. T. Smith/H. McKelvy P . F. Stordeur K. J. Wulfert H. H. Zeiss Managers, DSP, R&D Group Leaders, DSP, R&D N-Building Reports Technical Reports Library R1C B3SB 5040 B3SB 5045 TIB 1760 5040 B3SB T3B B3SB , G2WD 5040 ' B3SB R1C N3A N-Bldg N3A R2C -S7.1 > $ ZT1! m H V * \ 1 W hen no longer needed, or upon request, return th is re p o rt to ? e ^ Madder` . R2C. D&P R&D Monthly Summary -1- July, 1979 HIGHLIGHTS Manufacturing cost estimates for Builder U in the 25-30/lb. range look very encouraging. Oxidation studies to convert glycolate to glyoxylate are approaching the targeted 85% yield level. Distillation studies to separate glycolate/ glyoxylate are underway and additional work will be required to achieve the desired levels of separation. A process outline for expanding the NTA plant has been issued. In order to meet the target waste levels, the following changes in the process were proposed: 1) produce a higher concentration HMTA solution to allow mother liquor recycle; 2) remove volatiles from jet condensate for treatment in a surface unit; 3) reuse ammonia column bottoms; and 4) reduce the amount of liquid flow to agitator and pump seals by a recycle scheme. It has been reported that oxidation of NTA by hypochlorite bleach produces the ''unknown" environmental contaminant N-formyliminodiacetic acid. A sample of this material has been prepared and appropriate environmental and toxicological studies are underway. Continued analytical studies are needed to determine precise dioxin content in Chlorophenols. Analyses of dioxin contents of residue samples are complicated by interference by mixtures of chlorophenols so that it is as yet impossible to ascertain the precise level of the dioxins in the various samples. Additional analytical studies are underway to improve the methods of analysis.* The "field" tests with TCC in "clean" and in "natural" ponds indicate that TCC- in combination with natural systems where sediment is present is less detrimental in the environment than was indicated in laboratory concentration studies in the absence of sediment. Waste heat recovery from phosphoric acid plants received a minor setback when the first 31oss heat exchanger pipe failed prematurely. A second test is underway under more controlled exposure conditions and comparative corrosion tests are expected during August. Variations in DC?D with regard to fluoride stability have been traced to the kiln milling operation. The loss in ignition (LOI) has been shown to relate to fluoride stability and additional work is underway to devise conditions which will produce a uniform product. SAB Heavy recycle paraffin (HR?), freed of triolefins and aromatics to 99 wt. % by molecular sieve treatment:, was dehydrogenated, giving 14.9% mono-olefin conversion after 72 hours compared tc 10.5% for standard recycle paraffin. MO yields were lower (87%) compared to those for standard recycle paraffin (93%). Catalyst deactivation rates were nearly identical for the two materials. DP R&D Monthly Summary 2 July, 1979 An audit of the Avon Plant, which manufactures SAB catalyst, proved urgently necessary and very beneficial. Several process steps will be upgraded to assure specification catalyst quality. These include improved platinum analysis, better dispersion of salt solutions on the alumina and more controlled calcining conditions. Future efforts will also be required to improve industrial hygiene standards for operating personnel. Precalcination of alumina for low metals catalyst has been discontinued after 6,100 lbs. were treated. Manufacturing has decided to postpone the low metals catalyst test until the energy shutdown in March, 1980. ALKYLPHENOLS We have approved the use of Exxon propylene tetramer for alkylphenol production. This new source will augment our Texaco and Sun Oil tetramer supply which may become allocation-limited in the near future. A plant test will be made when the product can be obtained from the supplier. BUILDER U The CED estimate of Builder U economics based upon our partially demonstrated process was completed. At 10% ROI and 200M lbs./year, the 1979 price for purified product containing 92% solids and 8% water is 41c/lb., manufacturing cost 27c/lbAt 100M lbs./year, the price increases to 46c/lb. Elimination of the final puri fication step reduces these prices to 37<p/lb. at 200M lbs./year (manufacturing cost 25c/lb.) and_43c/lb. t 100M lbs./year, on a_ contained purified U basis. Base capital is $60-70M for 200M lbs./year and $40-45M for 100M lbs./year-T. In view of the performance data obtained by us and Procter & Gamble, these prices equate to a viable and realistic price performance. In our methyl glycolate oxidation studies a high purity (99.999%) silver catalyst has given us our highest yields to date. The best average yield over an entire run was 74.9% at 23% conversion, and the best single sample showed 84.0% yield at lb'% conversion. Use of pure 0 2 instead of air at the same 02/gIycolate ratio gives a higher conversion at essentially the same yield. A new moderate pressure reaction system has been set up in W Building for use in hydrocarbon oxidation studies under a broader range of conditions. Further work on our new organoaluminum EVE endcapping catalysts has shown that the cocatalysts formerly used can be replaced with a single commercially available material such as AlEtCl2. Raw material cost is essentially the same, but savings should result from cutting the number of catalysts to be stored and handled from two to one. Excellent yield, sequestration value, and biodegradability were obtained Acid forms of Builder U with different endgroups are surprisingly stable to acid hydrolysis so long as the end groups are not cleaved. Our patent claims will be extended to include acid forms. Solvay's polyhydroxyacrylate, a potential competitor of U with disputed biodegrada bility, shows Ca-*"* sequestration pertormance which steadily increases with increasing molecular weight. At a MW equal to ocr Builder U, it is only half as effective as U, but becomes comparable to 1 at 0- 50,000 (5 xU). Access to higher MW is limited by monomer purity nnei t er mechanisms, but we are already high enough to achieve '*'90% of r ;:>:i l i . e o i \ : ical perforhiance. *D&P R&D Monthly Summary -3- July, 1979 An interim report on the pilot plant production of methyl glyoxylate methyl hemiacetal will issue in August. Experiments demonstrating recycle in the thermal cracking of hemiacetal have begun. Using Vigreux columns, results to date are very favorable, giving 71% conversion in the first stage, and 76% in the second. Third stage cracking using recycle material and no distillation column yielded 68% conversion. Using no column in - the pilot plant should work, but additional temperature probes will probably have to be installed to insure proper control. Distillation following the cracking step has also given excellent results. As high as 92.4% monomer has been distilled using second stage recycle material and 'a 20 tray Oldershaw column. C0AL/01L MIXTURES (COM) Standard of Ohio (SOHIO) requested samples and information on our STEROX COM stabilizers. They are launching a COM evaluation program and learned of our work from D.O.E.'s Pittsburgh Energy Technical Center who recommended our stabilizers to them. Samples of BASF Wyandotte COM stabilizer, ES7071, and Fetrolite's stabilizer, Tol-Emul EM-230, have been obtained f r o m the field and will be compared to our best alkylphenol ethoxylates. Our analysis of the Wyandotte product shows it to. be an ethylene oxide/propylene oxide copolymer similar to other surfactants in their Plurafac line. DEWATERING AIDS Our nonyl- and dodecylphenol ethoxylates are more effective copper concentrate : dewaterers than the surfactants currently used by the mill in question. LAS surfactants were not effective with this ore. We also established that our dewatering aids can be effective on flocculated slurries, suggesting there may be a greater opportunity than we originally envisioned for dewatering of flocculated fineparticle slurries, such as coal refuse and sludges formed in S02 removal from stack gases at power plants. We plan to verify the good results with these sur factants on 2-3 additional copper concentrates. The current market for dewatering aids in the copper concentrate area is 2-4M lbs./year. INSOLUBLE SODIUM KETAPH03PHATE (IMP) AS A THRESHOLD AGENT It has been proposed that IM? could be used for its threshold value in scale inhibition in both industrial and consumer applications. Work has been initiated to define its performance in CaCo3 and CaSO* systems compared to other phosphates and the best Dequest products. This information is needed for patent coverage and potential customers visits. NEW USES FOR PHOSPHORUS A computer Chemical Abstracts search on gypsum additives produced 97 references since 1972, 23 of which deal with tne use of phosphates in gypsum products. We ar.d Commercial Development will review these applications with gypsum manufacturers to identify specific areas of interests, other need areas, and potential market sizes. 'd&P R&D Monthly Summary U July, 1979 The potential use of phosphate-based purification for sugar beets has been investigated through industry technical contacts and ruled out as a promising new use for phosphates because of cost and handling problems with the calcium phosphate precipitate. NEW DETERGENT PRODUCT A new powdered detergent product containing a low level of chlorine-based bleach is in a small consumer test in St. Louis. The composition is similar to CHEER and FAB but contains 1% available chlorine which would provide 15 ppm available chlorine in the wash water, insufficient'for stain bleaching but good *for whitene'ss maintenence on repeated use. We have not identified the chlorine bleach, but have ruled out chlorinated TSP. TSIS FOR BLEACH MITIGATION Clorox feels that the results from their wash and wear bundle tests are not promising enough to continue their TSIS program. We will soon receive a detailed report. We will now review TSIS interest with Procter & Gamble, Colgate, and Lever. We have also identified benefits from TSIS in protecting NTA from chlorine oxidation in zero-hardness systems, and will assess the significance of this finding before issuing our final recommendations on TSIS. NTA A Process Outline for expanding the NTA plant to 150M lbs/yr. at Chocolate Bayou has been issued and favorable comments have been received from CED and Manu facturing. We will now start to prepare Process for Engineering Design Report which is scheduled for completion next Donth. The criteria of the process for this expansion are developing ways to re duce the waste stream flow into the injection well to half, in order to meet the guideline. This is accomplished by four new innovations. 1. A new 1IMTA process is developed to use heat of reaction to preconcen trate the product solution, thus allowing more mother liquor recycle to the nitrile reactor. Significant raw material and energy savings are expected. 2. The vacuum jet condensate will be distilled to recover HCN and the cyanide-free water can be treated in a surface unit. 3. The ammonia column bottom will be reused in the process. 4. Agitator and pump seal water will be recycled. Plant tests will be made to demonitrate these innovations. D&P R&D Monthly Summary 5 July, 1979 In June, two scientists from SRI published an article describing a newlyidentified product from the interaction of bleach and NTA, and calling for a study of its safety. We have duplicated their preparation of this compound, called N-formyliminodlacetic acid (NFIDA). A biodegradation test has started, and when sufficient material has been accumulated, a mammalian toxicology screen will be carried out. We expect that it will degrade readily and prove practically non-toxic like its relatives NTA and IDA. The SRI workers reported it negative on the Ames test. CHLOROANILINES Nitration of ortho dichlorobenzene, the first step in producing 3,4-dichloroaniline, gives approximately 13% unwanted 2,3- isomer. This is now burned, at an annual cost (in disposal charge and yield loss) of nearly $1 million. Following a lead by M C I fs nitrochlorobenzene research group, we have found that use of acetic-anhydride as solvent for the reaction reduces the 2,3-content to about 8%. Because this solvent is expensive (compared to sulfuric acid) and its use would complicate workup, the economics would probably not be very attractive at this stage. Nevertheless, it looks interesting enough to warrant further investigation. During the second quarter, DSP and MCI-Process Chemicals cooperated on a plant trial of purified Monsanto ortho dichlorobenzene as raw material for 3,4-DCA. It has proved satisfactory, and has been approved for use. With capital investment to increase purification capacity MCI_vill be able to supply about 60% of our needs. Savings to Monsanto will be about $2M per year. CHLOROPHENOLS Analysis of six Santophen-1 samples produced after the change to "no caustic" distillation showed no detectable tetra- or higher-chlorinated dibenzodioxlns. Detection limit for the most toxic tetra- and pentachloro compounds was 10 ppb, 20 ppb for the others. Analyses for mono-, di-, and trlchlororiibeuzodioxins is hindered by the presence of serious interferences in Santophen-1. These unidentified impurities would hide up to 100-500 ppb (1000 ppb in one sample) of the three lower-chlorinated compounds; we can only set maximum limits. The new analytical method now under development should remove this source of uncertainty. TCC One of the key parts of our TCC environmental safety assessment,is a field study comparing its effects on fish and invertebrates in "clean" and "natural" ponds. Twelve 10-ft diameter, plastic-lined swimming pools, half with sediment on the bottom and half without, were filled with water and stocked with organisms. Five levels of TCC (1, 3, 9, 27, and 81 opb) were dosed into the water and its effects noted. (Two ponds were kept free of TCC as controls.) D&P R&D Monthly Summary -6- July, 1979 The last series of tests, of chronic effects on fish and of biomagnification, were finished at month's end. Final results won't be in until chemical analyses are completed, sometime in September. However, qualitative observations suggest that fish and invertebrates survive higher TCC concentrations in the sediment containing ponds. This may occur because TCC adsorb strongly to sediment particles, and thus becomes relatively unavailable to the animals. * i A pioneering study of TCC's metabolism in fish has yielded very interesting results. Catfish and bluegill appear able to detoxify TCC much as mammals (including humans) do, and eliminate it. Thus TCC will not build up in the food chain as do other water-insoluble chloroaromatics (like DDT, and PCBrs). Ed Schmidt, a Parkway high school teacher whose sabbatical year with us ended in June, developed techniques and equipment for fish metabolism studies that advanced the state of the art. With them he showed that catfish fed TCC absorb and eliminate TCC much as mice, monkeys, and men do - in feces and urine. In the process, their livers convert it to water-soluble "conjugates" that are mainly stored in the gall bladder prior to elimination. Over the next few months, Charles Lakinger of Clayton High, now on sabbatical with us, will finish this work, producing for the first time a complete picture of the uptake, metabolism, and elimination of an organic compound in fish. WASTE HEAT RECOVERY FROM PHOSPHORIC ACID PLANTS We have now accumulated 3 weeks experience in experimental operation of the water cooled metal heat recovery tubes in the crossover of the refractorylined No. 2 acid plant at Long Beach. Repeated failures of the water level control system in the test loop and of the electrical heaters on the con densed acid drain sump subjected the 310 SS tube to a variety of conditions well beyond those for which it was designed and it failed"after 2-1/2 weeks total exposure. The failure was at the liquid level line in the condensed acid sump and hot in the heat exchange test section itself. The condition that led to this failure was that condensed acid at less than 89% P305 collected in the sump during periods of low temperature operation of the acid plant with excess air of 300% or more. This weak acid stratified and remained in the sump floating on the denser pool of high concentration acid and corroded both the tube and the sump in a distinct wash line. The sump was modified to allow complete drainage by removal of the internal trap and fabrication of an external trap. A 316 SS tube was installed for the next test period. The water level control system has been modified for greater reliability and a sight glass has been installed on the surge tank to allow verification of water level. Both tubes exposed earlier are being returned to St. Louis for metallurgical examination. We have also asked the Research Center Instrument Group to develop an instrument to monitor concentration of the condensed acid drainage. TM Cl SCAPE CAKING Procter & Gamble has confirmed that our reduction in calcium and magnesium levels in STP produced at Long Beach i s reducing the summertime caking of CASCADE on the grocery shelves to an acceptable level. A July survey in Phoenix showed 83% of the boxes were lump-free compared with less than 50" last July. *D&P R&D Monthly Summary -7- July, 1979 At Carondelet, where almost all of the calcium and magnesium is attributable to unacceptably high levels in the Stauffer soda ash used as a raw material for STP, we have made two experimental runs aimed at reducing the raw mate rial calcium level. In one run, half of the necessary sodium was supplied as NaOH. In the second run, a low-calcium soda ash, supplied by Stauffer, was used as the sodium source. Analytical results are not yet available at month end, but it is expected that both runs produced STP with 75-100 ppm calcium instead of the current normal product level of 140-160 ppm. DCPD REPLACEMENT FOR COLGATE DENTAL CREAM The results of several recent plant tests, together with, laboratory studies, point out that the kiln milling operation appears to be a significant con tributor to the variability of our DCPD products with regard to fluoride stability. The loss on ignition (LOI) of product has been shown to be an important variable for fluoride stability. Based on plant lot samples, we could correlate increased fluoride stability with increasing LOI, even with in the present specification limits for LOI. Laboratory work in support of this correlation suggests that dehydration takes place during kiln milling and the dehydrated DCPD thus formed is detrimental to fluoride stability. The results to date strongly suggest that: the sojourn in the kiln mill should be shortened to reduce dehydration. Initially, the fluctuation of end pH in wet mixing was suspected also as one of 'the culprits. In spite of wide pH fluctuation, plant samples did not show the trend of forming basic calcium phosphate with high pH. Surprisingly, few lots had higher than theoretical titration (TV), an indication of basic calcium phosphate. Further programs to reduce the variability are being carried out by Research and Manufacturing. PERSONNEL Appointments - M. M. Crutchfield was appointed to a "TAG Recognition Committee,11 charged with reviewing existing systems for recognition of technical accomplish ment and recommending a new system to the TAC. Patents - U.S. Patent 4,162,236 issued July 24, 1979 to H. E. Feierstein and M. E. Davis, "Detergent Compositions Containing Mixtures of Alkyl Benzene Sulfonates as the Detergent Active." Statistics Exempt Non-Exempt 53 10 Total 63 H. W. Kilb.vjrne, E. A. Matzner, G. J. McEvan, and J. D. Wilson