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N* A A E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Serial No. KN-53-27 Copy No. ^ RETURN TO JACKSON LABORATORY FILE ROOM NEWARK PLANT PIGMENT COLOR RESEARCH REPORT "KOHASTKAL" BLUE - "AF" SULFATION Period Covered OCTOBER 1950 - APRIL 1951 FILE DATE. 223*41 9/24/53 | A NJ <W J Serial No* Copy No* KN-53-27 COPT TO: Numerical Nil# Research Pile,(223 *41) Libras Pile ( 3ii 3. B. Tully/A. Siegel J* H. Cooper F. F* Bhrich #14 Building B. F. Klenke, Newport M. 4* Perkins* Jackson Laboratory V* J. Clan, Chambers Works, Vila* Baetra Extra NEWARK PLANT PIOaSHTS COLOR RESEARCH REPORT FINAL REPORT "MOKASTRAL" BLOB - AF SULFATION PERIOD COVERED: OCTOBER 1950 to APRIL 1951 c h a r t s : a -i -c -20 SUBMITTED BT: F* F* ENRICH APPROVED Bit COOPER DATE SUBMITTED: S/26/53 DATE : h k n mi : DUP050069500 -1 KN-53-27 INTRODUCTION: Periodic sulfation difficulties at the Newport Plant have affected the production rate of CPC Slue crude* from the time of the plant startup* this hottleneek originates primarily from the variable behavior of the sulfation operation* particularly as it affects the physical characteristic# of the sulfated mass* The original plant process is based on the forestion and gravity settling from the kerosene reaction slurry of a dense* granular CPC sulfate* and subsequent removal of the kerosene by drainage IS hour cycle) through the sullkted twit in a basket-type filter. Optimum process performance depends largely on ths sulfuric acid usage* Both ths quantity and propsr distribution of ths acid by agitation ate* ars important to insure ths formation of a CPC sulfate with physical characteristics which will permit ease of transfer to ths sulfation basket and ths most efficient removal of the kerosene by drainage without loss of color* The amount of add required to fulfill ths above requirements in practice varies from batch to batch aa a result of Varli&ifW^ acid and blue synthesis and consequently gives rise to unpredictable and often difficult sulfation behavior* ' Another important consideration la that the basket presented a very serious source of contamination by virtue of the accumulation of iron rust therein* This was undesirable* because the rust could enter the CPC at this point and reault in deterioration of quality In both Blue and Green* Also, the corrosion of the basket necessitated periodic replacement* resulting in production delays and high maintenance coats. In addition to the above factors, the need for a kerosenefree erode pressoaks was emphasised by ths Kerch. 1951 fire 111 the Hewport Plant crude drying area. n>s *AF" or acid-flushing process is capable of giving a kerosene-free crude presscake. SUMMARY ABB OCMMMMl The "AF* or acid-flushing process involves the direct acid-pasting (complete solution) or soid-slurrying of copper phthalo- oyanine pigment directly from the hot kerosene synthesis mass without the prior Isolation of ths crude* Ths products isolated in this manner are strong, intense and green against current etandarde and exhibit in paint systems the undesirable properties associated with acid-pasted materials as contrasted to solvent-milled products prepared by the standard Newport process* Even after solvent-milling of the *A7" materials, the paint mill-bases are heavy and suggestive of reactivity* Many of the enamels flocculated severely end* though the tinctorial properties had been Improved, the working properties had deteriorated. DUP050069501 . -2 KH-53-27 The following possible advantages in tha acid-flushing process in contrast with tha standard sulfation prooaaa ara suggested by tha limited experience with its operation* 1. laid usage aa it affects tha physical oharactariatica of tha CPC sulfate granules ia not critical* 2* Tha praaant d-hour kerosene drainage pariod ia eliminated* So basket-filter equipment ia naoaaaary. 3 A substantially keroeene-free material ia obtained which offara tha following advantages* a - aaaa of hydrolyala (no balling etc*) b - mora efficient extraction and filtration of tha crude (no karoaana to hinder wetting of tha pigment)# 0 - shorter oven-drying oycla for tha oxide (no kerosene praaant)* d - elimination of fire haaard in crude oven-drying (no kerosene praaant)* a - absence of karoaana may facilitate solvent-silling in acetone (this possibility has not bean investigated} A* Greater purification of tha pigment, approaching and poaalbly equalling that obtainad by the acid-pasting prooaaa. 5* dona partiale-sise reduction inherent in the drowning operation way shorten the grinding cycle (able has not bean Investigated ) 6* Solvent-milling nay be eliminated by acid-pasting directly from tha karoaana reactor slurry without prior isolation of a dry crude* The following process disadvantages are indicated* 1* The use of sulfuric add in quantity greater than that used in the sulfation process will require greater quantities of neutraliaing materials either in presses or in a separate aoid-dieposal unit* 2* Additional plant investment* Equipment limitetione in the Newport Plant have prevented a thorough evaluation of the *AP* process DUP050069502 -3- KH-53-27 DISCUS3I0N OF RESULTS 8 A* Laboratory and 3emi-yorks The acid-flushing procsss can be described in outline as follows) Sufficient sulfuric sold is added to tbs hot kerosene reactor slurry so as to form a liquid interface between tbs lower acid &d the upper kerosene layers {sp*g* 1*3 vs. o*3 approx.}. The amount of acid required to effect this stratification is less than that needed to dissolve CPC in the conventional acid-pasting process, but more than that used in the standard sulfation process* It is not necessary to effect complete solution of tbs 0P0 in the acid, but merely to suspend it in tbs excess acid. The add require ment is lessened by virtue of the high temperature (approximately 150*0) at which this operation is performed* The lower add-layer is nm off or the upper kerosene layer is decanted in such a manner as to yield a substantially kerosene-free add solution or slurry of CPC. The acid layer ie then hydrolysed by the use of ice. or by the conventional add-pasting process by drip-drowning into water. The latter alternative ie preferred inasmuch as some particle else reduction undoubtedly occurs* Laboratory trial of tbs *AF* or add-flushing presses indicates that a quantity of add 3-1/2 - 4 tinea that currently used in the standard sulfation process is required to form a distinct fluid, acid-pigment layer under the deer pigment-free kerosene layer* This effect can be obtained either by adding the sulfuric add to the kerosene reaction slurry, or conversely, by adding the kerosene reaction slurry to the concentrated sulfuric add* In eithsr case, complete transfer of the pigment into the lower add layer is effected* The lower add-pigment layer ie rue off and finished as usual* The solvent-milled products so obtained are intense, v.v.s, green to equal in hue, and v*a* strong versus the best laboratory LB/CPC control, and 3-10$ strong, and intense versus standard BT-304-D. The products are 10$ strong and intense vs* Helioses Blue BA and Orchems Blue BHO* The masstone* are distinctly jet versus standard and versus laboratory controls prepared by the standard process. The extracted crudes proved to be intense, green and 30$ weak against the best laboratory LB/CPC solvent-milled materials. Ink mill evaluation of the toner materials produced by this process indicates the material to bo essentially equivalent, texturewise, and In rate of strength development to the standard process matsrials and to BT-304-D standard* Ink consistencies are likewise essentially equivalent* A modification of the *AF" method Involving undor-the-smrfaee addition of the kerosene reactor slurry to the sulfuric acid with Wild agitation proved to bo workable in the laboratory* A complete flushing of the pigment from the kerosene to the acid is thereby DUP050069503 KN-53-27 effected, the kerosene floating to the surface of the acid layer* Quality equivalent to that reported above eat obtained (strong* intense, v.a* groan w, control)* The add (4 parti par part of CPC) can bo neutralised in-prooeas after hydrolysis* without any sacrlfioa in quality* Whsreas the crudes obtained by the atandard sulfation process cannot be ground to full strength and tinctorial quality in an alkyd esaael system, the crudes from the *AF" process apparently can be so ground to give products fully squal to their solvent-milled counterparts as regards strength, tinctorial quality* flocculation* and can-stability* Semi-works trials of the AP* process using 1B/CPC kerosene reaetor slurry posed no problems* from an operating standpoint the process involves pumping of the kerosene synthesis charge under the surface of sulfuric acid (four times the quantity currently used for standard sulfation)* whereby the pigment is flushed into the acid layer* fher kerosene, eomplotoly free of pigment* forms an upper layer* Bo agitation appears to be necessary to effect the flushing* the lower acid-layer is run out and drowned in boiling water as in the standard acid-pasting process* 4 small quantity of the acid layer is loft behind so as to insure a kerosene-free aold layer. This residue is worked up with the sueeesding batch* 4 CPC pulp so obtained analysed for 0*p kerosene (solids basis) before oven- drying* in contrast with standard process (sulfated) crude cakes which contain 15-1*0$ kerosene. The acid amployed in the "AP* process is ultimately neutralised in-procees, which fact minimises the waste acid-disposal problem* The first attempt using Cl-fres CPC (kerosene reaetor charge at room temperature) yielded a crude product (laboratory drowned) which by fluahing was green* intenee and a*etrong vs ABT-31B-D (Pigments Dept, experimental soft powder treated add pasted chlorine free CPC - "Monastral" Blue R)* The second "A?* attempt using LB/CPC (kerosene reactor 130*0) yielded a crude product (laboratory drowned) by which was green* intense and equal in strength to BT-2S4-D The undertone was red and intenee against BT-2S4-D. Rubber testa of two of the laboratory *AP" materials (solvent** milled) showed them to bo satisfactory for such use (oxygen boob test). The results of seven Semi-works trials of the "AF* process ere summarised on the following page* DUP050069504 2610 2626 2629 2630 2636 2636 2639 Cl-free 25*0 LB 130*0 23 150*0 195*0 LB Cl*free 13 150*0 150*C 150*C 0*6 0*4 0.90 0*50 0*60 1.2 0*95 green* intense.a*strong vs. ABT-318-D green*intense *v.estrong, vs* BT-264-D green,intense,equal strength vs* BT-284-D green,v*a. intense, mrs.str. vs* BT-264-D ewaweeeeee Approximately 6 parte of mold per part of CPC nee need for lota 26X0 end 2636 (Cl-free CPC). Por toe LB/CPC triala 7 perte of eoid wee employed, except is 2639 where 5 perte of eoid wee weed* No difficulty wee experienced in the *AP* processing nor in the drowning operation, except in 2639 (5 perte aoid), where cooling of the Pigment-acid solution in tranefer gave rite to some CPC eulfate cryatallieation. Maximum particle eiee reduction will depend on main* teining optimum condition! at thie point* the only serious operating problem encountered with the *AP* process result# from the copious evolution of 8C1 fume#, indioeting the neceeeity for providing adequate fume disposal facilities* A 1*6 gallon acetone mill grind (46 hre.) of dried leap LB/CPC AF* crude (lot 2626) gate a product 5*6% strong and essentially equal in hue versus BT-304-D standard by varnish drier rubout* A Semi-worka 58 gallon acetone mill grind of dried lump LB/CPC "A?" crude (lot 2636) gave full strength against standard BT-304-D in 14 houre* The product was green end Intense against this standard and bad a Jet masstone. Analyne~efHe&r*tydd$tl *Af* products indicate that they contain fro 6.2 * io.2Vftuifu# expressed as tha CPC monoaulfonic aoid* PndoubtedTy eS^^rCTnation occurs during the BAP* proceaeing* Standard B7*304*B analyeea for 0.43* sulfur expressed aa the monosulfonie acid* A BL-282-D type lake prepared from a solvent-milled *AP LB/CPC was a. green* intense end approximately 12% strong versus DUP050069505 h 6- IH-53-27 standard BL-2S2-D toy varnish drier rubout. A BP-173-D type lake prepared from a solvent milled "AT* LB/CPC mas s* green. Intense and 5-o? strong vs* standard BP*173B A BL-237-D type lake (containing ea 25% CPC) and a BL-2BS-D type lake prepared from a solvent-milled "AT* LB/GPG mere tooth strong versus standard BL-38B-D toy the Afpetrong rutoont procedure. , BT-2S4-D type products prepared from solvent-milled 47* LB/CPC by both the cartoon tetrachloride and naphthalene treatments mere mean against standard ST-2B4-B* l.S gallon mill acetone grinds (At hrs.) of several *AF* crude tooth IB and chlorine-free yielded products strong, green and Intense against the appropriate standards* The BT-297-& products derived from the *AF* process mere essentially equal to the standard in texture and rate of strength development* In alkyd enamel systems, thsrs mas no ovldoncs of hssvy mill hast or othsr undeeirable rheologies! behavior* Flocculation militants was essentially equivalent tc that of standard BT-297-B* The BT-2S4-D and BT-30A-D materials derived from acetonemilled *AF* crudes mem Inferior to the respective standards In texture, rate of strength development and rheological properties* In alkyd enamel heavy mill bases suggestive of reactivity mem observed as well as severe flocculation in several instances. Some products, however, mere fully equal to standard in the latter respect* A Semi-works 56 gallon solvent-milling of an 33/CPC *AF* crude pulp yieldod a product of ssasntlally full strength after IB hours of milling* The product mas man and intense versus standard BT-304-D and gave a jst maaatene* The grind mas conducted in the equivalent of 72? acetone (i.e. based on mater content of the pulp}* , chlorination of chlorine-free crudes (2) menu* featured in the Semi-works toy the acid-flushing ("AF") process yielded groduets essentially equal to the control! although * dull vs* B. lag On April 10, 1951 orocess to accumulate onerat lent trial mas mads of ths "AF*1 awd to tho &&s ;sMr& d * P* B* Graham to J* H. Cooper, 4/13/51, and X* 7* Blanks to 7* C* 4/5/51), it appoam that a number of major equipment changes and installations mould be necessary to permit continued operation* DUP050069506 vasaB^.maihMt The work auaaarlted in this report ie recorded in the following notebookss HB 1362 Patent eonaideratien* are diacuaaed in letter* A* J. Stratton to J. H. Tully, 4/9/51, included herein. ie * DUP050069507