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Numerical File - Newark Research Office File - Newark Newark Library File M. HuntA* Goniek - Wilmington W. S. Struve - Newark F.F. Ehrich/E,,F,, Klenke/B.H. Perkins - Newark P. j. Monahan (Vital Records) - Newark N. G, Fisher - Central Res. Dept. - Expl. Station E.L. Rodowskas/R.M. Salemi/R.Z. Fortney - Newport R. H. Wetzel/J.W. Minnich/J.] W. A, West - Newport P. H. Griswold - Newport W. L. Monson - Expl. Station M, C. Crossan - Newport File Ex?t! ra
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NEWPORT PLANT
PIGMENT COLOR RESEARCH REPORT
SUBJECT;
CPC - Two-Stage Drowning Process Development
PERIOD COVERED; 6/1/69 to 3/1/70
SUBMITTED BY;
W, L. Monson ^^i^^^^^Date Submitted; 4/28/70
APPROVED BY:
W, A. West
Date Issued:
5/7/70
A3STRACT
An apparatus designed, constructed, and tested at Newport has demonstrated production, on a semi-works scale, of pigmentary
CPC in the alpha-I form by a unique new process: Two-Stage
Drowning. This report described the development of the process and the results of a study of factors controlling the quality of Two-Stage Drowned CPC.
r et ur n t o
JACKSON LABORATORY
FILE i >M
DUP050082125
TABLE OF CONTENTS
I. INTRODUCTION
II. OBJECTIVE
III. SUMMARY AND CONCLUSIONS
IV. PATENT SITUATION
V. RECOMMENDATIONS FOR FUTURE WORK
VI. DISCUSSION
A. Phase Equilibria
B. Two-Stage Drowning Aparatus
C. Experimental Runs
X. General Procedure
2. Results
a. Demonstration of Phase Control
b. Variable Study c. Combination of Optimum
Conditions
VII. EXPERIMENTAL DATA
Drowning and Development Conditions and Results of Evaluations.
VIII. APPENDIX
Page 1 1
2-4 4
4-5
5-9 9
10-12
12-15 1.5-23 23-24
DUP050082126
I. INTRODUCTION
The work reported here covers the demonstration of the production of pigmentary alpha-I phase CPC by a new process: Two-Stage Drowning, and an investigation of the factors controlling the quality of pigment so made. This study is a continuation of the development of the process for Acid Flushing - HT Drowning of CPC, first reported in KN-67-10.
Iiater work (to be covered in detail in a separate report by P. H. Griswold) had shown that ordinary (singlestage) drowning of BB-CPC (semichlor grade) yielded a mixture of CPC polymorphs alpha-I and alpha-II, whereas the goal product, equivalent to N-6.23 (semi-finished acetone-milled BB-CPC), consisted of alpha-I. The alpha-II phase was .shown to be unstable in paint grinds, converting to the more stable alpha-I form. This pro cess of phase conversion is accompanied by acicular growth, leading to undesirable physical properties of the HT drowned pigment in paint (higher viscosity and worse flocculation than the acetone-milledf product).
A thorough study by P,, H. Griswold of phase equi libria in the system CPC-H2S04-Ha0 revealed the existence of several (possibly four) salts of CPC and HgSO.4, each stable over a different range of H2SO4-H2O concentrations. More importantly, he showed that the crystal form of the CPC recovered by hydrolysis of these various salts differed from salt to salt, and that pure alpha-I CPC could be recovered by hydrolyzing CPG'^HgSO* (stable above about 66$ H2SO4) As might be expected, the particle size of this CPC, recovered by hydrolysis of CPC-4&S04 formed by equilibration for substantial periods of time, was much too large for good pigment quality.
II. OBJECTIVE
It became the objective of this study to devise a practical method of forming and then hydrolyzing CPC,^HaS04 to yield pigmentary alpha-I CPC, starting with "Flushed Acid" (CPC synthesis mass dissolved in 98$ H2SO4). The most direct and obvious way to do so appeared to be "Two-Stage Drowning," as covered in the Discussion Section.
Ill, SUMMARY AND CONCLUSIONS
Pigmentary chlorine-free and semichlor CPC in the pure alphal form can be produced easily by a continuous two-stage drowning of the acid layer from an "acid flushing" step following CPC synthesis. The slurry from the drowning
DUP050082127
-2 ~
XIX, SUMMARY AND CONCLUSIONS (Cont'd)
operation (about CPC in 35-^0$ HPSO4) must be digested under suitable conditions to develop a suffi cient degree of crystallinity to be a direct counter part with respect .to color strength, dispersibility, and rheology, of existing semi-finished product types such as N-623 (BBS), N-872 (BEA), and N-1'3 (BBX). Although some particle size growth takes place during this "development" step, the final size and masstone level are primarily determined in the drowning process; speci fically, during first-stage mixing and retention between stages, when the CPC is precipitated from solution in 9SHaS04, by dilution with a small amount of water, forming essentially pigmentary-sized particles of CFC-4H2S04. Apparently, in the subsequent hydrolysis of this substance, during the second-stage mixing (dilution with remaining water), the resulting CPC retains the external morphology and size of the hydrosulfate particles from which it forms.. CPC, isolated at this point, displays a low degree of crystallinity by x-ray diffraction. First-stage mixing factors shown to be controlling were mixer throughput rate (velocities at point of mixing), mass velocity ratio of diluent to acid, and composition and temperature of diluent (both pure water and 35$ H2SO4 were tested as first-stage diluents). The important factors involved during interstage retention, are time (controlled by length of pipe and flow rate), temperature (controlled by ingredient temperature and composition), and concentra tion (determined by ratio of diluent to acid).
Phase control was complete within the expected range of first-stage concentrations, in all but one of the 78 drownings covered here.
Separate-reports by others will discuss work-up of two-stage drowned material for the BRA and BBX grades.
With respect to the utility of two-stage drowning of semichlor CPC to produce an N-623 (BBX counterpart, it was determined that:
a) Attainment of sufficient crystallinity .requires use of an Arquad 16/Perelene treatment of the drowning slurry for several hours at 8oC,,
b) The effect of degree of crystallinity on paint rheology differs markedly between paint vehicles. Nonsolvent treated twostage BB is good in TAE-3 rheology but extremely poor in 30J.
DUP050082128
-3-
III, SUMMARY AMD CONCLUSIONS (Cont'd)
c) Increasing crystallinity by solvent treatment improved 301 rheology, but crystallinity equaling or even exceeding standard does not guarantee equal viscosity,
d) Increasing interstage retention time in drowning improves paint viscosity in all systems.
e) Standard 30J and TAE-3 rheology can be achieved simultaneously with standard color by solvent developing, -to standard level of crystallinity, a material which has been held between stages for a sufficient length of time at a sufficiently high temperature It has not been firmly established what factor is involved, in the viscosity improvement but it is hypothesized that the probably greater perfection of crystallinity of the tetrahydrosulfate crystals before hydrolysis may play a role by producing a more perfect solid solution or less reactive CPC crystallite after solvent, development.
f) Pure alpha-l BE-CPC as made by this process is metameric versus N-623, which contains a small amount of beta-phase CPC. The meta merism can be corrected by addition of beta-CPC, the exact amount needed depending on the chlorine content of the CPC.
g) The N-623 counterparts made by this new process require the same minimum Cl content (3-6ft) as solvent milled material for adequate crystal stability in paint. Cl level also affects color properties of pigments made by both pro cesses , Lower 01 .leads to lighter, redder, duller, weaker and more crystalline products. However, the MT level and strength are easily corrected by varying two-stage drowning conditions, if desired.
h) There was no particular discernible effect of use of "high-concentration" BB-CPC synthesis slurry on either flushing or drowning, insofar as the resultant CPC quality was concerned. It is probable, that the lower kerosene content of such slurry shouldbe beneficial in the flushing
DUP050082129
-iu
III, SUMMARY AMD CONCLUSIONS (Cont'd)
h) (Pontd)
operation, but because of sampling diffi culties from production synthesis kettles, the "high concentration" syntheses used were actually in the same range of kerosene contents as "normal concentration" material,
i) Acid/CPC ratios from 9/1 to 10/1 were used in various semi-works flushings. Little effect on resulting CPC quality could be noted from the data obtained. Any real effect was probably masked by the much larger quality effects of Cl level and drowning and development conditions.
3) The second-stage mixer was tested only in the form of a simple "Tee" mixer. Final HaSCU concentrations between 35-^0$ (filtrate basis) were demonstrated to produce good quality, in conjunction with suitable flushed acid quality, first-stage conditions and suitable development,
k) The required first-stage mixer operating pressure drop is an important factor in scale-up and is the resultant of through put rate, mass velocity ratio, and ratio of diluent to flushed acid. It was concluded that pressure drops in the range of 175-225 psi were required for production of suitable quality two-stage drowned material.
IV. PATENT SITUATION
The principle of two-stage drowning as applied to production of pigmentary CPC of desired phase (and perhaps also to production of QA and other colors) may be patentable. The patent status of the use of a "Bullet Mixer" in conjunction with Two-Stage Drowning is discussed in a letter from R, D. Nutting to R. H, Wetzel, shown in the Appendix.
V. RECOMMENDATIONS FOR FUTURE WORK
It seems likely that the general principle of pro ducing controlled polymorphic forms of pigments which are stable and protonatable in acid solution by a Two-Stage Drowning procedure, as described here for CPC,
DUP050082130
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V, EECOMMEITOATIONS FOR FUTURE WORK (Cont!d)
could be extended to quinacridones and other pigments which are salt-forming. The salt formed need not necessarily simply be that produced by solvation. For example, it is possible that the beta-QA produced by drowning an H3SO4 solution of QA containing PTSA is formed by hydrolysis of a QA-PTSA salt, or mixed salt with QA-H2SO4. Further work with CPC itself could prove fruitful, for example, to demonstrate production of pure alpha-II CPC by hydrolysis of CPC-SHeSO* (possibly a useful starting material for conversion to beta-CPC). It is even conceivable that the correct type of salt could hydrolyze directly to beta-phase CPC,
The necessary prelude to commercial exploitation of such possibilities is a knowledge of the phase equi libria in suitable selected three, four, and higher component systems and the determination of whatever specificity may exist in conversion to the various polymorphic forms of the pigments by hydrolysis of solid salts produced,
VI, DISCUSSION
A. Phase Equilibria
The principle of two-stage drowning is best understood by reference to the phase diagram for the three-component system CPC-HaS04-Ha0, as shown on the next page, This diagram was established by P, H, Griswold, using purified CPC, sulfuric acid, and water. It should be understood that in the "Acid Flushing" and drowning process one is actually dealing not with a simple three component, but a much more complex, system.
This is because in the process of dissolving CPC in 98# H3SO4 during the flushing step, there are also dissolved all other components In the synthesis mass, except kerosene. The exact compo sition of this mixture is not fully known, but it certainly includes decomposition products of excess urea, such as cyanuric acid; unreacted ingredients; by-products, such as phthalimide; and kerosene sulfonic acids. It Is known that these other compo nents are present to the extent of some 60-75# of the weight of the CPC itself. In order to simplify the analysis of phase equilibria, it is convenient
DUP050082131
J
\Al t-M 5-4-70
D'
-7-
'VI. Discussion (ConVd)
A. Phase Equilibria (Coni'd)
(but of course not strictly correct thermodynamically) to lump together all the other substances present as a "fourth component". We can then consider that we are dealing with a plane section of the fourcomponent isotherm (a tetrahedron) cut at a slight angle to the CPC-H2SO4-H2O plane, passing through the H2O vertex and the composition of the "flushed acid". The phase boundaries of such a section will be distorted as compared to the simple threecomponent system, but as long as entirely new "four" component phases do not appear, it seems valid to determine and allow for possible phase boundary shifts experimentally and keep the simpli city of the three-component diagram. A somewhat different approach is to treat the "fourth compo nent" as though it were water. In view of the experimental result that the critical phase boundary (fg in diagram) in the region of most interest is not significantly altered when using this approximation, it appears a practical and useful simplification. Of course the enthalpy, and therefore, the heat of dilution (and adiabatic temperature rise) of flushed acid is significantly higher than that of a threecomponent composition of the same $ CPC and $ H2SO4.
Referring to the three-component phase diagram, there is only one single-phase three-component region in the entire system. It is labeled "S", and is bounded by the HaS04-HaO axis from about 78-100$ H2SO4, the CPC-H3SO4 axis from 0 - about 12$ CPC, and the solubility curve for CPC. Inside "S" there exists a single homogeneous liquid phase. The compo sition of "Flushed Acid" falls Inside the region of complete solubility. A typical composition for BB-CPC might be 9$ CPC, 8l$ H2S04, 1.6$ HaO and 8.4$ "fourth" component.* On mixing such a solution with water, the total composition must always fall along the straight line connecting point "a" with the HaO vertex. On Adding water slowly to the acid/CFC solution the first
*The projection of this onto the three component plane falls at point "a", inside S.
DUP050082133
a-
VI. DISCUSSION (Cont'd)
A. Phase Equilibria (Cont'd)
appearance of a new phase is when the solubility curve "be" is reached. At this point a precipitate having the composition CfC'^HaS04 begins to form. As more water is added the proportion of CPC pre cipitated in the form of this salt increases until at point "d" virtually all the CPC is in the solid phase. If this two-phase mixture is filtered* it is possible to separate a liquid having the composi tion "b", the resulting filter cake having the composition "e". By the Phase Rule principle known as the "Law of the Straight Combining Line", a 'straight line extended from point "b" through point "e" will intercept the composition of the solid phase. This technique was used to identify the solid phase composition in equilibrium with various R2SQ4-H2O compositions when preparing the original phase diagram. By this means it was shown that above 66% H2SO4 the equilibrium solid phase is CPC'^HaSO*. Prom about 58 to 66% H2SO4 the equilibrium solid " phase is CBG'BHgSCU. Above about 78% H2SO4, there is appreciable solubility of the CPC. In order to precipitate all the CPC as the tetrahydrosulfate * then* enough water must be added to give a resultant liquid phase composition of 66-78# H2SO4. This mixture must then be allowed to equilibrate a sufficient length of time to ensure elimination of any localized regions of high or low concentration and to perfect the crystallinity of the precipitate. These processes are* based on experimental results* accompanied by growth of the crystals, and their rates are functions of the time held, temperature* and concentration. Once having been formed and equilibrated, the precipitate of CPC*4H2S04 can be hydrolyzed rapidly and completely by addition of enough water to drop the liquid phase composition to a value below about 40# H2SO4* for example* point "h" in the diagram. Below this concentration the only stable solid phase is CPC itself. Since the salt being hydrolyzed is pure CPC *4112304, the resulting form of CPC is the desired pure alpha-I.
Initially it was uncertain that sufficient phase purity could be achieved in pigmentary sized CPC* since the required equilibration of the tetrahydro sulfate Is accompanied by growth. The external morphology of hydrosulfate crystals has been shown by A. R. Hanke to be maintained on hydrolysis. In fact, it was quickly demonstrated that pigmentary
DUP050082134
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VI. DISCUSSION (Cont'd)
A. Phase Equilibria (Cont'd)
alpha-I CPC could be produced by careful control of mixing and equilibration conditions.
B- Two-Stage Drowning Apparatus
A schematic drawing of the apparatus designed and constructed at Newport to study two-stage drowning is given in the Appendix. The apparatus consists of the following elements.
1..... A nitrogen pressurization and flow measuring ................system.
2. Blowcases for flushed acid and the first stage diluent,
3. Shut-off (ball) and control (needle) valves for acid and first stage diluent.
4. First stage mixer, pressure gauges, and Chech valves.
5. Interstage holdup loops (various lengths to give various retention times),
6. Second stage mixer, in which the mixture from the interstage holdup loop is mixed with the balance of the water to give the final desired composition. Second stage water is pumped from a 20-gallon supply tank by a Jabseo centrifugal pump.
7. Product collection system permitting sampling of both first and second stage.
The unit was designed to operate in a range of throughputs up to about 1/2 scale of the proposed plant installation.
Sketches of the initially used first and second stage Tee mixers are shown in the Appendix. After the first few runs, various types of Bullet mixers were substituted for the Tee mixer in the first stage and were used in the balance of the work reported here. A sketch of one of these versions, used in most of the runs, is also shown in the Appendix.
DUP050082135
-10-
VI. DISCUSSION (Cont'd)
C. Experimental Runs
1. General Procedure
During the period covered in this report, 78 drowning runs were made. A number of these were made from chlorine-free CPC for work-up into N-872 (BRA) counterparts, several runs were made from BB-CPC for work-up into N-13 (BBX), and a few others were made from both types of CPC for filtration tests by the Expansion Task Force. The remainder, to be discussed here, were made from BB-CPC, to be worked up as candidate N-623 (BBS) counterparts.
To obtain satisfactory pigment quality with respect to tinting strength, dispersibility, and paint viscosity, it is necessary to develop the drowned BB-CPC and the experimental work reported here covers both drowning and develop ment variables.
In general, "as drowned" BB-CPC is too poorly crystalline to distinguish clearly bet ween modifications of the alpha form. This is true whether it is single or two-stage drowned. Only by a post-drowning development step is a sufficient degree of crystallinity obtained to make a clear distinction. The development step consists of treatment of the drowned slurry with a suitable solvent and surfactant, as des cribed by P. H. Griswold in KN-67-10. The development step can then be said to "reveal" the type of crystallographlc modification inherently present in the "as drowned" material. There are two significant exceptions to this:
a. Sufficient equilibration of the BB-CPC tetrahydrosulfate {for example, holding overnight at 100C) and subsequent hydrolysis without development can give a fairly crystalline product distinguishable as alpha-I CPC. Of course, this material is not of pigmentary size.
b. Chlorine-free CPC is much more mobile with respect to crystallographic transformation and will convert quickly to fairly crystalline pure alpha-I in hot "as drowned" slurry (about 30-40$ HaSO*) even when single-stage drowned, without use of solvent in development.
DUP050082136
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VI. DISCUSSION (Cont'd)
i C. Experimental Runs (Cont'd)
1. General Procedure (Cont'd)
It should be borne in mind that no practical
amount of ''development" will completely transform the mixture of alpha-I and alpha-II forms of CPC
obtained by single-stage drowning to pigmentary, crystalline, pure alpha-I BB-CPC. It follows that, when pure alpha-I phase is obtained after twostage drowning and development of BB-CPC, the hydrolysis product must have been inherently of that modification, even though of a low degree of crystallinity.
In general, the as-drowned product from a "TSD11 (Two-Stage Drowning) run was subjected to more than one development condition, a number of
which semi-finished products were then finished by suitably modified Newark processes into
BT-284-D, BT-425-D, etc., and evaluated by a variety of physical and end-use tests, including;
Rubout,
Paint Tests
(Alkyd and acrylic enamels, acrylic lacquer by ball and sand milling for hue, tinting
strength, dispersibility, flocculation, viscosity)
Ink Mill Tests (Lithographic tests)
Specific Surface
Electron Microscopy
Fluid Ink
X-Ray Diffraction (Phase, crystallinity)
For convenience, the complete data are tabulated in Section VII.
DUP050082137
12
VI. DISCUSSION (Cont'd) General Procedure (Cont*d)
The general plan of* experimental attach was as indicated belows a. Make a few initial runs to establish that
phase control was being reliably achieved in a pigmentary product the primary aim of the work. b. Undertake a study of drowning conditions to establish their effects on resultant pigment quality, other than phase.
c. Use this information to define conditions needed to produce goal quality BB-C3PC by Two-Stage Drowning and demonstrate produc tion of that quality in amounts sufficient for thorough evaluation.
.2 Results
a. Demonstration of Phase Control Drowning and development conditions for
TSD-1 are described in the Experimental Data, Sec. VII. The product examined as an N-623 by rubout and x-ray, then worked up into BT-284-D and tested in 30J, TAE-3, and 927 lacquer paints. The quality of this material was very encouraging for several reasonss (1) Rubout color reasonably close to N-623.
Basically pigmentary.
(2) X-ray diffraction pattern showed good crystallinity with no indication of presence of alpha-II.
(3) Paint results were reasonably goods
and 927 lacquer.
(e)) Slightly worse viscosity in 30J
DUP050082138
-13-
VI. DISCUSSION (Cont'd)
C. Experimental Runs (Cont'd)
2. Results (Cont'd)
a. Demonstration of Phase Control (Cont'd)
Overall, this type of quality exceeded that made by single-stage drowning. The most important result was that pigmentary size BB-CPC had been made in the desired pure alpha-I form by an acid pasting-HT drowning route; as far as is known for the first time. Electron micrographs*and specific surface indicated that pigment size was slightly larger than standard BT-284-D. At the time this was thought to be respon sible for the redness of tint and lighter masstone. The slightly worse viscosity in 30J was disappointing (particularly for a larger rather than smaller particle size material) since it had been expected to be good, in line with high alpha-I phase purity. However, paint viscosity is also partly deter mined by development conditions and it was felt that 30J viscosity could be improved by an appropriate adjustment of development.
In the second, third, and fourth runs (all made using the Tee mixer first stage), minor changes in drowning conditions and variations in solvent development were directed toward production of slightly smaller particle size material to give the desired darker masstone vs. N-623, while retaining alpha-I phase purity and the desirable properties obtained from working up TSD-1.
The following briefly summarizes sum marizes pertinent results of these four runs;
(Table on next page)
*See Appendix.
DUP050082139
1
i
U)
-14 VI. DISCUSSION (Cont'd)
C. 2. a. Demonstration of Phase Control (Cont'd)
SBC *un Drowning ffo. Variable 1 Control
No 2 Change
Development Variable
Control
Use 160# Perclene in place of 100# ODCB
No solvent
Reduce first stage 3 cone. from
71.8 to 68.6#
HaS04
Use 100# Perclene
No solvent
Like 3,
but
also
reduce
Use 100#
4
first stage
Perclene
reten
tion
from
.037 to .026 sec. No solvent
Rub out v s .N-623
MT r.s.
Ltl2 104
.. TW""* Spec. 27 Ph Brookfield Surf, V.P. ase 30J
66 56 t C-i V. 18 0.83
Ltl2 104 Ltl2 115
61 24
o c -i 51: 1,20
0 2.40
Ltia 106 67
oO-i 44 2.13
Lt6 110 20
0
3-00
Lti2 105 69
oC-X 43 1.67
Lt3 115 37
0
*Ratio of sample viscosity to that of Standard BT-284-D.
The results from this set of runs showed that alpha-I phase was being consistently produced, and that little change in M? level had been achieved except when solvent was entirely eliminated. However, this nonsolvent treated material was quite low in specific surface (indicating aggregation) and in degree of crystallinity (indicated by 27 Valley Parameter), resulting in poor dispersi bility,. tinting strength, and viscosity.
DUP050082140
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VI. DISCUSSION (Cont'd)
C. 2. a. Demonstration of Phase Control (Cont'd)
It had been hoped that the two-stage drowning procedure might eliminate the need for use of solvent development, but this series (and subsequent series of runs) con firmed that adequate dispersibility, and particularly 30J paint viscosity, required
the high degree of crystallinity which only solvent treatment is known to impart.
b. Variable Study
The general effect and relative impor
tance of the variables are summarized in
the tabulation below, and then discussed in more detail in the rest of this section.
Most Important Variables
Effect
% Cl in BB-CPC
Lower Cl results in lighter, duller, redder, weaker products. Need at least 3,656 for adequate crystal stability.
First-Stage Mixing Conditions
Control base particle size and MT depth of product.
Interstage Retention Conditions
Partly control base particle size. Strongly affects paint viscosity independently of size. Some mini mum condition essential for phase control.
Development Conditions
Imparts crystallinity needed for Good dispersibility and paint vis cosity. Lightens MT.
Variables of Lesser Importance
Effect
Second-Stage Mixing Conditions
Little observed effect by variation of final concentration from 2156 to
37% HaS04.
Ratio of Acid/CPC in Flushing
In range of 9/1 to 10/1, little or no observed effect on final CPC quality.
BB-CPC Synthesis Concentration
No observed effect. Possibly masked by other variables.
DUP050082141
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VI. DISCUSSION (Cont*d)
2. b. Variable Study (Cont*d)
(1) The Cl levels of the BB-CPC used in this work were as shown?
TSD Runs
$ Cl
Synthesis Cone.
1-18
19-56 57-68 69-78
4.0 Normal
3.4 High 3*6 High 4.0 Mixed
The specification range of $ Cl for acetone-milled BB is 3*6-4.5$. It had been planned to make a systematic study of the effect of Cl contents, within the specifi cation range, on quality of two-stage drowned CPC. Unfortunately, this plan could not be carried out, since it was thought to
be more urgent to test the combined effect of high BB synthesis concentration (as planned for the proposed CPC expansion) and two-stage
drowning. This meant that the number of. synthe ses from which starting material could be selected was restricted to the few made at
high concentration. As it happened, these
were below specification Cl levels, and far enough below to seriously affect color, as well as crystal stability (just as in the
acetone milling process).
After eleven runs had been made with the 2.6$ Cl material (Runs TSD-57 to TSD-68) which could not be worked up to a satisfactory tinctorial match with N-623 in paint and which
also were seriously deficient in crystal
stability, it was agreed to abandon use of
"High-Concentration" slurry and return to starting material of 4.0$ Cl. All the spec, material had same Cl content. Consequently, the exact effect of small variations in Cl
content within the specification range could not be determined experimentally. It
can reasonably be Inferred to be like the effect on quality of acetone-milled BB.
DUP050082142
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VI. DISCUSSION (Cont'd)
Results (Coat'd)
(2) First-Stage Mixing
A modified "Bullet" mixer (adapted from a DuPont BSD design) was constructed and used (in three versions) from Runs 5 through 78 as a replacement for the "Tee" mixer used in the first four runs. The decision to change to this type of mixer was based on several considerations:
(a) Reported easier scale-up to plant size.
(b) The increasing recognition that firststage mixing conditions were among the most important factors in two-stage drowning.
(c) Greater flexibility in altering mixer geometry, thus affecting flow conditions at the point of mixing relatively easily to suit process requirements.
Detail drawings of this mixer are shown r'\ in Section VIII - Appendix. The acid nozzle
shown (Part "B") is the eight-hole model. Four, eight, and sixteen hole nozzles were constructed and tested. The total crosssectional area for acid flow was held constant in this set of nozzles.
With this type of mixer, throughput rate (which determines velocity and Reynolds number at the point of mixing), diluent com position, and mass velocity ratio of water to acid (approximate decreasing order of effect) were found to be critical in deter mining the base particle size of the resulting pigment.
:W
DUP050082143
-18*
VI. DISCUSSION (Cont'd)
C. 2. Results (Conf'd)
b. (2) First-Stage Mixing (Cont'd)
Combined Effect of Varying Bullet Mixer
Flow Rate and Interstage Retention
BII Mixer
$> Cl: 2.6, Standard Development Conditions Diluent Compositions Ha0 Mass Velocity Ratio: 1.0 Interstage; Temp. 108-110C,
Cone. 715-73.8$ H2SO4, 57" x 1" Pipe
Rotameter TSD Readings No. Acid Water
stage Reten tion .
Sec.
* Perclene Devel.
R/0 vs. N-623
Relative 30J
Brookfield 6 REM
61 32 35 3.3 62 40 44 2.7 63 50 55 2.3
100 200
100 200 100 200
Lt25 100 RD
Lt25 100 RD
Ltl2 100 RD Lti2 100 RD Eq. 97 vsRD Eq. 97 vsRD
1.54 -
1.4 1,8 2.0 1.7
Effect of Mass Velocity Ratio*
BII Mixer
% Cl: 2.6, Standard Development Conditions,
Diluent Comp.; H2O
Interstage;
57" x 1" Pipe
M..V, TSD Ratio No, W/A
Rotameter Readings
Acid HaO
Clear ance Mils
Interstage Temp. Time
feso* *C Sec.
R/0 VS. N-65
51 0.23 60 66 35 52 0.53 60 66 15
,-
74.4
101 1*9
106 RD
96 1.9 it20 100 RD
60 0.8 61 1.0
32 35 10 32 35 8
72.7 71,5
108 3.5 ' Lt35 100 RD 109 3,5 Lt25 100 RD
Mass Velocity Ratio
(Water Vel. x^Sp.Gr.) at mixing point. Acid Vel.x Sp. gr.) which is at acid
hole circle in clearance.
DUP050082144
-19-
VI. DISCUSSION (Contd)
C. 2. Results (Cant'd)
b. (2) First-Stage Mixing (Cant'd)
Effect of First-Stage Diluent Composition
BIX Mixer
Mixer
First
Rotameter Clear-
TSD Stage . Readings ance.
NO. Diluent Acid Dil. Mils
Ret.
M.V. Time, Ratio Sec,
R/0 vs.
N-623
19 HsO
60 100
10
1.2 0.4 U3.2 99
20 35$kS04
31 100
35
1.0 0.6 E 100
Spec. Surf ^ Ma/g.
73
87
PT.-284--P Std.
70
Ave. 35^,,%S04 Dil'n
Ave.
H2O Dil'n
83 74
(3) Interstage Retention
Interstage retention conditions were found to strongly affect resultant paint viscosity, as well as having effects on W1 level. The effect on paint viscosity was
not simply due to CPC particle size, (as measured by MT level) or degree of crystal linity (as measured by X-ray diffraction). Final products with the same MT color and
27V.P. were substantially different in 30J viscosity depending on interstage tempera ture, time,and concentration (approximate order of decreasing effect). It is hypo thesized that one effect of retention is to perfect the crystallinity of the tetrahydro sulfate which might result in CPC of improved morphology, degree of solid solution, or reactivity. Particle size growth of the tetrahydrosulfate also must take place,
judging by the effects on resultant CPC size.
Techniques are not yet known for measurement
of transient crystallinity and particle size of the tetrahydrosulfate, so no direct physical tests could be made.
DUP050082145
VI. DISCUSSION (Cont'd)
C. 2, Results (Cont'd)
b. (3) Interstage Retention (Cont'd)
The following series of runs illustrates the effects described: Interstage Retention Conditions vs. Quality .
Interstage
TSD Temp. Time Cone. 27 No. c Sec. #B2S04 V.P.
30J Rel.Visc.
Spec.
R/0 Brookfield Ford Surf,
vs. N-623 6RPM 60RPti Cup M2/g.
8 110* 0.026 66.9 43 Dk2 9 110* 0.124 68.7 42 Lt2
2.29 1.90 1.52 73 1.15 1.34 1.13 66
13 110* 0.814 69.2 44 Lti2 95
14 110* O.287 70.7 33 Ltg 100 15 110* 0.071 70.0 29 Lt6 102
1,07 1.07 0.95
1.60 1.45 1,15 2.40 2.00 1.70
78
-
77
65 105.. 5.5
67 122
5.5
68 134
5-5
73.6 62 Dk2 100 ED
72.9 62 Lt6 98 RD 72,4 61 Lt99l02 RD
70 118 5.5 72.3 51 Lt29l04 RD 1.00 1.10 1.00 - 71 102 5-5 73,0 53 Ltg 106 RD 1.82 1.41 1.34 -
^Estimated.
(4) Development Conditions
Development conditions were adapted from those used on single-stage drowned BB, as reported in KN-67-10. For the most part, they involved the use of 5# Arquad 16 (based on pigment weight) and 0-200# Perclene or ODCB. A cationic agent like Arquad is needed
to effectively disperse pigment and emulsify solvent in the hot 35-40# H2SO4 - containing drowned pigment slurry. Most of the Arquad is retained by the pigment and improves its
dispersibility markedly. Since the Arquad is a diluent, the purity of the N-623 equivalent is lower than non-surfactant treated material
(about 92#, vs. 96# CPC for N-623). This was compensated for when extending with CaSx, so as to arrive at the same CPC content as BT-284-D, 88#.
DUP050082146
Oft* CCOM .O=3e-VVO.OV C(TM6V
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DUP050082147
-22-
VI. DISCUSSION (Cont'd)
C.2.b. (4) Development Conditions (ConVd)
Several experiments were run in attempts to increase MT depth by using Arquad in the
first stage drowning water, using an Arquad/ Perclene emulsion in the second stage drowning water and by application of shear (in a Waring Blendor) to the drowned slurry before develop ment. None of these was effective.
During this work it was found that the redness of tint of the products being made
was excessive vs. N-623, particularly with the low $ Cl material and with more severe
development. However, even with high Cl and the minimum development needed, products
were generally redder than desired. Even tually it was recognized that the redness xras partly associated with metamerism and
that this was due to absence of any betaphase in the drowned, developed material. Addition of beta, either by blending or
seeding corrected both redness and meta merism. Only a small amount is needed, with good Cl levels.
(5) Second-Stage Mixing
Second-stage mixing throughout this
series of runs was tested only in a Tee
mixer, designed to have the mass velocity
ratio of the side-entering stream (the
first-stage mixture) to that of the second
stage water be about 1.8. The velocity of
the mixture was designed to be in the range
of ordinary single-stage HT tubes. The only
variables in the series were throughput rate
and mixture ratio (which determines final
mixture ^HaS04 and $CPC). For chemical and
economic reasons, it is desirable to approach
but not exceed a final drowned
of
about h0$> (filtrate basis) as closely as
possible. Final concentrations of 21 to 37$
H2S04 were reached in this series. There was
no evident quality incentive to drown to con
centrations below 36$, based on the limited
data available.
DUP050082148
VI- DISCUSSION (Cpnt*cl)
-23-
C.2.b, (6) Ratio of HaSPa/CPC
The bulk of the flushed acid used in this work was nominally 9/1. It was found that at this level* crystallization would take place at an undetermined point some where below normal room temperature. Several batches of acid had to be discarded after outdoor exposure in winter. To con serve material, the ratio of aeid/CPC was increased to 10/1. Any real quality effect of this change was small or else masked by larger effects due to Cl level, etc.
(7) BB-CPG Synthesis Concentration
In conjunction with the proposed CPC expansion, BB synthesis concentration is
planned to be increased. All of the "high concentration" BB slurry used in this work was unfortunately also low in $ Cl. Conse
quently no clear-cut comparison of final
effect of high vs. normal, concentration could be made, since $> Cl and other importaut quality factors were also varied simultaneously,
,
c. Combination of Optimum Conditions
The best drowning and development conditions known at the time were used on flushed acid made
from 4.0$C1 BB in Run TSD-78 in an attempt to demonstrate production of completely satisfactory
material. When extended with CaSx to 88$ CPC, it compared favorably in ink and paint vs. BT-284-D with respect to color, crystal stability, floccu lation and viscosity (both 30J and TAE-3 paints.) The following table summarizes test results of this product.
TSD-78 - Drowning Conditions
Date Drowned; 2/I9/7O, Acid Lot; 0Q013, $C1; 4,0 Mixers BII(8 hole), 8 mils clearance. Acid Flow4.3 GFM Acid Temp.S 22C, 1st St. Water Flow 1.6 GPM, Temp. 59C. Pressure at Mixer Inlets Acid 200 psi. Water 180 psi. Interstage Conditions; 57" Length 1" pipe, 2,2 sec.
retention, 118G mixture temp., 73.2$ HaSO* first stage filtrate. Second Stage; 10.6 GPM water flow, mixture temp, 79C,
36.5^ HaS04 filtrate.
DUP050082149
DISCUSSION (C o n t?d )
C . 2 . e . C o m b in a tio n o f Optimum C o n d itio n s (C ent *d )
D e ve lo p m e n t and E v a lu a tio n as 11-623
mj vcout 2;
0 > o
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0
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4co33S
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csoo <u
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1m CD ^ 0 HI |
ft oj
0
i--!
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D D
ft ft ft w 0
ft ft ft ft ft ca
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fot
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H ft
P00
PCO
ft ft ft ft ft
ft
0
ft
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P04
ft
t3 053 03 f1C3ttS f<ote cCOs j O ft
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cm
C0-4~ t0^4r
a ffCttj
5^14fN.ftt-S-a \C<--M1 515 0* #>
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V0O4
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DUP050082150
-25VI. DISCUSSIOM (Contra)
C.2,c, Combination of* Optimum Conditions (Cont'd) Note that the translation of rubout color
from N-623 to BT-284-D involves a shift in relative MT level. For example. Sample A, which is Lt6 vs. N-623 is Dk2 vs. BT-284-D. This aoes not involve any change in the sample on laking, but is merely aue to the fact that the current N-623 in-process standard is darker than that from which the BT-284-D standard was made.
X-ray diffraction patterns for Samples A and E are shown in the Appendix, Sec. VIII.
DUP050082151
VII. EXPERIMENTAL DATA
DUP050082152
-26-
VII. EXPERIMENTAL DATA The drowning and development data and pertinent
evaluation results are tabulated, for runs TSD 1-77> on the next fourteen pages. Complete data for run TSD-78 are given in Section VI, G, 2,, Discussion of Results of Experimental Runs.
In general, the headings are self-explanatory. . Under "Mixer", BI, BII, and Bill indicate 4, 8, and 16 hole acid nozzle designs respectively. First stage diluent and acid flows are in percent of full scale Rotameter readings, A calibration Is shown on the next page. Where indicated, first-stage diluent and acid temperatures are given in the Flow column. Where not shown, temperatures were ambient. Up through run TSD-42, first and second stage mixture temperatures shown are dial thermometer readings. These are mainly inaccurate, reading much too low because of insufficient running time, and thermo meter lag. After TSD-42 readings are accurate and measured on samples taken out of the system. The "Clearance" shown in the "Mixer" column is the gap, in mils, between the acid nozzle and the impingement plate. This, with flow rate, determines water velocity at the mixing point.
DUP050082153
DUP050082154
DUP050082155
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DUP050082156
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DUP050082157
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DUP050082158
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DUP050082168
VIII. APPENDIX
DUP050082169
cc: M.Hunt/E. Gonick - Wilmington
F. R, Ortolan! -
nii
W. Struve - Newark, N.J.
J. W. Mirmieh -NNeewwppoortrt
J. F. Maurer W, A, West -
" "ii
P. H. Griswold - n
. L. Monson -
n
, E. Maerum - Newport
FOR DU PONT USE ONLY
Newport, Delaware August 22, 1969
Dr. R. H. Wetzel Pigments Dept. Newport
BULLET MIXER - PATENT STATUS
At the Newport Colors Steering Meeting on 8/22/69 in discussion of two stage drowning of CPC (Case No. CP-106), the question of patent status of the Bullet Mixer was raised,
I asked Engineering Department what they had done and was advised by Roll-in D. Morse of Engineering, that their patent attorney, H J. McCauley, had determined that prior art would prevent them from obtaining a patent on the mixer, when this was considered in 1958 and 1961
We might wish to consider process type claims incorporating the Bullet Mixer, with very specific limitations as to rates of flow, pressures, viscosities, concentrations, etc. However, we might be dis closing more than we would protect, and no disclosure of the Bullet Mixer, per se, would be preferable.
DUP050082170
E. I, DU PONT PE NEMOURS & COMPANY
PIGMENTS DEPARTMENT
cc: R. H. Wetzel J. P. Maurer
J. W. Minnich Research pile
Newport, Delaware July 18* 1969
MESSRS:
W, A. WEST
D. F. REDDISH P. H. GRISWOLD.
p; J. ROACH P. L. REIG B. D. CRAIG W. T. MC CRACKEN
C. STIGLIANO
RESEARCH - COLORS - NEWPORT PRE-STARTUP SURVEY
SEMI-WORKS TWO-STAGE DROWNING UNIT
You are requested to attend a Pre-Startup inspection today at 1:00 P.M. in Lab 307 > A-21 Bldg. The unit to be inspected is described in the attached write-up*
WLM/mc
W. L. MONSON RESEARCH DIVISION
DUP050082171
Newport, Delaware July 18, 1969
PRE-STARTUP SURVEY
' SEMI-WORKS TWO-STAGE DROWNING UNIT
LOCATION: Bldg. A-21, Lab 307
PERSONNEL RESPONSIBLE: . L. Monson, B. D. Craig
I. OPERATION TO BE PERFORMED
-
Continuous two-stage drowning of CPC/HaSO4 solution.*
*Frst-stage water and acid are pressurized to 600 psi in
blowcases and throttled to the first stage of the mixer. The first-stage product flows to the second stage where it mixes with a stream of water from the pump. The mixtures flow into a collecting drum under the mixer,
II. EQUIPMENT (See Sketch)
:.....
1. Two 5-gallon, 316 S/S blowcases, of 8" Sched. 80 pipe.
2. Two F&P S/S magnetic flowmeters, 1500 psi rating, for compressed Na to blowcases.
3- Nitrogen cylinder station. Pressure regulator system to provide 50 SCFM N2 at 600 psi.
Two-stage mixer block.
5* Second stage water pump, (1/2 HP, 110 V Jabsco) and 10-gallon supply tank.
6. Control valves. Check valves. Vent and relief valves.
III. SERVICE FACILITIES
Uses 110 V electricity for second-stage water pump.
IV. HAZARDS................. 1. High pressure. 2. Concentrated sulfuric acid. a. Splashing and squirting. b. Mixing with water in wrong place.
DUP050082172
V. SAFEGUARDS
f
Hydrostatic test.
:
Overpressure relief valve.
Check valves.
Splash shield.
VI. PROTECTIVE EQUIPMENT
Safety Shower Safety Goggles Safety Shoes Safety Gloves Face Shield
Page 2 Pre-startup Survey
Semi-Works Two-stage Drowning Unit
/me
DUP050082173
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DUP050082178
OPERATING PROCEDURE
TWO - STAGE DROWNING UNIT
7 - 23 - 69
1. Open both lab doors leading to safety shower. Cheek safety shower. Check that Main N2 shut off valve in hood is open; that N2 vent is open; and that N2 pressure gage reads zero,
2. Open acid and water blowcases, carefully. Pill water case. Rod acid case. Add acid not closer than '6" from top. Close blowcases after measuring and taking temperatures.
3. Fill up second stage water tank. Close curtains to hood.
4. Close Main N2 shut off valve in hood and close the vent over the acid and water blowcases. Check all lines to make sure all the lines are sealed. (See . Sketch)
5. The following procedure should be used in turning on the two N2 cylinders, (Refer to Sketch)
a. Make sure the vent valve between the Main Na flow and Main reducer is closed. Close the auxiliary vent valve and the Brass needle valve,
b. Open the cylinder valve on the Main N2 cylinder. (One on the left)
c. Make sure the regulator valve is open (turn to left until valve moves freely).
d. Open cylinder valve on the auxiliary N2 cylinder, e. Open the Brass needle valve. One or two turns to the left, f. Turn the regulator valve to the right; until the reducer
gage reads the correct pressure desired (595 to 605), g. Check all lines for leaks.
6. Open Main N2 shut off valve very slowly allowing pressure to build up slowly. Gas will flow through" water flowmeter, (Do not allow surge of gas to slug meter.)
7. Ball valve switch must be closed. Turn on second stage water pump switch.
8. Turn on 1st. stage water, adjust correct reading* (Plow meters)
9. Turn on acid flow. Adjust to correct reading (Plow meters). Readjust 1st. stage water if needed.
10. Note mixer temperature and pressure. When stable, take 1st* stage sample. (About 1/4 of container full).
11. Immediately open second stage water ball valve.
"^jL2. Note mixer temperature and pressure.
DUP050082179
Sample second stage mix. (Fill container.) 14. Immediately shut off acid flow and 1st. stage water flow. 15. Allow second stage water flow to continue for 10-15 seconds. 16. Shut off second stage water flow valve and water pump switch. 17. Close Main N2 shut off valve and open vent over the blowcases. 18. To shut off both cylinders: (See Sketch) Close the cylinder
valve on Main Ka cylinder. (Cylinder on the left). Open the vent between the main reducer and the hood. After this has bleed dovm--then close the auxiliary vent. This will bleed the left cylinder line. (Check gage.) Now open to the left the regulator valve. This will bleed the auxiliary cylinder discharge line. Close the small Brass needle valve. (Check gages.) Check pressure gage in hood - (Should read zero).
DUP050082180
SKETCH
Na CYLINDERS
CYLXHDEB VALVE
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DUP050082182
DUP050082183
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DUP050082185
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l 10 ME NTS, NEWARK
MAO, A0,000 X
DUP050082186
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MAG. 40.000 X
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