Approved: THEl ECONOMICS OF SUGAR HYDROGENLOYSIS FOR THE COllMERCIALPRODUCTION OF AN AUTOMOTIVE ANT:IFREEZre by William H. Clarke A Thesis Submitted tor Partial Fultillment of the Requirements for the Degree ot MASTER OF SCIENCE in CHEMICAL ENGINEERING In Charge ot Investi~ation Head of .Major Department Dean ot Engineering Division Director ot Graduate Studies Virginia Polytechnic Institute Blacksburg, Virginia 1948
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1. History 9 2. Conversion of Ethylene Dichloride to
Ethylene Glycol 10 3. Conversion of Ethylene Chlorohydrin to
Ethylene Glycol 11 4. Catalytic Vapor Phase Oridation of
Ethylene to Ethylene.Oxide 13 5. Procedure for Vapor Phase Oxidation of
Ethylene to Ethylene Oxide 15 6. Conclusions from Work of Oxidation of
Ethylene to Ethylene Oxide 16 7. Hydration of Ethylene Oxide to Ethylene
Glycol 18
o. Production of Propylene Glycol 20
l. Method of Production 20 2. History of Hydrogenation of Sugar 20 3. Conditions for the Hydrogenation of Sucrose 22 4. Production of Propylene Glycol from Sugar 28
INDEX OF CONTENTS (CONT'D}
Page D. Some Methods of.TestingAntifreeze Solutions 30
1. Free~ing Point 30 2. Viscosity • 32 3. Other Methods of Testing.Antifreeze Mixtures 33
III. EXPERIMENTAL 34
A. Purpose 34
B. Plan of Procedure 34
l. Literature Review 34 2. Experimental· Work 34 3. Economics of SUgar Hydrogenolysis for
Production of an Automotive Antifreeze 35
C. Materials 36
D. Apparatus 39
E. Method of Procedure 42
l. Introduction 42 2. Determination of Yield of Catalyst 42 3. Identification of Glycerol and Congeners
Fraction 44 4. Makeup of Propylene Glycol-Glycerol and
Congeners-Water Solutions 45 5. Determination of Viscosity and Specific
Gravity of Antifreeze Mixtures 46 6. Cooling Curve Data for Antifl.'eeze Mixtures 48 .7. · Plant Design and Location 49
F. Data and Results 50
l. Tables 2. Figures 3. laboratory and Semiworks Data 4. Theoretical Calculations 5. Material Balance 6. Equipment Specifications 7. Sample Calculations for Equipment Design
Yield of Produce~% by weight of sugar Typical Charge and Jiald in Hydrogenation of Sucrose by Lenth 3D.d DuPuis Catalyst Yields Calibration of Ostwald and Ostwald-Fenske Viscosimeters Identification of Glycerol and Congeners Fraction from Miner Laboratories Viscosity Data.for Antifreeze Mixtures Viscosity Data of 60 Per Cant sucrose Solution Data for Duhring's Plot of Antifreeze Wdxtures Cooling Curve Data for Antifreeze Mixtures Freezing Points with Corresponding Viscosities Estimate of Wholesale Selling Price
FIGURES
Calibration Curve for Ostwald Viscosimeter Calibration Curve for Ostwald-Fenske Viscosimeter Concentration Propylene Glycol-Glycerol vs. Kinematic Viscosity . Concentration Propylene Glycol-Glycerol vs. Absolute Viscosity Temperature vs. Absolute Viscosity Temperature vs. Absolute Viscosity 60% sucrose Solution Duhring's Plot Propylene.Glycol-Glycerol Water vs. Temperature 60% sucrose Solution Temperature vs. Specific Gravity Concentration Propylene Glycol-Glycerol vs. Specific GraVity Cooling Curves Freezing Point Curves rflB.terial Balance Flow Sheet Qualitative Flow Diagram Calculation of Plates for Bubble Cap Fractionating Column Plant Layout
Page 26
29 52
53
54 55
56.
57 58 59
124
60
61
62
63 64
65
66 67
68 69 70 84 85
110 114
I. INTRODUCTION
The growth ot the automotive industry during the past half
century has commanded the attention of every one, and many times
chemistry has been able to further its growth through timely dis-
coveries. The production of cheap gasoline, special motor fuels,
the introduction of spacial alloys, and the creation of the nitro-
cellulose lacquers constitute but a few examples of the recent ac-
complishments. Another problem of this industry has been to pro-
vide a satisfactory antifreeze to take the place of water during
the freezing months. With the current estimate of 35 million
automobiles of all classes in use at the present time, it is a
challenge to the chemist to discover and to the chemical manu-
facturer to produce at a reasonable cost a satisfactory antifreeze
to meet the specifications of the automotive engineers.
At present, there are principally two antifreeze compounds,
one having an alcohol base, and the other having a glycol base.
It is very obvious that alcohol solutions possess lower boiling
points from that of water, and these solutions lose their non-
freezing properties during continued use through the evaporation
of alcohol. As regards odor, inflanmability, and destructive ef-
fect on certain types of automotive finishes, alcohol fails to
meet the most exacting teats. Ethylene glycol possesses all
-2-
advantages of alcohols and in addition does not lose its anti-
freeze properties by evaporation. Furthermore, extended use of
these solutions does not alter the ethylene glycol through de-
composition or change in structure. At the end of the winter
these solutions, unless dissipated through leakage or other
mechanical losses, will be fully as effective against freezing
as when introduced.
Since the demand for ethylene glycol antifreezes is tar in
excess of the supply, competition is practically nil. Because
of this, the price has been maintained at a consistently high
level.
The purpose ot this thesis is to determine if it is eco-
nomically feasible to produce an antifreeze consisting of
propylene glycol and "glycerol and congeners" by the catalytic
hydrogenation of sugar.
-3-
·II. LITERATURE .REVIEW
Requirements of an Ideal Antifreeze Compound
It would not seem to be a difficult matter to produce an
ideal compound which would prevent water from freezing ill auto-
mobile radiators under ordinary winter conditions. However, the
chemists have given this matter serious consideration for a number
of years, and it is now generally accepted that the problem is far
from simple. In order to appreciate the complexity of the problem
it is necessary only to review the requirements of an ideal anti-
freeze as given by Keyes(44 ).
Major Requirements.
1. It should prevent freezing of the cooling medium
at all ordinary temperatures.
2. It must not· injure by corrosion any metal parts
of the engine or radiator and must not soften or
deteriorate the rubber connections.
3. There must be an adequate supply at a reasonable
price.
4. It should be stable.
Minor Requirements.
1. It should have a low viscosity at all working
temperatures.
-4-
2. Water solutions should have a high specific heat
and a high heat conductivity.
3. It should not materially lower the boiling point
01' solution.
4. It should not produce an unpleasant odor.
5. It should not attack automobile finishes.
6. It should keep its antifreezing property tor a
long period of time (low vapor pressure).
7. It should have a low coefficient of expansion. {44) . Keyes using these specifications reviewed the various
antifreeze compounds that had been used and pointed out the good
and bad characteristics of each.
Oils - The various hydrocarbons, notably kerosene, have been
used to replace water as a cooling medium, especially in tractors.
The general disadvantages of oil are as follows:
1. High viscosity at low temperatures.
2. Low specific heat and low heat conductivity.
3. Oils, especially kerosene, soften and dissolve
rubber.
4. Leaks permit oil to come through, and the vapors
are dangerous because they are inflammable.
5. High boiling points ma.y cause overheating of the
engine.
-5-
Salts - Calcium chloride was for many years·the popular
antifreeze compound, possibly because it not only depressed the
freezing point of water to a marked degree, but it also stayed
in the system and was not lost by evaporation. It was cheap,
easily obtained, and there was an adequate supply. Its real
fault, however, was that, in common with all chloride salt so-
lutions, it would corrode common metals. It was thought for a
time that the addition of chroma.tea, such as sodium chromate,
would prevent this corrosion by rendering the material passive.
This addition of chromate helped in some cases, but fell down in
others, especiall_y when parts were made of aluminum. Magnesium
chloride was found to be even more corrosive than calcium chloride.
Not only was trouble experienced with corrosion, but when leaks
occured, a tine salt spray would appear and have a tendency to
short circuit spark plugs and ignition wires. There was also a
tendency for the salts to crystallize out and clog pumps and cut
down the heat transfer in the radiator.
sugars - Honey, glucose, and various sugar airups or waste
sugar liquors have been suggested as antifreeze compounds, and
some tests have been ma.de. Unfortunately, the sugar molecule is
too large for this purpose, and the freezing point lowering is
therefore relatively small. The concentrated solutions, more-
over, are highly viscous.
-6-
Alcohols "'." Considering the problem from: a· .fundamental . stanq.-
point, a compound should be chosen that, first of all, is com-
pletely miscible with water at all temperatures and in all con-
centrations • .Also a compound would be chosen that would not only
lower the freezing point of the water but would be no more cor-rosive than water. In other words, a compound -would be chosen that resembled water as closely as possible. The alcohols re-
semble water more closely than any other class or compounds, and
methanol stands at the head of the list.
Methanol - It not only gives a marked lowering of the freez-
ing point, a greater lowering than other alcohols, but it is ab-
solutely non-corrosive in the pure state. Thanks to modern de~
velopments in synthetic chemistry, it can be obtained,from carbon
monoxide and hydrogen by direct synthesis in unlimited quantities
at reasonable prices. Unfortunately, however, it has a hiBh vapor
pressure in water solutions and a low boiling point, and the fumes.
from a boiling solution are hanni'ul to the ordinary individual.
Modern automobile radiators are designed to give adequate coolinB,
and little difficulty is experienced with boiling radiators.
Ethyl Alcohol - Much has been said for and against denatured
ethyl alcohol as an antifreeze. Some of the advantages of ethyl
alcohol are as follows:
-7-
· 1. The ability to reduce the freezing point
of wate~ is adequate when compared with
other antifreeze compounds.
2. It is no more corrosive towards metals or
rubber than water.
3. It boils without decomposition.
4. Its water solutions_have a low viscosity
. even at low temperatures.
5. It ia sold at·a moderate price, easily ob-
tained, and produced in adequate quantities.
Glycerol - Some of the advantages which make glycerol more appeal-
ing are:
1. Its vapor :P_ressure in water solutions is
low. There is very little loss due to
· _ evaporatiqn •.
2. It is odorless.
Some of its disadvantages are:
l. It has a tendency to soften rubber, there-
fore necessitating a replacement of hose
connections.
2. It has a high viscosity at low temperatures,
therefore necessitating forced circulation.
3. There is a shortage and its initial cost is high.
-8-
Ethylene Glycol - Ethylene glycol, which from a chemical
standpoint, is a cross between glycerol and ethyl alcohol, has
interesting properties. Some of its advantages are:
l. It has a low vapor pressure up to 45% by
volume, thus resembling glycerol.
2. It is no more corrosive towards metals
than ethyl alcohol or glycerol.
3. Unlike glycerol, it has only a slightly
greater viscosity at low temperatures
than alcohol solutions.
4. It does not appreciably change the boiling
point of water.
5. Water solutions of it have a high specific
heat and high conductivity.
6. As a synthetic product made from cracked
petroleum gases, it can be produced in
large quantities.
Some of the disadvantages are:
l. It has a tendency to soften rubber, there-
fore necessitating the replacement of hose
connections.
2. It has a high initial cost.
-9-
Production of Ethylene Glycol
History. (30) .
Ellis stated that the glycols or dihydric alco-
hols derived from the olefins contain two hydroxyl groups attached
to adjoining carbon atoms in the chain and are referred to as
1,2-glycols. Although ethylene glycol, the simplest and most im-
portant member of the series, was discovered as early as 1857 by
Wurtz, this material was merely a laboratory product until about.
1925. The commercial development and large scale production or
the glycols and especially of ethylene glycol, is undoubtedly due,
in a large measure, to the availability of large supplies of cheap
. ethylene as a by-product in the cracking of higher petroleum
fractions.
The conversion of olefins into glycols is exemplified by
the following reaction:
0~ CH20H /I +¾0+0 _,.I. . 0~ OH20H
Crawley{ 2S) stated that the economical production of ethylene
glycol by the methods. now used depends on cheap sources of ethylene
and chlorine. The ethylene is either produced from ethyl alcohol
or separated from the unsaturated gases produced in the cracking
of petroleum oils. For large scale production of ethylene glycol
three principal processes have been used industrially, namely
-10-
(1) the hydrolysis of ethylene dichloride, (2) the hydrolysis or
ethylene chlorohydrin, end (3} ·the hydrolysis of ethylene oxide •.
Briefly, the most common of these according to CrawleyC28) is the
co~version of ethylene to ethylene chlorohydrin with hypochlorous
acid. The monochlorohydrin is then hydrolyzed with a weak alkali
such as sodium bicarbonate. The product of this hydrolysis is
ethylene glycol, which must be concentrated by steam distillation.
Conversion of Ethylene Dichloride to Ethylene Glycol. Y..atter<48Ha3)
proposed to hydrolyze ethylene dichloride by heating it in a
closed vessel with an aqueous alkali bicarbonate solution in the
presence of sheet copper as a catalyst. For example, 100 parts by
weight of ethylene dichloride were heated nth a solution or 180
parts of sodium bicarbonate in 1900 parts of water in a closed
vessel for six hours at 130-140°c, the liquid being stirred con-
tinuously and a sheet of copper being used as a catalyst. After
cooling, the liquid was neutralized, concentrated, and fractional-
ly distilled. In this way about 50-55 parts by weight of glycol
were obtained. It was shown that aldehydes began to b_e formed in
quantity if the hydrochloric acid content of the liquid exceeded
1%. A method of autoclave treatment was therefore adopted, which
included the addition of alkali at intervals to neutralize excess
HCl.
-11-
Conversion ·of Ethylene Chlorohydrin to Ethylene Glycol. Eilis{ 30)
found that a number of processes used ethylene chlorohydrin as the
starting material tor the manufacture-of ethylene glycol. The hy-
drolysis of ethylene chlorohydrin was affected for the most part,
with aqueous solutions of weak alkalies, such as sodium bicarbonate
according to the reaction:
CH20H CH20H I + Ne.H003 -+- I + NaCl + CO2 C¾Ol CH20H
The use of anhydrous caustic alkalies resulted in the for-
~tion of olefin oxides, whereas more dilute caustic alkalies
· promoted the formation of tarry- non-distillable materials. (25) · Brooks stated that when aqueous solutions of ethylene or
propylene chlorohydrin were heated with aqueous sodium bicarbon-
ate, marked evolution of carbon dionde ensued at about 65° c. By refluxing w1 th sodi~ bicarbonate, yields of 44-48% of the
theoretical were obtained, the remainder being converted into
olefin oxides which, on account ot their volatility, were lost.
By carrying out the reaction in a closed autoc_lave at 105-110°0
tor two hours, yields of ethylene glycol of 90% were obtained.
The remaining 10-~ was converted into tarry material which could
not be distilled without decomposition even under 10 mm pressure.
Calcium and magnesium hydroxide were not satisfactory for the
hydrolysis as they firmly retain the glycol.
-12-
Sa~ders and Wignall(Gl){ 30) described a continuous process
for the vapor phase hydrolysis of. ethylene chlorohydrin to
ethylene glycol or ethylene on.de by a solution of sodium carbon-
ate or sodium hydroxide respectively•. At the bottom of a scrubber
tower lagged and filled uith_packing, a steady stream of steam
entered and was adjusted so t!18.t it was exactly sufficient to vol-
atilize and carry upwards the ethylene chlorohydrin contained in
the solution. The current of steam laden with chlorohydrin tra-
versed a fractionating column and passed·away at the top, carry-
ing 95% of the chlorohydrin contained in the crude solution. The
vapor then passed down a well-lagged pipe to the bottom of a
second packed ·tower. The admixed ethylene chlorohydrin vapors
and steam ascending this tower met a down-flowing solution of
sodium carbonate (if ethylene glycol was to be obtained) or caustic
soda (if ethylene oxide was desired) admitted in the correct pro-
portions. The _ethylene chlorohydrin was hydrolyzed to the glycol
with concomitant production of salt, while steam, carbon dioxide,
and volatile unhydrolyzable impurities passed away to a condenser.
The ethylene glyc?l dissolved in the salt solution and was carried
down to the bottom of the tower and then flowed from the trap
direct to a desalter. When ethylene oxide was formed, it passed
away at the top of the tower and was dried and collected.
-13-
Fieser and Fieser( 33} maintained that the preparation of
ethylene glycol from ethylene chlorohydrin was an improvement
because ot the greater rate of hydrolysis, and because, since
only half the amount of soda is required, separation ot sodium
chloride from the product was facilitated. This operation was
avoided completely by converting the chlorohydrin into ethylene
oxide with either caustic or soda lime which was rapidly hydro-
lyzed by a dilute acid, such as hydrochloric or sulfuric.
Catalytic Vapor Phase Oxidation of Ethylene to Ethylene
Oxide. The development of a suitable catalyst and the discovery
of the best method of applying it have been the aims of many in-
vestigators. McBee, Haes, and WisemanC50) stated that ot the
numerous materials tested and reported at least partially suc-
cessful, silver and certain of.its compounds seemed to be the
most desirable catalysts yet found. This metal was used either
alone or in alloys. More commonly, however, a silver compound,
such as the oxide, nitrate, carbonate, chloride, or cyanide,
was used to coat a suitable inert carrier.
Almost any inert material which provides a large surface
area can be used as a catalyst carrier. There is evidence, how-
ever, that both the.chemical nature and the physical state of
the carrier had an appreciable effect·upon the activity of the
-14-
catalyst • .Among the catalyst carriers which were tried were
25 mL; graduated cylinders - 250 ml'., 100 ml.; ring
stand and clamp; rubber tubing; crucible, porcelain,
30 ml.; tongs, monel.
-42-
. E. Method of Procedure
l. Introduction. In order to determine the feasibility ot
the process the catalyst yield had to be known. This was obtain--1 . •
ed experimentally sine~ it was n.ot given by Lenth and ~isC 46}.
The glycerol and congeners fraction donated by the Miner
Laboratories had to be identified with the product reported by
Lenth and DuPuis( 4s). The specific gravity and the glycerine
concentration by the bichromate method were determined.
The viscosity, specific gravity, and freezing point of
various mixtures of propylene glycol - glycerol and congeners-
water were compared with ethylene glycol-water mixtures to test
their suitability as an automotive antifreeze.
2. Determination of Yield of Catalyst. Two experimental
runs were made for the purpose of detennining the percentage
yield that could be ez:pected in the preparation of the copper
aluminate catalyst. The preparation consisted primarily of four
main steps, mixing, centrifuging, drying and ignition. The fol-
lowing procedure was used~
1. Following the procedure given by. Lenth and DuPuisC46 }
25 grams cupric sulfate was placed in a one gallon
jug, 64.7 grams aluminum sulfate dissolved in 328
ml. of hot water, and 51.8 grams soda ash dissolved
-43-
in 230 ml. of hot water. The aluminum sulfate
solution was then poured into the gallon jar
with the cupric sulfate. Then the soda ash
solution was added slowly with vigorous stirring.
The mixture was stirred for about 30 minutes .
atter all the soda ash had been added and was·
~hen allowed to stand for approximately 24 hours
with occasional stirring to assist in driving
out the carbon dioxide.·
2. The mixture was then centrifuged in a 5 inch
basket centrifuge with a maximum rpm of 3600.
The mixture was centrifuged five times in order
to recover as much of the precipitate as possible.
The cake was then washed with hot tap water until
the wash water showed only a faint cloudiness
when a few drops of a dilute barium chloride
solution was added.
3. The cake was then removed from the basket and
broken up into approximately one-half inch
lumps which were placed into a 1000 ml. evapo-
rating dish. The evaporating dish was then
placed in a.drying oven at uo 0c -5 for 24 hours.
-44-
Upon removal from the drying oven, the dried ·
cake was weighed on a double beam balance after
the cake had been allowed to cool for 30 minutes ...
4. Then a sample of this cake was placed in a cruci-
ble and weighed.· The crucible was then placed
in amuffle-fumace at 96o0 c -10° for five minutes.
After removal from the furnace, the samples were
allowed to cool one hour before weighing~
· Two additional runs were made to correlate
the first- two runs.
3. Identification of Glycerol and Con:gerers Fraction. Glycer-
ine content of the glycerol and conge:iierafraction·as received was
determined by the Bichromate method.(s 3} .A. sample of "glycerol and
congeners" of not more than 3 grams was weighed. This ws.s dis-
solved in 200 ml. of hot water in a 600 ml. beaker, end 25 ml.
of 1:4 sulfuric acid was added. This• solution was then allowed
to boil for 20 - 30 minutes. The contents were then cooled to
room temperature and diluted to about 400 ml. to which O. 25 gram
silver sulfate was added. ·. After the precipitate settled to the
bottom, a portion of the contents of the calibrated flask was
filtered discarding the first 10 - 15 ml. Fifty m1.·of the fil-
trate was pipetted into a 250 ml. beaker, and 50 ml. of water
-45-
was placed in a similar beaker as a blank. Seventy-five ml. of
a solution containing 74.553 grams of potassium bichromate per
liter were added to the sample, and_25 ml. of the same solution
was added to the blank.· Twenty-;'ive ml. of concentrated sul- _
furic acid was added to each, stirred thoroughly, end covered
with a watch glass. Both of these solutions were then kept at
a temperature of 90-100°0 for approximately two hours. The
solutions were cooled, transferred to one liter volumetric
flasks, and diluted to volume. After the solutions were mixed
well, 50 ml. of each was pipetted to which was added 50 ml. or
water and 20 ml. of 10--; potassium iodide solution. Each solution
was then titrated with O.lN sodiwn thiosulfate solution, usins
starch indicator when near the end point. The final color is
green. The calculation of the glycerine content was the same
as used by Snell.and Biffen( 63}.
4. 1IBkeup of Propylene Glycol-Glycerol and Congeners-Water
Solutions. Since the antifreeze to be tested was to consist of
only the propylene glycol and glycerol and congeners obtained in
the catalytic hydrogenation of sucrose, a solution of 61.2% by
weight propylene glycol and 38.8% by weight glycerol and con-
geners was made up. This ratio is the same as the yield given
by Lenth and DuPuis( 4G}. Solutions of 10, 15, 25, 30, 35, 40
-4:6-·
and 4:5% by volume of propylene glycol-glycerol and congeners-
were made up with distilled water to contain a total of 32 ml.
5. Determination of Viscosity and Specific Gravity of
Antifreeze 1ti:rtures of Propylene Glycol-Glycerol and Congeners-
Water. The Ostwald viscosimeter was calibrated against dis-
tilled water at 20°c and 85°c and against sucrose solutions of
20 and 40% at 20°c. Each viscosity time was taken using a 5 ml.
sample of the material being tested. Si~ce the viscositiea( 55 )
and the specific gravities( 40} of each were known at the tempera-
ture at which the experiments were carried out, the kinematic
viscosities could be calculated and.plotted against the corre-
sponding times giving a calibration curve by which the kinematic
viscosity of other solutions could be determined by kn.owing the
time (Figure 1).
The Ostwald-Fenske viscosimeter was calibrated against a . 0
60%.sugar, 76, ?0.3, 66.3 and 62.5% glycerol solutions at 25 C
in a similar manner as the Ostwald Viscosimeter (Figure 2).
The flow times of.the solutions were determined at the
temperatures shown in Table VI.
The specific gravity of these mixtures were determined at
the temperature of each test with a Westphal balance~ The tem-
peratures for the tests using the Ostwald viscosimeter were
obtained with an Aviation Engine Thennometer Test Unit Type
AVT-CHT-P. The temperatures for the tests using .the Ostwald-
Fenske viacoaimeterwere obtained by using crushed ice and
salt mixtures for temperatures below 25°c and by hot water
above 25°c.
To obtain the.viscosity o~ the solutions at their freez~
ing points, it was necessary to extrapolate this data by making
use of Duhring's plot( 55 )_ This was• done in the following
manner: the viscosity for a s~i sucrose solution;was plotted
against its corresponding temperature (Figure 6) •. Then by
using the curve of absolute viscosity vs. temperature in Figure
5 for each mixture of propylene glycol-glycerol and congeners-
water, several viscosities and their corresponding temperatures
were obtained. To obtain a Dµhring's plot, the temperatures at I
which the 60% sugar solution and the antifreeze solutions had
the same viscosities were plotted against each other_ in Figure
7. These points fell on.a straight line and could be extrapolated.
Since the freezing point of the antifreeze mixture was known,
the temperature of the 60% sucrose solution which had the same
viscosity was obtained from Figure 7. Then the viscosity of the
freezing mixture could be obtained fro::n Figure 6.
-48-
6. Cooling Curve Data for Antifreeze Mixtures of Propylene
Glycol-Glycerol and Congeners-Water. Cooling curve data was
collected for mixtures of 10, 15, 25, 30, · 35, 40 and 45% by
volume·propylene glycol-glycerol and congeners in the follow-
ing manner: · The Aviation Engine Thennometer Test Unit· was used
as the refrigerating· source •. The refrigerator was started and
allowed to cool to at least 10°c lower than room temperature
before the sample was placed in the cooling bath. The tempera~
ture of the cooling bath and the temperature of the antifreeze
mixture were recorded·every minute. After the antifreeze mix-
ture reached a constant temperature, when the antifreeze mix-
ture began to crystallize, the run was continued until the tem-
perature·of the mixture had reached a temperature at least 5°c below the constant temperature. This procedure was used for
all mixtures except the 45% mixture. In this test, a tempera-
ture 5°c below the constant temperature was not obtainable due
to the limits of the machine. The temperature of the cooling
bath was regulated so that at no time prior to the constant
temperature level the temperature of the mixture was within 5°c
of the cooling bath. In order to maintain this temperature dif-
ference for the higher percentages, 30, 35, 40 and 45% by volume,
the initial temperature difference between the mixture and the
cooling bath had to ba between 30 and 40°0.
-49-
7. Plant Design and Location. On the basis of the experi-
mental work and the data of Lenth and DuPuis{45) and stengel and
.Maple(54)(S 5),-a :plant was d~signed to produce 3000 pounds per 3 ' . .
hours of an antifreeze consisting of propylene glycol and glycerol
and congeners. Mate;ial ·and heat balances( 35-42 ) (54)( 59) were ·
made across each piece of equipment.· After these balances were . .
ma.de, equipment was either designed or selected from those used
in industry as to size(2-6)(8)(10)(13-l4){16-20)(47)(52)(56-60)
(66- 68)( 7i- 74) ~d location in the plant. The cost of equip-
ment, installation, and operation w.a"s determined< 36-42) (54) (69).
The plant location was selected on the basis of availa-
bility of raw materials, market, transportation, labor and
power< ?O).
-50-
F. Data and Results .
The yield that was obtained in the preparation of the copper
aluminate catalyst is given in Table III.
The comparison of the glycerol and congeners used and that
reported by Lenth and DuPuis is given in Table v. The calibration data for the Ost~~ld and Ostwald-Fenske
viscosimeters is given in Table IV, and this data is plotted in
Figures 1 and 2.
The specific gravity, temperature, time concentration,
absolute viscosity, and kinematic viscosity for varying mixtures
of propylene glycol-glycerol and congeners-water are given in
Table VI. This data is plotted in Figures 3, 4, 5, 8 and 9.
The absolute viscosity of a 60% sucrose solution at vary-
ing temperatures is shown in Table VII and is plotted in Figure 6.
The data f~r Duhring's plotC 55 ) is shown in Table VIII.
This data was obtained by using Figures 5 and 6 and plotting the
temperature of propylene glycol-glycerol and congeners-water mix-
tures against the temperatures of 60--p sucrose solutions having
the same vi sco si ty in Fi gur'a 7.
The cooling curve data for various mixtures of propylene
glycol-glycerol and congeners-water is given in Table IX and
plotted in Figure 10. The data before five minutes and after
sixteen minutes was not included since it was not important.
-51-
The freezing points and the viscosities at the freezing
points ot various mixtures are summarized in Tables X and
plotted in Figures 5 and 11.
A comparison of ethylene glycol and propylene glycol-
glycerol and congeners from the standpoint of viscosity and
freezing point is shown in Table n.
RUN NO.
l
2
3
4
-52-
TABLE III
DATA AND RESULTS
PREPARATION OF COPPER .ALUMINATE*FROM 25 GRAMS OF CUPRIC SOI.FATE, 64. 7 GRAMS OF .~UMINUM SUL-FATE IN 328 ML. OF HOT WATER, AND 51.8 GRAMS OF SODA ASH m 230 ML. OF HOT WATER.
Tnm YIELD BEFORE IGNITION YIELD .AFTER IGNITION LOSS IGNITION
(Hrs.) (Grams) (%) (Grams)
24 29.3 28.3 21.10 Aluminwn sul-
24 32.4 18.6 26.38 :rate used in Runs 2 and 3
24 28.5 15.0 24.25 not the same as Runs l and
24 26.4 20.0· 20.12 4.
*Lenth, C. W. and DuPuis, R. N. Polyhydric Alcohol Production. Ind. En.gr. Chem. ~' 152-7, (1945).
.... 53_
TABLE IV
DATA .AND RESULTS
CALIBRATION OF OSTNALD A.~D OSTV/ALD-FENSKE VISCOSIMETERS
TIME SP. GR. VISCOSITY (Centi. poises)
KINEMATIC VISCOSITY
(Centi-stokes)
TEMP.
OSTWALD
Water
water
20% sugar
40% Sugar
OSTW.ALD-FEN'SKE
(Sec.)
68.2 0.9982
28.8 0.9686
1.000
0.336
125.0 l.0810 . l.967
3158.0 l.1764 6.223
60Cp sugar 130.0 1.2856 44.02
76% Glycerol 103.0 1.1980 30.56
70.3% Glycerol 69.4 1.183 18~48-
66.3% Glycerol 47.6 1.172 13.54:
1.002
0.346
l.815
5.290
34.02
25.40
· 15.60
11.55
20
85
20
20
25
25
25
25
62.3% Glycerol 32.3 1.161 10.35 8.92 25 SUGAR DATA
l. Hodgman, C. D. ttHandbook of Chemistry and Physicstt. Pg. 1633-4. Chemical Rubber Publishing Co., Cleveland, Ohio. 1946. 30th Ed.
2. Perry, j. H. ttChe~ical Engineers' Handbook~. Pg. 788-98. McGraw-Hill Book Co., Inc., New York. 1941. 2nd Ed.
GLYCEROL·. DATA l. Hodgman, C. D. "Handbook of Chewistry and Physics".
Basis: 3000 pounds antifreeze per 3 hour cycle {All weights in pounds)
(See Figure 12}
Note: Left hand-entering; right hand-leaving
A-1 Copper Sulfate Storage
Copper Sulfate 563..4
A-2 Aluminum sulfate Storage
Aluminum sulfate 1455.8
A-3 Soda Ash Storage
Soda Ash Cat. Soda Ash Hydro.
1164.7 18.6
1183.3
A-5 Methanol storage Tank
Methanol supply 4644 Methanol -Loss 232.2
A.-6 Hydrogen Storage
Hydrogen
4876.2
155
A-7 Hot Water Pump (85-90°F)
Water Alum. Water Soda Ash· • Water, Wash
Steam
7382.0· 5172.4. 1411.0
. 13965.4
873.0 14838.4
Copper sulfate 563.4 to B-1
Aluminum sulfate 1455.8 to B-1
Soda Ash Cat. ll64.7 to B-3 Soda Ash Hydro. 18.6
1183.3
Methanol Supply 4644 Methanol Loss 232.2
Hydrogen
vrater Alum •. Water Soda Ash Water, Wash
Steam
4876.2
155
7382.0 to B-1 5172.4 to B-3 1411.0 to C-1
·13965.4
873.0 14838.4
-77-
B-l·Dissolving Tank (85-90°F}
From. A-l Copper Sulfate 563.4 .copper SUltate 563.4' A-2 Aluminum Sulfate 1445.8 Aluminum SUlfate 1344.8 to B-2 A-7 Water 7382.0 Water 7382.0
9401.2 9401.2
B-2 Dissolving Tank Pump
From .B-1 Sama as·B-1 Same as B-l to B-3
B-3 Reactor
From Copper Sulfate 563.4 Carbon Dioxide 388.7 to vent
B-2 Aluminum Sulfate 1455.8 Sodium Sulfate 1271.7 Water 7382.0 Soda Ash 231.3 to B-4 A-3 Soda Ash 1164.7 Copper Aluminate 402.9
A-7 Water 5172.4 Water 13443.7 15738.3 15738.3
B-4 Reactor Pump
From. Sodi µm Sulfate 1271.7 Sodium Sulfate 1271.7 Soda Ash 231.3 Soda Ash 231.3
to C-1 B-3 Copper .Aluminate 402.9 Copper Aluminate 402.9 Water 13443.7 Water 13443.7
15349.6 15349.6
C-1 Centrifugal Filter
From Sodium Sulfate 1271.7 As Solid Soda Ash 231.5 Sodium SUlt'ate ·46.4
B-4 Copper Aluminate 402.9 Soda Ash 15.1 Water 13443.7 Copper Aluminate402.9 to C-2
Water 2010.8 2475.2
From A-7 Wash V[ater
0-2 Belt ConTeyor
From Sodium Sulfate Soda Aeh
-78-
14ll.O As Liquid 16760.6 Water 11432.9
Wash Water 1411.0 Soda Ash 216.2 Sodium Sulfate 1225.3
Sodium Sulfate Soda Ash
14285.4 2475.2
16760.6
46.4 15.l
C-1 Copper Aluminate Water
46.4 15.l
402.9 2010.8 2475.2
Copper Aluminate Water
402.9 to D-1
D-1 Rotary Dryer (200-210°F)
Fran Sodium Sulfate
0_2 Soda Ash c·opper Aluminate Water Steam
46.4 15.l
402.9 2010.8 3592.5 6067.7
Air 211,252 cu. ft.
D-2 Belt Conveyor
From Sodium Sulfate 46.4 Soda Ash 15.1
D-1 Copper Aluminate 402.9 Water 154.3
618.7
D-3 Rotary Kiln (1810-1830°F) From.
Sodium Sulfate 46.4 D-2 Soda Ash 16.l
Sodium Sulfate Soda Ash Copper Aluminate Water Water Vapor Steam Condensate
2010.8 2475.2
46.4 15.1
402.9 164.3
1856.5 3592.6 606'7.7
Air 211,252 cu. ft.
Sodium Sulfate 46.4 Soda Ash 15.l Copper Aluminate 402.9 Water 164.3
618.7
Sodium Sulfate 46.4 Soda Ash 15.l
to D-2
to waste
to D-3
to D-4
From Copper Aluminate
D-2 Water
-79-
402.9 Copper .Alurninate 154.3 618.7 Water Vapor
402.9 to D-4 464.4 154.3 to waste 618.7
· Fuel 011 Air·
3 gals. Fuel 011 2085 cu. ft. Air
3 gals. 2085 cu. ft.
D-4 Conveyor Cooling Kiln (200-2200.F)
From Sodium Sulfate
D-3 Soda Ash Copper Aluminate
Air 61,000
E-1 Crushing Rolls
From Sodium Sulfate
D-4· Soda Ash Copper Aluminate
E-2 Belt Conveyor
From E-1 Same as E-1
F-1 Hydrogen Compressor
From· A-6 Same as A-6
F-2 Methanol Pump
From A-5 Same as A-5
F-3 Sugar Feed Hopper
Fran A-4 Same as A-4
46.4 15.l
402.9 464.4
cu. ft.
46.4 15.l
402.9 464.4
Sodium sulfate 46.4 Soda Ash 16.1 to E-1 Copper Aluminate 402.9
464.4 Air 61,000 cu. ft.
Sodium SUlfate Soda Ash Copper Aluminate
Same as E-1
Same as A-6
Same as A-5
Same as A-4
46.4 15.l to E-2
402.9 464.4
to F-4
to F-4
to F-4
to F-4 ·
-80-
F-4 Autoclave (1500 psig, 460-465°F)
From F-1 Hydrogen 1550 Methanol 4876.2 F-2 Methanol 4876.2 Catalyst 464.4 F-3 sugar 4644:.0 P. G. 1834.6 A-3 Soda Ash 18.6 G. C. 1165.6 to F-5 E-2 Catalyst 464.4 Water 1123.8
10158.2 Residue 510.8 Loss 182.8
10158.2
F-5 Condenser (135-140~)
From Methanol 4876.2 Methanol 4876.2 Catalyst 464:.4 ·. Catalyst 464.4 P. G. 1834.6 P. G. 1834.6
F-4 G. O. 1165.6 G. C. 1165.6 to F-7 Water 1123.8 Water 1123.8 Residue 510.8 Residue . 510.8 Loss 152.8 Loss 152.8
10128.2 10128.2 Cooling Water 3615 gals. Cooling Water 3615 gals.
F-6 Condenser Cooling Water Pump
Cooling Water 3615 gals. Cooling Water 3615 gals. to F-5
F-7 Condensate Pump
From Methanol Catalyst P. G.
F-5 G. O. Water Residue Loss·.
G-1 Basket Centrifuge
From F-7 Methanol
Catalyst
4876.2 Methanol 464.4 Catalyst
1834.6 P. G. 1165.6 G. C. 1123.8 Water
510.8 Residue 152.8 Loss
10158.2
4876.2 As Solid 464.4 Catalyst
4876.2 464.4
1834.6 1165.6 to G-1 1123.8 510.8 152.8
10158.2
464.4: to waste
-81-
P. G. 1834.6 As Liquid G. C. 1165.6 Methanol 4876.2
F-7 Water 1123.8 P. G. 1834.6 Residue 510.8 G. C. 1165.6 Loss 152.8 Water 1123.8 to G-2
10158.2 Residue 510.8 Loss 152.8
9693.8
G-2 Basket Centrifuge Pump
Fran Methanol 4876.2 Methanol 4876.2 P. G. 1834.6 P. G. 1834.6 G. C. 1165.6 G. C. 1165.6
G-1 Water 1123.8 Water 1123.8 to H-1 Residue 510.8 Residue 510.8 Loss 152.8 Loss 152.8
9693.8 9693.8
H-1 Atmospheric Still (140-212°F)
From Methanol 4876.2 As Vapor P. G. 1834.6 Methanol 4644 to H-2 G. C. 1165.6 Water 1123.8
G-2 Water 1123.8 5767.8 Residue 510.8 As Liquid Loss 152.8 P. G. 1834.6
9693.8 G. C. 1165.6 to I-1 Steam 6924.0 Residue 510.8
16,617.8 Loss 415.0 3926.0
Steam Condensate 6924:.0 Vapor 5767.8
· 16,617.8
H-2 Atmospheric Still Condenser (70-75°F)
From Methanol 4644 Methanol 4644 to H-:3
H-1 Water 1123.8 Water 1123.8 to waste 5767.8 5767.8
Cooling Water 14,617 gels. Cooling Water 14,617 gals.
-82-
H~3 Condensate Pump
From H-2 Methanol 4644 ?.."ethanol to A-5
H-4 Condenser Cooling Water Pump
Cooling Water 14.617 gals. Cooling Water 14,61J gals. to H-2
H-5 Atmospheric Still Pump
From P. G.
H l G. O. - Residue
Loss
1834:.6 1165.6 510.8 415.0
3926.0
P. G. G. O. Residue Loss.
1834.6 1165.6 to I-1 510.8
415.0 3926.0
I-1 vacuum Still (26 in. vac., 130-227°F)
From P. G.
H-5 G. C. Residue Loss
Steam
I-2 Vacuum still Condenser
From I-1 P. G.
G. C.
1834.6 ll65.6 510.8 415.0
3926.0 1874.0 5800.0
1834.6 1165.6 3000.2
Cooling Water 4646.9 @l!ls.
I-3 Vacuum Pump
As Vapor P. G. .1834.6 to I-2 G. O. 1165.6
3000.2 As Liquid
Residue 510.8 to waste Loss 415.0 925.8
Steam Condensate 1874.0 Vapor 3000.2
5800.0
· ~: ~: ~:::: to j-l 3000.2
Cooling Water 4646.9 gals.
Air 150 g.p.m. Air 150 g.p.m. to I-1
-83-
I-4 Condenser Cooling Water Pump
Cooling Water 4646. 9 €13,ls. Cooling Water 4646. 9 gals. to I-2
I-5 Condensate Pump .
From
I-2 p. G. 1834.6 G. c. 1165.6
3000.2
J-1 Antifreeze Storage·
From I-5 P. G. 1834.6
G. c. 1165.6 3000.2
Note:
P. G. = Propylene Glycol
G. C. = Glycerol and Congeners.
Cat. = Catalyst
Hydro.= Hydrogenation
Alum. = Aluminum Sulfate
P. G. G. c.
P. G. G. c.
1834.6 1165.6 to J-l 3000.2
1834.6 1165.6 3000.2
-86-
Equipment Specifications
A-l Copper SUlfate storage
Minimum supply: 4 weeks Repleni ahmen t period: 4 weeks . Capacity of area: 10 weeks Containers: 500 lb. barrel Requirement per 3 hour cycle: 563.4 lbs. or 1.125 barrels Cycles per day: 8 Requirement per day: 1.125 x 8 = 9.00 barrels Working days per week: 5 Requirement for 10 weeks: 9 x 5 x 10 = 450 barrels Dimensions or barrel: 30 in. dia. and 36 in. height Floor area required: 2.5 x 2.5 x 450 = 2812.5 sq. ft. Height or ceiling: 9 feet Type of floor: · concrete
A-2 Aluminum sulfate storage
Minimum supply: 4 weeks Replenishment period: 4 weeks Capacity of area: 10 weeks Containers: 400 lbs. barrel Requirement per 3 hr. cycle: 1455.8 lbs. or 3.64 barrels Cycles per day: 8 · Requirement per day: 5.64 x 8 = 29.l barrels Working days per week: 5 Reqµirement for 10 weeks: 29.l x 5 x 10 = 1450 barrels Dimensions of barrel: 22 in. die.. and 34 in. height Floor area required: 1.835 x 1.835 x 1450 = 4870 sq. tt. Type of floor: concrete Height of ceiling: 9 feet
A-3 Soda Ash Storage.
Minimum supply: 4 weeks Replenishment pertod: 4 weeks Capacity of area: 10 weeks supply, Containers: 100 lb. bags Requirement per 3 hour cycle: 1164.7 18.6: ll83.3 Cycles par day: 8 Requirement per day: 9466.4 lbs.
-87-
Working days per week: 5 Requirement for 10 weeks: 473,320 lbs. Number of bags: 4733 bags . Height of storage pile: 8 bags Area of bag: 2.5 x 1.5 = 3.75 sq. ft. Floor area required: 3.75 x~ = 2,220 sq. tt.
8 (Assume 10--~ of area for bags}
Height of ceiling: 9 feet Type of floor: concrete
A-4 SUgar Storage
Minimum supply: 2 weeks Replenishment period: 2 weeks Capacity of area: 5 weeks Containers: 100 lb. bags RequireIOOnt per 3 hour cycle: 4644 lbs. Cycles per day: 8 Requirement per day: 37,152 lbs. Working days pe.r week: 5 Requirement for 6 weeks: 37,152 x 5 x 6 = 1,014,560 lbs. Number of bags: 10,014.56 or 10,015 bags Height of storage pile: 8 bags Area of bag: 2.5 x 1.5 = 3.75 sq. tt. Floor area required: 10,015
3.75 X 8 = 4730 CU. ft. (Allow 10% of area for bags)
Haieht of ceiling: 9 feat Type of floor: concrete
A-5 Methanol Storage Tank
Minimum supply: 2 weeks Replenishment period: 4 weeks Capacity of area: 8 weeks Containers: 8000 gal. tenk car Capacity of tank car: 8000 x 8.335 x o •. 659 = Requirement per 3 hour cycle: 232.8 lbs • . Cycles per day: 8 . Requirement per day: 232.2 x 8 = 1857.6 lbs.
43,492 lbs.
Working days per week: 5 Requirement for 8 weeks: Necessary volume of tank:
1857.6 x 5 x 8 = 74,304 lbs. ..,,.,,.._7.,..4 .... , ... 3...,0,..4___,,,'""=" = 1510 cu. ft • 62.4 X 0.7913
Safety allowance 10-% 151 1661 cu. ft. or 12,200·gals.
-88-
Equipment available from: Lancaster Iron Works Inc., Lancaster, Pennsylvania Tank Dimensions: o.c., 96 in •
. Length, 41 ft. 2 in. Shell Thickness, 0.540 in. Capacity, 15,000 gals.
Number required: one tank
A-6 Hydrogen storage
Minimum supply: 2 weeks Replenishment period: 4 weeks Capacity of area: 8 weeks Containers: cylinders, 1600 psig, Requirement per 3 hour cycle: 155 Cycles per day: 8 ·
3 180 ft. , 101.75 lbs. lbs.
Requirement per day: 155 x 8 = 1240 lbs. Working days· per week: 5 Requirement for 8 weeks: l240 X 8 X 5 = 487 cylinders
101.75 Dimensions of cylinder: 9 in. dia. and 55 in. height
Floor area required: 9 x 9 x 487 • 274 sq. tt. 12 X 12
Height of ceiling: 9 feet Type of floor: concre.te
A-7 Hot Water Pump
Capacity: 90,gpm ~Iaterials handled: hot water Head : 10 . feet Type : open impeller, single stage, centrifugal Material of construction: caat iron. RPM: 1200 · · Motor: lBP, 220-440 volts, 3 phase, 60 cycles, .MJ, in-
Motor -·westingliouee Elec. and Mfg. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,
N. ;r., Type OF-1 Number re(lUir~d: one mot or and one pump
B-1 Dissolving Tank
Capacity: 1480.gal. Shape: cylindrical
-90-
B-3 A Agitator
Type: "Lightin" mixer, Model M-2 RPM:· 1150 Material of construction: mild steel shaft and blade Motor: 2 HP, 220-440volts, 3 phase, 60 cycles, AC Equipment available frcm:
Mixing Co., Inc., Rochester, N. Y. · Number required: one
B-4 Reactor Pump
Capacity: 134 gpm Materials handled: suspensions Head: 15 feet Type: open impeller, single stage, centrifugal Material of construction: cast iron RPM: 1200 · Motor: 2 HP, -220-440 volts, 3 phase, 60 cycles, AC, in-
duction, squirrel cage, splash-proof, 1750 rpm Equipment available from:
Motor - Westinghouse Elec. and Ivifg. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,
N. J., Type CF-1 Number required: one pump and one motor
C-1 Centrifugal Filter
Capacity: 15,349.6 x 4 = 61,400 lbs. per hour Volume capacity: 2176 3C> • 72.5 gpm
Type: Solid bowl continuous Material of construction: mild steel Equipment available as:
Size (in} - 24 x 38 HP - 25,220 440 volts, 3 phase, 60 cycles, AC
induction, squirrel cage, splash-proof, 1750 rpm
Solids, cu. ft. per hour - 60-90 Max. teed GPM - 70 Bird Machine Co. , East Walpole, Mass.
-91-
C-2 Belt Conveyor
Capacity: 165 lbs. per minute Length of belt: 10 f'eet Width of belt: 18 in. Speed of belt: 40 f'eat per minute Motor: 0.5 HP, 220-440 volts, 3 phase, 60 cycles, A. C.
induction, squirrel cage, splash-proof, 1750 rpm Belt: 4 ply, 23 oz. Link Belt "Service Brand" duck Equipment available from:
Link-Belt Co., -Chicago, Ill. -
D-1 Rotary Dryer
Capacity: Evaporation rate - 1856.5 lbs. water per hour Steam rate - 2237 lbs. per hour (5 lbs. gage) Air rate - 1760 cu. tt. per minute
Type : Rot'ary, · direct steam heated Material of construction: mild steel Dimensions: O.D. 8 feet
Roots-Connersville Blower Corp. Connersville, Indiana Victor Acme Blower No. 36
D-4 Convey or Cooling Kiln
Capacity: Air rate: 813 cu. ft. per minute Solids rate: 371 lbs. per hour
Type: Belt· conveyor
-93-
Material of construction: Belt - woven steel wire Housing -·i in. sheet steel
Dimensions: · Belt - 5 series of belts, 26 ft. long and 3 ft. Wide
. Housing - 5 x 5 x 26 feet Speed of belt: 2.2. feet per minute Motor: 2 HP, 220-440 volts, 3 phase, 60 cycles, AC, in-
duction, squirrel cage, splash proof, 1750 rpm Equipment available from:
Link-Belt Co., Chicago, Ill.
D-4 A Blower
Capacity: 1000 cu. ft. per minute Type: Single stage pedestal turbo blower RPM: 3500 . Pressure: 1 lb. gage Motor: 10 HP, 220-440 volts, 3 phase, 60 cycles, AC, in-
duction, squirrel cage, spiash-proo:f, 3500 rpm · Equipment available from:
Allis Chalmers·~ttg. Co., ~lwaukee, Wisconsin
E-1 Crushing Rolls .
Capacity: Feed - 928.8 lbs. per hour, i in. Product - 928.8 lbs. per hour, -50 mesh
Type of material:· very brittle Type of crusher: single roll crusher Material of construction: mild steel Dimensions {in): 18 x 18 Motor: 10 HP, 220-440 volta, 3 phase, 60 cycles, AC, in-
duction, squirrel cage, splash-proof, 1750 rpm Equipment available from:
C. o. Barlett and Snow Co., Cleveland, Ohio
E-2 Belt Conveyor
Capacity: 31 lbs. per minute Length of belt: 30 feet Width of belt: 18 in. Speed of belt: 40 ft. per minute
Insulation: 3 in. magnesia (85%} Equipment available from:
\ Blaw-Knox Co., Pittsburgh, Pa.
F-5 Condenser
Size of condenser tubes: · l½ in. O.D., 16 B.W.G. Tube spacing - 3/8 in. Inside surfaoe area of tubes: 819 sq. ft.
-96-
· Length of tubes: 23 feet Number 01' tubes: 100 Diameter of tube shell: 22 in. TU.bing material: 0.15 carbon steel Condenser shell material: cast iron Type of condenser: Horizontal, double pass, countercurrent
flow, floating head shell. Type of baffles: orifice Vapor path: outside tubing; in at 464°F, out at 140°F;
velocity 169.3 lbs. per minute Liquid path: Inside tubing; in at 50°F, out at 200°F;
velocity 60.2 gpm Equipment available from:
\Blaw-Knox Co., Pittsburgh, Pa.
F-6 Condenser Cooling Water Pump
Capacity: 60 gpm Materials handled: water Head: 15 feet Type: open impeller, single Materials·of construction: RPM: 1200 ·
Equipment available from: Motor - Westinghouse Elec. and Mfg. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,N.J".
Type CF-1 Number required: one motor and one pump
F-7 Condensate Pump
Capacity: 33.5 gpm Materials handled: fine suspensions Head: 15 feet Type: oper impeller, single stage, centrifugal Niateriala of construction: cast iron BPM: 1200 Motor: l HP, 220-440 volts, 3 phase, 60 cycles, AC, in-
duction, squirrel cage, splash-proof, 1750 rpm Equipment available from:
Motor: Westinghouse Elect. and Mfg. Co., Pittsburgh, Pa. Pump: Worthington Pump and Machinery Corp., Harrison,N.J".
Type CF-1 . . Number required: one motor and one pump
-97-
G-1 Basket Centrifuge
Capacity: 10,158 lbs. per hour Volume capacity: 24 gpm Type: under dri van basket centrifuge Material of construction: mild steel Equipment available as:
Basket capacity - 10.5 cu. ft. Basket diameter - 48 in. Motor - 10 HP, 220-440 volts, 3 phase, 60 cycles, AC,
explosion proof, 3500 rpm American Tool and Machinery Co., Hyde Park, Boston, Mass.
G-2 Basket Centrifuge Pump
Capacity~ 24 gpm Materials handled:· solutions Head: 10 feet Type: open impeller, single stage, centrifugal Material of construction: . cast iron BPM: 1200 Motor: 1/3 HP, 220-440 volts, 3 phase, 60 cycles, AC, in-
duction, squirrel cage, splash-proof, ,1750 rpm Equipment available from:
Motor - Westinghouse Elec. and Mfg. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,N.j.
Type CF-1 Number required: one motor and one pump
H-1 Atmospheric still Pot
Capacity: 1415 gals. Shape: cylindrical with round bottom Diameter: 6 feet Height: a·feet .Material of construction: mild steel Heating surface required: 255 sq. ft.
Steam heating pipes -O.D. (in.) - 2 Spacing (in.} - l Length (ft.) - 3 Number - 163
Connections: Charging entrance through left side, exit entrance in bottom, vapors through rie;ht side.
-98-
Attachments:. one, 0-250°F temperature recorder Insulation: 3 _in. magnesia (85%}. Equipment available from:
Blaw-Knox Co., Pittsburgh, Pa.
H-1 A Fractionating Column
Number of plates: 14: Plate spacing: 18 in. Type of plates: Bubble cap Plate diameter: 2 feet Column height: . 21 feet Liquid seal on plates: · li in. Vapor velocity: 3.25 feet per second Reflux ratio: 3 . :rr.aterials of construction: mild steel Insulation: 3 in. magnesia (85%) Equipment available from:
, Blaw-Knox Co., Pittsburgh, Pa.
H-2 Atmospheric Still Condenser
Size of condenser tubes: li in. O.D., 16 B.W.G. Tube spacing: 3/8 in. Inside surface area of tubes: 458 sq. ft. Isngth of tubes: 17 ft. Number of tubes: 75 Diameter of tube shell: 18 in. Tubing material: 0.15 carbon steel Condenser shell material: cast iron Type of condenser: vertical, double pass, counter current
flow, floating head shell Type of baffle: -orifice . Vapor path: outside tubing; in at 212°F, out at 70°F;
. velocity 81.3 gpm Equipment available from:
Blaw-Knox co., Pittsburgh, Pa.
H-3 Condensate Pump
Capacity: 5. 7 gpm Materials handled: methanol and water Head: 10 feet
-99-
Type: open impeller, single stage, centrifugal Material of construction: cast iron BPM: 1200 Motor: 1/3 BP, 220~440 volts~ 3 phase, 60 cycles, AC,
induction, squirrel cage, splash-proof, 1750 rpm Equillllent available from:
Motor - Westinghouse Elec~ and Mtg. Co., Pittsburgh, Pa. Pump -Worthington Pump and· Machinery Corp., Harrison, N. j.
Type.CF-1 Number required: one J!!-Otor and one pump
H-4 Condenser Cooling Water Pump
Capacity: 81.5 gpm. Niaterials handled: water Head: 30 feet Type: open impeller, single stage, centrifugal Material of construction: cast •iron RPM: 1800 Motor: 2 BP, 220-440 volts, 3 phase, 60 cycles, AC, in-
duction, squirrel cage, splash-proof, 1800 rpm Equipment available from:
Motor - Westinghouse Elec. and ~Itg. Co., Pittsburgh, Pa. Pump - Worthington Punip and Machinery Corp., Harrison,N.j •
. Type CF-1
H-5 Atmospheric Still Pump Capacity: ·33.4 gpm· :tiaterial handled: solutions Head: 10 feet Type:· open impeller, si~gle stage, centrifugal lTaterials of construction: cast•iron · BPM: 1200 Mot or: 1 BP, 220-440 volt a, 3 phase , 60 cycles, AC, in-
duction, squirrel cage, splash-proof, 1750 rpm Equipment available from:
Motor: Vlestinghouse Elec. and Mfg. Co., Pittsburgh, Pa. Pump: -Worthington Pump and Ua.chinery Corp., Harrison,N.j.
· Type CF-1 Number required: one motor and one pump
-100-
I-1 Vacuum Still
Capacity: 435 gala. Shape: cylindrical With round bot tom Diameter: 4 ft. Height : 5. 5 ft • 11aterial of construction: mild steel Heating surface reqµired: 127.5 sq. ft.
Connections: Charging entrance through left side, draw off in bottom, vapor exit through right side
Attachment: one, 0-500°F temperature recorder .one, 0-30 in. vacuum gage
Insulation: 3 in·. magnesia ( 85%) Equipment available from:
\ Blaw-Knox Co., Pittsburgh, Pa.
I-2 vacuum Still Condenser
Size of condenser tubes: l½ in. O.D., 16 B.W.G. TUbe spacing: 3/8 in. Inside surface area of tubes: 123 sq. ft. Length of tubes: 12 ft. Number of tubes: 30 Diameter of tube shell: 12 in. Tubing material: 0.15 ca:rbon steel Condenser shell material: cast iron Type of condenser: horizontal, double pass, counter current
flow, floating head shell Type of baffle: orfice Vapor path: outside tubing; in at lS0°F, out at 100°F;
velocity 16.6 lbs. per minute Liquid path: inside tubing; in at 50°F, out at 77°F;
velocity 25.8 gpm Equipment available from:
Blaw-Knox Co., Pittsburgh, Pa.
-101~
I-3 Vacuum Pu.mp
C~pacity: Piston displacement - 137 gpm Type: horizontal single air· and steam heating vacuum pump Materials of construction: mild steal Dimensions (in.}: x 8 x 7 Piston speed: 53 ft. per minute steam required: 1250 lbs.@ 105 psi Equipment available from:
Worthington Pump and Machinery Corp.,. Harrison, N. ;r. Type AE
I-4 Condenser Cooling Water Pump
Capacity: 25.8 gpm Materials handled: water Head: 15 f't. Type: open impeller, s~ngle stage, centrifugal Material of construction: cast iron El?M: 1200 Motor: . 1/3 HP, 220-440 volts, 3 phase, 60 cycles, AC, in-
duction, squirrel cage, splash-proof, 1750 rpm Equipment available from:
Motor - Westinghouse Elec. and YJ!'g. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,N.;r.
Type CF-1 Number required: one motor and one pump
I-5 Condensate Pump
Capacity: 1.83 gpm N..a.terials handled: propylene glycol and glycerol Head: 10 ft. Type: open impeller, single stage, centrifugal Materials of construction: cast iron BPM: 1200 Motor: 1/3 HP, 220-440 volts, 3 phase, 60 cycles, AC,
induction, squirrel cage, splash-proof, 1750 rpm Equipment available from:
Motor - Westinghouse Elec. and Mfg. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,N.;r.
Type CF-1 Number required: one motor and one pump
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J'-1 .Antifreeze storage .
Capacity: one week supply Requirement per 3 hour cycle: 330 gals. Cycles per day: 8 Requirement per day: - 330 x 8_ =. 2640 gals. Working days per week: 5 Requirement per week:· 2640 -x 5 = 13,200 gals. Equipment available from:
Lancaster Iron Works, ·Inc., Lancaster,Pa. Tank Dimensions: o.n. - 96 in.
Length - 41 tt., 2 in. Shell thickness - 0.540 in. Capacity - 15, 000 gals. ·
Number required: one tank
K-1 Hand Trucks
Type: ",Single Lift", hand operated Maximum ·capacity: 2500 lbs. Minimum lift: • l 1/3 in. Number of strokes tor maximum lift - 5 Number required: 5 Equipment available from~
The Yale & Towne .Mfg. Co., Philadelphia, Pa.
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Sample Calculations for Equipment Design
Rotary Drier.
Heat re4uired to raise mass to 212°F
Water {1856.5 154.3} X 1 X {212-75) = 275,479.6 Btu
Al203 223.5 X 0.198 X {212-75} = 6,062.3
Cu0 179.5 X 0.144 X (212-75) - 3,540.1 -Na2so4 46.4 X 0.22 X {212-75) = 1,398.8
Naf0 3 15.l x 0.256 x (212-75) = 526.l 287 ,006.,9
Heat re4uired to evaporate water
Using steam @5 lb. gage and assuming a steam efficiency
Moisture in feed material Moisture in discharge material Water to be evaporated
75% 25~~ 1856.5 lbs.
.Entering air 75°F 40% R.H. Humidity - 0.0075 lbs. water per lb. dry air
Leaving air 150°F 60% R. H. Humidity - 0.1255 lbs. water per lb. dry air
o.i!~~~o:oo75 = 15648.3 lbs. air
Specific volwne of air - 13.5 cu. ft. per lb. 15648.3 x 13.5 = 211,252 cu. ft. per cycle
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Drier Dimensions
Time operated - l hour 211,252 ·
60 = 3521 cu. ft. per minute
However, material is actually in drier only 30 minutes so dimensions are based on this assumption •
. . 30
3521 X 60 = 1760 CU. ft.
Assume a diameter of 8 feet for drier. 1760 _
8 8 - 33.7 or 34 feet for length of drier. 3.14 X :
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Sample Calculations (Cont'd.)
Autoclave:
Pressure - 1500 psig Temperature 465°F
Calculation of Viall Thiclmess{ 2l'
Assume diameter of 5 ft. I. D. of autoclave
t = R SE p SE-P - l
t = thickness of cylindrical shell, inches R = inside radius of cylinder, inches s = allowable working stress, lbs. per sq. in. E = efficiency of.longitudinal seam, per cent P ='design pressure, lbs. per sq. in.
t = 30 70,4000 X 0. 95 · 1600 ·
704000 X 0. 95 - 1
- 1600
= 2.86 in. plate thickness
Volume occupied by materials - 194 cu. ft. Assume 100% safety factor so that volume of autoclave will
now be 400 cu. ft. 400 ------ = 20.4 feet height of autoclave
3.14 XO: 5 Use 21 ft. as height
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Sample Calculations (Cont'd.)
Atmospheric still •.
Heat required to raise mass to 212°F
C%0H 4644 X 0.39 X (212-70) = 275~302
Water ·1123 X 1 X (212-70) = 171,817
C~5(0H)2 1834.4 X 0.525 X (212-70) : 136,761.8
C3%(0H)3 1165.6 X 0.299 X (212-70) = 95,997.0
Residue 510.8 X 0.299 X (212-70) = 21,710.2 701,588
Heat required to vaporize methanol and water
4644 X 262 X 1.8 : 2,196,797.4 1123.8 X 539.5 X 1.8: 1,090,545.3
3,287,342.7
Total heat required 701,588 3,287,342.7 3,988,930.7 Btu
Btu
Using steam@ 5 lb. gage and assuming a· steam efficiency or 60% ·
3,988,930.7 - 6924 l.b t 3 h 960.l x 0•60 - s. seam ~or ours
Total heat required in Btu per hour
329883930•7 = 1,329,643 Btu per hour
Heating surface required:
_q_ 1,329 643 A= Udt = 60 x (2g?-J.40) = 255 sq. ft.
Assume U = 60 dt = (227-140)based on constant temp. of steam 227°F and aver. temp. of feedJ4:00F.
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Sample Calculations ( Cont 'd. }
Use 2 in. O.D. tubes Area - sq. tt. per linear foot 0.5233
0_5:;; x 3 = 163 pipes requirea,each being 3 ft. long
Volume occupied by pipes
2 X 2 3.4 X 4 X 144 X 3 X 163: 10.65 CU. ft.
Volume of liquid material
189.0 10.65 = 199.65 or 200 cu. ft.
Assume a dia. of 6 ft. for still pot
200 · 6 x 6 = 7.2 tt. height of still
3.14 X 4 Use 8 ft. as height
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Sample Calculations (Cont'd.)
Fractionating·column.
Assume: Over all efficiency of 60% Reflux ratio of 3 to 1 . Distillate: 99.5 pure (mol %) Molecular weight of distillate: 32 Molecular weight of residue: 18 Methanol recovered: 95%
Material to be fractionated: 4644 lbs. methanol 1123· lbs. water
Calculation of Number of theoretical plates: McCabe-Thiele Diagram
A-7 Hot Water Pump Single Stage,Centrifugal $60 B-2 Dissolving Tank " " tt. 50
Pump B-4 Reactor Pump It n " 80 F-2 Methanol Pump n n n 50 F-6 Condenser Cool-
ing Water Pump " It " 50 F-7 Condensate Pump " n " 50 G-2 Basket Centri-
·:ruge Pump ti " It 50 H-3 Condensate Pump " ti It 50 H-4. Condenser Cool.-
ing Water Pump " " n 60 H-5 Atmospheric still
Pump ti n " 50 I-4 Condenser Cool-
ing .Water_. .Pump It " It 50 I-5 Condensat~ Pump n n It 50 - ·• .. I-3 Vacuum Pump Horizontal single.air 200
&. steam heating C-2 Bel.tConveyor Bel.t, 1.0 :rt. a. to c. 100 D-~ Belt Conveyor Belt, 1.0 tt. c. to c. 100 E-2 Belt.Conveyor_ Belt, 30 ft. c. to c. 200 K..;l Hand Trucks 5 C $100 500
Horizontal 123 sq. ft. 1,103 6 tt. dia., 8 ft. high 1,150 14 plates·,2 ft. dia.,21 rt.high 600 4 ft. dia., 5.5 ft. high 725
$10,477
8.
9.
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1tiscellaneous Equipnent
No. Item
F-4 Autoclave, 5 ft. I.D., 21 ft. high B-1 A Agitator, "Lightin" Mixer, 1 HP B-3 A .Agitator, "Lightin" Mixer, 2 HP E-1 Crushing Rolls, Single Roll, 18 x 18 (in} D-1 A Blower, 4,000 cu. ft. per min. D-3 A Blower, 45 cu. ft. per min. D-4 A Blower, 1,000 cu. ft. per min. F-1 Single Horizontal, 3 stage,
311 cu. ft. per min.
Instruments
No.
Flow meter, recording 11 Flow meter, non-recording 5 Thennometer, record and control 11 Thennometer, .non-record 3 Pressure, recorder and control 2 Pressure Gage 1 Fuel Gage 1 Vacuum Gage 2
a. Material storage b. Material Handling c. Motors d. Mixing Tanks e. Filtration t. Dryer Kiln and Cooler g. Stills, Column & Condensers h. Miscellaneous Equipment L Instruments