close

Вход

Забыли?

вход по аккаунту

?

CHLORINATION OF PETROLEUM FRACTIONS

код для вставкиСкачать
DOCTORAL DISSERTATION SERIES
Chlorination o
Petroleum Tractions
TITLE
%m*
AUTHOR
%lerf
ce/er
d at
ua.ma
UNIVERSITY
••-?>•
DEGREE
PUBLICATION NO.
111!111 i[11111
'l
y
1j111j1111[11 'I'l'l' 1111
'2
UNIVERSITY MICROFILMS
ANN
ARBOR
MICHIGAN
$HE PENNSYLVANT A STATE COLLEGE
The Graduate School
School of Chemistry and Physics
^ORIMTION OF PETROLEUM FRACTIONS
A Thesis
by
Robert Winston Keefer
hbmtted in partial fulfillment
of the requirements
for the degree of
Doctor of■■Philosophy
December f 194-2
ACKNOWLEDGMENT
Thei author wishes to express his deepest
appreciation to Dr. M. R. Cannon., without whose
aid and direction this investigation could not
have been accomplished.
INDEX
Page
Statement of Problem -- .-----------------------------
3
Summary
Apparatus------------------------- ---------------
4
Scope of Investigation ---------------------------
5
R e s u l t s ---------------------------- -------- ------
5
Introduction---------------------------- ------------
7
Experimental Work
Apparatus and-Procedure--------------------------
29
0 Derating Characteristics of Vacuum Engler,
Table I ------------- ---------------------
.46
..Operating Characteristics of Extraction
C o l u m n -----------Table I I
-
46
--- -------------
51
Discussion - *--- ---- ------------- ------ -------- ___ _---
56
Physical Properties of Original and Clay-Treated
Original O i l s ------Table I I I --
57
Ten imn. Distillation of Original Oil-Table IV — —
60
One -mm. Distillation of Original 011-Table V
61
Physical Property Determination
--
Solvent Extraction of Original'Oil — Table VI —
62
Physical Properties of Kerosene, Paraffin Wax and
Isopentane-----------Table VII - —
63
Summary of Chlorinations'of Gulfpride Oils■Table VIII--
65
■Summary of Chlorinations of Original Oils‘
Table IX ---
72
Pro >ert Los of Chlorinated Original Oils-Table X --
73
2
Vacuum Distillation of Chlorinated Oil -
Table XI
74
Summary of Chlorinations of Kerosene
Table
XII-- 85
Properties of Chlorinated Kerosene
Table
XIII- 85
Viscometer Efflux Time vs. HC1 Recovered-----Fig. 9-
86
Summary of Chlorinations of Paraffin Wax— Table XIV-
94
Properties of Liquid Chlorinated
94
Chlorination of Isopentane
Table
XV
Table XVI-
95
Distillation of Chlorinated Isopentane---- Table XVII- 95
^cryloid Blends of Residue from Distillation of
Chlorine.ted Isopentane
Table
Conclusion--------------------
XVIII 96
97
Appendix
Sample Calculations
--------
_---- _____ loo
Calibration of Flowmeter----------- ------- ---------101
Calibration of McCleod G a g e ---- --- --------------- 102
Calibration of' Vacuum Engler Thermocouple---------- 103
Calibration of Siphon C o u n t e r ------ --------------- 104
Calibration of Extraction ColumnThermocouple ------ 104
Bibliography----- :
----
105
STATEMENT OF PROBLEM
>
This investigation was of the nature of an
exploration into the possibilities available through
the reaction of chlorine with various petroleum
fractions.
A
SUMMARY
Apparatus
Two pieces of apparatus were constructed in connection
with the major object of the investigation.
These were a
self-contained vacuum Engler distillation apparatus and a
batch countercurrent solvent extraction column for solvents
lighter than the material to be treated.
The distillation
apparatus is capable of operating at any controlled pres­
sure between one millimeter of mercury absolute and atmos­
pheric pressure-.
The maximum deviation of the controlled
pressure is 2% when operating, at one millimeter and less
than 1% at pressures of ten millimeters or higher.
The
solvent extraction column consists of an 18-foot unpacked
length of one-inch inside diameter pyrex pipe with a con­
tacting and a stripping section and necessary controls.
It is capable of operating from very low solvent rates up
to five liters of acetone an hour.
The chlorination proper was carried out in a large
"test tube" provided with means for introducing chlorine,
stirring, temperature measurement and control, and gas
exit.
The necessary auxiliary equipment such as flowmeter,
purifying and absorbing trains were attached as required.
5
Scope' of Investigation
This investigation centered about the chlorination
of a 160 viscosity medium neutral lubricating oil, obtain­
ed from the Kendall Refining Company, which was used for
the more fundamental portion of the experimental work.
The research also included study of commercial oils,
kerosene, paraffin wax, and isopentane.
1
Results
Chlorination of the above materials under varying con­
ditions led to the following results:
1.
Chlorination in the presence of "actinic” light leads
to a rapid reaction at relatively low temperatures
without the formation of discolored products.
2.
Chlorination of lubricating oils in the presence of
iron leads to decomposition and tar formation.
3.
The density and refractive index increase with an in­
crease in chlorine content.
4-.
.
With increasing chlorine content, the viscosity of the
material at first increases very s l o w l y and then more
rapidly and finally very rapidly.
6
5.
The viscosity index of the chlorinated material de­
creases with increasing chlorine content.
6 . Fire resistance of the chlorinated products, tested by
heating them in an iron cup over a bunsen flame, in­
creases with increasing chlorine content and they
finally become entirely non-inflammable.
7.
An increase in temperature greatly increases the rate
of chlorination but may produce side effects.
8.
Chlorination apparently occurs to a greater or less
extent on all of the molecules present.
9.
Clay treatment of chlorinated products increases their
stability markedly.
1 0 . Highly chlorinated lubricating oils, kerosene and
paraffin waxes can be produced which are stable to
prolonged heating at 120-14-0° C.
7
INTRODUCTION
The very large resources of hydrocarbons, especially
of a saturated nature, found in petroleum and natural gas
makes them the cheapest source of pure organic raw materials.
Likewise, chlorine is one of the most abundant chemicals
produced and is available at the very low price of one and.
three-fourths cents a pound, in tank car lots.
These two
facts alone make it inevitable that attempts should be mad.e
to produce products of i no.us trial importance from the
chlorination of petroleum hydrocarbons.
Another important
fact not to be overlooked, is that halogens are among the
few substances which will react readily and directly with
paraffin hydrocarbons.
Much research has been done on chlorination of hydro­
carbons and, especially with the lower members of the
series, gratifying results nave been obtained.
today
There are
large markets for a considerable number of chlorinat­
ed solvents such as carbon tetrachloride, methyl chloride,
di- and. tri-chloromethane, ethyl chloride, etc.
When
chlorination is used "in conjunction with other reactions
which utilize a chlorinated intermediate, the number of
marketed products is very greatly increased.
Most of the work on the chlorination of hydrocarbons
has been done in the past fifty.'years and the number of
8
publications is staggering.
Fortunately, within the past
ten years Hass and Co-workers (25-29, 4^0 have succeeded
in clearing up the general picture of chlorination con­
siderably.
By assembling, analyzing and checking published
data, they have formulated eleven rules (20, 28, 29) which
fit the known facts very well and with only a very few
exceptions.
Before examining these rules, a few generalizations
of the chlorination reaction will be reviewed.
The reac­
tion can be carried out by the use of (l) pure chlorine,
(-2) chlorine compounds which give up some of their chlorine,
as antimony
pentachloride and sulfuryl
chloride,-
salt baths.
By far the most important method
chlorination by pure chlorine and this method
widely used
at present.
and (3)
is the direct
is most
The initial reaction of chlorine
with hydrocarbons can proceed in two ways; i.e., either by
substitution of a hydrogen yielding HC1, or by addition to
an unsaturated linkage.
Subsequent addition of chlorine
can either be by further substitution or by the loss of
HG1 from the monochlorinated derivative followed by addi­
tion of chlorine at the double bond thus formed.
There
is apparently no reason for choosing one or another of the
above methods as being the correct one.
Both probably are
occurring at the same time although with the proper choice
of conditions it is thought possible to make the one or
9
the other predominant.
Another property of chlorination which very often
leads to difficulty is the highly exothermic nature of
the reaction.
This may lead to very violent and dangerous
explosions unless conditions are very eai*efully controlled.
Another property which is troublesome is that partially
chlorinated derivatives are capable of being chlorinated
further so that it is impossible to stop the reaction at
any given point.
Thus, numerous by-products are always
produced in greater or less quantity.
Further complica­
tions arise from the fact that all the hydrogens present
in paraffin hydrocarbons will be substituted, although
generally at different rates, so that mixtures of isomers
will be obtained unless, of course, all the hydrogens are
equivalent.
.
Furthermore, the very corrosive nature of chlorine,
especially when moist, and hydrochloric acid makes the
handling of these materials difficult.
Recently, however,
these difficulties have been largely overcome.
The following generalizations are the rules derived
by Hass and co-workers mentioned above and apply to the
chlorination of the homologs of methane.
Rule 1.
Carbon skeleton rearrangements do not occur
during the chlorination of the simpler paraffins if pyroly­
sis temperatures are avoided..
All the isomers derivable
without such rearrangement are always formed.
This rule
10
has had more reported contradictions than any other but
by careful repetition of the contradictory work with modern
rectifying equipment Hass found that the error was not in
the rule but mainly in the published experimental work.
Rule 1, while based on the formation of monochlorides, has
been found to hold for the polychlorides as far as studied.
This, however, includes only the polychlorides of ethane,
propane, n- and iso-butane.
Rule 2.
The hydrogen atoms are always substituted at
rates which are in the order tertiary> secondary> primary.
Rule 3.
At increasing temperatures there is an in­
creasingly close approach to relative rates of the tertiary:.,
secondary:primary to 1 :1:1 in both liquid and vapor phase.
Rule 4-.
Liquid phase chlorination gives relative
rates of tertiary
secondary and primary substitution which
are obta.inable only at much higher temperatures in the vapor
phase.
This also means that a given temperature change pro­
duces a much greater effect upon the relative rates and
therefore ratios in liquid phase than in vapor — phase reac­
tion.
Rule 5.
The presence or absence of the following fac­
tors does not affect appreciably the relative rates of
tertiary, secondary and primary substitution:
(l) moisture,
(2) carbon surfaces, (3) light.
These results seem to indicate that the reaction
11
mechanism is the same whether initiated by the catalytic
effect of carbon surfaces or by light.
Rule 6 .
Excessive temperatures' and/or reaction times
result in appreciable pyrolysis of the chlorides in the
order tertiary/* secondary^ primary.
From this it will be
seen that from the standpoint of stability to heat the
primary chlorides are the most desirable.
Rule 7.
If a molar excess of hydrocarbon is used and
chlorination conditions are maintained constant, the yield
of monochlorides versus polychlorides may be obtained from
the equation
X = KY,
where X is the weight ratio of mono­
chlorides over polychlorides, Y is the ratio of mols of
hydrocarbon over mols of chlorine in inlet gases and K is a
constant peculiar to conditions.
Therefore, in order tq ob­
tain a larger amount of monochlorides the ratio of hydro­
carbon to chlorine must be large.
Rule 8 .
Dichlorination proceeds by two mechanisms,
(l) loss of hydrogen chloridie followed, by addition of chlor­
ine to the resulting olefin and (2) progressive substitution.
Rule 9.
The presence of a chlorine atom upon a carbon
atom exerts, what has been called a ’'vicinal effect” hinder­
ing substitution on the chlorinated carbon atom and on the
adjacent atoms.
This would seem to indicate that once a
chlorine atom is attached, to a molecule, that molecule
woild be more stable and not react as readily as unchlor-
12
inated molecules.
Rule 10.
Herzf elder *s Rule (stated in 1&93)
,fWhen
into a monohalogen compound a second halogen is introduced
it always attaches to that carbon atom which is situated
next to the carbon atom already united with halogen*' does
not apply to chlorinations and in this field must be—re­
placed by Rules 1 to 9.
Rule 11.
Increased pressure in vapor-phase chlorina­
tion of hydrocarbons gives results approaching those ob­
tained in the liquid phase.
The above rules have been generally accepted as
representing the known data on chlorination of hydrocarbons.
They have been substantiated unfortunately only for the
lower members of the methane series and mainly for mono­
chlorides but they certainly are an indication of-what to
expect.
As in all organic reactions, the chlorination of hydro­
carbons is greatly affected by the conditions under which
the reaction is carried out.
The classic example of this
is the chlorination of toluene.
Here the use of elevated
temperatures and sunlight results in practically all of the
reaction occurring on the side chain with the formation of
benzyl chloride.
Reaction at lower temperatures and in the
presence of halogen carriers such as iron results in chlor­
ination in the ring giving the chlorotoluenes.
Here the
choice of conditions completely changes the course of the
13
reaction.
Various investigators have studied the effect on
chlorination of the following factors
(19), (1) "actinic”
light, (2) halogen carrying catalysts as iron and iodine,
(3) metallic oxides, (4) water, (5) sulfur, (6) sulfur
dioxide, (7) porous materials, (8) carbon, (9) heat, alone
or in conjunction with others, and (10) a silent electrical
discharge.
Of these, "actinic” light and heat have re­
ceived the most attention and are the most important.
The exact wave length of light which produces the
catalytic effect is somewhat of a question.
Sunlight,
diffused daylight, carbon arc lamp, light from a metallic
filament and mercury vapor lamps have been used as sources
of "actinic” light (10).
In one study (4) on the chlori­
nation of natural gas an interesting comparison of the in­
fluence of light of different wave lengths was made.
A
chlorination was started using a carbon arc lamp as
catalyst.
After ..a.-.,while, a blue screen'was placed over
the arc lamp.
There was no noticeable change in the rate
of the reaction.
The blue screen was removed and in order,
green, red, and yellow screens 'were placed between the arc
lamp and the reaction vessel and the reaction rate meas­
ured in each case.
After each of these screens had been
interposed the rate of reaction decreased almost immediate­
ly.
By replacing the red., green, or .yellow screen with
the blue screen, the reaction rate immediately resumed its
original magnitude.
The screening out of the other colors
was of no assistance as the inactive colors caused no meas­
urable interfering influence.
They also studied the effect
of ultra-violet light and found that it had very little in­
fluence on the rate of reaction.
These results seem to
indicate that blue light is the wave length of light which
has the greatest accelerating effect.
Quite a few workers
have recommended "ultra-violet lamps,T as a source of activa­
ting light in chlorinations but it is quite possible that
light from these lamps of wave lengths other than ultra­
violet is the effective agent aiding reaction
Increased temperature also increases the reaction rate
and thus it. is usually used.to a greater or less extent along
with the catalysts.
However, the complete thermal chlorina­
tion of an aliphatic hydrocarbon always encounters two dif­
ficulties:
(l) chloroole-fins are formed which may .rapidly
polymerize and. form a carbonaceous deposit in the reactor
and (S) reaction becomes sluggish as the screening effect of
a chlorine atom is multiplied by an increased number.
In­
creasing temperature increases the reaction rate but exces*
sive temperatures also greatly increase pyrolysis and must be
avoided..
Work with halogen carriers has also been rather ex­
tensive.
Their action is based on the fact that the higher
halides are unstable and under proper conditions yield some of
their halogen.
Subsequent action results from the repeated addi-
15
tion and loss of the halogen.
Metals like iron and anti­
mony and materials like phosphorus,, iodine and bromine
which form loose compounds with chlorine are generally
used for this purpose.
Some work has been done using sulfuryl chloride and
phosgene as chlorinating agents.
These compounds decom­
pose at the prevailing conditions, yielding chlorine in a
very reactive state.
Porous substances and carbonaceous
material have been found effective and their action is
probably due to the increase in surface area which they
present.
The mechanism of the substitutive chlorination of
saturated hydrocarbons has been under discussion for
quite some time.
The most generally accepted theory is
that the chlorine molecules are broken down into chlorine
atoms.
This is brought about by the catalysts heat and
light by furnishing energy which the molecule absorbs, as
follows,
Cl2
+
Cl2
+
A
= Cl* +
Cl*
hv = Cl* +
Cl*
The reaction then- can proceed in one of two ways with in­
sufficient evidence at present to determine which is the
correct way.
(1)
Cl*
+ CH^ =CH3CI + H* ;
H* + Cl2
(2)
Cl*
+ CH^ = HC1 + CH3* ;
CH3* + Cl2
= HC1 +Cl*
-CH3CI
+ Cl*
16
The bulk of the present evidence points to mechanism No. 2
as being correct.
The recent discovery (12) that very
small amounts of tetraethyl lead, which is generally
thought to yield ethyl radicals when heated, accelerate
gas and liquid pha.se chlorinations enormously, tends to
support chain mechanism No. 2.
Also, hexaphenylmethane
which yields triphenylmethyl readily, catalyzes liquidphase chlorination, and. azomethane acts as a catalyst in
l
the vapor phase.
The chain reaction, once started, regenerates the
activated chlorine atom and no further catalytic action
should be necessary.
However, the loose atoms of chlorine
can recombine or trie chain may be terminated in several
different ways.
The collision of a radical or atom with
a solid surface such as a wall, collision with oxygen and
the collision and combination of radicals will all termi­
nate the chain.
Oxygen has been known for quite a while
as a strong inhibitor of chlorination (16, 9) and.this
fact is sometimes given as support to the chain mechanism.
The stability of chlorinated hydrocarbons to the in­
fluence of heat is an.important property and has been'
summarized quite well by Hurd (30).
With the exception of
methyl chloride, the lower members of the series and
especially the monochlorides, are quite stable to heat up
to 400° C.
However, the decomposition of the polychlorides
17
of the higher members of the methane series occurs at much
lower temperatures.
Gardner and Bielouss (19) state that the
dissociation point of the polychlorides lies between 120
and 250° C. and that by heating these chlorinated hydro­
carbons up to 250° C. a practically complete dechlorination
can be effected without the aid of any other agent.
They
also state that this dissociation does not necessarily lead
to olefins.
This is because the olefins primarily formed
undergo a further change in their nascent state; namely,
transformation into cyclic compounds by a mutual saturation
of their double linkages Aromatic compounds with chlorinated side, chains behave
in much the same way a s .aliphatic hydrocarbons.
However,
wliqn chlorination has taken place on the ring, the aromatic
compound is found to be very stable.
In. fact, ethyl tetra-
chlorobsnzene and ethyl pentachloro benzene mixtures have
been proposed (22) as heat transfer fluids.
Naphthenic
chlorides, on the other hand, appear to be exceptionally
unstable.
A large number of proposals (see 19) have been made
for inhibiting the decomposition of chlorinated hydrocar­
bons . Most of them involve the addition of basic or un­
stable materials such as amines, guns,. dyes, and hydro­
carbons but they generally involve the neutralization or
addition of the liberated HC1 rather than a true inhibition.'
13
Carlisle and Levine (7) state that trichloroethylene will
not decompose in the light unless oxygen is present and
recommend the addition of antioxidants.
There has been considerable work done on the chlorina­
tion of the higher members of the aliphatic and aromatic
series, chiefly in the form of complex, inseparable mix­
tures.
Such mixtures have consisted of petroleum fractions
such as kerosene (12, 45), vacuum flashed residues (53),
paraffin wax, (18, 23, 24, 35) light oil fractions (34, 58,
60) and creosote oil (51).
That much work has been done
which is unpublished is evident from the huge number of
patents granted for the use of chlorinated oils,, waxes,
etc. as intermediates in the preparation of other materials.
In the chlorination of liquid, paraffins (11), the fol­
lowing generalizations were found.
The chlorinations
showed an induction period, a gradual increase in the
velocity, a maximum reaction velocity, and a sharp de­
crease in speed to a constant velocity.
This indicates a
chain mechanism consisting of a period of activation and
one of chain reaction, with a maximum velocity at the trans­
ition point of the two.
The chlorination of kerosene by Padgett and Degering
(45) had for its purpose the preparation of detergents
using the chlorinated hydrocarbon as an intermediate.
They
used a narrow cut (95-100° G.) from the kerosene and were
19
interested only in obtaining monochlorides.
For this pur­
pose their chlorinations followed, in general, the rules
set forth by Hass and co-workers (25-29)j i.e., liquid
phase at about 100° C. and the use of a high hydrocarbon
to chlorine ratio.
They stopped the chlorination when the
chlorine equivalent to one-fourth or one-third of that
necessary to form monochlorides had been used.
They then
fractionated the product in order to separate the mono­
chlorides formed.
alcohols, alkyl
These monochlorides were converted to
sulfates, etc. for use as detergents.
The
commercial chi .urination of kerosene fractions has become of
interest in recent years because by condensation of the
mo no chlorides w i t h .aromatic hydrocarbons and subsequent
sulforation, surface-active agents have been produced (25).
Another chlorination of Pennsylvania kerosene is re­
ported in Ellis (11).
This was carried out by means of
antimony pentachloride in the presence of iodine at 350360° C.
However, at such elevated temperatures, pyrolysis
as well as chlorination takes place with the result that
the products were principally hexachloroethane and. hexa- .
chlorobenzene.
The chlorination of paraffin wax by bubbling dry
chlorine thru the melted wax held at about 70° C. was
carried out by Gardner (13).
He prepared a series of
chlorinated paraffins of varying chlorine content and
20
determined the relationships between chlorine content and
density, congealing point, viscosity, and surface tension.
The viscosity increased gradually until about k0 per cent
chlorine has combined and then increases very rapidly.
Density gradually rises at first also and then more rapid­
ly after 40 per cent chlorine has combined.
The congeal­
ing point (similar to pour point in petroleum) drops
rapidly with increase in chlorine content until at about
37 per cent chlorine it reaches a minimum.
It then in­
creases very rapidly again.
Hardie (23) chlorinated paraffin simply by passing
chlorine into a dispersion of the paraffin in water or
aqueous sodium hydroxid.e.
Wirth (60) chlorinated hard,
paraffin;and petrolatum by the use of chlorine in the
presence of manganese dioxide preferably in the form of
Welden mud.
The chlorination of cracked residue has been studied
somewhat by Tropsch and co-workers (53).
They diluted
their starting material with carbon 'tetrachloride and
carried out the chlorination in an ice bath.
mention made of a catalyst.
There was no
The chlorinated product, a
dark brown oil, was stripped of carbon tetrachloride by
heating to 125° C. under reduced pressure.
This product
was then treated with benzene and anhydrous aluminum chlor­
ide.
In conclusion, they state that the treatment raises
21
the viscosity and viscosity index and lowers the pour point.
However, the final product was "black and the color was not
improved by sulfuric acid and / or clay treatment.
In chlor­
inating some vacuum flashed oils they always obtained dark
colored products except when only a small amount of chlorine
had been introduced.
Even in this case, the product turned
dark upon standing overnight.
The chlorination of various petroleum fractions (nar­
row boil-ing cuts) corresponding to.. C13 - Cqg have been
carried out but no conclusions can be drawn from the
meagre data except that the chlorination proceeds very
readily, even without catalysts.
The chlorination of one
fraction try Barth (3) , assumed to be mainly tetracosane,
was carried out by bubbling a mixture of chlorine and. sul­
fur dioxide thru it at a temperature of 90-95°C.
The
product was a moderately viscous oil, light yellow in color
and liquid at 20° C.
The presence of sulfur dioxide was
said to promote substitution on adjacent carbon atoms so
that the resulting halide could be hydrolyzed to a polyhydric alcohol.
The chlorination of light oil fractions has been
carried out by Koch and Ibring (34-) •
They passed the
chlorine into the liquid hydrocarbon under unspecified con­
ditions.
Carbon dioxide was admitted simultaneously in
order.to cool the material and remove the HC1 which was
22
formed.
The stabilization of the chlorinated products is a
matter of prime importance and has been the object of much
study and many patents (5, 42, 44* 49, 56, 59, 61).
They
range from materials which combine with the liberated
hydrogen chloride,, the removal or conversion of the most
active or unstable constituents, and the removal of all of
the chlorine and formation of hydrocarbons or hydrocarbons
pins other elements.
Bishop (5) uses a wash of aqueous
sodium hydroxide followed by an extraction with ether or
toluene.
Montgomery (42) advocates the addition of 0.5 -
1.0% of a hydrocarbon of the pinene or terpene groiip, such
as turpentine, pinene, etc.
Muskat (44) gives the chlori­
nated material a concentrated sulfuric acid treatment at
40-100° C. for from 2-5 hours.
One of the standard
methods seems to be the use of the condensing action of
aluminum chloride with the subsequent removal of the sludge
formed.
The addition o f 'calcium phenyl stearate to remove
HC1 formed by decomposition is said (56) to be effective
in the case of chlorinated naphthalene.
Wirth (59) de­
scribes the stabilization of chlorinated oils-by heating
them with a basic reagent and causing them to absorb sul­
fur at a temperature below 100° C.
In another patent (61)
he uses a current of steam after the addition of a small
amount of caustic alkali.
23
The uses made of chlorinated products are very numer­
ous.'
The use of large quantities of chlorinated solvents
was mentioned in the earlier paragraphs.
They consist
wholely of the lower members of the methane series and are
used as the chlorinated material itself.
The chlorinated
kerosenes, waxes, etc. are generally not used as the chlor­
inated material but only as intermediate.
An exception to
this statement is in the preparation of fire- and water­
proofing materials.
the desired products.
Here the chlorinated molecules are
One method, of flame-proofing con­
sists (13) of chlorinating solvent naphtha until AO to 50
per cent of chlorine has been absorbed, and a crystalline
product"separates from the mother liquor.
This crystal- '
line chlorinated.product is then incorporated with wax,
asphalt, or similar combustible organic insulating material
and gives them flame-proof qualities.
Another substance
used in a similar manner is s. chlorinated heavy petroleum
such as.. "asphaltic oil".
A.recent development (2) for imrjarting fire resistance
to fabrics has been advocated in England.
Preparations of
a chlorinated organic material such as petroleum oil on a
relatively inert material preventing premature dechlorina­
tion - manganese and zinc borate - with a volatile solvent,
filler, sand pigment are recommended for imparting resist­
ance to fire, -water.and mildew.
The degree of chlorination
24
is 40 to 80%.
When the textile fabric is exposed to fire
or the temperature at which it undergoes combustion, chlor­
ine is released in the form of hydrogen chloride which
tends to exclude oxygen and stop the flame.
The borates
added to the composition not only prevent premature de­
chlorination hut cover the fibers where they are highly
heated, preventing glowing and creeping of the fire.
The
pigment .protects the chlorinated material from decomposi­
tion by light.
The preparation of lubricating oils by chlorination
usually involves the condensation of the chlorinated
material with an aromatic compound in the presence of
anhydrous aluminum chloride.
TTew Jersey
Paraflow (8), Standard.Oil of
pour point lowerer, is prepared by slowly adding
paraffin wax, chlorinated to approximately 10-12 per cent,
to a mixture of equal weights of an aromatic hydrocarbon
(e.g., benzene, naphthalene or anthracene) and aluminum
chloride.
Kerosene is used as a solvent. After the reac­
tion, the aluminum chloride sludge is withdrawn and the
Kerosene and unreacted wax removed by distillation.
The
extreme complexity of the mixtures so obtained can be
estimated if we recall that there are over three and one
third million possible eicosaries (C20H46)> ea°fr
these
gives all the theoretically possible mono- and poly-chlor­
ides and a single naohthalene nucleus may condense with
25
from one to eight of the various chlorides.
It seems
possible that a sample of pour point depressant might be
made up to a considerable extent of molecules of which no
duplicate is present.
Fisher and Koch (16) studied the production of lubri­
cating oils from the lighter hydrocarbons obtained from
carbon monoxide-hydrogen synthesis.
This material was
chlorinated up to the equivalent of six chlorine atoms per
molecule and
was then treated with xylene, benzene-,
na phtha1ene, etc., and ab o ut 5 per cent a1umlnum chi orId e .
The final products, lubricating oils, are said to contain
less than 0 .IS of chlorine and to have an average molecu­
lar weight of 450.
As mentioned previously, Tropsch and co-workers (53)
obtained a more viscous oil with a higher viscosity index
by a similar procedure.
opaque black.
Their product, however, was an
Anderson (l) recommends a small portion of
synthetic oil, obtained by condensing chlorinated paraffin
wax and benzene in the presence of aluminum chloride, bee
added to heavy transmission gear lubricants to increase
their effectiveness.
ricating oil.
Lowes (39) similarly obtains a lub­
Sanders (51) recommends a chlorinated
creosote oil be blended with lubricating oil to form a
good cutting oil.
A process for producing resins by chlorinating the
2.6
polymeric constituents of cracked petroleum distillate has
been developed by Morrell and Egloff (4.3) .
Such consti­
tuents,. after being separated from the distillates, were
mixed with phenols, cresols, tar acids, or other 'compounds,
then heated, to 300° F. and chlorine introduced until the
mixture became relatively viscous.
Fulton (17) also ob­
tained resins by chlorinating a cracked petroleum fraction
up to 10-15% and then distilling the product.
Distilla­
tion removes chlorine, hydrogen chloride and any volatile
oily constituents.
The preparation of pour point depressors are made in
general by the same method as outlined above for Paraflow.
Lieber (35) catalytically condenses paraffin, chlorinated
to approximately eleven per cent, and. then distilled up to
600° F.
The residue is used.
He later (36) also used 1;%
of "a condensation product of a halogenated "tall oil" and
benzene, naphthalene or xylene.
Pier et al (46) have
patented a similar process as has Rieff and Badertscher
(50).
High or "extreme" pressure lubricants are also pre­
pared, by the use of chlorinated materials.
One process
comprises mineral lubricating oil, free sulfur, and chlor­
inated paraffin wax.
Chlorinated hexane is also said to
improve the lubricating properties of mineral oil.
Lincoln
and Byrkit (37) have patented an extreme pressure lubricant
27
consisting of a paraffin base oil mixed with 20$ or less
of halogenated foots oil containing 10$ chlorine.
McNulty
and Simmer (71) describe a lubricant prepared by adding an
active chlorine compound, such as chlorinated wax, plus a
small amount, 0.01-1.0%, of an old. soluble cycloaliphatic
amine such as dicyclohexylamine serving to avoid corrosion.
Whittier (5 7) advocates a mineral lubricating oil plus
five per cent of a phosphorized fatty oil plus 1 to 6 per
i
cent of a highly chlorinated hydrocarbon such as heptachloro Propane as an extreme pressure lubricant.
Wetting and emulsifying agents are in general obtained
by converting the chlorinated hydrocarbon into an alkyl
sulfate.
Keller and Gofferye (33) obtained■wetting agents
by treating polychlorinated hyclrocsirbons with alkalies and
sulfonates giving products containing sulphonic and. bisul­
phate groups.
Kowakani and Maruyama (31) treated chlori­
nated hydrocarbons with caustic alkali or carbonates to
cause salt formation and dechlorination.
The use of chlorinated paraffin wax in the preparation
of antioxidants has been described by Loane (38).
The
method consists of a condensation with naphthols or polyhydroxy benzenes in the presence of aluminum chloride.
Pier and. Christmanu (77) recommend a product obtained by
condensation of a high molecular weight halogenated hydro­
carbon and elementary sulfur for prevention of oxidation of
lubricating oils.
Gardner and Bielouss (19) produced drying oils in an
interesting manner.
They chlorinated liquid paraffin and
then dechlorinated it by heating to 250° C., in the absence
of catalysts, driving off the chlorine as hydrogen chloride.
The products consist of olefins mixed with cyclic hydro­
carbons produced by ring closure during the dechlorination.
Ellis states (12) that chlorinated hydrocarbons containing
more than nine carbon atoms and at least two halogen atoms
may be reacted with alkalies to obtain a drying oil.
Monohalogenated paraffin wax may be reacted with a
mixture of potassium acetate and acetic acid or potassium
stearate, butanol, sodium Iodide or dibutylarnine and
xylene to yield a plasticising or impregnating agent.
29
EXPERIMENTAL WORK
Apparatus and Procedure
In order to properly carry out this investigation it
was necessary to construct certain pieces of apparatus.
For separation'of chlorinated products as well as for
analytical Insights of the starting materials, a self-con­
tained vacuum Engler distillation apparatus was built.
This apparatus, complete with pumps and control features Is
mounted on a laboratory table and needs only water, gas and
electrical connections to.make it operatable anywhere.
The general arrangement of the distillation apparatus
is shown in Fig. 1.
The Hy-vac oil pump, being rather old
and. inefficient, was used to back up a three-stage mercury
vapor pump.
The capillary leak was placed in the line
between the pumps and the surge tank so that the pulsations
caus.ed by the intermittent operation of the leak would be
smoothed out as much as possible and not be felt at the
distillation flask.
The regulator, shown In Fig. 2 is con­
nected directly opposite the leak so that It will react
instantly to any pressure surges and thus give closer pres­
sure control than would otherwise be possible.
From the
surge tank are the necessary leads to the IvlcCleod Gage and
to the distillation flask and receiver.
The vapor lines
i
Gages
Surge
Tank
Flask
Receiver
v/afor
Fig. /
Flow Diagram o f Vacuum Enaler
o
F ig . 2
P re ssu re
R e g u la to r
32
all constructed of standard nine millimeter glass tub-
Thc temperature was controlled by the capillary leak
method; that is, the pumps were capable of pulling a greater
vacuum than required and the leak left in enough air, inter­
mittently, to keep the pressure at the proper value.
The
leak was controlled by the regulator shown in Fig. 2, act-
licaids.
33
tain requirements:
(l) Their vapor pressures must be low
enough at ordinary temperatures so that they do not evap­
orate uncler operating conditions; i.e., one rum. pressure;
(2) The upper liquid ”D !t must not be capable of conducting
even a small electric current while (3) the lower liquid
”Gn must carry this current readily.
The most trouble was
encountered in obtaining the liquid (ft) since most liquids
with suitable vapor pressure characteristics can not be
made to conduct electricity.
This difficulty-was overcome
by dissolving sodium chloride in glycerin.
Although the
solubility of the salt is low, it is sufficient to conduct
the current providing the two contacts are placed close
enough to one another.
The upper liquid (D) wa.s dibutyl
phthalate and is entirely nonconducting.
The density of pure glycerine is 1.260 gr,/. ml. and
that of ■dibutyl phthalate is 1.04-5' gr./ml.
effective density of 0.215 gr./ml.
This
gives an
When operating at one
millimeter of mercury absolute pressure, a change in pres­
sure of 1.6/ would theoretically move the interface by one
millimeter and a change of 3.2% would move this interface
two millimeters.
Much less than a two millimeter movement
is required to operate the relay; in fact, by observation,
it moved about one millimeter.
The maximum deviation of
pressure would therefore be about two per cent.
Glycerine has quite a high viscosity and it was
34
thought that tliis might make the action of the relay slug­
gish and lead to a greater deviation of pressure.
In order
to help overcome this the U-bend tubing connecting the two
lower bulbs of the regulator was constructed of quite
large (13 mm.) glass tubing.
This., along with the very
slight movement necessary for operating the relay, was very
successful since In actual practice the pressure at the
MeCleod gage did not vary by more than 2.0%. . This excel­
lent control is probably aided by the large (ten gallon)
surge tank and the location of the capillary leak directly
opposite the regulator.
The purpose of the upper bulbs
was to provide as nearly as possible a constant liquid
level which increases the accuracy of the regulator.
The
lower bulbs were designed to prevent momentary strong
pulsations from pushing the upper liquid from one side down
around the U-bend and over into the other side, thus ruining
the pressure control.
The determination of the pressure of the system next
to the distillation flask was made by means of a MeCleod
gage and a closed-end U-tube manometer.
The MeCleod gage
was calibrated using two scales, one which gave a compres­
sion ratio of 30:1 and the other 90:1 when the pressure was
in the vicinity of one millimeter of mercury absolute.
During all distillations at one millimeter, readings were
taken using both, scales.
If condensable gases were present
In the MeCleod gage, the compression of it to different
35
ratios would condense a diffei’ent amount of this gas and
hence give different readings for the apparent pressure of
the system.
Therefore, if the pressures shown hy hoth
scales are Identical then the readings are accurate and no
condensable gas was present to cause Inaccuracy.
When
operating at ten millimeters of mercury pressure the MeCleod
gage was used as a primary standard but the closed-end
U-tube gave accurate enough, readings for a continuous check
on the pressure.
The distillation flask shown in Fig. 3 is similar to
the Vacuum Engler flask in use in the Petroleum Refining
Laboratory.
A one liter flask was used so that large
samples could, be 'accommodated although usually the charge
amounted to 300 ml.-and each cut was thirty ml. or ten per
cent.
The vapor temperatures were obt'ained at the top of
the columnar extension of the flask neck by means of a
eopper-constantan thermocouple constructed of No. 22 Leeds
and Northrup wire.
This couple was -standardized against
another thermocouple which had been calibrated by means of
a Bureau of Standards thermocouple.
The e.m.f. developed
was read by a Leeds and Northrup Portable Precision Poten­
tiometer which is capable of readings to 0.001 millivolts
or approximately 0.1° C.
The flask was heated by means, of
a Glass-Col hemispherical mantle and controlled by the use
of a Variac.
The fla.sk and neck up to the lip were well
/
0.5c cm
37
lagged while the upper area acted as a condenser.
material
Any
condensing above the lagged section was prevented
from flowing back down the column by the lip which directed
the condensate down the side arm to the product receiver.
The product receiver and fraction cutter are shown in
Fig. A-
It consists of a flat base plate constructed of
half inch boiler plate upon which rests the sample bottles
and the distribution device.
It is covered by means of a g
glass bell jar through the top of wdiich are the product
receiver line and the vacuum line.
This bell jar is sealed
to the base plate by means of melted paraffin, applied
while the receiver is under a slight vacuum.
A perfectly
air-tight seal is obtained in this manner although care
must be taken not to form too thick a coating of paraffin
as a thick coat tends to crack, thus breaking the seal.
The distillate flowing down from the flask, drops into the
funnel (A) and is distributed to the proper bottle by the
copper tubing spout (B).
The funnel is supported by the
cylinder (C) which rotates upon the stationary vertical
shaft (D).
On the lower end of the rotating cylinder (C)
is fastened-a: wheel (E) containing ten spokes.
The two
rods (F) extending up through the spokes of the wheel,
shown at the lower right in the figure, prevent the wheel
and hence the funnel and spout from rotating.
These two
rods are so placed that when -a spoke of the wheel (E) is
38
v//n n j /irrm
F ig . 4
P ro d u c t
R e c e iv e r &
F r a c tio n
C u tte r
39
resting against one, the other is midway between two
spokes.
When it is desired to change from one bottle to
another one of these rods is pulled down and a spring, not
shown, rotates the wheel against the other rod, pulling
the spout of the funnel about half way to the next bottle.
This first rod. is then pushed back up into place and the
other one pulled down allowing the spoke of the wheel to
come against the first rod by rotation of the wheelT- This
sequence of operations moves the spout of the funnel com­
pletely to the next bottle.
The rods (F) which are used
for these operations are merely one-quarter inch steel
rods covered by pressure tubing.
This pressure tubing is
fastened at the lower end to the rod and at the upper end
to a short section of pipe soldered to the base plate.
One source of difficulty in the pressure regulation
arose from the fac.t that the. dibutyl phthalate absorbed
air or moisture when not in use and these gases 'would slow­
ly come out of the liquid during operation at one milli­
meter of mercury pressure.
Since control is based on main­
taining the system at a pressure equal to that of the closed
side of the regulator, this gas coming up in the closed-off
side would naturally ruin any pressure control.
This dif­
ficulty was overcome by wrapping some resistance ribbon
around that side of the regulator and heating the liquids
while the vacuum was being obtained on the system.
This
40
procedure effectively drove out the gases and no trouble
was then experienced with the pressure control.
After a
distillation, it is advisable to open stopcock (A) and
close stopcock (B), thus keeping the regulator under vacuum.
The other major piece of apparatus built was the 23foot solvent extraction column.
Essentially, it consists of
18 feet of 1 inch inside diameter pyrex pipe with a contact­
ing section, stripping section and. auxiliary equipment.
It
was designed to operate with solvents lighter than the
material to be treated.
In operation the heated solvent
enters the bottom of the column, forced in by virtue of its
greater pressure head, and comes in contact with the
material to be treated, which remains mainly down in the
contacting section where' it is thoroughly agitated.
The
solvent oil solution rises through the column t o :the
stripping section on top where the solvent is vaporized,
precipitating the oil which-drops back down the column as
reflux.
This reflux consists of numerous bubbles of oil,
fairly uniform in size, which drop slowly down through the
rising acetone.
The vaporized solvent is carried as a
vapor up to a condenser where it is condensed and run into
a solvent -supply tank.
This supply is higher tha.n the
stripping section of the column so that sufficient head is
available to force the solvent in at the bottom of the column.
The main section of the column, consisting of the 1 inch
4-1
pyrex pipe, is jacketed by 45 mm. glass tubing provided
with inlet and outlet lines so that cooling water may be
passed through the jacket.
In Fig. 5, the contacting section of the solvent ex­
traction column is shown.
It Is a 10 inch length of 2 Inch
inside diameter pyrex pipe joined to a 4 inch length of 1
inch pyrex pipe.
Passing through the brass plate on the
bottom are, reading left to right, (l) drain pipe, (2)
stirx’er, (3) solvent entrance line, and (4) a small copper
tubing carrying thermocouple wires.
The liquid in the con­
tacting section is very vigorously stirred by the motordriven stirrer.
The solvent entering the contacting sec­
tion is hot, having been heated by a lo-lag immersion
heater placed Inside the solvent line.
The entire contact­
ing section Is well' lagged to prevent the loss of heat.
This method of operation; i.e., mixing hot oil and solvent,
enables us to approach equilibrium much more rapidly than
would be possible if the solvent and oil were contacted in
the cold.
As the hot solution starts up the column it is
cooled by the jacket water and the excess oil will precipi­
tate out .
In actual operation the entire lower 3 or 4 foot
of the column looks like a cloud due to this precipitation.
The copper tubing carrying the thermocouple wires is sealed
at the top along with the junction of the wires.
Thus, the
temperatures recorded for the contacting section are for
F ig . 5
C o n ta c tfn g
.
S e c tio n
43
t hi s ther mo c o up 1 e .
The stripping section located at the top of the column
is shown in Fig. 6.
Vaporization of the solvent is accom­
plished by means of the steam heated steel cylinder (S) in
the center.
The condensate line from this cylinder extends
to near the bottom so that the steam entering at the top
forces the condensate out and keeps the cylinder practically
clear of condensate.
The solvent vapors formed pass out
through the 3/4 inch opening on the plate and hence to the
steam heated heat exchanger (li) which carries them up to
the condenser.
From the condenser the solvent flows through
a siphon counter into a supply tank.
A constant head is
maintained on 'this supply tank .by the apparatus shown in
Fig. 7.
A 300 cc. supply of acetone was stored in auxiliary
tank (T).
When the level in the main supply tank falls
below the en%gs£j$^ the glass tubing (V) ? air will pass up
through i t s p l a c e
some of the solvent in (T) .
This
solvent flows down the tube (L) into the reservoir bring­
ing the level back up_, sealing tube (V) and stopping any
further flow o
f
t
h
e
tank.
This extraSKHMSEuiiil is very easy to operate and
once conditions
an occasional 'check.
it
-
requires no attention other than
When the desired equilibrium is
reached the extract sample is withdrawn from the stripping
section through the small copper tubing (P) by means of
44
O
/-~;q .O
Sfr/pp/ng- :- -h ec n o n
%
■44&
Fa.
7
C o n s ta n t
H ead
A p p a ra tu s
45
vacuu.ru and a raffinate sample, if desired, can be drained
from the bottom of the column.
Table II, page 46, gives a
summary of the operating characteristics of the column.
A flow diagram of the actual chlorination apparatus
is shown in Fig. S.
The chlorine coming from the cylinder
passes through a flowmeter, containing concentrated sulfuric
acid, and hence through chromous sulfate solutions which re­
move any oxygen present in the chlorine stream.
Leaving
these bubblers, the chlorine enters a drying tube contain­
ing anhydrous calcium chlorid_e which dries the chlorine
before it passes into the hydrocarbon in the reactor.
The
exit gases from the reactor pass into a 25% solution of
potassium iodide where they are absorbed, as explained
later.
The reactor consists of a 16 inch length of 3 Inch
inside diameter pyrex pipe with one end sealed shut, form­
ing a large tTtest tube” .
The hydrocarbon, to be chlorinat­
ed, is placed In this reactor and the chlorine introduced
under the surface by means of a
tube.
4 m m * glass tubing delivery
An air-driven stirrer, acting through a mercury seal,
is used to agitate the mixture.
A long-stern thermometer
is also placed In the liquid and, on some runs, a rough
viscometer is present.
Surrounding the reactor there is an
outer js.cket consisting of a 12 inch length of 4 in.cn in­
side diameter pyrex pipe covered on the lower end by a brass
plate.
Connections are made to this jacket, enabling the
46
TABLE I
Operating Characteristics of Vacuum Distillation
Apparatus
1.
Controlled Operating Pressure - 1 ram. Hg to .atmospheric
2.
Pressure Deviation - 2% at 1 mm.- Hg, much less at higher
pressures.
3.
Charge
4.
Number of Fractions - 10
5.
Operation of Fraction Cutter - Manual
6.
Maximum Temperature ----------
100 to 500 cc.
4O0°Cin still.
TABLE II
Operating Characteristics of Solvent Extraction
Column
1.
2.
Solvent ------------------- Lower density than treated
material.
S o l v e n t ------------ ------ Boiling Point under 100° C.
3.
Solvent B a t e
4 . Operating Temperature ----
0—5 liters
per hour.
10° to Boiling Point of solvent
5 . Maximum C h a r g e ------------ 600 cc.
6.
Maximum Total Extract - - - - 1 0 0
7.
Amount of Solvent Needed—
8.
Batch Operation
cc. at
4 liters.
one time.
0o
0o
oa
On Removal
Reacf or
Chlorine
XJ
Absorber
an
M
Fig. 8
Chlorination
Flow Diagram
-n
<2
48
reactor to be heated by steam or hot water or cooled by
cold water.
This jacket covers the lower 12 inches of the
16 inch reaction "test
at its top by
tube" and is sealed to the reactor
a rubber gasket.
Sometimes during chlorinations the chlorine delivery
tube would become clogged by solid chlorinated materials
building up a dangerous pressure in the chlorine purifica­
tion train.
This danger also occurred when the inlet tube
to the exit gas absorber became plugged, as very< frequent­
ly occurred.
To avoid the danger of flooding the room
with chlorine
when the pressure increased,a safety trap
was inserted in the chlorine line just before the drying
tube.
This consisted of a 17-tube of sufficient length
filled with concentrated sulfuric acid.
When the pressure
built up to a certain value, the chlorine would bubble out
through the U-tube, whence it was carried by tubing to the
outdoors.
For purposes of safety all connections of rubber to
glass between the chlorine tank and the reactor w e r e 'se­
cured by copper wire.
The rubber stoppers on the chronpus
sulfate bubblers were also fastened with copper wire.
Care must be used during chlorinations to prevent any.
i
rapid decrease in temperature of the reactor.
When the
temperature drors there is a decrease of pressure within
the reactor from the twin reasons of contraction of the
49
gases above the liquid and the greater. .solubility of gases
in trie liquid.
If the temperature drops too rapidly the
potassium iodide solution will be drawn back into the re­
actor ruining the run.
For the removal of any oxygen present in the chlorine,
chromous sulfate solutions were chosen
according to the
recommendations of Stone and Beeson (52).
The preparation of the chromous sulfate solution is
brought about by reducing a freshly prepared 0.1 molar
sulfuric acid chrome alum solution by means of a Jones
redactor.
Detailed procedure follows:
The amalgamated
zinc was prepared by stirring approximately 250 grams of
C.P. zinc in 100 ml. of 3 N hydrochloric acid for thirty
seconds.
Then 100 ml. of 0.013 M mercuric chloride solu­
tion (5 ml. of a saturated solution at 25° C. diluted to
100 ml.) were added to the zinc acid mixture.
The stirring
was continued for three minutes, after which the amalga­
mated. zinc was washed thoroughly with water by decantation.
The amalgamated zinc was then put into a piece of glass
tubing approximately 30 cm. long and 22 ram. in diameter.
The chrome'alum solution (0.4 molar) was passed up
through the amalgamated zinc, after the. set-up had been
thoroughly flushed with 00^.
The light blue chromous solu­
tion emerging from the top "was run directly into the flasks
which were to be used.
These flasks must also be flushed
50
with CO2 before the chromous sulfate solution is run into
them.
\vhen tne ame.1 g s.ma t ed zinc solution is not in use it
must be stored, under water after washing all the acid from
it.
The absorption and subsequent analysis of the exit
gases was carried out by a 25% solution of potassium iodide
(21) in distilled water.
The use of this solution enables
the determination and differentiation of absorbed chlorine
and the hydrogen chloride from the same sample.
The hydrogen
chloride in the gases is absorbed by the potassium iodide
forming potassium chloride and hydrogen iodide.
The chlor­
ine absorbed, again forms potassium chloride and liberates
free iodine.
For analysis, an aliquot portion is'with­
drawn from the absorber and titrated directly with sodium
thiosulfate.
The amount of this solution used represents
the amount of free chlorine' which was present in the gases.Then, to the same sample, a small quantity of potassium
iodate crystals are added.
These react, with the hydrogen
iodide present in the solution, liberating free iodine
which is again titrated by sodium thiosulphate.
The
amount used this time is representative .of.the hydrogen
chloride in the absorbed gases.
■The chlorine cylinder was weighed on tne heavy—duty
fulcrum balance in the Chemical Engineering Laboratory.
Teighings on this balance are accurate to one gram.
By
51
making weighings before and after the chlorinations and byabsorbing and analyzing all of the exit gases, a chlorine
balance can be made.
This chlorine balance can be checked,
when no volatile material is present in the reactor, be ­
cause any excess chlorine entering over that leaving has to
be equal to the increase in weight of the reactor after the
loss of hydrogen as hydrogen chloride is accounted for.
Physteal Proyerty Petermlnation
Buring the course of the investigation it was neces­
sary to obtain and interpret certain physical properties
of the materials encountered..
The densities of the
materials were determined by pvcnometers.
Viscosities were,
determined by the use t»f the modified Ostvald viscometers
as described by -Cannon and Fenske (6) and A.S.T.M. viscos­
ity index calculated.
The Indices of refraction were ob­
tained by use of the Abbe type refractometer situated in
the Chemical Engineering Laboratory.
Melting points were
obtained in the standard -manner and softening points by a
modification of -■the proposed A.S.T.L. ring and ball method.
It was necessary to know the approximate composition
of the original oil used.
For this purpose use was made of
the methods advanced by Waterman (5 5) and further developed
by the Petroleum Refining Laboratory.
In order to run a
52
Waterman analysis on an oil it is necessary first, to liave
certain physical properties of the oil and second, to have
certain charts relating these properties.
The 'physical
properties necessary are (l) index of refraction (n§3),
(2) density (dpo)* (3) viscosities in centistokes at 100° F.
and. 210° F ., and. (4 ) aniline point.
The charts used were
obtained from the Petroleum Refining Laboratory of The
Pennsylvania. State College.
The aniline point of an oil
is the temperature at which a 50-50 volume mixture of the
oil and water-white, double-distilled aniline become com­
pletely miscible.
In order to illustrate the calculations necessary, the
Waterman analysis, of the original oil will be made.
‘The
necessary data are:
n|°
=
■d2o
1.
1.4778
~
0.8620 gr./ml.
Visln0O F
=
36.33 Centistokes
ViSp1Q
=
5.67 Centistokes
Aniline Point
=
105.0° 0.
First it Is necessary to calculate the specific refrac­
tion from density and index of refraction.
(ng0)2 - 1
Speoific Refraction =
( m u s k
=
_
-
°-3283
1
d
_
=
fi.A778’)2-I x
(1.a 7 7 8 ) W
53
2.
Next the molecular weight is determined from the chart
of Keith and Roess (32) or calculated by the equation
of Fenske, McCluer and Cannon (15)* using the viscosi­
ties at 100 and 210° F.
The value determined is in­
creased by ten per cent.
Mol Wt. = (360)(1.10) = 396
3.
Using the chart (ref. 55,"p. 667) relating molecular,
weight, specific refraction, and aniline point, we get
an aniline point known as ”chart aniline point”;
theoretically, the aniline point of the completely sat­
urated oil.
Chart aniline point = 111.6
4.
The per cent aroma tics present can now be calculated by
using the experimental and ”chart” aniline point.
T>er cent Aromatics = (0.6S)(chart A.P. - experi­
mental A. P.)
Per cent Aromatics = (0.68)(111.6 Per cent Aromatics
5.
=
105.0)
4
The aniline point of the hydrogenated 011 is tnen detenu
ined (theoretically) by use of same values.
Aniline
Point Hydrogenated '= Exptl. A.P.
(Chart A.P.
+ (0.8)
- Exptl. A.P
=.105.0 + (0.8)(111.6-105.
= 110.3
54
6.
The specific refraction of the theoretically hydrogenat­
ed oil is then determined using the molecular weight
and the aniline point hydrogenated from same chart as in
3.
Specific Refraction, Hydrogenated = 0.3274
7.
From the chart (ref. 55, p. 663), using the molecular
weight and hydrogenated specific refraction we calcu­
late the total per cent cyclics. This is the ratio:
l
Specific refraction of all paraffins - specific refrac­
tion, hydrogenated and divided by specific refraction
paraffins - specific refraction of six membered con­
densed naphthalenes, all values read using the molecular
weight found in 2 .
fa Cyclics = (
8.
p ^ — ) (100) - ('0 *333^ - '0;3074) (10Q) ~ 23
The percentage of naphthenes is therefore the total per
cent total cyclics minus the per cent aromatics.
Per cent Haphthenes = 19
9.
The percentage of paraffins is 100 minus the per cent
cyclics.
Per cent Paraffins = 7 7
10. Using the same chart as in 7, the number of rings per
molecule is determined, using the specific refraction,
hvdroeenated and the molecular weight.
The horizontal
55
curved lines on this chart are labeled from one to
six rings per molecule and the value read by interpola­
tion.
Rings per Molecule = 1.5+
11.
Calculation of the value of nx Tt in the empirical for­
mula CnHp +x is as follows:
x
\% Aromatics
7 C „. 1 r-, ^ , fe l ^ hthenes
'% Total Cyclics] LRo * R±nSsJ (I-6) + [%. Total Cyclic
. Rings * 1)(-2)
x - ('23) (1*5) (-6) t
12.
(1.5 - l) (-2) - -2.5
The value of n is then obtained by a weight balance:
(12) (n) + (2)(n) + (l) (x) = -M.W.
14n +. (-2.5) = 396
n
13.
= 28 .5
Our oil has the formula
c2 8 .5 H54-5
56
DISCUSSION
Since this investigation was of the nature of an
exploration, various fractions of petroleum were chlori­
nated.
The fractions used included kerosene, lubricating
oil, paraffin wax, and isopentane.
The preliminary runs
were made on lubricating oils which Included Gulfpride
S.A.E. 10 and S.A.S. AO commercial oils and a. 160 viscosity
medium neutral oil obtained from the Kendall Refining
Company.
This neutral had been treated In the following
manner.
It had. been dewaxed to zero pour point and had a
flash point of /i.25/A30° F.
Prior' to solvent treating, its
viscosity was approximately 195 S.S.U.- (A2 Centistokes) at
100° F.
Ten per cent of the dewaxed, stock was removed by
phenol treating and the raffinate-filtered to a yield of
100 barrels of oil per ton of clay, based on new earth.
A summary-of the properties of this Kendall oil, here­
after known as "original oil”, are shown in Table III.
The
runs on the Gulf pride oils ’were mainly qua.llta.tive in
nature and thus no physical property data were determined.
Included in Table III are the .pro.pert.ies of the claytreated original oil.
-This clay-treated oil was obtained
by treating the original oil in a. A2 mm. inside diameter
tower, filled with activated clay, until the oil was waterwhite .
The yield of water-white.material was about 33h of
the amount charged.
The properties listed in Taole III
TABLE III
Physical Properties of Lubricating Oils Used
in this Investigation
Oil
Untreated Original
Clay Treated
Original ■
Density (doo)
0.8620
0.8586
R.I.
1.4778
1.1752
(ng°)
Viscosity-Cent!stokes
100° F.
36.33
35.23
'210° F.
5.67
5 .63
V .I . (A.S.T.M.)
Color (A.S.T.M.)
104
2y
Aniline Point °C.
105-0
Molecular' Weight
396
% Aromatics
^
7o Naphthenes
% Paraffins
Formula
4
.19
77
C28.5H54-5
108
0
107.3
5a
were determined by the procedures outlined in the preced­
ing section.
Prior to the actual chlor inations of the original oil,
it was subjected to vacuum distillations at one and ten
millimeters of mercury pressure and to solvent extraction
in the extraction column, using acetone as the solvent.
These distillations and extractions were carried out with
the dual purpose of testing the equipment and of obtaining
additional data on the original oil.
The results of the
two vacuum distillations are given in Tables IV and V.
As
can be seen, reducing the pressure from ten to one milli­
meter of mercury'lowers the vapor temperatures recorded
-L
or the fractions by about 5Q° C. (90° F.).
The other
propertie s are approxrina tely the same, at both pressures.
The six solvent extractions on the original were
carried out under as nearly identical conditions as pos­
sible.
In each case the charge was 500 ml. and the tem­
peratures and solvent rate ad-justed to the same values.
Table VI summarizes the results of these runs.
Runs E-l
and E-2 .were apparently contaminated by material such as
p i p e 'compound present in -the system due to construction.
These two were therefore not used although data on Run E-l
are included in the table.
The raffinates from tne last
four runs were combined and clay treated In order to im­
prove their color.
This clay treated raffinate was then
59
used for some of the chlorinations and its properties are
listed in Table VII.
The kerosene used in this investigation is a commer­
cial grade which was obtained from the stock room.
This
material was used as obtained but it had a slight yellow
tinge and therefore, for one of the runs, it was subjected
to clay treatment which readily gave a water-white product.
The properties of the untreated and the clay treated kero­
senes are also given in Table VII.
The isopentane was ob­
tained. from the Petroleum Refining Laboratory and its
properties are listed in Table VII.
sity data are for pure Isopentane.
The viscosity and den­
These values are un­
doubtedly close enough to the actual properties.
.of the Iso­
pentane used for the purposes of this investigation.
The , -
paraffin wax, likewise, was obtained from, the stock room.
It was a hard white wax with a melting point of 51-53° C.
A survey of the literature on chlorination indicates
that, in order to obtain the most stable materials, primary
chlorides should, be the main chloride present in the product.
Also, a review' of H a s s T rules of chlorinations shows that
liquid phase chlorinations at elevated temperatures favors
high yields of nrimary chlorides over the secondary and.
tertiary chlorides.
For thus reason, all ch3-orinations in
this I lives tigation were carried out In the liquid phase.
In fact only, the chlorination of isopentane and pernaps
kerosene would have been feasible in the vapor phase.
60
TABLE IV
Distillation No. D-3-10
10 mm. Distillation of Original
Pressure = 10.00 ± 0.05 mm. H g .
Material
Vapor Temp.
OF.
°C.
n20
D
20
1.4778
0.8620
Viscosity--Centistokes V.I,
100® F.
210° F.
;
Original
-
-
36.33
5 .67
104
Cut* 1
245
473
1.4760
0.8588
22.94
4.24
96
Cut 2
2.53
487
1.4763
0.8595
26.14
4-83
101
Cut 3
256
493
1.4766
0.8599
28.38
4*85
101
Cut L
260
500
1.4769
0.8606
30.75
5.10
102
Cut 5
265
509
1.4771
0.8611
33-15
5.35
104
Cut 6
2.70
518
1.4773
0.8617
35.75
15.65
106
Cut 7
274
52.6
1.4778
0.8622
38. 71
■5.90
104
Cut 8
278
533
1.4781
0.8627
42.05
6.23
104
Cut 9
283
542
1.4782
0.8631
4 6 .24-
6.66
105
1.4822
0.8691
77.06
9.27
104
Residue
_
—
* Each cut represents 10% of the charge.
61
TABLE V
Distillation No. D-5-1
10 mm. Distillation of Original
Pressure = 1.00 ± 0.02 mm. H g .
Vaoor Temp
OF'.
Mate rial °C.
Orig inal
-
—
ngO
d
20
Vi scosity--Centistokes
100° F .
210°F.
V.I
1.4776 0.8620
36.33
5.67
104
Cut* 1
195
363
1.4771 0 .8617
22.86
4.19
91
Cut
2
201
394-
1.4771 0.8613
26.52
4.61
97
Gut
3
206
403
1.4771 0.8616
29.10
4.91
100
Cut
4
210
411
1.4772 0.8612
31.47
5 .18
103
Cut
5
21A
419
1.4772 0.8615
34-10
5.41
102
Cut
6
217
423
1.4776 0.8615
36.41
5.70
105
Cut
7
222
431
1.4776 0.8616
39.11
5.94-
104
Cut
8
226
439
1.4776 0.8615
42.27
6.29
106
Cut
9
232.
449
1.4778 0.8612
46.03
6 .65
106
—
_
1.4313 0.8673
78.30
'9.56.
108
Residue
Each cut reoresents 10% of the charge.
62
TABLE VI
Extraction of Original Oil
Column Temp. = 22° C.
Contacting Section Temp. = 40° C.
Solvent Rate = 3*8 liters Acetone per Hour
Run No.
E-l
'
jjj
Fraction
% of Charge
20
nD
Viscosity-Centistokes
100°F.
210°F. V.I
Extract 1
7.3
1.4922
Extract 2
4.6
1.4890
Raffinate
88.1
1.4700
Extract 1
9.0
1.4982
11.8
1.4950
8.2
1.4998
11- 0
1.4949
7.0
1.5025
11.0
1.4947
6.8
1.5.020
55.64
6.38
57
10.8
1.4960
48.60
6.11
70
—
1.4728
34»02
5 .57
112
—
1.4778
36.33
5.67
104
4?
Comb .
Ext. 2 & 3
Extract 1
Comb .
E xt. 2 & 3
Extract 1
E-5‘
Comb.
Ext. 2 & 3
Extract 1
E-6
Comb.
Ext. 2 Sc 3
* Combined Raffinates
from E-3, E-4, E —5X
E-6 Clay-Treat ted
Charge
TABLE VII
Physical Properties of Combined Raffinate, Kerosene and
Isopentane
Material
on
p,
Clay-Treated
Combined
Raffinate
1.4728
from
Untreated
Kerosene
1.4461
Vi sco sity-Centistoke s
100° g.
2X0° F.
V.I.
34-02
5.57
112
1.60
-
-
n
a20
Color
0.8545 1 (A.S.T.M.)
0.7980 Yellowish
Tinge
Clay-Treated
Kerosene
1.4457
1.62 ';
-
-
0.7980 Water-White
Isopentane
0.363*
-
-
0.620
1.3570
* At 20° C.
Water-White
64
As mentioned previously, the;preliminary work was per­
formed on commercial oils of light (S.A.E. 10) and heavy’
(S.A.E. 40) grades.
A compilation of the general results of
the five chlorinations
is
show, in Table VIII.
These
runs were made mainly in order to test the general proced­
ure of the chlorination and to iron out any difficulties or
awkward operations in the chlorination apparatus.
These first runs were made without much control over
the conditions which are known to be catalytic; i.e., light
and heat.
The chlorinations were run during the day and at
night so that at times the sunlight catalyzed the reaction
and the rest of the time the chlorination was run in the
dark.
Since iron was present in the reactor conditions
varied so as to produce directly opposite types of chlorina­
tion; cf., chlorination of toluene.
ho attempt was made
to hold the temperature constant and so it varied as the
heat of reaction varied; i.e., the faster the chlorine was
passed in, the' greater heat of reaction developed and the
higher the temperature of the reaction mixture.
Run C-l-10, chlorination of the light S.A.E. 10 oil,
was started, using a small electric motor to operate the
stirrer but it was soon found that the continuous operation,
especially when the chlorinated material became vrscous,
.was too severe for it.
The brushes wore out very Q u i c k l y
and the armature became -badly scored, so that an air—driven
TABLE VIII
amrnsry of the Preliminary Buns on Gulfpride Oils
Iron Tacks Served as Catalysts in all of the Following Runs
Approx.'
* Increase Hydrogens
Temp. °E’. in height
Run Ho.
Oil
C-1-4-0
Gulfpride
S.A.E.
10
40
C-2-99
10
99
Gulfpride
S.A.E.
40
C-3-35
0-4-102
C-5-100
''
JD cl
3.0.
Gulfpride
C fi'•1
?•
it
’•
10
■
U>’ • -
80
124 .
Replaced
17
Fluid
Very tacky
26
Black
1ax xy
Deep
Barely
reddish flows
brown
Asphaltic ^
appearance
free carbon
Fluid
Very tacky
35
51
102
92
19
105
Remarks
Barely
Deep
Reddish flows
Brown
11
100
Color
Fluidity
100°C.
20°E.
22
Solid
Very
deep
red
Solid
Black
Solid
Heavy Brittlesyruuy friable
appearance
of rosin
O
L O
Heavy
syrupy Very brittle
sed on assumed formula CnH2n where n = 28
^ Mey be due somewhat to water which.entered or to local overheating during
stripping operations.
O'
66
stirrer was substituted clnd used very successfully.
The
air-driven stirrer even operated very well on viscous
materials although the air pressure had. to be quite high.
In this first run sodium hydroxide solutions of about 2.5%
strength were used in the gas absorbers.
Much trouble was
encountered due to the plugging, by precipitated sodium
chloride, of the constricted gas delivery tube in the abj
sorber.
This tube had been constricted in order to de­
crease the size of the escaping- gas bubbles and thus aid
their absorption.
As the chlorination continued, the oil gradually be­
came more viscous and darker colored.
As it became, vis­
cous, it foamed considerably and towards the end. there
aoneared
to be nothing
-—
i *—3 but foam in the reactor.
This foam
had a rather light orange color but when the oil had set­
tled. its- very dark color was apparent.
The removal of the chlorine and hydrogen chloride
gases dissolved in tie■reaction mixture was attempted by
the use of heat and vacuum.
.The reactor was heated to
100° C. by means of steam condensing in the jacket and
vacuum was applied by a water-jet aspirator.
This method,
of gas removal apparently is not successful since the
product still smelled strongly of hydrogen chloride after
several hours treatment.
Run C-2-99 'was a chlorination of the same type oil
67
(S •A •a » AD) ®-t an average temperature of 99^ C. using iron
as a catalyst.
During this run steam condensing in the
jacket held the temperature of the reactor mixture at 99°C.
The oil darkened very rapidly and at the conclusion of the
run considerable black solid material lined the inside of
the reactor.
Although the oil definitely darkened more
rapidly than it had when chlorinated at room temperature,
the final very asphaltic appearance is probably due, in
part, to other causes.
These include (l) the add.ition of
a small amount of water which was drawn back into the re­
actor from a manometer when the temper a ture dropped, sudd.enly, and (2). the decomposition of the product during, subse­
quent gas removal attempts.
Since the gas removal from
the chlorinated lubricating oil in the first run (C-l-40)
had been unsuccessful, a higher temperature, obtained by
electrical' heating, was tried,.
No better results were ob­
tained and due to difficulties in stirring some local over­
heating with its accompanying decomposition undoubtedly
occurred.
The sodium hydroxide solution absorbers plugged
frequently even when the gas delivery tube was flared.
The next two chlorinations were carried out on the
more viscous S.A.E. AO commercial' -oi l . : One of .tne- runs
(C-3-35) was made at room temperature and the other (C-A-102)
at 102° C. witil steam in the jacket.
cases was iron.
The catalyst in both
At room temperature tne oil became too
68
viscous before very much, chlorine had. "been introduced..
Like the previous runs on the less viscous oil, the color
gradually changed from its original yellow through.- orange
and. finally to deep red or brown.
At the higher tempera­
ture, however, this darkening was much more ra~pid and the
oil was darker for any comparative chlorine content.
The
removal of dissolved gas was brought about by bubbling car­
bon dioxide through the heated (100° G.) chlorinated pro­
ducts while maintaining a. high vacuum on the system.
This
method: proved satisfactory except that the time necessary
was long - ten hours in the case of the more highly chlori­
nated oil (0-1-102).
Considerable success was had in keeping the sodium
hydroxide absorbers open.
This was' brought about by the
simple'expedient of using a more dilute solution.
A 10%
solution was used for these runs and, although requiring
more frequent changing, it eliminated the constant checking
feviously required..
During the early part of the chlorina
tion of the S.A.E. 4,0 oil at 102° C . with an iron catalyst
(Run C-4-102), a dry ice-acetone trap, maintained at tem­
peratures lower than -35° C., was placed between the reac­
tor ail the absorption flasks.
This trap was maintained at
the low -temperature.for a period of several hours but aosolute'ly nothing was condensed.
This indicates tnat all of
the chlorine during the early stages of cnlorina oion- reacts
69
completely since tne boiling point of liquid chlorine i s '
-34*6° C.
The liquifying point of hydrogen chloride (-84°C.)
cannot be reached using acetone and dry ice.
Chlorination C-5-100 was made on the light S. A. Eh 10
commercial oil at 100° C. using an iron catalyst.
In the
belief that the darkening of the oil may be due to oxida­
tion, an antioxidant,, urea, was added to the oil.
amount of urea represented .1.0% by weight.
The
There was no
noticeable slackening in the rate of discoloration of the
oil- in fact,, it appeared to have been hastened.
The rate
of reaction of the chlorine was considerably slower and
much ..more chlorine passed through the oil unreacted than in
the parallel run w i t h o u t :urea; i.e., Run C-2-99•
Aside
from these differences and the fact that the product con­
tained no asphaltic material, the results of. this run are'
similar to those of the parallel run on this oil.
An attempt to use pyrogallol for removing oxygen from
the chlorine steam instead of chromus sulfate solutions,
which are time-consuming in preparation, proved to be a
failure’ since the chlorine reacted directly with tne pyro­
gallol.
Unfortunately* the samples of the absorbers were
lost and thus no material balance check could b e o d t a m e d
of the run on the S.A.E. 10 oil using urea (C-5-100).
From, these first five runs there were certain obser­
vations and conclusions to be drawn as to the conauc o of
70
subsequent chlorinations- The major ones were:
(l) hie'her
temperatures favor the more rapid darkening of the oil
under the conditions studied; i.e., iron catalyst;
(2) the
apparatus needs the safety trap, explained under the
apparatus and procedure section, with an exit outdoors to
prevent accidents which would release chlorine into the
room;
(3) chlorinations should be carried out under more
controlled conditions of catalyst and temperature .and^ (l)
a less time-consuming method of gas removal was desired.
It was desirable to know how much of the absorbed
exit gas was chlorine and how much was hydrogen chloride.
A knowledge'of this enables one to determine how much of
the entering chlorine reacts by addition and how much by
substitution.
The hydrogen chloride absorbed represents
an. equivalent amount of. chlorine which reacted substitutively.
A t o t a l .chlorine balance shows how much more chlorine
entered than was accounted for in the absorbers and this
Is therefore the amount of chlorine which reacted by addi­
tion.
In order to distinguish between the chlorine and
hydr-ogen chloride' the solution in the absorbers was changed
to potassium i o d i d e .
A 25% solution appeared to be the
strongest concentration which could be used witnout causing
excessive plugging of the delivery tube: during aosorption.
The chlorination of the lubricating oil fraction of
petroleum was accomplished in runs 0—6 to C—13 and C—19 •
71
A summary of these chlorinations is given in Table IX and
the physical properties of a few of the products is given
in Table X.
Four of the runs (C-6 to C-9) were made on the clay
treated combined raffinates from extractions E-3 to E-6
described above.
Run C-6-S2 was performed in a carbon
tetrachloride solution and with enough steam in the jacket
to maintain this solution at its boiling point.
No iron
or other catalyst was used except the action of daylight
during the day.
The reaction proceeded more rapidly than
any of the proceeding chlorinations, which may have been
due to the decreased viscosity caused by the addition of
the solvent.
ficulties.
The solvent, however, caused operational dif­
Since the reactor w a s 'maintained at the boiling
point of the solution, CCl^ was condensing on the cover
plate and the w a l l s .
This condensate attacked the neoprene
rubber gasket sealing the top of the reactor and also rubber
stoppers causing black solutions of the rubber to drop into
the oil.
This probably hastened the blackening of the oil
although It was definitely darkening before any dissolved
rubber entered it.
The final product was very black, although no solid,
matter was present.
This product was stripped of gases by
flushing with C.Og under vacuum for some time.
It still
smelled faintly of hydrogen chloride and so'was placed in a
TABLE IX
■Summary of Chlorinations of Original Oils
See Tables III and VII for properties of charging material
No.
Tenro.
°C. Catalyst
Charge
C-6-82 :Combined Raf- 82
: finat.es from
E-3 to E-6(S)
103
C-7-103
”
Per cent Increase
in Weight
Due"to Due to
Audi- Substition tution Total
None
Approx.
Per cent
Hydrogen
Replaced
Remarks
36
36
8
Black, very fluid
Black, asphaltic
deposits
Black, fluid, some
deposit
Actinipv
light’™'
Fe in dark
-
43
43
9
-
48
43
10
C-3-100
■"
C-9-30
»»■ .
30
I!
0
37
37
8
Original
100
I!
0
38
38
3
Black, much asphaltic
deposits (Table X)
Jj ack, fluid(Table X)
0
48
43
10
Black, asphaltic dep.
21*
36
57
10
97
115
20
144
167
31
ikv
Deep orange,
(Table X)
Light orange, very
viscous
Light orange, solid
C-10-100
C-ll-30
C-12-36
100
it
30
36
It
18
it
■ 18-
t 20
Original (S$
t!
*J>A
(s)
C-13-18
—
/
tr
Actinic
light**
W
- - W W W -
n
** Carbon Arc Lamp.
■>*
ice of solvent (ccip.
should be 22/o to satisfy all unsaturati<
ro
Properties of Chlorinated Original Oils Studied in this
Investigation (See Table IX)
Run
20
Treatment__________ ^20______ nD
C-9-30
(Chlorinated Product
(
neutralized by
<
Aaimonia and Filtered (
C-10-100
C-12-36
Clay Treated Chlorinated
.Product •
Viscosity-Centistokes
100° F.
210° F.
7.1.
1.019
1*499
2044
H .21
64
1.019
1.510
357.4
18.61
4.9
1.5175
297.7
49.17
-5
1.128
74
TABLE XI
Distillation No. D- 6-1
Vacuum Distillation of Original Oil Chlorinated at
100° C., with iron, to a 30 Weight Per Cent
Increase
Pressure = 1.5 - 0.1 mm. Hg
Each cut represents 10% of charge
Material
Vapor Temp.
20
a
nD_______ 20
Viscosity-Centistohes
100°F.
210°F. V.I.
Cut 1
*
1.4790
0.8803 19.63
3.99
114
Cut 2
*
1.4790
0.8816
27.64
4 .81
104
1.4802
0.8832
30.02
5.20
115
1.518
0.9470 1126
74-05
U7
Cut 3
Residue
-
* hot reliable (See tent p. 79 )
Petroleum Ether soluble portion.
75
condensing vapor bath stripper employing
(b.p. 25 3
C.) as tne neating medium.
Dowtherm A
However, the mater­
ial when removed from the stripper smelled -much more strong­
ly of HC1 than it had previously.
When cold, it was
solid and had an asphaltic appearance.
Undoubtedly,
almost
decom­
position took place and therefore a lower temperature should
be used for stripping.
"Actinic” light, obtained through the use of a carbonarc lamp, and elevated temperature were used as catalysts
for the next run (C-7-103) .
All equipment coming in con­
tact with the oil was made of glass.
The oil turned
gradually but the reaction rate was very good.
dark
In fact, so
far as the chlorination was continued, no slackening of the
rate as had always been noticed previously was observed.
The final oil was
jet black, however, and contained quite, a
bit of asphaltic material.
It -was. stripped of dissolved
gases by flushing with CGg at 100° C.
There was a distinct
odor of HC1 in the stripped'product.
A similar run was then made, again with the combined
r affiliate at 100° C . , but an iron stirring rod was'used as
a catalyst arid, the reactor was completely enclosed.
This
prevented daylight from entering and catalyzing the reaction.
The oil darkened almost at once and. soon was jet black.
The
reaction was also slower . than the previous run and there'was
more tendency for the chlorine to pass through unreacteu.
76
The final product was found t o .contain some asphaltic
material indica.ting decomposition.
Carbon dioxide and
vacuum were used to remove the dissolved gases but were
not entirely successful.
In the above runs a rough scale, weighing to 1/2 oz.
(14 g r .) , was still being used so that no attempt to check
material balances or determine chlorine by difference was
made.
This procedure is upheld by noting that in the
usual run which would involve approximately 100-120 grams
of chlorine from the cylinder,
the difference between the
chlorine entering and that accounted for by the absorbers
was never more than 15 grams.
That is just about what the
accuracy in weighings was and therefore the error in addi­
tion reaction calculations would, be about ±100/.
In order
to avoid this large error, a heavy duty fulcrum balance in
the Plant Testing Laboratory was tested and found satisfactory f or- -1he weighing of the 30- 0 ound chlorine cylinder
to ±1 gram.
'This, balance was used in all subsequent runs.
In the next run (C-9-30) , again using the -combined
raffiliate and an iron catalyst, conditions were maintained
the same except for the temperature which was controlled
at about 30° C. by proper adjustment of cooling water to:
the jacket.
Once again the oil turned -black soon after
chlorination was started and a considerable amount of
asphaltic material was formed.
.The reaction was very slow
77
compared to the chlorination of this oil using actinic
lignt (Hun C— 7—103) anct also quite a hit slower than the
similar chlorination at 100° C .
A material balance indi­
cated that more PiCl had been evolved than should have been
even if all of the chlorine reacted by substitution.
This
indicates that decomposition has occurred, giving rise to
unsaturation or ring coupling and loss of an extra amount
of hydrogen chloride.
The chlorinated material this time was first given
the same treatment for gas removal as had the preceding
runs; i.e., heat, vacuum and CO2 flushing.
Then gaseous
ammonia was passed through the oil, under vacuum, for an
hour or so.
This use of ammonia was recommended by several
factors. " First, ammonia being basic would readily neutral­
ize any acidic gases like HC1 and the resulting ammonium
chloride could be filtered, or water washed out of the oil.
Second, from consideration of Hass1 rules of chlorination
it is evident -that tertiary chlorides are the most unstable
Also, the reaction of ammonia and tertiary -chloride's occurs
■easily and the net result would be the substitution of an
unstable chloride with a more stable amine.
Third, amines
have been advocated as stabilizers for chlorinated hydro­
carbons and this fact along with the second one would lead
to a much more stable product.
The last' two runs on the combined raffinate oil were
78
repeeted. using iris original oil in order 'bo check and see
whether or not natural stabilizing compounds of the original
oil had b e e n removed by solvent extraction.
The run on the
original at 100° C. with an iron catalyst (C-10-100) dif­
fered from the similar run on the combined raffinate
(C-8-100) only in the fact that no asphaltic material was
formed.
However, this chlorination of the original was
not continued as far and it is possible that the same result
would have b e e n obtained had the same amount of chlorination
been attained.
temperatures
The chlorination of the original at room
(C-ll-30) gave the same final product as its
counterpart on the combined raffinate (C-9-30)
the oil did not darken nearly so rapidly.
although
Both chlorina­
tion products of the 100° C. and the room temperature runs
on the original were treated with COp, vacuum and then
ammonia for removal of gases.
The ammonium chloride was
filtered off in coarse fritted glass funnels.
The physical properties of the products obtained by
■ the above chlorination of the original at 100° C. and 30° C .
with iron -catalyst (Table
a
),
tend to bear out the general­
izations found in the literature; i.e., the density, refrac­
tive index, and viscosity, all increase witn increasing
chlorine content.
The. viscosity incisx nas dropped from ius
original 104- to 64 and 49*
It is interesting to note un«.t,
although both products contain almost identical amounts of
79
chlorine, the one obtained by chlorination at the higher
temperature
(C-10-100) has had a greater increase in these
properties.
The product from the chlorination of the original
(100° C.,
iron catalyst, 3&fo weight increase) was subjected
to a vacuum distillation (D-6-l) in an attempt to separate
the non-chlorinated material from the chlorinated products.
The pressure was meant to be one millimeter of mercury and
when that pressure had been reached the still heat was
turned on.
However, before any product had been obtained,
the pressure increased and got out of control.
It was
soon discovered that, instead of d.is tilling, the chlorinated
oil was cracking and giving off gases so rapidly, that the
pumps could not maintain a pressure of 1 mm. . A Thermo­
couple was'therefore inserted between the heating mantle
and the distillation flask, the heat was -..regulated' to such
a value that the pumps could hold a pressure of approximate­
ly. 1.5 mm." of Eg and the distillation continued.
Three 1C$
cuts v/ere obtained before the temperature of tne neating
mantle reached, its safe limit.
The distillation, proceeded.
so slowlv that no reliable vapor temperatures were obtained.
The lack of any light boiling.material in the chlori­
nated uroduct is an indication that all of tne moj.ecu.xes. in
the oil have been chlorinated to a greater or .Less degree.
This is in agreement with the general chlorination rule
so
which states tnat once a chlorine atom, lias entered a
molecule,
that molecule becomes more stable to further
chlorination.
The first two cuts were
third one was Quite dark.
jet black and the
Some of this color was probably
due to impurities from the bumping of the liquid in the
flask.
The residue was a semi-solid asphaltic mass.
This,
mass was treated with petroleum ether at a temperature of
about 70° C. and the soluble material removed.
-.When
stripped of solvent this was the residue sample.
The
properties of these cuts and the residue are given in
Table XI.
A comparison of these cuts obtained from the above
distillation brings out some interesting details.
The
refractive index and the density indicate that a con­
siderable portion, i f -not all, of the chlorine had been
lost-. . These properties are almost as low as the original
oil was before chlorination.
The viscosities, compared to
the original oil, have been lowered and the viscosity index
increased appreciably in the case of two of the cuts. ' Tne
most surprising material is the residue which has tne
highest viscosity index although it is a much more viscous
material.
This material is jet black and its viscosity had
to be obtained-by use of a special viscometer for opaque
liquids -developed by Cannon and llenske (6a) .
A review of the preceding runs showed'that, of the
81
possibilities available by use of iron, "actinic” light
and neat, only one nad not Deen tried. — low temperature
and "actinic” light.
These accordingly were made the con­
ditions for the next run (C-12-36).
The temperature during
this run was maintained at approximately 36° C. and the
carbon arc lamp used as a light source.
The oil quickly
turned orange and then gradually became deeper orange as
the chlorination progressed.
But, for the first time, the
chlorination gave a relatively light colored product.
On
standing overnight, however, the chlorinated oil gradually
darkened.
To test the effect of heat, a sample of this
material was heated, to 100° C. for a short while.
Ib
immediately became black, gave off considerable hydrogen
chloride, and practically solidified into an asphaltic mass.
It looked very much like some of the preceding products.
The oroduct obtained above by the chlorination of tlieoriginal at 36° C. with "actinic” light was;tested for
solubility.in various solvents.
By comparison with the
original oil, the only difference was that, whereas the
original was. soluble to a h extent of only about 6 ml. in
100 ml. of acetone at room temperature, the chlorinated
Product was completely soluble.
This is another indica­
tion that chlorination occurs on all of the molecules
present in the original oil.
The chlorinated product did
not tend to darken when it na<x been uilxuced. v/±th a solvent
82
as It had v/hen no solvent was present.
Also, that small
portion of chlorinated product which, as soon as the
chlorination vi/as completed, was removed and. roured Into a
beater did not darken at all.
Since the material left in
the reactor turned dark, it would appear that the darken­
ing may not be due to oxidation as had been thought, but to
condensation or polymerization.
Fortunately, the dark col­
ored product, when passed through activated clay regained
Its color and was now stable to prolonged heating at 100° C.
Clay treatment, therefore, seems to be a good method for
stabilising chlorinated products.
The properties listed in
Table X for Run 0-12-36 are for this clay treated material,
host noticeable is the fact that the viscosity at 100°- F .
is about ten times as great as that of the product from
the chlorination of this original at. 100° C. with iron
(C-10-100) while it 'actually contains little more chlorine.
The viscosity' index likewise dropped more -than would be ex­
pected.
These changes may be due •to either a change in
type of product, obtained or to -the more rapid change In
property oer Increase in chlorine content In tins region.
The former reason is indicated by tne fact t.nat a consider­
able araount of chlorine reacted by addition while none .wad
. ' k '
I
apparently done so previously.
Run C-13-1S on the original was then made at as low a
temperature as could be obtained py tne cooling uc. uer in
S3
-jacket -18° C.
ca mu h- s f .
the
T>le caroon arc lanap ias- used as
Tne reaction proceeded somewhat slower tlian in
wecs u i n g run which. must have been due to the decreased
tftiii arature since CCl^, had been added to decrease the vis­
cosity-
The oil hardly changed color during the chlorina­
tion but once the run was completed it gradually darkened
upon standing.
Clay treatment was used to remove the dark
color and stabilize the product since heat again caused de­
composition of the untreated product.
The final product
was- a very viscous orange red. liquid which was very tacky.
The water -7/hi t e clay treated original oil was chlori­
nated (C-19-20) i n an attempt to get.a water-white chlori­
nated product.
The conditions were practically identical
to B u n C-13-18 - low temperature and actinic light.
•,The
oil slowly turned.yellow and at the end was as yellow as
.the product of
more chlorine.
C-13-lo
.although it contained considerably
This material was clay treated and stripped;
h o w e v e r t h e high temperature necessary for complete strip­
ping caused discoloration.-
The final stripped -product was
solid.
It is -very Interesting to note that the per _cent in­
crease in weight due to addition (Table IX) is just about
the same In the three runs (C-12-36, C— i3-lcJ and C--l9-20)
on the original oil even though the total increo.se in
of the oil varies from 5 7 to 167.
Tne value
s.j.so
is very
"
84
close to toe theoretical amount necessary to sat.urate the
original oil.
The important observations and conclusions which can
be drawn from this series of runs are:
(l) chlorination
at low tenner at ures in the presence of actinic light as
opposed to other conditions studied produces desirable light
colored products,
(2 ) clay treatment is a very satisfactory
method of stabilizing chlorinated materials,
(3) all of the
molecules present in an. oil are apparently chlorinated, (4)
viscosity, density and refractive index increase greatly
while the viscosity index drops rapidly with, an increase
i n chiorine content.
The next series of runs was carried out on kerosene
both untreated a m
clay treated.
The properties of these
kerosenes have been given in Table VII.
A summary of
chlorinations of kerosene is given in Table X I I .
in accord­
ance with the results of the shove runs on lubricating oil,
these chlor Inations were made with nact ini c,T light as cr
O
catalyst.
The first run (C-14-19) on kerosene at 19“ C
’honed that reaction was much more rapio. unan nati oeen une
case for the oil fraction.
11
The chlorinated product was a
t vel low, non—viscous fluid •
it was stripped of
as previously and then clay treated in a tower.
It caiue
through the clay yellow but gradually turned to a purple
color . ;A second clay treatment gave a light yellow proauct
TABLE XII
Summary of Chlorinat-ions of Kerosene
Actinic 1ight wa s activator in all cases.
% Increase
Run Mo.
Material
C-14-19
Kerosene
Tenro.
r.
in Weight
% hydrogens*
Total By Addition
Replaced
Product
19
69
19
14
Light jellow fluidburns
C-15-21
H
21
95:
19
19
Light yellow fluidburns
C-16-19
I!
19
187
9
38
Light yellow plaster
does not burn
70
200-
9
41
Light orange plaster
does not bin’ll
Clay Treated
Kerosene
TABLE XIII
d20
=
1.138
ii
Properties of Kerosene Chlorinated to a. 69% Weight Increase
at 19° C. Using nActinic,!.Light
o
C-22-70
1.5020
Vis*100
=
15.33
Vis‘210
7.1.
=
2.76
=
-36
03
Ul
Viscomjeffr. E ffluxJIim t
R un
...
cove
C.-i
Chlon'natim^. of.. Kermm
0
80
160
HC!
R ecovered
240
~
9 r•
300
87
which was stable to prolonged heating at 100° C.
The
product thus obtained burned slowly with a very sooty flame
The properties of this product are given in Table XIII.
R un C-15-21 was made under Identical conditions but
the chlor ination was carried further»
A rough viscometer
was put in the reactor so that its lower end was in the
chlorinated material' and its upper part extended through
the plate covering the reactor.
By this arrangement a
rough measure of the viscosity of the kerosene could be ob­
tained without removing any from the reactor.
Figure 9 is
a. plot of the efflux time of the kerosene against the
amount of hydrogen chloride recovered in the absorbers.
This .graph is very similar' to one which would be obtained
by plotting viscosity against chlorine content.
This graph
bears out the observation that the viscosity increase grad­
ually with chlorine content initially but soon starts to
increase very rapidly.
The final --product of this run
showed the same tendency to become purple as had the pre­
vious one but repeated clay treatment stabilized It.
This
product also burned with a sooty flame.
The extensive chlorination of kerosene was next car­
ried out (Run c-16-19) under the same conditions as before.
Although chlorinated to the- high degree of 187^ increase
in weight
which is equivalent to a compound containing
about 63f> chlorine by weight, there was practically no dis­
coloring of the kerosene .
The chlorxuca. ueu-
o..>ene v.as
88
was lied with water and dilute soda ash solutions, clay
treated and finally stripped under vacuum at 100° C.
The
product is a light yellow, almost plastic substance at
room temperature which is very stable to prolonged heating
she 100° C.
It will ignite- in direct -flame but immediately
goes out when the flame is removed.
Run C-22-70 was a similar chlorination using, however,
the clay treated kerosene -and chlorinated at a higher tem­
perature.
The increased temperature was used to speed up
the reaction which had been very slow towards the end of
the previous chlorination.
An attempt was made during this
run to use a mercury vapor ultraviolet light as a catalyst
in place of the carbon arc lamp.
The results were
dis­
appointing. -.Although supplying a little catalytic effect it
was by- no means adequate and therefore the carbon arc lamp
was again used.
This result tends to bear out the work of
Baskerville and Riederer (4 ), who found tnat blue light
and not ultraviolet catalyzed the chlorination of methane.
The final product was treated as in Run C-16-19 but,
due -probably to the fact that dark colored material had
entered the kerosene as a result of tne action of GCl^ on
the wire insulation, tne final product was somewhat ciamer.
It was like a plastic, very tacky semi-solid, which would
not burn except in an open flame.
The increase in tem­
per at ure very effectively speeded up tne reuccion r/ithout
89
causing any harmful discoloration.
It is interesting to
note, in Table X I I , the amount ox the increase in weip:ht
which is due to addition.
The two chlorinations yielding
low chlorine content products (C-14-19 and C-15-21) had
199a of their total per cent increase in weight caused by
addition.
The run . giving highly chlorinated products
(C-16-19 and. C-22-70) had only 9% of their total per cent
increase in weight caused, by addition.
Here there is an
agreement between runs of similar chlorine contents but
wide dissimilarity between the runs of different chlorine
content.
Decomposition in the more highly chlorinated
products is indicated since decomposition of chlorinated
molecules yields hydrogen chloride which, when absorbed in
the absorbers, indicates a greater amount'of reaction by
substitution than actually occurs.
This reduces the
apparent reaction by. addition which is determined by dif­
ference .
The assumed formula of the kerosene (CnPl2n ) re-
auires a 39^ increase in weight for complete satisfaction
of unsaturation.
Three runs were made on the 51—53° C . melting point
paraffin wax mentioned previously.
marized in Table XIV.
The results are sum­
The first two runs (C-17-21 and
C-2I-4.O) were carried out atHlow temperatures with
"actinic” light as catalyst and to a very hign ■.cnlorine
content.
The third, run ^C—23 — 50) was mau.e at a slightly
higher tern Denature in order to speed up reaction wxiich was
90
very rapid at first bat which, after a while, slowed up
consider ably.
Both were washed and clay treated before
being stripped.
The stripping was attempted at I400 C.
with high vacuum and. a stream of C02 to remove solvent but
the products were too viscous at this temperature.
They
were finally stripped at 160° C. but turned slightly yellow
during the process, having been water-white previously.
This product -was a very brittle and friable, clear solid
with a softening point of about 65° C.
A n attempt to
pla.sticize it with 20% castor oil yielded a very tenacious
non brittle plaster solid with a softening point of just
about room temperature.
The other run (C-23-70) was made to obtain a liquid
clilorinated wax since Gardner
(18) had shown that the con­
gealing point of paraffin wax decreases to a minimum, -18° C.
in his case, and then rises sharply again with increase in
chlorine content.
The product obtained in this investiga­
tion, after washing and clay treatment, was a water-white
slightly viscous liquid with a congealing point (similar to
Pour Point) of -17° C.
This congealing point was in almost
Perfect agreement .with Gardner!s work.
perties are listed in Table XV.
Tne physical pro­
It has a high viscosity
index and a density greater than that of water.
There is
very little unsaturation in the paraffin wax s m c e o.ll of
the chlorine appeared.to react by substitution as shown in
Table XIV.
91
Next a chlorination was run on isopentane (Run C-1&-20)
maintaining the conditions of low temperature, 20° C ., and
"actinic” light.
The reaction was very rapid and very
little chlorine passed through unreacted.
Quite a bit of
the isopentane was lost by evaporation even though an ice
trap was put in the exit line.
When approximately one-
fourth of the hydrogens had been replaced with chlorine,
the water-white material was flushed with ammonia, washed,
and dried with CaCl2 •
sharp odor.
The finished product had a very
A summary of this run and the properties of
the product are presented in Table XVI.
The density and
refractive index are quite high compared to the original
material.
This product will burn.
In anattempt to separate the chlorinated compounds, a
distillation (D-7-735) at atmospheric pressure was per­
formed on the chlorinated isopentane. ...When the still heat
was turned on, the first product obtained was a white
crystalline solid which condensed on the delivery line. and.
above the flask lagging.
The distillation was discontinued
and this white' material collected..
The still temperature
had risen to about 220° C. and this solid may have been
due to decomposition or condensation.
The aistilia oio.h was
continued and five liquid cuts .obtained.
xhe residue las
quite discolored which usually is evidence of decomposition.
To improve the color, this residue was c h y treated.
The
92
properties of tlie several cuts and the clay treated residue
are given in Table X V I I .
The cuts all had a. very sharp
characteristic odor while the white•crystalline solid had a
strong odor of camphor.
This white material did not have a
definite melting point but melted over a range from 130 to
145° C.
One form of artificial camphor, bornyl chloride,
has 3- melting point of about 130° C. and another, isoborryl
chloride, a melting point of 1A5-1500 C.
The camphors sub­
lime at low temperatures and most of the material obtained
above was lost by sublimation.
Blends of the clay treated residue and acryloid KF,
55.7 weight per cent active, were made and viscosities and
viscosity indices calculated.
In Table X V I I I .
These values are tabulated
They show remarkably high viscosity indices
approaching very close to maximum values at the higher weight
per cent b lends.
•
A n attempt was made to chlorinate purified cotton in
the solid state.
The cotton was held, at a temperature of
100° C. by steam and exposed to the rays of the carbon arc
lamp while In an atmosphere of chlorine.
After several
hours it was evident tnat tnere was no reaction and tne run
discontinued.
Commercial rosin, mainly abietic acid., Wets o.lso chlor­
inated .
Trouble was encountered, however, In obtaining a-
good solvent for it.
o
The solvent finally used was benzene.
93
Of course benzene will react with chlorine also but under
the conditions of the chlorination, elevated temperature
and ’’actinic” light, the chlorination was supposed to be
quite difficult.
Quite a large amount of the chlorine did
react with benzene however.
The final chlorinated rosin
was a light, pink colored solution.
When ammonia was passed
through this solution it turned to a dark muddy brown which
clay treatment did not clear at all.
necessary temperature
When stripped at
(160° C.) the product decomposed and
gave a black carbonaceous mass.
% Increase in Weight
Run No.
C-17-21**
Temp.
°F.
21
Due to
Due to
Addition Substitution
.0
C-21-10
40
0
C-23-50
50
0
175
% Hydrogen
Total
175
173
49
Replaced
34
173
34
49
10
Product
Light yellow fri­
able solid
Softening Point=
65° C.
Softenfing Point=
65° n
Water white viscous liquid
Burn
Ho
Ho.
Yes
* Based on CnH2n+2 where n = 28.
*** All runs made in presence of CCly
TABLE XV
Properties of Paraffin Wax Chlorinated to 49$ Weight Increase at 50°C.
with Actinic Light Catalyst•(C-23-50)
rip0 = 1.4.918
& 2 Q = 1.087
Viscosity (210° F.)= 12.60
-
Viscosity (100° F.) = 138.8
Viscosity Index = 89
Congealing Point = -17° C.
95
TABLE XVI
Chlorination of Isopentane (C-lo-20)
Conditions:
Carton arc lamp and 20° C.
Increase in Weight:
Product:
-1.
137fo corresponding to tricliloride.
c5h9ci3
2.
Clear,- colorless liquid with character­
istic odor.
ngO = 1.5042
3.
dpQ = 1.421
4.
Viscosity (100° F.) = 3.64
TABLE XVII
Distillation No. D - 7-735
DistIlla.tion of- Chlorinated Isopentane
Pressure - Atmospheric (735 mm. Hg.)
Each cut represents 1.0% of charge
Material
Cut F
.Temp. ° E .
^
n^
^20
?
1.4928
-
Viscosity-Centlstokes
100° F .
210 F.
-
Cut
2
175
1.4972 1.360-
3.05
Cut
3
180
1.5022
1.408
3.24
Cut
4
208 ’
1.5031
1.415
3.32
Cut
5
200
1.5051
1.423
3•48
1.5172
1.497
4*91
Residue-'''-
-
Clay treated.
■if- Solid material present in this cut.
I .42
96
TABLE XVIII
AcryJ-oid Blends of Residue from Distillation
of Ch.lorina.ted Isopentane
W t . % Aoryloid
in Blend
Viscosity-Centistokes
100° F.
~~210° E.
Viscosity % of Max.
Index______ V.I.
4.4
11.44
3.36
185
51
7.6
18.58
5-43
197
71
11.9
31.92
3.95
175
82
. 15.0
45.52
12.43
167
35
97
CONCLUSIONS
As s. result of tnis Investigation trie following con­
clusions liave been drawn:
1.
Chlorination in the presence of "actinic” light leads
to a rapid reaction at relatively low temperatures
without the formation of discolored product’s.
2.
Chlorination of lubricating oils in the presence of
iron leads to decomposition and tar formation.
3.
The density and refractive index increase with an in­
crease in chlorine content.
A.
With increasing chlorine content, the viscosity of the
material at first increases very slowly and then more
rapidly and final Iv1
" very rapidly.
5.
The viscosity index of the chlorinated-, material de­
creases with increasing chlorine content.
6.
Fire resistance of the chlorinated products, tested by
heating them in an iron cup over a bunsen flame, in­
creases with Increasing chlorine content and. they
finally become entirely non-inflammable.
7.
An increase- in temperature greatly increases tne raoe
of chlorination but may product side effects.
8.
Chlorination apparently occurs to a greater or less
extent on all of the molecules present.
98
9.
Clay treatment of chlorinated products increases their
stability markedly.
10. Highly chlorinated lubricating oils, kerosene and
paraffin waxes can be produced which are stable to
prolonged heating at 120-140° C.
11. Gardner1s (18) work on paraffin wax indicating a
minimum congealing temperature at Increasing chlorine
contents is substantiated.
12. The observation (4) that ultraviolet light is not the
active constituent of TTactinic,! light in catalyzing
chlorinations is supported.
13* The darkening of some chlorinated products upon stand­
ing seems not to be caused by oxidation.
.
14. The production of high viscosity index materials by
chlorination and subsequent treatment is a definite
possibility.
99
A P P E N D. I X
1
100
Sample Calculations
Run C-16-19 (Kerosene at 20° C. with actinic light)
Data for absorber A,
Amount of solution = 210 ml.
Sample used
= 1.0 ml.
Normality of sodium thiosulfate = 0.1367
Thio used to titrate nClprr = 0.55
Thio used to titrate r,HClT! = 22.80
Or. Cl2 as Cl2 = (0 .55) (0.1367) ( ^ ) (0.0355) = 0.56 gr
>■
Gr. Cl2 as HC1 = (22 .80) (0.1367) (-21Q) (0.0355) - 23.2 gr.
"i
For total run
g r . Clp as Cl2 = 120
. g r . Cl2 as H01 = 2 5 7
g r . Cl2 introduced (from Gl2 cylinder) = 6 5 7
■gr. Clp accounted for = (2) (257) +■120 = 634
g r . Cl2 unaccounted for =-23 - gr. Cl2reacting
by addition.
Increase in weight = 257 + 23 -
~
Sr .
Original weight of Kerosene = 146 gr.
% Increase in weight = (~p^r) (100) = 137
Increase in weight per 'fo i-Iycirogen replaced — 4,.93/
(Based on CnH2n where n = 13)
101
Increase in weight due to substitution =
273 - 23 = 250 gr.
% Increase in weight due to substitution =
23o x 100 = 171
116
% of* Hydrogen replaced = 23LL
= 35^
1
A-72
/
■>
c?
-
/'■> o
9
Calibration of Flowmeter
The flowmeter was calibrated by the use of chlorine
which was absorbed in potassium iodide solution.
Readings
of time and scale reading were made and titration gave the
amount of chlorine used.
Scale reading
Liters Chlorine oer Hour
12.5 mm.
1.10
23 .0
1.74
42.5
3.25
29.0
2.23
This calibration holds only in the range covered.
When the flowmeter was used at. higher rates, it served
merely; as a running check on the chlorine flow.
102
McGleod Gage Calibration
V-j_ = vo 1 tune or bulb and capillary
V2
=.volume of capillary
“ pressure on system
P2
- pressure on gas when compressed into capillary
(Vs)
4 H
•
= difference in level of mercury
in capillary and
side arm when gas is compressed
into volume
V2
its pressure will be:
P2 = Pi +
but
(1)
” ^2^*2
or
assuming perfect gas.
PlVi
h2
(3)
—
V2
Substituting in (l)
Pi V-t
-P. - P-i +
V2
Solving
a
/
(A)
H
1
/
\
H(y~l'Y0""v
3— ?
Py -
—
Data on Me C Leoa Gage:
Diameter of caxiillary = 0.262 mm.
Volume of flask to capillary. ='57.00 ml.
Length of capillary = 35.5 cm.
2
=
yT
D 2 t _ (yf) (0.262)2 (35.51 = 1.92 ml.
n r ~
L"
4
-t
m m
?! “ ^
II
=
1.92
57.00-1.92
.
23.0 ?!
t
J
I
103
Vacuum Engler Thermocouple Calibration
The vapor temperature thermocouple was calibrated
against a standard thermocouple in constant temperature
baths and the e.ui.f. read by a Leeds and Northrup Portable
Precision Potentiometer.
Unknown T.C.
e .m .f .
Microvolts
T e mp era tur e
Standard T.C.
e .m .f .
Microvolts
100° F.
(37.78° C.)
150.2
150.2
210° F.
(98.88° C.)
419.0
419.0
Since the thermocouple was in perfect agreement with the
standard, the calibration of the latter was used.
E = 38.84 T
+
O.O4532 T2 - 0.00003011 T3
E = microvolts
T = 0 C. The sta.ndard thermocouple was standardized by J. M.
Geist against the Petroleum Ps.efining Laboratory *s std.no.ard
D. P. 1 thermocouple which in turn, had been standardized
against a platinum resistance tnermomecer•
104
Siphon Counter Calibration
Ace tone was nun from a constant head, reservoir through
the siphon counter.
The number of* trips, the volume and the
time were recorded from which the trips per minute and
liters per hour were calculated.
N o . of
Trips
1
2
3
1
1
1
1
Time (Sec.)
Volume (ml.)
Trips/Min.
Liters/hr.
45.0
38.2
34-2
29.3
45.7
48.9
54-3
13
27
40
14
14
14
14
1.33
3.14
5 .23
2.05
1.31
1.23
1.11
1.04
2.54
4-21
1.72
1.10
1.03
0.93
Extraction Column Thermocouple Calibration
A thermocouple made in the same manner as the ones on
u
the extraction column was standardized against a standard
thermocouple in constant temperature baths and tne e.m.f.
read by a Leeds and Northrup Portable Precision Potentiom­
eter.
-The .standard thermocouple was the same as the one
listed above under Vacuum Engler Thermocouple Calibration.
Temperature
e.m.f. Microvolts
100° F . (37.78° C.)
150.2
210° F . (98.88° C.)
419.0
The equation for this calibration therefore is identical
with that for the Vacuum Engler Thermocouple.
105
BIBLIOGRAPHY
1.
2
Anderson, J., J. Inst. Pet. Tech., 21, 222A (1935).
. Anonymous^ News Ed., American Chemical Soc., 1 9 , 1155
3.
Barth, E. J., U. S. Patent 1,953,286, April 3, 1934.
4.
Baskerville, C. and Riederer, II. S., 'Ind. Eng. Chem. *
5 (1913).
5.
Bishop,
6.
Cannon, M. R., and Fenske, M. R.,
45 (1936).
W. T., U. S. Patent 2,119,149, May 31, 1938.
Oil and Gas J., 3A,
6a. Cannon,
M. R . , and Fenske, M. R . , Ind.
Anal. Ed., 12, 301 (1941).
*
Eng. Chem.,
7.
Carlisle, P. J., and Levine, A.A., Ind. Eng. Chem.,
24. 146, 1164 (1932).
8
Davis, G. ii. B., U. S . Patent 1,815,022, July 14, 1931.
9.
Dickinson, R. G., and Leermakers, J. A., J. Am. Chem.
Soc., 54, 3852 (1932).
10 .
11
.
Ellis, C., ,fThe Chemistry of Synthetic Resins”, p. 1157,
Vol. II (1935).
Ellis, C., "The Chemistry of Petroleum Derivatives”,
P. 738, 756, Vol. I (1934).
12.
Ibid., pp. 1223-1235, Vol. II (1937).
13.
Ellis, C., U. S. Patent 1 ,248,638, December. 4 , 1917.
14.
Fgloff, G., Sc ha ad, E., and. Lowry, C ., C hem • Rev,, _8>
1 (1931) .
15.
Fenske, M. R., McCluer, W. B. and Cannon, M. R., Ind.
. Eng. Chem., 2.6 % 97o (1934) •
16.
Fisher, F., and Koch, H. , Brermsteff Chemie,
(1933) .
17.
Fulton, S. C., U. S. Patent 1,981,824 j November 2.0 , 1934 *
463
106
IS.
Gardner x F. T ., Ind. Eng. Chem., 2j5, 1211 (1933).
19.
Gardner, H. A., and Bielouss, E., ibid., 1 4 , 619 (1922).
20.
Groggins, P. H . , "Unit Processes in Organic Synthesis",
p. 153, Second Ed. (1938).
21.
Groll, H. P. A., Iiearne, G. , Rust, F. F., and Vaughn,
N. E., Ind. Eng. Chem., Jl, 1239 (1939).
22.
Hamor, W. A,
News Ed., American Chemical Soc.„ 18,
6 (1940).
23 .
Hardie, D. A. F ., British Patent 482,658, April 1, 1938.
24-
Hardie, D. W. F., and QcKrent, C., British Patent
479,195, February 1, 1938.
25.
Hass, H. B., Priestley Lecture at The Pennsylvania State
College, March 16-20, 1942.
26.
Hass, H. B . , McBee, E. T., and Hatch, L. F . , Ind. Eng.
Chem., 22, 1335 (1937).
27.
Hass, H. B., McBee, E. T., Hinds, G. E... and Gluesenkamp, E. W. , ibid., .28, 1178 (1936) .
28.
Hass, H. B., McBee, E. T., and Weber, P., ibid., 2.7.
1190 (1935).
29.
Ibid., 28, 333 (1936).
30.
Hurd, C. D., "The Pyrolysis of Carbon Compounds",
P. 125-144 (1929).
31.
Kawakami, Y ., and Maruyama, T., Japanese Patent 132,630,
October 13, 1939.
32.
Keith, J. R., and. Roess, L. C., Ind. Eng. Chem., .29,
460 (1937).
33.
Keller, K., and Gofferye, E., German Patent 622,296 (1935)
34-
K o c h ,
H., and Ibring, C., Brennstoff Chemie, 16, 185
(1935).
35.
Lieber, E., U. S. Patent 2,249,317,' July 15, 1940.
36.
Lieber, E ., U. S. Patent 2,262,809,. November 18, 1941-
107
3 7.
Lincoln, B. H. , and Byrkit, G. D._ U. S. Patent
2.,26A,319, December 2, 1941.
38.
T
Loane, C. 1
i1
fj
i
39.
Lowes, A. D
i.
40.
McB e e , E. T
41.
McNulty, G. M . , and Zimmer, J. C., U. 8 . Patent 2,268,60S,
January 6 , 194 2 .
42.
Montgomery, T. N ., British Patent 495,410, November 14,
1938.
43.
Morrell, J, C., and Egloff, G., U. S. Patent 1,744,135,
January 21, 1930.
44.
Muskat, I. E., and King, L., ibid., 2,178,695, November
7, 1939.
45.
Padgett, A. E., and Degering, E. F,, Ind. Eng. Chem.,
32, 204 (1940).
46.
Pease, K. N., and Wals, G. F., J. Am. Chem. Soc., 5-3.
3728 (1931).
47.
Pier, M., and Cliristrnann, F., U. S. Patent 2,258,806,
October 14, 1931.
48.
Pier, M., Christmann, F., Eisenhut, A., and Hirschberger,
V., ibid., 2, 189,924, February 13, 1940.
49.
Prutton, C. F . , ibid., 2,155,204, April' 18, 1939.
50.
Fiieff, 0. M . , and Bader tscher, D. B., ibid., 2,138,809,
November 29, 1939.
51.
Sanders, T. II., British Patent 537,033, June 5, 1941*
57.
Stone, Hr W . , and Beeson, C., Ind. Eng. Chem., Anal, ud.,
8, 188 (1936).
53.
Iropsch, H, , Thomas, C. L., Morrell, J. C., ana Lgj-off,
C., Ind! Eng. Chem., H , 1112 (1939).
54.
Vaughan, N. E., and Rust, F. F., J. Org. Chem., 5., 449
(1940).
108
55.
-5 6.
Vlngter, J . C., Waterman, H. I., and Wes ten, H. A. van.,
J. Inst. Pet. Tech., 2 1 , 661 (1935).
Vobach, A.
1940.
C ., u. S. Patent 2,222,961, November 26 ,
57.
Whittier,
N. A., ibid., 2,254,337, September 2, 1941.
58.
Wiezevich, P. J., and Vesterdal, H. G., Chem. Rev., 19,
101 (1936 ).
59.
Wirth, J. K., German Patent 654,118, December 10, 1937.
60.
ibid., 673,521, March 23, 1939-
61.
ibid., 674*442j April 14, 1939.
Документ
Категория
Без категории
Просмотров
0
Размер файла
6 129 Кб
Теги
sdewsdweddes
1/--страниц
Пожаловаться на содержимое документа