1. * GB784943 (A)
Description: GB784943 (A) ? 1957-10-23
Improvements in and connected with arc welding
Description of GB784943 (A)
PATENT SPECIFICATION
Inventors: RICHARD GILLOCK BRAITHWAITE and JOHIN LEONARD PRATT 784,943
Date of filing Complete Specification: Oct 19, 1955.
Application Date: Nov 18, 1954.
No 33391154.
Complete Specification Published: Oct 23, 1957.
Index at acceptance: -Class 83 ( 4), T( 2 D 2: 2 J: 6).
International Classification:-B 23 k.
COMPLETE SPECIF'ICATION Improvements in and Connected with Arc Welding
We, BRAITHWAITE & COMPANY ENGINEERS LIMITED, of "The Moordings,"
Church Road, Great Bookham, Surrey, a British Company, do hereby
declare the invention, for which we pray that a patent may be granted
to us, and the method by which it is to be performed, to be
particularly described in and by the following statement: -
This invention is concerned with an improved method of and means for
arc welding with continuous electrode wire.
It is known in connection with such welding that if an electrode,
charged with welding current at sufficiently high density, is fed into
the arc at constant rate, the;arc length is automatically
self-adjusted to that determined by the magnitude of the said welding
current and the feed rate, that is, if the,arc tends to lengthen, the
burn-off rate correspondingly reduces and vice versa, without any
intervention Welding heads have accordingly been proposed for
supplying current to a, single electrode wire Whilst feeding it
through the head at constant rate.
It is also known to be sometimes desirable to apply more than one arc
simultaneously to the same weld, using separate electrode wires which
Fare supplied with currents having differing characteristics, for
which purpose it has been proposed thus to feed such wires by;a single
drive.
2. According to the present invention two or more continuous electrode
wires are mutually insulated and supplied individually with electric
welding currents of differing characteristics, whilst being fed to the
weld simultaneously at constant rate By 'differing characteristics' we
intend here land in the claims any of the following: D C of differing
magnitudes; A GC differing in phase, frequency and/or magnitude; A C
in one electrode;and D C in another; A C or D C, in, one electrode and
A C inm,conjunction with D.C min another; and differing compositions
of A C and D C thus in conjunction.
lPric 3 s 6 d l The electrode wires may thus be fed at the same rate,
as for example when they are of equal thickness On the other hand it
may be desirable for the constant feeding rates to differ, 'as for
example when the electrode wires are not of equal thickness.
The advantages of the aforementioned selfadjusting and differential
arc methods can thus be combined, with appropriate relative adjustment
of the currents according to their differing characteristics, so that
the respective arc lengths are maintained Thus, using two electrode
wires supplied with multi-phase A.C current impedances may be
introduced in the different phases to alter and adjust the phase
angles and currents and thereby control the relative currents in the
electrode wires :and also the interphase current between them.
The invention ialso provides suitable apparatus for carrying out the
aforementioned' improved method, consisting of a welding head wherein
the electrode wires are fed each at a constant rate by a single drive,
and whereby the electrode wires are kept mutually insulated and
separate current connections are provided thereto individually, each
of the electrode wires being preferably insulated also from the head
itself Moreover the separate current connections to the individual
wires may make contacot therewith forwardly of the drive and as
closely as practicable to the outlet from the head The feeding of the
respective electrode wires from the single drive may be effected by
means of separate rollers, as by mounting the latter on the same
shaft, such rollers being of the same or differing diameter.
A welding head for feeding two electrode wires simultaneously in
accordance with the invention is illustrated by way of example in the
accompanying drawings, of which: Figure 1 is a plan view of the head,
partly in section and with the body,cover plate removed; Figure 2 is a
side elevational view, partly in section, on the line 2-2 of Figure 1,
omitting A the motor and driving gear-box beyond their centre lines;,
Figure 3 is a side elevational view, opposite:to that of Figure 2,
omitting the electrode delivery nozzle and current leads thereto;
Figure 4 is a cross sectional view on the line 4 4 of Figure 1,
omitting certain background detail; Figure '5 is a front end view half
in crosssection of the delivery nozzle and current leads thereto, on
3. the line 5-5 of Figure 2.
The head as shown comprises as its main components a body 1 within
which are two drive feed rollers 2 a and 2 b mounted on the same shaft
2 c and a delivery nozzle 3 into which the electrode wires El and E 2
pass from the respective feed rollers and wherein they pick up current
through the contacts 3 a and 3 b respectively, from the leads 4 a and
4 b, 'as hereinafter described The shaft 2 c is rotated by an
electrode motor 5 of substantially constant speed characteristic
through a fixed ratio, speed reduction gearbox 6, neither the motor
nor the gear box calling for further description as they are entirely
conventional.
The electrode wires are electrically separated throughout, both from
one another and from the conducting parts of the head, the necessary
insulation for ensuring this being shown throughout the drawings
thickly cross hatched Thus each of the aforementioned drive feed
rollers 2 a 'and 2 b has a metallic wear-resisting rim for engaging
the electrode wire and an insulating sleeve portion by whch this rim
is mounted on shaft 2 c.
Associated with each drive feed roller and freely rotatable in the
same plane therewith is an idler roller 6 a, 6 b adjustably urged
towards the drive roller by a screwed spring plug 7 a, 7 b acting on a
pivotal carrier 8 a, -8 b in which the idler roller is mounted These
idler rollers are also formed each with an insulated metallic rim and
serve to hold the electrode wires against the respective drive rollers
so that they are fed forwardly thereby at a rate dependent onr the
peripheral speeds of the latter.
As shown, the drive rollers are of differing diameters so that they
thus feed the wires at correspondingly different, although constant,
rates If, on the other hand, feeding of both Wires at the same rate is
required, drive rollers equal in diameter can readily be substituted
Within reasonable limits the size of the idler rollers is not material
and can be uniform.
Forwardly of the feed rollers the electrode wires pass immediately
through parallel metal tube-lined passages 9 a and 9 b of an
insulating guide block 9 of the body 1 and thence through similarly
lined passages 10 a and 10 b of another insulating block 10 within the
nozzle 3 In spite of the necessary operating clearance given to the
wires by the lining tubes ila and lib of the last mentioned passages,
these tubes are sufficiently long to ensure proper electrical contact
of the wires therewith, being themselves fed with current through the
aforementioned contacts 3 a and 70 3 b, which are mounted in 'a
clamping saddle 12 and pressed against the respective tubes through
registering openings in the wall of nozzle 3 and in block 10, by the
tightening of said saddle about the nozzle Rearwardly 75 of the feed
4. rollers the electrode wires must be kept apart right back to their
respective upply spools, full mutual insulation between which is also
necessary.
The cover plate la of body 1 (omitted from 80 Figure 1) is shown in
Figures 2, 3 and 4 and provides an, upper bearing 2 d for shaft 2 c
and a top mounting besides for the pivot 8 c of the idler roller
carriers 8 a and 8 b The side walls of the body may be formed with
projecting 85 nnilon stubs lb for supporting the head in use.
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* GB784944 (A)
Description: GB784944 (A) ? 1957-10-23
Improvements in or relating to stable petroleum distillate fuels
Description of GB784944 (A)
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and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
-7 2 _ i T
PATENT SPECIFICATION
784,944 Date of Application and filing Complete Specification: Nov 26,
1954.
% ' B No34326/54.
Application made in United States of America on Nov 30, 1953.
5. Application made in United States of America on Nov 30, 1953, Complete
Specification Published: Oct 23, 1957,
Index at acceptance:-Class 91, G 1 A 1 L International
Classification:-C 1 Og.
COMPLETE SPECIFICATION
Improvements in or relating to Stable Petroleum Distillate Fuels We,
STANDARD OIL COMPANY, a corporation organised under the laws of the
State of Indiana, United States of America, of 910, South Michigan
Avenue, City of Chicago State of Illinois, United States of America,
do hereby declare the invention, foe which we pray that a patent nvay
be granted to us, and the method by which it is to be performed, to be
particularly described in and by the following statement: -
This invention relates to stable petroleum oils and it is particularly
concerned with the stabilization of hydrocarbon oils normally
susceptible to oxidative deterioration at normal storage temperatures.
The deterioration of petroleum fractions, e.g in the distillate oil
range, manifests itself through the appearance of color, sediment, etc
in the oil Sediment formation is particularly troublesome in oils used
as fuels, particularly in the diesel olil and furnace oil range,
because it often results in clogging of equipment such as filters,
screens, and nozzles.
Such deterioration is particularly bad in connection with the use of
cracked distillates and since it is common practice to blend
substantial portions of such distillates with virgin furnace oil stock
to obtain commercial fuel oils, the problem of preventing
deterioration of the ultimate commercial product is indeed important
Petroleum fractions generally, however, with the possible exception of
highly refined lubricating oils, are subject to oxidative
de,terioration in storage And the prevention of such deterioration
along with provision for finally dispersing the insoluble matter
present in an oil are problems of extreme importance to the refiner.
It is an object of the present invention to, provide an additive for
petroleum oils which will inhibit sedimentation, color formation, and
other undesirable deterioration It is another object to disperse, and
to thus render harmless, any sludge or color deterioration products
occurring tin such oils Still another object is to provide a fuel oil
resistant to Price 3 s 6 d l sediment formation and sludging.
It is a further object of the present invention to provide
corrosion-inhibiting, sludgepreventing additives for fuel oils
comprising mixtures of virgin distillate and a cracked oil in the
distillate fuel boiling range These and additional objects will be
apparent from the following detailed description of the present
invention.
In accordance with the present invention, sediment formation may be
6. prevented and oils of good color and overall stability may be assurted
by adding to petroleum oils a small amount of at least one polyamino,
compound of the hereinafter defined class along with a neutralized
reaction product of a phosphorus sulfide and a hydrocarbon More
specifically, it has been found that a high degree of stabilization of
petroleum fractions normally subject to oxidative deterioration upon
storage at normal temperatures may be obtained by adding thereto a
small amount of a neutralized reaction product of a phosphorus sulfide
and a hydrocarbon, e g that of PS, land a butylene polymer, and at
least one N-alkyl alkylene polyamino compound (containing from about 6
to about 30 carbon atoms as the N-alkyl radical) selected from N-alkyl
alkylene polyamines containing at least one primary amino nitrogen
atom iand carboxylic acid salts thereof These constituents are added
in amounts sufficient to inhibit deterioration, e.g generally from 0
001 %' to 0 1 % and preferably from 0 005 to 0 05 % Thus, foir
etample, distillate fuel oils containing about 0.005,0 % of an
additive comprising 0 004 % of an N-alkyl alkylene polyamine, 0 001 %
of an oleic acid salt of such amine, and 0.005 % of a neutralized
reaction product of PS, and butylene polymerhave shownstriking
stability as compared to the same oils without such additive Not only
has such additive shown an outstanding ability to stabilize such oils
from deterioration resulting in discoloration and sediment but in
addition to be able to disperse any sediment which might form or o
784,944 which might have been present in the oil prior to introducing
ithe additive and to impart substantial corrosion inhibiting
properties to the oil.
Amines suitable for use,in accordance herewith are those N-alkyl
alkylene polyamines containing at least one primary amino nitrogen
atom Such amines, tin general, may be represented by the structural
formula:
H 1 R-N(CHI,)m C-(CIHI) N-('1 I 1 I H R' H wherein R represents:an
alkyl or substituted alkyl (i e by hydroxy, carboxy, nitro or halo-,
groups) hydrocarbon radical containing from about 6 to about 30, and
preferably at least about 16 carbon atoms; R' may be hydrogen or an
aliphatic hydrocarbon radical, i e ialkyl or cycloalkyl radicals and
it is preferably hydrogen; R" may be hydrogen, an,alkylene primary
amino radical (i e -(CH 2)NH 2, wherein x is a positive integer from 1
to about 10) or a palyalkylene polyamino radical containing ia primary
ammno nitrogen atom; m is a positive integer from 1 to about 10 and
preferably 1 or 2; and N may be either 0 or a positive integer from 1
to about 10.
Typical examples of such compounds are alkyl derivatives of ethylene
diamine, or propylene diamines ( 1,3-diamino propane, 1,2 diamino
propane), of diethylene triamine, or triethylene tetramine.
7. More specifically, there may be employed such amines as N
actyl-:ethy;ene diamine, N-n-dodecyl diethylene triamine,
N-n-cetylpropylene diamine, N-octadecyl triethylene tetramine,
N-hydroxyl dodecyl diethylene triamine, N-chloro-decylet
Lhylenediamine, Nbromo octyl ethylene diamine, the various "Duomeens"
(products of Armour Chemical Division) which liave the general formula
RNHCHZCH 2 CHNH, wherein R may be derived from coconut fatty acid
("Duomeen C "), from tallow fatty acid (" Duomneen T "), from lauric
acid (" Duomeen 12 "), or from soya fatty acid (" Duomeen S ") The
word "Duomeen" is a registered Trade Mark and the "Duomeens " are
industrial or technical grade chemicals with an amine content of
approximately 80 % calculated as diamine.
The approximate melting ranges for each of the aforementioned
"Duomeens" are: "Duomeen C "-20 ' to 24 C, "Duomeen 12 "28 to 32 C,
"Duonteen S"-38 to 42 C, and "Duomeen T "-44 to 48 C.
It should be understood that the enumeration of the foregoing specific
amino-compounds is by way of illustration and not of limitation and
that any polyamine falling within the broad definition above recited
may be employed.
Phosphorus sulfide-hydrocarbon reaction products of the type which may
be employed in accordance herewith may be readily obtained by reacting
a phosphorus sulfide with a hydrocarbon at a temperature of from about
F to about 600 F, and preferably from about 250 ' F to about 500 F,
using from about 1 % to about 50 %, and preferably from about 5 % to
about 25 %, by weight, of the phosphorus sulfide in the reaction It is
advantageous to maintain a non-oxidizing atmosphere, such as for
example, an atmosphere of nitrogen above the reaction mixture Usually,
it is preferable to use an amount of the phosphorus sulfide that will
completely react with the hydrocarbon so that no further purification
becomes necessary; however, an excess of phosphorus sulfide can be
used and separated from the product by filtration or by dilution with
a solvent, such as hexane, filtering and subsequently removing ithe
solvent by suitable means, such as by distillation The phosphorus
sulfide-hydrocarbon reaction products contain both sulfur and
phosphorus The reaction may if desired be carried out in the presence
of an additional sulfurizing agent or the phosphorus
sulfide-hydrocarben reaction product can be sulfurized.
The hydrocarbon constituent of this reaction is preferably a
mono-clefin hydrocarbon polymer resulting from the polymerization of
low molecular weight monoelefinic hydrocarbnis or isomono-olefinic
hydrocarbons, such as propylene butylenes, and amylenes or the
copolymers obtained by the polymerization of hydrocarbon mixtures
containing iso-monoolefins and mono-olefins or mixtures of olefins in
the presence of a catalyst, such as sulfuric acid, phosphoric acid,
8. boron fluoride, aluminum chloride or other similar halide catalysts of
the Friedel-Crafts type.
The polymers employed are preferably irono-olefin polymers or mixtures
of monoolefin polymers and isomono-olefin polymers having molecular
weights ranging from about to about 50,000 or more, and preferably
from about 300 to about 10,000 Such polymers can be obtained, for
example, by the polymerization in the liquid phase of a hydrocarbon
mixture containing mono-olefins and isomono-olefins such as butylene
and isobutylene at a temperature of from about 80 ' F.
to about 100 F in the presence of a metal halide catalyst of the
Friedel-Crafts types such as, for example, boron fluoride and aluminum
chloride In the preparation of these polymers there may be employed,
for example, a hydrocarbon mixture containing isobutylene, butylenes
and butanes recovered from petroleum gases, especially those gtses
produced in the cracking of petroleum oils in the manufacture of
gasoline.
Essentially paraffinic hydrocarbons such as 784,944 bright stock
residuums, lubricating oil distillates, petrolatums or paraffin waxes
may be used The condensation products of any of the foregoing
hydrocarbons or their halogen derivatives, with aromatic hydrocarbons
can also be employed.
Examples of high molecular weight olefinic hydrocarbons which can be
employed as reactants are cetene (C,), ceroitene (C 6), melone (C 30),
and mixed high molecular weight alkenes obtained by cracking petroleum
oils.
Other clefins suitable for the preparation of the herein described
phosphorus sulfide reaction products are olefins having at least 20
carbon atoms in the molecule of which from about 12 carbon atoms to
about 18 carbon atoms, and preferably iat least 15 carbon atoms, are
in a long chain Such olefins can be obtained by the dehydrogenatibn of
paraffins, such as by the cracking of paraffin waxes, or by the
dehalogenation of alkyl halides, preferably long chain alkyl halides,
particularly halogenated paraffin waxes Also, olefins derived from the
synthol or hydrocarbon syntheses process may be employed.
These arm essentially straight chain ccmpounds varying widely in
molecular weight.
Also contemplated within the scope of the present invention are the
reaction products of a phosphorus sulfide with aromatic hydrocarbons
such as benzene, naphthalene, anthracene, toluene and diphenyl and alk
Slated aromatic hydrocarbon such as, for example, an alkyl benzene
characterized by having at least one alkyl group of at least four
carbon atoms, and preferably at least eight carbon atoms such as a
long chain paraffin wax.
The phosphorus sulfide reactant can be any phosphorus sulfide, such as
9. for example, P 25, P 4 S,, PS,, and preferably PS,.
The phosphorus sulfide-hydrocarbon reaction product normally shows a
titratable, acidity which is neutralized by treatment with a basic
reagent The phosphorus-sulfide-hydrocarbon reaction product when
neutralized with a basic reagent containing a metal constituent is
characterized by the presence of retention of the metal constituent of
the basic reagent Other metal constituents such as a heavy metal
constituent can be introduced into the neutralized product by reacting
the same with a salt of the desired heavy metal.
The term "neutralized phosphorus sulfidehydrocarbon reaction product"
as used herein means a phosphorus sulfide hydrocarbon reaction product
having at least about 1 % of its titratable acidity neutralized by the
reaction with a basic reagent and includes 'the neutralized phosphorus
sulfide-hydrocarbon reaction products containing a metal constituent
resulting from said neutralization or resulting from the double
decomposition of the phosphorus sulfide-hydrocarbon reaction product
treated with a heavy metal salt.
The neutralized phosphorus sulfide-hydrocarbon reaction product can be
obtained by treating the reaction product with a suitable basic
compound such as a hydroxide, carbonate, sulfide, or an oxide of an
alkaline earth metal, e g calcium or barium, and preferably 70 the
latter, or an alkali metal such as, for example, potassium hydroxide
oar sodium hydroxide Other basic reagents can be used such as, for
example, 'ammonia or an alkyl or aryl substitute of ammonia such as
atnines 75 The products are neutralized by mixing a suitable base (e g
a 50 %' solution of KOH) therewith and heating to a temperature in the
range of from about 2000 to about 400 F.
After the base and phosphorus sulfide hydro 80 carbon reaction product
are mixed and neutralized, they are preferably steamed at a
temperature of about 400 F to about a half hour The steaming may take
place during neutralization 85 The salts of the polyamines which may
be employed in accordance herewith may be prepared by reacting, under
carefully controlled, non-dehydrating conditions, i e below about F
and preferably below about 195 F, 90 a carboxylic acid containing from
about 6 to about 20 carbon atoms, and preferably 'at least about 12
carbon atoms, e g hexanoic, non-, anoic, lauric, stearic, oleic,
linoleic, linolenic or palmitic, with any of the hereinabove de 95
scribed amnines to obtain either the mono or di substituted acid salts
of the amines Care must be taken in the preparation of such salts
inasmuch as prolonged exposure to temperaturs higher than about 2000 F
results in the 100 formation of amides or even glyoxalidines (if
1,2-substituted polyamines are employed) upon splitting out water
Among the very economical, commercially available salts of this type
are the olic acid mono and/or di 105 salts of the Duomeens (above
10. described), particularly of Duomteen T.
Whereas the additive of the present invention is generally useful in
petroleum distillates, and particularly cracked distillate fuels, 110
it is especially useful in stocks of the type generally referred to as
light catalytic cycle oil and fuels containing such an oil Such a
catalytic cycle oil is obtained from a catalytic hydrocarbon cracking
operation in which a 115 gas oil or heavier hydrocarbons such as
reduced crude is cracked at a temperature of about 800 F to about
10500 F at a pressure of about atmospheric to about 50 pounds per
square inch sin the presence of suitable 120 catalysts, such as for
example silica-magnesia, silica-alumina, and other well-mknown
cracking catalysts The product fraction referred to herein is Ithe
heavier-than gasoline fraction ordinarily called light gas oil or
catalytic light 125 cycle stock A catalytic fight cycle stock of the
type particularly suitable for blending with virgin heavy distillates
is a fraction having an aromatic content of at least about 40 to about
50/%' and a distillation range be 130 tween about 425 F and about 560
' F A typical analysis of a suitable light catalytic cycle stock shows
the material to be composed substantially of about 10 % normal C,<
paraffins, about 45 % of other paraffins and naphthenes, about 5 %'
mononuclear aromatics which are mainly mono to hexa alkylated
benzenes, and about 40 %' polynuclear aromatics which are mainly alkyl
naphthalenes, largely methylated naphthalenes The boiling range of a
typical light catalytic cycle stock by A S T M distillation may be
approximately:Initial boiling point 10 % over % over % over Maximum
boiling point 430 F.
448 F.
478 F.
518 F.
552 F.
The boiling range of particular cycle oils may, of course, vary over a
considerably wider range, depending upon catalyst, cracking conditions
and charge stock Thus, catalytic cycle oils, generally, may boil
within the range from about 350 F to about 750 F.
It should be understood that the additives of this invention will
inhibit oxidative deterioration in normally liquid petroleum fractions
which are subject to the same under normal storage conditions Such
fractions may be cracked (thermally or catalytically) or virgin or
mixtures of these Thus, petroleum distillates generally such as
internal combustion engine fuels, furnace oils, burner oils, heater
oils, kerosene, heavy industrial residual fuels (e g, Bunker C), jet
fuels, blending oils and stripper stocks, may be stabilized in
accordance herewith The oils to which the additives of the present
invention are added may have been refined by any of the many
11. well-lknown techniques, e g, caustic alkali washing, acid treatment,
Doctor sweetening and clay treating, prior to additive introduction.
The oils which may be stabilized by the additives of the present
invention may be cracked, virgin or mixtures of these Even blends of
two different virgin oils, which because of solubility differences
result in the formation of sediment when admixed, may be stabilized
thereby.
In one embodiment the present invention provides a stable petroleum
fuel oil comprising at least 10 % cracked constituents.
In another embodiment there is provided a stable petroleum distillate
fuel comprising a predominant amount of virgin fuel oil distillate, at
least 10 % of catalytic cycle oil derived from the catalytic cracking
of a petroleum gas oil fraction which cycle oil boils chiefly in the
range of from 3500 F to 700 F, from O 001 %, to O 1 % of a neutralized
reaction product as herein before defined of P 2 S and a butylene
polymer and from 0.001 V% to 0 1 % of an N-alkyl alkylene polyamine
having the general structure:
RNHCH 2 CHCH NH.
wherein R represents an alkyl radical containing from 6 to 30 carbon
atoms and up to 0.01 % of the oleic acid salt of such an alkylene
polyamine compound.
The herein described additives are out 70 standing m many ways Thus,
the additive imparts rust protection to metal surfaces in contact with
the oil inhibits sediment formation, improves filterability by
dispersing any sediment formed, inhibits colour degradation and 75
decreases wear of internal combustion engine parts (as demonstrated by
the data in Table 3).
In Table 1, therefore, laboratory data are set forth which serve to
demonstrate many of these improvements The footnotes ( 1 to 4) 80 to
Table 1 explain the tests employed and their significance Field tests
have borne out the expected superiority of the additive in commercial
use Many gallons of potentially sediment-containing fuel oil have been
success 85 fully inhibited against this and other results of
deterioration by the use of the additive of the present invention in
actual commercial shipments Filters which were on the verge of
clogging when the use of oil containing such 90 an additive was begun
were found to have been substantially de-cclted and unclogged after
using the inhibited oil for several months.
In those tests where new, clean filters were installed at the outset
of the test they were like 95 new several months later whereas other
new filters installed at the same time in systems employing
uninhibited oil were heavily coated and subject to clogging at any
moment.
Additional tests of the type set forth in o 100 Table 1 on the same
12. type fuel oil inhibited with a small amount of a neutralized P
S,butylene polymer reaction product and an cleic acid salt of Duomeen
T demonstrated the effectiveness of such combination to be 105 about
the equal of the polyamine plus the neutralized phosphorus and sulfur
containing compound Whereas, a two-component additive, ie polyamine or
polyamine oleate plus neutralized P S, butylene polymer, gives ex 110
cellent protection, the combination of polyamine, polyamine salt and
neutralized phosphorus sulfide-hydrocarbon reaction product gives a
substantially improved result.
784,944 584,944 TABLE 1
KOH-Neutralized Neutralized P 255-butylene P 255-butylene polymer (ca
1000 (ca 1000 mol wt) No additive mol wt) product (a) product (a) plus
plus A (b) A (b) B (c) Rust Protection ( 1) ( 1) Water Layer 24 hours
severe rust no rust no rust 144,,,,,,,, 300,,,, ,, rust on edges,, ,,
( 2) Oil layer 24 hours,, ,, no rust,, ,, 144,, , , 300 Filterability
( 2) after 50 ml 110 seconds 26 seconds 22 seconds ml 335, 30, 24;, ,
400 ml 34,, 26,, J Crucible Mat ( 3) many brown brown tint and few
small gray gray specks specks specks Appearance after aging ( 4)
cloudy slightly cloudy bright Color after aging ( 4) dark light light
Sediment after aging ( 4) very much trace none (a) Employed in amount
of 0 005 %.
(b) A=Duomeen T (Armour Chemical Division)-employed in an amount of O
05 '%.
(c) B=Duomeen T Oleate (Armour Chemical Division)-employed in amount
of 0.001,%.
( 1) 50 milliliter samples of furnace oil were filtered into bottles
and doped with additive Bright steel strips were immersed in the oil
for 5 minutes, then withdrawn Twentyfive milliliters of water were
added to the bottles, and the bottles were thoroughly shaken The steel
strips were then reimmersed and left to stand in the open bottles for
144 hours The strips were then withdrawn, dipped in mineral oil,
allowed to drain, and hung in room air The strips were examined after
24, after 144, land after 300 hours.
( 2) 500 milliliter samples of furnace oil, with and without additive,
were aged in open bottles in an oven for 20 hours at about 220 F The
samples were allowed to cool, and then filtered through 1 square
centimeter of filter paper having a pore size of 10 microns, using a
constant head of 12 inches of oil.
The time necessary to collect successive 50 ml increments of oil was
recorded The time required for the first, fourth and eighth 50 mil.
portions is given above -The high sediment and gum content oil becomes
progressively harder to filter whereas the time for those containing
the additive change very lilttle from start to finish.
( 3) 500 milliliter samples of furnace oil, with and without additive,
13. were shaken from 500 ml of tap water in a separatory funnel.
The oil and water layers were allowed to separate for 30 minutes; the
free water was then drawn off, and theinterfacial rag and the oil
layer were filtered through a medium porosity sintered glass crucible
The color and nature of the mat retained in the crucible indicate the
tendency of tha oil to sludge after contact with water The lighter the
mat the less the sludging tendency.
( 4) At the completion of the filtration, data for which are set forth
above under "filterability", the filtered samples were returned to
bottles and stoppered and then allowed to S 784,944 stand art room
temperatures for seven days.
The results given are a result of visual examination.
Run with different sample of control oil but under essentially
identical conditions.
Accordingly, it should be understood that whereas either of such twa
component additives will given excellent results in accordance
herewith it ds preferred to employ all three, i e polyamine,
polyamine-carboxylic acid salt,and neutralized phosphorus
sullfidehydrocarbon reaction product Of the two component additives,
it is preferred to employ that comprising the polyamine rather than
salt thereof.
In Table 2 are set forth data demonstrating the effectiveness of a
rather wide variety of amines and phosphorus-sulfide hydrocarbon
reaction products These data are of a qualitative nature 'and clearly
demonstrate on a laboratory scale the ability of the additives of the
present invention to inhibit color degradation and sediment formation,
in a furnace oil comprising 60 % virgin distillate and 40 % fresh,
caustic washed catalytic cycle oil Data are included which compare the
effectiveness of the herein disclosed polyamines with other amines
which have heretofore been added to petroleum oils for various
purposes The data in Table 2 with the exception of the appearance of
the crucible mat {are based on the appearance of a furnace oil having
the same composition as that employed in the tests recorded in Table'l
1, containing the additives indicated, after being heated for 20 hours
at 200 F and then held at room temperature for an additional 48 hours
The crucible data are obtained on the same oils in accordance with the
test described in footnote ( 3) of Table 1 prior to heating the oils
for 20 hours at 200 F.
TABLE 2
P 255 Butylene Polymer (ca 1000 mol wt) Reaction Prod.
Amount Appearance of "Duomeen T Crucible after Oleate" Test (c) Color
Brightness Sediment 1 (Control) Deep purple flecks Duomeen T 4, C 4
Duomeen C Duomeen T 6 Duomeen S 7 Duomeen 12 8
N-n-Dodecylethylenediamine 9 N-n-lauryl diethylenediamine Duomeen T 11
14. Phenylene Diamine 12 N-Hydroxy dodecyldiethylenetriamine 004 004 004
004 004 004 A (a) B (b) A B A A A 004 A 004 004 A A A co 005 001 001
001 001 001 001 001 001 Lt Pink Cast Gray Cast Gray Brown Cast Deep
Gray Cast Pink Cast Pink Cast Chocolate Mat Tan Gray Cast Dark Light
,1 , , , ,3 , V Cloudy Much Clear None SI, Cloudy,, V Clear,, Clear,,
Cloudy Moderate , 51 Cloudy , V Clear Dark Cloudy Light 51 Cloudy
Trace None Much Trace (a) -A = KOH neutralized and steamed (at 400 F)
reaction product of P 255 and butylene polymer.
(b) B Ba(OH)2 neutralized and steamed (at 400 F) reaction product of P
25, and butylene polymer.
(c) See footnote ( 3) to Table 1 (supra) for explanation of test
resulting in these observations.
Example
Amine Amount (DO,, 00 4.P The surprising ability of additives of the
present invention in preventing wear of internal combustion engine
parts, is demonstrated in Table 3 A diesel fuel comprising 60 %
straight run and 40 %' catalytic cycl.
oil having 01:% concentration of an additive comprising 40 % Duomeen
T, 10 % Duomeen T-mono-oleate and 50 % of a potassium hydroxide
neutralized reaction product of P 2 S, and a butylene polymer having a
molecular weight of about 1000, was compared with the same oil without
the additive in a General Motors 1-71 Diesel engine This engine is a
typical one-cylinder model of the General Motors " 71 " series
engines.
TABLE 3
Control Diesel Fuel (Undoped Diesel Plus Fuel) Additive Top
Compression Ring (a) Weight Loss (grams) 0 91 0 29 (b) Gap Increase
(inches) 0 032 0 006 Total Compression Rings (a) Weight Loss (grams) 2
03 0 38 (b) Gap Increase (inches) 0 078 0 013 Other tests in which a
diesel fuel comprising 100 % of a lower sulfur catalytic cycle oil was
employed in the same engine the improvement resulting from the
presence of 0 1 % of the additive was about 80 %, reduction of top
ring wear and about 90 %' of total compression ring wear Additional
tests in a Caterpillar one cylinder test diesel engine demonstrated
much the same improvement in wear characteristics.
As indicated above, the additives of the present invention are useful
in straight run stocks (virgin) and blends of differest virgin stocks.
Thus, as shown in Table 4, the improved 30 color inhibition in such
oils when employing an additive of the present invention is
substantial.
TABLE 4
Color (Saybolt) Initial Aged ( 4) Control (A) ( 1) + 13 -2 ,, + 0 01 %
of Additive ( 2) 13 + 10 , + 0 0025,,,, + 13 + 10 , + O 001,,,, 13 + 8
Control (B) ( 3) 13 -6 + 0 0025 % of Additive ( 2) + 13 + 5 ( 1) Blend
15. of Cu Cl, sweetened Mid continent virgin heater oil distillate and
sulfuric acid treated West Texas virgin heater oil distillate.
( 2) 50 % KOH neutralized reaction product of PSS, and butylene
polymer of about 1000 molecular weight, 40 % of Duomeen T and 10 % of
Duomeen T monooleate.
( 3) Sulfuric acid treated West Texas heater oil distillate.
( 4) Heated for one hour at 290 F and observed The introduction of the
additive of the present invention to distillate fuels is greatly
facilitated by the use of concentrated oil solutions of such additives
It has, for example, been found especially desirable to use a 10 %
concentrate of -such additive in,an oil such as light catalytic cycle
oil A typical concentratecomprises 90 % solvent and 10 % of an
additive consisting of 50 % neutralized phosphorus sulfide-hydrocarbon
reaction product, 40:% alkylene polyamine and 10 % carboxylic acid
salt of such amine Such concentrate is used for blending with the oil
in proportions to obtain a finished product containing the specifled
percentages of individual constituents.
Whereas a 10 % concentrate is specifically referred to, it should be
understood that such concentration may vary widely and that those as
high as 50 % or more may be found useful under certain circumstances
and are within the scope of the present invention Moreover, although
the light catalytic cycle oil is especially well adapted for use as
the carrier or sol784,944 784,944 9 vent in such a concentrate, any
other suitable hydrocarbon oil may be employed.
Percentages given herein and in the appended claims are by weight
unless otherwise specified.
Because of the diispersion of water into the oil effected by the
additives of the present invention, it is sometimes desirable to
employ a surface active agent in addition thereto to prevent hazy oils
Thus, various oil-soluble anionic and cationic surface active agents
such as the di-alkyl sodium sulfosuccinates, sodium cetyl sulfate,
petroleum sulfonates, cetyl pyridinium chloride and octadecylamine
acetate, may be employed Such surface active agents will vary in
effectiveness with the particular oil, the amount of water, the
physical state of the water in the oil, i e whether it is suspended or
dissolved, the range of temperature over which the oil may be stored,
but in general tare effective in amounts between about 0.001 to about
0 05 % by volume based on total oil Greater and lesser an:ounts may be
found useful under certain circumstances Thus haze was successfully
inhibited in a fuel oil composition comprising an oil consisting of %
virgin furnace oil distillate and 401 % catalytic cycle oil which had
been stabilized against color and sediment formation with 0 01 % of an
additive comprising 0 005 %' of neutralized P 2 S, butylene polymer
reaction product, 0 004 % of Duomeen T and 0 0011 %.
16. of Duomeen T-monooleate, by the addition of 0.002 i% by volume of
sodium; mahogany soap derived from the fuming sulfuric acid treatment
of a hydrocarbon oil in the preparation of a Technical White Oil In
place of the sodium mahogany soap of the above example, other surface
active agents of the type above enumerated may likewise be employed.
In the appended claims the term "N-alkyl radical" wherever employed
shall include alkyl radicals of the type described and substituted
alkyl radicals, i e substituted by groups such as halo or hydroxy.
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* GB784945 (A)
Description: GB784945 (A) ? 1957-10-23
Improvements in or relating to internal combustion engines
Description of GB784945 (A)
PA Tt N SPECIFICATIOI
my Date of filing Complete Specification Jan 12, 1956.
Application Date Jan 15, 1955.
No 1286155.
Complete Specification Published Oct 23, 1957.
Index at Acceptance:-Class 7 ( 6), B 2 Q 5 (A: B: F).
International Classification: -FO 2 f.
COMPLETE SPECIFICATION
Improvements in or relating to Internal Combustion Engines I, JOHN
HAY, A M I Mech E, (of British Nationality), of " Southlands ", Sea
Lane, Ferring, near Worthing, Sussex, do hereby declare the invention,
for which I pray that a patent may be granted to me, and the method by
which it is to be performed, to be particularly described in and by
the following statement: -
17. In giving a description of this invention it is necessary to draw
attention in the first instance to the fact that the reciprocating
internal combustion engine (as designed at the present time) suffers
from an inherent defect in that its expansion or working stroke is no
longer than its compression stroke.
Many attempts have been made to design a differential stroke engine, i
e, an engine in which the piston makes, say, one long stroke, followed
by a short stroke.
One case of an engine of this kind was described in " Engineering " on
November 11th, 1927, page 613 but naturally, as one would expect, the
mechanical complication and increased number of moving parts involved
was somewhat grotesque The chief point which emerged from the
published tests was the impressive fact that the fuel consumption was
reduced from approximately 5 7 lbs per B.H P hour, to 3 7 lbs per
bralke horsepower hour, as compared to the consumption of an engine of
ordinary four-stroke design.
My proposals in this invention are really extremely simple, although
the results might prove extremely important, as by the use of the
valves hereinafter described it is possible to obtain the functional
characteristic of a differential stroke engine without any increase in
the number and complication of the main components.
The functional characteristics of a differential stroke engine may be
assumed to be for the purpose of this particular application:An engine
in which the working medium or gases are enabled to expand over a
longer period of time and distance than that occupied by the preceding
compression period.
The type of parallel cylindrical valves described in my prior Patent
17865/10 have been l.Pice 3 s 6 d l found useless in practice owing to
leakage My new design of valve put forward in this application is
tapered in that region containing the inlet, exhaust, or scavenging
air ports.
The cylinder head or cylinder barrel is also tapered to receive the
similarly tapered valve or valves, all as shown on the accompanying
drawings.
This application also covers the use of this type of valve in engines
working on all cycles (when practically applicable) in addition to the
ordinary four-stroke engine as used on motor vehicles.
The kind of valves described in Patent 17865/10 really only had this
last mentioned type of engine in view, as it was not foreseen by me at
that date that designers would one day be faced with the problem of
arranging for the inlet of scavenging air or egress of exhaust gases
of cylinders of dimensions capable of developing approximately 1000 h
p.
per cylinder.
18. I should like to make it clearly understood that I consider one of the
most important applications of this valve gear is to large engines of
the marine type both double acting two-stroke and single acting
two-stroke.
My idea being to render unnecessary exhaust pistons and eccentrics for
actuating them, which are now thought necessary simply to open and
close a ring of ports in the cylinder barrel.
Also this valve gear may be used on engines, both single and double
acting, two or fourstroke now being manufactured by continental
makers, my idea being to render the B shaped rotary valve at present
being fitted in the exhaust port, unnecessary.
It should be clearly understood that the application of an oscillating
yalve according to the invention (having one conical and two
cylindrical portions) would usually only require one such valve to
effect the opening and closing of a ring of ports in the cylinder
barrel, but two valves can be fitted (one outside the other) where
great speed of port opening is required.
Twin valves are necessary in order to 784,94 784,945 obtain
satisfactory port opening and closing movements for the ordinary
four-stroke cycle motor car engine.
In the accompanying drawings:Fig 1 shows a four-stroke cycle internal
combustion engine forming one embodiment of the invention.
Fig 2 is a section on the line XX of Fig 1.
Fig 3 shows a second embodiment of the invention.
It should be clearly understood that the valve arrangement shown in
Figs 1 and 2 portrays the application of this invention as it might be
applied to the ordinary motor car engine, this arrangement has nothing
to do with the question of a differential stroke engine.
Fig 3 shows how this invention can be applied so to produce the
functional characteristics of a differential stroke engine (as defined
on page 2) In Figs 1 and 2 of the complete specification A and B are
oscillating valves each having cylindrical end portions separated by a
conical portion, the control ports of the valve being formed in the
conical portion thereof.
C=Cylinder head casting.
D= Outer head or valve casing.
E=Cylinder head cover.
F and G=Circular valve driving rings, castellated on lower edge, to
fit castellations on upper edge of valves These driving rings have
actuating arms to which rods actuated by eccentrics are attached,
vwhereby the valves are oscillated.
H=High pressure joint I = Cylinder barrel J Cylinder inlet and exhaust
ports controlled by the corresponding ports in the conical portions of
the valves A, B K=Part of water jacket L=Low pressure joint M =Low
19. pressure joint.
This design provides ready access to the valves A and B for
inspection, etc, when the cylinder cover E and the outer head or valve
casing D are removed.
In this particular design shown in Figs 1 and 2 it will be noted that
the water jacket is external to the valves, this of course enables the
valve diameter to be reduced from what it would have had to be if the
water jacket had run up inside the valves (i e, between the valves and
the cylinder head casting).
It is desired to retain in this patent application the very important
design feature, i e, that the water jacket may be designed to run up
internally to the valves, water passages in the cylinder head port
bars making connection between the cylinder head water jacket and the
main cylinder barrel jacket as described in my prior Patent 17865/10.
The manner in which the valves A and B cooperate to control the ports
is as follows: In the case of the ordinary four-stroke engine (Figs 1
and 2) the valves are oscillated by two small eccentrics situated on a
vertical shaft (not shown on Figs 1 and 2) but similar to that shown
on the right hand side of the differential stroke application shown in
Fig 3.
It will be found that if these two small 70 eccentrics are placed on
the vertical shaft with a relative displacement to one another of
approximately 70 % and appropriate ports are then cut in the valves,
the resulting opening and closing periods for both inlet side and 75
exhaust side form a very fair approximation of the valve timing in a
modern engine fitted with ordinary mushroom valves actuated by the
orthodox camshaft.
The description and action of the engine 80 shown in Fig 3 of the
complete specification is as follows:It should be clearly understood
that the design shown is intended to provide differential stroke
characteristics in that the period 85 allotted for expansion is
greater than that allotted for compression.
The engine is two-stroke (i e, one power impulse at every down stroke)
and is superficially like an ordinary heavy marine engine 90 of the
two-stroke type.
On closer inspection it will be noticed that the cylinder barrel is
provided with three rings of ports, one at the top end, one at the
bottom end, and another very approximately at mid 95 stroke The top
ring of exhaust ports (E, Fig 3) sheet 1 are controlled by a yalve " A
" similar to the valve A or B shown in Fig 1.
The mid-ring of secondary air ports J, Fig 3, Sheet 1, are controlled
by a similar valve 100 "B " The lowest ring of ports (primarily air
scavenge) C, Fig 3, Sheet 1, is controlled by the main piston During
the working or power stroke, the valve B, Fig 3, remains closed during
20. the entire downward stroke of 105 the piston, which finally uncovers
the ring of scavenging air ports C, Fig 3.
At or about this period in the cycle, the exhaust valve A at the
cylinder head opens, so that straight through, or end-to-end 110
scavenging is obtained The exhaust valve A would remain open while the
piston is making the first portion of its return stroke, and the valve
"B" opens soon after the exhaust valve " A " has closed and high pres
115 sure air is admitted to the cylinder just before the piston on its
upward stroke closes the secondary air ports " J ".
The distance between the primary scavenging air ports C, Fig 3, at the
extreme lower 120 end of the cylinder, and the secondary air ports J,
Fig 3, controlled by the valve B situated very aproximately at about
mid-stroke of the main engine piston is, of course, at the discretion
of the designer, but judging from 125 the published trial results of
large marine engines in which the scavenging air and exhaust belts are
in close proximity, this distance can have an altogether unexpected
influence on the performance of the engine 130 784,945 In this
particular design it cannot be said that these two port belts are
really in close proximity, but the designed distance between them
would naturally govern the expansion ratio it was wished to use in the
working cycle of any particular engine Reverting again to the cycle of
operations I am outlining, it is contemplated that the air pressure
supplied to the middle belt (J, Fig 3) of ports would not necessarily
be of the same order as that used in the primary scavenging belt,
indeed, it would, in all likelihood, be very considerably higher, so
as to supercharge the main cylinder.
In other words, the air pressure in the main cylinder would be under
external control at the period of the upward stroke immediately
preceding the final closing of the secondary air ports by the main
piston.
In view of the above facts, the ultimate or terminal degree of the
main cylinder compression could be varied at will Moreover, the
working gases expand over a longer period of time than that occupied
by the preceding compression period due to the valve " B" remaining
closed on the downstroke and the valves A and B opening for a portion
of the up stroke of the piston.
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21. * GB784946 (A)
Description: GB784946 (A) ? 1957-10-23
Process of decorating textile materials
Description of GB784946 (A)
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
PATENT SPECIFICATION
784,946 Date of Application and filing Complete Specification: Jan 18,
1955.
No 1537/55.
Application made in Germany on Jan 18, 1954.
(Patent of Addition to No 729,122, dated Oct 24, 1951).
Complete Specification Published: Oct 23, 1957.
Index at acceptance:-Classes 2 ( 6), P 2 A, P 2 D( 1 A: 8), P 2 K( 7:
8), P 2 P( 1 E 5: 2 A 1: 2 A 4: 4 A), P 2 T 2 A, P 7 A, P 7 D( 2 A
1:8), P 7 K( 2:8), P 7 P( 1 E 5:2 A 1:2 A 4:4 A), P 7 T 2 A, P 8 A, P
8 D( 1 A: 2 A: 3 A: 8), P 8 K( 2: 7:10), P 8 P( 1 E 5: 2 A 1: 2 A 4: 4
A), P 8 T 2 A, Pi 10 A, P 10 (D 2 A: K 8: P 2 A 4: T 2 A); and 15 (
2), B 2 C 1 A 3; B 2 C 2 (B:
C: D 1 A: D 1 B: F), B 25.
International Classification:-C 08 f D 06 p.
COMPLETE SPECIFICATION
Process of Decorating Textile Materials We, FARBENFABRIKEN BAYER
ARTIENGESELLSCHAFT, a body corporate organised under the laws of
Germany, of Leverkusen, Germany, do hereby declare the invention, for
which we pray that a patent may be granted to us, and the method by
which it is to be performed, to be particularly described in and by
the following statement -
22. In Specification Serial No 729,122 there is claimed a process for
decorating, e g, printing or padding, textile materials which
comprises applying to such material an emulsion of a vinyl or divinyl
polymer or copolymer and a high molecular basic compound which, as
such or as a salt, is soluble or emulsifiable in water, and, if the
basic compound is not a cross-linking agent as such, causing to react
therewith, on the material, a compound containing two or more groups,
capable of reacting with the basic groups of the high molecular
compound, at ordinary temperature or, if necessary, at an elevated
temperature.
The present invention is an improvement in respect of said process and
consists in using basic high molecular weight compounds containing
amino and/or imino groups and reactive epoxy groups as compounds
containing two or more groups, capable of reacting with the basic
groups of the high molecular compound, at ordinary temperature or, if
necessary, at elevated temperature Such compounds include condensation
products which can be obtained from di or poly-amrnines by the action
of epihalohydrines or di-halohydrines As di or poly-amines there can
be used, for example, tetramethylene diamine, hexamethylene diamine,
dipropylene triamine, ?Y, l diaminopropyl methylamine, y,7
diaminopropyl ether, diaminopropyl tetramethylene diamine, bis (y
aminopropyl)piperazine, or N ( 1,6 hexanediamine) 3pyrrolidone, -_
lPrice H 2 N C Ha C Ha C H CH CHL CHA-NHZ H 2 C-LL 1 The preparation
of these condensation products is described in Specification Serial
No.
774,101 The reaction of di or poly-amines with epichlorohydrin or
dichlorohydrin is carried out with such proportions of the reagents
and under such conditions that not all of the hydrogen atoms available
on the nitrogen are replaced This ensures the possibility of further
cross-linking of the products obtained.
It is possible by appropriately selecting the p H-value,
concentration, temperature and mode of reaction to prepare
condensation products having a wide range of viscosities The
condensation reaction can be interrupted at any time by the addition
of acid This addition of acid acts also to stabilise the condensation
products The condensation products react, when heated to temperature
of about C, due to their content of epoxy groups as well as of -NH
and/or NH -groups, with self-cross-linking to form water insoluble
products.
The aforesaid basic high molecular weight compounds containing epoxy
groups possess film-forming properties and act not only by
self-cross-linking but also by cross-linking the other basic higher
molecular weight compounds contained in the composition applied to the
textiles The compounds containing epoxy groups are, therefore, binding
23. agents (e.g, for pigments) and cross-linking agents at the same time.
The employment of such cross-linking agents which act at the same time
as binding agents has the advantage over the majority of other
cross-linking agents in that on account of their self-cross-linking
capacity they can be applied in excess When the usual watersoluble
cross-linking agents non-volatile on drying at 100-150 C, are used in
excess they remain partly unchanged in the film after fixation and
thus cause a low resistance to water In spite of this disadvantage, a
small excess is preferred in practice, because even a small deficit of
cross-linking agents would produce even less favourable results Though
an excess does not become apparent in the process according to the
present invention, it is best to avoid the application of too great an
excess in certain combinations in pigment printing because otherwise
the shade may sometimes become dull.
Moreover, in application, the condensation products containing epoxy
groups have the great advantage over most other cross-linking agents
in that they cross-link very rapidly on drying, on the one hand, and
in that they are practically stable in aqueous acidic solution up to
temperatures of about 50 C, on the other hand An extremely prolonged
stability of the printing pastes is thus obtained.
Compared with other cross-linking agents, those used in the present
invention have a greater inherent viscosity and therefore printing
pastes produced therewith do not need any thickening agents Therefore
a better feel and a better fastness to washing of the printed textiles
are obtained.
The following Examples are given for the purpose of illustrating the
invention, the parts and percentage concentrations mentioned being by
weight: EXAMPLE 1.
In 150 parts of a 3 % aqueous solution of the sodium salts of
sulphonated long chain paraffins is dissolved 0 7 part of the sodium
salts of sulphinated long chain paraffins The mixture is emulsified
with 50 parts of styrene, 48 parts of acrylic acid butyl ester and 2
parts of acrylic acid The emulsion is rendered acid with 2 parts of IN
sulphuric acid and then polymerised at 30 C until the reaction is
practically complete An emulsion is thus obtained having about 40 % of
solids In order to increase the pigment compatibility and the
mechanical stability, this emulsion is treated with 12 5 parts of the
conversion product of cetyl alcohol with ethylene oxide.
205 Parts of this latex are mixed with parts of a 10 % aqueous
solution ( 800 cp/25 C) of the acetate of a basic polyurea produced
from 0.05 mol of diethylene triamine Z 0 95 mol of
7,y-diaminopropylmethylamine 1.01 mol of hexane diisocyanate parts of
a 30 %' aqueous solution of the hydrochloride of a basic epoxy
produced from 0.28 mol of dipropylene triamine 1.00 mol of
24. epichlorohydrin and 15 parts of 50 % acetic acid, and the whole is
stirred until homogeneous; whereupon parts of a 20 % red pigment paste
are stirred in It is then treated with parts of urea parts of isooctyl
alcohol parts of methyl cellulose ( 70:1000) 235 parts of water;
making a total of 1000 parts.
Instead of the basic polymer from dipropylene triamine and
epichlorohydrin used as cross-linking agent, there can be used the
polymer formed from /,,y'-diamino-propylmethylamine and
epichlorohydrin.
The above mixture yields a very satisfactorily stable and pliable
printing paste which can easily be rinsed off with water from the
printing roller or film-printing screens The printing paste is printed
on to cotton or staple fibre in the usual manner The after-treatment
consists for cotton in drying at 80 C, and for other kinds of fibres
in heating at 110-130 C after normal drying.
The prints obtained on cotton, staple fibre or rayon excel in depth of
colour, brightness of shade, very good fastness to drying and good
fastness to wet rubbing,-very good to rubbing by hand in
laundering-very good fastness to boiling soda and to light.
EXAMPLE 2.
1 Part of the sodium salts of sulphonated 100 long chain paraffins, 12
5 parts of the reaction product of cetyl alcohol and ethylene oxide,
0.7 part of the sodium salt of sulphinated long chain paraffins and 0
15 part of potassium persulphate are dissolved in 150 parts of 105
water.
0.4 Part of di-iso-propyl xanthogenic disulphide, 40 parts of
butadiene, 40 parts of acrylonitrile and 20 parts of styrene are
emulsified in this solution in a pressure vessel 110 The emulsion is
rendered acid with 2 parts of IN sulphuric acid and polymerised under
its own pressure until a yield of about 100 per cent is obtained The
resulting 40 % emulsion is emulsified with 3 parts of the formaldehyde
115 conversion product of o-cyclohexyl-p-cresol as anti-ageing agent:
-GO H W HO Ca 784,946 611 (viscosity value zq= 245 x 10-3) produced
from diaminopropyl tetramethylene diamine and oxalic ester, and the
whole is homogenised Then are added parts of glycerol parts of methyl
cellulose ( 70:1000) parts of a 15 % aqueous paste of copper
phthalocyanine parts of a 15 % aqueous solution of the hydrochloride
of a basic polymer produced from 0.22 mol of diaminopropyl
tetramethylene diamine and 1.00 mol of epichlorohydrin and 285 parts
of water, making a total of 1000 parts.
The property of being rinsed off the printing roller and the stability
of the printing paste is similar to those according to Example 1 The
carrying out of the process is effected similarly to that in Example 1
Prints are obtained on cotton, staple fibre and rayon which excel in
25. depth of colour, brightness of shades, very good fastness to drying
and to wet rubbing.
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* GB784947 (A)
Description: GB784947 (A) ? 1957-10-23
Improvements in or relating to an improved burner and processes for
producing carbonblack
Description of GB784947 (A)
PATENT SPECIFICATION
784,947 Date of Application and filing Complete Specification: Feb 1,
1955.
No 2950155.
Application made in United States of America on Feb 8, 1954.
Complete Specification Published: Oct 23, 1957.
Index at acceptance:-Classes 75 ( 1), TN 3, TP 3 D; and 90, K 4.
International Classifieation:-CO 1 b, F 23 f.
COMPLETE SPECIFICATION
Improvements in or relating to an Improved Burner and Processes for
Producing Carbon Black We, PHILLIPS PETROLEUM COMPANY, a corporation
organised under the laws of the State of Delaware, United States of
America, of Bartlesville, Oklahoma, United States of -5 America, do
hereby declare the invention, for which we pray that a patent may be
granted to us, and the method by which it is to be performed, to be
particularly described in and by the following statement:-
This invention relates to an apparatus and to a process for the
production of carbon black.
It is known in the art to produce carbon black by reacting a
26. hydrocarbon thermally by virtue of heat imparted to said hydrocarbon
from a hot combustion gas Such a process is described in U K Patent
Specification
679,818 Such a process utilizes a reactor comprising a combustion zone
positioned coaxially and in open communication with a reaction zone of
smaller diameter than said combustion zone A fuel and an oxidant in
combustible proportions are introduced at high velocity, tangentially,
into said combustion zone and resulting combustion gas travels in a
spiral path toward the axis of said zone Combustion of the fuel is
completed near the periphery of the combustion zone The combustion gas
travels, from the combustion zone, in a helical path into the reaction
zone A reactant capable of being converted to carbon black is
introduced longitudinally into the combustion zone and is reacted in,
the reaction zone by virtue of heat directly imparted thereto by the
combustion gas.
This invention provides an apparatus and a method whereby combustion
of the tangential fuel gas is effected in an improved manner.
According to the invention there is provided a burner for use in a
carbon black production reactor comprising an inner conduit
longitudinally positioned within an outer conduit, orifice means in
the outlet end of lPrice 3/61,.
said outer conduit; closure means at the corresponding end of said
inner conduit; a plurality of peripheral openings in said inner
conduit adjacent said closure means; and at least one other peripheral
opening in at least 50 one of said conduits positioned upstream from
the orifice means.
The invention also includes a carbon black production reactor
comprising a substantially cylindrical reaction chamber coaxial with
55 adjacent and in open communication with a substantially cylindrical
combustion chamber having a larger diameter than said reaction
chamber, an axial inlet to said combustion chamber, at least one
tangential inlet 60 to said combustion chamber and a burner according
to the preceding paragraph positioned within said tangential inlet.
Finally the invention provides a process wherein carbon black is
produced by tangen 65 tially introducing a fuel and a free
oxygencontaining gas in combustible proportions into a substantially
cylindrical combustion zone, completing the combustion of said fuel in
a peripheral part of said zone, passing re 70 sulting combustion gas
in a helical path into a substantially cylindrical reaction zone
coaxially positioned adjacent said combustion zone and in open
communication therewith, said reaction zone having a smaller diameter
75 than said combustion zone, injecting a reactant hydrocarbon axially
into said combustion zone, and reacting said reactant hydrocarbon to
form carbon black which is recovered as a product, which is character
27. 80 ised by mixing said fuel with -said free oxygen-containing gas
during said tangential introduction in a zone of turbulent mixing
maintained adjacent the outlets of coaxially disposed conduits
supplying said fuel and 85 said oxygen-containing gas, and causing
part of the contents of at least one of said conduits to flow out of
the interior of its conduit and along the exterior thereof at a point
upstream from said zone of turbulent 90 : is 784,947 mixing.
In one modification the burner comprises the elements set forth above,
and the inner conduit is provided with a group of peripheral openings
positioned upstream from the openings adjacent the closed end Said
openings can be arranged in staggered relationship with the openings
adjacent the closed end; thus, each of said openings can be
longitudinally non-aligned with respect to each of the openings
adjacent the closed end.
In another embodiment of the invention, the burner comprises the inner
conduit and the outer conduit as set forth above, and the outer
conduit is provided with a group of circumferentially spaced
peripheral openings upstream from the openings in the inner conduit
The inner conduit can be provided with additional peripheral openings
upstream from the peripheral openings adjacent the closure end
thereof, or such additional openings can be omitted.
According to another embodiment of the invention, a burner of the type
above described, utilized in a carbon black apparatus of the type
above described, is protected from the effects of the high
temperatures produced in said apparatus by causing part of the air
which is supplied through the outer conduit to pass along the outside
of said conduit, whereby a cooling effect is provided.
By the process of the invention, the fuel supplied to a carbon black
process of the type described may be mixed with the free
oxygen-containing gas in two stages, the first stage occurring
upstream of a zone of turbulent mixing which zone exists adjacent the
outlet ends of the conduits supplying the fuel and the free
oxygen-containing gas.
In the drawings, Fig 1 is an elevational flow diagram, partly in
section, of a process in connection with which the present invention
is utilized; Fig 2 is a sectional view taken along line 2-2 of Fig 1;
Fig 3 is an enlarged sectional view of the tangential burner
diagrammatically shown in Fig 2; Fig 4 is a sectional view taken along
line 4-4 of Fig 3; Fig 5 is a sectional elevation of a modified burner
according to this invention; Fig 6 is a sectional view taken along
line 6-6 of Fig 5; Fig 7 is a sectional elevation of another modified
burner according to this invention; Fig 8 is a sectional view taken
along 8-8 of Fig 7; Fig 9 is a sectional view taken along line 9-9 of
Fig 7.
28. Fig 1 illustrates an apparatus and process of the type described in U
K Patent 679,818, previously cited, and illustrates the use of one
embodiment of the present invention in connection with such a process
The process described in the cited patent is known as a tangential
flame process of the precombustion type.
As shown in Fig 1, there is provided a 70 carbon black reactor
designated generally as 7 and comprising an outer metal shell 8,
insulation 9, and refractory liner 10 The reactor contains combustion
zone 11 and reaction zone 12 These zones are coaxially 75 positioned
in open communication with each other, and are generally cylindrical
Combustion zone 11 is of greater diameter than reaction zone 12 and
preferably has a shorter length than zone 12 and a length shorter 80
than its own diameter.
A reactant, which is ordinarily a liquid hydrocarbon and preferably an
aromatic gas oil, but which may be sither liquid or gaseous, enters
the system through inlet 2 and is 85 preheated, and preferably
vaporized, in heater 3 The heated oil passes to axially positioned
inlet 4 and is axially injected into the furnace 7 A small amount of
air enters through inlet 5 into annular inlet 6, which 90 surrounds
the oil inlet 4 Only sufficient air is added at this point to prevent
deposition of carbon around the outlet of oil injector 4.
Simultaneously, as shown in Fig 2, air is injected through inlets 20
and 23 and a fuel, 95 such as natural gas, is injected through inlet
22 As shown in Fig 2, combustion zone 11 is provided with tangential
inlets or tunnels 13 Positioned within each of said tunnels is a
burner according to this invention 100 The burner comprises air inlet
20 and gas inlet 21 which is preferably positioned coaxially within
conduit 20 Air and fuel gas enter combustion zone 11 at a very high
velocity Combustion is ordinarily com 105 pleted within tunnels 13 but
may continue to some extent beyond said tunnels The combustion of the
fuel gas at high linear velocity produces a combustion gas which moves
spirally inward toward the axis of 110 chamber 11 The hot combustion
gas then proceeds in a helical path into reaction zone 12, thus
heating reaction zone 12 to a carbon black-forming temperature The
axially introduced oil is thermally reacted in chamber 115 12 to form
high-quality carbon black in high yields A resulting mixture of carbon
black anl resulting gas passes from reaction zone 12 into pipe 14 The
reaction mixture is preferably initially cooled to a temperature 120
below 1250 F by means of water directly injected through quench inlet
15 The resulting mixture proceeds through pipe 14 and can be further
cooled therein by exposing an uninsulated section of pipe 14 to the
atmos 125 phere or by the use of a water jacket or additional quench
inlets, not shown The cooled mixture of carbon black and combustion
gas passes to gas-solids separation zone 18, which can be one or more
29. cyclone sepa 130 784,9-47 rators, Cottrell precipitators, bag filters,
or any combination of these, or other known equipment for the
separation of solids from gases Combustion gas is withdrawn through
outlet 16 and product carbon black is withdrawn through outlet 17.
Fig 3 shows structural details of one modification of a burner
according to this invention, said burner being positioned in tunnel
1013 of the carbon black reactor, as indicated in Fig 2 An air tube or
blast tube 20 is provided with an annular orifice plate 25, which can
be secured to tube 20 by any suitable means such as welding Flange 30
is provided for connection to an air pipe 23, as shown in Fig 2 Fuel
gas tube 21 is positioned within blast tube 20 and is preferably
coaxial with tube 20 at the outlet ends Tube 21 extends through the
wall of blast tube 20 and can be secured thereto by welding, as
indicated at 32 Gas tube 20 is suitably threaded as indicated at 31,
for connection to a gas line A support or saddle 29 is provided within
tube 20, and tube 21 rests on said support At the outlet end of gas
tube 21 is a closure means 26 which completely closes the end of tube
21 Adjacent closure means 26 are circumferentially spaced peripheral
outlets 27, which can be formed, for example, by drilling Upstream
from openings 27 and orifice 25 is a second set of openings 28 which
are peripherally non-aligned longitudinally with openings 27.
Fig 4, which is a section view of the burner, shows an end view of
support or saddle 29 with tube 21 resting thereon.
The modification of the burner shown in Figs 3 and 4 affects a partial
premixing of part of the fuel gas which passes out of pipe 21 through
openings 28, mixes with the air in blast tube 20 and flows along the
exterior of the pipe 21 The outlet end of tube 21 is positioned
adjacent orifice plate 25, so that a zone of turbulent mixing of gas
and air occurs adjacent said orifice Combustion occurs downstream from
said orifice plate in tunnel 13 The end of tube 21 can be positioned
as shown in the drawing or can be slightly retracted within blast tube
20 or can be flush with orifice plate 25 The partial premixing
therefore occurs upstream from the zone of turbulent mixing In any
event, it is preferred that openings 27 be near the zone of turbulence
adjacent orifice plate 25.
Another modification of the burner, according to this invention, is
shown in Figs 5 and 6 In this modification, the additional gas
openings 28 (Fig 3) are omitted Openings are provided, in blast tube
20, upstream from openings 27 These openings 40 cause part of the air
to flow out of blast tube 20 and along its outer surface providing a
cooling effect and thus protecting the burner from the high
temperatures to which it is subjected.
Figs 7, 8 and 9 illustrate a modification of the invention wherein
both air outlet openings 40 and premix gas openings 28 are provided in
30. the same burner openings 40 preferably being upstream from openings 28
70 Figs 8 and 9 show the relative arrangement of openings 27 and 28 As
shown in these figures, openings 27 and 28 are 45 out of alignment
with each other.
Although in each of the above cases a 75 group of 4 openings has been
shown, any desired number of openings within one set of openings can
be used Also, the different groups can contain, different numbers of
openings from each of the other groups 80 Also, the openings need not
be of circular cross-section, indicated in the drawings.
They can be elipticaf, elongated either transversely or
longitudinally, or a group of slots can be used instead of a plurality
of drilled 85 holes.
It will also be evident to those skilled in the art that any desired
preheating of the air or gas supplied to the burner can be utilized.
Although two tangential inlets in combustion 90 zone 11 have been
shown in Fig 2, any desired number can be used, including a single
inlet.
Burners of the type shown in Figs 3, 5 and 7 have been utilized in
connection with 95 the commercial production of carbon black according
to the method described in the cited patent Thus, in one plant,
burners of the type illustrated in Fig 3, each having a blast tube 7
inches in internal diameter 100 and a gas tube 1 inch in outside
diameter was utilized at a volume ratio of air to natural gas of 15:1
The carbon black reactor had a reaction section 15 inches in diameter
and 12.5 feet long and a combustion section 33 105 inches in diameter
and 1 foot long The combustion section was provided with two
tangential tunnels 101 inches in diameter and 16 inches long The
tunnels were spaced apart The blast tube of each burner 110 extended 1
inches into the tunnel Air was supplied through the blast tube at a
rate of 105,000 cubic feet per hour, and a pressure of 4 psi The gas
was supplied at a pressure of 30 psi Extremely smooth combustion 115
is obtained in this apparatus.
Although certain process steps, structures and examples have been
described for purposes of illustration, the invention is clearly not
limited thereto The preferred feature 120 of the invention is that
there has been provided a process and a burner which effect partial
premixing of fuel and free oxygencontaining gas, and a burner which is
protected, from high temperatures, by flow of 125 air from within an
air conduit along the outside thereof Variation and modification are
possible within the scope of the disclosure and the claims of the
invention Thus, the free oxygen-containing gas can be pure 130 784,947
oxygen or oxygen-enriched air and the fuel gas can be for example
ethane, propane, butane, nethane, natural gas or residue gas.
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