4486 4490.output

* GB784893 (A)
Description: GB784893 (A) ? 1957-10-16
Improvements in or relating to the use of certain methyl-irone isomers in
perfumes
Description of GB784893 (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
784,893 Date of Application and filing Complete Specification: Sept
20, 1955.
No 26847/55.
Application made in Switzerland on Sept 27, 1954.
Complete Specification Published: Oct 16, 1957.
Index at acceptance:-Classes 2 ( 3), C 3 A 14 A(l C: 2 D: 6: 8 A: 8
C); and 81 ( 1), L 5.
International Classification:-A 61 k C 07 c.
COMPLETE SPECIFICATION
Improvements in or relating to the use of certain Methyl-Irone Isomers
in Perfumes We, L GIVAUDAN & CIE, SOCIATA ANONYME, a Company organised
under the laws of Switzerland, of Vernier, Geneva, Switzerland, 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:-
Applicants have found that while 2,-methyla-irone (formula I) the
semicarbazone of which, melting at 214-216 (corr), was originally
described by their chemists (Helvetica Chimica Acta, vol 30, p 1612 (
1947)) and which was obtained by hydrolysis of said semicarbazone
(Patent No 2740817 in the United States of America registered the 4th

February 1948) possesses only mediocre olfactive properties, its
stereoisomer, the semicarbazone of which melts at 188-189 ' (corr),
develops persistent, expansive, pervasive odorous properties with a
woody powdery note of the greatest interest, capable of important
applications to the making of perfumes.
The ketone is obtained, together with its isomers, with a satisfactory
yield, for example by subjecting a technical mixture of stereoisomer
9-methyl-pseudoirones (formula II) containing no, or only a minor
proportion of, 11-methyl-pseudoirones to cyclisation by boron
trifluoride in accordance with the processes stated in the British
patents granted to the Applicant, Nos 666,881 and 666,993.
This ketone is again identified by its 2 4dinitro phenylhydrazone,
melting at 165 5166 It has the following characteristics:
d 42:= O 936; n D'02 = 1 5029; its infra-red absorption spectrum has
two characteristic bands of wave-numbers 795 and 1067 cm-1 and the
structure cis( 2 6) may be attributed to it, the ketone the
semicarbazone of which melts at 214-216 having the structure trans( 2
6) It may be utilised after purification either by distillation or
through the medium of one of its crystallised derivatives, such as the
semicarbazone The purification by distillation may lPrice 3 sijfgj, e
be limited, according to economic conditions, to the partial
elimination of the isomers, particularly of the stereoisomer the
semicarbazone of which melts at 214-216 (corr) when the presence of
said isomers does not interfere with the exploitation of the odorous
properties of the 22-methyl-c-irone the semicarbazone of which melts
at 188-189 (corr) It should also be noted that, within certain
percentage limits ( 80 % at most), the presence of the
22methyl-a-irone the semicarbazone of which melts at 214-216 (corr)
can be sought in fact, owing to the fact that certain of its odorous
properties are exalted and amplified by synergic action, thus
effectively rendering valuable a product having only a mediocre yield
under other conditions.
The subject of Applicant's invention is therefore a perfume This
perfume is constituted at least in part by the 22-methyl-c-irone the
semicarbazone of which melts at 188189 (corr), used separately or in
mixture with its isomers and particularly with its stereoisomer the
semicarbazone of which melts at 214-216 (corr) It may contain other
substances, particularly a-irone preparations according to the Swiss
patent granted to Applicant under the number 276,421, vetivert oil,
extracts of odorous plants containing coumarin, extracts prepared from
oak moss, ambergris, vanilla pods or their odorous constituents
reproduced by synthesis, and so on.
Some compositions of the perfume forming the subject of the present
invention are given below by way of example.

EXAMPLE 1.
Perfume constituted by 22-methyl-2-irone the semicarbazone of which
melts at 188189 (corr).
A MIXTURE OF THE 9-METHYL-PSEUDOIRONES 750 g of
3-methyl-dehydrolinalool (l 3,4-dimetho-3-pentene-yll, methyl,
ethynyl, carbinol), and 1950 g of ethyl a-methyl-acetoacetate ( 3 mol
per mol of 3-methyl-dehydrolinalool) were brought to a temperature of
+ 5 for 55 hours in a distilling apparatus.
At the end of the operation there was obtained, per mol of
3-methyl-dehydrolinalool used, 1.10 mol of ethyl alcohol and 0 65 mel
of carbon dioxide Distillation of the crude product of the reaction
remaining in the flask gave 1220 g of recuperated ethyl
a-methylaceto-acetate (thus 1 8 mol thereof was consumed per mol of
3-methyl-dehydrolinalool used), 148 g of intermediate fractions, 465
g.
of crude mixture of 9-methyl-pseudoirones and 280 g of non-distilled
residues.
The crude mixture was recovered by systematic fractional
distillations, first through a column provided with rings and equipped
with a total reflux head permitting withdrawal with a reflux
coefficient of 25 to 30, then through Widmer columns of adequate
dimensions at 0 1 to 0 15 mm Hg.
412 g were obtained of a mixture of the stereoisomers having:
B P oao 15 = 85-95 ; d 42 = 0 9059; nh, = 1.5342; An= 258; assaying,
by oximation, 97.6 % and having the absorption maximum at 292 my/ (e=
24200) in alcohol 95 5 % and at 282 my (e= 26100) in isooctane.
B CYCLISATION BY BORONTRIFLUORIDE.
Cyclisation was carried out on 200 g by 1 2 molecular equivalent of
boron trifluoride in the manner described in British Patent No.
666,881 regarding the cyclisation of pseudoirones After entrainment of
the crude product in steam super-heated at 135-140 at 30 to mm Hg, 165
g were obtained of rectified product.
B.P,2 o= 104-108 ; d'2 = 0 934-0 939; n D 2 = 1 5018-1 5040; An=
135-137; titer, by oximation-96 8 %.
C SEMICARBAZONES 136 g of product treated by semicarbazide acetate in
a wateralcohol medium, gave 158 g of semicarbazones ( 93 % of theory)
of which, by recrystallisation in alcohol at 95 5 % and in petroleum
ether B P = 60-80 , there was obtained: 74 g of semicarbazone MP =
214-216 and 63 g ( 40 % of the mixture) of semicarbazone MP.
188-189 .
D ( 2,6)-cis-2 -Mrr THYL -IRONE 32 g of semicarbazone MP 188-189 were
hydrolysed at boiling point with 34 g of phthalic acid in 170 ml of
water plus 170 ml of 1,2propanediol, with cohobation of the distilled
aqueous phase The methyl-irone was distilled on copper powder, in a

nitrogen atmosphere, through a Widmer column of a 180 mmn spiral.
22.4 g ( 88 % of theory) of ketone were obtained.
B.P 2,= 114-115 o; d,0 = 0 9363; nc O = 1,49932; n 20 = 1 50330; nf =
1 51296; An= 136 4; MRD= 69 54; EM Ro= + 1 19; Ama= 233 my (e= 15300)
in alcohol at 95 5 %; 227 my (e-= 15200) in isooctane.
The ketone, treated by semicarbazide acetate, gave up the crude
original semicarbazone MP= 188-189 , identified by its infrared
spectrum.
EXAMPLE 2.
Perfume constituted by the mixture containing the 2 -methyl-7-irone
the semicarbazone of which melts at 188-189 (corr), in the pro 70
portion of at least 20 %, such as results for example from fractional
distillation, with elimination of head and tail and fractions, of the
product of the cyclisation of a technical methylpseudoirone
preparation rich in 9-methyl 75 pseudoirones by means of boron
trifluoride according to Swiss patent No 277, 981 granted to
Applicant.
This mixture can be produced as follows: g of the product of
cyclisation by boron 80 trifluoride obtained according to the methods
A and B described above are fractionated by distillation at 2 to 2 5
mm Hg through a Widmer column All the fractions not having d 2 e lying
between 0 933 and 0 936; 85 n D 20 lying between 1 5026 and 1 5036 are
systematically treated again by distillation.
The fractions having d/2 ' and n D 2 lying between these limits are
examined by infrared spectography and olfactively The bands of ab 90
sorption of 1060 and of 795 cm-l are considered, characterising the
22-methyl irone whose semicarbazone melts at 188-189 and of 1052 cm-'
and 807 cm-' characterising the isomeric ketone whose semicarbazone
melts at 95 214-216 and it is found that the only fractions
interesting olfactively are those whose intensity ratios between the
bands of absorption of 1060 and of 1052 cm-' or of 795 and of 807 cm
indicate the presence of more than 100 %, of 22-methyl- -irone whose
semicarbazone melts at 188-189 The mixture of fractions, containing
more than 20 ,0 of this latter with fractions, containing less than 20
% thereof so that the titer of the mixture exceeds 105 %, also gives a
product adapted to use in perfumes with the advantages claimed.
Spectrographic graduation is carried out by mixing, in the desired
proportions, the 2 _methyl a -irone, whose semicarbazone melts at 110
o 188-189 obtained as in Example 1 hereinabove and the 2
-methyl-5-irone whose semicarbazone melts at 214-216 obtained by
hydrolysis of this semicarbazone in the same manner as in Example 1
(D) hereinabove 115 EXAMPLE 3.
Perfume constituted by (parts by weight):
22-methyl-a-irone the semicarbazone of which melts at 188-189 (corr)

400 "cetone alpha" ( 22-methyl-a-ionone) 250 alpha ionone 250 alpha
irone 10 ylang-ylang oil 30 "laurine" (hydroxy citronellal) 50 "MNA
aldehyde" (methylnonylacetic aldehyde) 2 5 lauric aldehyde 2 5 methyl
heptine carbonate 5 784,893 784,893 EXAMPLE 4.
Perfume constituted by (parts by weight).
Mixture rectified by distillation containing 22-methyl-a-irone the
semicarbazone of which melts at 188-189 (corr) with % at most of
isomer methyl-irones 60 lavender oil 70 bergamot oil 50 sweet orange
oil 80 CH 3 CH 3 CCR CA 3-AH CA-CA-C-CO-CA 3 CH CH$ I.
All temperatures specified herein are on the Centigrade scale.
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* GB784894 (A)
Description: GB784894 (A) ? 1957-10-16
Improvements relating to the regeneration of contact materials
Improvements relating to the Regeneration of Contact Materials.
We, SOCONY MOBIL OIL COMPANY INC., a company organised under the laws
of the
State of New York, United States of America, of 26 Broadway, New York
4, New
York, United States of 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
fol- loving statement:
This invention relates to improvements in the method and apparatus for
the continuous conversion of or transformation of hydrocarbons in

the presence of a granular contact material. It is particularly
concerned with improvements in the contact material regeneration
system of such processes.
Typical of processes to which this invention applies is the catalytic
conversion of high boiling hydrocarbons to lower boiling hydrocarbons
wherein a granular, absorbent, catalytic contact material is passed
cyclically through successive zones or vessels, in the first of which
it is contacted with a high boiling hydrocarbon charge at temperatures
of 850"F., and upward, to effect the conversion of said charge to
lower boiling hydrocarbons which may contain large percentages of
gasoline, and in the second of which contaminants deposited on the
contact material are removed so that the contact material will be in a
suitable condition for re-use in the conversion zone.
Other exemplary processes are thermal visbreaking, coking or cracking
of hydro-carbon charge by contact with heated granular inert contact
materials, or the reforming of gasoline-boiling constituents in the
presence of suitable catalyst for the purpose of improving the fuel
quality.
In processes wherein the contact material is catalytic in nature, it
may partake of the nature of natural or synthetic clays, bauxite,
activated alumina or synthetic associations of silica, alumina or
silica asd alumina to which other substances, such a certain metallic
oxides, may be added in small amounts. Nhen the contact material is
inert in character, it may partake of the form of refractory
materials, such as mullite or it may partake of the form of stones, or
metallic particles, or balls, or particles of coke.
The contact material should be of palpable particulate form as
distinguished from finely divided powders, and the term " granular" as
used herein, should be understood to include any contact material of
this form.
The contact material may take the shape of pellets, tablets, spheres,
capsules, or pac ticles of irregular shape, such as are obtained from
grinding and screening operations. Generally, the contact material
granules should be within the range 3 to 100 mesh and, preferably,
within the range 4 to 20 mesh of Tyler Standard Screen Analysis.
In processes of the above-mentioned types, the cracking of the high
boiling hydrocarbons to lower boiling hydrocarbons results in the
deposition of carbonaceous or more properly, hydrocarbonaceous
contaminants on the contact material. These hydrocarbonaceous
contaminants consist principally of compounds of hydrogen and carbon,
sometimes with impurities, such as sulphur and nitrogen, etc.,
compounds present. Often at least a portion of the deposit may
comprise tarry or heavy oily hydrocarbon material, or heavy organic
material. These carbonaceous contaminants must be removed before the

contact material can be re-used for conversion. The usual method of
removal is by burning these contaminants of with an oxygen-contain-
ing gas, such as air, the oxygen-containing gas being converted to
flue gas. During the transfer of the contact material to the
regeneration chamber, a portion of the contaminant deposit, usually
the heavy hydrocar bon portion, may be converted to lover boiling
combustible material, or hydrocarbons which are vaporized under the
existing operation temperatures. These materials vaporize either
during transfer of the contact material to the regeneration vessel, or
while the material remains in a supply bed above the regeneration zone
proper.
This vaporized organic or hydrocarbon material disengages from the
supply bed in the top of the regenerator and mixes with the effluent
flue gas into the atmosphere, generally through a stack. In addition
to conversion of the hydrocarbonaceous deposit, combustible vapours
may be carried into the regeneration zone in the voids between contact
material particles where the purging of the contact material as it
leaves the conversion zone, is not adequate. Also, vapours may exist
in the pores of the contact material which will expand under the lower
pressure of the regeneration zone. A further source of combustible
vapours is from liquid material in the contact material which
vaporizes under the reduced pressure of the regeneration zone. More
efficient purging of the contact material with inert gas as it leaves
the conversion zone is not a complete answer to this problem, since
purging only removes the vaporized material in the void spaces between
contact material particles and will not remove those portions of the
contaminant deposit which may be converted during transfer to the
regeneration zone, any vapours in the pores of the contact material.
or liquid hydrocarbons in the contact material.
The contact material is discharged from the bottom of the supply zone
onto the top of the gravitating substantially compact mass of solids
in the regeneration zone. Air is introduced into the regeneration zone
at one or more intermediate levels to travel upwardly through part of
the bed downwardly through the other part of the bed, thereby burning
contaminant from the solid material. In the uppermost portion of the
regeneration zone, the gas is passed upwardly and disengages from the
solid mass at the top of the regeneration zone. This gas mixes with
the gas distilled from or discharged from the granular material in the
supply zone and the combined stream of gas is discharged into the gas
stack for discharge into the atmosphere. The oxygen content of the gas
discharged from the top of the regeneration zone is generally low and,
in the newer moving bed systems, may he less than about 3 per cent by
weight.
While the temperature of the gas is high enough to effect combustion,

therefore, the low oxygen content provides only partial combustion.
Furthermore, the temperature f the mixed stream of gas rapidly drops
below the combustion temperature. Thus,
the gas discharged from the kiln during re
generation has therefore carried with it a
certain quantity of undesirable hydrocar
bons which commingle with the atmosphere
and cause the colour of the gas to bear a
yeliowish or orange hue. This has been
termed a ' smoke plume or simply
"plume." Inasmuch as the refineries in
which these cracking processes are located
are usually in or near large cities, it is un
desirable to contaminate the atmosphere
with this material and efforts have been
made to eliminate the plume. This inven
tion is directed to the prevention of this type
of air pollution.
The accompanying drawings are pro
vided for the purpose of illustrating 'the in
vention. In the drawings: -
Fig. 1 is a fragmentary view in vertical
section of a kiln of the type used in the re
generation of moving bed catalysts, the
burner of the present invention being shown
in detail;
Fig. 2 is a view in transverse section taken
on the line 2-2 of Fig. 1;
Fig. 3 is a view in vertical section taken
from the line 3-3 of Fig. 2;
Fig. 4 is a view in vertical section of a
kiln of the type shown in Fig. 1, but with
a modified type of burner according to the
present invention;
Fig. 5 is a view in transverse section taken
on the line 5-5 of Fig. 4; and
Fig. 6 is a view in vertical sec ion taken
on line 6-6 of Fig. 5.
Before describing in detail the structures depicted in the drawings,
the invention will
be described in general terms.
The invention comprises a method and
apparatus for the regeneration of used
granular contact material wherein the used

contact material is supplied to a bed of con
tact material in a confined supply zone or
plume burner bearing a carbonaceous de
posit and having combustible vapours asso
ciated therewith. Air. or other gas having
a suitably high oxygen content, is intro
duced into the supply zone in
amounts sufficient to burn the com
busible vapours, without causing any matial increase in the
temperature of the
solid material. The air is passed in con
current flow with the contact material and
withdrawn at or near the bottom of the
supply zone. The used contact maternal is
gravitated from the supply zone into the up
per section of a confined regeneration zone
and passes therethrough as a substantially compact column. An
oxygen-containing
gas, such as air, is passed through this col
umn under conditions suitable for the burn
ing of the remaining hydrocarbonaceous
contaminants on the contact material, with
the gas being passed in countercurrent flow
with the solids at least near the top of the zone. The flue gas
discharged from the column is mixed with the gas discharged from vhe
supply zone at or near the top of the regeneration zone and discharged
from the regenerator to the atmosphere.
The current moving bed cracking process now used widely for cracking
heavy hydrocarbons to produce increased amounts of motor gasoline,
comprises a continuous system with the reactor being located above the
kiln or regenerator and connected thereto by means of suitable
conduits. Catalyst is elevated from a level beneath the kiln by
pneumatic means to a separating vessel above the reactor and the
catalyst is gravitated at a compact stream from the separator
downwardly through an elongated gravity feed leg into the reactor. The
feed leg is long enough to permit the catalyst to feed smoothly anto
the reactor against an advanced pressure, such as about 10 p.s.i.
gauge The reacting material is prepared for treatment and introduced
into the reactor as a vapour, liquid or mixture thereof, and passed
through the void spaces in the bed. The cracked products are removed
from the bed continuously. The catalyst is contacted with a stripping
gas in the bottom of the reactor to remove as much of the reaction
product or reaction material as possible, and the stripped solids pass
in com pact form to the top of the regenerator, with the pressure

being reduced on the solids, usually during transfer to the
regenerator, to about atmospheric. As can be seen in
Figs. 1, 2 and 3, the conduit 10 leads the spent contact material from
the reactor, not shown, into a plume burner or confined supply zone
located in the regenerator 11 above the regeneration zone generally
designated at 14. The regenerator 11 is of annular cross-sectional
shape. Beneath the regenerator 11 is a lift tank, not shown, which is
connected to the bottom of the regenerator by conduits depending from
the bottom of the regenerator. The lift pipe projects substantially
vertically upward from the top of the lift tank passing through the
central opening 75, as shown on Figs.
1 and 4, in the regenerator. The Figs. 1 through 4 represent,
therefore, a cut through one side of the annular regenerator, with the
other side being arranged substantially equivalent. A series of
conduits 44 are arranged about the top of the annular regenerator to
feed the catalyst uniformly about the top of the vessel.
Referring specifically now to Figs. 1, 2 and 3, contact material
issuing from the conduit 10 passes through the supply zone or plume
burner 12, which includes a depending skirt or hood portion 13. It
then passes downwardly to a regeneration zone generally designated at
14. Both the supply and pre-burning zone 12, and the regeneration zone
]4, are within the insulated wall of the regenerator 11, although the
preburner could, if desired, be located outside the said vessel. Since
it is desired, however, to keep the height of the unit from becoming
excessive, the burner is most suitably localed in the uppermost
portion of the regenerator, occupying only that space normally
required to expand the column of catalyst discharged through the
conduit 10 to a column covering substantially the entirecross section
of the vessel, or that portion of the vessel served by conduit 10.
In the uppermost portion of the regenerator or kiln 11, is located a
plurality of wedge-shaped header boxes 18 uniformly distributed about
the annular cross-section of the vessel, but covering less than the
entire cross-section. Space is left between adjacent boxes 18 and
between each header box and the inner and outer walls of the vessel so
that gas flowing upwardly can pass by the boxes to reach an exit in
the top of the kiln 11. One of the header boxes 18 is illustrated on
Figs. 1, being formed by horizontal plates 15 and 19, and vertical end
walls 76. The header box 18 provides an enclosed gas manifold. Air is
introduced into the manifold 18 through conduit or pipe
17, and this air is discharged through a plurality of drop pipes 20,
to a discharge level intermediate the top and bottom of the
regeneration zone. The air stream splits on discharge wiLh some
passing concuriently with the gravitating catalyst to effect final
burning of th X con:aminants on the catalyst.

The flue gas formed is withdrawn near the bottom of the regeneration
zone and discharged through an exhaust stack. The remaining portion of
the air travels upwardly from the discharge level through the mass of
catalyst to effect initial burning of the contaminant. The gas, with
its oxygen content substantially exhausted, issues from the top of the
catalyst bed at the upper end of the regeneration zone and passes
around the header box or gas manifold 18, in the space provided for
this purpose, and is withdrawn from the kiln 11 through the pipe 23
and a suitable exhaust stack, which communicates freely with the
atmosphere.
A large number of vertical pipes 16 pass through the header box 18 to
feed catalyst from a pile or mass located on the upper sheet 15 of the
box, and distribute it uniformly across the cross-section of the
regeneration zone 14. The pipes 16 project only a short distance below
the bottom sheet 19, of the header box 18, so as to provide a gas
disengaging space beneath the header box. The pipes 16 are long
enough, however, to prevent any substantial amount of gas from passing
upwardly through the pipes rather than through the desired gas flow
path around and between adjacent header boxes. An upwardly extending
-all 21 is located on the top of the header box 18, or each header
box, being continuous about each box to provide lateral confinement of
the column of catalyst so that the entire flow of catalyst is
restricts to the pipes 16. A probing rod 24 is shown on Fig. 1 for
checking the level of catalyst mass within the enclosing wall 21.
if, now, reference is made to Figs. 2 and 3. the actual structure of
the upper portion of the plume burner of the present invention will be
described. The plume burner is wedge-shaped and corresponds in plan
view to the plan of the header box with which it co-operates. The
upper section of the burner is pentagonal in shape.
as shown On Fig. 2, being formed by vertical walls 26 and cover 33.
The conduit 10 discharges through the cover 33. Spaced below the
discharge end cf the conduit 10 is an upper horizontal sheet 31, on
which the catalyst accumulates in the form of a pile.
The sheet 31 is sufficiently bellow the end of the conduit 10. so that
the pile o catalyst covers the sheet 31. A multiplicity of pipes 36
are distributed across the tube sheet 31.
A second horizontal sheet 32, is located a spaced distance below the
upper sheet 31, so as to provide a gas plenum chamber 30,
The pipes 36 project through this shed.
Annular openings are left in sheet 32 about each pipe to provide
passage for gas from the plenum zone 30, into the confined ree- ion
therebelow. Spaced outwardly from The-vertical wail 26, are vertical
members 25 conneKontinuously about the wall of the pre-burner. The
space between the members 25 and the vertical wall 26, is enclosed by

the horizontal roof 34 and floor 35, thereby providing a continuous
gas manifold about the top of the pre-burner. A series of orifices 29
are cut in the vertical wall of the burner and communicate the
manifold 12 with the plenum chamber 30.
The Openings 29 are uniformly distributed about the pre-burner, as
shown on Fig. 2.
The apertures 29 are sized to provide a substantial pressure drop
thereacross, providing substantially uniform gas distribution to all
parts of the plenum chamber 30. Simimarly, the annular apertures 39
about the catalyst transfer pipes 36, are sized to provide a
substantial pressure drop, so that gas is distributed uniformly across
the catalyst bed. Air is supplied to the manifold 12 through the pipe
28.
The contact material discharged from pipe 10 first enters the space
below the cover 33 and below the sheet 31. The catalyst is then passed
downwardly through the conduits 36, which are of uniform size, and
which are symmetrically distributed around a larger central conduit
37. These conduits subdivide the flow of contaminated contact
ma.ceriai and distribute that flow, more c
lays, evenly within the zone defined by th
hood 13. Air, which is supplied through
conduit 2S, manifold 27, and apertures 29,
enters the plenum chamber 30 and, from
there, flows through the orifices 39 to en-
gage the contact material below pipes 36.
fhis system of air distribution has been
found to provide uniform gas flow through
the mass of catalyst in the conical shaped
hood 13, thereby burning the undesirable
plume forming constituents from tile cata
lyst without substantially raising the tem
erature of the catalytic mass. As a safety
measure to insure continuous flow of cata
left under all possible circumstances, the
iarge diameter pipe 37, has been provided..
in order to insure that adequate air is sup
plied to the region beneath the large pipe,
a plurality, such as, for example, four pipes:
have been located dependent from the lower
sheet 32, about the exterior of pipe 37, and
term.,nated in the region directly below the These These pipe 38,
therefore, carry an
aflditional suppi: of air to the catalyst mass
at a point or points directly below the large

diameter pipe 37. The hood 13 is of gen
rally pyramidal shape. terminating at its
lower end within the bounds and beneath
the top of the vertical confining wall 21.(
The catalyst, therefore, travels in compact
form downwardly through the region 12, en
closed by the hood 13, and discharges from
the hood onto the mass of contact material
confined between vertical wall 21 above the
header box 18. The distance across the hood
at the lower end thereof is substantially less than the distance from
one side of confining
wall 21 to the opposite wall, thereby leav
ing a sufficient horizontal space about the
hood 12 ',cre the catalyst forms a free up.
per surface and the gas is enabled to disen-
gaze from the catalyst and flow upwardly
into the region 22 about the exterior of the
hood 13. Thus. the products of combustion
of the pre-burner zone are admixed in the
regeneration zone and transferred upwardly
about the header box to the withdrawa'
conduit 23. The gas streams mingle in the
region 22 about the hood 13 and are re
moved together through the conduit 23 to a
stack. not shown, through which they even
tually reach the atmosphere. The sides of
the frusto-conical or frusto-pyrainidal hocd
13 preferably make an angle with the hori
zontal greater than the normal angle of re
pose of the contact material. By this means,
segregation of the contact material accord
ing to partical size as it passes through the
pre-burner is prevented, since, if the bed
therein were allowed to assume its normal
angle of repose, the larger particles would
tend to accumulate toward the outer por
tions of the bed and the smaller particles
would accumulate near the centre. This: would lead to channelling of
tile gas flow in the regeneration zone. The normal angle of repose
usually is within the range about 25 to 40 degress with the
horizontal. As previously indicated, the catalyst discharged from the
conduit 10 has associated with i; the combustible vapours.
These vapours consist principally of condensible and non-condensible

hydrocarbons.
These vapours are burned as soon as the air distributed from the
plenum chamber 18 contacts the catalyst and the combustion of these
vapours is substantially completed by the time the vapours disengage
from the catalyst around the lower end of the hood 13. The catalyst is
thereafter supplied by means of the conduit 16 to the top of the
gravitating mass of catalyst in the regeneration zone 14, and the coke
contaminant on the catalyst is largely or substantially completely
removed therefrom during passage through the regeneration zone. The
regenerated catalyst is withdrawn from the bottom of the regenerator
11, and transferred back to the top of the reaction zone for reuse in
the process. The cracking conversion occurs at elevated pressure of,
say about, 10 pounds, and, at this pressure, a certain amount of
normally liquid and vaporized oils are absorbed in the pores of the
catalyst. This oil is not removed by the seal gas or purging gas at
the bottom of the reactor, which is introduced at that point to strip
the wet material from the catalyst as it leaves the reaction zone.
Therefore, the catalyst transferred from the reaction to the top of
the kiln, contains a solid or substantially solid carbonaceous deposit
in addition to the liquid or vaporized hydrocarbonaceous material. At
the lower pressure prevailing in the kiln, this lighter material tends
to leave the pores of the catalyst as free gas. It is this material
that is burned within the hood 13 and leaves the system in innocuous
form through a discharge conduit 23.
The form of the invention shown in Figs.
4, 5 and 6 is generally similar to Figs. 1 through 3 inclusive, except
that the air for the pre-burners is supplied by tapping the main air
duct. In Figs. 4 through 6, inclusive, the numeral 40 represents the
regeneration chamber or kiln. The chamber 40 is provided with a stack
outlet 41. The regeneration zone is generally designated by reference
numeral 42 and the preburner zone by reference numeral 43. The spent
contact material is introduced into the kiln 40 through a chute 44,
which discharges into the top of a somewhat frusto-conical hood 45.
The hood 45 contains the preburner zone 43 and has a gas outlet port
at 46. Air is admitted to the kiln 40 through a duct 47, which leads
to a header zone 48, located between spaced parallel tube sheets 43
and 50. From the header space 48, air is delivered through conduits 51
to the middle of the regeneration zone 42 in order to support the
combustion which burns off the carbonaceous contain ants on the
contact material. The tube sheet 49 supports a plurality of conduits
52, which lead upwardly to a header zone 53, located near the upper
end of the hood 45 and defined between parallel spaced tube sheets 54
and 55. The tube sheet 49, in addition to supporting the air conduits
52, likewise supports a plurality of contact material conduits 56,

which pass from the pre-burner zone 43, through the header 48, to the
regeneration zone 42. These conduits 56 lead to funnels 57, which
distribute the contact material to form the moving bed in the
regeneration zone 42, of the kiln.
The contact material discharged from the chute 44 is conducted through
the header zone 53 by a group of small conduits 58, by a single large
central conduit 59, and by four diagonally extending corner conduits
60.
The arrangement of conduits 58, 59, and 60, is such as to bring about
an even distribution of the contact material in the space defined by
the hood 45.
Within the space below the tube sheets 55 and above the tube sheets
49, pre-burning occurs. To this end the air, which is supplied from
conduit 47, header 48, tubes 52 and header 53, is distributed through
annular ports 61 surrounding the conduits 5E and 59. These annular
ports are made by cutting the holes in the tube sheet 55 oversize in
relation to the respective contact material conduits.
From the foregoing description, it will be appreciated that the
contact material enters the kiln 40 under pressure and temperature
conditions conducive to releasing gaseous plume forming hydrocarbons
which is contacted with fresh combustion supporting air in zone 43,
whereby gaseous contaminants are burned before the contact material is
delivered to the main regeneration zone for removal of the solid coky
contaminants which render the reactivation necessary.
In the embodiment shown on Fig. 4, the gas for the pre-burner is
supplied upwardly through the conduits 52 and uniformly distributed
across the region between tube sheets 54 and 55, and then is
distributed uniformly through the annular orifices surrounding each
catalyst transfer pipe to travel downwardly with the catalyst under
the confining hood 45. The catalyst and gas from the pre-burning zone
pass through the conduits 56, which extend through the header box 48
and discharge into cup members 57. The cup members 57 have a discharge
outlet at their lower end of smaller cross-section than the
cross-section of the pipes 56, thereby maintaining within the
cup, at all times, a compact mass of cata
cyst. The upper end of the cup members
extend a substantial distance above the
lower end of the transfer pipes 56. The
catalyst discharge from the transfer pipe 56
spreads outwardly in accordance with the
angle of repose of the catalyst to form a
free surface in the cup members, and this
provides a region in which the gases travel
ling with the catalyst can disengage there

from and travel upwardly and out of the
upper ends of the cup members 57. The dis
engaged gases then mingle with the gases
being discharged from the upper surface of
the catalyst in the regeneration zone 42, and
the commingled gases pass around the
header box 48 and discharge together from
the regeneration vessel through the outlet
41 located near the top of the vessel. The
confining hood 45 has side walls which
slope at an angle with the horizontal
greater than the angle of repose of the cat
alyst, similarly to prevent particle segrega
tion while the catalyst s
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* GB784895 (A)
Description: GB784895 (A) ? 1957-10-16
Improvements in and relating to the measurement of fluid
COMPLETE SPECIFICATION Improvements in and relating to the Measurement
of Fluid
We, BARBER-GREENE COMPANY, a Corporation organised and existing under
and by virtue of the laws of the State of Illinois,
United States of America, of Aurora, Illi- nois, United States of
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 a method of measuring fluid materials such
as asphalt and to apparatus for carrying out the method. The invention
is particularly applicable to the charging of a pugmill of a batch
asphalt plant with bitumen for mixture with aggregate and mineral
fines.
According to the invention, a method of measuring fluid materials such
as asphalt comprises introducing fluid material into a receptacle,
then withdrawing the material from the receptacle and weighing the
material as withdrawn, stopping the withdrawing operation upon
withdrawal of the required weight of material from the recap tacle,
and thereafter withdrawing only to the level of the initial
withdrawing operation for each operation of a succession of
withdrawing operations.
Apparatus for carrying out this method preferably comprises a weigh
bucket having an overflow, a pump for supplying material to the weigh
bucket, and a second pump for withdrawing material from the weigh
bucket, in which means are provided for measuring material withdrawn
from the weigh bucket, and in which the second pump has a suction pipe
extending within the weigh bucket to a predetermined level therein,
the suction pipe being adjustably movable so that it can be set to
withdraw a measured weight of material from the weigh bucket during
each measuring operation.
Apparatus in accordance with the invention will now be described by
way of example with reference to the accompanying drawings, wherein:
Figure 1 is a diagrammatic view of an asphalt batch plant having an
asphalt charging and measuring means constructed in accordance with
the invention embodied therein:
Figure 2 is a schematic drawing illustrating the asphalt circulating
system and the means for filling the weigh bucket and withdrawing a
predetermined volume of asphalt from the weigh bucket for spraying in
the pugmill;
Figure 3 is a plan view of the weigh bucket and casing therefor with
certain of the fluid connections broken away;
Figure 4 is a sectional view taken through the weigh bucket and its
container, substantially along line IV-IV of Figure 3;
Figure 5 is a fragmentary detail view taken substantially along line
V-V of Figure 3, and illustrating the adjusting means for the suction
pipe and one of the float controls, for controlling and initiating a
filling cycle of the weigh bucket;
Figure 6 is a fragmentary sectional view taken substantially along
line VI-VI of
Figure 3;
Figure 7 is a fragmentary detail view looking toward the suction tube

and switch arm shown in Figure 6 in order to illustrate certain
details thereof not shown in Figure 6;
Figure 8 is a horizontal sectional view taken substantially along line
AIIIIVIII of
Figure 6;
Figure 9 is a view illustrating the support for the weigh bucket on a
scale for weighing; and
Figure 10 is a plan view looking downwardly on the scale and showing
the weigh bucket in dotted lines.
In the embodiment of our invention illustrated in the drawings, we
have diagrammatically shown in Figure 1, a bituminous batch plant 10,
including generally a plurality of storage bins 11 for aggregate,
arranged to discharge aggregate into aligned aggregate measuring bins
12 carried in a drop
bottom weigh hopper 13.
Dried aggregate may be supplied to the storage bins 11 directly from
an aggregate
drier (not shown) by means of an elevator 15, which may be a bucket
elevator of a well known form. The elevator 15 may elevate
and discharge the dried aggregate directly
onto sizing screens 16, one sizing screen being
provided for each storage bin 11 to supply the properly sized
aggregate thereto.
The weigh hopper 13 also contains a bin 17
for mineral fines, herein shown as being posi
tioned between two intermediate aggregate
bins 12 and receiving mineral fines elevated
by an elevator 19, discharging into a supply
or storage chute 20 in direct communication
with the bin 17 through a sliding gate 21.
The weigh hopper 13 is supported on
spaced beams 23 connected with a scale lever
24 through a linkage and lever arrangement
35 for indicating the weight of aggregate and
mineral fines contained in the weigh hopper
13 for discharge into a pugmill 27, where the
aggregate and mineral fines are mixed and
asphalt is sprayed thereon by means of spray
bars or pipes extending transversely of said
pugmill and spaced therealong.
The weigh hopper 13 is provided with a
clam shell discharge gate 30 for simultane
ously discharging aggregate from all of the
bins in said weigh hopper into the pug

mill 27.
The pugmill 27 is shown as having a plur
ality of spaced paddles 31 therein, power
driven to rotate toward each other along the
bottom of the pugmill, and as having a dis
charge gate 32 slidable to discharge the
mixed aggregate, mineral fines and asphalt
into a truck or the like (not shown). The pug
mill 27 is no part of our present invention so
need not herein be shown or described fur
ther.
Asphalt is measured in a weigh bucket or
tank 33 supported on parallel spaced beams
35 having connection with a scale 36 through
a linkage and leverage arrangement 37 which
will hereinafter be more fully described as
this specification proceeds. The weigh buc
ket 33 is shown as having a suction pipe 39
extending therein and adjustable to withdraw
a predetermined weight of asphalt therefrom
as, will hereinafter more clearly appear as this -speeificatidn
proceeds. The adjustable suc
tion pipe 39 is connected with a supply pipe
40 having a valve 41 therein, which may be
power operated under manual or automatic
control to supply hot asphalt to a spray
pump 43, when the valve 41 is open. The
valve 41 is vented to the atmosphere when
closed, through an air vent 44. A pipe 45
is connected with the discharge side of the
spray pump 43 and has connection with the
spray bars or pipes 29 through a header 46
extending along the pugmill 27.
The weigh bucket 33 has an overflow duct 47 leading therefrom adjacent
the upper end thereof for conducting asphalt overflowing said weigh
bucket into a vertical duct 49 connected with a storage tank 50
through a pipe 51.
Asphalt is supplied to the weigh bucket 33 from the storage tank 50 by
means of a including pump 53 having connection with the storage tank 5
50 through a suction pipe 54. l The pressure side of the circulating
pump 53 has a pressure pipe 55 connected therewith having connection
with a threeway valve 56. The valve 56 may operate under manual or
automatic control and controls the flow of asphalt to the weigh bucket
33 through a pressure pipe 57 leading within the weigh bucket 33 to a

position adjacent the bottom thereof. The valve 56 may also be
positioned to by-pass asphalt back to the tank 50 through a by-pass
line 59, when the weigh bucket 33 is full. A drain 58 leads from the
bottom of said weigh bucket.
The weigh bucket 33 is carried in an outer casing 60 which is shown as
being jacketed to accommodate the circulation of steam around said
weigh bucket and along the wall of the duct 49 (Figure 4). The casing
60 is suspended independently of the weigh bucket 33, suspended from
the scale 36. Said casing has a cover 61 which also may be jacketed
for the circulation of steam therethrough to maintain the asphalt in
the weigh bucket hot and fluid.
The cover 61 forms a support for the suction pipe 39 on an adjusting
mechanism 62 supported on said cover and extending upwardly therefrom
and affording a means for adjusting the elevation of the suction pipe
39 with respect to the bottom of the weigh bucket, and thus
determining the amount of asphalt that may be withdrawn from the weigh
bucket, as will hereinafter more clearly appear as this specification
proceeds.
The weigh bucket 33 has lower and upper floats 63 and 65 respectively
therein for controlling the spraying of asphalt in the pugmill.
The upper float 65 serves to operate a suitable switch 117 on a
pivoted switch arm 118 pivotally mounted on top of the cover 61, to
effect operation of the valve 41 and the spray pump 43 when the weigh
bucket is full, and to prevent the spraying of asphalt until the weigh
bucket is full, as will hereinafter more clearly appear as this
specification proceeds.
The lower float 63 serves to operate a suitable switch 115 on a switch
arm 112, to close said switch when all of the asphalt has been pumped
from the weigh bucket down to the bottom rn of the suction pipe 39 to
hold the cycle timer for the system (not shown) from coming into
operation to effect refilling of the weigh bucket until the required
weight of asphalt has been sprayed in the ptlgmill, as will
hereinafter more clearly appear as this specification proceeds.
The scale linkage and leverage arrangement 37 to effect weighing the
weigh bucket 33 and the asphalt therein on the scale 36 is shown as
including a plurality of eye-bolts 69 secured to each beam 35 on
opposite sides of the weigh bucket and suspending said weigh bucket
from spaced support beams 73, by links 75 in the form of eye-bolts
connected with belicranks 70 on torsion bars 76.
The eye-bolts 69 are connected with the bellcranks 70 inwardly of the
point of connection of the lings 75 thereto through devises 71.
The torsion bars 76 are operatively connected with the scale 36
through lever arms 79 connected with a lever 77 through a suspension
link 80. The lever 77 is suspended from the beam 73 through an

eye-bolt and link indicated generally by reference character 81. A
linkage 84 is provided to connect the lever 77 with a dial 83 of the
scale 36 through the usual balancing capacity and tare bars indicated
generally by reference character 85.
The adjustable suction pipe 39 has a packing gland 87 at its upper
end, sealing said suction pipe to a pipe 88 and mounted for slidable
movement along the pipe 88. The adjustable suction pipe 39 is
adjustably moved along the pipe 88 by the adjusting mechanism 62,
herein shown as comprising a screw 89 rotatably carried adjacent its
ends in a vertically extending support standard 90 secured to the top
of the cover 61 and extending upwardly therefrom. The upper end of the
screw 89 is squared as indicated by the reference character 93 to
accommodate a crank or hand wheel to be detachably placed thereon to
rotate said screw.
A carriage 95 threaded on the screw 89 is slidably guided between the
side walls of the standard 90 and is vertically moved therealong upon
turning of said screw. The carriage 95 has supporting connection with
the suction pipe 39 by a means of spaced saddles 96 extending from
said carriage and engaging the inner side of said suction pipe, and
spaced bolts 97 extending along opposite sides of the pipe 39 and
secured to a clamping member 99 by means of nuts 100, threaded on the
outer ends of said bolts.
The low level float 63 is carried on the lower end of a vertical rod
103 slidably extending through a plate 101 extending outwardly from
the clamping member 99. Lock nuts 104 are threaded on the upper end of
the rod 103 and abut the top surface of the plate 101 when the float
is in its lowermost position (see Figure 6). The nuts 104 engageable
with the plate 101 also effect movement of the float 63 with the
suction pipe 39. An arm 106 extends inwardly from the lower nut 104
along the top surface of the plate 101 and extends between two spaced
vertical rods 107 connected between the plate 101, and a vertically
spaced parallel plate 109.
The plate 109 has two spaced depending arms 111, between which is
pivoted the switch arm 112 on a pivot pin 113. The switch arm 112 has
the switch 115 mounted thereon (see Figure 7). The switch 115 may be a
mercury switch and serves to complete a cycle timer power circuit (not
shown) when the float 63 is in its lowermost position. This will
effect closing of the valve 41 supplying hot asphalt to the spray pump
43 and then effect opening of the valve 56 to a position to conduct
hot asphalt through the pipe 57 to fill the weigh bucket 33.
The low level float 63 moving the rod 103 upwardly, as the weigh
hopper 33 is filled with asphalt, will operate the switch arm 112 and
mecrury switch 115 to open said switch and maintain said switch open
until the float 63 drops to its lowermost position. When the float 63

is in its lowermost position, the mercury switch 115 will close and
complete the previously mentioned cycle timer power circuit, which may
effect closing of the spray pump valve 41. The float 63 thus serves to
hold the cycle timer power circuit open until the level of asphalt in
the weigh bucket 33 drops below the bottom of the suction pipe 39.
The upper float 65 serves to operate the mercury switch 117 on the
switch arm 118.
The float 65 is connected with the switch arm 118 through a rod 120
slidably extending through the cover 61, and having said switch arm
pivotally carried on the upper end thereof on a transverse pivot pin
121. The opposite end of the switch arm 118 is slidably guided on an
upright support 123.
Movement of the switch arm and rod 120 is controlled by a lever arm
119 pivoted to a rock shaft 1 19a (Figure 3).
The valves 56 and 41 may be operated automatically under a control of
a cyclic timer or may be operated under manual control when it is
desired to initially measure asphalt to be supplied to the pugmill for
mixture with the aggregate therein. In Figure 2 we have
diagrammatically illustrated a hydraulic ram 125 for operating the
valve 41 and another hydraulic ram 126 for operating the valve 56. The
hydraulic rams may be double acting to move the respective valve into
one position upon the admission of fluid under pressure to one end
thereof and into another position upon the admission of fluid under
pressure to the opposite end thereof.
The supply and admission of fluid under pressure to the respective
hydraulic rams 125 or 126 may be through suitable valve means, which
may be solenoid operated and manually operated as desired.
As herein shown, a solenoid operated and manually controlled valve 135
is provided to control the supply and release of fluid under pressure
to the hydraulic ram 125, while a solenoid and manually operated valve
136 is provided to control the supply and release of hydraulic fluid
under pressure to opposite
ends of the hydraulic ram 126.
In initially setting up the system for automaticaliy measuring a batch
of asphalt of a predetermined weight for mixture with aggregate in the
pugmill 27, the suction pipe 39 may be raised to its uppermost
position by
operation of the screw o9, as previously de
scribed. The valve 136 may then be oper
ated, preferably manually to operate the valve 56 to supply hot
asphalt to the weigh bucket 33 and fill the weigh bucket to overflow
over the overflow duct 47.
The valve 135 may then be operated to
open the valve 41 to effect the pumping of asphalt into the pugmill by

operation of the
spray pump 43. During the spraying operate tion the suction pipe 39
may gradually be
lowered into the weigh bucket until the correct weight of asphalt has
been pumped to
the pugmill as indicated by the scale 36.
Lowering of the suction pipe 39 may then be
stopped. The suction pipe 39 will then be
set to deliver the same amount of asphalt for mixture with e ? ch
succeeding batch of aggregate.
The system may then be automatically
operated under the control of the cycle timer
(not shown), the floats 63 and 65 and the
mercury switches 115 and 117, operated by
the respective floats. The cycle timer and
electrical control circuit as well as the hy
draulic control circuit form no part of the
present invention so need not herein be
shown or described further.
During automatic charging of the pugmill, the circulation pump may
first fill the weigh bucket to the overflow by operation of the valve
56, the excess asphalt overflowing the top thereof along the overflow
duct 47. The valve 56 will then be operated under control of the float
65 to circulate asphalt back to the storage tank 50, while the valve
41 may be operated to effect the spraying of asphalt in the pugmill
through the spray bars 29. The spraying operation will continue until
the level of the asphalt in the weigh bucket 33 reaches the level of
the bottom of the suction pipe 39, at which time the valve 41 will be
turned off and after a time delay governed by operation of the rest of
the plant, the cyclic control circuit energised by the float 63 will
effect the turning on of the valve 56 to initiate a next succeeding
filling operation of the weigh bucket 33.
It may thus be seen that when the correct amount of asphalt has once
been withdrawn from the weigh bucket 33, as determined by weighing on
the scale 36, and the suction pipe 39 has been adjusted to the level
of the top surface of the asphalt remaining in the weigh bucket, that
a predetermined weight of asphalt will be deliverer < . he pugmill for
mixture with the aggregate t-1'erein, and that the weight of the
ashpalt may readily be varied when it is desired to change the
proportion of the mixture of the asphalt with the aggregate.
Whit we claim is :
1. A method or measuring fluid materials such as asphalt, which
comprises int.'oducing fluid material into a receptacle, ttnell
withdrawling the material from the receptacle and weighing the

material as withdrawil. stopping the withdrawing operation upcn With-
drawal of the required weight of material from the receptacle, and
thereafter withdrawing only to the level of the initial withdrawing
operation for each operation of a succession of withdrawing
operations.
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* GB784896 (A)
Description: GB784896 (A) ? 1957-10-16
Improved method and device for the manufacture of artificial threads and
like products
A high quality text as facsimile in your desired language may be available
amongst the following family members:
BE550120 (A) CH337977 (A) DE1112604 (B) FR1144219 (A)
NL84656 (C) US2908937 (A) BE542542 (A) CH341597 (A)
DE1123795 (B) FR70444 (E)
BE550120 (A) CH337977 (A) DE1112604 (B) FR1144219 (A)
NL84656 (C) US2908937 (A) BE542542 (A) CH341597 (A)
DE1123795 (B) FR70444 (E) less

P'ATENT SPECIFICATION
7843896 4, Date of Application and filing Complete Specification Nov7,
1955.
& No 31819/55.
Application made in Netherlands on Jan 11, 1955.
Complete Specification Published Oct 16,1957.
Index at acceptance: -Class 2 ( 2), l BD( 1 A: 11 B: 2).
International Classification: -1 D 01 d.
Improved method and device for the Manufacture of Artificial Threads
and like Products We, ALGEMENE KUNSTZIJDE UNIE N V, a Corporation
organized and existing under the Laws of the Kingdom of The
Netherlands, of 76, Velperweg, Arnhem, Holland, 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 a method for the manufacture of artificial threads
and like products according to the wet spinning process, in which the
spinning process is favourably influenced in that the spinning bath
liquid moves in the same direction as the product being formed.
Several methods are known in which exterior means, such as a
difference in level, pressure in conduits etc are used for putting in
motion the spinning bath quite independently of the presence of a
product being formed, and in which the spinning bath, moving per se
either in tubular devices or not, exercises an influence on the
coagulating and coagulated thread as soon as the latter is present.
On the other hand methods are known in which the coagulating thread
itself imparts to the spinning bath liquid surrounding the spinneret
after the spinneret a movement in the same direction as that of the
threads.
Contrary to the first-mentioned methods a movement of the spinning
bath only occurs in this case as soon as a product being formed is
present.
For example according to the British Patent Specification No 655,516 a
tube open at both ends is disposed in the spinning bath coaxially with
the spinneret, the spun threads being guided through this tube The
threads being formed and moving through this tube cause the spinning
bath liquid to flow in the direction of movement of the threads.
This measure offers the possibility of using a higher spinning
velocity without increasing the number of thread ruptures.
lPrice 3 s 6 d l According to this older proposal tubes having the
same cross section over their entire length are disposed in the

spinning bath.
According to the present invention there is provided an apparatus for
the manufacture of artificial threads according to the wet spinning
process in which a bundle of filaments is formed by extruding a
spinning solution from a spinneret which has a number of extrusion
orifices and is submerged in a bath of a coagulation liquid contained
in a spinning trough, in which apparatus the filaments travel from the
spinneret to a thread guide through a completely submerged straight
tube open at both ends, the centre of the spinneret face, the axis of
the tube and the point of contact of the filaments with the thread
guide being in alignment and the inlet end of the tube being a short
distance from the face of the spinneret characterized in that said
tube comprises two cylindrical portions of different diameter, the
first portion of the tube, starting from the spinneret having an
internal diameter which somewhat exceeds that of the outer ring of
pinneret orifices, the first portion of the tube being connected by
means of a gradually widening intermediate portion having the shape of
a truncated cone to a second portion of the tube of which the internal
diameter is greater than that of the first portion of the tube.
In spinning processes, in which a slow coagulation takes place so that
the thread being formed is extremely sensitive near the spinneret to
exterior influences, a considerable improvement in the quality of the
product is obtained.
In such an apparatus, in which the product being formed imparts to the
spinning bath liquid surrounding the spinneret a movement in the same
direction as that of the threads, energy taken from the movement of
the already coagulated threads is used to raise the velocity of the
liquid in the first portion of the spinning path, where the thread is
still in coagulating condition, to a velocity practically 784,896
equal to that of the coagulating threads.
By coagulated thread is understood in this case a thread in which the
coagulation and the possible decomposition to cellulose have advanced
to such a degree that this thread may absorb or yield exterior forces
without a risk of damage By coagulating threads are understood threads
in the first portion of the spinning path which are very sensitive to
exterior forces and are readily damaged.
In many cases the transition of what is understood in this application
by coagulated thread and coagulating thread coincides with the
so-called neutralisation point.
It should be noted that, to be sure, in the known methods the spinning
bath liquid is put in movement in the same direction as the direction
of movement of the threads being formed but that the velocity of the
liquid in the first portion of the spinning path is appreciably less
than that of the threads It has now been found that on account of this

difference in velocity in the first portion ox the spinning path,
where the threads are still very sensitive to mechanical influences,
the threads rupture easily when the velocity of the threads is raised.
The operation of the device may be explained as follows:Under the
influence of the force exercised by the drawing-off means the thread
is drawn through the coagulation liquid in the second portion of the
tube At the same time, due to friction, the threads puts the liquid in
said second portion in movement in the drawingoff direction The liquid
flowing along with the thread has to be replaced in the second portion
of the tube Consequently it exercises a sucking action on the
coagulation liquid in the first portion of the tube so that this
latter coagulation liquid is moved in the direction of movement of the
thread at a speed higher than the speed in the second portion of the
tube and in a ratio substantially corresponding to the ratio between
the cross section surfaces of both portions of the tube.
It is easy in a certain case to select the cross section and length of
the second portion of the tube in such a way that the coagulation
liquid in the first portion of the tube moves at the same velocity as
the thread so that the spinning bath liquid will not excercise any
mechanical action on the thread.
In order to achieve the most favourable results it is desirable, but
not strictly necessary, to take the following additional measures.
In order to bring the inlet opening of the tube as close as possible
to the spinneret and to avoid turbulence as much as possible when the
coagulation bath is sucked into the tube, this inlet opening is given
the shape of a short and flat trumpet.
In order to prevent turbulence as much as possible at the transition
between the narrow and the wide tube portion, it is preferred that the
intermediate portion of the tube should have the shape of a truncated
cone in which the sloping sides are at a small angle to one another 70
For the sake of completeness in acknowledging the prior art it should
be noted that it is already known 1 rom the U S Patent Specification
827,434 to guide the threads, after leaving the spinneret, by means of
a flowing spin 75 ning bath liquid through a cylindrical tube In the
case of this patent specification, however, the coagulation liquid is
supplied under pressure and is forced past the spinneret to the
spinning tube proper so that the liquid carries 80 the freshly spun
thread along due to friction.
In this case it would be possible, namely by a certain adjustment of
the pressure of the coagulation liquid to adapt the velocity of the
coagulation liquid in the first portion of the 85 spinning path in
such a way to the velocity of the spinning thread that an accelerating
or retarding friction does not occur.
However, this method creates considerable complications in the

construction of the device 90 Further it has not been clearly
established that an adaptation of the velocity of the coagulation
liquid to the velocity of the thread in the first portion of the
spinning path is required 95 An embodiment of an apparatus according
to the invention which has given full satisfaction is described below
by way of example with reference to the accompanying drawing.
In a spinning bath trough 2 filled with 100 coagulation liquid up to a
level 1 a tube 3 is mounted by means of supports 4 and 5 This tube 3
consists of a narrow first portion 6, a wider second portion 7 and a
conical intermediate portion 8 connecting the first portion 105 6 to
the second portion 7.
The first portion 6 has a trumpet-shaped inlet opening 9 The tube 3
has been mounted in the spinning bath trough 2 at a short distance
from and coaxially with a 110 spinneret 10 A spinning solution is fed
to this spinneret 10 through a tube 11.
A thread 12 formed from a plurality of filaments formed by the
spinneret 10 is guided by means of a guiding device 13 co-axially 115
through the tube and is finally led to a guiding device 14 disposed
outside the spinning trough.
The tube dimensions are appropriately adapted to the total titre of
the thread and 120 the spinneret to be used.
As stated above the diameter of the narrower tube portion 6 should be
taken somewhat larger than the diameter of the outer ring of spinneret
orifices 125 Experiments have shown that for a uniform coagulation of
all filaments it is essential that the bundles of those filaments fill
up the narrow first portion of the tube as much as possible and that
they remain separate while 130 784,896 travelling through the narrow
portion of the tube This is achieved by the aforesaid selection of the
diameter of the narrow first portionl 6 in relation to the diameter of
the spinneretl 10.
In the manufacture of artificial silk having a titre of 80-120 denier
for which the outer ring of spinneret openings has, for example, a
diameter of about 9 mm, an inner diameter of the narrow tube portion
of about 10-12 mm is very suitable.
The inner diameter of the wide tube portion 7 is 1 2 to 1 5 times that
of the narrow portion of the tube (which is approximately 20-50 %)
larger than the diameter of the narrow tube portion so that in the
given example the inner diameter of the wide portion of the tube is
13-17 mm.
It has been found that for the wide portion of the tube a length of
25-40 cm is required in order to exercise a satisfactory suction.
For the manufacture of threads having a high titre, for instance of
1600 denier, which are used for manufacturing automobile tyre cord,
the diameter of the outer ring of spinneret orifices is often about 16

mm In that case the inner diameter of the narrow first portion 6
should be approximately 20-22 mm.
At a primary thread velocity of 30 m /min.
and a velocity after stretching of 60 m /min a tube may be used of
which the first portion has a length of 30 cm and a diameter of 21
min, the second portion a length of 20 cm and a diameter of 27 mm, the
intermediate portion between the first and second portions having a
length of 5 cm.
The inlet opening of the narrow portion of the tube, which, as already
said, is preferably provided with a trumpet-shaped inlet, is placed as
close as possible to the spinneret face without unduly impeding the
free admission of the coagulation liquid into the tube or causing
turbulence in the tube The distance in question is selected to be
smaller or larger according to the titre of the thread, the dimensions
of the spinneret face and especially also the spinning velocity As a
rule it is preferred to work with a distance of 5-20 mm.
With respect to the cone-shaped intermediate portion between the
narrow and the wide portions of the tube it has been found that the
length of this intermediate portion, namely the height of the
corresponding truncated cone, should generally amount to approximately
twice the inner diameter of the wide portion of the tube.
The invention will be further illustrated with reference to an
embodiment relating to the manufacture of artificial threads from
viscose.
EXAMPLE
A viscose prepared from cotton linters having a cellulose content of 7
7 % by weight, a sodium hydroxide content of 5 5 % by weight, a
xanthate ratio of 0 47 and a falling ball viscosity of 60 sec, to
which 0 16 % by weight f quinoline has been added, was spun, by means
of a device of the type described above, in a spinning bath at 600 C
containing 6 % by 70 weight of sulphuric acid, 19 % by weight of
sodium sulphate and 3 8 % by weight of zinc sulphate In this spinning
operation a goldplatinum spinneret was used in which 1060 orifices
each having a diameter of 60 microns 75 had been drilled The diameter
of the outer ring of spinning orifices amounted to 16 mm.
The narrower portion of the tube had an inner diameter of 21 mm, and
the wider portion of the tube had an inner diameter of 27 mm, the 80
length of the narrow portion being 30 cm and that of the wider portion
19 cm The intermediate portion between these two portions was 4 cm
long The outer diameter of the trumpet-shaped inlet opening amounted
to 4 85 cm This inlet opening was situated at a distance of 2 cm from
the spinneret The primary drawing-off speed amounted to 40 m /min.
and the winding-up speed to 80 m /min.
Stretching was therefore 100 % This stretch 90 ing was effected in a

bath of 90 C containing 3 % by weight of H 2504.
The threads thus obtained had a titre of 1815 denier, the dry strength
amounted to 392 g /100 denier and the dry elongation to 95 22.8 % When
no tube was used spinning at the aforesaid speed proved to be
impossible owing to frequent thread ruptures.
In addition to the spinning of threads from quinoline containing
viscoses, the use of which 100 is illustrated by the above example,
the present invention is important for the spinning of viscoses
containing other substances which retard coagulation regeneration of
the cellulose As examples thereof organic substances 105 may be cited
which, at the coagulation of the viscose, may form temporarily stable
chelates with the zinc salts present in the acidic spinning bath used
for spinning As to the definition of chelates reference is made to the
book 110 by Martell & Calvin, " Chemistry of the Metal Chelate
Compounds ", New York, 1952/53, page 1.
It should be noted, however, that the invention is not restricted to
the processing of these 115 spinning solutions, but also offers the
possibility of increasing the spinning velocity when processing
spinning solutions other than viscoses to which special substances
have or have not been added 120
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* 5.8.23.4; 93p
* GB784897 (A)
Description: GB784897 (A) ? 1957-10-16
Improvements in or relating to a new piperazine derivative and salts thereof
including penicillin salts thereof

PATENT i P ECWF CATION
784 L 897
4 Date of Application and filing Complete Specification Nov29, 1955.
No.34162/55.
Application made in France on Sept 29, 1955.
Complete Specification Published Oct 16, 1957.
Index at Acceptance: -Classes 2 (s), AA( 1 C 2 A: 2 C 1), B 14 (A 1:
M); 5 ( 2), J 33 F 2; and 81 ( 1), B 2 (C:
H: N: R), E 1 A 14 D o International Classification: -Z 23 A 6 k, 1 C
07 go COMPLETE SPECIFICATION
Irnproveklments in oh relatingg to a new Lniperazine Derivative and
Salts thereof including Penicillin Salts thereof We, LES LABORATOIRES
FRANCAIS DE CHIMIOTHERAPIE, of 89, Rue du ChercheMidi, Paris VIP,
France, a French Body Corporate, do hereby declare the invention, for
S 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: -
The present invention relates to 2,5-diphenyl-piperazine, salts of
penicillin with 2,5-dipheny 1-piperazine and a process for their
production; these new penicillin salts may be used in veterinary
medicine, treatment of humans, in agriculture and stock raising.
The definite salts which penicillin forms with organic bases have
become of increasing importance; for example, the salts of
benzhydrylamine, of procaine, of quinine or of
N,N-dibenzyl-ethylenediamine are used to a 2 ( large extent.
It has now been found that penicillins form salts with
2,5-diphenyl-piperazine (itself a new compound), which salts are
sparingly soluble in water The new salt of 2,5-diphenylpiperazine and
penicillin G enables the maintenance of an effective concentration of
penicillin in the blood for a prolonged period Its low toxicity
permits reasonable use thereof without risks of complications The
solubility in water of the salt of penicillin G with
2,5-diphenyl-piperazine in accordance with the invention places it
very advantageously in relation to other "delayed action" forms of
this antibiotic normally used The new salt gives the medical
practitioner a new weapon which is at least equivalent to the existing
forms of penicillin salts; in certain cases, the new salt enables a

more accurate dosage of penicillin, to avoid the formation of
resistant strains of microbes and to keep under control certain
individual sensitiveness, for example due to allergy.
Solubility in water in grams Salts of-penicillin-G-with: per litre
Benzhydrylamine 6 4 Procaine 4 5 Quinine 2 7 2,5-diphenyl-piperazine 0
35 Tests carried out with the new salt of penicillin G and
2,5-diphenyl-piperazine suggest that this new salt does not contain a
grouping in its molecule which grouping has a sensitizing effect on
being administered medicinally.
For example, it is lmown that the use of procaine penicillin can lead
to grave mishaps owing to sensitization of the human organism due to
the presence of a p-amino grouping in the procaine molecule These
mishaps are particularly described by Tzanck, Sidi and Dobkevitch (cf
C Albahary, "Maladies Medicamenteuses, Masson-Paris, 1953, page 121).
In accordance with the invention new compounds are
2,5-diphenyl-piperazine, the hydrochloride of 2,5-diphenyl-piperazine,
the acetate of 2,5-diphenyl-piperazine and the salt of penicillin G
with 2,5-diphenyl-piperazine.
Salts of any penicillin other than penicillin G or of any other
organic acid or any mineral acid with 2,5-diphenyl-piperazine also
fall within the scope of the present invention.
Also in accordance with the invention, a process for the production of
2,5-diphenylpiperazine comprises hydrogenating a
2,5-diphenyl-dihydro-pyrazine in the presence of a hydrogenation
catalyst and an inert solvent for said pyrazine; 2,5-diphenyl-pyrazine
may replace the said dihydro-pyrazine.
Further in accordance with the invention, a process for the production
of a salt of penicillin with 2,5-diphenyl-piperazine, comprises
reacting a water soluble salt of 2,5-diphenyllPrice 3 s 6 d l : -L
784,897 piperazine with a water soluble salt of penicillin in an
aqueous solution and isolating the resulting precipitated salt.
The salts of penicillins with 2,5-diphenylpiperazine may be produced
in an aqueous medium or in an aqueous organic medium by reacting a
solution in water, or in an organic solvent which is miscible with
water, of a salt of 2,5-diphenyl-pip erazine with an aqueous solution
of a penicillin salt Preferably 2,5-diphenyl-piperazine acetate is
used as the water soluble salt, and a triethylamine penicillinate is a
suitable water soluble salt of a penicillin, the double decomposition
reaction being effected in water and the salt being isolated by
filtering with suction or centrifuging, washing with water and drying.
It is self evident that the process of producing the new salts of
penicillin must be effected under sterile conditions when one requires
a product which may be used therapeutically.
As 2,5-diphenyl-piperazine combines with 2 molecules of a penicillin,

the new penicillin salts have the advantage of a very high activity in
relation to its weight which enables one to avoid administering
undesirably large amounts of products which is always troublesome.
The new salt of 2,5-diphenyl-piperazine with penicillin G is usually
administered parenterally in the form of a suspension in a suitable
suspension agent such as distilled water a normal saline solution, in
solution in an aqueous propylene-glycol ( 20 %) solution or other
aqueous diluents normally used It is likewise possible to administer
the new penicillin G salt in an oil such as arachis oil, sesame oil,
cotton seed oil or other triglycerides capable of being assimilated A
stabilising agent, a thixotropic agent, a viscosity modifier or a
wetting agent may be added in known manner to the preparation
containing the new salt of penicillin G, said agents being of a nature
such as to confer to the preparation the required properties for
injection in the patient by means of a hypodermic syringe.
The crystals may be previously ground The new salt of penicillin G may
likewise be used in the form of other known pharmaceutical or
industrial preparations such as compressed tablets, lozenges, granules
or on liquid carriers enabling its addition to animal feedstuffs or
its spreading on plants.
2,5-diphenyl-piperazine has never yet been described and is produced
by the reduction of a 2,5-diphenyl-dihydropyrazine; the
2,5-diphenyl-3,6-dihydro-pyrazine may be produced in accordance with
Gabriel (Ber, 1908, 41, 1127) 2 5-diphenyl-piperazine in accordance
with the present invention, having a melt.
ing point of 195-196 C, should not be confused with
NN-diphenyl-piperazine which has been known for a long time and melts
at 164-165 C.
The following examples illustrate the invention without, however,
limiting it Thus it is possibl to produce 2,5-diphenyl-pipea azn
starting from any 2,5-diphenyl-dihydro-pyrezine, to change the nature
of the solvents, that of the hydrogenation catalyst, the tempertures
and times of reaction without going outside the scope of the present
invention In order to produce the salt of a penicillin wikh
2,5-diphenyl-piperazine it is likewise possible to change the nature
of the solvents, the temperatures and times of reaction or to replace
the 2,5-diphenyl-piperazine acetate by any other salt of this base
having the required solubility properties, or even to substitute for
the triethylamine penicillinate a salt of penicillin with an alkali
metal, of an alkaline eartn metal or of an organic base providing th 1
at the solubility of the salt enables doub e decon_position to take
place It is l Jikewise possible to react penicillin acid with
2,5-diphenyl piperazinc in the medium of on oganic so vent for the
compounds and to separate th:

resulting salt e g, by precipitationr by means of a third solvent or
by evaporation to dryness of the react'aion mixture, which i: be
lo-wed by suitable washing operations.
Although it is in general preferred to use the salt of penicillin G it
is likewise possible, for special purposes, to use the salt of any
other penicillin (e g F, X or K) or a mixture of two or more of these
salts The new salt of the invention may likewise be used for
separating and purifying penicillin during i manufacture and
isolation.
so EXAMPLE 1
PRODUCTION OF 2,5-DIPHENYL-PIPERAZINE 100 STARTING FROM 2,5-Lr
IPHENYL-DIHYDROPYRAZINE g ef 2,5-diphenyl-3,6-dihydro-pyrazmne
produced in accsrdance with Gabril (Ber, 1908, 41, 1127), are
dissolved in 450 cc of 105 fcrirc acid, 5 g of palladium/carbon
catalyst containing 2 ' of 3 palladium are added and hydrogenation is
effected for six hours at ambient temperature Filtration is effected
in order to eliminate the pa'ladiu n/carbon 110 catalyst and 1800 cc
of animonia ( 22 Be) ae added to the fitrate while:ir ng and cooling
is eiected on arn ice bath so as not to exceed a temperature of 20 C,
the addition taking 2 hours Filtering with suction is effected, 115
washing with 300 cc of water and drying in a vacuum in order to obtain
44 g ( 87 %,) of 2,5-diphenyl-piperazine The product is purified by
dissolving in 10 volumes of ethanol, the addition of 2 volumes of
concen 120 trated hydrochloric acid is effected, cooling to 0 C,
separation of the hydrochloride, dissolution of the last named
material in 35 volumes of water and precipitation by 2 volumes of
ammonia ( 22 Be) 125 The product is present in the form of colourless
crystals which are sparingly soluble in wvater, soluble in alcohol at
an elevated temperature, insoluble in ether Melting point 784,897 =
195-196 C The ultra-violet spectrum comprises three characteristic
maxima:e 328 at 263 5 m/A e 453 at 257 5 mt e 405 at 251 5 my
Analysis: CH,-Is N 2 = 238 3 Calculated: C%' 80 6 H% 7 6 Found: 80 6 7
7 This product is new.
N%/ 11 7 11.7 EXAMPLE 2
PRODUCTION OF 2,5-DIPHENYL-PIPERAZINE STARTING FROM
2,5-DIPHIENYL-PYRAZINE g of 2,5-diphenyl-pyrazine in 100 volumes of
formic acid are reduced with hydrogen in the presence of 0 5 g of
palladium/ carbon catalyst containing 2 % of palladium.
After fixation of the theoretical amount of hydrogen worlding
conditions strictly analogous with the preceding example are used.
In this way there is obtained a product melting at 195-196 C with a
yield of 85 %, having all the characteristics of
2,5-diphenylpiperazine obtained in Example 1 On mixing the material
obtained in this example with a sample of this compound produced in

the preceding example no depression of the melting point is caused.
EXAMPLE 3
PRODUCTION OF THE SALT OF PENICILLIN G WITHI 2,5-DIPHENYL-PIPERAZINE 1
g of 2,5-diphlenyl-piperazine having a melting point of 195-196 C (on
a block), produced in accordance with the preceding examples, is
introduced into 100 cc of distilled water, 0 55 cc of crystallizable
acetic acid are added and heating on a water bath at 60-80 C is
effected until complete dissolution has taken place Filtering is
effected and cooling is allowed to proceed to ambient temperature A
solution of 4 g of triethylamine penicillinate G in 20 cc of distilled
water is then added to the resulting solution while stirring Cooling
to 10 C is effected and the crystalline mass is filtered with suction
and washed with distilled water In this way, after drying in a vacuum
in the presence of phosphorus pentoxide, there is obtained 3 5 g of
the bipenicillinate G of 2,5-diphenyl-piperazine having a melting
point (on a block) of 219 C (decomposition), lD 2 '0 =-212 + 2 ( 1 %
concentration in dimethylformamide) The yield amounts to 94 %o This
product is new It is present in the form of colourless prismatic
needles which are soluble in formamide, dimethylformamide,
methoxyethanol, soluble in an amount of 0 35 parts per 1000 in water,
insoluble in acetone, alcohol, chloroform, ether and other common
organic solvents.
Anaiysis: C Qs Hs 4 00 N So = 907.
Calculated: C% 63 6 H% 6 0 N% 9 2 S% 7 0 Found: 63 4 6 0 9 0 7 0
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