* GB784893 (A)

Description: GB784893 (A) ? 1957-10-16

Improvements in or relating to the use of certain methyl-irone isomers inperfumes

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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 BORON TRIFLUORIDE. 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

Description of GB784894 (A)

COMPLETE SPECIFICATION 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 hy- drocarbons 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 opera- tions. 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-burn- ing occurs. To this end the air, which is supplied from conduit 47, header 48, tubes 52 and header 53, is distributed through an- nular 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 sur- rounding 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

Description of GB784895 (A)

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 aggre- gate. 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 with- drawing 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 andlike products

Description of GB784896 (A)

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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 Translate this text into Tooltip

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up-to-date or fit for specific purposes.

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. COMPLETE SPECIFICATION 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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* GB784897 (A)

Description: GB784897 (A) ? 1957-10-16

Improvements in or relating to a new piperazine derivative and salts thereofincluding penicillin salts thereof

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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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