5046 5050.output

* GB785453 (A)

Description: GB785453 (A) ? 1957-10-30

Improvements in cracking hydrocarbons

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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 SPECICATION Inventors: WILHELM FLESCH and PAUL FEILER 785453 Date of Application and filing Complete Specification July 30, 1954. No 22267/54. Complete Specification Published Oct 30, 1957. Index at Acceptance:-Classes 55 ( 1), B( 3 B: 11); and 55 ( 2), D 2 (E: F). International Classification: -Cl Ob, j. COMPLETE SPECIFICATION Improvements in Cracking Hydrocarbons' We, BADISCHE ANILIN & SODA-FABRIK AKTIENGESELLSCRAFT, a joint stock company, organised under the laws of Germany, of Ludwigshafen on Rhein, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: It is already known to carry out the thermal cracking of gaseous liquid or solid hydrocarbons or materials containing the same, such as tars, mineral oils, oil residues or the like, for the purpose of producing hydrocarbons of lower boiling point, in particular olefines, as for example ethylene, or carburetted gases, by means of highly heated granular solid substances which serve as heat carrier and which are kept in rolling motion in a coherent layer.

These granular heat carriers can be for example coke, lignite coke, brown coal, charcoal or inert solid materials The drawback is encountered that considerable amounts of dust of the moving solid material, depending on the 2 conditions, are entrained with the gaseous and vaporous reaction products This dust collects in an attached condensation Plant together with the high boiling cracked products and asphalts, often in the form of difficultly senarable emulsions with condensed water It is then only possible with difficulty and expense to separate it from the liquid products and the water and can only be exploited with difficulty. We have now found that the thermal cracking of hydrocarbons in the presence of a layer of moving granular heat carrier at high temperatures of about 6000 to 9000 C can be carried out especially advantageously by separating the entrained finely-grained heat carrier in more than one stage after it leaves the reaction chamber The first separation, for example in cyclones, electrical high voltage fields or by ultrasonic or similar measures, takes place preferably at temperatures between about 400 and 600 C, at which practically no reaction lPrice 3 s 6 d) product is precipitated on the separating heat carrier The bulk of the entrained heat carrier is thus recovered free from oil In any case it contains only small amounts of asphalt The 50 further separation or separations then are carried out at such a low temperature that the high boiling cracked product is deposited as oil together with the remaining heat carrier particles 55 The oil-free and oil-containing portions of the heat carrier removed in the said manner from the cracked product can then be returned to the reaction chamber, the oil-free carrier material preferably separately from the oil 60 containing carrier material and the former preferably in the hot state. The return of the fraction obtained by separation of the dust together with the high boiling products is best when the said separa 65 tion is effected between 2000 and 4000 C by spraying in oil, in particular high boiling cracked products or the initial material itself. There is thus obtained a mass rich in dust and asphalt which flows well above 1000 C and 70 can be withdrawn without difficulty from the reaction chamber, either in the liquid form together with the initial material or in solid, broken form together with the heat carrier. The composition of the dust entrained bv the 75 cracked products depends on the nature, grain size and resistance to abrasion of the heat carrier, on the nature of the movement and on the cracking temperature In many cases the dust consists of fines or coke, lignite coke, 80 peat coke, charcoal or brown coal, mixed with carbon formed during the cracking and preferably in the form of carbon black. The first and also the second separation phase can be carried out in a

plurality of 85 stages. The main advantage of the process according to this invention consists in the fact that in this way no sticky deposits are formed which would clog the pipes and other parts of the 90 apparatus following the reaction chamber. Other advantages include the ready and simple AS, '2 c Ci, return and exploitation of the solid and high boiling substances entrained with the reaction gases, and the good separation of the dust and asphalt from the more valuable oil components. The following example will further illustrate this invention but the invention is not restricted to this example. EXAMPLE A cylindrical reaction chamber is charged to a height of 1 metre with coke (granulation 0 to 6 millimetres) The coke, originally situated on a grate, is kept in rolling motion bv the introduction of superheated steam At the same time oxygen is supplied above the grate by nozzles and a petroleum distillation residue through other nozzles above the first nozzles, so that a temperature of 7500 C is set up in the bed of coke Considerable amounts of coke dust are entrained by the gaseous and vaporous cracked products About 75,' of this dust is separated at 500 C in an attached cyclone; the dust is obtained in the dry state and contains only 4 % of asphalt and high boiling tarry components It flows back directly to the moving, incandescent coke bed through a return tube Immediately behind the cyclone, a mixture of asphalt and high boiling oil residue is injected into the hot gas-vapour stream and the residual dust is washed out with asphalts and high boiling oil at 3000 to 400 C The liquid mixture of dust and oil is returned to the incandescent coke bed through the oil supply pipe. The returned fine coke dust and the entrained carbon black formed by cracking is very reactive and readily gasified in the gas producer. The returned asphalts and oils are also decomposed to the desired gases and vapours.

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* GB785454 (A)

Description: GB785454 (A) ? 1957-10-30

Improvements in and relating to hydraulic accumulators

Description of GB785454 (A)

We, THE ENGLISH ELECTRIC COMPANY LIMITED, of Queens House, 28 Kingsway, London, W C 2, a British Company, do hereby declare the invention, for which we S 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 hydraulic accumulators which incorporate a flexible bag. According to the invention, a hydraulic accumulator of the kind containing a flexible gas-filled bag has separate liquid inlet and outlet ports and porous partition means separating the inlet port, the outlet port, and said flexible bag, said partition means being non-perforate and having a very fine porous structure so as to act as a filter and a smooth surface so as to be unlikely to puncture the bag. According to a feature of the invention, said partition means is so designed that the resistance offered by said means to liquid flow through the outlet Dort is less than the resistance offered by said means to liquid flow through the inlet port. According to a further feature of the invention, said porous partition means comprises a single member having a substantially homogeneous structure and a generally flat configuration, one side of which is smooth and faces the bag and the other side of which faces the inlet and outlet ports 3,5 and is shaped so as to provide a barrier between these ports which serves as a filter for liquid passing directly between the inlet and outlet ports. In order that the invention may be well understood two embodiments thereof will now be described with reference to the drawings accompanying the Provisional Specification in which:lPrice 3 s 6 d l Fig 1 shows a cross-section of a hydraulic accumulator having separate inlet and outlet ports but with a single porous partition; and Fig 2 shows a cross-section of a hydraulic accumulator having separate inlet and outlet ports but with two porous partitions. With reference to Fig 1, a hydraulic accumulator is shown to comprise

a cylindrical casing 4, having at one end an endplate 5 and at the other end an endplate 14 The endplates are attached by means of locking rings 7 A seal is afforded between endplate 5 and the casing 4 by the rim 8 of the rubber bag 9 and a seal between endplate 14 and the casing 4 is afforded by the gasket formed by the rubber ring 10 A gas pipe 11 forms an inlet and outlet duct for gas entering the accumulator, this gas serving to inflate the bag 9 within the accumulator The endplate 14 is ducted to provide distinct outlet and inlet ports 17 and 18 respectively and a porous partition 15 or sintered bronze is provided within the casing 4 adjacent the endplate 14, this partition having a projection 16 which separates the outlet ports 17 and the inlet port 18. The surface of the partition 15 which faces the rubber bag is smooth and curved so that it forms a rest for the bag Its purpose is two fold It prevents the bag from being trapped in the liquid outlet port when the liquid is discharged and it serves to prevent particles carried by the liquid from entering the part of the accumulator which contains the rubber bag This latter precaution protects the bag since if particles were to settle on the inner surface of the container casing they may puncture the bag when the bag is highly inflated and in close contact with the casing. An important feature of the accumulator construction shown in Fig 1 is that the inlet port 18 is separated from the main chamber Price 2 785,454 PATFENT SPECIFICATION Inventors:-JAMES LANGLEY RUSSELL and ERIC POTTAGE. Date of filing Complete Specification: Aug 16, 1955. Application Date: Aug 19, 1954 No 24159154. Complete Specification Published: Oct 30, 1957. Index at Acceptance: -Class 69 ( 2), Al. International Classification:-FO 3 c. COMPLETE SPECIFICATION. Improvements in and relating to Hydraulic Accumulators. of the accumulator by a portion of the porous partition which has a relatively small area in comparison with the area of the part of the porous partition which separates the main chamber from the outlet port Since the thickness of the partition is uniform, this results in the Dorosity of the partition in the inlet path being smaller than that in the outlet path. With reference to Fig 2, a hydraulic accumulator is shown which has two porous partitions One partition 19 is fitted in the liquid inlet port 20 and the other partition 21 is fitted in the liquid outlet port 22. The partitions are such that they rest flush with the inner surface of the endplate 23, which has a smooth surface The partition 21 besides

having a greater surface area is of thinner section than the partition 19 and, therefore, has a greater porosity It could have a different structure for this purpose. It is desirable that the porosity of the outlet path be greater than that of the inlet path. In an application in which the accumulator ' is required to afford an intermittent supply of liouid from a steady source, the rate of flow of liquid along the outlet path will be greater than the rate of flow along the inlet path The pressure difference across the :' partitions depends upon the porosity and the rate of flow of liquid and to reduce the pressure difference in the case of the high rate of flow along the outlet path the porosity of the part of the partition in this 3 path should be as large as the design criteria permit.


* GB785455 (A)

Description: GB785455 (A) ? 1957-10-30

Improvements relating to thermionic valve amplifier circuit arrangements


PATENT SPECIFICATION Inventor: JOHN ANGUS LESLIE Date of filing Complete Specification: July 21, 1955. Application Date: Aug 20, 1954. 785,455 No 24312/54. Complete Specification Published: Oct 30, 1957. Index at acceptance:-Class 40 ( 6), W 1 H( 1 A: 5: 8). International Classification:-HO 3 f. COMPLETE SPECIFICATION

Improvements relating to Thermionic Valve Amplifier Circuit Arrangements We, THE BRITISH THOMSON HOUSTON Co MPANY LIMITED, a British Company having its registered office at Crown House, Aldwych, London, W C 2, 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 thermionic valve amplifier circuit arrangements and has an important application in arrangements comprising a photoelectric cell feeding an amplifier. In many cases it happens that a photo-electric cell or other detecting device is at a considerable distance from the amplifier stage it feeds with the result that the capacitance of the connecting cable has a significant effect on the overall frequency characteristic and this capacitance combined with stray input capacitance may cause appreciable attenuation at high frequencies. The main object of the invention is to provide an improved arrangement for avoiding this drawback. According to the present invention a circuit arrangement comprises a two stage thermionic valve amplifier having positive feedback provided by a series resistancecapacity coupling between a tapping point on the anode resistor of the second stage valve and the grid of the first stage valve, and an input circuit having a photo-electric cell or similar detecfng device situated remote from the first stage and having a load resistor directly connected to the grid of the first stage by a cable, the values of the resistor and capacitor in the feedback circuit being chosen so that in conjunction with the load resistor and the capacitance of the cable, they modify the frequency response characteristic of the amplifier so as to compensate for any distortion due to the capacitance of the cable. In order that the invention may be more lPrice 3 s 6 d l clearly understood, reference will now be made to the drawing accompanying the Provisional Specification which shows a circuit arrangement embodying the invention, and to the accompanying drawing (numbered Figure 2) which shows a graph of frequency corrections obtainable by practising the invention. In the circuit arrangement shown the detecting device P is a photo cell in series with a load resistance R 2 whilst the voltage developed across R 2 is amplified by a two-stage resistance capacity coupled amplifier consisting of the valves V 1 and V 2. Positive feed-back is provided by the feedback coupling R 1, Cl between the points Q and P where Q is a tapping point in the anode resistor R, of the valve V,. It will be appreciated that the combined cable capacity and stray

capacity C 2 in shunt with the ballast resistance R 2 forms a shunt circuit in series with the series coupling circuit C 1 R,. The frequency at which maximum compensation occurs is determined by the products R 1 R 2 and CQ,C and the magnitude of the compensation is dependent upon the gain of the amplifier between the points P and Q. In the circuit shown the maximum compensation will be provided by the feed-back circuit when the feed-back voltage at the grid of V 1 is in phase with the signal voltage. This will occur at the frequency f O of maximum response of the feed back circuit at which 1 fo = 2 r V/R 1 RC 1 C 2 then if we make R, = 10 R 2 and C, = 10 C it follows that 1 f or and it will be observed that R, and C, are D comnponents, the values of which can be selected to meet any particular requirements. Having determined the frequency of maximum response, the magnitude of the response at this frequency is dependent upon the gain of the amplifier between the points P and Q as stated previously. Typical values for the elements of a circuit according to the invention in which the input is provided by a photoelectric cell situated ft from an amplifier having a pentode valve as the first stage, would be as follows: Cable capacitance at 15 p F/ft + Stray capacitance= 160 p F. Load resistance R 2 = 1 M -I. This will produce an attenuation of 3 d B at 1000 cycles per second as shown by the Graph ( 1) in Figure 2, but by the addition of R, and Cl, where R,= 10 m -7 and C,= 16 p F, and by altering the value of R, to modify the gain of the amplifier between points P and Q, desired frequency corrections can be produced These are shown by Graphs 2, 3 and 4 of Figure 2. For Graph 2 the amplification in one embodiment was 10 5 and f,,= 2 kc/s; for Graph 3 amplification was 15 and f O = 3 kc/s; while for Graph 4 amplification was and f O = 4 kc/s.


* GB785456 (A)

Description: GB785456 (A) ? 1957-10-30

Improvements in or relating to wire, rope, strip and like feeding apparatus


PATENT SPECIFICATION 785,456 Invenztois:-JOHANN OTTO SMERD, DONALD ERNEST SHEWARD and GEORGE ERNEST LOWETH BULLOCK. Daftnf of fliny Com Sbplete Speciftcation: Nov 30, 1955. Application Date: Aug 31, 1954 No 25293154. O Jg Complete Specification Published: Oct30, 19577. Index at Ac Oeptanee:-Classes 78 (b), 114; and 83 ( 4), G(M;: 2 A 4: 213 4). International Classification:-B 211 B 66 d. COMPLETE SPECIFICATION. Improvements in or relating to Wire, Rope, Strip and like Feeding Apparatus. We, BRITISH WIRE PRODUCTS LIMITED, a British Company, of Stourport-on-Severn, Worcestershire, 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 apparatus for feeding wire and the like and has for its chief object to evolve such an apparatus which may be applied to or employed in conjunction with wire using machines, such, for example, as automatic chain forming machines. In works employing wire using machines it has hitherto been the Dractice either to obtain from an independent source supplies of wire already drawn to the correct size for use in such machines or alternatively to draw the wire as a separate operation and subsequently to reel it on to swifts or the like which are stored until the wire is required for use in the machines. It is a further object of the invention to provide an apparatus of the kind indicated above for use in conjunction with a withdrawing die so that machines such as chain forming machines may be operated to use hot rolled rod, or the like as the raw material, the latter being by the operation of such apparatus, drawn into wire at the rate at which it is required, at the time it is required, and without the necessity for reeling or storing or for employing any labour additional to that

required for operating the wire using machine By drawing the wire immediately before feeding it to a wire using machine it (the wire) will be in a more suitable condition for forming than it would be after long periods of lPrice 3 s 6 d l storage subsequent to wire drawing and furthermore a considerable amount of transport and handling associated with conventional methods of wire drawing will be completely eliminated. It may be mentioned here that the apparatus when used in conjunction with a wire drawing die is not confined to the use of hot rolled rod since extruded bar, partly processed wire, strip or profiled sections or any other material processed in long lengths of uniform cross section which it is desired to pass through a drawing immediately adjacent to and in conjunction with any machine consuming such material may be utilised. According to the invention the apparatus will comprise a rotatable drum around the periphery of which the wire may be passed and having a plurality of means adapted positively to grip or clamp the wire against movement relatively to the drum when the drum is rotated whereby on rotation of the drum the last-mentioned means act positively to grip or clamp the wire for part at least of each revolution of the drum and to release the same after a predetermined passage around the drum In one preferred embodiment the drum is provided at its periphery with a plurality of clamping devices and means are incorporated whereby said clamping devices will be caused successively to grip the wire and to maintain a gripping or clamping action thereon for a predetermined part of each complete revolution of the drum The operation of the clamping devices may conveniently be controlled by means of a cam, the arrangement being such that each device will be rendered operative during movement through a predetermined arc e g through 1800 and inoperaS( 1 785,456 tive through the remainder of each complete revolution of the drum It will be appreciated that it would be equally possible to used instead hydraulically operated clamps which could be timed by means of mechanically or electrically operated valves. Instead of providing clamping devices of the kind described, it may be feasible to employ one or more radially directed plunger elements or the like fitted with rollers which are separate from the drum and are adapted to remain stationary relatively thereto, such element or elements being effective to hold the wire tightly against the periphery of said drum. In order that the said invention may be clearly understood and readily carried into effect the same will be hereinafter more fully described with reference to the accompanying drawings, in which:Figure 1 is a plan view and illustrates a layout wherein the apparatus of the

invention is employed in conjunction with a stationary wire drawing die the drawn wire being fed to a wire using machine, Figure 2 shows in cross section one form of apparatus according to the invention, Figure 3 is a side elevational view illustrating diagrammatically a modified form of apparatus. Referring now to Figure 1, 10 denotes a length of hot rolled rod or partly processed wire which, by means of the apparatus indicated generally by 11, is drawn from one or other of two swifts 12 through a stationary wire drawing die 13 of conventional design and thereafter fed into a automatic wire using machine indicated at 14. The apparatus 11 as will be seen from Figures 1 and 2 comprises a drum 15 which is conveniently journalled for rotation about a fixed vertical shaft or post 16 The drum is provided with a worm wheel or ring 17 and is adapted to be driven through the medium of a worm 18 carried by a shaft 19 to which a drive is transmitted from a power source 20 Disposed at spaced points around the periphery of the drum is a plurality of clamps or the like 21, each clamp or the like comprising a stationary lower jaw 22 and a movable upper jaw 23 which latter is capable of limited vertical movement towards and away from the lower jaw in order to effect closing and opening of the clamp Each movable jaw 23 is carried by a vertical rod or the like 24 and is constrained by virtue of the provision of suitable guides on the perinhery of the drum to move in a vertical Dath The rod or the like 24 is pivotally connected at its upper end to one end of a lever arm 25 which is in turn pivoted at a point intermediate its ends, the other end of said lever arm having pivotally connected thereto a second verti6.3 cally depending rod or the like 26 The second rod or the like 26 which is supported for free vertical movement in guides 27, 28 mounted internally of the drum, carries at its lower end a freely rotatable roller 29 which is adapted to co-operate with a circu 70 lar cam track 30 fixedly located below said drum and concentrically with respect to the axis of rotation of the latter 31 denotes a coiled spring which is interposed between a flange on the lower guide 28 and a flanged 75 collar 32 fixedly mounted on each rod or the like 26 As will be appreciated the function of the springs 31 is to urge the rods or the like 26 downwardly thereby to effect raising of the associated movable jaws 23 80 The cam track 28 may be so formed that in the course of one complete revolution of the drum the aforesaid rollers 29 will travel along an elevated path during approximately one half revolution thereby to maintain the 85 movable clamping jaws 23 in their lower or operating position while during the next half revolution, said rollers will move at a lower level, the rods or the like 26 being moved downwardly under the action of their res 90 pective springs 31 thereby to cause the movable jaws 23 to be

retracted upwardly so that the clamp will be inoperative. Obviously by appropriate designing of the cam 30 the relative period of clamp opening 95 and closing may be varied to suit any particular requirements In operation of the apparatus above described the rot rolled rod or partly processed wire 10 (Figure 1) which is preferably in the form of a coil, and 14 t 3 carried by a swift or the like such as is indicated at 12 (Figure 1) will initially be pointed and passed through the stationary drawing die 13 In one simple and convenient mode of starting the drawing operation a drive 105 will be imparted to the drum 15 and the first few feet of wire will be drawn through the die 13 by means of an auxiliary grip of known type which is connected to a convenient anchorage point on the drum by a 110 length of chain, wire rope or the like As the first few feet of wire is drawn from the die 13 it will by the action of the apparatus be bent around the periphery of the drum and thus automatically be fed,into the 1153 clamps 21 The arrangement is such that as each clamp 21 is moved by virtue of the rotation of the drum into the nath of the wire leading to the latter from the die it will be caused to close on the wire and 120 tightly to hold the same on to the drum during approximately half of one revolution. It will be appreciated that as soon as the wire is effectively gripped by one or more clamps 21 the auxiliary grip and its asso 1 '25 ciated chain will be removed Numerous other methods of starting the drawing operation would appear to be possible and practicable Thus the pointed end initially passed through the die 13 can be made long 1230 arrangement of somewhat the form -indicated in Figure 3 Referring now to the construction shown in that Figure the pointed end of the rod which is initially inserted through the stationary die 13 may be gripped 70 as before by an auxiliary grip of known type which is coupled to a rotatable drum 34 by means of a chain so that on rotation of said drum the wire will be wound around the latter In this case a plurality of turns 75 of wire, e g three, is taken around the drum and one or more radially directed plunger elements 35 are employed to hold the wire sufficiently tightly against the drum to pre. vent slippage upon the removal of the 80 auxiliary grip and its associated chain The or each plunger element 35, which as indicated in Figure 3 incorporates one or more rollers 36 at the head portion thereof adapted to engage the wire as it passes 85 around the drum, may be urged by one or more springs into its operative position or it may be actuated hydraulically or by mechanical means. It will be ap Dreciated that the aforemen 90 tioned drum provided with its plurality of clamping means is not limited in its application to the continuous drawing of wire and feeding the same to a wire-using machine but that it may also be used for 95 any purpose where it is

desired to pull a length of flexible material such as wire, string, rope, thread, ribbon, tape, cable or the like continuously and forward the same. It is to be understood, therefore, that in the 100 claims relating to the said drum the references to wire are to be taken as including references to any such long flexible material as aforesaid. It will be appreciated that it is not neces 105 sary that the plurality of clamping means be arranged around the periphery of a drum as herein described but that the same result can be achieved by means of a plurality of clamps arranged in any manner that will 110 enable them successively to grip the wire, draw it continuously and then release it so as to pass it forward e g to the wire using machine Thus the clamus might be arranged Upon an endless chain caused to 115 travel a path of circular oval or other form arranged so that the clamps may grip the wire, draw it continuously and then release it so as to pass it forward as aforesaid It is to be understood therefore that the refer 120 ences to the drum in the claims relating to the drum are to be taken as including references to any drum, cage, endless belt, endless chain or the like whereby the said plurality of clamping means may be caused 2-5 to perform the desired sequence of operations. Finally it may be mentioned that in some cases it may be desirable to instal a heating unit between the wire drawing unit and the 130 enough to be fed into one or more clamps 21 without the aid of intermediate gripping devices Furthermore, it should be possible to form a temporary, or permanent, junction between the end of one coil and the beginning of the next so as to render a repetition of the described starting operation unnecessary once a long production run has been initiated At the end of approximately 1800 travel from its initial closure point each clamp 21 will be opened to release the wire which will tend to leave the drum in a tangential direction In order to guide the wire and to prevent it from springing outwardly from the drum on release from the clamps it may be desirable to provide a freely rotatable guide roller such as in indicated at 33 (Figure 1) The wire leaving the drum may be passed over or through guide means which will cause the same to form a loose loop and will also guide it into the machine to be served, i e in the present case the automatic wire using machine 14 Preferably the arrangement will be such that the loose loop will provide sufficient reserve of wire to enable the machine to which the wire is being fed, if of an intermittently operating nature such as a chain-forming machine, to complete :30 one or possibly two or more operative cycles without any interference being caused between the wire drawing equipment and the machine feed The described manner of providing a reserve of wire in the form of a

loop is of particular advantage where the intermittent operating cycle of the consuming machine or other causes render complete synchronisation impracticable Whereas the provision of such a loop is also an advantage in other cases, it may be possible in some application to pass the wire directly from the drum into the machine to be served. By providing, for example, a variable speed motor for driving the drum 15 and by incorporating known devices for controlling such a motor, it will be feasible so to control the speed of rotation of the drum that wire drawing will proceed at a rate appropriate to that at which the wire is being consumed by the machine being served Instead of employing a variable speed motor, it is, of course, possible to use any other form of equipment such as variable speed gears, mechanical, electrical or hydraulic slipping clutches and the like which lend themselves to controlling the speed of one driven member in relation to that of another By using a device of that kind it should be possible to use one common d O prime mover for both the wire drawing unit and for the wire consuming machine. The apparatus above described may conceivably be modified in several respects For example, it may be feasible to dispense with 635 the clamps 21 entirely and to employ an 785,456 using machine for the purpose of stress rel-ieviing the drawn wire belore entry into said machine.


* GB785457 (A)

Description: GB785457 (A) ? 1957-10-30

Phosphated metallisable azo dyestuffs

Description of GB785457 (A) Translate this text into Tooltip

[75][(1)__Select language] Translate this text into

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 785457 Date of filing Complete Specification: Aug 8, 1955. Application Date: Sept 10, 1954. No 26268/54. Complete Specification Published: Oct 30, 1957. Index at acceptance:-Classes 2 ( 3), C 2 (A 2: E: T 17), C 3 A 14 B( 3 C: 8 A); and 2 ( 4), D 1 L, P 1 A 2 82 B, P 2 G( 2 B: 3: 5 A: 6 A: 6 X), P 2 H( 3: 9:10:11: 21: X), P( 3 D: 4 F: 9 A 4 B). International Classification:-CO 7 d 2, f C 09 b. COMPLETE SPECIFICATION Phosphated Metallisable Azo Dyestuffs We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, of Imperial Chemical House, Millbank, London, S W 1, a British Company and ALEXANDER ROBERTUS TODD, of the University Chemical Laboratory, Pembroke Street, Cambridge and GERALD BOOTH and ROBERT RONALD DAVIES, both of Hexagon House, Blackley, Manchester, all British Subjects, 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 metallisable azo dyestuffs and more particularly it relates to phosphated metallisable azo dyestuffs derived from diazotised o-aminophenol phosphoric esters. It has been proposed and claimed in British Specification No 747,872 to manufacture metallisable azo dyestuffs by diazotising an oaminophenol sulphuric acid ester and coupling the diazo compound so formed under alkaline conditions with a coupling component which contains at least one coupling position adjacent to a metallisable group, the coupling being effected in the said coupling position. We have now found that in the said process there may be used, in place of the o-aminophenol sulphuric acid ester the corresponding o-aminophenol phosphoric acid ester The diazotised o-aminophenol phosphoric esters show similar rapid coupling behaviour to the diaztosed o-aminophenol sulphuric esters and, provided that diazotisation be conducted under conditions designed to avoid hydrolysis, namely at a temperature below O C and using substantially

the theoretical quantity of sodium nitrite, offer a method of synthesising dyes not readily obtainable from diazotised orthoaminophenols which are very slow couplers. Thus according to our invention we provide in the first place a process for the manufacture of new phosphated metallisable azo dyestuffs which comprises diazotising an o-aminophenol phosphoric acid ester and coupling the diazo compound so formed under alkaline conditions with a coupling component which contains at least one coupling position adjacent to a metallisable hydroxyl or potential hydroxyl group, the coupling being effected in the said coupling position. Also according to the invention we provide the new phosphated metallisable azo dyestuffs obtainable by the process stated above. The new dyestuffs of the present invention are more readily soluble in water than are the corresponding sulphuric acid esters and are thus useful for application to cellulosic fibres and other fibres and fabrics for example those made from or containing nylon and other polyamide and polyester fibres and/or from cellulose acetate rayon by the after-coppering process by which process they readily give insoluble copper complexes on the fibre and so produce dyeings possessing very good light fastness in the same way as do the corresponding sulphuric acid ester dyestuffs of British Specification No 747,872 The new dyes often possess greater stability under dyebath conditions than the corresponding sulphuric ester dyes. The o-aminophenol phosphoric acid esters which are used as starting materials may be obtained from the corresponding nitrophenol by phosphation by means of for example phosphorus pentoxide in triethylamine followed by reduction of the nitro group. The coupling components used in the process of this invention may be any azo dyestuff coupling component containing at least one coupling position adjacent to a metallisable group, that is to say a hydroxyl group or a potential hydroxyl group, being one available by keto-enol tautomerisation Suitable coupling components are more fully described in British Specification No 747,872. The invention is illustrated but not limited by the following Examples in which the parts are by weight. EXAMPLE 1 A solution of 1 89 parts of o-aminophenol phosphoric acid ester dissolved in 100 parts of water is cooled to 5 s C 2 4 parts of i ON aqueous hydrochloric acid are added to the solution kept at 00 C to -50 C and then a solution of 0 7 part of sodium nitrite in 20 parts of water is added rapidly below 00 C. The resulting mixture is stirred for 5 minutes at -5 to 00 C and then added at 00 C to a solution of 1 73 parts of 4:41-bis(

311-methylpyrazol-511-one-lll-yl) diphenyl and 7 parts of 2 N-aqueous caustic soda solution in 25 parts of 3 ethoxyethanol and 75 parts of water The mixture is maintained alkaline to Brilliant Yellow by the simultaneous addition of 70 1 S parts of 2 N aqueous sodium carbonate solution The mixture is then stirred for 2 hours at 00 C to 50 C and filtered The solid residue is washed, mixed with 0 15 part of dextrine and dried. The product dyes cotton from an alkaline bath in orange shades which become very fast to light and washing when given a normal after-coppering treatment. is Replacement of the 4:41-bis-( 311-methylpyrazol-511-one-1 " 1-yl)diphenyl by 1 86 parts of 4:4 -bis-( 311-methylpyrazol-511-one-111-yl)stilbene in the above process gives a dyestuff of similar properties which gives yellow-brown after-coppered shades. Replacement of the 4:41-bis-( 3 '1-methylpyrazol-511-one-111-yl)diphenyl by 2 92 parts of bis-( 61 "-hydroxy-2 " 1-naphthoyl) 3: 31-dimethoxybenzidide in the process of the above Example gives a disazo dyestuff of similar properties which gives bluish-red aftercoppered shades. Replacement of the 4:41-bis-( 311-methylpyrazol-511-one-111-yl)diphenyl by 0 75 part 5:6-dihydroxyindazole in the process of the above Examples gives a disazo dyestuff of similar properties which gives a blue aftercoppered shade on cotton. The solution of o-aminophenol phosphoric acid ester used in the process of the above Example may be obtained as follows: 17 parts of phosphorus pentoxide are added over a period of 5 minutes to a mixture of parts of triethylamine and 125 parts of ethylene dichloride stirred at a temperature SO below 10 WC 14 parts of o-nitrophenol are then added and the resultant mixture is heated to 82 WC and agitated under reflux for 2 hours at 82-840 C The mixture is then added to a solution of 15 parts of sodium carbonate in 100 parts of water and the mixture is steamdistilled to remove ethylene dichloride and triethylamine The solution of o-nitrophenol phosphoric acid ester thus obtained is reduced by addition to a mixture of 75 parts of iron, 4 parts of ferrous sulphate and 80 parts of water at 90 C with the simultaneous addition of 10 parts of glacial acetic acid The mixture is stirred at 85-90 C for 2 hours and is then made alkaline to Brilliant Yellow by the addition of 2 parts of sodium carbonate It is then filtered at 85-90 C, and the solid residue is washed with 50 parts of hot water The combined filtrate is extracted with ether and may then be used directly for the preparation of azo dyestuffs 70 Preparation of 4:4 '-bis-( 311-methylpyrazol511-one-1 " 1-yl)-stilbene used in the above

Example may be carried out as follows: 21 parts of 4:41-diaminostilbene are suspended in a mixture of 150 parts of water and 75 parts of concentrated hydrochloric acid and tetrazotised at a temperature below 10 C by the addition of a solution of 14 parts of sodium nitrite in 50 parts of water The tetrazo solution is filtered and the filtrate is added at 80 0 C to a solution of 120 parts of stannous chloride in 140 parts of concentrated hydrochloric acid and the mixture is stirred at a temperature below 10 C for 18 hours The 4: 41-bis-hydrazine stilbene dihydrochloride 85 thus obtained is separated by filtration and, after washing with 100 parts of 10 % hydrochloric acid, is stirred with 500 parts of water and neutralised to Delta paper by the addition of sodium carbonate 26 Parts of ethyl aceto 90 acetate are added and the mixture is stirred for 2 hours at 40-50 C 75 Parts of l ONsodium hydroxide solution and 200 parts of ethyl alcohol are added and the mixture is heated at 90 C for 2 hours The resultant 95 solution is filtered and the product is precipitated by the addition of 70 parts of concentrated hydrochloric acid The precipitate is filtered off, dissolved in sodium carbonate solution, reprecipitated with hydrochloric acid 100 and dried The 4:41-bis-( 311-methylpyrazol511-one- 11 l-yl)stilbene thus obtained melted at 320 C with decomposition. EXAMPLE 2 A solution of 1 89 parts of o-aminophenol 105 phosphoric acid ester in 100 parts of water is diazotised as is described in Example 1 and the resulting diazo solution is coupled in the manner described in Example 1, using as coupling component 1 76 parts of 4: 41-bis 110 (acetoacetamino)diphenyl in solution in a mixture of 75 parts of 13-ethoxyethanol, 75 parts of water and 6 parts of 2 N aqueous caustic soda solution, the mixture being maintained alkaline by simultaneous addition of 50 parts 115 of 2 N aqueous sodium carbonate solution The dyestuff obtained dyes cotton from an alkaline bath in yellow shades which are rendered very fast to light and washing by an acidic aftercoppering 120 Replacement of the 1 76 parts of 4: 4 '-bis(acetoacetamino)-diphenyl in the process of the above Example by 1 9 parts of 4: 41-bis(acetoacetamino)-1: 11-azobenzene gives an equally valuable dyestuff of yellow-brown after 125 coppered shade of good light and wash fastness. Replacement of the 4: 4 '-bis(acetoacetamino)-diphenyl in the process of the above Example by 2 06 parts of 4:41-bis(acetoacet 130 785,457 2 hours at 0-5 C and is then filtered The solid residue is washed with 20 parts of N/2 aqueous sodium carbonate solution, mixed with 0.15 part of dextrine and dried The product dyes cotton from an alkaline bath in reddish 60 brown shades which become very fast to light and washing when given a normal acidic aftercoppering treatment.

EXAMPLE 5 A solution of 1 89 parts of o-aminophenol 65 phosphoric acid ester in 100 parts of water is diazotised as is described in Example 1 and the resulting diazo solution is coupled in the manner described in Example 1, using as coupling component 1 5 parts of fl-naphthol in 70 solution in a mixture of 75 parts of,,-ethoxy ethanol, 75 parts of water and 6 parts of 2 N aqueous caustic soda solutiori, the mixture being maintained alkaline by the simultaneous addition of 50 parts of 2 N aqueous sodium 75 carbonate solution The dyestuff is isolated and dried as described in Example 1 When the dyestuff is applied to nylon from a neutral dyebath in the presence of ammonium acetate and the dyeing is subsequently given an acidic 80 after-coppering treatment, a rubine shade of good fastness to light and washing is obtained.


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