EP1036236B1 - Verfahren zur herstellung von zellstoff - Google Patents

Verfahren zur herstellung von zellstoff Download PDF

Info

Publication number
EP1036236B1
EP1036236B1 EP98944033A EP98944033A EP1036236B1 EP 1036236 B1 EP1036236 B1 EP 1036236B1 EP 98944033 A EP98944033 A EP 98944033A EP 98944033 A EP98944033 A EP 98944033A EP 1036236 B1 EP1036236 B1 EP 1036236B1
Authority
EP
European Patent Office
Prior art keywords
boiler
screw
solution
pulp
feeder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98944033A
Other languages
English (en)
French (fr)
Other versions
EP1036236A1 (de
Inventor
Vladimir Krotov
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB9719479.9A external-priority patent/GB9719479D0/en
Application filed by Individual filed Critical Individual
Publication of EP1036236A1 publication Critical patent/EP1036236A1/de
Application granted granted Critical
Publication of EP1036236B1 publication Critical patent/EP1036236B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C7/00—Digesters

Definitions

  • This invention relates to a method for the production of pulp from raw plant material, preferably by percolation organic solvent boiling. Most particularly the invention relates cellulose production from ground hemp stocks from the preliminary hemp processing at the fibre plants.
  • bast-fibre plants consist of two different raw materials, the bast which comprises 20-25% of the plant, and the woody fibres that comprise the remainder of the plant. It was found initially when using these plants as raw materials that typical pulping conditions may be optimum for the bast portion but may not be optimum for the fibrous portion.
  • bast fibre plants such as hemp, flax, and kenaf
  • kenaf is based on the separation of stalks into its two parts: bast (fibre) and woody (shive).
  • the mechanical separation of stalks by this conventional technology typically involving stock preparation and its processing on breaking, scutching and hackling machines, is not only expensive, but also generates large quantities of waste, including both dust and chemical waste.
  • AAS pulping is unrivalled in both the selectivity and the extent of delignification of the raw plant materials.
  • a significant advantage of this drip percolation and the unit disclosed by Krotov et al. was the effective reduction in environmental pollution. It is ensured by the closed-cycle production which is carried out in a space entirely isolated from the environment, with complete absence of effluents, including dirty condensates. Non-condensable gases are collected without entrained air and can be taken for neutralisation. This differs from multi-unit plants with a great number of unpressurized vessels where gas emissions are distributed along the production line, entrain air and are inevitably released into the atmosphere.
  • Prex impregnation Before the raw material enters the digester, it undergoes a process known as Prex impregnation. A small portion of the raw material within the feeder apparatus (for a digester) is compressed and then expanded. At the point of expansion, the pulping liquor is injected into the feeder apparatus, whereby the raw material acts as a sponge and absorbs the liquid. This technique allows a significant proportion of the raw material to come into contact with the pulping liquor. However, it is unlikely that using the disclosed apparatus results in all the material being saturated. There thus exists the possibility of improving the technique by developing an improved feeder apparatus. Further, the prior art document does not discuss variations in condition, such as temperature for example that might improve this method of impregnation.
  • the document GB-A-753,377 discloses a method as defined in the pre-characterizing portion of claim 1.
  • the document US-A-3,096,234 discloses a continuous digester system with a pressure differential between a digester and a dilution tank.
  • the present invention seeks to create an improved method by which a single, closed unit can be operated continuously for cellulose production from fibrous raw plant material.
  • the unit in an embodiment must use AAS pulping technology and drip percolation and thus retains the advantages of these methods of delignification.
  • the unit must simultaneously perform the operations of saturation of the raw plant material by boiler solution, boiling (delignification) of the raw plant material, washing of the fibrous product, regeneration of the organic solvent, residue water and chemicals from the used boiler - washing solution, dehumidification of the washed fibrous product, collection and absorption of the steam and gases and preparation of the boiler solution from the recovered and fresh chemicals.
  • the unit seeks to provide the improved Prex impregnation of the raw material.
  • a further object of the invention is to improve the processing of the washed and cooked plant material and in particular to improve the efficiency of the collection - particularly from the cooking apparatus - dewatering and predrying of the fibrous product (pulp). Also the invention seeks to improve the collection, condensation and absorption of vapours released in the delignification, the collection, cleaning and centralised discharge for neutralisation and utilisation of non-condensable gases and also the preparation of pulping liquor from the recovered chemicals.
  • Another object of the invention is to produce a method which realises few waste products, and does not need fresh water technology or gas treatment facilities for processing the raw plant material into high quality cellulose.
  • the method should be raw material, cost and energy efficient.
  • a method for the production of pulp from raw plant material comprising in sequence: regulating the input of raw material into a boiler by means of a first feeder containing a screw having a prolonged stem which extends beyond the screw thread; cooking the raw material in said boiler to generate pulp; receiving cooked material from the boiler in a second feeder extracting liquid from the cooked material in a liquid extraction apparatus; treating the material received from the liquid extraction apparatus with steam in an unloader maintained at a lower pressure than the liquid extraction apparatus; receiving pulp from the unloader in an accumulation reservoir; and removing pulp from the accumulation reservoir; characterised in that the regulating step includes injecting boiler solution into the raw material through a passage in the prolonged stem and that said second feeder is maintained at a lower pressure than the boiler.
  • the unit used to carry out the method is composed of two sections whereby the first section for the preparation of the boiler solution comprises: a first mixing device into which water is fed, a plunger pump with adjustable inputs, a first scrubber into which ammonia is fed by a first output tank, a first "tube in tube” heat exchanger, a second scrubber the contents of which are fed into a second tank; and the section for the boiling of raw material comprises; an input bunker, a spiral feeder, an inclined spiral conveyor, a boiler, a second mixing device, a second "tube in tube” heat exchanger, a rotor feeder, a dividing bunker, a screw apparatus, a screw unloader, a fluffer, an accumulation reservoir, a screw conveyor, a first casing tube heat exchanger, a fourth output tank, a first vaporising apparatus, a steamer, a second casing tube heat exchanger, a fifth output tank, a second vaporiser apparatus, a third vaporiser apparatus, a first cyclone,
  • the two sections that together comprise the unit are respectively shown in Figures 1 and 2.
  • the two sections are not separate entities but are constructed to interlink through specific pieces of apparatus; the two sections together form the closed cycle of the unit.
  • Figure 1 relates to the section for the preparation of the boiler solution.
  • ammonia water with an ammonia concentration between 25 and 27% is used, as well as sulphur dioxide, technical (95%) ethanol and water.
  • Water for the preparation of the boiler solution is supplied into the mixing device 2, which can also serve as a pot for the preparation of hard or liquid chemicals.
  • the water is sent via the means of the plunger pump with adjustable input 7, 7a (working and spare respectively) from the mixing device 2 to the first scrubber 3 which is in the tail.
  • Condenser 28 supplies non-condensable gases in to the first scrubber 3 where they are absorbed by the water which thus removes impurities. Non-purified gases also enter the first scrubber from the second scrubber 4.
  • the section for the preparation of the boiler solution is hermetic and works under raised pressure.
  • the first scrubber 3 works under atmospheric pressure, and in the all the following apparatuses the pressure is slowly raised depending on the aerohydrodynamic resistance.
  • the weak solution from the first scrubber 3 goes via the pump 7b through the first 'tube in tube' heat exchanger 5 to the second scrubber 4.
  • the 'tube in tube' heat exchanger has a different temperature within the tubes than between the tubes.
  • the temperature within the tubes is considerably lower than that between them, typically the inside of the tubes being between 25 and 75 degrees celsius and that between the tubes being about 100 degrees.
  • Sulphur dioxide is fed into the second scrubber 4 from the tank system. Sulphur dioxide feeding is also provided for the scrubber 3 as well.
  • the scrubber 4 is also supplied with ammonia water for irrigation from the output tank 6 by the pump 7c.
  • the output tank 6 is equipped with injectors, from which water is supplied to ensure safety of the servicing.
  • the solution from the second scrubber 4 is fed by the pump 7d to the tank with ready boiler solution, the mixing device 2a.
  • Plunger pumps with regulated flow 7a, 7b, 7c and 7d work without reserve but the scheme allows for these pumps to be interchanged.
  • Figure 2 shows the section of the unit for the boiling down of the raw plant material, typically composed of ground down hemp stock from the fibre plants.
  • the raw material comes from storage into the input bunker 8.
  • the input bunker 8 is situated immediately above the loading carbine of the spiral feeder 9 as illustrated in Figure 2.
  • the input bunker 8 itself is illustrated in Figure 3. It is equipped with a stirring device 80 which prevents raw material from getting stuck, as well as with a screw 81 for pressing the raw material.
  • the stirring device 80 is typically rotated at between 0.25 and 0.52Hz (15 and 31 rotations per minute).
  • the number of arms of the stirring device 81 is not limited to the two illustrated in the figure, but can be varied according to the required input rate of the raw material.
  • the amount of raw material passing through the input bunker 8, and also the extent to which the raw material is pressed are controlled by changing the spinning speed of the screw 81, the speed being controlled by a thyristor converter. Such a converter serves as a control over the engines driving the equipment.
  • the input bunker 8 will have a working volume of not more than 1.8 cubic metre. This volume ensures that the raw material is efficiently pressed before passing out of the bunker 8. Input and output from the bunker 8 are closely controlled such that the productivity of bunker 8 is within the range of 3.7 to 10.0 cubic metres / hour.
  • the pressed raw plant material is loaded from the input bunker 8 directly into the spiral feeder 9 situated immediately beneath it.
  • a cross-section through the feeder 9 (along the line illustrated in Figure 2) is illustrated in Figure 4.
  • the purpose of the feeder 9 is to further regulate the movement of the raw material to ensure a continuous flow of raw material into the boiler 11.
  • the feeder 9 consists of cylindrical and conical parts, as well as a screw 90 which extends the entire length of the feeder 9.
  • the shape of the screw by analogy to the shape of the feeder itself, has both cylindrical 90a and conical 90b parts.
  • the diameter of the screw decreases as it passes from the cylindrical to the conical part of the feeder 9, as illustrated in figure 2.
  • the screw of this feeder has a prolonged stem 91 which extends beyond the screw thread in the conical region 90b of the screw 90.
  • the raw material is depressurized it, similarly to a sponge, absorbs the injected boiler solution such that a fast saturation of the raw material occurs.
  • the feeder engine is shut off and the output opening of the feeder is closed off by closing the disc of a hydrocylinder.
  • the boiler solution is fed through the hollow shaft 92 in the spiral feeder 9 by the pump 7f, 7g (working and spare respectively) from the apparatus 2a.
  • the solution from 2a passes through the heat exchanger 5a, where it is heated to temperature of 75°C.
  • the spinning speed of the spiral feeder's screw 90 determines the efficiency of compression of the raw material.
  • the speed of rotation also determines the time for which the raw material remains in the feeder 9; typically the throughput of the feeder 9 is maintained at a similar level to that of the input bunker 8.
  • the spiral feeder 9 is maintained at a temperature of approximately 100°C.
  • This preliminary temperature increase of the raw material enables some preliminary cooking of the material when it is first impregnated with boiler solution in the depressurization zone of the feeder 9. Obviously most cooking occurs in the boiler 11 later in the unit, but the temperature increase in combination with this initial impregnation ensures increased cooking efficiency within the unit as a whole.
  • the impregnation of the material is further improved by the hole in the centre of the plug generated by the prolonged stem of the screw 91.
  • the feeder contains attachments such that different screws 90 can be mounted within it. Obviously these screws will have both cylindrical 90a and conical 90b parts in correspondence to the shape of the feeder 9 but can differ in the length and diameter of the prolonged stem 91. This allows for the possibility of varying the size of the hole formed in the plug as it is extruded from the conical end 90b of the screw. As discussed, the hole is important for the impregnation of the central part of the raw material plug. However, no batch of raw material will be identical and changing the prolonged stem will allow for more efficient impregnation of material that may vary in fibrous or bast composition. It is also useful where the unit is adapted for use in processing different types of bast-fibred plants.
  • the raw material is sent to the lower part of the boiler 11, which is equipped with a vertical screw 111 that moves the raw material up and down and rods that both loosen the pulp and preclude the appearance of dense and stagnant zones in the boiler 11.
  • the raw material is submerged in boiler solution.
  • This is pumped from the second mixing device 2a by pump 7f into the boiler through the vertical screw 111 which has a perforated shaft.
  • the level of the liquid is regulated by controlling the flow of the solution entering the boiler 11 and also by pumping away the used solution, through two circular pockets (not shown), protected by two to three rows of circular sieves (not shown), using the pumps 7h and 7i.
  • the pockets together with the sieves are vital for changing the liquid level; this control is essential as it allows for the efficiency of the delignification process to be maintained even if slight fluctuations in raw material volume entering the boiler 11 occur. Any solution pumped out through the pockets in this way is heated in the casing tube heat exchanger 19 and returned to the boiler 11 through the perforated shaft of the vertical screw 111.
  • the temperature and pressure conditions of the boiler 11 are strictly controlled The temperature is maintained at 170 ⁇ 10°C throughout the circulation of the boiler solution.
  • the working pressure of the boiler is held at not more than 1.3MPa.
  • the boiler 11 is equipped with a preventive valve, which will open at the pressure of 1.5MPa and also with features which allow for unloading of the boiler 11 when the pressure is raised. Unloading the material from the preventive valve is done into the tank 6b with the casing tube heat exchanger 22a. Those gases that do not condense in heat exchanger 22a, pass through cyclone 32 into the heat exchanger 28.
  • Raw material in the boiler 11 is raised from the liquid and enters into a steam and gas zone, where it is subjected to boiling and irrigation with drops of liquid condensed from the steam of the used solution on the surface of heat exchanger-condenser 25. Consequently, there is simultaneous washing and boiling of the fibrous product.
  • the boiler-washing liquid used for irrigation becomes saturated with the reaction products.
  • a coil of the reverse screw 116 with spirally welded ribs 117 is provided in the upper part of the boiler 11 .
  • the reverse screw 116 besides preventing the pulp from entering the steam portion of the boiler 11, also serves to distribute the irrigation liquid. As boiling liquid enters the boiler 11 it strikes the reverse screw 116 and the ribs serve to break up the stream and thus disperse the liquid over a larger area. This ensures that as large a portion of the raw material as possible comes into contact with the irrigation liquid and improves the effectiveness of the drip percolation.
  • the shaft 112 is rotated at about 0.53 Hz (32 rotations/min.).
  • the rate at which the pulp is raised through the boiler 11 is controlled such that it spends between 1 and 4 hours within the boiler 11. This ensures sufficient boiling and washing of the raw material. Additionally any gases released from the upper part of the boiler are blown away through tank 6b.
  • the pulp passes from the boiler into a stepped series of screw feeders referred to as the discharge unit.
  • the pulp is subjected to limited compression within this apparatus, which serves to press out some of the pulping liquor remaining in the material.
  • the raw material passes through a sequence of apparatus components which greatly improves the ease of removal of the material from the boiler 11 and which result in far more effective removal of liquid from the washed and boiled pulp.
  • the resultant boiled and washed pulp is unloaded from the upper part of the boiler by the spiral conveyor 12.
  • the pulp is supplied to the conveyor 12 by means of paddles 118 which are illustrated in Figure 5.
  • the paddles are mounted on the rotating boiler shaft and thus the unloading process is regulated by varying the speed of rotation.
  • spiral conveyor One important feature of the spiral conveyor is its high speed of rotation.
  • the screw within it is rotated at approximately 16.7 Hz (1000 rot /min). This ensures a very high rate of throughput and helps to prevent congestion of the pulp at the top of the boiler.
  • Pulp unloaded in this way passes from the spiral conveyor 12 into a rotor feeder 13.
  • the pressure in the rotor feeder 13 is lower than that of the boiler (1.3MPa), and is typically maintained at c. 0.7MPa to ensure an approximate pressure difference of 0.6MPa. Secondary boiling gases from the boiler 11 expand on entering the rotor feeder 13 allowing for their separation and removal.
  • the rotor feeder 13 supplies the pulp into a dividing bunker 14.
  • This is constructed in the same way as the input bunker 8 and thus consists of both conical and cylindrical parts, and also comprises a corresponding stirrer 14a (within the conical part) and a pressing screw 14b (within the cylindrical region).
  • the action of the stirrer 14b prevents the raw material getting stuck as in the input bunker 8. Again the screw 14b serves to compress the pulp and consequently squeeze liquid from the material.
  • the use of a dividing bunker 14 gives far more efficient pulp compression.
  • the spinning speed of the pressing screw 14b can be varied which allows for greater control of both the throughput of pulp and the extent to which the pulp is actually compressed.
  • the cellulose pulp is loaded into the screw apparatus 15, where extra liquid is pressed out.
  • This apparatus is illustrated in Figure 6.
  • the loading sequence is maintained airtight by fitting the screw apparatus 15 with a closing device.
  • the rotors of the closing device are set to a closed position, by which a steep decline of pressure of the system is prevented.
  • cams After closing the device the cellulose pulp is ground in the block of cams. These blocks are shown in detail in Figure 6.
  • the cams is varied; in Figure 6 there are three identified types of cam (150, 151, 152) which are interchanged as illustrated. This arrangement of cams is in no way limiting. Other cams can be used, or the order of the cams changed.
  • the variation of cams within the screw apparatus 15 means that the pulp is ground with variable intensity along its length, which improves the efficiency with which extra liquid within the pulp is squeezed out.
  • the rotation of the screw is typically maintained between 1.6 and 3Hz (100 to 180 rotations / min). It is also possible for each different type of cam to be rotated at a different frequency by connection of each part to a different driving engine.
  • the pressed pulp is unloaded into the screw unloader 16 which serves to both unload and steam the cellulose pulp.
  • the screw unloader 16 is maintained at a pressure between 0.1 and 0.2 MPa such that gases are removed by the lowering of pressure. Additionally the screw unloader 16 is supplied with steam to take away the remnants of alcohol.
  • the temperature of the pulp entering the screw unloader 16 is approximately 150°C but within this apparatus the temperature is set at 100°C.
  • the pulp is transported to the fluffer 17, which is designed to divide larger pieces of the pulp into separate packs of fibre so as to facilitate the process of blowing away and removal of the highly volatile fraction of any liquid still contained in the pulp.
  • the fluffed up pulp then is sent to the conical accumulation reservoir 18 shown in Figure 7.
  • the conical accumulation reservoir 18 In the upper part of this reservoir 18 there is an aperture through which steam is blown for the purpose of removing alcohol and other volatile species from the pulp. To prevent significant condensation of this steam, the reservoir 18 is maintained at a temperature of approximately 100°C.
  • this accumulation reservoir 18 has a 'live bottom' formed by four screws, as illustrated in the cross-section of Figure 8.
  • the four screws have identical diameters and are divided into two sets 181, 182 each set rotating out of step with the other.
  • the screws are driven by a motor such that they rotate at a speed of between 15 and 30 rotations per minute. This serves to keep the pulp in constant motion.
  • each screw or set of two screws could be different, or each screw could be attached to a different motor such that they rotate at different speeds if this improves the efficiency with which the steam blown into the apparatus removes alcohol or other remaining volatile liquids still remaining in the pulp after fluffing.
  • the cellulose pulp passes out of the accumulation reservoir on to a screw conveyor 18a for packing.
  • the screw acts upon the pulp to press out any further liquid (filtrate) from it; liquid collected in this way is gathered in the apparatus 6c, which also receives the condensate from the heat exchanger (condenser) 22.
  • the apparatus 6c is maintained at the same pressure as the screw apparatus 15, c. 0.7MPa. From apparatus 6c the boiler solution is recycled by pump 7j to the boiler 11 for use in irrigation of the raw material.
  • the extra solution flows from the apparatus 6c to vaporising apparatus 20, where the pressure is lowered. When necessary the extra solution is sent by the pump 7k out of the system.
  • Used boiler solution is concentrated in a steamer apparatus 24 equipped with a flowing down pellicle consisting of a series of parallel tubes 25 as illustrated in Figure 2.
  • This steamer apparatus 24 is made with a separate heating tank and a separator 26.
  • the temperature within the tubes is maintained about 15°C lower than the temperature in between the tubes.
  • the temperature in the tubes is set at 175 ⁇ 5°C whilst that in between the tubes is set at 190 ⁇ 5°C.
  • the pressure inside the steamer apparatus is also closely controlled.
  • the working pressure inside the tubes is set at 1.25 ⁇ 0.05MPa and that between the tubes is also set at 1.25 ⁇ 0.05MPa.
  • the steamer For effective boiling down of the used boiler solution the steamer must have a large surface area; the working surface area of a typical steamer used in the method according to this invention is about 25m 2 .
  • the solution From the boiler the solution enters the separator 26 from where it is pumped by pumps 7n and 7o (working and spare respectively) into the upper part of the steamer apparatus 24; the solution comes through a distribution device in the steamer apparatus 24 and flows down evenly on the inner surface of the tubes 25 in the form of a thin layer. Simultaneously the solution is being boiled down to the required concentration. The gases released in the steamer pass into the heat exchanger 27 (condenser). The condensed boiler solution is collected is gathered in tank 6d and later sent by pump 7m to the boiler 11 for irrigation. The extra solution from the tank 6d flows into the vaporiser apparatus 20a - which is maintained at a lower pressure - and if necessary is pumped away to be used in preparation of the boiler solution.
  • the concentrated boiler solution from the steamer apparatus is sent away to the vaporiser apparatus 20b, where it is further boiled down and collected in the an output tank.
  • the gases separated in the vaporiser 20b are sent through a first cyclone 31 to the 'casing-tube' heat exchanger 28. Secondary gases from the screw unloader 16, from the vaporisers 20 and 20a are also sent to this heat exchanger 28 through the second cyclone 32.
  • the purpose of both cyclones 31, 32 is to catch fibres supported within the gases of the boiler solution. Both cyclones are held at a temperature of 100°C and work at atmospheric pressure.
  • the first cyclone 31 has however a smaller working volume than the second cyclone 32 which directly relates to the relative volumes of gas circulated to each of them.
  • the condensed liquid is sent to the tank 2a and non-condensable gases go to scrubber 3 for the absorption and cleaning process.
  • the pulp caught in the second cyclone 32- is periodically unloaded from it into a helper tank.
  • a means of emptying the contents of the boiler 11 in emergency is provided.
  • an emergency tank 30 equipped with a stirrer and a net for removing drops of liquid.
  • the lower part of the boiler 11 is connected through a blower tube 34 to the middle part of the emergency tank 30.
  • the tank's working pressure is typically atmospheric pressure - secondary boiling gases form in the emergency tank 30, which pass through the second cyclone 32 into the condenser 28 and later into the first scrubber 3.
  • the incoming solution from the boiler has a temperature of approximately 170°C but this is lowered to 100°C within the tank 30. At this point it is needed to maximise the usage of cooling water for the condenser 28 and the irrigation liquid Cl.
  • the emergency tank 30 is unloaded periodically into the movable helper bunker 35.
  • the unit used in the method of the present invention comprises two more vaporisers throughout (described as flashers in the prior art document).
  • the function of each vaporiser apparatus is to lower the pressure and temperature of the boiler solution passing through it.
  • the three vaporisers are of identical volume and all work at atmospheric pressure. Their increased number and their respective positions within the unit serve to improve the temperature efficiency of the apparatus. This contributes to an improvement in the preparation of the pulping liquor from recovered chemicals in this embodiment compared to the prior art unit.
  • pump H7 directs the boiler solution into a diversionary path not encountering the heat exchanger T.
  • a number of the apparatus components are of standard construction within the field of pulping.
  • the standard equipment include the mixing devices 2, 2a which are fixed with turbine mixers, the tanks (6 to 6e) and all pumps. With respect to the standard pumps used, these have a maximum working pressure flow of 16 kg/cm 2 .
  • the automation scheme of the unit provides for blocking of the pumps when the pressure inside exceeds this value.
  • the basic construction material for the unit is steel and more particularly most component apparatus are constructed from carbon steel.
  • the unit could be constructed from other materials with similar mechanical and chemical properties as steel, for example the resistance to the pH conditions within the boiler.
  • the carbon steel may also be treated to enhance its resistance to corrosion or subjecting it to other preservation processes.
  • the unit of the embodiment does contain more component parts than the aforementioned prior art pulper.
  • the importance of the increased number of vaporisers has already been discussed. Despite this increase the unit can be constructed in compact form such that it requires little more floor space than the known unit.
  • the embodiment can be constructed as a highly-profitable low-capacity plant which even offers scope for the development of mobile units that can be used in the growing regions for the raw materials.
  • the integration of the individual parts and assembly units used in the method of the invention is indicated by its high level of unification.
  • the invention has a typical coefficient of unification of 52%.
  • the unit although particularly suitable for ground hemp stocks, is not restricted to this type of raw material.
  • Other bast-fibred plants such as flax or kenaf are obvious alternatives. These would require a different composition of pulping liquor i.e. a different relative proportion of components and also a different cooking and treatment time.
  • the throughput of material through the unit can readily be varied to allow for this.
  • the following example illustrates the typical construction and operation details for a unit used in the method according to this invention.
  • the unit described hereafter may be used for the production of cellulose at a rate of no more than 300 kg/hr.
  • the conditions listed are the optimum for this total productivity limit.
  • the volumes and operating temperatures and pressures represent the preferred values but are not limiting.
  • the size of each component of the unit can be varied according to its location. For example, if a mobile unit is required, the dimensions of each piece of apparatus comprising the unit will be reduced correspondingly in scale.
  • the unit is of direct importance to countries where wood supplies are limited and the unit must be sized according to the regional growth of bast-fibred plants and the associated demand of paper.
  • the amount of ethanol used is not given. This raw material is only supplied for the start-up of the unit since during pulping methanol, ethanol and acetone as formed from the components of the fibrous raw material, this being a well-known effect of the AAS delignification method. Subsequently, as organic components are accumulated in the pulping liquor, ethanol can be recycled. Excess organic solvent can be drawn and processed as a market chemical. Hence in a continuously operating unit there is no need to supply ethanol.

Landscapes

  • Paper (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Claims (35)

  1. Verfahren zum Herstellen einer Pulpe aus einem Rohpflanzenmaterial in folgender Schrittabfolge:
    Regulieren der Eingabe von Rohmaterial in einen Kessel (11) durch eine erste Zugabevorrichtung (9), die eine Schraube (90) mit einem verlängerten Schaft (91) aufweist, der sich über das Schraubengewinde hinaus erstreckt;
    Kochen des Rohmaterials in dem Kessel (11), um die Pulpe zu erzeugen;
    Empfangen des gekochten Materials aus dem Kessel (11) in einer zweiten Zugabevorrichtung (13);
    Entziehen von Flüssigkeit aus dem gekochten Material in einem Flüssigkeitsentziehungsgerät (15);
    Behandeln des aus dem Flüssigkeitsentziehungsgerät empfangenen Materials mit Dampf in einem Entlader (16), der auf einem geringeren Druck als das Flüssigkeitsentziehungsgerät gehalten wird;
    Empfangen der Pulpe aus dem Entlader (16) in einem Sammelreservoir (18); und
    Entfernen der Pulpe aus dem Sammelreservoir;
       dadurch gekennzeichnet, dass
       der Regulierschritt das Einspritzen einer Kessellösung in das Rohmaterial durch einen Durchgang (92) in dem verlängerten Schaft (91) beinhaltet, und dass die zweite Zugabevorrichtung (13) auf einem geringeren Druck als der Kessel gehalten wird.
  2. Verfahren nach Anspruch 1, wobei die erste Zugabevorrichtung (9) aus einem zylindrischen (90a) und einem konischen (90b) Teil besteht, und sich der verlängerte Schaft (91) der Schraube sich über den konischen Teil des Schraubengewindes hinaus erstreckt.
  3. Verfahren nach Anspruch 1 oder 2, wobei der verlängerte Schaft (91) eine variable Länge und einen variablen Durchmesser aufweist.
  4. Verfahren nach Anspruch 1, wobei der Kessel (11) zum Kochen des Rohmaterials eine im wesentlichen vertikale Schraube (111) mit einem drehbaren perforierten Schaft umfasst.
  5. Verfahren nach Anspruch 4, wobei der Kessel (11) weiterhin eine der im wesentlichen vertikalen Schraube gegenläufige Schraube (116) aufweist.
  6. Verfahren nach Anspruch 5, wobei die gegenläufige Schraube (116) zumindest eine spiralförmig verlaufende Rippe (117) aufweist.
  7. Verfahren nach einem der Ansprüche 4 bis 6, wobei das gekochte Material aus dem Kessel (11) mittels Schaufeln (118) entfernt wird, die an dem Schaft der im wesentlichen vertikalen Schraube (111) angebracht sind.
  8. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Flüssigkeitsentziehungsgerät zum Entziehen der Flüssigkeit aus dem gekochten Material ein Schraubengerät (15) mit mindestens zwei unterschiedlichen rotierenden Nocken aufweist.
  9. Verfahren nach Anspruch 8, wobei sich jede Nocke innerhalb des Schraubengeräts (15) mit einer unterschiedlichen Frequenz dreht.
  10. Verfahren nach einem der Ansprüche 1 bis 9, wobei die Pulpe in dem Sammelreservoir (18) in konstanter Bewegung gehalten ist.
  11. Verfahren nach Anspruch 10, wobei der Boden des Sammelreservoirs (18) aus drehbaren Schrauben gebildet ist.
  12. Verfahren nach Anspruch 11, wobei sich zumindest eine der Schrauben in dem Sammelreservoir (18) nicht synchron mit den anderen Schrauben dreht.
  13. Verfahren nach Anspruch 12, wobei sich zwei der Schrauben in dem Sammelreservoir (18) mit der gleichen Frequenz drehen.
  14. Verfahren nach einem der Ansprüche 11 bis 13, wobei jede der Schrauben in dem Sammelreservoir (18) einen unterschiedlichen Durchmesser aufweist.
  15. Verfahren nach einem der Ansprüche 1 bis 4, wobei weiterhin der ersten Zugabevorrichtung Rohmaterial mittels eines ersten Bunkers (8) zugeführt wird, der oberhalb der ersten Zugabevorrichtung (9) angeordnet ist und eine Rührvorrichtung (80) und eine drehbare Schraube (81) aufweist.
  16. Verfahren nach einem der Ansprüche 1 bis 15, wobei weiterhin gekochtes Material, das aus dem Kessel mit einer zwischen dem Kessel (11) und der zweiten Zugabevorrichtung (13) angeordneten Fördervorrichtung (12) entfernt wird, empfangen wird.
  17. Verfahren nach einem der Ansprüche 1 bis 16, wobei weiterhin das gekochte Material in einem zwischen der zweiten Zugabevorrichtung (13) und dem Flüssigkeitsentziehungsgerät angeordneten zweiten Bunker (13) zusammengepresst wird, der einen Rührer (14a) und eine Pressschraube (14b) aufweist.
  18. Verfahren nach einem der Ansprüche 1 bis 17, wobei weiterhin das gekochte Material zur Erleichterung der Flüssigkeitsentfernung aus dem Material mittels einer Auflockervorrichtung (17), die zwischen dem Entlader (16) und dem Sammelreservoir (18) angeordnet ist, in unterschiedliche Faserpacks geteilt wird.
  19. Verfahren nach einem der Ansprüche 1 bis 18, wobei die Pulpe aus dem Sammelreservoir (18) mittels eines Schraubenförderers (18a) entfernt wird.
  20. Verfahren nach einem der Ansprüche 1 bis 19, wobei die Kesselflüssigkeit gemäß folgender Schritte hergestellt und an dem Kessel und/oder der ersten Zugabevorrichtung bereitgestellt wird:
    Zuführen vom Wasser zu einer Mischvorrichtung (2);
    Empfangen des Wassers aus der Mischvorrichtung in einem ersten Wascher (3) und Zugeben von Schwefelgas, um eine schwache Lösung zu erzeugen;
    Weiterführen der schwachen Lösung aus dem ersten Wascher durch einen Wärmetauscher (5);
    Empfangen der schwachen Lösung aus dem Wärmetauscher in einem zweiten Wascher (4) und Zuführen von Ammoniakwasser und Schwefeldioxidgas zu dem zweiten Wascher (4);
    Weiterführen der Lösung aus dem zweiten Wascher (4) zu einem Ausgabetank (6) in welchem die Kessellösung erzeugt wird;
    Transferieren der Kessellösung aus dem Ausgabetank (6) zu dem Kessel und/oder der ersten Zugabevorrichtung; und
    Regulieren des Gas- und/oder Flüssigkeitsstroms mit einer oder mehreren Pumpen (7a-d).
  21. Verfahren nach Anspruch 20, wobei der Wärmetauscher (5) einen Rohr-in-Rohr-Wärmetauscher umfasst.
  22. Verfahren nach einem der Ansprüche 1 bis 21, wobei weiterhin die Kessellösung aus der benutzten Lösung, die sich innerhalb des Kessels gebildet hat, mittels folgender Schritte zurückgewonnen wird:
    Empfangen der benutzten Lösung aus dem Kessel (11) in einer Trennvorrichtung (26);
    Einkochen der benutzten Lösung auf die erforderliche Konzentration in einem Dampfgerät (24), wobei das Dampfgerät eine Heizvorrichtung aufweist, Dampf empfängt und Gase, die aus dem Einkochen der benutzten Lösung stammen, entfernt; und
    Zurückgeben der wiedergewonnenen Lösung aus dem Dampfgerät zu dem Kessel.
  23. Verfahren nach Anspruch 22, wobei das Dampfgerät (24) weiterhin eine Verteilvorrichtung zum Verteilen der benutzten von der Trennvorrichtung empfangenen Lösung und eine Reihe von parallelen Röhren (25) aufweist.
  24. Verfahren nach Anspruch 23, bei welchem die Innentemperatur der parallelen Röhren (25) von der Außentemperatur der parallelen Röhren verschieden ist.
  25. Verfahren nach Anspruch 22 bis 24, wobei die wiedergewonnene Kessellösung zeitweise in einem Tank (6d) aufbewahrt wird, bevor sie an den Kessel zurückgegeben wird.
  26. Verfahren nach einem der Ansprüche 22 bis 25, wobei die benutzte Lösung weiterhin in einem Verdampfgerät (20b) eingekocht wird, bevor sie an den Kessel zurückgegeben wird.
  27. Verfahren nach Anspruch 26, wobei ein Zyklonabscheider die in dem Verdampfgerät erzeugten Gase empfängt und Materialfasern, die von den Gasen getragen werden, entfernt.
  28. Verfahren nach einem der Ansprüche 1 bis 27, wobei weiterhin Fluide, die in dem Kessel erzeugt werden, mit zwei Verdampfgeräten, einem Zyklonabscheider zum Entfernen der in den Gasen, die von den Verdampfgeräten in den Zyklonabscheider eintreten, getragenen Fasern und einem Wärmetauscher, um die von dem Zyklonabscheider empfangenen Gase zu kondensieren, behandelt werden.
  29. Verfahren nach Anspruch 28, wobei der Schritt der Fluidbehandlung ebenfalls umfasst, dass Gase, die in dem Entlader (16) erzeugt werden, empfangen werden.
  30. Verfahren nach Anspruch 28 oder 29, wobei der Schritt der Fluidbehandlung ebenfalls umfasst, dass Gase, die in der Auflockervorrichtung (17) erzeugt werden, empfangen werden.
  31. Verfahren nach einem der Ansprüche 28 bis 30, wobei der Schritt der Fluidbehandlung umfasst, dass Gase, die in dem Sammelreservoir (18) erzeugt werden, empfangen werden.
  32. Verfahren nach einem der Ansprüche 28 bis 31, wobei weiterhin eine kondensierte Flüssigkeit aus dem Wärmetauscher in einem Tank aufgefangen wird.
  33. Verfahren nach einem der Ansprüche 28 bis 32, wobei weiterhin Gase, die nicht in dem Wärmetauscher kondensiert sind an dem ersten Wascher (3) für die Benutzung zur Vorbereitung der Kessellösung bereitgestellt werden.
  34. Verfahren nach einem der Ansprüche 1 bis 33, wobei ein Nottank (30) mit dem Kessel über eine Druckröhre (34) verbunden ist.
  35. Verfahren nach einem der Ansprüche 1 bis 34, wobei weiterhin die in dem Nottank oder den Zyklonabscheidern aufgefangene Pulpe in einen Hilfsbunker (35) entladen wird.
EP98944033A 1997-09-15 1998-09-14 Verfahren zur herstellung von zellstoff Expired - Lifetime EP1036236B1 (de)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
GBGB9719479.9A GB9719479D0 (en) 1997-09-15 1997-09-15 The Krotov Pulper
GB9719479 1997-09-15
GBGB9807593.0A GB9807593D0 (en) 1997-09-15 1998-04-08 The crotov pulper
GB9807593 1998-04-08
PCT/GB1998/002712 WO1999014424A1 (en) 1997-09-15 1998-09-14 Pulp production method and apparatus
GB9819865 1998-09-14
GB9819865A GB2329192B (en) 1997-09-15 1998-09-14 Pulp production method and apparatus

Publications (2)

Publication Number Publication Date
EP1036236A1 EP1036236A1 (de) 2000-09-20
EP1036236B1 true EP1036236B1 (de) 2003-07-16

Family

ID=27269018

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98944033A Expired - Lifetime EP1036236B1 (de) 1997-09-15 1998-09-14 Verfahren zur herstellung von zellstoff

Country Status (6)

Country Link
EP (1) EP1036236B1 (de)
AT (1) ATE245222T1 (de)
AU (1) AU9171298A (de)
CA (1) CA2304027A1 (de)
DE (1) DE69816478T2 (de)
WO (1) WO1999014424A1 (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8545633B2 (en) 2009-08-24 2013-10-01 Abengoa Bioenergy New Technologies, Inc. Method for producing ethanol and co-products from cellulosic biomass
US8778084B2 (en) 2008-07-24 2014-07-15 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for treating a cellulosic feedstock
US8900370B2 (en) 2008-07-24 2014-12-02 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for conveying a cellulosic feedstock
US8911557B2 (en) 2008-07-24 2014-12-16 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for conveying a cellulosic feedstock
US8915644B2 (en) 2008-07-24 2014-12-23 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for conveying a cellulosic feedstock
US9004742B2 (en) 2009-01-23 2015-04-14 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for conveying a cellulosic feedstock
US9010522B2 (en) 2008-07-24 2015-04-21 Abengoa Bioenergy New Technologies, Llc Method and apparatus for conveying a cellulosic feedstock
US9033133B2 (en) 2009-01-23 2015-05-19 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for conveying a cellulosic feedstock
US9127325B2 (en) 2008-07-24 2015-09-08 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for treating a cellulosic feedstock

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060182693A1 (en) 2005-01-28 2006-08-17 Gumlink A/S Chewing gum possessing tooth cleaning effect and a teeth cleaning method
DE102015108222A1 (de) * 2015-05-26 2016-12-01 Hochschule Magdeburg-Stendal Verfahren zur Abtrennung von Lignin aus Biomassen und daraus gewonnene Stoffe

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2673690A (en) * 1951-10-27 1954-03-30 Hercules Powder Co Ltd Method for the digestion of cellulose-bearing material
US2698789A (en) * 1954-02-08 1955-01-04 Hercules Powder Co Ltd Method for the digestion of cellulose-bearing material
GB753377A (en) * 1954-03-12 1956-07-25 Hercules Powder Co Ltd Improvements in or relating to method for the digestion of cellulose-bearing material
US3096234A (en) * 1958-10-29 1963-07-02 Nolan Continuous digesting system
DE2855052A1 (de) * 1978-12-20 1980-06-26 Nicolaus Md Papier Verfahren und vorrichtung zum kontinuierlichen aufschliessen von pflanzenfasermaterial
FR2741638B1 (fr) * 1995-11-29 1998-02-20 Clextral Procede et installation de preparation en continu d'une pate de cellulose

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8778084B2 (en) 2008-07-24 2014-07-15 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for treating a cellulosic feedstock
US8900370B2 (en) 2008-07-24 2014-12-02 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for conveying a cellulosic feedstock
US8911557B2 (en) 2008-07-24 2014-12-16 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for conveying a cellulosic feedstock
US8915644B2 (en) 2008-07-24 2014-12-23 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for conveying a cellulosic feedstock
US9010522B2 (en) 2008-07-24 2015-04-21 Abengoa Bioenergy New Technologies, Llc Method and apparatus for conveying a cellulosic feedstock
US9127325B2 (en) 2008-07-24 2015-09-08 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for treating a cellulosic feedstock
US9004742B2 (en) 2009-01-23 2015-04-14 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for conveying a cellulosic feedstock
US9033133B2 (en) 2009-01-23 2015-05-19 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for conveying a cellulosic feedstock
US8545633B2 (en) 2009-08-24 2013-10-01 Abengoa Bioenergy New Technologies, Inc. Method for producing ethanol and co-products from cellulosic biomass
US9335043B2 (en) 2009-08-24 2016-05-10 Abengoa Bioenergy New Technologies, Inc. Method for producing ethanol and co-products from cellulosic biomass

Also Published As

Publication number Publication date
DE69816478T2 (de) 2004-05-27
ATE245222T1 (de) 2003-08-15
WO1999014424A1 (en) 1999-03-25
EP1036236A1 (de) 2000-09-20
DE69816478D1 (de) 2003-08-21
AU9171298A (en) 1999-04-05
CA2304027A1 (en) 1999-03-25

Similar Documents

Publication Publication Date Title
EP1036236B1 (de) Verfahren zur herstellung von zellstoff
US5698667A (en) Pretreatment of wood particulates for removal of wood extractives
US5080755A (en) Process for the continuous digestion of cellulosic fiber material
US6719880B2 (en) Process for producing paper and absorbent products of increased strength
SE531498C2 (sv) Matning av finfördelat fibermaterial
CZ219098A3 (cs) Způsob a zařízení pro zpracování vláknité suroviny
DE68928632T2 (de) Verfahren und Vorrichtung zum Behandeln von Faserbrei
EP4162107A1 (de) Kontinuierliches dampfexplosionsverfahren und zerfaserungssystem
US3259538A (en) Comprehensive pulping system for producing paper pulp
JPS61152892A (ja) セルロースパルプの製造法
JPS60500578A (ja) 繊維パルプ製造の方法と装置
CZ69998A3 (cs) Dodávání propírací kapaliny do frakcionačního vícestupňového propíracího zařízení
US20030192660A1 (en) Paper and absorbent products with reduced pitch content
US5680995A (en) Continuous digester
US5192396A (en) Process for the continuous digestion of cellulosic fiber material
US2427495A (en) Apparatus for producing fiber from vegetable growth materials
FI69130B (fi) Foerfarande och anordning foer kontinuerlig uppslutning av vaextfibermaterial
US6280567B1 (en) System and method for treatment of cellulose-containing material prior to pulp digestion
GB2329192A (en) Pulp production method and apparatus
US4190490A (en) Impregnation and digestion of wood chips
JPH01502206A (ja) セルロースパルプの製造方法および／または再生繊維の脱リグニン法
US3814662A (en) Pulping system with impregnation digester having liquor recirculation and cleaning loop
JPS6312719B2 (de)
CA2363158A1 (en) Feed preconditioning for chemical pulping
FI60040C (fi) Foerfarande foer impregnering av flis

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20000413

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI NL PT SE

17Q First examination report despatched

Effective date: 20001018

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

RTI1 Title (correction)

Free format text: PULP PRODUCTION METHOD

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030716

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030716

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20030716

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030716

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030716

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030716

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030716

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69816478

Country of ref document: DE

Date of ref document: 20030821

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030915

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20031016

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20031016

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20031016

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20031027

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20031216

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

26N No opposition filed

Effective date: 20040419

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20050823

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20050909

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070403

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060914

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060914

REG Reference to a national code

Ref country code: GB

Ref legal event code: 728V

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061002

REG Reference to a national code

Ref country code: GB

Ref legal event code: S28

Free format text: RESTORATION ALLOWED

Effective date: 20090127

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20171030

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20180913

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20180913