SE1950386A1 - A method and a system for extracting hydrolysate in a continuous cooking process for producing pulp - Google Patents

A method and a system for extracting hydrolysate in a continuous cooking process for producing pulp

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Publication number
SE1950386A1
SE1950386A1 SE1950386A SE1950386A SE1950386A1 SE 1950386 A1 SE1950386 A1 SE 1950386A1 SE 1950386 A SE1950386 A SE 1950386A SE 1950386 A SE1950386 A SE 1950386A SE 1950386 A1 SE1950386 A1 SE 1950386A1
Authority
SE
Sweden
Prior art keywords
hydrolysate
prehydrolysis
vessel
prehydrolysis vessel
content
Prior art date
Application number
SE1950386A
Other languages
Swedish (sv)
Other versions
SE542991C2 (en
Inventor
Hunphrey Landman
Lari Lammi
Magnus Hägglund
Original Assignee
Valmet Oy
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
Application filed by Valmet Oy filed Critical Valmet Oy
Priority to SE1950386A priority Critical patent/SE1950386A1/en
Priority to PCT/SE2020/050285 priority patent/WO2020204783A1/en
Priority to CN202080025300.9A priority patent/CN113646481B/en
Priority to EP20782621.5A priority patent/EP3947808A4/en
Publication of SE542991C2 publication Critical patent/SE542991C2/en
Publication of SE1950386A1 publication Critical patent/SE1950386A1/en
Priority to ZA2021/04457A priority patent/ZA202104457B/en

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C7/00Digesters
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C1/00Pretreatment of the finely-divided materials before digesting
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C1/00Pretreatment of the finely-divided materials before digesting
    • D21C1/02Pretreatment of the finely-divided materials before digesting with water or steam
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C1/00Pretreatment of the finely-divided materials before digesting
    • D21C1/04Pretreatment of the finely-divided materials before digesting with acid reacting compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00Pulping cellulose-containing materials
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00Pulping cellulose-containing materials
    • D21C3/22Other features of pulping processes
    • D21C3/24Continuous processes
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C7/00Digesters
    • D21C7/08Discharge devices
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C7/00Digesters
    • D21C7/12Devices for regulating or controlling
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2201/00Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis

Abstract

A method and a hydrolysate extracting arrangement in a continuous cooking process for producing pulp, said method comprising the steps of:(e) cooling a content in a prehydrolysis vessel (5a; 5b; 5c; 5d) of a continuous pulp production system such that the content has been cooled down when the content arrives at a hydrolysis outlet (9) of the prehydrolysis vessel (5a; 5b; 5c; 5d) on its way from an inlet (13) provided in one end of the prehydrolysis vessel to an outlet (15) provided in an opposite end of the prehydrolysis vessel;(f) removing a hydrolysate of said content through the hydrolysate outlet (9) of the prehydrolysis vessel,wherein said content in the prehydrolysis vessel is cooled to such a degree that the removed hydrolysate has a temperature between 70°C and 130°C .

Description

A method and arrangement in a continuous pulp production process TECHNICAL FIELD The present invention relates to a method for extracting hydrolysate in a continuous cookingprocess for producing pulp. It furtherrnore relates to a prehydrolysis vessel system and to a hydrolysate extracting arrangement in a continuous cooking system for producing pulp.
BACKGROUND In some pulp production, for example in dissolving pulp production, a lignocellulose raw material is first subject to a hydrolysis before an alkaline cooking is performed. The hydrolysis is norrnally performed by adding steam or liquid to the lignocellulo se raW material.
During the hydrolysis the hemicellulo se, mainly C5 sugars, are degraded and released fromthe Wood. If the sugars should be extracted a hydrolysate comprising the dissolved sugarsneeds to be removed from a vessel Where the hydrolysis is performed before the pH ischanged and an alkaline cooking is performed. In the alkaline cooking process the dissolved sugars after the hydrolysis are broken-down to non-valuable components.
Handling of hydrolysate may be problematic due to its very sticky consistence and tendencyto create scaling for example in pipes, screens and on tank surfaces. Hydrolysate can beremoved through screens provided in the prehydrolysis vessel in a continuous cookingsystem. HoWever, due to the sticky consistence of the hydrolysate and its tendency to createscaling there Will be problems With scaling in the screens. Hereby the screens need to becleaned and the production efficiency may be decreased. In the Worst case the productioneven needs to be stopped during cleaning. Any need for cleaning and any interruption in production processes are of course negative.
SUMMARY An object of the present invention is to improve production efficiency in a continuous pulp production process.
A further object of the present invention is to improve hydrolysate extraction efficiency in a continuous pulp production system.
This is achieved by a method for extracting hydrolysate in a continuous cooking system for producing pulp and by a prehydrolysis vessel in a continuous cooking system for producing pulp and by a hydrolysate extracting arrangement in a continuous cooking system for producing pulp according to the independent claims.
According to one aspect of the invention a method for extracting hydrolysate in a continuous cooking process for producing pulp is provided, said method comprising the steps of: cooling a content in a prehydrolysis vessel of a continuous pulp productionsystem such that the content has been cooled down when the content arrives ata hydrolysis outlet of the prehydrolysis vessel on its way from an inletprovided in one end of the prehydrolysis vessel to an outlet provided in anopposite end of the prehydrolysis vessel; removing a hydrolysate of said content through the hydrolysate outlet of the prehydrolysis vessel, wherein said content in the prehydrolysis vessel is cooled to such a degree that the removed hydrolysate has a temperature between 70°C and 130°C .
According to another aspect of the invention a prehydrolysis vessel system in a continuous pulp production system is provided, wherein said prehydrolysis vessel system comprises: (a) a prehydrolysis vessel comprising: an inlet provided in one end of the prehydrolysis vessel for receiving a contentto be treated in the prehydrolysis vessel;an outlet provided in an opposite end of the prehydrolyses vessel; and a hydrolysis outlet; and (b) a hydrolysate extracting arrangement connected to the prehydrolysis vessel, said hydrolysate extracting arrangement comprising: a hydrolysate removing conduit comprising a prehydrolysis vessel connectorwhich is connected to the hydrolysate outlet of the prehydrolysis vessel; and at least one cooling device which is provided to the prehydrolysis vessel suchthat it can cool down a content of the prehydrolysis vessel such that the content has been cooled down when the content arrives at the hydrolysis outlet of the 2 prehydrolysis vessel on its way from the inlet of the prehydrolysis vessel to the outlet of the prehydrolysis vessel, wherein said cooling device is configured for cooling down the content in theprehydrolysis vessel to such a degree that a hydrolysate removed through thehydrolysate outlet has a temperature between 70°C and l30°C .
According to another aspect of the invention a hydrolysate extracting arrangement configuredfor being connected to and extracting hydrolysate from a prehydrolysis vessel in a continuous pulp production system is provided, said hydrolysate extracting arrangement comprising: - a hydrolysate removing conduit comprising a prehydrolysis vessel connectorwhich is arranged for being connected to a hydrolysate outlet of theprehydrolysis vessel; and - at least one cooling device configured such that it can be provided to theprehydrolysis vessel and such that it can cool down a content of theprehydrolysis vessel such that the content has been cooled down when thecontent arrives at a hydrolysis outlet of the prehydrolysis vessel on its wayfrom an inlet provided in one end of the prehydrolysis vessel to an outletprovided in an opposite end of the prehydrolysis vessel, wherein said coolingdevice is configured to cool down the content in the prehydrolysis vessel tosuch a degree that a hydrolysate removed through the hydrolysate outlet has atemperature between 70°C and l30°C .
Hereby a method and a system for extraction of hydrolysate in a pulp production system isprovided which is more effective and reliable than prior art systems. Thanks to the cooling ofthe hydrolysate before it is removed through a hydrolysate outlet of the prehydrolysis vesselthe tendency of the hydrolysate to create scaling, for example in the hydrolysate outlet whichcan be one or more screens, is much decreased. When cooling the hydrolysate the furfuralformation is reduced and also the lignin degradation is reduced. This will reduce the tendencyto build scaling. Furthermore the stability of the sugar solution is radically improved due tolowering the sugar degradation rate and a more effective sugar extraction from thehydrolysate can be provided. A more reliable process is provided thanks to less scaling andless need for cleaning of the system and a better sugar yield can be provided thanks to reduced sugar degradation.
In one embodiment of the invention said prehydrolysis vessel comprises a cooling sectionwhere said cooling is perfomred, which cooling section is a length section of theprehydrolysis vessel, in which length section the hydrolysis outlet is provided and whichlength section is less than 1/3 or less than l/5 of a total length of the prehydrolysis vessel and wherein said cooling section is closer to the outlet than to the inlet of the prehydrolysis vessel.
In one embodiment of the invention said cooling of a content in the prehydrolysis vesselcomprises cooling the content to such a degree that the removed hydrolysate has atemperature between 70°C and l20°C or between 90°C and ll0°C. In this embodiment of theinvention the cooling device is conf1gured to cool the content to such a degree that theremoved hydrolysate has a temperature between 70°C and l20°C or between 90°C and ll0°C.
In one embodiment of the invention said cooling comprises adding liquid with a temperaturebetween 20°C and l00°C or a temperature between 30°C and 80°C or a temperature between40°C and 70°C to the content in the prehydrolysis vessel. In this embodiment the coolingdevice comprises a liquid adding device which is conf1gured to add a liquid having atemperature between 20°C and l00°C or a temperature between 30°C and 80°C or atemperature between 40°C and 70°C to the content of the prehydrolysis vessel In one embodiment of the invention said cooling comprises circulating a part of the removedhydrolysate through a heat exchanger (41) for cooling it down to a temperature between 20°Cand l00°C or a temperature between 30°C and 80°C or a temperature between 40°C and 70°Cand adding the cooled hydrolysate to the content of the prehydrolysis vessel. In thisembodiment the cooling device comprises a hydrolysate circulation arrangement which isconfigured to circulate a part of the hydrolysate removed through the hydrolysate removingconduit through a heat exchanger for cooling it down to a temperature between 20°C andl00°C or a temperature between 30°C and 80°C or a temperature between 40°C and 70°C and add the cooled hydrolysate to the content of the prehydrolysis vessel.
In one embodiment of the invention said cooled hydrolysate is added into the prehydrolysisvessel through nozzels provided around a periphery of an enclosing wall of the prehydrolysis vessel.
In one embodiment of the invention at least a part of said cooled hydrolysate is added to the content of the prehydrolysis vessel through an outlet of a liquid adding pipe protruding into the prehydrolysis Vessel, Wherein said Outlet is positioned closer to a central axis (A) of the prehydrolysis Vessel than to an enclo sing Wall.
In one embodiment of the inVention the step of removing a hydrolysate comprises removingthe hydrolysate through at least one screen provided in an enclosing Wall of the prehydrolysis Vessel, Wherein said at least one screen is the hydrolysate outlet.
In one embodiment of the inVention the step of removing a hydrolysate comprises displacingthe hydrolysate out through the hydrolysate outlet by adding a liquid into the prehydrolysis Vessel from a bottom part of the prehydrolysis Vessel.
In one embodiment of the inVention the method further comprises the step of extracting sugar from the removed hydrolysate.
In one embodiment of the inVention the continuous cooking process is a process for producing dissolving pulp.
Further embodiments of the inVention are described in dependent claims and in the detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS Figures la-ld are schematic illustrations of different embodiments of prehydrolysis Vesselsystems comprising a hydrolysate extracting arrangement connected to a prehydrolysis Vessel in a continuous cooking system according to the invention.
Figure 2 is a flow chart of a method for extracting hydrolysate according to one embodiment of the inVention.
DETAILED DESCRIPTION OF EMBODIMENTS Figures la-ld are schematic illustrations of different embodiments of prehydrolysis Vesselsystems la, lb, lc, ld comprising a hydrolysate extracting arrangement Sa, 3b, 3c, 3dconnected to a prehydrolysis Vessel 5a, 5b, 5c, 5d in a continuous cooking system accordingto the inVention. Some of the components are the same in all embodiments and Will also be given the same or corresponding reference numbers.
Common for all the embodiments is that the hydrolysate extracting arrangement 3a; 3b; 3c;3d comprises a hydrolysate removing conduit 7 comprising a prehydrolysis vessel connector 8which is arranged for being connected to a hydrolysate outlet 9 of the prehydrolysis vessel 5a;5b; 5c; 5d. The hydrolysate outlet 9 can for example be one or more screens provided in anenclo sing wall 21 of the prehydrolysis vessel. A reason for removing hydrolysate from theprehydrolysis vessel can be that the hydrolysate can be used in some way, for example forextraction of sugar. Another reason for removing the hydrolysate is that less alkali will beneeded in the next step of the pulp production process if at least some of the hydrolysate isremoved because the hydrolysate is acidic. Such a prehydrolysis vessel is a pressurized vessel.
The continuous cooking process of the invention can be a process for producing dissolving pulp.
The hydrolysate extracting arrangement 3a; 3b; 3c; 3d comprises furtherrnore at least onecooling device 1 la, 1 lb; 11b”; 11c, 11c”, 11c” °; 11d configured such that it can be provided tothe prehydrolysis vessel 5a; 5b; 5c; 5d and such that it can cool down a content of theprehydrolysis vessel such that the content has been cooled down when the content arrives atthe hydrolysis outlet 9 of the prehydrolysis vessel on its way from an inlet 13 provided in oneend of the prehydrolysis vessel 5a; 5b; 5c; 5d to an outlet 15 provided in an opposite end ofthe prehydrolysis vessel. A scraper 16 is often provided in the bottom part of theprehydrolysis vessel. The cooling device 1 la, 1 lb; 11b°; 11c, 11c°, 11c° °; 11d is configured tocool down the content in the prehydrolysis vessel to such a degree that a hydrolysate removedthrough the hydrolysate outlet 9 has a temperature less than 130°C . For example atemperature between 70°C and 130°C. In one embodiment of the invention the coolingdevice 1 la, 1 lb; 11b”; llc, 11c°, 11c° ”; 11d is conf1gured for cooling down the content in theprehydrolysis vessel to such a degree that a hydrolysate removed through the hydrolysateoutlet 9 has a temperature less than 120°C or between 70°C and 120°C and in anotherembodiment the cooling device 1 la, 1 lb; 11b”; 11c, 11c”, 11c” °; 11d is configured for coolingdown the content in the prehydrolysis vessel to such a degree that a hydrolysate removedthrough the hydrolysate outlet 9 has a temperature less than 110°C or between 90°C and 1 10°C.
The hydrolysate outlet 9 can be provided in the enclosing wall 21of the prehydrolysis vessel somewhere between the inlet 13 and the outlet 15 of the prehydrolysis vessel and can as mentioned above suitably be one or more screens provided in the enclosing wall. Thehydrolysate outlet 9 can be provided closer to the outlet 15 than the inlet 13 of the prehydrolysis vessel.
A norrnal temperature of the content in the prehydrolysis vessel 5a; 5b; 5c; 5d (i.e. before thecooling according to the invention) can for example be around l60-l80°C. At thattemperature the hydrolysate is very sticky and difficult to handle. For example heavy scalingis easily produced in components such as tank walls, tubes and screens coming into contactwith the hydrolysate. Hereby there are often problems related to scaling in equipment used forremoving the hydrolysate. The sticky consistence of the hydrolysate and its tendency toprovide scaling is probably due to furfural which is produced from the dissolved sugars andalso due to lignin. The furfural production is a function of time, i.e. longer exposure time ofsugars in such conditions leads to higher furfural concentration in the solution. Lignin contentalso increases during the hydrolysis time. Scaling consists much of lignin and furfuraltogether with sugars. Surprisingly it has been found that by cooling down the hydrolysate tofor example less than around l30°C or less than l20°C or less than ll0°C the stickyconsistence and tendency to provide scaling is greatly decreased and extraction of hydrolysisfrom a pulp production process can be much improved. Hereby also extraction of sugars froma hydrolysate can be improved. The positive effect of the cooling, i.e. the reduction of scaling,is surprisingly high also for relatively small temperature reductions. By cooling the contentdown before a hydrolysate is removed from the prehydrolysis vessel of a continuous pulpproduction system according to the invention a much more effective extraction of thehydrolysate will be achieved thanks to less problem with scaling. Hereby the system forcontinuous production of pulp can also be operated in a more effective way when the problem with scaling is reduced.
Furthermore in these types of cooking systems for producing pulp it is traditionally veryimportant to keep up the high temperatures of the material in order to avoid energy loss.Hereby it would not be obvious for a skilled person to adopt this solution to cool down thecontent in the prehydrolysis vessel before a hydrolysate is removed as elevated temperature is required for the alkaline lignin removal step after the hydrolysis.
Also common for all the embodiments as shown in Figures la-ld is that said at least onecooling device lla, l lb; llb°; llc, llc”, llc” °; lld is conf1gured such that it can provide a cooling effect to a content in the prehydrolysis vessel 5a; 5b; 5c; 5d in a cooling section 23 of said prehydrolysis vessel when the cooling device is provided to the prehydrolysis vessel. Thecooling section 23 is a length section of the prehydrolysis vessel, in which length section thehydrolysis outlet 9 is provided. Said length section is in one embodiment of the invention lessthan l/3 of a total length of the prehydrolysis vessel and in one embodiment less than 1/5 of atotal length of the prehydrolysis vessel. Said cooling section 23 is positioned closer to theoutlet l5 than to the inlet l3 of the prehydrolysis vessel. The cooling of the content in theprehydrolysis vessel 5a; 5b; 5c; 5d is suitably performed in the vicinity of the hydrolysateoutlet 9. The cooling section 23 can be defined as a length section of the prehydrolysis vesselwhich length section comprises a part of the enclo sing wall 2l and the space inside the enclo sing wall 2l within this length section. The hydrolysis outlet 9 is positioned within thislength section. The cooling is perforrned somewhere within this cooling section 23 and herebythe cooling is perforrned in vicinity of the hydrolysate outlet 9. The cooling can be perforrnedin a number of different ways and the cooling device can be embodied in a number ofdifferent ways which will be further described in relation to Figures la-ld. These differentcooling methods can also be combined in different ways which are all covered by this invention.
The removing of a hydrolysate from the prehydrolysis vessel 5a; 5b; 5c; 5d according to theinvention can comprise displacing the hydrolysate out through the hydrolysate outlet 9 byadding a liquid into the prehydrolysis vessel from a bottom part 25 of the prehydrolysisvessel. Therefore said prehydrolysis vessel 5a; 5b; 5c; 5d can comprise a liquid adding device27 which is conf1gured for adding liquid to the bottom part 25 of the prehydrolysis vessel fordisplacing cooled hydrolysate out through the hydrolysate outlet 9. The liquid that is addedcan be for example cooking liquor, such as white or black liquor and it can be added fromnozzles in the enclosing wall 2l in the bottom part 25 and/or from a central tube 27” providedinto the vessel through a bottom 26 of the vessel as shown in Figures la-ld. Such a liquidadding device 27 is norrnally provided in this type of prehydrolysis vessel for allowingtransfer of the material out through the outlet l5 of the prehydrolysis vessel. The central tube27” of the liquid adding device 27 is provided according to the invention for providing the further effect of displacing the cooled hydrolysate out through the hydrolysate outlet 9.
The hydrolysate extracting arrangement 3a; 3b; 3c; 3d can in some embodiments furthercomprise a sugar extracting arrangement 3l (only shown in Figure la, but it can be providedin all embodiments of the invention). The sugar extracting arrangement is connected to the hydrolysate removing conduit 7 and is arranged for extracting sugar from the hydrolysate. 8 Sugar extraction will be more effective compared to in prior art because of the lowertemperature of the hydrolysate. Sugar degradation reaction is reduced in the hydrolysatethanks to the lower temperature of the hydrolysate and a total sugar yield can hereby be improved.
Figure la shows one embodiment of a prehydrolysis vessel system la according to theinvention. A hydrolysate extracting arrangement 3a which is connected to the prehydrolysisvessel 5a comprises in this embodiment a hydrolysate removing conduit 7 and a coolingdevice l la. The cooling device l la is in this embodiment a liquid adding device which isconfigured for adding a liquid having a temperature between 20°C and l00°C or atemperature between 30°C and 80°C or a temperature between 40°C and 70°C to the contentof the prehydrolysis vessel 5a. The liquid can be for example water or washing liquid oranother liquid and should be provided to the prehydrolysis vessel 5a inside the cooling section23. The liquid can suitably have a pH around 7 or can be slightly acid or slightly alkaline. Inthis embodiment a liquid adding pipe 33a is provided to the prehydrolysis vessel 5a. Saidliquid adding pipe 33a is protruding into the prehydrolysis vessel 5a and has an outlet 34apositioned within the cooling section 23 and suitably closer to a central axis A of theprehydrolysis vessel than an enclosing wall 21 of the prehydrolysis vessel, i.e. centered withinthe prehydrolysis vessel 5a in vicinity of the hydrolysate outlet 9. The cooling device l la ofthe hydrolysate extracting arrangement 3a can therefore be connected to the liquid addingpipe 33 for providing a liquid into the prehydrolysis vessel for cooling the content of theprehydrolysis vessel. Hereby the content inside the prehydrolysis vessel 5a can be cooleddown in vicinity of the hydrolysate outlet 9 and a hydrolysate removed through thehydrolysate outlet 9 can have a lower temperature than without this cooling. The temperatureof the removed hydrolysate can be measured and a temperature of the liquid added throughthe liquid adding pipe 33 can be controlled such that a suitable temperature of the removedhydrolysate is achieved, such as for example less than l30°C or less than l20°C or less than ll0°C as discussed above.
Figure lb shows another embodiment of a prehydrolysis vessel system lb according to theinvention. A hydrolysate extracting arrangement 3b which is connected to a prehydrolysisvessel 5b comprises in this embodiment a hydrolysate removing conduit 7 and a coolingdevice llb, llb”. The cooling device comprises in this embodiment two parts. A first part llbcan be connected to a liquid adding pipe 33b provided to the prehydrolysis vessel 5b. Saidliquid adding pipe 33b is protruding into the prehydrolysis vessel 5b and has an outlet 34b 9 positioned within the Cooling section 23 and suitably closer to a central axis A of theprehydrolysis vessel than an enclosing wall 21 of the prehydrolysis vessel, i.e. centered withinthe prehydrolysis vessel 5b in vicinity of the hydrolysate outlet 9. The second part 11b° of thecooling device is in this embodiment configured for adding a cooling liquid into theprehydrolysis vessel 5b through nozzels 37 provided around a periphery of an enclosing wall21 of the prehydrolysis vessel 5b. Said nozzels 37 are provided within the cooling section 23of the prehydrolysis vessel 5b, i.e. in vicinity of the hydrolysate outlet 9. Hereby a coolingliquid can be both added into the prehydrolysis vessel 5b from the enclosing wall 21 and beadded to the content in the prehydrolysis vessel from a central place within the prehydrolysisvessel in vicinity of the hydrolysate outlet 9. Hereby the hydrolysate can be effectivelydisplaced and cooled down. Said nozzles 37 can be provided such that they direct a coolingliquid into the prehydrolysis vessel. Nozzles 37” can however also be provided within anouter compartment 38 which is provided outside the prehydrolysis vessel such that itsurrounds the screen 9 (the prehydrolysis outlet) provided in the enclosing wall 21 of theprehydrolysis vessel. Hereby cooling liquid can be added to the hydrolysate when it has beenremoved out from the prehydrolysis vessel through the screen 9 and when the hydrolysate is provided in said outer compartment 38.
In the embodiment as shown in Figure lb the hydrolysate extracting arrangement 3bcomprises further a hydrolysate circulation arrangement 39. The hydrolysate circulationarrangement 39 is conf1gured for circulating a part of the hydrolysate removed through thehydrolysate removing conduit 7 through a heat exchanger 41 for cooling it down to atemperature between 20°C and 100°C or a temperature between 30°C and 80°C or atemperature between 40°C and 70°C and adding the cooled hydrolysate to the content of theprehydrolysis vessel 5b through the first and/or the second part 1 lb, 11b° of the coolingdevice. In another embodiment the cooling device may comprise only one of the first andsecond parts 11b, 11b°. The hydrolysate circulation arrangement 39 hereby connects thehydrolysate removing conduit 7 with the first and/or second parts 1 lb, 11b° of the coolingdevice through a heat exchanger 41 and transfers a part of the removed hydrolysate from thehydrolysate removing conduit 7, through the heat exchanger 41 and to the cooling device 1 lb,11b° for adding it to the cooling section 23 of the prehydrolysis vessel 5b when thehydrolysate extracting arrangement 3b is connected to the prehydrolysis vessel 5b. Thecooling provided by the heat exchanger 41 to the circulated hydrolysate can be controlled in dependence of a measured temperature of the removed hydrolysate. As discussed above a temperature of the removed hydrolysate should be controlled to be less than l30°C or less than l20°C or less than ll0°C.
Recirculation of the hydrolysate may be advantageous because no additional liquid fromoutside the system need to be added into the prehydrolysis vessel for providing the coolingand hereby unnecessary dilution of the hydrolysate is avoided. However in some processes itmay be suitable to add some extra liquid as shown in the embodiment in Figure la. Forexample hydrolysis extraction yield may be improved by the addition of some extra liquid. Itmay be suitable to have a system where both these altematives can be utilized in combination or independently. One such system is shown in Figure lc.
Figure lc shows another embodiment of a prehydrolysis vessel system lc according to theinvention. A hydrolysate extracting arrangement 3c which is connected to a prehydrolysisvessel 5c comprises in this embodiment a hydrolysate removing conduit 7 and a coolingdevice llc, llc°, llc” ”. The cooling device comprises in this embodiment three parts,whereof a first part llc and a second part llc” are identical to the first and second parts l lb,llb” as described above in relation to Figure lb and will not be described in detail again. Thefirst and second part llc, llc” are hereby connected to a hydrolysate circulation arrangement39 and to a liquid adding pipe 33b and to nozzles 37 as described above. The third part llc”is identical to the cooling device lla as described in relation to Figure la and will not bedescribed in detail. The third part llc” of the cooling device is connected to a liquid addingpipe 33a and can add a cooling liquid to the content of the prehydrolysis vessel 5c. Hereby, inthis embodiment these three altemative ways of cooling the content in the prehydrolysisvessel 5c can be combined for an optimal cooling effect. Altematively an operator of thesystem can choose one or more of the separate parts llc, llc°, llc” of the cooling device forcooling the content. The temperature of the added liquid (either circulated hydrolysate orother liquid added through the third part llc” ”) can be controlled such that the removed hydrolysate has a suitable temperature such that scaling is minimized.
Figure ld shows another embodiment of a prehydrolysis vessel system ld according to theinvention. A hydrolysate extracting arrangement 3d which is connected to a prehydrolysisvessel 5d comprises in this embodiment a hydrolysate removing conduit 7 and a coolingdevice lld. It comprises furtherrnore a hydrolysate circulation arrangement 39 as describedabove in relation to Figure lb. The hydrolysate circulation arrangement 39 is configured for circulating a part of the hydrolysate removed through the hydrolysate removing conduit 7 11 through a heat exchanger 41 for cooling it down to a temperature between 20°C and 100°C ora temperature between 30°C and 80°C or a temperature between 40°C and 70°C and addingthe cooled hydrolysate to the content of the prehydrolysis vessel 5d through the coolingdevice 11d. The cooling device 11d transfers the cooled circulated hydrolysate to a number ofnozzles 37. The nozzles 37 are in this embodiment distributed not only around the peripheryof the enclosing wall 21 but also distributed along the length of the prehydrolysis vessel 5bwithin the cooling section 23. In this embodiment the prehydrolysis vessel 5d comprises anumber of screens 51 which are provided in sections and nozzles 37 are provided in betweensaid screens 51. Hereby the cooled hydrolysate can be more effectively distributed over thescreens and prevent scaling in the screens. Of course the prehydrolysis vessel system 1daccording to this embodiment can also be provided with another cooling device 11a which is adding another cooling liquid as described in relation to Figure 1a.
Figure 2 is a flow chart of the method for extracting hydrolysate in a continuous cookingprocess for producing pulp according to one embodiment of the invention. The steps are described in order below: S1: Cooling a content in a prehydrolysis vessel of a continuous pulp production system suchthat the content has been cooled down when the content arrives at a hydrolysis outlet of theprehydrolysis vessel on its way from an inlet provided in one end of the prehydrolysis vesselto an outlet provided in an opposite end of the prehydrolysis vessel. Said cooling is suitablyperformed in a cooling section of said prehydrolysis vessel, which cooling section is a lengthsection of the prehydrolysis vessel, in which length section the hydrolysis outlet is providedSaid length section is in one embodiment of the invention less than 1/ 3 of a total length of theprehydrolysis vessel and in one embodiment less than 1/ 5 of a total length of theprehydrolysis vessel. Said cooling section is closer to the outlet than to the inlet of theprehydrolysis vessel. The cooling can be provided by adding liquid with a temperaturebetween 20°C and 100°C or a temperature between 30°C and 80°C or a temperature between40°C and 70°C to the content in the prehydrolysis vessel. The liquid can be for example water or washing liquid or circulated hydrolysate as described above.
S2: Removing a hydrolysate of said content through the hydrolysate outlet of the prehydrolysis vessel.
Said content in the prehydrolysis vessel is cooled to such a degree that the removed hydrolysate has a temperature less than 130°C or less than 120°C or less than 110°C as 12 described above. This can also be described as in interval between 70°C and 130°C or 120°C or 1 10°C.The method can optionally also coniprise a further step: S3: Extracting sugar from the removed hydrolysate. Thanks to the cooling of the content inthe prehydrolysis Vessel the sugar degradation is reduced and the sugar extraction yield can be increased. 13

Claims (9)

1. . A method for extracting hydrolysate in a continuous cooking process for producing pulp, said method coniprising the steps of: - cooling a content in a prehydrolysis vessel (5a; 5b; 5c; 5d) of a continuouspulp production system such that the content has been cooled down when thecontent arrives at a hydrolysis outlet (9) of the prehydrolysis vessel (5a; 5b; 5c;5d) on its way fron1 an inlet (13) provided in one end of the prehydrolysisvessel to an outlet (15) provided in an opposite end of the prehydrolysis vessel; - ren1oving a hydrolysate of said content through the hydrolysate outlet (9) ofthe prehydrolysis vessel, wherein said content in the prehydrolysis vessel is cooled to such a degree that the ren1oved hydrolysate has a ten1perature between 70°C and l30°C . . Method according to clain1 1, wherein said cooling is perforrned in a cooling section (23) of said prehydrolysis vessel (5a; 5b; 5c; 5d), which cooling section is a lengthsection of the prehydrolysis vessel, in which length section the hydrolysis outlet (9) isprovided and which length section is less than 1/3 or less than 1/5 of a total length ofthe prehydrolysis vessel and wherein said cooling section is closer to the outlet (15) than to the inlet (13) of the prehydrolysis vessel. . Method according to clain1 1 or 2, wherein said cooling of a content in the prehydrolysis vessel (5a; 5b; 5c; 5d) con1prises cooling the content to such a degreethat the ren1oved hydrolysate has a ten1perature between 70°C and l20°C or between90°C and ll0°C. . Method according to any one of the preceding clainis, wherein said cooling con1prises adding liquid with a ten1perature between 20°C and l00°C or a ten1perature between30°C and 80°C or a ten1perature between 40°C and 70°C to the content in the prehydrolysis vessel. 14 10. 11 1
2. Method according to any one of the preceding claims, wherein said cooling comprisescirculating a part of the removed hydrolysate through a heat exchanger (41) forcooling it down to a temperature between 20°C and l00°C or a temperature between30°C and 80°C or a temperature between 40°C and 70°C and adding the cooledhydrolysate to the content of the prehydrolysis vessel. Method according to claim 5, wherein said cooled hydrolysate is added into theprehydrolysis vessel (5a; 5b; 5c; 5d) through nozzels (37) provided around a periphery of an enclosing wall (21) of the prehydrolysis vessel. Method according to any one of the claims 5-6, wherein at least a part of said cooledhydrolysate is added to the content of the prehydrolysis vessel through an outlet (34b)of a liquid adding pipe (3 3b) protruding into the prehydrolysis vessel (5b; 5c), whereinsaid outlet (34b) is positioned closer to a central axis (A) of the prehydrolysis vessel than to an enclosing wall (21). Method according to any one of the preceding claims, wherein the step of removing ahydrolysate comprises removing the hydrolysate through at least one screen (9; 51)provided in an enclosing wall (21) of the prehydrolysis vessel (5a; 5b; 5c; 5d), wherein said at least one screen is the hydrolysate outlet (9). Method according to any one of the preceding claims, wherein the step of removing ahydrolysate comprises displacing the hydrolysate out through the hydrolysate outlet(9) by adding a liquid into the prehydrolysis vessel (5a; 5b; 5c; 5d) from a bottom part(25) of the prehydrolysis vessel. Method according to any one of the previous claims, wherein the method further comprises the step of extracting sugar from the removed hydrolysate. . Method according to any one of the preceding claims, wherein the continuous cooking process is a process for producing dissolving pulp. A prehydrolysis vessel system in a continuous pulp production system, wherein said prehydrolysis vessel system (la; lb; lc; ld) comprises: (c) a prehydrolysis vesse1 (5a; 5b; 5c; 5d) comprising: an in1et (13) provided in one end of the prehydro1ysis vesse1 for receiving acontent to be treated in the prehydro1ysis vesse1;an out1et (15) provided in an opposite end of the prehydro 1yses vesse1; and a hydro1ysis out1et (9); and (d) a hydro1ysate extracting arrangement (3a; 3b; 3c; 3d) connected to the prehydro1ysis vesse1 (5a; 5b; 5c; 5d), said hydro1ysate extracting arrangement (3a; 3b; 3c; 3d) comprising: a hydro1ysate removing conduit (7) comprising a prehydrolysis vesse1connector (8) which is connected to the hydro1ysate out1et (9) of theprehydro1ysis vesse1(5a; 5b; 5c; 5d); and at 1east one coo1ing device (11a, 11b; 11b°; 11c, 11c”, 11c”; 11d) which isprovided to the prehydro1ysis vesse1 (5 a; 5b; 5c; 5d) such that it can coo1 downa content of the prehydro1ysis vesse1 such that the content has been coo1eddown when the content arrives at the hydro1ysis out1et (9) of the prehydrolysisvesse1 (5a; 5b; 5c; 5d) on its way from the in1et (13) of the prehydro1ysis vesse1(5a; 5b; 5c; 5d) to the out1et (15) of the prehydrolysis vesse1, wherein said coo1ing device (11a, 11b; 11b°; 11c, 11c”, 11c”; 11d) is conf1gured for coo1ing down the content in the prehydro1ysis vesse1 to such a degree that a hydro1ysate removed through the hydro1ysate out1et (9) has a temperature between70°C and 130°C . 1
3. Prehydrolysis vesse1 system according to c1aim 12, wherein said prehydro1ysis vesse1 comprises a coo1ing section (23) in which coo1ing section said coo1ing of the content by the coo1ing device (11a, 11b; 11b°; 11c, 11c°, 11c”; 11d) is performed, which coo1ing section (23) is a 1ength section of the prehydro1ysis vesse1 (5a; 5b; 5c; 5d), in which 1ength section the hydro1ysis out1et (9) is provided and which 1ength section is 1ess than 1/ 3 or 1ess than 1/5 of a total 1ength of the prehydrolysis vesse1 and wherein said coo1ing section (23) is c1oser to the out1et (15) than to the in1et (13) of the prehydro1ysis vesse1. 1
4. Prehydrolysis vesse1 system according to c1aim 12 or 13, wherein the coo1ing device (11a, 11b; 11b°; 11c, 11c°, 11c”; 11d) is configured to coo1 the content to such a 16 1
5. 1
6. 1
7. 1
8. degree that the removed hydrolysate has a temperature between 70°C and l20°C orbetween 90°C and ll0°C. Prehydrolysis vessel system according to any one of the claims 12-14, wherein said atleast one cooling device (1 la, 1 lb; llb°; llc, llc”, llc” °; lld) comprises a liquidadding device (1 la) which is configured to add a liquid having a temperature between20°C and l00°C or a temperature between 30°C and 80°C or a temperature between40°C and 70°C to the content of the prehydrolysis vessel. Prehydrolysis vessel system according to any one of the claims 12-15, wherein said atleast one cooling device (1 la, 1 lb; llb°; llc, llc”, llc” °; lld) comprises ahydrolysate circulation arrangement (3 9) which is conf1gured to circulate a part of thehydrolysate removed through the hydrolysate removing conduit (7) through a heatexchanger (41) for cooling it down to a temperature between 20°C and l00°C or atemperature between 30°C and 80°C or a temperature between 40°C and 70°C and addthe cooled hydrolysate to the content of the prehydrolysis vessel (5b; 5c; 5d). Prehydrolysis vessel system according to any one of the claims 12-16, wherein theprehydrolysis vessel comprises nozzels (37) provided around a periphery of anenclosing wall (21) of the prehydrolysis vessel (5b; 5c; 5d), wherein said at least onecooling device (1 lb; llb°; llc, llc”, llc”; lld) of the hydrolysate extractingarrangement (3b; 3c; 3d) can be connected to the nozzels (37) for providing a liquidinto the prehydrolysis vessel (5b; 5c; 5d) for cooling the content of the prehydrolysis vessel. Prehydrolysis vessel system according to any one of the claims 12-17, comprising atleast one liquid adding pipe (33a; 33b) protruding into the prehydrolysis vessel (5 a;5b; 5c) and having an outlet (34a; 34b) positioned closer to a central axis (A) of theprehydrolysis vessel than to an enclo sing wall (21) of the prehydrolysis vessel,wherein said at least one cooling device (1 la, 1 lb; 11b°; 11c, 11c”, 11c”) ofthe hydrolysate extracting arrangement (3a; 3b; 3c) can be connected to the at least one 17 1
9. 20. 21. 22. liquid adding pipe (33a; 33b) for providing a liquid into the prehydrolysis vessel (5a;5b; 5c) for cooling the content of the prehydrolysis vessel. Prehydrolysis vessel system according to any one of the claims 12-18, wherein said continuous pulp production system is a system for producing dissolving pulp. Prehydrolysis vessel system according to any one of the claims 12-19, wherein saidprehydrolysis vessel comprises a liquid adding device (27) conf1gured for addingliquid to a bottom part (25) of the prehydrolysis vessel (5a; 5b; 5c; 5d) for displacinghydrolysate out through the hydrolysate outlet (9). Prehydrolysis vessel system according to any one of the claims 12-20, wherein saidhydrolysate outlet (9) of the prehydrolysis vessel (5 a; 5b; 5c; 5d) is at least one screen(9; 51) provided in an enclosing wall (21) of the prehydrolysis vessel. A hydrolysate extracting arrangement (3a; 3b; 3c; 3d) conf1gured for being connectedto and extracting hydrolysate from a prehydrolysis vessel (5a; 5b, 5c; 5d) in acontinuous pulp production system, said hydrolysate extracting arrangement (3 a; 3b;3c; 3d) comprising: - a hydrolysate removing conduit (7) comprising a prehydrolysis vesselconnector (8) which is arranged for being connected to a hydrolysate outlet (9)of the prehydrolysis vessel (5a; 5b; 5c; 5d); and - at least one cooling device (1 la, 1 lb; 11b°; llc, 11c°, llc” ”; 11d) conf1guredsuch that it can be provided to the prehydrolysis vessel (5a; 5b; 5c; 5d) andsuch that it can cool down a content of the prehydrolysis vessel such that thecontent has been cooled down when the content arrives at a hydrolysis outlet(9) of the prehydrolysis vessel (5a; 5b; 5c; 5d) on its way from an inlet (13)provided in one end of the prehydrolysis vessel (5a; 5b; 5c; 5d) to an outlet(15) provided in an opposite end of the prehydrolysis vessel, wherein saidcooling device (1 la, 11b; 11b°; llc, 11c°, 11c”; 11d) is conf1gured to cooldown the content in the prehydrolysis vessel to such a degree that ahydrolysate removed through the hydrolysate outlet (9) has a temperaturebetween 70°C and 130°C . 18 23. 24. 25. 26. 27. Hydrolysate extracting arrangement according to claim 22, wherein said at least oneCooling device (1 la, llb; llb°; llc, 11c°, llc”; 11d) is conf1gured such that it canprovide a cooling effect to a content in the prehydrolysis vessel (5a; 5b; 5c; 5d) in acooling section (23) of said prehydrolysis vessel, when the cooling device is providedto the prehydrolysis vessel, which cooling section (23) is a length section of theprehydrolysis vessel (5a; 5b; 5c; 5d), in which length section the hydrolysis outlet (9)is provided and which length section is less than 1/3 or less than 1/5 of a total lengthof the prehydrolysis vessel and wherein said cooling section (23) is closer to the outlet (15) than to the inlet (13) of the prehydrolysis vessel. Hydrolysate extracting arrangement according to claim 22 or 23, wherein the coolingdevice (1 la, 1 lb; llb°; llc, 11c°, 11c° °; lld) is configured for cooling the content tosuch a degree that the removed hydrolysate has a temperature between 70°C and120°C or between 90°C and 110°C. Hydrolysate extracting arrangement according to any one of the claims 22-24, whereinsaid at least one cooling device (1 la, 1 lb; 11b°; llc, 11c°, llc”; 11d)comprises aliquid adding device (1 la) which is conf1gured to add a liquid having a temperaturebetween 20°C and 100°C or a temperature between 30°C and 80°C or a temperature between 40°C and 70°C to the content of the prehydrolysis vessel. Hydrolysate extracting arrangement according to any one of the claims 22-25, whereinsaid at least one cooling device (1 la, 1 lb; 11b°; llc, 11c°, llc”; 11d)comprises ahydrolysate circulation arrangement (3 9) which, when connected to the prehydrolysisvessel (5b; 5c; 5d), is configured to circulate a part of the hydrolysate removedthrough the hydrolysate removing conduit (7) through a heat exchanger (41) forcooling it down to a temperature between 20°C and 100°C or a temperature between30°C and 80°C or a temperature between 40°C and 70°C and add the cooledhydrolysate to the content of the prehydrolysis vessel (5b; 5c; 5d). Hydrolysate extracting arrangement according to claim 26, wherein said hydrolysate circulation arrangement (3 9) is configured to add the cooled hydrolysate into the 19 28. 29. prehydrolysis vessel through nozzels (3 7) provided around a periphery of an enclosing Wall (21) of the prehydrolysis Vessel (5b; 5c; 5d). Hydrolysate extracting arrangenient according to any one of the clainis 26-27, Whereinsaid hydrolysate circulation arrangenient (3 9) is configured for adding at least a part ofsaid cooled hydrolysate to the content of the prehydrolysis Vessel (5b; 5c) through anoutlet (34b) of a liquid adding pipe (3 3b) protruding into the prehydrolysis Vessel (5b;5c), Wherein said outlet (34b) is positioned closer to a central axis (A) of the prehydrolysis vessel than to an enclo sing Wall (21).Hydrolysate extracting arrangenient according to any one of the clainis 22-28, Wherein the hydrolysate extracting arrangenient (3a; 3b; 3c; 3d) further coniprises a sugar extracting arrangenient (31) connected to the hydrolysate renioving conduit (7).
SE1950386A 2019-03-29 2019-03-29 A method and a system for extracting hydrolysate in a continuous cooking process for producing pulp SE1950386A1 (en)

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CN202080025300.9A CN113646481B (en) 2019-03-29 2020-03-18 Method and arrangement in a continuous pulp production process
EP20782621.5A EP3947808A4 (en) 2019-03-29 2020-03-18 A method and arrangement in a continuous pulp production process
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US3530034A (en) 1969-05-16 1970-09-22 Itt Rayonier Inc Continuous aqueous prehydrolysis of wood chips
US4436586A (en) * 1982-01-22 1984-03-13 Kamyr, Inc. Method of producing kraft pulp using an acid prehydrolysis and pre-extraction
US20070131363A1 (en) * 2005-10-24 2007-06-14 Andritz Inc. Fiberline systems, processes and methods
BRPI0505212A (en) * 2005-11-01 2007-08-07 Dedini Sa Ind De Base improvements in fast acid hydrolysis process of lignocellulosic material and hydrolysis reactor
FI123036B (en) * 2006-02-10 2012-10-15 Metso Paper Inc Method for recovering hydrolysis products
US8734610B2 (en) * 2007-05-23 2014-05-27 Andritz Inc. Two vessel reactor system and method for hydrolysis and digestion of wood chips with chemical enhanced wash method
US9260818B2 (en) 2007-05-23 2016-02-16 Andritz Inc. Single vessel reactor system for hydrolysis and digestion of wood chips with chemical enhanced wash method
EP2212467B1 (en) * 2007-11-01 2014-06-11 Eau-Viron Incorporated Methods and apparatus for hydrolyzing cellulosic material
US8192549B2 (en) 2008-06-10 2012-06-05 Andritz Inc. Apparatus and method for hydrolysis of cellulosic material in a two-step process
JP5378306B2 (en) * 2010-06-15 2013-12-25 月島機械株式会社 Biomass processing apparatus and processing method
EP2707539B1 (en) * 2011-05-13 2019-05-08 Valmet Aktiebolag Compact process for producing prehydrolyzed pulp
WO2016112203A1 (en) * 2015-01-07 2016-07-14 Andritz Inc. System and method for monitoring and control of multiple processing zones within pressurized vessels
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