WO1996025553A1 - Procede de traitement de matieres lignocellulosiques par hydrolyse sous pression constante, et installation correspondante - Google Patents

Procede de traitement de matieres lignocellulosiques par hydrolyse sous pression constante, et installation correspondante Download PDF

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Publication number
WO1996025553A1
WO1996025553A1 PCT/CZ1996/000005 CZ9600005W WO9625553A1 WO 1996025553 A1 WO1996025553 A1 WO 1996025553A1 CZ 9600005 W CZ9600005 W CZ 9600005W WO 9625553 A1 WO9625553 A1 WO 9625553A1
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WIPO (PCT)
Prior art keywords
pressure
water
reservoir
hydrolysate
furfural
Prior art date
Application number
PCT/CZ1996/000005
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English (en)
Inventor
Zdenek KRATOCHVÍL, Sr.
Ivo ROUS^¿AR
Frantis^¿ek MACHEK
Zdenek KRATOCHVÍL, Jr.
Original Assignee
F + S Market, Spol. S.R.O.
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 F + S Market, Spol. S.R.O. filed Critical F + S Market, Spol. S.R.O.
Priority to AU44805/96A priority Critical patent/AU4480596A/en
Publication of WO1996025553A1 publication Critical patent/WO1996025553A1/fr

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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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C07D307/50—Preparation from natural products
    • 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
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention concerns the method of processing of 1ignocellulose materials by continuous pressure hydrolysis giving rise to lignin, furfural or furane , furfuralalcohol , acetic and formic acid, cellulose or glucose and 10 corresponding equipment for performance of this method.
  • Hydrolysis of lignocellulose materials was carried out 15 by sulphuric acid, later utilisation of sulphurous acid was tested. More modern percolation procedure of hydrolysis was elaborated by Scholler, who used equipment, where vapour, containing sulphuric acid, passed through raw material to be hydrolysed . Countercurrent hydrolysis 20 of moist raw material by 37 % hydrochloric acid or by gaseous hydrogen chloride is known .
  • Non-hydrolysed fractions may form suspensions with poor filtrability .
  • Vhen using fluid procedure decrease in yields is caused also by thermooxidising decomposition of furfuralaldehyde in reaction with air oxygen. Oxygen flows into the reaction space in chamber method during dosing.
  • Prehydrolysis does not fulfil its expected function of hemicellulose decomposition and transition to so called pure fraction, to the second stage of lignin and cellulose.
  • Prehydrolysis remnants of cellulose exist in range, causing inhibition of consequent fermentation procedures.
  • the substance of the invention consists mainly in moisturising of disintegrated raw material at pressure and heating it by pressure water of temperature 170 to 200 °C at the ratio of water to dry substance 0.5 to 1:1. For the mixture obtained excessive water is pressed off to the ratio of water to dry matter 1:0.3 to 0.5.
  • Arising salt of furoic acid is melted at the temperature 200 to 240 °C to furane or catalysts at the temperature 350 to 430 °C act on furane .
  • the first expansion proceeds with advantage at the temperature 130 to 170 °C and the pressure 0.25 to 0.9 MPa and the second expansion proceeds at the temperature 105 to 120 °C and the pressure 0.12 to 0.2 MPa.
  • the equipment consists of the reservoir of raw material , which is via feeding press of worm type and insert connected with the first section of the hydrolyser, where worm conveyor is situated.
  • Output from the last section of the hydrolyser is equipped by high-pressure expansion slide valve, which is followed by middle-pressure expander and low-pressure expander.
  • middle-pressure expander and low-pressure expander In the upper part of the expanders the second and third tubing for outlet of the gaseous phase are located, the second tubing for outlet from the middle pressure expander is directed to the system of recuperation exchangers with its mouth in the upper part of the rectification column.
  • In the upper part of the column exhaust of furfural and methanol and in the bottom part exhaust of the mixture of formic acid, acetic acid and water are located.
  • the third tubing for outlet of the vapour phase from the low-pressure expander may pass through the lower part of the rectification column and it leads in the middle part of the rectification column.
  • the lower part of the middle-pressure expander is connected via middle-pressure slide valve with the first tubing for hydrolysate and solid phase with the low-pressure expander.
  • This expander is connected via low-pressure expansion slide valve by the fourth tubing for hydrolysate and solid phase with the reservoir for hydrolysate and solid phase, from which outlet of vapours is directed to the rectification column.
  • the reservoir for hydrolysate and solid phase is via pump connected with the separation equipment.
  • the separation equipment is provided by the fifth tubing for outlet of the liquid hydrolysate to the reservoir of hydrolysate and by conveyor for output of the solid phase after hydrolysis, which is connected to extractor and reservoir of the raw material .
  • Filling press consists of the cylindrical part and conical part. A worm with constant lead in the cylindrical part and with decreasing lead in the conical part goes through both parts of the press, while the conical part consists of segments, among which are gaps for outlet of the liquid to the reservoir of liquid, the conical part is provided inside by longitudinal guide bars, the front face of the cylindrical part is perforated .
  • the insert is tightly connected with the filling press and it leads to the first section of the hydrolyser and it consists of input conical narrowing part. cylindrical part and conical widening part. Opposite the outlet of the conical widening part safety closing piston, controlled by adjustable pressure is situated .
  • the expanders have the form of cyclone separators and the outlet of hydrolyser enters tangentially the middle-pressure expander and the first tubing 10 for hydrolysate and solid phase enters tangentially the low-pressure expander.
  • the second and third tubes for outlet of the vapour phase from expanders are recessed to the upper parts of expander below the level of the mouth of the outlet from the hydrolyser and the first tubing for hydrolysate and solid phase.
  • middle-pressure expansion slide valve is situated and in the bottom part of the low-pressure expander low-pressure expansion slide valve is situated.
  • the hydrolyser consists of at least one section, sections are connected by vertical tube or by widening cone. All sections are provided by exhaust of inert gases and worm conveyor passes through all sections.
  • the material In the reservoir for raw material the material is preheated to the temperature of 85 to 90 °C by feed of small amount of technological pressure water of the temperature 170 to 200 °C, which acts thanks to its expansion very intensively on the material. Moistened preheated material is relieved of excessive moisture in the conical part of the filling press, which is equipped by effective dewatering system, which reliably removes the excessive liquid, which represents great problem for most current equipment.
  • the filling press presses material into the insert, in which it forms compact plug. Its purpose is to separate atmospheric medium of the filling press from the high-pressure medium in the hydrolyser. In this model the insert is in addition in contrast to all known solutions provided by conical widening part, which substantially improves the main function of the plug, i .e.
  • the material In the hydrolyser the material is mixed with pressure water in the ratio of dry matter to water 1:2.5 to 1:4. Water may contain sulphuric acid in the amount of 0.1 to 0.3 % mass related to the suspension mass .
  • Concentrated sulphuric acid is mixed with water to the concentration 0.2 to 0.4% mass, before feeding into the hydrolyser in such way, that into the hydrolyser diluted solution with minimal corrosive effects is added.
  • Mixture of water and material moves on through the equipment due to rotation of worm conveyor and substantially by plug flow. From the upper part of the hydrolyser inert gases are continuously removed trough exhaust. Material falls into other sections of the hydrolyser through the vertical widening tube. At the end of the last section the decomposed material is squeezed out into high-pressure expansion slide valve, from which the expanded mixture is displaced into the middle pressure-expander, where the temperature is in the range 130 to 175 °C and pressure is in the range 0,25 to 0,9 MPa.
  • expander in the form of cyclone separator is utilised with great advantage.
  • the material is brought in tangentially to the cylindrical part.
  • the hydrolysate and solid phase expand further in the low-pressure expander to the temperature 105 to 120 °C and pressure 0,12 to 0,20 MPa.
  • Expander functions on the same principle of the cyclone separator.
  • the last vapour fraction is released from the hydrolysate in the reservoir of hydrolysate and solid phase, from which the liquid is pumped together with the solid phase into separator, where solid phase is separated, which consists of lignin and cellulose, from the liquid hydrolysate. Due to the rotation flow perfect separation of the solid phase and hydrolysate from the vapour phase occurs.
  • the hydrolysate contains 0,1 mass% of furfural at maximum and in the same time faultless outlet of the solid phase from expander is guaranteed.
  • the main advantage of the equipment is high energetic efficiency, which is enabled by double expansion.
  • Vapour leaves the middle-pressure expander at the temperature 130 to 170 °C.
  • This vapour is used in the system of recuperation exchangers for preheating of fresh technologic water to the temperature 125 to 165 °C, so the pressure boiler gives heat only for heating to the temperature of hydrolysis.
  • Other substantial saving of heat results from usage of vapour in the low-pressure expander for heating in the boiler of the rectification column.
  • Double expansion has also the advantage of perfect exhaust of furfural from hydrolysed solution, where its presence is undesirable due to consequent fermentation.
  • the vapour phase from expanders is separated in the rectification column to furfural and methanol and to water solution of inorganic acids.
  • Furfural may be further purified in distillation column, it is obtained in high purity and yielding, 60% related to original pentosanes in the hydrolysed material. Furfural maybe processed further to furane.
  • the equipment is capable to process wide range of types of input raw materials - continuous exhaust of inert gases
  • cellulose glucose eventually, lignin, furfural, furane, acetic acid, formic acid, methanol, ethanol - high yielding of individual products, yielding of furfural is 48 to 60%, of cellulose 95% of input cellulose, of glucose 65% related to input cellulose, of lignin 80 to 90% of input raw material related to wheat straw - production of highly reactive lignin
  • Fig. 1 is the scheme of the whole equipment for hydrolysis .
  • Fig.2 shows the filling press 51.
  • Fig.3 shows the insert 52.
  • Fig.4 Shows the scheme of the equipment for production of furane from furfural via furoic acid.
  • Fig. 5 shows the scheme of the equipment for direct production of furane from furfural.
  • the disintegrated straw is moistened and heated by pressure water of temperature 200 °C in the ratio of water to the dry matter 0.8:1 to the temperature of 90 °C. From obtained mixture the excessive water is removed by pressing to the ratio of dry matter to water 1:0.4 and consequently it is hydrolysed at the temperature 200 °C and corresponding pressure for 8 minutes under simultaneous feed of pressure water of the temperature 200 °C in the ratio to the dry matter 1:3.5.
  • the hydrolysis proceeds with uniform steady process of solid and liquid phases. After termination of hydrolysis the material is expanded in two stages giving rise to vapour phase and hydrolysate.
  • the vapour phase contains furfural, methanol and lower organic acids, the hydrolysate contains cellulose, lignin and water.
  • vapour phase is rectified and separated to furfural mixture and mixture of acetic and formic acids and water. Water is removed from the hydrolysate by pressing and the solid remnant undergoes extraction by acetone for 30 minutes. Into the acetone phase lignin is extracted and after evaporation of the solvent reactive lignin is obtained, cellulose remains in the solid phase .
  • Wheat straw contained 480 kg of cellulose, 270 kg of pentosanes and 130 kg of lignin related to 1000 kg of dry matter. Using procedure according the invention 456 kg of pure cellulose was obtained, which represents 95 % yielding, 100 kg of furfural, which is 53% yielding and 117 kg of pure lignin, which is 80% yielding. Furfural was further processed to furane. Yielding of furane in respect to furfural was 60% using the direct method, via furoic acid it was 50%.
  • the equipment consists of the reservoir 5_0 of raw material, which is via the filling worm press 5_1_ and the insert 5_2 connected with the first section of the hydrolyser 5_3, where the worm conveyer 5_4 is situated.
  • the filling worm press 5J is connected with the reservoir 6_7 for liquid removed by pressing.
  • the reservoir 5_0 of raw materials and hydrolyser 5_3 are equipped by feed of pressure water from the boi ler 6 .
  • the hydrolyser 5 consists of three sections, sections are connected by vertical tube or by widening cone. Outlet from the last section of the hydrolyser 5_3 is equipped by the worm equipment 6_8 and the high-pressure expansion slide valve 5_5 , which is followed by the middle-pressure expander 5_6 , which followed by the low-pressure expander 5_7_. Al l sections of the hydrolyser 5_3 are provided with the exhaust 6 of inert gases.
  • the expanders 5_6 and 5_7 have the form of cyclone separators and the outlet £ from the hydrolyser 5_3 enters tangentially into the middle-pressure expander 5_6.
  • the first tubing 1. for hydrolysate and solid phase enters tangentially the low-pressure expander 57.
  • the second tube 2 and third tube 3_ for outlet of vapour phase from the expanders 5_6_ and 5_7 are embedded in to the upper parts of expanders 5_6 and 5_7 under the level of the mouth of the output £ from the hydrolyser 5_3 and the first tubing 1_ for hydrolysate and solid phase.
  • middle-pressure expansion slide valve 6 In the bottom part of the middle-pressure expander 5_6 middle-pressure expansion slide valve 6) is situated and in the bottom part of the low-pressure expander 5_7 low-pressure expansion slide valve 6_1_ is situated.
  • the second tubing 2 for outlet of the vapour phase from the middle-pressure expander 5_6 is directed to the system of recuperation exchangers 5_8 and it is connected with the upper part of the rectification column 5_9 , in the upper part of which the outlet 1_ of furfural and methanol is situated and in the bottom part the outlet of mixture of acetic acid, formic acid and water is situated.
  • the third tubing . 3 for outlet of the vapour phase from the low pressure expander 5_7 goes through the bottom part of the rectifica ion column 5_9 and has its mouth in the middle part of the rectification column 59.
  • the bottom part of the middle-pressure expander 5_6 is connected via middle-pressure expansion slide valve 60 by the first tubing 1 for hydrolysate and solid phase with the low-pressure expander 57.
  • Expander 57 is connected via low-pressure expansion slide valve 6J_ by the forth tubing 4_ for hydrolysate and solid phase by the reservoir 6_2 for hydrolysate and solid phase which is via the pump 63 connected with the separation equipment 6_4.
  • Separation equipment 6_4 is provided by the fifth tubing 5. for outlet of liquid hydrolysate to the reservoir 6_5 and by the conveyor i for outlet of the solid phase after hydrolysis, which is connected with the extractor 6_6 or with the reservoir .5(3 for the raw material .
  • Exhaust 2 of furfural and methanol is connected with the purification block of furfural .
  • Figure 2 shows the filling press 51_ , which consists of the cylindrical part 3_i and conical part 3_2.
  • the worm 33 with constant lead in the cylindrical part 3_1 and with decreasing lead in the conical part 3_2 passes through both parts, while the conical part 3_2 consists of segments .3_4 among which there are gaps 3_5 for outlet of liquid into the reservoir 6_7 for liquid removed by press, the conical part 3_2 is inside equipped by longitudinal guide bars 3_6_, the front face 3_7 of the cylindrical parts 3_1_ is perforated.
  • the insert 5.2 is shown in the figure 3. It is tightly connected with the filling press 51_ and it leads into the first section of the hydrolyser 5_3. It consists of inlet conical narrowing part 3_8, the cylindrical part 39 and the conical widening part 4_0. Opposite to the outlet of the conical widening part 4O the safety closing piston 4 ⁇ , controlled by adjustable pressure is located .
  • the equipment consists of the furfural reservoir 22 . which is via the first exchanger 7_2 connected with the first vessel 7_3, which is connected with the reservoir 7_5 of sodium hydroxide and with the second vessel 76 , which is followed by the third vessel 7_7. All 3 vessels are equipped by stirrers and cooling.
  • the third vessel 77 is connected with extraction column 74 * which is connected with the forth vessel ⁇ H) for removal of water from ether extract, which is connected with the reservoir 7_9 of magnesium sulphate and with the first drum filter 81.
  • Filter is followed by the conveyer 8_2 and by the annealing furnace 8_3 for magnesium sulphate.
  • the annealing furnace is via the second exchanger 8_4 connected with the ether reservoir 7_8 and with the reservoir 7_9 of magnesium sulphate.
  • the first drum filter 8J_ is connected via the reservoir 8.5 of semi-product with the distillation column 8.6.
  • the upper plate of the column £6_ is connected with the reservoir 23 . of ether and bottom plates are connected with the reservoir 8_7 of 2-furfuralalcohol .
  • the bottom part of the extraction column 7_4 is connected via the fifth vessel 8_8 with the crystal1i sator 90 , which is provided by cooling.
  • the crystal 1isator £0 is connected to the sixth vessel 1_, which is connected via the conveyor £2 with the reservoir £. of activated carbon, the sixth vessel £_ is via the second drum filter £4 and the third exchanger convinced and other third drum filter £6 connected with the reservoir £7 of furoic acid.
  • This reservoir is via the third conveyor £8 connected with the melting furnace ££, which is followed by the reservoir 100 of furane.
  • Fig. 5 shows the scheme of direct production of furane from furfural, which consists of reservoir of furfural 2_L. which is followed by the pressure melting furnace 101. which is via the exchanger 102 connected with the reservoir of furane 103.
  • the pressure melting furnace 101 is further connected with burning chamber 104.
  • Vegetable raw material is dosed via continuous balance to the reservoir of raw material 5j0, from which it is swept out by worm _5_2 to the fi lling press 51 , where in the front cylindrical part 3 i t is preheated by pressure water or steam to about 90 °C.
  • the filling press 5 presses the material via narrowed insert 5_2 into the hydrolyser 5_3. Liquid removed by pressing in the filling press 5J_ flows to the reservoir 6_7 of the removed liquid, from which it is pumped back to the feed of the filling press 5.1.
  • the insert _5_2 compact plug is formed, which separates the hydrolyser from the view of pressure. Compactness and impermeability of the plug is assured by the safety piston 4 .
  • Material entering the first section of the hydrolyser 5_3 is wetted from above by pressure water of the temperature 170 to 200°C, eventually by sulphuric acid, in case when decomposition of cellulose is the purpose. Material is uniformly moved forward by the worm conveyor _5_4 with liquid in the hydrolyser 5_3 at the temperature 160 to 230 °C at the pressure 0.6 to 2.8 Mpa.
  • the whole time of retention (delay) of material and liquid is the same, i.e. from 3 to 12 minutes.
  • All sections of the hydrolyser 5_3 work at the same pressure. From the upper part inert gases are removed continuously by the exhaust 6_. From the last section of the hydrolyser 5_3 material and liquid are swept out by the worm equipment 6_8 into the high-pressure slide valve 5_5, behind which the mixture is expanded to middle pressure 0.25 to 0.9 MPa and temperature from 130 to 175 °C. In the middle-pressure expander 5_6 vapor phase is separated.
  • the condensed vapour phase is brought into the rectification column 5_9.
  • Liquid and solid phases from the middle-pressure expander ⁇ 6 are directed via middle-pressure expansion slide valve 6_0 to the low-pressure expander 5_ , in which the temperature is in the range 105 to 120 °C and pressure 0.12 to 0.2 MPa.
  • the released vapour is used for heating in the boiler of the rectification column 5_£.
  • Liquid and solid phase is removed via low-pressure expansion slide valve 61 to the reservoir 6.2 for hydrolysate and solid phase. From this reservoir released vapour phase is also directed into the rectification column 5_£.
  • Liquid and solid phases proceed into the separator 6_4, where they are separated to solid phase, which consists mostly of lignin and non-reacted cellulose. Both substance are separated in the extractor 66.
  • Liquid hydrolysate with monosacharides is removed in case of acidic hydrolysis via the reservoir 6_5 for further treatment e.g. for fermentation.
  • Liquid hydrolysate contains in case of acidic hydrolysis 12 to 15% mass, of glucose and it is further processed e.g. to ethanol .
  • Furfural fraction is further purified by distillation and it is collected in the reservoir 21 of furfural .
  • the furnace 8_3 is blown through by air and ether vapours are removed, which are further on condensed in the second exchanger J ⁇ 4 and return to the ether reservoir 2 ⁇ • Water from hydrate MgS04 is then removed by roasting, regenerated magnesium sulphate is returned by conveyor to the reservoir 7 .
  • Filtrate from the first drum filter 82. is removed to the reservoir of semi -product 8 ..
  • This mixture contains only 2-furfuralalcohol and ether, impurities ( water, magnesium sulphate, furoic acid) eventually.
  • This mixture is pumped into vacuum distillation column 86. From the upper plate ether is removed, which is directed back to the reservoir 28 and from the bottom plate 2-furfuralalcohol is removed, which is stored in the 2-furfuralalcohol reservoir 87.
  • the second steam, leaving the extraction column 74 contains sodium salt of furoic acid. Conversion to furoic acid proceeds by acidification in the fifth vessel £18. By cooling in the crystalliser £0 crystals of furoic acid are precipitated and sodium hydrogensulphate (according to pH precipitation of sulphate may occur) . After separation of these two substances it is necessary at first to suck away excessive water. This is done in the crystallisator £0_. Then the mixture is boiled with activated carbon in the sixth vessel £2. Activated carbon is dosed by the second conveyor of activated carbon £2 from the reservoir of activated carbon 93. Boiling lasts for about 45 minutes. Activated carbon is then removed from the mixture on the second filter £4 and is regenerated in simple way by blowing-through by air in the reservoir of activated carbon 93.
  • Filtrate is transported by pump via the fourth exchanger £5. to the third drum filter £6_.
  • the fourth exchanger £5 the mixture is cooled to the temperature 16 to 20 °C (below the temperature 10 °C even the rest of hydrogen sulphate is separated out and above the temperature 20 °C crystallisation is not sufficiently intensive) . Crystals separated out are then removed on the third filter £6.
  • the invention may be utilised for complex and effective processing of sources of phyto ass sources as new perspective sources of non-fossil raw materials in the tight bond to chemical , pharmaceutical and food industries .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé et installation pour le traitement de matières lignocellulosiques par hydrolyse sous pression constante, éventuellement en présence d'un acide minéral, puis par détente et séparation de l'hydrolysat et de la phase gazeuse. Selon le procédé, on mouille (50, 52, 67, 69) une matière brute désagrégée à l'aide d'eau sous pression à une température allant de 170 à 200 °C, le rapport entre l'eau et les matières sèches étant de 0,5 à 1:1, on extrait l'excédent d'eau du mélange ainsi obtenu, par pressage (51) jusqu'à obtention d'un rapport eau/matières sèches de 1:0,3 à 0,5, puis on effectue une hydrolyse à une température allant de 160 à 230 °C, sous une pression comprise entre 0,6 et 2,8 MPa, et ce pendant 3 à 18 minutes, avec une alimentation simultanée en eau sous pression à une température allant de 170 à 200 °C, le rapport entre cette eau et les matières sèches étant de 1:2,5 à 4, et l'hydrolyse se poursuit avec un avancement homogène simultané (54) des phases liquide et solide. Ensuite, après la fin de l'hydrolyse, on fait dilater la matière en deux étapes (56, 57) de manière à obtenir une phase gazeuse (2, 3) et un hydrolysat (62), la phase gazeuse renfermant du furfural, du méthanol et de l'acide acétique, et l'hydrolysat renfermant de la cellulose, de la lignine et de l'eau, et on réalise une rectification (59) de la phase gazeuse et une séparation de celle-ci afin d'obtenir un mélange à base de furfural (7) et un mélange d'acide acétique, d'acide formique et d'eau (8). On extrait l'eau de l'hydrolysat par pressage (64), puis on extrait (66) un reste solide (11) à l'aide d'un solvant choisi dans le groupe constitué d'éthanol et d'acétone, on extrait la lignine du solvant, et on obtient une lignine réactive après évaporation du solvant. La cellulose demeure en phase solide, on purifie par une distillation supplémentaire le furfural obtenu à partir de la phase gazeuse, et on peut soumettre le furfural pur à un traitement supplémentaire en vue d'obtenir un furanne.
PCT/CZ1996/000005 1995-02-08 1996-02-01 Procede de traitement de matieres lignocellulosiques par hydrolyse sous pression constante, et installation correspondante WO1996025553A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU44805/96A AU4480596A (en) 1995-02-08 1996-02-01 Method of processing of lignocellulose materials by continuous pressure hydrolysis and corresponding equipment

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CZ95320A CZ281504B6 (cs) 1995-02-08 1995-02-08 Způsob zpracování lignocelulózových materiálů kontinuální tlakovou hydrolýzou a zařízení
CZPV320-95 1995-02-08

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000047569A1 (fr) * 1999-02-11 2000-08-17 Steiner, Philipp, Daniel Procede servant a preparer furfural
WO2002053829A1 (fr) * 2000-12-29 2002-07-11 Chempolis Oy Procede de production de furfural, d'acide acetique et d'acide formique a partir de liqueur noire de cuisson
WO2003071025A2 (fr) * 2002-02-22 2003-08-28 Gilles Gervais Procede de traitement de matiere ligno-cellulosique pour produire du bio-ethanol
WO2006024242A1 (fr) * 2004-08-31 2006-03-09 Biotech Progress, A.S. Procédé et dispositifs de traitement continu de matières premières renouvelables
WO2008011839A2 (fr) * 2006-07-24 2008-01-31 Coramexport S.R.O. Équipement pour l'électrolyse discontinue ou continue de matière organique
WO2009015614A1 (fr) * 2007-07-30 2009-02-05 Kmps Financial Group, S.R.O. Procédé et équipement de production de glucose, d'éthanol, de furfural, de furane et de lignine à partir de matières premières renouvelables
EP2075347A1 (fr) * 2006-10-26 2009-07-01 Kawasaki Plant Systems Kabushiki Kaisha Procédé de saccharification/décomposition d'une biomasse à base de cellulose et dispositif de saccharification/décomposition
EP2420560A1 (fr) * 2010-08-18 2012-02-22 Biomass Technology a.s. Installation de traitement en continu d'une part significative de matériaux contenant de la phytomasse
US8328947B2 (en) 2008-08-29 2012-12-11 Iogen Energy Corporation Method for low water hydrolysis or pretreatment of polysaccharides in a lignocellulosic feedstock
CN102864668A (zh) * 2012-09-18 2013-01-09 北京林业大学 木质纤维素原料预处理方法
CN108912072A (zh) * 2018-10-08 2018-11-30 肥城金威机械有限公司 利用植物秸秆制取糠醛的制备装置和方法及应用
US10240006B2 (en) 2014-05-01 2019-03-26 Renmatix, Inc. Upgrading lignin from lignin-containing residues through reactive extraction
CN110128379A (zh) * 2019-04-18 2019-08-16 南京工业大学 一种连续化制备糠醛的方法
RU2740758C2 (ru) * 2016-05-03 2021-01-20 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Растворители на основе лигнина и способы их получения

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WO2000047569A1 (fr) * 1999-02-11 2000-08-17 Steiner, Philipp, Daniel Procede servant a preparer furfural
US6743928B1 (en) 1999-02-11 2004-06-01 International Furan Technology (Pty) Limited Process for the manufacture of furfural
WO2002053829A1 (fr) * 2000-12-29 2002-07-11 Chempolis Oy Procede de production de furfural, d'acide acetique et d'acide formique a partir de liqueur noire de cuisson
US6955743B2 (en) 2000-12-29 2005-10-18 Chempolis Oy Method for producing furfural, acetic acid and formic acid from spent pulp-cooking liquor
WO2003071025A2 (fr) * 2002-02-22 2003-08-28 Gilles Gervais Procede de traitement de matiere ligno-cellulosique pour produire du bio-ethanol
WO2003071025A3 (fr) * 2002-02-22 2004-06-03 Gilles Gervais Procede de traitement de matiere ligno-cellulosique pour produire du bio-ethanol
US7189306B2 (en) 2002-02-22 2007-03-13 Gervais Gibson W Process of treating lignocellulosic material to produce bio-ethanol
WO2006024242A1 (fr) * 2004-08-31 2006-03-09 Biotech Progress, A.S. Procédé et dispositifs de traitement continu de matières premières renouvelables
EA011136B1 (ru) * 2004-08-31 2008-12-30 Биотек Прогресс, А.С. Способ и устройство для непрерывной переработки возобновляемого сырья
WO2008011839A2 (fr) * 2006-07-24 2008-01-31 Coramexport S.R.O. Équipement pour l'électrolyse discontinue ou continue de matière organique
WO2008011839A3 (fr) * 2006-07-24 2008-03-27 Coramexp S R O Équipement pour l'électrolyse discontinue ou continue de matière organique
CN101517062B (zh) * 2006-07-24 2012-08-29 科拉出口S.R.O.公司 用于有机物不连续或连续水解的设备
EP2075347A1 (fr) * 2006-10-26 2009-07-01 Kawasaki Plant Systems Kabushiki Kaisha Procédé de saccharification/décomposition d'une biomasse à base de cellulose et dispositif de saccharification/décomposition
US8562747B2 (en) 2006-10-26 2013-10-22 Kawasaki Plant Systems Kabushiki Kaisha Method and system for hydrolytic saccharification of a cellulosic biomass
EP2075347A4 (fr) * 2006-10-26 2011-06-22 Kawasaki Heavy Ind Ltd Procédé de saccharification/décomposition d'une biomasse à base de cellulose et dispositif de saccharification/décomposition
EP2520671A1 (fr) * 2006-10-26 2012-11-07 Kawasaki Jukogyo Kabushiki Kaisha Procédé et système de saccharification hydrolytique d'une biomasse cellulosique
EP2520673A1 (fr) * 2006-10-26 2012-11-07 Kawasaki Jukogyo Kabushiki Kaisha Procédé et système de saccharification hydrolytique d'une biomasse cellulosique
EP2520672A1 (fr) * 2006-10-26 2012-11-07 Kawasaki Jukogyo Kabushiki Kaisha Procédé et système de saccharification hydrolytique d'une biomasse cellulosique
WO2009015614A1 (fr) * 2007-07-30 2009-02-05 Kmps Financial Group, S.R.O. Procédé et équipement de production de glucose, d'éthanol, de furfural, de furane et de lignine à partir de matières premières renouvelables
EA017476B1 (ru) * 2007-07-30 2012-12-28 Кмпс Файненсиал Груп, С.Р.О. Способ и оборудование для производства глюкозы, этанола, фурфурола, фурана и лигнина из возобновляемого сырья
US8328947B2 (en) 2008-08-29 2012-12-11 Iogen Energy Corporation Method for low water hydrolysis or pretreatment of polysaccharides in a lignocellulosic feedstock
EP2420560A1 (fr) * 2010-08-18 2012-02-22 Biomass Technology a.s. Installation de traitement en continu d'une part significative de matériaux contenant de la phytomasse
CN102864668A (zh) * 2012-09-18 2013-01-09 北京林业大学 木质纤维素原料预处理方法
US10240006B2 (en) 2014-05-01 2019-03-26 Renmatix, Inc. Upgrading lignin from lignin-containing residues through reactive extraction
RU2740758C2 (ru) * 2016-05-03 2021-01-20 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Растворители на основе лигнина и способы их получения
CN108912072A (zh) * 2018-10-08 2018-11-30 肥城金威机械有限公司 利用植物秸秆制取糠醛的制备装置和方法及应用
CN110128379A (zh) * 2019-04-18 2019-08-16 南京工业大学 一种连续化制备糠醛的方法

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