EP0432015A1 - Verfahren und Einrichtung zur Herstellung einer zumindest 80% Xylose enthaltende Zuckermischung aus einem lignocellulosischen Substrat - Google Patents

Verfahren und Einrichtung zur Herstellung einer zumindest 80% Xylose enthaltende Zuckermischung aus einem lignocellulosischen Substrat Download PDF

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Publication number
EP0432015A1
EP0432015A1 EP90403374A EP90403374A EP0432015A1 EP 0432015 A1 EP0432015 A1 EP 0432015A1 EP 90403374 A EP90403374 A EP 90403374A EP 90403374 A EP90403374 A EP 90403374A EP 0432015 A1 EP0432015 A1 EP 0432015A1
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EP
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Prior art keywords
substrate
impregnation
reactor
hydrolysis
xylose
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EP90403374A
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English (en)
French (fr)
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EP0432015B1 (de
Inventor
Daniel Ballerini
Francis Nativel
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00—Sugars not otherwise provided for in this class
    • C13K13/002—Xylose

Definitions

  • the invention relates to a method and a unit for the continuous production of a mixture of sugars containing at least 80% by weight of xylose from a lignocellulosic substrate. It applies in particular to the transformation of xylose into xylitol which is a natural sweetener.
  • lignocellulosic substrates wood, annual plants
  • a heterogeneous composition in which there are usually three predominant fractions which are cellulose, hemicelluloses and lignin. This heterogeneity complicates their valuation.
  • a separation of hemicelluloses which have a variable sugar composition but are often rich in pentoses, in particular xylose
  • cellulose composed exclusively of glucose
  • This interest requires that the objective targeted is chemical use or fermentation since if most fermentations use glucose from the hydrolysis of cellulose, fewer are those that use, for example, the pentoses of hemicelluloses.
  • a so-called water vapor explosion treatment is already known in which the lignocellulosic substrate is subjected for a variable time to the action of water vapor under pressure at a temperature generally above 150 ° C. for example 150 at 250 ° C. This action ends with an explosive trigger.
  • This treatment formerly known for improving the digestibility of forages, also increases the susceptibility of lignocellulosic substrates to enzymatic hydrolysis (K. BUCHHOLZ, J. PULS, B. GADELMANN, MM DIETRICHS, Process Biochemistry, Dec / Jan. 1980 / 1981, pp 37-43).
  • This device cannot be used in an acid medium and at high temperature, of the order of 200 ° C., because of the corrosion levels that the hydrolysis treatment in the presence of acid would generate.
  • One of the objects of the invention is to respond to the problems raised above.
  • the device can operate continuously under severe temperature and pressure conditions, for example at a pressure which may be between 1 and 7 bar.
  • the invention therefore relates to a process for the continuous production of a mixture of sugars in solution containing at least 80% by weight of xylose from a lignocellulosic substrate comprising a step of grinding, a step of impregnation in aqueous solution of preferably acid, a hydrolysis step in the presence of water vapor, a dilution step in the presence of water, a step of extracting the mixture of sugars produced from the hydrolysed substrate, and a step of recovering xylose.
  • the lignocellulosic substrate is generally wood, cobs and stalks of corn or straw. However, we prefer to use corn cobs.
  • the wood is usually debarked and cut in the form of chips while the stems are crushed and obtained at a particle size generally between 0.1 and 40 mm, preferably between 1 and 5 mm.
  • the straw is chopped and used in the form of strands.
  • the term grinding is used for the step of dividing to the appropriate dimension of each of these substrates.
  • the dry matter content of the substrate is generally at least 50%, for example that of wood is approximately 50% while that of straw is approximately 80% and that of stalks approximately 80%.
  • the impregnation is generally carried out in an impregnation zone, supplied separately or not, with water and an acid. It could be a base if you wanted to do an alkaline treatment.
  • the water and acid supply rate is adjusted as a function of the supply rate of ground substrate, its initial dry matter content, its desired final content and its transfer speed in the impregnation zone.
  • These water and acid flows are advantageously distributed annularly by suitable injection means known to those skilled in the art and generally located in the first quarter of this zone, upstream side.
  • the proportion of acid used relative to the dry matter content of the substrate is generally between 0.1 and 10%, advantageously between 2 and 5%.
  • the dry matter content at the outlet of the impregnation zone is approximately 35 to 55%.
  • the impregnation is generally carried out at ambient temperature and pressure during a residence time which depends on the nature of the substrate used and which is conditioned by the speed of transfer into the impregnation zone and by the percentage of material. dries when entering and leaving this area. It is usually 1 to 60 mins and preferably from 10 to 40 minutes. Operating substantially in the absence of a separate liquid phase, the quantities of reactants and the size of the reactors are minimized.
  • the supply of substrate impregnated with the hydrolysis zone is generally carried out by an airlock controlled by servo and control means connected to a high level measurement in the airlock and to a timer controlling the opening or closing of the airlock valves.
  • This supply is advantageously gravitational and the pressure is balanced by three-way valves connecting the airlock, either to the hydrolysis reactor described below and operating under pressure, or for example to the impregnation reactor operating substantially at pressure. atmospheric.
  • the hydrolysis of the acidified substrate is generally carried out in the presence of medium-pressure water vapor, preferably 1 to 7 bar, advantageously 2 to 5 bar, and at a temperature of 120 to 170 ° C, advantageously of 120 to 150 ° C and preferably from 135 to 145 ° C.
  • the residence time of the substrate in the hydrolysis zone is conditioned by the rate of transfer of the substrate in this zone. It is generally 10 minutes to 1 hour, preferably 20 to 40 minutes. It is all the better controlled as the hydrolysis is carried out in the absence of a separate liquid phase in the hydrolysis reactor.
  • the quantity of vapor introduced is a function of the dry matter content of the acidified substrate and the operating conditions in temperature and pressure of the hydrolysis reactor. It is introduced with a flow rate such that at the outlet of the hydrolysis zone, the impregnated and hydrolysed substrate contains substantially no separate liquid phase.
  • the dry matter content is then generally between 25 and 55% by weight and preferably from 40 to 50% by weight.
  • the invention also relates to a unit for the continuous production, in particular of xylose, from lignocellulosic substrate.
  • This unit includes means for grinding this substrate to an adequate size connected to means for supplying ground substrate.
  • the unit comprises in combination a reactor for impregnating this ground substrate, of substantially cylindrical shape having an inlet connected to the substrate supply means and an outlet, means for continuously transferring the substrate into the impregnation reactor and means for supplying a solution comprising water and at least one acid (or at least one base), said impregnation reactor comprising servo means connected to the substrate supply means , to the means for transferring this substrate into the impregnation reactor and to the means for supplying said solution and adapted to impregnate the substrate under conditions such that the latter is substantially free of separate liquid phase,
  • the production unit being further characterized in that it comprises a continuous and pressurized hydrolysis reactor, of substantially cylindrical shape, made of stainless steel comprising at one of its ends emitted a sealed member for continuous supply of imp
  • the transfer means of the impregnation reactor can comprise either a single endless screw for conveying the stalks or a twin screw for the other substrates which are by nature less porous.
  • the hydrolysis reactor can be substantially horizontal or substantially inclined and the member for feeding the impregnated substrate and the member for discharging the hydrolyzed substrate at least in part are substantially vertical.
  • the sealed member for supplying impregnated substrate comprises an inlet valve and an outlet valve, means for level measurement inside the member, means for pressure balancing connected alternately to the pressurized hydrolysis reactor and to the atmosphere impregnation reactor and of the first means for controlling the level measurement means at the inlet and outlet valves of the supply member .
  • the sealed member for discharging the hydrolyzed substrate comprises an inlet valve and an outlet valve, second pressure balancing means connected alternately to the pressurized hydrolysis reactor and to the impregnation reactor for example which operates at atmospheric pressure and second means for controlling the inlet and outlet valves of the evacuation member to said second pressure balancing means.
  • the hydrolysis reactor can be tilted according to a downward slope of 0.1 to 1% directed towards the discharge member, so as to recover any condensates.
  • the means for continuously transferring the impregnated substrate into the hydrolysis reactor can comprise an endless screw.
  • This endless screw can, according to a particularly advantageous embodiment, consist of a thick shaft with screw thread tightened in the first quarter, for example, of its length and of a smaller shaft with larger screw thread over the rest of its length. This configuration allows better distribution of the substrate and better regulation of the feed rate.
  • the apparatus makes it possible in particular to extract the lignin and to recover polymers based on easily hydrolyzable sugars.
  • the corn cobs after having been ground in a conventional type of grinder 1, at an appropriate particle size, are sent using an elevator 2, for example with discs, to an impregnation reactor 5 via a gravimetric doser 3 supplying as a substrate, the inlet 4 of this reactor.
  • This substantially cylindrical-shaped reactor comprises an endless transfer screw 7 conveying the ground substrate to the outlet 10. This screw is controlled by a motor 6.
  • the acid supply flow is ensured by conventional injectors 8a arranged substantially annularly around the reactor, via a line 8 and a metering pump while the water flow is provided by injectors 9a identical to the injectors 8, arranged substantially annularly around the reactor and connected to a supply line 9 via a pump 9b.
  • injectors distribute their respective fluid substantially radially by means of pumps 8b, 9b and are advantageously located at a distance from the upstream end corresponding to a quarter of the length of the reactor.
  • First control and servo-control means make it possible to control the injection or supply flows in acid solution to the supply flow of the ground substrate, to its dry matter content and to the speed of transfer in the reactor. such that the dry matter content of the stems goes from about 90% to about 50% and that there is substantially no separate liquid phase at the outlet 10 from the impregnation zone.
  • the stems are discharged by gravity and by an outlet perpendicular to the axis of the reactor 5 in a feed member 12 which is an airlock comprising an upper valve 18 called a guillotine valve in relation to the outlet 10 of the impregnation zone and a lower valve guillotine 19 which controls the entry of substrate into an acid hydrolysis reactor 11.
  • the latter of elongated shape , substantially cylindrical, and arranged in a substantially inclined downstream direction with a downward slope of approximately 0.5%, operates under pressure and at high temperature by means of the supply of water vapor injected substantially radially via a line 14.
  • the entry airlock arranged substantially vertically and substantially perpendicular to the axis of the reactor 11 comprises a level indicator 20 controlled by the first servo means 16 closing a valve 18 when the airlock is sufficiently filled, pressurizing the airlock in equilibrium with the internal pressure of the hydrolysis reactor via a 3-way valve 21 and finally l opening of the valve 19 so that the content of the airlock can flow into the hydrolysis reactor.
  • the 3-way valve 21 ensures successive alternative pressurization and atmospheric pressure.
  • the hydrolysis reactor 11 supplied with impregnated substrate ensures the transfer of the latter to the discharge member 15 by a transfer screw 13, set in motion by a motor 22.
  • This screw advantageously comprises a first part 22a over a distance corresponding to about a quarter of its length, consisting of a shaft with a larger diameter than that which comes continuously on the second part 22b and with a pitch tighter than that of the second part.
  • the feed rates of impregnated substrate and of vapor and the speed of transfer into the hydrolysis zone are controlled by second control means 16 so that an at least partly hydrolyzed substrate is obtained which does not contain substantially no separate phase and a dry matter content lower than that which it had at the entry of the hydrolysis zone, for example 40 to 45%.
  • the pressure and the temperature of the hydrolysis reactor are regulated by sensors (not shown in the figure) and by the means 16 around a set value.
  • the setpoint value When the setpoint value is exceeded, the steam supply is stopped. However, it is open when the setpoint is not reached.
  • a solenoid valve 17 therefore controls the opening and closing of the steam supply 14 as a function of a signal delivered by the servo means 16 connected to the sensors.
  • the hydrolyzed substrate is then removed via an airlock 15 arranged vertically and substantially perpendicular to the axis of the hydrolysis reactor.
  • This airlock comprises an upper guillotine valve 23 and a lower guillotine valve 24 operating using the second control means, the pressure balancing being effected by a 3-way valve 25 as already described in the case of the upper airlock.
  • the hydrolyzed substrate flows into a buffer tank 26, from which this same hydrolyzed substrate is recovered to supply a diffuser 27 performing continuously, in the presence of diffusion water supplied by a line 28, a solid liquid extraction against the current , the diffusion water first meeting the hydrolyzed substrate whose content of soluble sugars is practically completely exhausted.
  • the non-hydrolyzed organic material (lignin, cellulose) is recovered at one end 29 of the extraction line while the mixture of sugars in solution containing at least 80% by weight of xylose is recovered at the other end 30.
  • the mixture of sugars in solution is then concentrated, generally neutralized with lime, demineralized and discolored by passing, for example, through ion exchange resins.
  • Purified xylose (purity greater than 95%) can be obtained by crystallization from this solution of discolored sugars.
  • composition of the roundups is as follows:
  • the dry matter content at the exit from the impregnation zone is 50.6%.
  • the concentration by weight of acid relative to the dry matter is 4.0%.
  • the operating conditions of the hydrolysis reactor are 140 ° C. and a pressure of the order of 4 bar with an average residence time of 30 min.
  • the total quantity of product recovered at the outlet of the hydrolysis reactor is 1060 kg.
  • the material content of the hydrolyzed substrate is 42.9%.
  • the cobs having undergone the hydrolysis treatment are sent to a continuously operating diffuser in which the extraction of the sugars with water is carried out against the current.
  • an aqueous solution of sugars is recovered and, on the other hand, stems exhausted in monomeric sugars which are drained on a belt filter, the filtrate then being added to the aqueous sugar solution, the final volume of which is 2200 liters. .
  • the total sugar content is 61.8 gl-1 with respective concentrations of xylose, glucose, arabinose of 51.8 gl-1, 5.4 gl-1 and 4.5 gl-1, i.e. a xylose content of 83.9%.
  • the aqueous solution is then evaporated under vacuum to reach a concentration of total sugars close to 150 g.l-1.
  • the evaporation temperature does not exceed 60 ° C. 920 l of a concentrated sugar solution are recovered, to which 10.1 kg of CaO are added.
  • the precipitate of calcium sulphate obtained is separated by filtration on a band filter.
  • the filtrate is then demineralized and discolored by passage over ion exchange resins and adsorbent resins.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Processing Of Solid Wastes (AREA)
  • Seasonings (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
EP90403374A 1989-12-07 1990-11-28 Verfahren und Einrichtung zur Herstellung einer zumindest 80% Xylose enthaltende Zuckermischung aus einem lignocellulosischen Substrat Expired - Lifetime EP0432015B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8916321A FR2655661B1 (fr) 1989-12-07 1989-12-07 Procede et unite de production en continu d'un melange de sucres contenant au moins 80% de xylose a partir d'un substrat lignocellulosique.
FR8916321 1989-12-07

Publications (2)

Publication Number Publication Date
EP0432015A1 true EP0432015A1 (de) 1991-06-12
EP0432015B1 EP0432015B1 (de) 1994-10-26

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EP90403374A Expired - Lifetime EP0432015B1 (de) 1989-12-07 1990-11-28 Verfahren und Einrichtung zur Herstellung einer zumindest 80% Xylose enthaltende Zuckermischung aus einem lignocellulosischen Substrat

Country Status (5)

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EP (1) EP0432015B1 (de)
DE (1) DE69013652T2 (de)
ES (1) ES2066173T3 (de)
FI (1) FI100254B (de)
FR (1) FR2655661B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1058996C (zh) * 1996-05-14 2000-11-29 安徽省科苑应用技术开发(集团)股份有限公司 由玉米芯提取木糖的改进方法
EP0951347A4 (de) * 1996-09-30 2004-12-29 Midwest Research Inst Hydrolyse und fraktionierung von lignocellulose-biostoff

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3027821B1 (fr) 2014-10-31 2018-11-16 Centralesupelec Procede de purification d'oses.
EP3416740B1 (de) 2016-02-19 2021-01-06 Intercontinental Great Brands LLC Verfahren zum erzeugen von mehrfachwertströmen aus biomasse

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2413306A1 (de) * 1973-05-04 1974-11-21 Sulzer Ag Verfahren zum herstellen von xyloseloesung und erzeugnis
DE2458386A1 (de) * 1974-12-03 1976-06-10 Sulzer Ag Vorrichtung zum herstellen von zukkern aus hemicellulosehaltigen rohstoffen, insbesondere von xylose aus xylanhaltigen rohstoffen
US4136207A (en) * 1977-01-24 1979-01-23 Stake Technology Ltd. Method of treating lignocellulose materials to produce ruminant feed
US4350766A (en) * 1980-08-01 1982-09-21 Purdue Research Foundation Pentose syrup production from hemicellulose
FR2580669A1 (fr) * 1985-04-18 1986-10-24 Inst Francais Du Petrole Procede de conversion de substrats lignocellulosiques en pentoses

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2413306A1 (de) * 1973-05-04 1974-11-21 Sulzer Ag Verfahren zum herstellen von xyloseloesung und erzeugnis
DE2458386A1 (de) * 1974-12-03 1976-06-10 Sulzer Ag Vorrichtung zum herstellen von zukkern aus hemicellulosehaltigen rohstoffen, insbesondere von xylose aus xylanhaltigen rohstoffen
US4136207A (en) * 1977-01-24 1979-01-23 Stake Technology Ltd. Method of treating lignocellulose materials to produce ruminant feed
US4350766A (en) * 1980-08-01 1982-09-21 Purdue Research Foundation Pentose syrup production from hemicellulose
FR2580669A1 (fr) * 1985-04-18 1986-10-24 Inst Francais Du Petrole Procede de conversion de substrats lignocellulosiques en pentoses

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1058996C (zh) * 1996-05-14 2000-11-29 安徽省科苑应用技术开发(集团)股份有限公司 由玉米芯提取木糖的改进方法
EP0951347A4 (de) * 1996-09-30 2004-12-29 Midwest Research Inst Hydrolyse und fraktionierung von lignocellulose-biostoff

Also Published As

Publication number Publication date
ES2066173T3 (es) 1995-03-01
FI906037A0 (fi) 1990-12-05
DE69013652D1 (de) 1994-12-01
FR2655661A1 (fr) 1991-06-14
EP0432015B1 (de) 1994-10-26
FI100254B (fi) 1997-10-31
FI906037A7 (fi) 1991-06-08
FR2655661B1 (fr) 1994-06-03
DE69013652T2 (de) 1995-03-02

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