EP0078023B1 - Procédé pour traiter des matières cellulosiques avec de l'acide fluorhydrique gazeux - Google Patents

Procédé pour traiter des matières cellulosiques avec de l'acide fluorhydrique gazeux Download PDF

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Publication number
EP0078023B1
EP0078023B1 EP82109718A EP82109718A EP0078023B1 EP 0078023 B1 EP0078023 B1 EP 0078023B1 EP 82109718 A EP82109718 A EP 82109718A EP 82109718 A EP82109718 A EP 82109718A EP 0078023 B1 EP0078023 B1 EP 0078023B1
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EP
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Prior art keywords
desorption
gas
reactor
substrate
sorption
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Expired
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EP82109718A
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German (de)
English (en)
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EP0078023A1 (fr
Inventor
Rüdiger Dr. Erckel
Raimund Dr. Franz
Rolf Dr. Woernle
Theodor Dr. Riehm
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Hoechst AG
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Hoechst AG
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Priority to AT82109718T priority Critical patent/ATE12258T1/de
Publication of EP0078023A1 publication Critical patent/EP0078023A1/fr
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Publication of EP0078023B1 publication Critical patent/EP0078023B1/fr
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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
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials

Definitions

  • cellulosic material such as wood or waste from annual plants
  • mineral acids such as mineral acids.
  • the cellulose contained which is a macromolecular substance, is broken down into glycosidic bonds into water-soluble, smaller molecules down to the monomer units, the glucose molecules.
  • the sugars obtained in this way can be fermented into alcohol or used as a fermentation raw material for the production of proteins.
  • This is the technical meaning of wood saccharification.
  • mineral acids suitable for this purpose dilute sulfuric acid (Scholler process) and concentrated hydrochloric acid (Bergius process) were used on an industrial scale decades ago; see, for example, " Ullmann's Encyclopedia of Technical Chemistry", 3rd ed. Kunststoff-Berlin, 1957, Vol. 8, p. 591 ff.
  • DE-C No. 585318 describes a method and a device for treating wood with gaseous hydrogen fluoride, in which hydrogen fluoride gas, which may be diluted with an inert gas, is reacted with wood in a first zone of a reaction tube with a screw conveyor that this zone is cooled from the outside below the boiling point of the hydrogen fluoride. After the digestion, which may take place in an intermediate zone, the hydrogen fluoride is expelled with an inert gas stream by external heating and / or blowing, in order to be brought back into contact with fresh wood in the cooling zone mentioned.
  • hydrogen fluoride gas which may be diluted with an inert gas
  • gaseous hydrogen fluoride in a mixture with an inert carrier gas can be circulated almost without loss, producing a loading of the substrate required for good yields, without the technically highly disadvantageous cooling below the boiling point of the hydrogen fluoride being necessary.
  • This is achieved by dividing the desorption process into several stages, in which the desorption takes place in cocurrent or countercurrent of HF gas mixtures and reaction material (substrate).
  • HF gas mixtures of different HF concentrations are formed, which act on the substrate at different points in the sorption stage in such a way that low-HF gas mixtures affect unloaded or little loaded HF , Gas mixtures with higher HF concentrations act on already heavily loaded material.
  • the subject of the invention is thus a continuous process for the digestion of cellulose-containing substrate with gaseous hydrogen fluoride by sorption of the HF and subsequent desorption, which is characterized in that the HF is sorbed by the substrate at a temperature above its boiling point in a sorption stage, and after that the The substrate is freed of the sorbed H by heating in n desorption stages, where n is an integer and the stages mentioned are carried out in gas-tight separate reactors, and the substrate is introduced through a gas-tight lock into the sorption reactor, passes through it and then one after the other passes through gas-tight locks into the first, second, ..., nth desorption reactor and is discharged from the last (nth) desorption reactor, and the desorption in each case by the action of one of n heated gas streams in countercurrent to or, preferably, DC with the
  • the substrate is enriched with the respective gas stream with the HF released during the desorption, and the n HF-enriched gas streams, which contain an inert carrier gas in
  • n is an integer, preferably from 2 to 6, in particular from 2 to 4.
  • the reactors separated from one another by gas-tight locks can be of the same or different types: for example, stirred vessels, rotary tubes, flight dryers, slide beds, screw conveyors, vertical countercurrent or fluidized bed reactors are suitable. If necessary, they can be provided with a heating or cooling device.
  • Wood or waste from annual plants e.g. straw or bagasse
  • a pre-hydrolyzate of wood or waste from annual plants or, also preferably, waste paper can be used as cellulose-containing material.
  • This water can either be introduced by being present in the substrate as residual moisture of 0.5 to 20, preferably 1 to 10, in particular 3 to 7,% by weight, or by being contained in the HF / inert gas mixture, or in both.
  • reaction material (substrate), the cellulose-containing material, is transported from one reactor to another, for example, by free fall, via rotary feeders and / or by screw conveyors.
  • the gas is routed in such a way that the gas outlet opening of a sorption reactor via a gas line with an intermediate gas pump (blower) and n-1 branches with the gas inlet openings of n desorption reactors, and the gas outlet openings of these n desorption reactors via gas lines n gas inlet openings of the sorption reactor are connected.
  • a valve and a heat exchanger are interposed in front of the gas inlet openings of the desorption reactors.
  • Heat exchangers can also be arranged in front of the gas inlet openings of the sorption reactor. They may have the task of bringing the gas mixture intended for sorption to the optimum temperature for this. They may also have the task of condensing out any accompanying substances in the feed, such as water, acetic acid, essential oils, which are released during the desorption, while allowing the hydrogen fluoride to pass through in gaseous form.
  • the gas stream leaving the sorption reactor and containing a maximum of 5% by weight HF, preferably almost completely HF-free, is divided by the branches into n partial gas streams, the size of which depends on the respective setting of the valves.
  • These partial gas flows are heated in the heat exchangers to the temperature required for the desorption and are allowed to act on the substrate in the desorption reactors in countercurrent to, or preferably in cocurrent with, the substrate.
  • the n partial gas flows are again enriched with H F by the HF released during the desorption.
  • This enrichment with HF is of different sizes in the individual partial gas streams.
  • a lot of H F is released during the desorption of the substrate, which is introduced here with maximum HF loading.
  • desorption takes place on substrate that has always been freed of HF in the previous desorption stages.
  • the last (nth) desorption reactor only a little HF is released since the substrate is already largely depleted in H F and is introduced into it.
  • the substrate only contains HF traces.
  • n partial gas streams can also take place in such a way that the gas stream leaving the gas outlet opening of the sorption reactor is first fed completely through the pump to the last (nth) desorption reactor - after heating in the upstream heat exchanger - in which it is largely based on HF impoverished. acts substrate. Only after leaving this last (nth) desorption reactor is the gas stream divided into an (nth) partial gas stream which is fed directly to the corresponding gas inlet opening of the sorption reactor and n-1 partial gas streams which are the penultimate ([n-1] th ) to the first desorption reactor, after heating in the respective upstream heat exchanger.
  • the HF concentration in the n-th HF carrier gas stream leaving the last (n-th) desorption reactor is relatively low and increases more and more in the penultimate ([n-1] th) and the previous ones and is in the the first HF carrier gas stream leaving the first desorption reactor is the highest (up to over 95% by weight).
  • the HF carrier gas streams of different HF concentrations are fed through gas lines to the n gas inlet openings of the sorption reactor, in such a way that the nth HF gas flow onto only a substrate loaded with HF and the first HF gas flow onto the substrate with HF ( almost) maximum loaded substrate.
  • the remaining HF gas streams are fed to the substrate at gas inlet openings of the sorption reactor located in between.
  • the maximum HF loading of the cellulose-containing material depends on its type and nature and on the residence time in the sorption stage and is accordingly between 10 and 120, preferably between 30 and 80%, based on the weight of the material used.
  • the substrate loaded with HF after leaving the sorption reactor and before entering the first desorption reactor, can still pass through a dwell reactor which may have a comminution device for coarse reaction material and the temperature of which is expediently kept in a range which is dependent on the temperatures in the last part of the sorption reactor and is trapped in the first desorption reactor.
  • the optimal dwell time i.e. the average length of stay of the substrate in the apparatus from the beginning of the sorption to the end of the desorption depends on the type and nature of the material to be digested and must be tailored to the particular case. Accordingly, it can range from about 30 minutes to about 5 hours.
  • Substrate temperatures in the range from 40 to 120, preferably from 50 to 90 ° C. are selected for the desorption, the temperatures for the individual stages being different, on the other hand, a temperature in the range from 20 to 50, preferably 30 to, for the respectively assigned sorption 45 ° C.
  • the arrangement according to the invention allows the flow rate and temperature of the HF / carrier gas mixture to meet the different requirements in the individual areas of the sorption stage and in the individual desorption stages, depending on the HF loading degree of the substrate adapt.
  • the sorption reactor 1 is connected to the desorption reactor 3a via the gas line 8a, the pump 4, the valve 9a and the heat exchanger 5a, and this is connected to the sorption reactor 1 via the gas line 7a and the heat exchanger 6a. Furthermore, the sorption reactor 1 is connected to the desorption reactors 3b and 3c via the gas line 8a, the pump 4, the gas lines 8b and 8c, the valves 9b and 9c and the heat exchangers 5b and 5c, and these are connected via the gas lines 7b and 3c. 7c and the heat exchangers 6b and 6c connected to the sorption reactor 1.
  • the cellulosic material (substrate) to be digested is introduced into the sorption reactor 1. This process is symbolized by the arrow 12a in FIGS. 1 and 3.
  • HF / inert gas mixtures the HF concentration of which is lowest in the gas line 7a and highest in the gas line 7c, are supplied to the sorption reactor 1 through the gas lines 7a, 7b and 7c. In the sorption reactor 1, they flow against the substrate and emerge from the reactor 1 as an almost completely HF-free total gas stream.
  • the substrate loaded with H F is transported from the sorption reactor 1 to the residence reactor 2 (arrow 12b) and from there successively into the first, second and third desorption reactors 3c, 3b and 3a (arrows 12c, 12d and 12e).
  • the gas stream leaving the sorption reactor 1 is divided into three partial flows after passing through the gas line 8a and the pump 4, in accordance with the respective setting of the valves 9a, 9b and 9c. After heating in the heat exchangers 5a or 5c, these partial gas flows enter the desorption reactors 3a or 3b or 3c and flow through them in countercurrent to or, preferably, in cocurrent with the substrate.
  • H is desorbed by the action of the heated gas streams on the H F-loaded substrate.
  • the first desorption reactor 3c since the substrate with the maximum HF loading is introduced, most HF is released by desorption, a smaller amount is released in the reactor 3b, and in the last desorption reactor 3a, in which the substrate already largely frees from HF, the least amount of HF is released. Accordingly, the HF concentrations in the gas streams leaving the desorption reactors are highest in reactor 3c and lowest in reactor 3a.
  • the HF base stream exiting the reactor 3b has an intermediate HF concentration in between.
  • the HF gas streams of different HF concentrations are fed through the gas lines 7a or 7b or 7c - after passing through the intermediary heat exchangers 6a or 6b or 6c - at different inlet points of the sorption reactor 1.
  • the HF gas flow from the gas line 7a with the lowest HF concentration strikes substrate which is only very slightly loaded with HF.
  • the HF gas stream from the gas line 7c with the highest HF concentration strikes the substrate which (almost) has the maximum HF loading.
  • the HF gas flow from the gas line 7b is allowed to act on the substrate at an intermediate point of the sorption reactor 1, which substrate already has a relatively high HF load.
  • the substrate After desorption has taken place in the reactor 3a, the substrate leaves it in an open form (arrow 12f). It only contains traces of residual hydrogen fluoride and is processed, which is carried out in a manner known per se.
  • a special embodiment is shown schematically in FIG. 2.
  • a three-way valve 10 is interposed in the gas line 7a, which allows a (more or less) part of the HF gas stream emerging from the desorption reactor 3a to be returned to a special circuit via a gas line 11 and between the valve 9a and an intermediate pump 4a into the gas line 8a via a branch.
  • the three-way valve 10 can also be a control valve.
  • the part of the HF / inert gas mixture which is returned in this special circuit is about 10 to about 90, preferably about 50 to about 90%, of the total mixture which leaves the desorption reactor 3a.
  • This particular arrangement which analogously also allows partial recirculation of the HF / inert gas mixtures leaving the desorption reactors 3c or 3b, allows the gas velocities of the HF / inert gas mixtures passing through to be optimized.
  • FIG. 3 shows a further special embodiment of the method according to the invention.
  • the gas line 7a is interposed with a three-way valve 10a, which allows the gas stream leaving the sorption reactor 1 to be divided into partial gas streams only after it has passed the desorption reactor 3a. While a partial stream only passes through the reactor 3a and is fed directly to the sorption reactor 1, the other two partial streams are still passed through a second desorption reactor 3c or 3b before they are fed to the reactor 1 through the gas lines 7c or 7b.
  • This particular embodiment allows the largest possible amount of gas, that is to say the total amount of carrier gas, to act on the substrate in the last desorption stage, as a result of which the desorption is accelerated.
  • the digested material produced by the process according to the invention is a mixture of lignin and oligomeric saccharides. It can be worked up in a manner known per se by extraction with water, expediently in the heat or boiling heat, and by simultaneous or subsequent neutralization with lime. Filtration provides lignin, e.g. can be used as fuel, as well as a small amount of calcium fluoride, which results from the residual fluoride contained in the reaction material. The filtrate, a clear, slightly yellowish sugar solution, can be added to the alcoholic fermentation or fermentation either immediately or after setting an appropriate concentration. The dissolved, oligomeric sugars can also be treated by brief post-treatment, e.g. with highly diluted mineral acid at temperatures above 100 ° C, almost quantitatively converted into glucose.
  • Example 1 was carried out in an apparatus arrangement which is shown schematically in FIG. 1. It consisted of a sorption reactor 1, a residence reactor 2 and three desorption reactors 3a, 3b, 3c, which were connected to one another by pipelines and cellular wheel locks.
  • a vertical tube made of stainless steel with a clear width of 5 cm and a length of 80 cm was used as the sorption reactor, which carried a gas-tight rotary valve with a filling funnel at the upper end and was also provided with a gas-tight rotary valve at the lower end.
  • In the longitudinal axis of the tube was a slowly rotating shaft with narrow wings. At 3 points, which were distributed over the lower two thirds of the pipe length, there were inlets for HF-containing gases.
  • the gas outlet opening was located just below the top rotary valve.
  • the indwelling reactor was a cylindrical vessel of approx. 2 l made of semi-transparent polyethylene.
  • the desorption reactors were made of stainless steel and were designed as heatable rotary tube reactors through which the substrate and the flowing gases could flow in the same direction.
  • the usable volume of the desorption reactors was about 3 I.
  • granular lignocellulose which had been obtained as a residue from a pre-hydrolysis of spruce wood chips and had a water content of about 3% by weight, was continuously conveyed from top to bottom by its own weight.
  • HF / nitrogen mixtures of various concentrations originating from the desorption were introduced through the three gas introductions, specifically at the lowest introduction point with the highest, at the uppermost with the lowest HF concentration.
  • the conveying speed was adjusted so that the reaction mixture emerging from the reactor contained about 60 g HF per 100 g lignocellulose used. From the lower cellular wheel sluice, the substrate passed freely into the dwell reactor 2 and remained there for an average of 30 minutes.
  • First desorption reactor 3c Lignocellulose was loaded from the dwelling reactor 2 by means of a gas-tight cellular wheel sluice in a weight ratio of 60: 100; a substrate with a loading of approx. 35: 100 (weight ratio HF to lignocellulose) was discharged; the desorption temperature was 60 to 70 ° C; the escaping gas mixture contained approx. 65% by weight H F.
  • Second desorption reactor 3b The HF-loaded product from the first desorption reactor 3c was introduced by means of a gas-tight rotary valve; a substrate with a loading of approx. 10: 100 was discharged; the desorption temperature was 70-80 ° C; the exiting gas mixture contained about 25% by weight of HF.
  • Third desorption reactor 3a The product loaded with HF F was entered from the second desorption reactor 3b by means of a gas-tight rotary valve; a substrate with approximately 0.5% by weight HF was discharged; the desorption temperature was approx. 90 ° C; the exiting gas mixture contained about 5% by weight of HF.
  • the three gas mixtures generated in the desorption reactors were passed through the pipes 7a, 7b, 7c and the heat exchangers 6a, 6b, 6c, where they were cooled to 25 to 30 ° C., in the above already described in the sorption reactor 1, so that with continuous delivery of substrate through the apparatus circuits of carrier gas (nitrogen) and HF came about.
  • the digested substrate largely freed of HF, was extracted in the usual way with hot water, the solution thus obtained was neutralized with calcium hydroxide, filtered and evaporated. Wood sugar of light color was obtained in a yield of 90%, based on the cellulose originally present.
  • raw spruce wood shavings were broken down to a residual moisture content of about 5% by weight.
  • wood accompanying substances such as acetic acid were driven off and condensed and separated in the heat exchangers 6c to 6a.
  • wood sugar was obtained in a yield of about 70% by weight, based on the carbohydrates contained in the material used.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Claims (5)

1. Procédé continu de digestion d'un substrat contenant de la cellulose par du fluorure d'hydrogène gazeux, par sorption puis désorption du HF, procédé caractérisé en ce que la sorption du H F.par le substrat s'effectue, dans une étape de sorption, à une température supérieure au point d'ébullition du HF et qu'ensuite le substrat est débarrassé de HF sorbé, par chauffage dans n étapes de désorption, n étant un nombre entier et les étapes citées se déroulant à chaque fois dans des réacteurs séparés les uns des autres de manière étanche aux gaz, le substrat étant introduit par un sas étanche aux gaz dans le réacteur de sorption puis parcourant celui-ci et parvenant ensuite successivement, par des sas étanches aux gaz, au premier, au deuxième, ... et au nième réacteur de désorption et étant retiré du dernier (nième) réacteur de désorption, et la désorption étant effectuée à chaque fois par l'action de l'un des n courants de gaz chauffés circulant à contre-courant, ou de préférence dans le même sens que le substrat, avec enrichissement de chaque courant de gaz en H libéré par la désorption, et en ce que les courants de gaz enrichis en HF et qui, en plus du H F, contiennent un véhicule gazeux inerte, agissent à contre-courant du substrat, dans un réacteur de sorption, sur ce substrat de manière que des courants de gaz à faible concentration en HF agissent sur le substrat non chargé ou encore peu chargé en HF et que des courants gazeux à plus forte concentration en HF agissent sur le substrat plus fortement chargé en H F, et en ce que le courant gazeux total résultant des courants gazeux individuels quitte le réacteur de sorption, une fois la sorption achevée, largement appauvri en H F et, après subdivision en des courants gazeux individuels, est introduit dans le circuit des étapes de désorption, ou bien parcourt tout d'abord la dernière étape de désorption puis est subdivisé et acheminé aux autres étapes de désorption et au réacteur de sorption.
2. Procédé selon la revendication 1, caractérisé en ce que n est un nombre entier valant 2 à 6, notamment 2 à 4.
3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce qu'on utilise comme substrat un produit d'hydrolyse préliminaire du bois, des déchets de plantes annuelles ou du vieux papier.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on utilise comme véhicule gazeux inerte de l'air ou de l'azote.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'un ou plusieurs courants de gaz comportant H F sont, après avoir quitté le ou les réacteurs de désorption, subdivisés et en ce qu'une partie est recyclée directement vers l'entrée du ou des réacteurs de désorption.
EP82109718A 1981-10-24 1982-10-21 Procédé pour traiter des matières cellulosiques avec de l'acide fluorhydrique gazeux Expired EP0078023B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82109718T ATE12258T1 (de) 1981-10-24 1982-10-21 Verfahren zum aufschluss von zellulosehaltigem material mit gasfoermigem fluorwasserstoff.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813142215 DE3142215A1 (de) 1981-10-24 1981-10-24 "verfahren zum aufschluss von zellulosehaltigem material mit gasfoermigem fluorwasserstoff"
DE3142215 1981-10-24

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EP0078023A1 EP0078023A1 (fr) 1983-05-04
EP0078023B1 true EP0078023B1 (fr) 1985-03-20

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EP82109718A Expired EP0078023B1 (fr) 1981-10-24 1982-10-21 Procédé pour traiter des matières cellulosiques avec de l'acide fluorhydrique gazeux

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US (1) US4556432A (fr)
EP (1) EP0078023B1 (fr)
AT (1) ATE12258T1 (fr)
CA (1) CA1192706A (fr)
DE (2) DE3142215A1 (fr)

Families Citing this family (10)

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Publication number Priority date Publication date Assignee Title
US4650689A (en) * 1985-03-25 1987-03-17 Urban Fuels, Inc. Process for ethanol production from cellulosic materials
US5876505A (en) * 1998-01-13 1999-03-02 Thermo Fibergen, Inc. Method of producing glucose from papermaking sludge using concentrated or dilute acid hydrolysis
US7815876B2 (en) 2006-11-03 2010-10-19 Olson David A Reactor pump for catalyzed hydrolytic splitting of cellulose
US7815741B2 (en) 2006-11-03 2010-10-19 Olson David A Reactor pump for catalyzed hydrolytic splitting of cellulose
DE102007030957A1 (de) * 2007-07-04 2009-01-08 Siltronic Ag Verfahren zum Reinigen einer Halbleiterscheibe mit einer Reinigungslösung
BR112012032999B1 (pt) 2010-06-26 2022-11-29 Virdia, Llc Hidrolisado lignocelulósico e métodos de hidrólise ácida e desacidificação para gerar misturas de açúcar a partir de lignocelulose
IL206678A0 (en) 2010-06-28 2010-12-30 Hcl Cleantech Ltd A method for the production of fermentable sugars
IL207329A0 (en) 2010-08-01 2010-12-30 Robert Jansen A method for refining a recycle extractant and for processing a lignocellulosic material and for the production of a carbohydrate composition
IL207945A0 (en) 2010-09-02 2010-12-30 Robert Jansen Method for the production of carbohydrates
GB2524906B8 (en) 2011-04-07 2016-12-07 Virdia Ltd Lignocellulose conversion processes and products

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Publication number Priority date Publication date Assignee Title
DE577764C (de) * 1930-03-18 1933-06-03 I G Farbenindustrie Akt Ges Verfahren zur Umwandlung von Polysacchariden
DE585318C (de) * 1930-06-21 1933-10-02 I G Farbenindustrie Akt Ges Verfahren zur Behandlung fester oder fluessiger Stoffe mit Gasen oder Daempfen
US3481827A (en) * 1968-08-02 1969-12-02 Grace W R & Co Process for bleaching wood pulp with fluorine,hydrofluoric acid,and oxygen difluoride
US3919041A (en) * 1969-02-06 1975-11-11 Ethyl Corp Multi-stage chlorine dioxide delignification of wood pulp
US3619350A (en) * 1969-07-11 1971-11-09 Richard Marchfelder Chlorine dioxide pulp bleaching system
DE3040850C2 (de) * 1980-10-30 1982-11-18 Hoechst Ag, 6000 Frankfurt Verfahren zur Gewinnung wasserlöslicher Saccharide aus cellulosehaltigem Material

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ATE12258T1 (de) 1985-04-15
DE3142215A1 (de) 1983-05-05
EP0078023A1 (fr) 1983-05-04
DE3262696D1 (en) 1985-04-25
CA1192706A (fr) 1985-09-03
US4556432A (en) 1985-12-03

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