EP0078023A1 - 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
EP0078023A1
EP0078023A1 EP82109718A EP82109718A EP0078023A1 EP 0078023 A1 EP0078023 A1 EP 0078023A1 EP 82109718 A EP82109718 A EP 82109718A EP 82109718 A EP82109718 A EP 82109718A EP 0078023 A1 EP0078023 A1 EP 0078023A1
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EP
European Patent Office
Prior art keywords
desorption
gas
substrate
reactor
sorption
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EP82109718A
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German (de)
English (en)
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EP0078023B1 (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
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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 e.g. Wood or waste from annual plants that can chemically digest with 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 include 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 e.g. Ullmann's Encyclopedia of Technical Chemistry, 3rd edition, Kunststoff-Berlin, 1957, Volume 8, pp. 591 ff.
  • DE-PS 585 318 describes a method and a device for treating wood with gaseous hydrogen fluoride, in which hydrogen fluoride gas, which can 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 by external heating and / or blowing out with an inert gas stream in order to be brought back into contact with fresh wood in the cooling zone mentioned.
  • the high technical outlay in this process is not only due to the vacuum technology itself, but also due to the fact that the boiling point of hydrogen fluoride falls below the value of -20 ° C at 150 mbar; this means that condensation is no longer possible without the aid of complex coolants or units.
  • gaseous hydrogen fluoride in a mixture with an inert carrier gas can be circulated almost without loss, producing a load 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 HF-loaded material, Act gas mixtures with higher HF concentrations on already heavily loaded material.
  • the subject of the invention is thus a continuous process for the digestion of cellulose-containing material (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 that the substrate is then freed from the sorbed HF by heating in n desorption stages, n being an integer and the stages mentioned running in gas-tight reactors, and the substrate being introduced into the sorption reactor through a gas-tight lock and then successively through gas-tight locks into the first, second ).
  • 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 are suitable.
  • Wood or waste from annual plants e.g. straw or bagasse
  • a pre-hydrolyzate of wood or waste from annual plants e.g. straw or bagasse
  • waste paper e.g., a pre-hydrolyzate of wood or waste from annual plants, or, also preferably, waste paper
  • 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.
  • Air and nitrogen are suitable as inert carrier gases.
  • the gas flow takes place according to the invention in such a way that the gas outlet opening of a sorption reactor is connected via a gas line with an intermediate gas pump (blower) and n-1 branches to the gas inlet openings of n desorption reactors, and the gas outlet openings of these n desorption reactors are connected via gas lines to n gas inlet openings of the sorption reactor.
  • 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 accompanying substances in the feed material, such as water, which may have been released during the desorption. Condense acetic acid, essential oils, but let the hydrogen fluoride pass in gaseous form.
  • the gas flow 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 flows, the size of which depends on the respective setting of the. Valves depends.
  • n 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 HF by the HF released during the desorption.
  • This enrichment with HF is of different sizes in the individual partial gas streams.
  • a lot of HF is released during the desorption of the substrate, which is introduced here with maximum HF loading.
  • the desorption takes place with substrate, that in the previous desorption stages HF has already been freed ever further.
  • the last (nth) desorption reactor only a little HF is released, since the substrate is already introduced into HF, largely depleted in HF.
  • the substrate only contains HF traces.
  • the division into n partial gas streams can also be carried out 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 acts on the already largely depleted HF 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 flows, which are directed to 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 first HF carrier gas stream, which leaves the first desorption reactor, is 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 little HF-loaded substrate and the first HF gas flow onto the 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 matched to the respective case. Accordingly, it can range from about 30 minutes to about 5 hours.
  • the arrangement according to the invention allows the flow rate and temperature of the HF carrier gas mixture to be adapted to the requirements which are different in the individual regions of the sorption stage and in the individual desorption stages and are dependent on the HF loading degree of the substrate.
  • 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 or 3c via the gas line 8a, the pump 4, the gas lines 8b or 8c, the valves 9b or 9c and the heat exchangers 5b or 5c, and this is via the gas lines 7b or 7c and the heat exchangers 6b and 6c are 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 arrows 12a in FIGS. 1 and 3.
  • HF-inert gas mixtures the HF concentration of which is lowest in gas line 7a and highest in gas line 7c, are supplied to sorption reactor 1 through 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 HF is transported from the sorption reactor 1 into the dwell 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 5b 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.
  • HF is desorbed by the action of the heated gas streams on the HF-loaded substrate.
  • the first desorption reactor 3c since the substrate with 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, into which the substrate already largely frees from HF, the smallest 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 gas stream which emerges from the reactor 3b has an intermediate HF concentration in between.
  • the HF gas streams of different HF concentrations are fed into the sorption reactor 1 at various inlet points through the gas lines 7a or 7b or 7c after passing through the interposed heat exchangers 6a or 6b or 6c.
  • 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 Figure 2.
  • a three-way valve (10) is interposed in the gas line 7a, which allows a (more or less large) part of the HF gas stream emerging from the desorption reactor 3a to be passed into a gas line (11) special circuit again and to be introduced 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 cycle 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.
  • a three-way valve (10a) is interposed in the gas line 7a, 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 flow only passes through the reactor 3a and is fed directly to the sorption reactor 1, the other two partial flows 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, ie 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, advantageously 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 hydrogen 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 each other 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 1 contents made of semi-transparent polyethylene.
  • the desorption reactors were made of stainless steel and were heatable rotary tube reactors trained, which could be flowed through in the same direction by the substrate and by the flowing gases.
  • the usable volume of the desorption reactors was approximately 3 l each.
  • Second desorption reactor (3b) The product loaded with HF was introduced from the first desorption reactor (3c) 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 was introduced 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 fed through the pipelines (7a, 7b, 7c) and the heat exchangers (6a, 6b, 6c), where they were cooled to 25-30 ° C., into the sorption reactor ( 1) passed so that circuits of carrier gas (nitrogen) and HF came about with continuous conveyance of substrate through the apparatus.
  • the digested substrate largely freed from HF, was extracted in the usual way with hot water
  • 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)
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
DE3142215 1981-10-24
DE19813142215 DE3142215A1 (de) 1981-10-24 1981-10-24 "verfahren zum aufschluss von zellulosehaltigem material mit gasfoermigem fluorwasserstoff"

Publications (2)

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

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ID=6144759

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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

Country Status (5)

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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)

* Cited by examiner, † Cited by third party
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
EP2585606A4 (fr) 2010-06-26 2016-02-17 Virdia Ltd Mélanges de sucres, méthodes de production et d'utilisation associées
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
US9512495B2 (en) 2011-04-07 2016-12-06 Virdia, Inc. Lignocellulose conversion processes and products

Citations (2)

* Cited by examiner, † Cited by third party
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
EP0051237A1 (fr) * 1980-10-30 1982-05-12 Hoechst Aktiengesellschaft Procédé de préparation de saccharides à partir de matériaux cellulosiques

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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
EP0051237A1 (fr) * 1980-10-30 1982-05-12 Hoechst Aktiengesellschaft Procédé de préparation de saccharides à partir de matériaux cellulosiques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BIOTECHNOLOGY AND BIOENGINEERING, Band XXIV, Nr. 4, April 1982, Seiten 903-918, John Wiley & Sons, New York, USA *
CHEMICAL ABSTRACTS, Band 96, Nr. 24, 14. Juni 1982, Seite 169, Nr. 202455v, Columbus, Ohio, USA *

Also Published As

Publication number Publication date
DE3262696D1 (en) 1985-04-25
US4556432A (en) 1985-12-03
ATE12258T1 (de) 1985-04-15
DE3142215A1 (de) 1983-05-05
EP0078023B1 (fr) 1985-03-20
CA1192706A (fr) 1985-09-03

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