Production of a fermentation product
20 claims: 13 independent, 7 dependent
- 1Zastrzeżenia patentowe 1. Sposób wytwarzania produktu fermentacji obejmujący etapy, w których:(i) tworzy się zakwaszoną zawiesinę celulozowego ziarnistego materiału pochodzenia roślinnego zawierającego hemicelulozę jako pierwszy polisacharyd, który łatwiej hydrolizuje, oraz celulozę jako drugi polisacharyd, który trudniej hydrolizuje, (ii) poddaje się pierwszy polisacharyd hydrolizie pod działaniem kwasu o pKa niższym od 4 i o stężeniu do 2% wagowych, w temperaturze co najmniej 50°C, w których to warunkach pierwszy polisacharyd hydrolizuje i tworzy się mieszaninę roztworu wodnego zawierającego rozpuszczony cukier oraz stałej pozostałości zawierającej drugi polisacharyd, (iii) poddaje się mieszaninę jednej lub kilku operacjom separacji, w których stała pozostałość i roztwór wodny cukru są oddzielane od siebie, (iv) ewentualnie przemywa się pozostałość pozbawioną kwasu i cukru, (v) koryguje się pH roztworu wodnego do co najmniej 4, (vi) przeprowadza się roztwór wodny z etapu (iv) do stadium fermentacji, w którym rozpuszczone cukry pod działaniem mikroorganizmu w bulionie fermentacyjnym przekształca się w produkt fermentacji, (vii) kontaktuje się drugi polisacharyd z enzymem, który to enzym hydrolizuje drugi polisacharyd na cukry składowe i poddaje się cukry składowe działaniu mikroorganizmu w bulionie fermentacyjnym z wytworzenia produktu fermentacji, (viii) oddziela się produkt fermentacji od bulionu, znamienny tym, że stadium/stadia separacji w etapie (iii) wspomaga się przez flokulację stałego produktu ubocznego, przy czym stosuje się co najmniej jeden środek flokulujący wybrany z grupy PL 208 652 B1 obejmującej rozpuszczalne w wodzie polimery, pęczniejące w wodzie polimery, oraz naładowane materiały mikroziarniste.
- 2Sposób według zastrz. 1, znamienny tym, że stałą pozostałość z etapu (iv) zawierającą drugi polisacharyd dzieli się na strumień główny i strumień drugorzędny i przepuszcza się główny strumień bezpośrednio do stadium fermentacji, natomiast strumień drugorzędny pozostałości polisacharydowej wprowadza się do stadium wytwarzania enzymu, w którym wytwarza się enzym przez pozostawienie grzyba do działania na pozostałość polisacharydu, co prowadzi do wytworzenia enzymu i cukrów wskutek przekształcenia drugiego polisacharydu zawartego w drugorzędnym strumieniu, a nastę pnie enzym i cukry z etapu (vi) wprowadza się do stadium fermentacji, w którym enzym dzia ł a na drugi polisacharyd w naczyniu fermentacyjnym i prowadzi się hydrolizę drugiego polisacharydu do cukrów składowych.
- 3Sposób według zastrz. 1, znamienny tym, że stałą pozostałość z etapu (iv) zawierającą drugi polisacharyd wprowadza się do stadium obróbki enzymem, w którym to stadium wytwarza się enzym przez umożliwienie rozwoju grzyba na polisacharydzie i wymienionym enzymem prowadzi się hydrolizę polisacharydu na cukry składowe, a następnie wprowadza się uzyskane cukry do stadium fermentacji, w którym cukry przekształca się w produkt fermentacji.
- 4Sposób według zastrz. 1-3, znamienny tym, ż e stosuje się materia ł pochodzenia roś linnego stanowiący materiały wybrane z grupy obejmującej biomasę zieloną, biomasę drewna z drzew iglastych, biomasę drewna z drzew liściastych, szlam ściekowy, szlam papierniczy i biomasę części odpadów komunalnych.
- 5Sposób według zastrz. 1-3, znamienny tym, że stosuje się kwas wybrany spośród kwasu siarkowego i kwasu solnego.
- 6Sposób według zastrz. 1-3, znamienny tym, ż e hydrolizę pierwszego polisacharydu przeprowadza się w temperaturze między 120 a 220°C przez okres od 1 minuty do 15 minut.
- 7Sposób wedł ug zastrz. 1-3, znamienny tym, ż e stosuje się ś rodek flokulują cy wybrany z grupy obejmują cej rozpuszczalne w wodzie lub pę cznieją ce w wodzie naturalne, pół syntetyczne i syntetyczne polimery.
- 8Sposób według zastrz. 7, znamienny tym, że polimer tworzy się z monomeru rozpuszczalnego w wodzie lub mieszanki monomerów.
- 9Sposób według zastrz. 7, znamienny tym, że polimer jest wybrany z grupy obejmującej sole poliakrylanowe, poliakrylamid, kopolimery akrylamidu z kwasem (met)akrylowym lub jego solami, kopolimery akrylamidu z (met)akrylanem dialkiloaminoalkilu, lub sole addycyjne z kwasami lub czwartorzędowe sole amoniowe, polimery chlorku diallilometyloamoniowego, poliaminy i polietylenoiminy.
- 10Sposób według zastrz. 1-3, znamienny tym, że stosuje się środek flokulujący, którym jest naładowany materiał mikroziarnisty.
- 11Sposób według zastrz. 10, znamienny tym, że naładowany materiał mikroziarnisty jest wybrany z grupy obejmującej pęczniejące glinki, anionowe, kationowe lub amfoteryczne mikroziarniste materiały krzemionkowe i organiczne sieciowane mikrocząstki polimerowe.
- 12Sposób według zastrz. 1-3, znamienny tym, że mieszaninę poddaje się flokulacji z użyciem rozpuszczalnego w wodzie lub pęczniejącego w wodzie polimeru oraz naładowanego materiału mikroziarnistego.
- 13Sposób według zastrz. 1-3, znamienny tym, że mieszaninę poddaje się flokulacji, wprowadzając anionowy materiał mikroziarnisty do mieszaniny, a następnie reflokuluje się dodając niejonowy polimer.
- 14Sposób według zastrz. 1-3, znamienny tym, że mieszaninę poddaje się flokulacji, wprowadzając kationowy polimer do mieszaniny, a następnie reflokuluje się dodając anionowy materiał mikroziarnisty.
- 15Sposób według zastrz. 1-3, znamienny tym, że mieszaninę poddaje się flokulacji, wprowadzając kationowy polimer do mieszaniny, a następnie reflokuluje się dodając anionowy polimer.
- 16Sposób według zastrz. 1-3, znamienny tym, że mieszaninę poddaje się flokulacji wprowadzając anionowy polimer do mieszaniny, a następnie reflokuluje się dodając kationowy polimer.
- 17Sposób według zastrz. 1-3, znamienny tym, że wytwarza się stały produkt uboczny, którym jest lignina i podobne materiały.
- 18Sposób według zastrz. 1-3, znamienny tym, że podczas procesu fermentacji wytwarza się produkt fermentacji wybrany z grupy obejmującej etanol, glicerol, aceton, n-butanol, butanodiol, izopropanol, kwas masłowy, metan, kwas cytrynowy, kwas fumarowy, kwas mlekowy, kwas propionowy, PL 208 652 B1 kwas bursztynowy, kwas itakonowy, kwas octowy, aldehyd octowy, kwas 3-hydroksypropionowy, kwas glukonowy, kwas winowy i aminokwasy, takie jak kwas L-glutarowy, L-lizyna, kwas L-asparaginowy, L-tryptofan, L-aryloglicyny lub sole którychkolwiek z tych kwasów.
- 19Sposób według zastrz. 1-3, znamienny tym, że produkt fermentacji wydziela się z bulionu przez wprowadzanie bulionu zawierającego produkt fermentacji do stadium destylacji, w którym związek fermentacyjny zbiera się jako destylat, a resztki podestylacyjne usuwa się.
- 20Sposób według zastrz. 1-3, znamienny tym, że produkt fermentacji wydziela się z bulionu przez wprowadzanie bulionu zawierającego produkt fermentacji do stadium zatężania, w którym związek fermentacyjny zbiera się w koncentracie i ekstrahuje się co najmniej jednym środkiem wybranym z grupy obejmującej żywicę jonowymienną, ekstrakcję rozpuszczalnikową i elektrodializę.
Independent claims20
111 paragraphs in 3 sections, as filed
Description of the invention
The present invention relates to a method of producing a fermentation product by processing plant-derived material to produce an aqueous sugar-containing fluid to be fermented. Fermentation produces fermentation products such as, for example, ethanol, glycerol, acetone, n-butanol, butanediol, isopropanol, butyric acid, methane, citric acid, fumaric acid, lactic acid, propionic acid, succinic acid, itaconic acid, acetic acid, acetic aldehyde, 3-hydroxypropionic acid, gluconic acid, tartaric acid, and amino acids such as L-glutaric acid, L-lysine, L-aspartic acid, L-tryptophan, L-arylglycine, or salts of any of these acids.
It is known to produce a fermentation product by treating biomass with acid in order to hydrolyze the polysaccharides into constituent sugars that can be further used in the fermentation process. For example, US-A-4,384,897 discloses a method of treating biomass material by subjecting the seed to a two-stage hydrolysis. In the first stage, they hydrolyze polysaccharides, e.g. hemicellulose, which are more easily subjected to this process, and then in the second stage, with a more severe hydrolytic treatment, more difficult to depolymerize materials, e.g. cellulose, are depolymerized. First and second stage products include sugar solutions, organic acids and aldehydes. The monosaccharides are fermented to produce ethanol and the fermented digestate can be rectified to produce commercial ethanol. US-A-4,384,897 establishes improvements in more efficient solids leaching, the use of co-current and countercurrent solids leaching, and proposes the use of iron or aluminum ions as flocculating agents to separate fine dispersed solids formed during the neutralization of the hydrolyzate fluid stream.
Kyoung Heon Kim et al. (Applied Biochemistry and Biotechnology, vol. 91-93, pp. 253-267) investigated the continuous countercurrent hydrolysis and hemicellulose extraction from acid pretreated wood residues and considered the effect of the drainage rate of such pretreated biomass. The use of a continuous countercurrent coil extractor relies on the gravity percolation of water through the pretreated biomass. The only difficulty observed is that the pretreated biomass has poor drainage properties and channeling or blocking can occur inside the reactor, which can lead to low sugar recovery or low process efficiency.
Thus, it would be desirable to improve the dewatering performance of the acid treated plant material in order to maximize sugar recovery.
It is known from the publication of the National Renewable Energy Laboratory (NREL) entitled "Lignocellulose Biomass to Ethanol Process Design and Economics of Co-Current Dilute Acid Prehydrolysis and Enzymatic Hydrolysis Current and Future Scenarios" NREL / IP-580-26157 (July 1999) treatment of cellulose as a second polysaccharide with a cellulase enzyme to hydrolyze cellulose to the constituent sugars. In one embodiment of this process, the byproduct solid residue formed in the first hydrolysis step and containing cellulose is separated into a main stream and a secondary stream. The main stream is fed directly to the fermentation vessel and the secondary stream is fed to the cellulase production stage where fungi are allowed to develop and act on cellulose such that sugars and cellulase are formed. The sugars and cellulase are then fed into the fermentation vessel and the cellulase acts on the cellulose from the mainstream and converts it into constituent sugars, which in turn can be fermented to form a fermentation product.
Typically, it is necessary to wash the solid by-product to ensure that it is substantially free of acids, especially acetic acid, which is used in the hydrolysis of hemicellulose. This is necessary because acetic acid or other contaminants can poison the fungi used to make cellulase or the cellulase produced. Typically the wash water is recycled water, for example the water separated from the still in the distillation of the recovery of the fermentation product from which the suspended solids have been removed.
As the washing water may contain other impurities that can be detrimental to both the cellulase and the fermentation processes, it would be desirable to minimize the amount of washing water used.
A particular problem that may arise is that the yield of the process may be variable, sometimes leading to a reduction in the production of the fermentation product. There is therefore a need to improve the yield of the fermentation product produced by this process and increase the production rate.
PL 208 652 B1
The invention relates to a method of producing a fermentation product comprising the steps of:
(i) an acidified suspension of cellulosic granular plant material containing hemicellulose as the first polysaccharide that is more easily hydrolyzed and cellulose as the second polysaccharide that is more difficult to hydrolyze, (ii) the first polysaccharide is hydrolyzed by an acid with a pKa lower than 4 and with a concentration up to 2% by weight, at a temperature of at least 50 ° C, under which conditions the first polysaccharide is hydrolyzed and a mixture of an aqueous solution containing dissolved sugar and a solid residue containing the second polysaccharide is formed, (iii) the mixture is subjected to one or more separation operations in which the solid residue and the sugar aqueous solution are separated from each other, (iv ) optionally wash the acid and sugar-free residue, (v) adjust the pH of the aqueous solution to at least 4, (vi) the aqueous solution from step (iv) is passed to the fermentation stage, in which the dissolved sugars are converted into a fermentation product by the action of the microorganism in the fermentation broth, (vii) the second polysaccharide is contacted with the enzyme which hydrolyzes the second polysaccharide into sugars the constituent sugars are treated with the microorganism in the fermentation broth to produce a fermentation product.
(viii) the fermentation product is separated from the broth,
The process according to the invention is characterized in that the separation step (s) in step (iii) are promoted by flocculation of the solid by-product and at least one flocculating agent selected from the group consisting of water-soluble polymers, water-swellable polymers, and charged micronized materials is used. .
Preferably, in the process of the invention, the solid residue from step (iv) containing the second polysaccharide is divided into a main stream and a secondary stream, and the main stream is passed directly to the fermentation stage, while the polysaccharide residue secondary stream is fed to the enzyme production stage in which the enzyme is produced. by allowing the fungus to act on the residual polysaccharide, leading to the production of enzyme and sugars by converting the second polysaccharide contained in the secondary stream, and then the enzyme and sugars from step (vi) are introduced into a fermentation stage where the enzyme acts on the second polysaccharide in the fermentation vessel and the second polysaccharide is hydrolyzed to sugars components.
As an alternative to the above preferred variant, the solid residue of step (iv) containing the second polysaccharide is fed to the enzyme treatment stage, in which stage the enzyme is produced by allowing the fungus to grow on the polysaccharide, and said enzyme hydrolyzes the polysaccharide into component sugars, and then introduces the enzyme into the enzyme treatment stage. the resulting sugars to a fermentation stage in which the sugars are converted into a fermentation product.
In the method according to the invention, preferably vegetable material is used which is materials selected from the group consisting of green biomass, softwood biomass, hardwood biomass, sewage sludge, paper sludge and biomass of part of municipal waste, and the acid is used as acid. an acid selected from sulfuric acid and hydrochloric acid. Hydrolysis of the first polysaccharide is preferably performed at a temperature between 120 and 220 ° C for a period of 1 minute to 15 minutes, and the flocculating agent is preferably an agent selected from the group consisting of water-soluble or water-swellable natural, semi-synthetic and synthetic agents. polymers, preferably the polymer is formed from a water-soluble monomer or a mixture of monomers, and particularly preferably the polymer is selected from the group consisting of polyacrylate salts, polyacrylamide, copolymers of acrylamide with (meth) acrylic acid or its salts, copolymers of acrylamide with dialkylaminoalkyl (meth) acrylate, or acid addition salts or quaternary ammonium salts, polymers of diallylmethylammonium chloride, polyamine and polyethyleneimine.
Also preferably, in the process of the invention, a charged micronized material is used as flocculating agent, especially one selected from the group consisting of swellable clays, anionic, cationic or amphoteric silica microparticles and organic cross-linked polymer microparticles.
PL 208 652 B1
In the process of the invention, the mixture is flocculated with a water-soluble or water-bursting polymer and charged material in a micro-grain, or alternatively the mixture is flocculated by introducing an anionic micro-grain material into the mixture, and then reflocculating by adding a non-ionic polymer or mixture. is flocculated, introducing a cationic polymer into the mixture, and then reflocculated by adding an anionic micro-grain material, or the mixture is flocculated by introducing a cationic polymer into the mixture and then reflocculated by adding an anionic polymer, or the mixture is flocculated by introducing an anionic polymer into the mixture and then reflocculated by adding a cationic polymer.
The process of the invention produces a solid by-product of lignin and similar materials, and the fermentation process produces a fermentation product selected from the group consisting of ethanol, glycerol, acetone, n-butanol, butanediol, isopropanol, butyric acid, methane, citric acid. , fumaric acid, lactic acid, propionic acid, succinic acid, itaconic acid, acetic acid, acetic aldehyde, 3-hydroxypropionic acid, gluconic acid, tartaric acid and amino acids such as L-glutaric acid, L-lysine, L-aspartic acid, L-tryptophan, L-arylglycine, or salts of any of these acids.
Preferably, the fermentation product is separated from the broth by introducing the broth containing the fermentation product to a distillation stage in which the fermentation compound is collected as a distillate and the distillation residues are removed, preferably the fermentation product is also separated from the broth by introducing the broth containing fermentation product to the concentration stage. wherein the fermentation compound is collected in the concentrate and extracted with at least one agent selected from the group consisting of an ion exchange resin, solvent extraction and electrodialysis.
It has been found that by using the flocculation method according to the invention, unexpectedly high yields of the fermentation product can be obtained in the separation stage. It is believed that the residual acid and sugar in the solid residue of the raw material interact with the enzyme formation and the action of the enzyme on the second polysaccharide in the solid residue. This in turn leads to incomplete conversion of the second polysaccharide to the constituent sugars, and results in a reduction in the yield of the fermentation product.
The improvement of the separation stage in the process has the advantage that the sugar solution obtained from the first hydrolysis stage is substantially free of foreign solid material such as cellulose fibers.
In the method of the invention, the enzyme which acts on the second polysaccharide may be introduced directly to the residual solid by-product after separation from the sugar liquor formed during the hydrolysis of the first polysaccharide, or it may be added when the second polysaccharide has been introduced into the fermentation process. The enzyme can be introduced by allowing the fungus to grow on the second polysaccharide, during which the fungus generates an enzyme that hydrolyzes the polysaccharide into its constituent sugars.
Fungi capable of producing the respective enzymes can be Trichoderma reesei, Aspergillus niger, Humicola insolens and Thermo-monospora fusca.
Alternatively, a solid by-product containing the second polysaccharide is fed to the fermentation vessel and a commercially available enzyme is added directly to the fermentation vessel to act on the second polysaccharide.
In one preferred embodiment of the invention, the solid residue from step (iv) containing the second polysaccharide is divided into a main stream and a secondary stream. The main stream is passed directly to the fermentation stage, while the polysaccharide residue secondary stream is fed to the enzyme production stage. At this stage, the enzyme is produced by allowing the fungus to act on the residual polysaccharide, which leads to the production of the enzyme and conversion of the second polysaccharide into its constituent sugars. The enzyme and the resulting sugars are introduced into the fermentation vessel. The enzymatic process produces enough enzyme to act on the second polysaccharide introduced into the fermentation stage from the main stream. Thereby, the second polysaccharide in the fermentation vessel is then hydrolyzed to the constituent sugars.
Alternatively, all solid residues from step (iv) containing the second polysaccharide are fed to the enzyme treatment stage in which the enzyme is produced by allowing the fungus to grow on the polysaccharide. The enzyme hydrolyzes the polysaccharide into constituent sugars and then the sugars are passed to the fermentation stage, where the sugars are converted to fermentation product. However
Increasing the sugar concentration would inhibit the enzyme production process and thus it may be necessary to continuously remove the sugars formed.
The plant-derived material is usually any readily available source of polysaccharides, in particular cellulosic materials. Typically the cellulosic material is materials selected from the group consisting of green biomass, softwood biomass, hardwood biomass, sewage sludge, paper sludge, and biomass of some municipal waste. The green biomass may be, for example, cane pomace, rice straw, rice hulls, corn straw, wheat straw, grass, trees, and cotton gin waste.
Preferably, the plant-derived material is cellulosic and comprises hemicellulose as the first polysaccharide and cellulose as the second polysaccharide. Generally, plant derived material also includes lignin or lignin materials which remain in the solid by-product.
An acidified slurry can be formed by combining a granular material containing cellulose, hemicellulose, and lignin with dilute acid. Alternatively, the slurry may be prepared by treating cellulosic biomass with sulfur dioxide gas, steam and water at elevated temperature. Typically the process may be carried out by impregnating the biomass material with SO2 gas followed by steam at 205 to 215 ° C for 5 minutes, followed by adding water to form a slurry (Stenberg et al., Recycling of Process Streams, Applied Biochemistry, Vol. 70-). 72, 1998, pp. 697-707,1998).
By dilute is meant the acid having a concentration generally lower than 10% by weight. Typically, however, the concentration will be much lower, for example less than 5%. The acid can be a strong mineral acid such as hydrochloric acid, sulfuric acid, sulfuric acid, hydrofluoric acid, nitric acid, and phosphoric acid. Alternatively, the acid may be an organic acid, for example, carbonic acid, tartaric acid, glucuronic acid, formic acid, trichloroacetic acid, or other carboxylic acids.
Most preferably, the acid has a pH of less than 4. Useful results are obtained with either hydrochloric acid or sulfuric acid.
Hydrolysis of the first polysaccharide is preferably performed at a temperature between 120 and 220 ° C for a period of 1 to 15 minutes, although lower temperatures are possible if the treatment time is longer.
At each of the first and second stages of hydrolysis, the resulting hydrolyzate is then separated from the solids, preferably by pressing the treated material to separate the residual solid product. The separated solid product may be subjected to at least one washing cycle to remove residual sugar solution from the solid. The washing cycle includes washing the solid product with an appropriate washing liquid. The flushing liquid may be water. Typically the wash water is recycled water, for example water that has been separated from the still liquor in the distillation recovery of the fermentation product, from which I will remove these suspended solids.
The liquid hydrolyzate, which contains sugars and acid, can then be collected for further processing. When the first polysaccharide is hemicellulose, the resulting hydrolyzate is generally C5 sugars, and if the second polysaccharide is cellulose, the hydrolyzate is generally C6 sugars.
In any case, it is essential to adjust the pH of the aqueous sugar liquids to a pH of at least 4. The pH adjustment can be made by adding a base or by using an ion exchange resin that is capable of neutralizing the acid. Preferably, the pH of the acidified aqueous sugar fluid that is formed in the digestion is adjusted to a pH of at least 10 by adding an alkaline material such as sodium carbonate, followed by further adjusting the pH to a more neutral or slightly acidic pH. It is advisable that the pH be adjusted to a value between 10 and 12, preferably around 11, by adding a base followed by titration to a pH of 4-5, preferably a pH of around 4.5.
Alternatively, acid may be removed from the fluid by passing the hydrolyzate through a bed of resin beads to remove the acid. The aqueous sugar stream which preferably contains at least 98% of the sugar present in the hydrolyzate may then be recovered.
After the acid is separated from the aqueous sugar stream, the acid is preferably concentrated for reuse, e.g. by evaporation.
The fermentation process of the present invention usually consists of allowing the fermentation to run for 3 to 5 days. Volatile fermentation products can be continuously removed by recirculating carbon dioxide through a cooled condensation column. Conveniently, the fermentation products are collected from the condensation column after three to five days and then distilled. Favorable
Volatile fermentation products are separated from the broth by introducing the broth containing fermentation products to a distillation stage, where the digestate is collected as a distillate and the remaining still bottoms are removed. Microorganisms can be separated from the fermentation broth or preferably from the still bottoms, preferably by centrifugation, and can be recycled for reuse. In one preferred aspect of the invention, the fermentation product is separated from the broth by introducing the broth containing the fermentation product to a concentration stage in which the digestate is collected in a concentrate and extracted with at least one agent selected from the group consisting of ion exchange resins, solvent extraction and electrodialysis.
The process can be used to produce numerous fermentation products, but preferably the fermentation product is selected from the group consisting of ethanol, glycerol, acetone, n-butanol, butanediol, iso-propanol, butyric acid, methane, citric acid, fumaric acid, lactic acid, propionic acid, succinic acid, itaconic acid, acetic acid, acetic aldehyde, 3-hydroxypropionic acid, gluconic acid, tartaric acid and amino acids such as L-glutaric acid, L-lysine, L-aspartic acid, L-tryptophan, L-arylglycine or salts of any of these acids.
The microorganisms used in the fermentation process of the present invention may be, for example, yeasts such as Klyveromyces species, Candida species, Pichia species, Brettanomyces species, Saccharomyces species such as Saccharomyces cerevisiae and Saccharomyces uvarum, Hansenula species and Pachysolen species. Alternatively, the microorganism may be a bacterial species such as Leuconostoc, Enterobacter, Klebsiella, Erwinia, Serratia, Lactobacillus, Lactococcus, Pediococcus, Clostridium, Acetobacter, Gluconobacter, Lactobacillus, Aspergillus, Propionibacterium, Rhizopus and Zymomonas mobilis. In addition, genetically modified strains can also be used.
Since the solid product generally contains lignin and the like, it can be particularly difficult to separate it from the fluid. We have surprisingly shown that the production of the fermentation product can be significantly improved by using at least one flocculating agent to separate the hydrolyzate from the solid product. We have found that the solid product can be more effectively dewatered by this method and a higher proportion of solids in the cake can be obtained. Since the solid product can be more effectively dewatered, this reduces the performance requirements of the separation equipment, and so less capital intensive and less expensive equipment to operate, such as a filter press, can be used. Since a higher proportion of solids in the cake can be obtained, less acidic sugar solution remains in the residual solid by-products. Thus, the amount of water required to wash the solid by-product to be freed from the acid sugar solution is greatly reduced, which improves the processability and the efficiency of the process.
A suitable flocculating agent is selected from the group consisting of water-soluble or water-swellable natural, semi-synthetic and synthetic polymers. Preferably the polymer is synthetic and may be formed by polymerizing at least one cationic, non-ionic and / or anionic monomer (s) or with other water-soluble monomers. By water-soluble it is meant that the monomer has a solubility of at least 5 g / 100 ml at 25 ° C.
Preferred polymeric flocculating agents are formed from ethylenically unsaturated water-soluble monomers which are readily polymerized to form high molecular weight polymers. Particularly preferred polymers contain monomers selected from the group consisting of polyacrylate salts, polyacrylamide, copolymers of acrylamide with (meth) acrylic acid or its salts, copolymers of acrylamide with dialkylaminoalkyl (meth) acrylate, or acid addition salts or quaternary ammonium chloride polymers, diallylmethylammonium, polyamine and polyethyleneimine. The polymers can be linear, branched, or cross-linked.
The polymers may be prepared according to any convenient method, for example, by solution polymerization, gel polymerization, reverse phase suspension polymerization, and reverse phase emulsion polymerization. Suitable methods include those disclosed in EP-A-150933 or EP-A-102759.
Suitable polymers include anionic, cationic and nonionic polymers. Preferred polymers are nonionic and cationic polymers of sufficiently high molecular weight, such that have an intrinsic viscosity of at least 4 dl / g. Such an intrinsic viscosity is generally indicative of a polymer with a molecular weight of several million, for example generally greater than 5,000,000, and typically
The polymer preferably has an intrinsic viscosity greater than 6 dl / g, often at least 8 or 9 dl / g. The intrinsic viscosity can be as high as 30 dL / g or more. In many cases, however, suitable cationic polymers have an intrinsic viscosity in the range of 7-25 dl / g, especially 10-20 dl / g, especially about 14 or 15 dl / g.
Suitable cationic monomers include quaternary or acid salts of monomers that contain amino groups. Preferably, the cationic polymer is formed from a monomer or monomer blend comprising at least one cationic monomer selected from the group consisting of quaternary ammonium salts and acid salts of dimethylaminoethyl (meth) acrylate, quaternary ammonium salts and dimethylaminoethyl (meth) acrylamide acid salts and diallylmethylammonium chloride. The cationic monomers may be homopolymerized or copolymerized with other monomers, for example acrylamide. Thus, the cationic polymers may be polymers that contain a cationic moiety, provided that they obviously have a sufficiently high molecular weight to exhibit an intrinsic viscosity of at least 4 dl / g. The intrinsic viscosity is measured using a suspended level viscometer in 1M NaCl buffered to pH 7.5 at 25 ° C.
The cationic polymers of the invention can be prepared as substantially linear polymers or as branched or structured polymers. Structured or branched polymers are usually produced by incorporating polyethylene unsaturated monomers such as methylene bis acrylamide into a monomer blend, for example as described in EP-B-202 780. Preferably, however, the polymers are substantially linear and are obtained as beads or as a powder product.
Suitably the polymeric flocculating agent may be added as an aqueous solution or as an aqueous dispersion. The polymer may be added in an amount sufficient to effect flocculation. Typically, the amount of polymeric flocculating agent sufficient to induce flocculation would be at least 0.002% by weight based on the weight of the suspended solids. Typically, better flocculation and therefore separation can be achieved if at least 0.01% is used. The dose can be significantly higher, for example up to 1%. However, optimal flocculation and separation are usually achieved with doses in the range 0.015% to 0.2%, especially 0.02% to 0.1%. After flocculation of the suspended solids, the solid product can be separated from the aqueous hydrolyzate fluid by mechanical means, for example a filter press, centrifuge, belt press, horizontal belt filter or pressure filter. The action of the flocculating agent greatly enhances the solid-fluid separation compared to separation using purely mechanical means. We have shown that the process of the present invention provides cakes with a higher proportion of solids while trapping less aqueous fluid, meaning that a greater proportion of sugar fluid is available for conversion to fermentation product. Likewise, we have found that the aqueous fluid contains much less of the outer suspended cellulosic materials. Furthermore, we have found that there is less need for rinsing water.
The solid product from the separation step should be as dry as possible to avoid any loss of sugar as this would not enter the fermentation process.
In another embodiment of the present invention, the flocculating agent is a charged micro-grain material. Particularly suitable examples of charged microparticle materials include swellable clays, anionic, cationic or amphoteric silica micronized materials, and organic cross-linked polymer microparticles.
The silica material may be any of the materials selected from the group consisting of silica particles, silica microgels, colloidal silica, silica sols, silica gels, polysilicates, aluminosilicates, polyaluminosilicates, borosilicates, polyborosilicates, zeolites or swellable clay.
The silica material may be in the form of an anionic micro-grain material. Alternatively, the silica material may be cationic silica. Conveniently, the silica material may be selected from silicas and polysilicates.
The polysilicates of the invention can be prepared by lowering the pH of an aqueous alkali metal silicate solution. For example, polysilicic acid microgels, otherwise known as active silica, can be obtained by acidifying an alkali metal silicate to a pH between 2 and 10 with mineral acids or acidic ion exchange resins, acid salts, and acid gases. Fresh aging with the polysilicic acid formed may be desirable to allow for the formation of a sufficient three-dimensional network. Generally, the aging time is insufficient to gel the polysilicic acid. Particularly preferred silica materials are polyaluminosilicates. The polyaluminosilicates can be, for example, aluminized polysilicic acid
Prepared by first preparing the polysilicic acid microparticles and then treating them with aluminum salts. Alternatively, the polyaluminosilicates can be polysilicate polysilicon microgels with a surface area exceeding 1000 m<sup>2</sup>/ g formed by the reaction of an alkali metal silicate with acid and water-soluble aluminum salts. Typically, polyaluminosilicates have an aluminum: silicon molar ratio of between 1:10 and 1: 1500.
Polyaluminosilicates can be formed by lowering the pH of an aqueous alkali metal silicate solution to a pH between 2 and 10 with concentrated sulfuric acid containing 0.2 to 2.0% by weight of a water-soluble aluminum salt, for example aluminum sulfate. The aqueous solution may be aged enough to form a three-dimensional microgel. Typically, the polyaluminosilicate is aged for about two and a half hours before the aqueous polysilicate is diluted to 0.5% by weight of silica.
The silica material may be colloidal borosilicate. Colloidal borosilicate can be obtained by contacting a dilute aqueous alkali metal silicate solution with a cationic ion exchange resin to form silicic acid, and then forming a layering by mixing a dilute alkali metal borate solution with an alkali metal hydroxide to form an aqueous solution containing 0.01 to 30 % B2O3 with a pH from 7 to 10.5.
Swellable clays, for example, may typically be a bentonite clay. Preferred clays are water-swellable clays and include clays that naturally swell in water or clays that can be modified, for example, by ion exchange to make them water-swellable. Suitable water-bursting clays include, but are not limited to, frequently referred to clays such as hectorite, smectites, montmorillonites, nontronites, saponite, sauconite, hormites, attapulgites, and sepiolites.
Most preferably the clay is a bentonite clay. Bentonite can be supplied as alkali metal bentonite. Bentonites occur naturally as an alkali metal bentonite salt such as sodium bentonite or an alkaline earth metal salt, typically a calcium or magnesium salt. In general, alkaline earth bentonites are activated by the action of sodium carbonate or sodium bicarbonate. Activated swellable bentonite clay is often supplied as a dry powder. Alternatively, the bentonite may be provided as a high-solids liquid suspension, for example at least 15 or 20% solids.
Where the charged microparticle contains organic cross-linked polymer microparticles. Microparticles can be made as microemulsions by a process using an aqueous solution containing a cationic or anionic monomer and a crosslinking reagent; saturated hydrocarbon oil; and an effective amount of surfactant sufficient to produce particles less than 0.75 microns in average non-swollen diameter size. Microbeads are also made as microgels according to the procedures disclosed by Ying Huang et al., Makromol. Chem., 186, 273-281 (1985) or can be obtained commercially as microgrids. The term "microparticle" as used herein should encompass all these configurations, ie, beads as such, microgels and microgrids. The charged microparticulate material may be used in an amount of at least 0.002% based on the weight of the suspended solids. Typically, however, these doses are as high as 0.8 or 1.0% or more. When the charged microparticulate material is inorganic, the dose usually exceeds 0.06%, preferably 0.1-0.6%. When the charged microparticulate material is organic, the dose is typically less than 0.3%, preferably 0.02-0.1%.
We have surprisingly shown that the hydrolyzate fluid can be separated particularly quickly if the flocculation is carried out using a water-soluble or water-swellable polymer and charged micro-grain material. In one aspect, we have found that particularly effective flocculation and solid-fluid separation is achieved when flocculation is carried out by introducing an anionic micronized material into the mixture, followed by reflocculation by adding a cationic or substantially non-ionic polymer. In another embodiment of the present invention, we have found that a particularly fast and effective separation of the solids is achieved by a process in which flocculation is performed by introducing a cationic polymer into a mixture followed by reflocculation by adding anionic microgrid material.
The following examples illustrate the invention.
Example 1
Initial hydrolysis. The ground wood chips are steamed under low pressure steam up to about 100 ° C. After evaporation, diluted concentrated sulfuric acid is added to the mixture until obtained
With 0.52% acid and 22% solids in the reactor. The mixture is then steam heated to 175 ° C for 15 minutes. The mixture is cooled rapidly for 15 minutes, removing 6.5% acetic acid and 61% furfural and hydroxymethylfurfural.
Separation. 26% of undissolved bodies in the pre-hydrolyzed suspension (containing 0.38% of sulfuric acid) are separated on the filter press. Prior to applying pressure to the feed stream, flocculant or flocculants (down to 0.2-0.5% solids) and / or particle suspensions (down to 0.2-0.5% solids) are added with the necessary agitation at a dose rate. 0.2 to 2 kg per ton of solids. The flocculants increase the rate of free gravity drainage through the porous belt before forming a filter cake in the wedge zone and further draining in the pressure zone. The method of reducing the toxins remaining in the liquid fraction is by washing with (recycle) water.
After ion exchange to remove acetic acid, the liquid fraction of the hydrolyzate is acidified to pH 2 by adding sulfuric acid. Lime is then added to raise the pH to 10 and the liquid is heated to 50 ° C. The liquid is then adjusted to a fermentation pH of 4.5 for 4 hours so that gypsum crystals for separation by filtration are formed.
Simultaneous sugar and co-fermentation (SSCF). The detoxified and diluted hydrolyzed solids are cleaved into cellulase fermentations, Z. Mobilis graft production and SSCF fermentors. The hydrolyzate feed is a 22% combination of soluble and insoluble solids. The proportion of the residual hydrolyzed solids that is cleaved off to produce Z. mobilis for seeding is 10%. The portion of the hydrolyzate detached for cellulase production is dependent on the cellulase yield, the amount of cellulose and xylose present, and the required enzyme loading in the SSCF. For cellulase production, pre-hydrolyzed hydrolyzate fluid with treated solids, recycled water, corn steep extract (up to 1%) and nutrients ((NH4) 2SO4, KH2PO4, MgSO4.7H2O, CaCI2.2H2O and Tween 80) and corn oil are combined. as defoamer (0.1% v / v), to a final cellulose concentration of 4%. The process using this feed then runs 160 hours at 28 ° C to form the cellulase. The detoxified hydrolyzate suspension (22% total solids) is cooled to 30 ° C into the SSCF and added to the fermentor with a total of 10% (v / v) inoculum. Corn steep extract to 0.25% and cellulase are added to a final concentration of 15 FPU / g cellulose and an initial cellulose concentration of 22%. SSCF fermentation, in which cellulose is converted to fermentable sugars by cellulase and fermentable sugars converted to ethanol by Z. mobilis, lasts 7 days.
Example 2
Initial hydrolysis. Softwood shavings with a dry solids content of 48% are added to 400 g of water and heated to 190 ° C. At 190 ° C, sulfuric acid is added to a concentration of 0.7% under a positive nitrogen pressure and the mixture is left for 3 minutes. The temperature is rapidly lowered to 80 ° C and the insoluble matter in the suspension (containing 0.32% sulfuric acid) is separated on a filter press. Prior to applying pressure, solutions of flocculant or flocculants (down to a level of 0.2 to 0.5% solids) and / or particle suspensions (down to a level of 0.5 to 15% solids) are administered with the necessary agitation at a dose of 0.2 to 2 kg per ton of solids.
Enzymatic hydrolysis. Tap water is added to the separated pre-hydrolyzed solids to adjust the dry matter content of the slurry to 7.5% (w / w). The pH is adjusted to 4.8 with calcium hydroxide and then 10% (w / w) sodium hydroxide is used to maintain the pH = 4.8 during the hydrolysis. To carry out the hydrolysis, cellulase (activity 75 FPU / g) is added at a dose of 0.175 g / g of fibrous material supplemented with 0.025 g / g of cellobiase (β-galactosidase activity 400 IU / g). The hydrolysis is carried out for 4 days. The solid residues are separated on the filter press. Before applying pressure to the suspension, solutions of flocculant or flocculants (down to 0.2 to 0.5% solids) and / or particle suspensions (down to 0.5 to 15% solids) are added with the necessary agitation at a dose of 0.2 up to 10 kg per ton of solids.
Fermentation. The hydrolyzate is made up to a final concentration of 0.5 g / L (NH4) 2SO4 and 0.025 g / L MgSO4.7H2O and inoculated with yeast to a concentration of 1% (w / v). Fermentation is carried out at 30 ° C at pH 4.8 by adding 10% (w / w) sodium hydroxide.
Example 3
The separation of acid and sugar from the fermentation product according to the invention was evaluated using the equipment and the results obtained are based on the accompanying drawings in which:
Fig. 1 is a schematic axial section of the syringe, Fig. 2 shows the syringe of Fig. 1 containing the test sample,
Fig. 3 illustrates the introduction of flocculant into a sample, Fig. 4 is a partial sectional elevation view of the test rig, Fig. 5 is a partial sectional top view of the apparatus of Fig. 4, Figs. 6 and 7 are vertical sections of the apparatus for of separation of liquid from the sample, Fig. 8 is a graph showing the total conductivity that results from acid removal from the separated liquid, and Fig. 9 is a graph of the cumulative amount of sugar removed in the separated liquid.
Referring to Figure 1 of the drawings, the open end of a 10 circular view syringe housing is adapted to receive the syringe plungers 12 and 14 in each open end 16 and 18, respectively.
As shown in Figure 2, the test sample 20 of the hydrolyzate, possibly together with some support, is placed in the syringe housing substantially in the center and held in place by the plungers 12 and 14. The syringe, together with the sample, is incubated for a period of time, e.g. minutes at a temperature, usually about 90 ° C. After incubation, one plunger is withdrawn from the syringe and, as shown in Figure 3, the polymer flocculant 24 is introduced into the sample using a pipette 22. The removed plunger is replaced and the syringe shaken to ensure distribution of the polymer throughout the sample. The syringe is incubated again for, for example, about 10 minutes at a temperature of, for example, 90 ° C.
The rate at which liquid separates from solids can now be measured using the apparatus shown in Figures 4 and 5. It consists of a vertically oriented tube 30 fitted to receive the syringe at its upper end. The lower end of the tube 30 is positioned just above the paper tube 32. Contacts 34 are positioned on the filter and adapted to provide a signal to timer 36 to start the timer when liquid reaches the contacts 34 from the tube. An additional contact 38 connected to the timer is to turn off the timer when the liquid from the pipe reaches contact 38. Thus, the device measures the time required for the liquid to pass through the paper filter from style 34 to style 38. This time is called capillary suction time (CST). and is a measure of the rate of separation of liquids from solids in a test sample.
To obtain a CST for the sample, one plunger is removed and the syringe is inserted into the tube 30, the other plunger is pushed into the syringe housing to bring the sample into contact with the paper filter 32, as illustrated in Figure 4. paper filter outward from the contact of the sample with the filter paper, starting the timer when it reaches the contacts 34 and stopping the timer when it reaches the contact 38.
Using the apparatus shown, the CST was determined for 5 g samples of the hydrolyzate to which the flocculating polymer was added as given in the table below. The target CST was 98.8.
<td>Polymer addition</td><td>CST in seconds</td>
<td>Control sample + 100 μl H2O</td><td> 127,9</td>
<td>100 μl of polymer 1</td><td> 91,8</td>
Polymer 1 is an acrylamide homopolymer with an IV of about 14 dl-g.
Example 4
Following the procedure set forth with reference to Figs. 1-3, after the second incubation, one of the plungers is removed from the syringe and, as shown in Figs. 6 and 7, the open end of the syringe is inserted into the opening of a larger syringe 40 having a perforated base 42 to support a screen 44. Receiver cylinder 46 is positioned around the lower end of syringe 40 and syringe assembly 40 and barrel 46 are mounted in flask 48 connected to a vacuum. The sample is washed and the filtrate 52 collected in the receiver cylinder can be tested.
An apparatus with reference to Figures 6 and 7 was used to test the separation of acid and sugar from a sample of hydrolyzate treated according to the invention.
g of the hydrolyzate derived from corn stover is placed in the syringe housing 10 including some support and held in place by plungers during incubation. 0.1 ml of a 1% polymer solution 1 is pipetted into the sample as shown in Figure 2. After the second incubation, the sample and flocculant are transferred from the syringe housing 10 to the syringe 40, in which a 58 micron screen is placed on a perforated base 42. 10 ml of rinse water are added to the syringe and a vacuum is applied. The conductivity of the filtrate is measured for each 1 ml of recovered liquid, and the overall conductivity results are shown in the graph in Figure 8, which also gives the results obtained for the control.
PL 208 652 B1
As can be seen, the introduction of the flocculant causes a sharp increase in conductivity upon addition of the wash water, indicating acid removal.
Figure 9 shows the increase in sugar concentration in the filtrate after the addition of the wash water.
Example 5
Following the same procedure as in Example 4, the amount of sugar recovered was estimated for the two different polymers at two different polymer concentrations. The tests were performed in duplicate for each concentration and the results are shown in Table 1 below.
Polymer 2 is a copolymer of 8% sodium acrylate, 92% acrylamide, with an IV of about 9 dl / g.
Polymer concentration
<td></td><td colspan="2">200 ppm</td><td colspan="2">600 ppm</td>
<td>Control sample</td><td>190 mg 7.8 ml</td><td>181 mg 7.4 ml</td><td>249 mg 8.3 ml</td><td>237 mg 7.8 ml</td>
<td>Polymer 2</td><td>211 mg 7.4 ml</td><td>200 mg 7.0 ml</td><td>257 mg 8.1 ml</td><td>244 mg 7.7 ml</td>
<td>Polymer 1</td><td>386 mg 7.2 ml</td><td>367 mg 6.8 ml</td><td>246 mg 8.9 ml</td><td>233 mg 8.5 ml</td>
Polymer 2 is a copolymer of 8% sodium acrylate, 92% acrylamide, with an IV of about 9 dl / g.
The above results are based on a recovery of approximately 95% of the wash water.
After converting the figures, assuming theoretically that 10 ml of wash water is recovered, the results are as follows.
Polymer concentration
<td></td><td colspan="2">200 ppm</td><td colspan="2">600 ppm</td>
<td>Control sample</td><td>243 mg</td><td>231 mg</td><td>300 mg</td><td>285 mg</td>
<td>Polymer 2</td><td>285 mg</td><td>271 mg</td><td>317 mg</td><td>301 mg</td>
<td>Polymer 1</td><td>536 mg</td><td>509 mg</td><td>276 mg</td><td>262 mg</td>
Patent claims
Contents3
4 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4
21 members in 13 offices
Priority claims3
| Document | Office | Kind | Date |
|---|---|---|---|
| 0218019 | United Kingdom | A | |
| 02180198 | – | – | – |
| GB20020018019 | – | – | – |
Members21
| Document | Office | Kind | |
|---|---|---|---|
| CA2494664A1 | Canada | A1 | |
| WO2004015145A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2003250185A1 | Australia | A1 | |
| NO20050970L | Norway | L | |
| MXPA05001411A | Mexico | A | |
| EP1530646A1 | European Patent Office (EPO) | A1 | |
| BR0313272A | Brazil | A | |
| PL373121A1 | Poland | A1 | |
| CN1675379A | China | A | |
| US2005233031A1 | United States of America | A1 | |
| ZA200500272B | South Africa | B | |
| IN131CH2005A | India | A | |
| CN1325654C | China | C | |
| AU2003250185B2 | Australia | B2 | |
| US7455997B2 | United States of America | B2 | |
| NO327342B1 | Norway | B1 | |
| MX270158B | Mexico | B | |
| PH12005500085B1 | Philippines | B1 | |
| PL208652B1This record | Poland | B1 | |
| CA2494664C | Canada | C | |
| BR0313272B1 | Brazil | B1 |
Numbers
- Publication
- 208652
- Publication, DOCDB
- 208652
- Publication, EPODOC
- PL208652B
- Application
- 373121
- Application, DOCDB
- 37312103
- Application, EPODOC
- PL20030373121
Titles2
- English
- PRODUCTION OF A FERMENTATION PRODUCT
- Polish
- Sposób wytwarzania produktu fermentacji
Classification
- CPC, 7
- C12P7/08
- C13K1/02
- Y02E50/16
- Y02E50/10
- Y02E50/17
- Y02E50/30
- Y02E50/343
- IPC, 3
- C13K1 02
- C12P7 08
- C12P7 10
