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    • 专利摘要:
    Summary The invention relates to a salt for producing diesel and petrol-like products from lignin frail lignocellulose. Characteristic of the invention is that the lignocellulose is separated by solvent-based extraction into a lignin fraction and a second fraction mainly containing cellulose, the lignin fraction is concentrated by the solvent used in the separation, separated for recycling, after which this concentrated lignin fraction is catalyzed and subjected to catalyst. The concentrated lignin fraction, including residual solvents from the separation, was subjected to catalytic depolymerization at temperatures between 150 and 350 degrees C, giving diesel and gasoline-like products as the main fraction, a gaseous fraction comprising latte carbohydrates, carbon monoxide and carbon dioxide the gaseous fraction and the carbonate column are used as fuel for generating the required heat required for the separation.
    公开号:SE1300378A1
    申请号:SE1300378
    申请日:2013-05-24
    公开日:2014-11-25
    发明作者:Anders Östman
    申请人:Skandinavisk Kemiinformation Ab；
    IPC主号:
    专利说明:

    Production of fuel Background In the production of cellulose from wood products, large amounts of lignin are obtained as a by-product. In conventional cooking processes, the lignin comes out in lost form together with the cooking chemicals (black liquor). The latter are recycled in a combustion and reprocessing process (the so-called "chemical cycle") where lignin is a fuel. Lignin production is so large that heat surplus is obtained. Since time immemorial, the pulp industry has had alternative uses for the surplus lignin in the form of extra electricity generation and reprocessing of lignin into more valuable products. Progress has been limited and, with the exception of certain sulphite boiling products, virtually no lignin chemicals have been commercialized.
    In the production of fuel from lignocellulose, interest has largely been focused on biochemical conversion of the carbohydrates in lignocellulose. Ethanol production via hydrolysis and fermentation of these are well-known examples. This meant that a large part of the raw material is processed without fuel formation because few microorganisms break down lignin into the substances that can be used as fuel. The residual product from these processes is thus the unreacted lignin (with unreacted carbohydrates, etc., which is determined by the efficiency). It is in principle also set aside as fuel.
    Even with thermochemical methods for fuel production, the yield of suitable fuels from the lignin part in wood, etc. is small. During pyrolysis, a pyrolysis oil (tar) is formed, which must be obtained by further extensive reprocessing for real fuels. By using higher temperatures (gasification), the lignocellulose can be completely decomposed into carbon monoxide, hydrogen gas, etc. This gas can then be converted to "synthesis gas" from which potential and real fuels can then be synthesized. With this technology, however, large parts of the raw material (including lignin) are still used as fuel.
    Since the beginning of the 2000s, renewed, major efforts have been made to produce more valuable chemicals from lignin or to more efficiently produce fuel from the residual products from both cellulose production and fuel production. An example of this is the so-called "black liquor gasification" where gasification of the black liquor from the pulp industry is used as an alternative to, or supplementation of, the traditional black liquor combustion.
    For several decades, an alternative method for lignin separation from lignocellulose has been developed which, instead of traditional cooking as above, uses solvents; "solvent extraction" or solvent-based lignin solution. As solvents, a large number of more or less unpolar solvents have been proposed - and used in certain contexts; acetone, ethanol, dioxane, ethylene glycol, formic acid, tetrahydrofuran, organic esters, etc. Depending on the solvent, the process conditions vary, but the lignin falls out continuously on different salts, after which the solvent is reused in the extraction process. Among the advantages of these processes it is usually stated that the lignin obtained has a higher quality than lignin frail traditional cooking processes. The end result, however, is the same: lignin is obtained as a residual product whose value is sought by reprocessing. The present invention relates to a process combination in which two techniques are combined for efficient production of propellant alien from the lignin. Through certain modifications of the existing techniques, the combination makes it possible to utilize substantially the entire content of lignocellulose for fuel production.
    The invention in brief and its background preconditions Lignin is chemically a complex polymer which contains phenol-like atoms linked to each other via e.g. a. some organic acids where, for example, attic acid occurs. Chemically, lignin can be characterized as rather non-polar than polar, ie it contains a smaller amount of oxygen (in the couplings) in an otherwise carbon-like material. The oxygen content is in the order of 15% by weight, which can be compared with about 40% in trawl in its entirety.
    Thermochemical attempts to depolymerize lignin usually result in a tar-like mixture of the substances as above (pyrolysis). A number of chemical methods to crack the bonds between the monomeric phenol-like building blocks of the polymer usually result in relatively complex processes with considerable separation problems.
    A technique that has been reported for 10 years for, for example, "catalytic depolymerization". This uses a commercial "cracking catalyst" from the oil industry at a moderate temperature rise (200-300 degrees C) in an oil phase. The technology is stated in, among other things, a German patent, DE 100 49 377 A1. The technology is sometimes called KDP (Catalytic Depolymerization) (in different languages, ie in English CDP) and has in the form of AlphaKat been established in 5-10 smaller plants. In another design, where microwaves are used for heating, it has been launched by, for example, Bionic. You can also find it from UOP on the Internet.
    Among professionals, the technology has often been viewed with hesitation and the results from the various plants vary. So far, it seems to have only been partially tested on straw and similar materials, while pure wood products have not yet been officially reported. The existing, commercial plants are obviously based on plastic waste, waste oil and similar materials, and in these contexts the process is perhaps more like a conventional cracking.
    The hesitation of "professional marine" is partly due to the theoretical preconditions for the reactions as lignocellulose is involved. These include water supply and oxygen deposition, which are discussed below in the detailed description. From the marketers' point of view, the KDP repeatedly points out that the technology does not contain any thermal pyrolysis, which would lead to tar and similar products, while the KDP technology provides simple piston chains.
    According to thorough experiments, the basic precondition for the technology is that the raw material must not only consist of the hydrocarbons. In this case, with eg waste oils, only a conventional cracking takes place where, for example, carbon chains are broken in the C-C bonds. Tests with pure lignin have not given naintivarda amounts of carbohydrates of lines type. On the other hand, about 60% yields of "hydrocarbons" are obtained with straw raw material and the like, the spectra of which on gas chromatographs are very similar to diesel. 3 In order for the catalytic depolymerization to be based on lignin, clays thus have additional raw material components. They can be of carbohydrate character (cellulose and hemicellulose) as in the straw raw material but can also be excreted by other oxygen-rich compounds such as organic acids, esters and for example shorter alcohols. To achieve this raw material mixture, the invention combines a slightly modified solvent-based lignin extraction with a similarly slightly modified KDP technique.
    In practice, a separation or fractionation of lignocellulose is first carried out by an existing extraction technique in which solvents of the acetone, formic acid, dioxane, glycerol or other solvent capable of dissolving the lignin are used. The released lignin is transported together with by-products formed in the solvent-based extraction to a KDP process, where it is converted to a diesel- and petrol-like carbonate mixture. In the solution for the KDP process, lignin, the other substances from the raw material discharged in the separation process (hemicellulose residues, terpenes / tall oil, etc.) as above were called "by-products" and solvents from the separation are included. The content of solvents in the "lignin effluent" is determined on the basis of the conditions of the KDP process. See below.
    The invention allows by its combination that lignin can be efficiently depolymerized into a diesel-like product at the same time as other residual products from, for example, a cellulose production can be worked up into a more valuable product. Furthermore, the process combination provides an additional degree of freedom for the solvent-based lignin separation. In the latter, as mentioned, a storm or a small part of the solvent is separated from the lignin and returned to the lignin separation. In the process combination, by appropriate choice of solvent, the separation does not become critical. Residues of solvents in the lignin can be converted into a fuel product in the KDP process. In an expanded form, residual products from hydrolysis / fermentation of the cellulose can also be transferred to the KDP process.
    Through the combination of processes of the invention, a more efficient production of fuel from the lignin fraction is made possible. The residual lignin from the separation of lignocellulose has hitherto only been able to be worked up into propellant in either a large, complex black liquor gasification with subsequent synthesis processes or in pyrolysis processes which require extensive further work-up.
    Due to tests carried out with lignin-only tests in the KDP process, fuel product has not been obtained. In the process combination, this is made possible.
    Chemistry of the Invention As stated above, "those skilled in the art" have expressed some doubt as to the fundamental conditions for catalytic depolymerization of lignocellulose. This is related to aft dA lignocellulose to be converted to the "carbonate" most oxygen is removed from the raw material. In thermal processes, gasification and pyrolysis, this takes place through aft oxygen emissions in water vapor, carbon dioxide and carbon monoxide. If vale is not present to a sufficient extent, it leads to a C: H ratio which is too high for hydrocarbon formation (C: H = 1/1 1 aromatics, C: H> 1: 2 in 4 linear, matted hydrocarbons, etc.) whereby a coking happens. This coke, which also contains a little oxygen, is called "char".
    In practice, this meant that in the traditional processes aft Tate must be supplied for aft the hydrocarbons to be formed. This also happens in eg "hydrocracking" processes.
    In the KDP process, however, the developers of an internal, catalytic water production take place from a probe division of carbohydrates. The reaction is stated in principle according to: C61-10-43CO2 + (CH2) 3 + 4H (1) This meant that alit oxygen is removed via carbon dioxide which also contributes to improving the C: H ratio in the material. The result is the hydrocarbons in the form of CH2 units which form linear hydrocarbons and liberated whale, H. The reaction is said to take place on the surface of the catalyst and the water, H, is assumed to be bound to the catalyst surface.
    In the next step, the choice, H, reacts with the aromatic rings and bonds of the lignin so that the polymeric structure is broken up and further hydrocarbons are formed, preferably C7-C10, in accordance with the individual building blocks of the lignin; phenol - cresol, etc., ie in principle for eg phenol: C6H5OH (phenol) + 8H -> (CH2) 6 + H2O (2) The reaction is assumed to take place, not as a radical reaction in solid phase - gas phase, but as an ionic reaction by the catalyst. The mechanism also explains why lignin alone cannot be depolymerized to the hydrocarbons, but even further, water-donating substances are present. Furthermore, the process requires an intimate contact between the lignocellulose and the catalyst. Such contact generally benefits from the reaction taking place in the water phase and at moderate temperatures. Whether it is carried out in the oil phase, as in AlphaKat's design, or with microwaves, as in the case of Bionic, the maintenance temperatures below 300 degrees C to avoid pyrolysis reactions. within the scope of the invention has been found to be potentially water-donating. In the catalytic reaction, not only are carbohydrates in lignocellulose (formula 1 above). The edge of formic acid can already be divided into carbon dioxide and hydrogen gas, and tests with attic acid and formic acid in pure lignin have qualitatively shown that the KDP reactions give carbon-like products.
    This results in a combination between a solvent-based separation process and a KDP process potentially benefiting relative to a combination of a conventional sulphate or sulphite boiling cellulose process and KDP processes. In the latter combination, the amount of potentially water-donating hearth is limited to the hemicellulose residues that accompany the black liquor, while an increased amount of such can be added to the lignin fraction in the form of solvent residues from the solvent-based lignin separation. Glycol-type solvents should be sufficiently "carbohydrate-like" for possible type 1 reactions above.
    A "loss" of solvents in the recovery to the separation process can not only be used in the KDP process but can also "stimulate" it. Mimed does not constitute a "loss" in total a loss.
    Detailed description of the invention, examples Lignocellulose, which can be obtained from tara, straw, bagasse, maize residues, etc., are separated in a solvent-based extraction process into a cellulose fraction and a lignin fraction. The invention can be applied using several different such techniques and the choice of a specific technique is an optimization issue in the ordinary case. Saledes Ors a description which in this respect encapsulates several alternatives.
    The design of the separation process depends on the solvent used. Usually the solvent is used in a 40-80 percent aqueous solution. Mixtures of solvents occur and in some process concepts anyands aven catalyst. With regard to pressure, fire risks, etc. and a required dewatering of the lignin, more high-boiling solvents such as butanol, ethylene glycol, glycerol and, for example, formic acid and acetic acid are preferred in this case. The extraction temperatures are usually between 100 and 200 degrees C.
    Most solvent-based processes focus on the cellulose fraction and the halate in it is usually between 5 and 10%. This does not affect the design of the invention. The solvent (boiling water) is recovered in a distillation process and the remaining lignin solution is passed to the KDP process. With the use of the more boiling Boiling Risks, water is driven by the combination with these. The restriction for remaining water in the lignin fraction is a maximum of 20%.
    The lignin fraction also contains most of the constituents of hemicellulose.
    The hemicellulose decays in the separation mainly by so-called autocatalysis where the pH drops of the acids present in the material. The decomposition is accelerated by any acid in the solvent. Furthermore, the lignin fraction contains other substances present in the raw material; terpenes, so-called extraction substances, etc .. Finally, the lignin fraction contains solvents from the separation in a proportion that must be calculated.
    As in the case of solvent-based extraction of lignin, the invention contains several techniques for the KDP process. In the following, two designs are given as examples, which does not limit the patent claims to these.
    After dewatering the lignin fraction to <20% water, the material is mixed with catalyst and passed to the KDP reactor. In AlphaKat's design, lignin fraction / catalyst is initially mixed with a high-boiling oil which is successively replaced with product formed during the reaction. The process works at 250-300 degrees C at atmospheric pressure and in it the reactions stated above take place. The pressure / temperature in the reactor must be adjusted according to the solvent present from the solvent-based separation of lignocellulose. As the reactions proceed, the "diesel" fraction is withdrawn through a distillation column where heavier material is returned to the reactor for further reaction. The yield of 6 "diesel" and "petrol" products is in the order of 350 liters per 1000 kg of TS lignin fraction.
    Other products are about 100 kg "char", smaller amounts of "latte carbohydrates" and carbon dioxide. Using milcrovag technique for the KDP reactions, the feed to the reactor takes place in the "empty" or "semi-solid" state of the lignin fraction / catalyst. With this technique, no heavier material is fed from the distillation column even if a similar equipment is used for the extraction of product and gases (including the "light hydrocarbons").
    In order to obtain these products and product quantities, a certain calculation of how much solvent should remain in the lignin fraction is required. Tests have shown that all pure lignin does not give either the desired "diesel" product or product quantity. On the other hand, the frail pure trativara is obtained, which consists of 25-30% lignin, about 30% hemicellulose and about 40% cellulose, which meant that the ratio between carbohydrates and lignin by weight is approximately = 2.5. Since the carbohydrates according to the previous mechanism assumption in principle constitute the water source for the hydrogenation of the lignin and all carbon, C, is removed as carbon dioxide (and thus changes the C: with the composition of 6 C, 10 H and 50 racks for all to satisfy the conversion of lignin. The degradation products of hemicellulose have a similar composition, but they do not constitute a large amount of the order of 1: 1 relative to lignin. For all commas higher in the ratio, the remainder of the solvent present in the lignin fraction after the separation for reuse in the separation is used.
    The by-products char and "Mita kolvaten" from the KDP process are used as fuel for the generation of kip for the separation of lignocellulose.
    The "petrol" and "diesel" products can be worked up by distillation and, in the best case, used directly as fuel. Preferably, however, the aggregate product constitutes a distillery for refinery. Analyzes of the products mainly show the carbohydrates, even if smaller proportions of retailers have a small oxygen content. The simulated distillation curve showed -10 percent of the total product within the petrol specification while the rest was within the diesel specification.
    In case the cellulose is used as raw material for hydrolysis / fermentation to ethanol, biogas or other fermentation product, the residual product from the fermentation can be added to the lignin fraction as additional raw material for the KDP process. In this case, a new calculation of the amount of residual solvent in the lignin fraction must be carried out, since the residual product from the fermentation affects the C: H: 0 ratio. With this transfer of residual product, the previously mentioned lignin content in the cellulose fraction does not constitute any loss because it belongs to the KDP process. The only figure in the drawing schematically shows the combination between a solvent-based separation of lignocellulose into a cellulose fraction and a lignin fraction where the latter is processed into propellant in a KDP process. In dashed form, an alternative design is given where the cellulose fraction is hydrolyzed and fermented biochemically and the residual product from the fermentation is also added to the KDP process.
    权利要求:
    Claims (10)
    [1]
    1. Set to produce diesel and gasoline-like products from lignin from lignocellulose, can be drawn & ray, that lignocellulose is separated by solvent-based extraction into a lignin fraction and a second fraction mainly containing cellulose, the lignin fraction is concentrated by separating solvents such as anyridides in the separation. the concentrated lignin fraction is ground with catalyst and subjected to catalytic depolymerization, the concentrated lignin fraction, including residual solvents from the separation, is subjected to catalytic depolymerization at temperatures between 150 and 350 degrees C, obtaining diesel and gasoline-like products as the main fraction, a gaseous fraction , carbon monoxide and carbon dioxide as well as a solid carbonate column, and the gaseous fraction and the carbonate column anyands as brat-isle for generating the heat required for the separation.
    [2]
    2. A process according to claim 1, characterized in that the catalytic depolymerization takes place at 200-300 degrees C.
    [3]
    A kit according to claim 1 or 2, characterized in that the catalyst is an aluminosilicate catalyst.
    [4]
    4. Sart according to eft or more of the seas 1-3, can clarify, that the solvents in the separation of the lignin fraction have boiling points> 100 degrees C.
    [5]
    5. Salt according to one or more of the oceans 1-4, characterized in that the solvents consist of organic acids, alcohols, esters and other solvents with the property of generating selection on the catalyst surface.
    [6]
    6. Set according to eft or more of the seas 1-5, can ddray, that the solvent-containing lignin fraction is dewatered to <20% by weight of water.
    [7]
    7. According to one or more of the claims 1-6, it can be deduced that the catalytic depolymerization is carried out in an oil-like liquid.
    [8]
    Salt according to one or more of Oceans 1-6, characterized in claray, that the catalytic depolymerization is carried out in solid phase with heating of micro-waves
    [9]
    9. Sat according to eft or more of the oceans 1-6 and 7 or 8, characterized in that the second, cellulose-containing fraction is subjected to hydrolysis and fermentation.
    [10]
    A kit according to claim 9, characterized in that the residual product from the fermentation is transferred to the lignin fraction for subsequent catalytic depolymerization. Lignocellulose 1 Separation of cellulose frail lignin (and hemicellulose) via solvent based extraction Liquid recovery Extraction Product: Hydrolysis + Alternative use of cellulose Deportation 11, Distillation; SSF ILignin (solvent) "Drying" Catalytic depolymerization of Cellulose distillation
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    同族专利:
    公开号 | 公开日
    SE537244C2|2015-03-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1300378A|SE537244C2|2013-05-24|2013-05-24|Preparation of lignin fuel from lignocellulose|SE1300378A| SE537244C2|2013-05-24|2013-05-24|Preparation of lignin fuel from lignocellulose|
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