Patent Application
20160289256
The present disclosure relates to a novel method for the depolymerization of lignin which starts from a black liquor which contains it obtained from the delignification of the biomass.
The current methods for degrading lignin in the state of the art are diverse and although they use a wide range of operating methods and conditions, they all have similar disadvantages. There are numerous processes which allow for the degradation of lignin but all of them have some problems which limit the use thereof on an industrial scale. Amongst other things, due to inadequate adaptation to the industrial needs and/or incompatibility with the increasingly stricter environmental requirements.
Among these methods for the depolymerization of lignin, the following can be cited as an example: the method described in U.S. Pat. No. 5,807,952 based on pyrolysis; a solvothermal method described in U.S. Pat. No. 5,959,167; methods which use catalysts based on transition metals (U.S. Pat. No. 2,220,624), a method in the presence of melted salts of a hydroxide of general formula M(OH)n or a mixture of alkaline or alkaline earth hydroxides (US 20130066116) or a hydrothermal method in which the lignin is subjected in a basic medium to pressure and temperature.
All these current methods of depolymerization of lignin, which allow the revaluation thereof and obtaining of phenolic products with high added-value, nevertheless, have disadvantages, of which one is common to all; they depart from the precipitated solid lignin. The solid lignin is obtained from biomass in general which is subjected to a pasting step, from which a black liquor (or black lye) to which is added an acid which causes the precipitation of the lignin. The lignin precipitate is isolated and the resulting precipitated solid lignin is subjected to a depolymerization method.
In order to precipitate the lignin it is necessary to carry out a series of process steps which extend the global method of the treatment of biomass to obtain aromatic compounds. Furthermore, the precipitation of the lignin comprises the use of additional elements such as filters and reagents which obviously make the method more expensive as a whole and complicate it.
In view of what has been stated, there is still a need to provide a simpler, more efficient and economic method which is scalable to an industrial level which provides aromatic compounds with high yields, overcoming at least part of the disadvantages of the methods of the current state of the art.
In a first aspect, the disclosure relates to a method for the depolymerization of lignin comprising the following steps:
The type of biomass which can be subjected to this method, hereinafter the method of the disclosure, is lignocellulosic biomass which contains, amongst other polymers, lignin. Lignin is a phenolic macromolecule, the structure of which is still not perfectly elucidated. It is present between the cell walls of numerous plants, specifically wood, to which they give rigidity. The biomass usable in the present disclosure can be derived from wood, green residues in general or straw for example. In one particular embodiment, it comes from the shell of dried fruits, such as the shell of almond.
Lignin is available in the black liquors which result as by-products of the delignification treatments of the biomass, for example, that which takes place during the production of paper to obtain cellulose (paper paste) which generates these by-products also called black lyes or from the production of second generation bioethanol.
The delignification of the biomass is a process known in the state of the art which includes carrying out an alkaline treatment of the biomass, by preferably using sodium hydroxide or potassium hydroxide in a typical concentration of 15% by weight of base with respect to the weight of the solution used in the delignification (see
The product which is produced from the delignification is generally firstly filtered with a metallic mesh and then a cloth filter to separate any solid residue from the liquid phase where the lignin is dissolved (black liquor) (see
In the step (ii), the black liquor (4) is concentrated by means of any conventional technique (
The concentration of the black liquor (4) is carried out until the initial volume of the same is reduced (see (7) in
The hydrothermal treatment to which the black liquor is subjected is a conventional treatment well known by a person skilled in the art. During the treatment, the depolymerization of the lignin takes place. This step (iii) is depicted in
In order to separate the products obtained which are in the reaction mixture (
The step of separating the precipitate from the liquid phase is then carried out, for example by means of filtration, although any other conventional separation means can be used. In one particular embodiment, the filtration is carried out using a filter with a pore diameter of 7-12 μm. In
The liquid phase (13) separated in the previous step is subjected to an extraction step of the depolymerization products (14). The extraction produces an aqueous phase (16) and an organic phase (15). The extraction is preferably carried out with ethyl acetate since it is the most appropriate product for dissolving the monomers formed, although other organic solvents can also be used such as diethyl ether, vinyl acetate or n-Butyl acetate.
The method of the disclosure also comprises recovering the depolymerization products.
The recovery is carried out by means of the steps of: (a) evaporating the solvent of the organic liquid phase resulting from the extraction; (b) resuspending the organic oil resulting from step (a) in an organic solvent; and (c) subjecting the resulting suspension to separation by chromatography.
The evaporation (depicted in (17),
These compounds are generally aromatic and they are essentially of the family of phenols. Among the compounds that can be obtained, in the form of a mixture, there are phenol, cresols, catechol and the derivatives thereof (3-methylcatechol, 4-methylcatechol and 4-ethylcatechol).
The method of the disclosure is more economic and more interesting from an environmental point of view due to what has been previously mentioned. It allows an industrial by-product, the black lye, to be disposed of and the revaluation thereof by means of obtaining a mixture of organic compounds of high added-value which can be used in numerous industries and applications.
50 grams of almond shell were triturated into a Retsch 2000 hammer mill to produce chips of 4-6 mm free of small stones, powder and earth.
The 50 grams of milled almond shell were then introduced into a 1 liter recipient implemented in borosilicate 3.3 glass according to the standard DIN EN ISO 4796-1 together with 500 grams of a solution of 15% by weight of KOH. The delignification process was carried out in an autoclave for 90 mins, at a temperature of 121° C. and a pressure of 0.2 MPa.
After the delignification process, the reaction mixture was firstly filtered with a metallic mesh (hole size of 2 mm) and subsequently with a cloth filter to separate the solid residue from the black liquor where the lignin was dissolved. After this, the black liquor was concentrated until the volume thereof was reduced to half, using a rotary evaporator, at 60° C. in a vacuum atmosphere (0.02 MPa). Once the liquor was concentrated, the depolymerization process was carried out.
The depolymerization process was carried out in the following manner. 30 grams of concentrated liquor were introduced into a steel reactor under pressure. The conditions were: 300° C., 80 mins, 9 MPa and continuous agitation. Once the depolymerization process of the lignin contained in the black liquor had been carried out, the products were then separated.
To this end, the reaction mixture obtained after the depolymerization process was acidified with HCl until a pH of 1 was reached. When this addition of acid was carried out, a precipitate (residue) was produced which was eliminated by filtration with a filter paper with a pore diameter of 7-12 μm. A liquid-liquid extraction was carried out with ethyl acetate at the liquid phase, where the depolymerization products of the lignin were found. This extraction process was carried out until, upon adding the ethyl acetate, no change was observed in the color in the solvent, that is to say, no more products were extracted from the aqueous phase. After said extraction process, the phenolic products derived from the lignin were in the organic phase. This organic phase was subjected to an evaporation process to eliminate the solvent and isolate the depolymerization products of the lignin. The evaporation was carried out in a rotary evaporator at 50° C. and in a vacuum atmosphere (0.02 MPa).
Once the entire solvent (ethyl acetate) had been eliminated, the evaporation was concluded and 0.337 grams of an oil were obtained which contained the depolymerization compounds of the lignin.
The specific results for the case described are shown below and for the case using 15% by weight of NaOH instead of KOH.
The calculations of the oil obtained were carried out with respect to three parameters: lignin contained in the black liquor, organic material contained in the black liquor and with respect to the total of the black liquor.
The products generated after the direct depolymerization of the lignin have been identified by means of gas chromatography mass spectrometry (GC-MS). The most representative compounds and those which have also been quantified are shown in the following table:
In
The disclosure is not limited to the specific embodiments which have been described, but rather also encompass, for example the variants which can be carried out by the person skilled in the art.
| Number | Date | Country | Kind |
|---|---|---|---|
| P201331705 | Nov 2013 | ES | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/ES2014/070854 | 11/18/2014 | WO | 00 |
