CN103382512A - Glucose preparation method by hydrolyzing cellulose through microwave heating - Google Patents
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Abstract
The invention discloses a glucose preparation method by hydrolyzing cellulose through microwave heating. The glucose preparation method by hydrolyzing the cellulose through the microwave heating comprises steps of (1) dissolving cellulose raw materials into phosphoric acid of 81 wt % to 85 wt % to obtain a solution with the mass percent of 5% to 30 %, preprocessing for 10 to 180 minutes at the temperature of 40 to 60 DEG C, adding organic reagents and filtering and washing to obtain processed cellulose; (2) performing microwave heating of 800 to 1200 watts on the processed cellulose and performing diluted acid catalytic hydrolyzing at the temperature of 120 to 160 DEG C; (3) neutralizing, desalting, decoloring and precipitating a sugar solution obtained from the step (2) to obtain glucose solid. According to the glucose preparation method by hydrolyzing the cellulose through the microwave heating, the glucose is prepared by efficiently and high selectively hydrolyzing the cellulose through the microwave heating, the reaction temperature is low, the time is short, the energy consumption is low, the conversion rate of the cellulose achieves 80% to 95 %, the selectivity of the glucose is from 80% to 95 %, the glucose separation process is simple, and the purity is high.
Description
Technical field
The present invention relates to cellulosic hydrolysis field, relate in particular to a kind of method that microwave heating hydrocellulose prepares glucose.
Background technology
Along with petering out of petrochemical industry resource becomes increasingly conspicuous with problem of environmental pollution, people more and more pay close attention to the development and utilization of green renewable resources, and wherein the utilization of biomass is study hotspots of people in recent years.Utilize biomass to produce fuel and chemical, not only can break away from people to the dependence of oil, reduce simultaneously the petrochemical industry resource and use the carbonic acid gas that produces.The organism that biomass refer to directly or indirect utilization green plants photosynthesis forms is mainly starch and Mierocrystalline cellulose.Compare with starch, Mierocrystalline cellulose is as non-food crop, and wide material sources, reserves reach 1,000 hundred million ton/years, considerably beyond existing prospective oil, and cheap, environmental friendliness is a kind of desirable biological material.
Mierocrystalline cellulose passes through β-1 by glucose unit, the linear natural polymer that 4 glycosidic link links form, its component units---glucose, as important hardware and software platform compound, can be used for producing various chemical (5 hydroxymethyl furfural (HMF), levulinic acid, polyvalent alcohol etc.), be used for the fields such as chemical industry, fuel, therefore, it is effectively to utilize one of cellulosic important channel that cellulose hydrolysis prepares glucose.Yet cellulosic molecule interchain, the strong hydrogen bond action of interior existence have the chemical structure of quite stable, thereby the feedwater solution is brought very large difficulty.At present, cellulosic method for hydrolysis mainly contains enzyme hydrolysis method and acid catalyzed hydrolysis.The enzymic hydrolysis selectivity is high, mild condition, but the hydrolysis cycle is long, and the cellulase preparation is difficult, cost is high.The acid-catalyzed hydrolysis technical maturity mainly contains concentrated acid and diluted acid catalytic hydrolysis.
The concentrated acid catalytic hydrolysis refers to surpass in concentration the method that catalysis biomass in 30% sulfuric acid or hydrochloric acid is hydrolyzed into monose.In concentrated acid catalyzing cellulose hydrolysis technology product sugar be separating of catalyst acid insoluble problem.
Chinese patent CN101157445A discloses the sugared also method of reclaim(ed) sulfuric acid of organic solvent deposit in vitriol oil hydrocellulose.Point out in this patent working example 1, the oligosaccharides that is settled out from principal hydrolysis solution by organic reagent, need in the 10% further catalytic hydrolysis of sulfuric acid, calcium carbonate and after just can obtain glucose solution.The a large amount of sulfuric acid of this process need consumption and calcium carbonate reclaim the residual sugar in solution, and need further to process purifying collection glucose.In addition, sulfuric acid has strong oxidizing property and strongly-acid, the implementation Process difficulties such as concentrated, purification.
Chinese patent CN102690899A discloses the method that the strong phosphoric acid hydrolysis of lignocellulose is refined sugar and reclaimed phosphoric acid.At first Mierocrystalline cellulose becomes soluble sugar through the strong phosphoric acid catalytic hydrolysis, adds subsequently organic reagent with sugared precipitate and separate.The technology implementation condition that this patent is reported for work is harsher, the organic reagent that requires sepn process to adopt to be slightly soluble in water and control in solution phosphorus acid content greater than 65%.In addition, contain great amount of hydroxy group in the soluble sugar molecular structure, solubleness is large in water and phosphoric acid, and the method also comprises the concentrated removal process of follow-up sugar.
In addition, in the soluble sugar that the phosphoric acid catalyzed cellulose hydrolysis obtains, polysaccharide is main, and monose is less.Sun Xiaofeng seminar has reported that Mierocrystalline cellulose strong phosphoric acid fast hydrolyzing under the microwave action prepares the experimental technique [Wang Guangzheng, Sun Xiaofeng etc., the fast hydrolyzing of Mierocrystalline cellulose in phosphoric acid under microwave condition, Chinese sizing agent, 2012,7(21) 19-23.] of reducing sugar.Although concentrated acid is hydrocellulose effectively, do not provide the separation method of strong phosphoric acid and reducing sugar.Because reducing sugar solubleness in strong phosphoric acid is large, be difficult to carry out sugar and effectively the separating of acid in prior art, the also report of relevant isolation technique, the acid recovery process of bringing thus is also very complicated.Therefore, the disclosed technology of this report is not suitable for following large-scale production, does not also possess the feature of creative invention technology.
It is that catalyzer is with the method for cellulose hydrolysis saccharogenesis less than 10% mineral acid or organic acid that dilute acid hydrolysis refers generally to working concentration.Due to the Mierocrystalline cellulose highly crystalline, steady chemical structure, often need to be under hot conditions during dilute acid hydrolysis (〉 200 ° of C) could realize.The research of having reported explicitly points out, and side reaction easily occurs in hydrolytic process the glucose that under hot conditions, rare catalytic hydrolysis obtains simultaneously, causes productive rate low also poor selectivity (Jeong et al.Renew.Energ.2012,42, the 207-211 of glucose; Xiang et al.2004, Appl.Biochem.Biotech.115 (1-3), 1127-1138.).
To sum up, the technical bottleneck that cellulose hydrolysis prepares glucose is how economical, hydrocellulose and simple and effective separation and purification glucose efficiently, key technical problem wherein is how to suppress the decomposition of glucose when the catalyse cellulose effectively hydrolyzing, namely guarantees productive rate and the selectivity of glucose.
Summary of the invention
The object of the present invention is to provide a kind of, method that highly selective hydrocellulose prepare high purity glucose efficient through gentle simple and convenient process.
For achieving the above object, at first the present invention improves its hydrolysis reaction activity by phosphoric acid pretreatment of fiber element, then make under microwave heating Mierocrystalline cellulose under low temperature, low acid concentration condition fast, highly selective is converted into glucose, and obtains high purity glucose by simple separation.Specifically take following technical scheme:
A kind of microwave heating hydrocellulose prepares the method for glucose, comprises the steps:
(1) it is 5～30% solution that the phosphoric acid that cellulosic material is dissolved in 81wt%～85wt% obtains the quality percentage composition, is adding organic reagent after pre-treatment 10～180min under 40～60 ° of C, filters, the Mierocrystalline cellulose of washing after being processed;
(2) Mierocrystalline cellulose after the processing through 800～1200W microwave heating, carries out the diluted acid catalytic hydrolysis at 120～160 ° of C;
(3) sugar soln that obtains of step (2) obtains glucose solids through neutralization, desalination, decolouring, sedimentation.
Mierocrystalline cellulose is a kind of polyhydroxylated polymer, and stronger polarity is arranged, and only surpasses in the phosphoric acid of 80wt% and can occur with the polar functional group of phosphoric acid significantly to interact and fully dissolving in concentration.The Mierocrystalline cellulose that is dissolved in phosphoric acid can by partially catalyzed generation chain rupture under 40～60 ° of C, form the Mierocrystalline cellulose oligopolymer similar to cellulosic structure.In this process, the concentration of palpus reduce phosphoric acid in order to avoid the cellulose chain fracture excessively, causes the Precipitation separation difficulty, is 81wt%～85wt% through preferred definite phosphoric acid concentration.After phosphoric acid is processed, add polar organic solvent at Mierocrystalline cellulose, be better than the effect of Mierocrystalline cellulose oligopolymer and phosphoric acid due to the effect of polar solvent and phosphoric acid, make the Mierocrystalline cellulose oligopolymer be easy to precipitate from phosphoric acid and separate.In addition, the Mierocrystalline cellulose oligopolymer that is obtained by precipitate and separate, in its crystalline texture and settling process, the viscosity of solution is closely related: during low viscosity that and if only if, in solution, the extension degree of cellulose molecular chain is high, the interchain entanglement is few, form unbodied Mierocrystalline cellulose oligopolymer, therefore, in preferred solution, the Mierocrystalline cellulose percentage composition is 5～30%, both can avoid Mierocrystalline cellulose phosphoric acid dissolution process viscosity excessive being unfavorable for to decrystallize, can avoid again processing rear cellulose solution viscosity too low and affect productive rate.
Be to guarantee effective precipitate and separate of Mierocrystalline cellulose oligopolymer and the efficient recovery of phosphoric acid, as preferably, the organic solvent in step (1) is C1～C8 alcohol, and the volume ratio of organic solvent and phosphoric acid is 1～5:1.
Further preferred, described organic solvent is methyl alcohol, ethanol, propyl alcohol, propyl carbinol or isopropylcarbinol.
Linked the linear natural high moleculer eompound that forms by β-Isosorbide-5-Nitrae glycosidic link by glucose unit due to the Mierocrystalline cellulose oligopolymer, and glycosidic link hydrogen ion (H in solution
+) effect under fracture, finally form glucose.In this process, too much hydrogen ion will be induced glucose generation side reaction, also just reduce productive rate and the selectivity of glucose.Therefore, as preferably, in step (2), the concentration of diluted acid is 0.005～0.05mol/L, and the quality of dilute acid soln is 1～100 times of the Mierocrystalline cellulose quality after processing.
As preferably, described diluted acid is made into by one or more mixing in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, toxilic acid, tosic acid, citric acid.Preferred several acid is all strong protonic acid, has the very strong hydrogen ion ability of dissociating, and only needs low acid concentration can satisfy the requirement of required hydrogen ion concentration, also is conducive to separating of product glucose and acid catalyst in solution.
Cellulosic acid-catalyzed hydrolysis is the fracture that proton attack glycosidic link causes glycosidic link, and hydrolysis rate and protonic acid concentration are closely related.Because general fibre element material crystal degree is high, the effective collision probability of protonic acid and cellulose sugar glycosidic bond is too low, the carrying out that common dilute acid hydrolysis Mierocrystalline cellulose often comes intensified response by high temperature or high acid concentration can not realize that effectively glucose is produced in hydrolysis under low temperature, low acid concentration.Though but use high temperature, high acid concentration can realize cellulosic effective hydrolysis, and inevitably cause the decomposition of product glucose, greatly reduce productive rate and the selectivity of glucose.
The fiber method for hydrolysis that the present invention builds, obtain unbodied Mierocrystalline cellulose oligopolymer by phosphoric acid pretreatment of fiber element, greatly promote infiltration and the motion of proton in cellulosic matrix, improved the effective collision probability between hydrogen ion and glycosidic link, having reduced the difficulty of follow-up hydrolysis, is the steps necessary that realizes that glucose high yield, highly selective transform.And step (2) has realized interior utilization to the hydrogen ion catalysis efficiency of short period of time by microwave heating technique, has avoided the side reaction of glucose to decompose when having reduced sour consumption.
Microwave is as a kind of heating technique, and its heating is highly sensitive, and heating finishes rear without thermal hysteresis; And rate of heating is fast, homogeneous heating, and whole reaction system is heating simultaneously under microwave action, does not have thermograde, thereby has suppressed to a certain extent the generation of side reaction.Due to the type of heating of microwave uniqueness, can greatly improve speed of reaction in reaction, reduce the time of hydrolysis, as preferably, in step (2), the time of diluted acid catalytic hydrolysis is 1～15min.
The sugar soln that obtains through catalytic hydrolysis can obtain the high purity glucose solids through purge processes such as neutralization, desalination, decolouring, sedimentations.As: the gained sugar soln neutralizes by calcium carbonate and removes acid catalyst, after oven dry with dissolve with ethanol glucose and remove by filter due to the not dissolved salt that adds calcium carbonate to produce, the ethanol liquid glucose reclaims ethanol by underpressure distillation after activated carbon decolorizing, and the gained solid obtains the high purity glucose solids through water/acetone precipitation again.As preferably, after neutralization, drying temperature is 55～70 ° of C; The activated carbon decolorizing temperature is 65～80 ° of C, and activated carbon dosage is 1～3wt% of ethanol liquid glucose, and bleaching time is 5～10min; In the water of glucose/acetone settling process, the consumption of water is 1～1.5 times of glucose solids, and the acetone consumption is 15～30 times of water, can obtain highly purified glucose through above-mentioned subsequent disposal.
Cellulosic dilute acid hydrolysis process is an out-phase reaction system, and hydrolysis efficiency and mass transfer process are closely related.When microwave electric field polarization reactant molecule, the electric field energy of microwave is absorbed by system and is converted into interior energy, when microwave frequency is 2450MHz, and molecular polarization → be converted into to the direction of an electric field arrangements → system configurational entropy decline → electric field process per second generation 2.45 * 10 of interior energy
9Inferior, system temperature rises rapidly, and the increase of the reaction entropy of activation in this process, and it is large that the effective collision probability becomes, and makes reaction rate accelerates.In addition, under the microwave electric field effect, electric field exerts an influence to the cellulose sugar glycosidic bond, promotes the fracture of glycosidic link, thereby realizes that Mierocrystalline cellulose is efficient, highly selective is converted into glucose.
The invention has the advantages that, realize efficient under the catalysis of Mierocrystalline cellulose diluted acid, highly selective hydrolysis preparation glucose under microwave heating condition, this technology has the advantages such as speed of reaction is fast, selectivity is high, reaction conditions is gentle; And operating process is simple, energy consumption is low, sour consumption is few, the glucose productive rate and selectivity high, can obtain the high purity glucose solids by simple separation.
Description of drawings
Fig. 1 is the schema that microwave heating hydrocellulose of the present invention prepares glucose;
Fig. 2 is the glucose shape appearance figure that the present invention prepares;
Fig. 3 is the infrared spectrum of the glucose for preparing of the present invention;
Fig. 4 is the nuclear magnetic spectrogram (hydrogen spectrum) of the glucose for preparing of the present invention;
Fig. 5 is the nuclear magnetic spectrogram (charcoal spectrum) of the glucose for preparing of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, it is pointed out that following examples are intended to be convenient to the understanding of the present invention, and it is not played any restriction effect.
Embodiment 1
Utilize microwave heating effectively hydrolyzing Mierocrystalline cellulose to prepare high purity glucose according to flow process shown in Figure 1, concrete steps are:
2.0g after Mierocrystalline cellulose is dissolved in 18g85wt% phosphoric acid, add 40mL ethanol after stir process 60min under 50 ° of C, after filtration, the cellulose solids after being processed after washing, drying.The Mierocrystalline cellulose of getting after 0.5g processes mixes with 10g0.04mol/L sulfuric acid, selects microwave heating to the 160 ° C of 800W, insulation 5min.After temperature was down to room temperature, centrifugation obtained sugar aqueous solution.Calculating transformation efficiency according to quality change before and after fibrin reaction is 90.5%, and detecting the glucose productive rate by high-efficient liquid phase chromatogram HPLC is 72.6%, and its selectivity is 80.2%.The gained sugar aqueous solution neutralizes by calcium carbonate and removes sulfuric acid, and under 65 ° of C, evaporation obtains solid, by dissolve with ethanol glucose separated salt; The ethanol sugar soln adds the 2wt% gac subsequently, and 70 ° of C decolouring 5min repeat 1～2 time; Underpressure distillation ethanol and glucose under 40 ° of C add water dissolution sugar by solid-to-liquid ratio 1:1, add subsequently 20 times of volume acetone with the sedimentation of glucose sugar, and filtration, drying obtain glucose solids, as shown in Figure 2.
Embodiment 2
Utilize microwave heating effectively hydrolyzing Mierocrystalline cellulose to prepare high purity glucose according to flow process shown in Figure 1, concrete steps are:
2.0g after Mierocrystalline cellulose is dissolved in 18g83.5wt% phosphoric acid, add 40mL ethanol after stir process 120min under 50 ° of C, after filtration, the cellulose solids after being processed after washing, drying.The Mierocrystalline cellulose of getting after 0.5g processes mixes with 10g0.04mol/L sulfuric acid, selects microwave heating to the 160 ° C of 1200W, insulation 5min.After temperature was down to room temperature, centrifugation obtained sugar aqueous solution.Calculating transformation efficiency according to quality change before and after fibrin reaction is 93.5%, and detecting the glucose productive rate by high-efficient liquid phase chromatogram HPLC is 78.9%, and its selectivity is 84.4%.The gained sugar aqueous solution neutralizes by calcium carbonate and removes sulfuric acid, and under 65 ° of C, evaporation obtains solid, by dissolve with ethanol glucose separated salt; The ethanol sugar soln adds the 2wt% gac subsequently, and 70 ° of C decolouring 5min repeat 1～2 time; Underpressure distillation ethanol and glucose under 40 ° of C add water dissolution sugar by solid-to-liquid ratio 1:1, add subsequently 20 times of volume acetone with the sedimentation of glucose sugar, and filtration, drying obtain the high purity glucose solids.
Embodiment 3
Utilize microwave heating effectively hydrolyzing Mierocrystalline cellulose to prepare high purity glucose according to flow process shown in Figure 1, concrete steps are:
1.0g after Mierocrystalline cellulose is dissolved in 19g85wt% phosphoric acid, add 40mL ethanol after stir process 30min under 50 ° of C, after filtration, the cellulose solids after being processed after washing, drying.The Mierocrystalline cellulose of getting after 0.5g processes mixes with 10g0.04mol/L sulfuric acid, selects microwave heating to the 140 ° C of 1200W, insulation 5min.After temperature was down to room temperature, centrifugation obtained sugar aqueous solution.Calculating transformation efficiency according to quality change before and after fibrin reaction is 91.3%, and detecting the glucose productive rate by high-efficient liquid phase chromatogram HPLC is 74.2%, and its selectivity is 81.3%.The gained sugar aqueous solution neutralizes by calcium carbonate and removes sulfuric acid, and under 65 ° of C, evaporation obtains solid, by dissolve with ethanol glucose separated salt; The ethanol sugar soln adds the 2wt% gac subsequently, and 70 ° of C decolouring 5min repeat 1～2 time; Underpressure distillation ethanol and glucose under 40 ° of C add water dissolution sugar by solid-to-liquid ratio 1:1, add subsequently 20 times of volume acetone with the sedimentation of glucose sugar, and filtration, drying obtain the high purity glucose solids.
Embodiment 4
Utilize microwave heating effectively hydrolyzing Mierocrystalline cellulose to prepare high purity glucose according to flow process shown in Figure 1, concrete steps are:
2.0g after Mierocrystalline cellulose is dissolved in 18g85wt% phosphoric acid, add 40mL ethanol after stir process 180min under 50 ° of C, after filtration, the cellulose solids after being processed after washing, drying.The Mierocrystalline cellulose of getting after 0.5g processes mixes with 10g0.02mol/L sulfuric acid, selects microwave heating to the 160 ° C of 1200W, insulation 10min.After temperature was down to room temperature, centrifugation obtained sugar aqueous solution.Calculating transformation efficiency according to quality change before and after fibrin reaction is 92.6%, and detecting the glucose productive rate by high-efficient liquid phase chromatogram HPLC is 77.8%, and its selectivity is 84.2%.The gained sugar aqueous solution neutralizes by calcium carbonate and removes sulfuric acid, and under 65 ° of C, evaporation obtains solid, by dissolve with ethanol glucose separated salt; The ethanol sugar soln adds the 2wt% gac subsequently, and 70 ° of C decolouring 5min repeat 1～2 time; Underpressure distillation ethanol and glucose under 40 ° of C add water dissolution sugar by solid-to-liquid ratio 1:1, add subsequently 20 times of volume acetone with the sedimentation of glucose sugar, and filtration, drying obtain the high purity glucose solids.
Embodiment 5
Utilize microwave heating effectively hydrolyzing Mierocrystalline cellulose to prepare high purity glucose according to flow process shown in Figure 1, concrete steps are:
1.5g after Mierocrystalline cellulose is dissolved in 18.5g81wt% phosphoric acid, add 40mL ethanol after stir process 150min under 50 ° of C, after filtration, the cellulose solids after being processed after washing, drying.Get Mierocrystalline cellulose and 10g0.02mol/L mixed in hydrochloric acid after 0.5g processes, select microwave heating to the 160 ° C of 1000W, insulation 2min.After temperature was down to room temperature, centrifugation obtained sugar aqueous solution.Calculating transformation efficiency according to quality change before and after fibrin reaction is 91.3%, and detecting the glucose productive rate by high-efficient liquid phase chromatogram HPLC is 80.2%, and its selectivity is 87.8%.The gained sugar aqueous solution neutralizes by calcium carbonate and removes sulfuric acid, and under 65 ° of C, evaporation obtains solid, by dissolve with ethanol glucose separated salt; The ethanol sugar soln adds the 2wt% gac subsequently, and 70 ° of C decolouring 5min repeat 1～2 time; Underpressure distillation ethanol and glucose under 40 ° of C add water dissolution sugar by solid-to-liquid ratio 1:1, add subsequently 20 times of volume acetone with the sedimentation of glucose sugar, and filtration, drying obtain the high purity glucose solids.
Fig. 2 is the glucose that separation and purification obtains, and the Infrared Characterization of Fig. 3 shows that the spectrogram absorption peak is consistent with the glucose standard specimen, does not find 1740cm
-1The ester bond structure at place illustrates acidic impurities such as not finding formic acid, levulinic acid, gluconic acid.The nuclear magnetic spectrum of Fig. 4 and Fig. 5 confirmed that further gained glucose structure is the mixture of α and two kinds of configurations of β, and there is no obvious impurity peaks.
Claims (6)
1. a microwave heating hydrocellulose prepares the method for glucose, it is characterized in that, comprises the steps:
(1) it is 5～30% solution that the phosphoric acid that cellulosic material is dissolved in 81wt%～85wt% obtains the quality percentage composition, is adding organic reagent after pre-treatment 10～180min under 40～60 ° of C, filters, the Mierocrystalline cellulose of washing after being processed;
(2) Mierocrystalline cellulose after the processing through 800～1200W microwave heating, carries out the diluted acid catalytic hydrolysis at 120～160 ° of C;
(3) sugar soln that obtains of step (2) obtains glucose solids through neutralization, desalination, decolouring, sedimentation.
2. microwave heating hydrocellulose according to claim 1 prepares the method for glucose, it is characterized in that, the organic solvent in step (1) is C1～C8 alcohol, and the volume ratio of organic solvent and phosphoric acid is 1～5:1.
3. microwave heating hydrocellulose according to claim 2 prepares the method for glucose, it is characterized in that, described organic solvent is methyl alcohol, ethanol, propyl alcohol, propyl carbinol or isopropylcarbinol.
4. microwave heating hydrocellulose according to claim 1 prepares the method for glucose, it is characterized in that, in step (2), the concentration of diluted acid is 0.005～0.05mol/L, and the quality of dilute acid soln is 1～100 times of the Mierocrystalline cellulose quality after processing.
5. according to claim 1 or 4 described microwave heating hydrocelluloses prepare the method for glucose, it is characterized in that, described diluted acid is made into by one or more mixing in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, toxilic acid, tosic acid, citric acid.
6. microwave heating hydrocellulose according to claim 1 prepares the method for glucose, it is characterized in that, in step (2), the time of diluted acid catalytic hydrolysis is 1～15min.
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| CN110346457A (en) * | 2018-04-04 | 2019-10-18 | 青岛大学附属医院 | A kind of detection method using monosaccharide composition in acid hydrolysis of microwave and anion-exchange chromatography-pulsed amperometric method analysis polysaccharide |
| CN109321688A (en) * | 2018-09-28 | 2019-02-12 | 中国科学院宁波材料技术与工程研究所 | The preparation method of water-soluble sugar |
| CN109289871A (en) * | 2018-10-31 | 2019-02-01 | 湖南师范大学 | A kind of preparation method of the carbon-based solid super-strong acid of biomass with classification duct |
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