Method, container and uses for converting biomass materials into soluble substances by one-step

Abstract

The present invention discloses a method for converting biomass material into soluble substances by one-step, comprising: converting biomass materials into soluble substances by one-step by electrolyzing at a certain time under the condition of constant current using bipolar three-dimension-electrodes system, wherein bipolar three-dimension-electrodes system including an anode, a cathode, particle electrodes and electrolyte, and in electrolyzing process, the particle electrodes and the biomass materials being suspended in the electrolyte. The present invention also discloses a container for converting biomass materials into soluble substances by one-step, comprising: A tank which holds electrolyte at the interior thereof, wherein the side wall of the tank is provided with an opening, the opening is provided with a permeable membrane, and the opening also communicates with a discharge pipe; A pair of electrode plates which are immersed into the electrolyte by at least a part thereof, wherein the pair of electrode plates space from each other and connect to positive pole and negative pole of power supply respectively to form anode and cathode in energized state respectively; and, Particle electrodes which are in granular form and are suspended in the electrolyte. The present invention also discloses uses of soluble substances that are prepared by any one of the methods.

Description

FIELD OF THE INVENTION

The present invention relates to a method for converting biomass materials into soluble substances by one-step, and relates to a container for converting biomass materials into soluble substances, and also relates to uses for soluble substances that are converted from biomass materials.

BACKGROUND ART

Biomass materials are the most abundant and cheapest renewable resources. The production of fuel ethanol and the chemicals from biomass materials that have abundant resources, such as agricultural wastes (straw, bagasse, corn stover), forestry wastes (sawdust, wood branches, etc.) and marine algae (green algae, brown algae, red algae), has become a research hotspot at home and abroad. The conversion of biomass materials into chemicals may meet the growing energy needs of human society, reduce dependence on increasingly scarce fossil fuels, and achieve the goal of lowering pollution and protecting the environment. However, the natural biomass materials are resistant to enzymatic hydrolysis due to having the characteristics of dense structure, composition diversity and complexity of the chemical structure, etc. The process for converting biomass materials into high value-added products is more complex, which needs pretreatment process that can destroy the barrier of biomass materials that are resistant to degradation, needs enzymatic saccharification process of producing sugars, and needs organisms to produce high value-added products from sugars. The entire process often takes at least more than a week, which costs too much and does not apply to industrial applications. Therefore, it is urgent need to find a method for converting biomass materials into high value-added products quickly.

Lignin is polymer having three-dimensional structure, which is composed of phenylpropane units linked by carbon-carbon bond and ether bond. The content of lignin is very rich, which enhance cell wall and bond fibers in plant tissue. The content of lignin may account for 50 percent of wood, and the content of lignin are only after cellulose in plant cell walls. Lignin whose reserves is only next to cellulose in nature, regenerate at a speed of 50 billion tons every year. About 140 million tons of cellulose are isolated from plants in pulp and paper industry every year, and about 50 million tons of lignin are obtained at the same time. But so far, lignin is rarely used effectively. More than 95% of lignins are still discharged into rivers in the form of “black liquor” directly or burned after concentration. As the resources crisis and the improving of consciousness of human environmental protection, how to use lignin that are waste and natural renewable resources comprehensively and effectively has been put into national strategy by many countries. The research of converting lignin and lignin compounds to useful industrial products is underway, such as coupling agents of rubber, reinforcing agents, dye dispersants, viscosity reducers of drilling mud, desulfurizers of industrial waste gas and etc. But the process of conversion of lignin is relatively complex and costly. There needs a method that has mild condition and is environment-friendly and energy-saving to convert lignin effectively. Thus, lignin can be utilized at low cost and with high efficiency.

SUMMARY OF THE INVENTION

One purpose of the present invention is to solve at least the above problems and/or defects, and to provide at least the advantages that will be described later.

In nature, there are methods that utilizing biomass materials quickly and subtly in the bodies of wood-eating termites and white rot fungus. The research work of the applicant for the present invention finds the reason why the organisms can utilize biomass materials quickly is that their bodies produce radicals, and the radicals oxidize and destroy the crystalline region of biomass materials and modify lignin at the same time, to greatly reduce the barrier of biomass materials that are resistance to degradation and to utilize hydrolysis process in the bodies. Based on this finding, the present invention is produced.

Further, the purpose of the present invention is to provide a method for converting biomass materials into soluble substances by one-step, whose reaction conditions are mild. It does not need to add additional enzymes and acid and alkali reagents, and realizes the conversion of biomass materials into organic acid at high efficiency at neutral pH in the energized conditions.

Further, the purpose of the present invention is to provide a container for converting biomass materials into soluble substances by one-step.

Further, the purpose of the present invention is to provide uses of soluble substances that converted from biomass materials.

To this end, the technical solution provided by the present invention is:

A method for converting biomass materials into soluble substances by one-step, comprising:

converting biomass materials into soluble substances by one-step by electrolyzing at a certain time under the condition of constant current using bipolar three-dimension-electrodes system, wherein the bipolar three-dimension-electrodes system including an anode, a cathode, particle electrodes and electrolyte, and in electrolyzing process, the particle electrodes and the biomass materials being suspended in the electrolyte.

Preferably, in the method for converting biomass material into soluble substances by one-step, the constant current is 0.1˜0.9 A.

More preferably, in the method for converting biomass material into soluble substances by one-step, the constant current is 0.3˜0.7 A.

Preferably, in the method for converting biomass material into soluble substances by one-step, converting biomass materials into organic acids which are some kinds of soluble substances by using bipolar three-dimension-electrodes system to electrolyzing the biomass materials at 10˜190 minutes under the condition of constant current by one-step.

Preferably, in the method for converting biomass material into soluble substances by one-step, the electrolyte contains NaCl or KCl with molarity and volume ratio of 20 mmol/L˜2 mol/L.

Preferably, in the method for converting biomass material into soluble substances by one-step, the particle electrodes are activated carbon microparticles, the mass/volume ratio of the activated carbon microparticles in the electrolyte is 1%˜9%.

Preferably, in the method for converting biomass material into soluble substances by one-step, the diameter of the activated carbon microparticle is 3˜5 mm.

Preferably, in the method for converting biomass material into soluble substances by one-step, the biomass materials are lignin or corn stalks.

Preferably, in the method for converting biomass material into soluble substances by one-step, the mass/volume ratio of the biomass materials in the electrolyte is 2%˜20%.

Preferably, in the method for converting biomass material into soluble substances by one-step, both the anode and the cathode are graphite plate electrodes.

A container for converting biomass materials into soluble substances by one-step, comprising:

A tank which holds electrolyte at the interior thereof, wherein the side wall of the tank is provided with an opening, the opening is provided with a permeable membrane, and the opening also communicates with a discharge pipe;

A pair of electrode plates which are immersed into the electrolyte by at least a part thereof, wherein the pair of electrode plates space from each other and connect to positive pole and negative pole of power supply respectively to form anode and cathode in energized state respectively; and,

Particle electrodes which are in granular form and are suspended in the electrolyte.

Preferably, in the container for converting biomass material into soluble substances by one-step, the upper portions of the pair of electrode plates is level with the upper portion of the tank.

Preferably, in the container for converting biomass material into soluble substances by one-step, the electrolyte contains NaCl or KCl with molarity and volume ratio 20 mmol/L˜2 mol/L.

Preferably, in the container for converting biomass material into soluble substances by one-step, the particle electrodes are activated carbon microparticles, the mass/volume ratio of the activated carbon microparticles in the electrolyte is 1%˜9%.

Preferably, in the container for converting biomass material into soluble substances by one-step, the pair of electrode plates are graphite electrode plates.

Preferably, in the container for converting biomass material into soluble substances by one-step, further comprising: air sparger which is disposed at the bottom of the tank, and communicates with an intake pipe, to blow air to make the electrode particles to be suspended in the electrolyte.

Uses of soluble substances that are prepared by any one of the methods.

The present invention at least includes the following beneficial effects:

The present invention is under mild reaction conditions, does not need to add additional enzymes and acid and alkali reagents, and realizes the conversion of biomass materials into organic acid at high efficiency at neutral pH in the energized conditions. The present invention also realizes the conversion of lignin into soluble organic acid by one-step, without adding other chemical agents and heat treatments.

Other advantages, purposes and features of the present invention will be partly showed as follows, and will be partly understood by those skilled in the art through studying and practicing the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a gas detection diagram for converting biomass materials into organic acids in one embodiment of the present invention.

FIG. 2 is a gas detection diagram for converting biomass materials into organic acids in one embodiment of the present invention.

FIG. 3 is a gas detection diagram for converting biomass materials into organic acids in one embodiment of the present invention.

FIG. 4 is a structure diagram of the container for converting biomass materials into organic acids in one embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be further described in detail with the accompanying drawings, to make those skilled in the art can implement the invention according to the text of the specification.

It should be understood that, as used in this text, the terms of “having”, “including” and “comprising” are not involved with the presence or addition of one or other components or the combination.

The present invention provides a method for converting biomass material into soluble substances by one-step, comprising:

Converting biomass materials into soluble substances by one-step by electrolyzing at a certain time under the condition of constant current using bipolar three-dimension-electrodes system, wherein bipolar three-dimension-electrodes system including an anode, a cathode, particle electrodes and electrolyte, and in electrolyzing process, the particle electrodes and the biomass materials being suspended in the electrolyte.

The so-called bipolar three-dimension electrode is a traditional two-dimension electrolyzer with granular substances packed between the two electrodes. And the surface of the granular substances is charged to become the new pole, namely the third pole. Then the granular substances are called particle electrodes. The particle electrodes packed become bipolar due to static induction by applying voltage between the anode plate and the cathode plate. That is, one end of the particle electrode become anode where anodic reaction occurs, and the other end of the particle electrode become cathode where cathodic reaction occurs. Particle electrodes in the system form a three-dimension electrode and constitute numerous micro electrolytic cell between particles. O₂ produced by electrolysis reduce on cathode to produce H₂O, while the reaction system generates catalytically hydroxyl radicals which can destroy the molecular structure of the substances that are electrolyzing. The surface-area-to-volume ratio of three-dimension electrode increases and particle spacing of three-dimension electrode reduces, which significantly improve the effect of the mass transfer.

In one embodiment of the present invention, the present invention uses activated carbon microparticles as packed particle electrodes, which is different from other experiments that are using low impedance activated carbon particles as an extension of the anode or the cathode to constitute unipolar three-dimension electrodes. The activated carbon particles are suspended in the solution relatively dispersedly under blowing air condition, and bipolarized in the effect of electric field to form bipolar three-dimension electrodes. This electrode system can make use of the direct oxidation of anode and the indirect oxidation of .HO that is produced by anode surface, and can make use of H₂O₂ that is produced by cathode. Thus, the electrodes can be used effectively.

O₂+H—+e----H₂O₂

O₂+H₂O+2e-----HOO.—+OH—

HOO.—+H₂O+2e----H₂O₂+OH—

The mass/volume ratio of the activated carbon microparticles in the electrolyte is preferably 1%˜9%, more preferably 1% to 6%, even more preferably 1% to 5%, and most preferably 3%.

In some embodiments of the present invention, the diameter of the activated carbon microparticles is 3˜5 mm.

In some embodiments of the present invention, the constant current is preferably 0.1˜0.9 A, more preferably 0.3˜0.7 A, and most preferably 0.5 A.

In some embodiments of the present invention, preferably, converting biomass materials into organic acids by one-step by electrolyzing 10˜190 min under condition of constant current using bipolar three-dimension-electrodes system.

In some embodiments of the present invention, preferably, the electrolyte contains NaCl or KCl with molarity and volume ratio of 20 mmol/L˜2 mol/L. NaCl or KCl is used as conductive agent and aimed having conductive effect in the energized conditions.

In some embodiments of the present invention, the biomass materials are lignin or corn stalks, and preferably, the mass/volume ratio of the biomass materials in the electrolyte is 2%˜20%. Lignin is provided from waste lignin of cellulosic ethanol plant, waste lignin of paper mill and industrial waste of other sources.

In some embodiments of the present invention, preferably, both the anode and the cathode are graphite plate electrodes.

As shown in FIG. 4, the present invention also provides a container for converting biomass materials into soluble substances by one-step, comprising:

A tank 1 which holds electrolyte at the interior thereof, wherein the side wall of the tank 1 is provided with an opening, the opening is provided with a permeable membrane, and the opening also communicates with a discharge pipe 10;

A pair of electrode plates 2, 3 which are immersed into the electrolyte by at least a part thereof, wherein the pair of electrode plates 2, 3 space from each other and connect to positive pole and negative pole of power supply respectively to form anode and cathode in energized state respectively; and,

Particle electrodes 8 which are in granular form and are suspended in the electrolyte.

In one embodiment of the present invention, preferably, the upper portion of the pair of electrode plates 2, 3 is level with the upper portion of the tank.

In some embodiments of the present invention, preferably, the electrolyte contains NaCl or KCl with molarity and volume ratio of 20 mmol/L˜2 mol/L.

In some embodiments of the present invention, preferably, the particle electrodes 8 are activated carbon microparticles, and the mass/volume ratio of the activated carbon microparticles in the electrolyte is 1%˜6%.

In one embodiment of the present invention, preferably, both the pair of electrode plates 2, 3 are graphite plate electrodes.

In one embodiment of the present invention, preferably, further comprising: air sparger 5 which is disposed at the bottom of the tank 1, and communicates with an intake pipe 6, to blow air to make the particle electrodes 8 to be suspended in the electrolyte.

Or, particle electrodes are suspended in the electrolyte by using a mixer. It should be known that the particle electrodes 8 and the biomass materials can be evenly suspended in the electrolyte by various devices and means, and it is not limited to the two ways listed here.

As shown in FIG. 1, reactions occur at the anode and the cathode when a constant current is applied in the container of the present invention. Biomass materials 7 and particle electrodes 8 mix well after blowing air from the intake pipe. After applying a constant current, free radicals are rapidly produced and the free radicals can oxidize the biomass materials to produce organic acids, sugars, and aromatic compounds. When the reaction is complete, 9 is opened and organic acids through selectively permeable membrane can be efficiently discharged into the collecting barrel 11 through the discharge pipe 10. It should be known that the pore diameter or the material of the selectively permeable membrane here is not limited, and the selectively permeable membrane that organic acids are selectively allowed to permeate can work.

Wherein, the organic acids can be used in the food industry, the cosmetics industry and the jet fuel industry.

Experimental Method: The Method of Electrolytic Conversion.

Step one: NaCl solution with a certain concentration was prepared, which was used as conductive agent and aimed at having conductive effect in the energized conditions.

Step two: The biomass materials with the adding amount 2%˜20% were added to the NaCl solution above.

Step three: A certain concentration of activated carbon microparticles were added, which were used as electrode particles and can be used again and again. In the condition of blowing air or using a stirring rotor, the activated carbon particles were suspended in the solution relatively dispersedly, and bipolarized in the effect of electric field to form bipolar three-dimension electrodes. Every microparticles in the solution constituted a micro electrolytic cell, and anodic reaction occurred at one end of the microparticle, cathodic reaction occurred at the other end of the microparticle.

Step four: Two graphite plate electrodes were putted into the solution that mixed with biomass materials, which were used as the anode and the cathode respectively.

Step five: Both the anode and the cathode were energized by using a DC power supply that control the voltage and electric current invariable.

Step six: After reacting for a period of time, the solution was taken out, and centrifuged to retain the supernatant. A certain amount of n-hexane were added to extract organic acids and the supernatant were retained. The varieties and concentration of the organic acids were detected by using GC-MS.

Detecting the Varieties and Concentration of the Organic Acids by Using GC-MS:

Sample Preparation: 5 ml supernatant of reaction mixtures was taken and 5 mL n-hexane solution was added. Then the mixture was oscillated for 10 h. After standing for stratification, the upper organic phase was retained, and washed 3˜5 times with n-hexane solution until the organic phase remains colorless. The organic phases were combined. The solvent was removed by volatilization under N₂ to obtain fat and oil. Weighing and calculating.

Methyl esterification of fat and oil: 0.05 g oil was taken and placed in 10 ml stoppered test tube, and then 1 ml of 0.5 mol/L solution of KOH in methanol was added. Saponification was conducted in a 60° C. water bath for 15 min with shaking. After cooling, 2 ml of 14% boron trifluoride-methanol solution was added and oscillated in a 60° C. water bath for 2 min. After cooling to room temperature, 1 ml n-hexane was added and oscillated. 1 ml saturated NaCl solution was added. Anhydrous sodium sulfate was added. 980 μL the supernatant was taken, 20 μL methyl nonadecanoate was added as an internal standard and was taken into the bottle for gas chromatographic analysis after filtering.

Gas analysis and detection: chromatographic column specifications: sp-2560, 100 m×0.25 mm×0.20 μm; carrier gas: N₂; split ratio: 30/1; injector temperature: 250° C.; oven temperature: 180° C.; sample size: 1 μL; Initially, the column temperature was 180° C., and then the temperature was increased to 240° C. at a rate of 30° C./min and maintained 18 min.

Embodiment 1

With the method above, an experiment was carried out in the present invention by using the following conditions. current intensity: 0.3 A; reacting at different times; molarity and volume ratio of NaCl: 0.4 mol/L; mass/volume ratio of the particle electrodes in the electrolyte: 2%; mass/volume ratio of the lignin in the electrolyte: 5%; After reaction, samples were taken and extracted by ethyl acetate and n-hexane. The varieties of the products were analyzed by GC-MS. The result of GC-MS showed the product mainly included two substances: hexadecanoic acid, methyl ester and 9-octadecenoic acid, methyl ester. The main products from the biomass materials were hexadecanoic acid and 9-octadecanoic acid. This was because products need to be methyl esterified before the GC-MS analysis, and the real products should accordingly remove methyl ester moieties. Yields and conversion rates of every product were analyzed by GC-MS. The gas detection diagram was shown in FIG. 1, and the varieties and conversion rates of products were shown in table 1 and table 2.

TABLE 1
identification of the varieties of products by GC-MS
peak			CAS
appearance		matching	registry	chemical		molecular
time	compound name	factor	number	formula	peak area	weight
13.1504	Hexadecanoic acid,	86.2	112-39-0	C17H34O2	776852.1	270.256
	methyl ester
13.7495	9-Octadecenoic acid,	93.4	1937-62-8	C19H36O2	360996.8358	296.272
	methyl ester, (E)-

TABLE 2
conversion rates of two products at different reaction
time in the present embodiment
	hexadecanoic	9-octadecenoic
product	acid	acid
conversion rate (100 min)	28.1%	25.5%
conversion rate (190 min)	30.3%	27.5%

Embodiment 2

With the method above, an experiment was carried out in the present invention by using the following conditions. current intensity: 0.3 A; molarity and volume ratio of NaCl: 0.2 mol/L; mass/volume ratio of the particle electrodes in the electrolyte: 2%; mass/volume ratio of the lignin in the electrolyte: 5%; After different reaction time, samples were taken and extracted by ethyl acetate and n-hexane. Yields and conversion rates of every product were analyzed by GC-MS, as shown in table 3. The gas detection diagram was shown in FIG. 2.

TABLE 3
conversion ratios of two products in the present embodiment
		hexadecanoic	9-octadecenoic
	product	acid	acid
	conversion rate (57.5 min)	24.2%	23.4%

Embodiment 3

With the method above, an experiment was carried out in the present invention by using the following conditions. current intensity: 0.3 A; molarity and volume ratio of NaCl: 0.4 mol/L; mass/volume ratio of the particle electrodes in the electrolyte: 3%; lignin: 5%; After different reaction time, samples were taken and extracted by ethyl acetate and n-hexane. Yields and conversion rates of every product were analyzed by GC-MS, as shown in table 4. The gas detection diagram was shown in FIG. 3.

TABLE 4
conversion ratios of two products in the present embodiment
		hexadecanoic	9-octadecenoic
	product	acid	acid
	conversion rate (90 min)	18.3%	20.7%
	conversion rate (120 min)	27.6%	23.7%

Embodiment 4

With the method above, an experiment was carried out in the present invention by using the following conditions. current intensity: 0.3 A; reaction time; molarity and volume ratio of NaCl: 0.4 mol/L; mass/volume ratio of the particle electrodes in the electrolyte: 2%; mass/volume ratio of the lignin in the electrolyte: 5%; After different reaction time, samples were taken and extracted by ethyl acetate and n-hexane. Yields and conversion rates of every product were analyzed by GC-MS, as shown in table 5.

TABLE 5
conversion ratios of two products in the present embodiment
		hexadecanoic	9-octadecenoic
	product	acid	acid
	conversion rate (120 min)	52.0%	54.0%

Embodiment 5

Lignosulfonate was used as substrate, current intensity: 0.5 A; molarity and volume ratio of NaCl: 0.4 M; mass/volume ratio of the particle electrodes in the electrolyte: 3%; mass/volume ratio of the lignin in the electrolyte: 5%; After different reaction time, samples were taken and extracted by ethyl acetate and n-hexane. Yields and conversion rates of every product were analyzed by GC-MS. Lignosulfonate was disposed by free radicals for 180 min. Hexadecanoic acid and 9-octadecenoic acid were still mainly detected by GC-MS. As shown in Table 6, the conversion rates of hexadecanoic acid and 9-octadecenoic acid were 27.0% and 33.8% respectively.

TABLE 6
conversion ratios of two products in the present embodiment
		hexadecanoic	9-octadecenoic
	product	acid	acid
	conversion rate (180 min)	27.0%	33.8%

Embodiment 6

Corn straw was used as a process object. The corn stalk contained three main ingredients: 35% cellulose, 31% hemicellulose and 13% lignin. Corn stalks that were used as biomass materials were added into an 8 L reactor with mass/volume ratio of the corn stalks in the electrolyte of 5% (w/v). NaCl was used as a conductive agent and the molarity and volume ratio of NaCl was 0.1 mol/L. With the extension of the reaction time, the solid matter was decreasing. When 80 g corn stalks were disposed by the radicals for 300 min, the solid matter disappeared. Maybe, the biomass materials were oxidized by the radicals, and cracked to produce some small molecule substances. The supernatant was extracted by hexane, and then was detected by GC-MS. After reacting 30 min, the yields of palmitic acid and 9-octadecenoic acid were 23.4% and 27.6%, respectively. The highest yields of palmitic acid and 9-octadecenoic acid from the corn straws were observed at 30 min.

TABLE 7
conversion ratios of two products in the present embodiment
		hexadecanoic	9-octadecenoic
	product	acid	acid
	conversion rate (30 min)	23.4%	27.6%

Embodiment 7

With the method above, the applicant of the present invention used radicals that are produced by electrolysis to dispose lignin under the all combined conditions shown in Table 8. The soluble substances were extracted, and analyzed by GC-MS.

In the Table 8, A represented the current intensity, −2, −1, 0, 1 and 25 represents 0.1 A, 0.3 A, 0.5 A, 0.7 A and 0.9 A respectively.

B represented reaction time, −2, −1, 0, 1 and 25 represented 10 min, 20 min, 30 min, 40 min and 50 min respectively.

C represented molarity and volume ratio of NaCl, −2, −1. 0, 1 and 25 represented 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L and 0.5 mol/L respectively.

D represented mass/volume ratio of the particle electrodes in the electrolyte, −2, −1, 0, 1 and 25 represented 1%, 2%, 3%, 4% and 5% respectively.

TABLE 8
central composite experimental table of four factors and five levels
					hexadecanoic	9-octadecenoic
group	A	B	C	D	acid	acid
1	0	0	0	0	0.144867	0.162866
2	0	0	0	0	0.157344	0.193386
3	0	0	0	0	0.191825	0.230963
4	−1	−1	1	−1	0.086879	0.085864
5	−1	−1	−1	1	0.176914	0.211655
6	0	−2	0	0	0.406808	0.365074
7	1	1	−1	1	0.218405	0.252838
8	0	0	0	0	0.008236	0.008236
9	−2	0	0	0	0.175655	0.192652
10	1	1	1	1	0.243954	0.297085
11	0	0	0	−2	0.03898	0.038371
12	−1	1	−1	1	0.333484	0.385746
13	1	1	−1	−1	0.173807	0.203513
14	0	0	−2	0	0.433372	0.414312
15	0	0	0	0	0.14899	0.024299
16	0	0	0	0	0.022454	0.02421
17	1	−1	1	−1	0.237911	0.230334
18	0	0	0	1	0.177761	0.220107
19	1	−1	−1	1	0.248679	0.276587
20	0	0	2	0	0.191121	0.223355
21	1	−1	−1	−1	0.161825	0.173457
22	0	2	0	0	0.22304	0.234281
23	−1	1	1	−1	0.026166	0.028116
24	−1	1	1	1	0.307737	0.33964
75	2	0	0	0	0.169941	0.207316
26	1	−1	1	1	0.1472	0.189042
27	−1	−1	−1	−1	0.230439	0.262821
28	−1	−1	1	1	0.19226	0.246194
29	−1	1	−1	−1	0.437172	0.410281
30	1	1	1	−1	0.30826	0.391302
31	0	0	0	0	0.022528	0.024249

The results were shown in Table 8. Under the conditions of the group 14 (current intensity: 0.5 A, reaction time: 30 min), molarity and volume ratio of NaCl: 0.1 mol/L, mass/volume ratio of the particle electrodes in the electrolyte: 1%), the conversion rate of lignin conversion into palmitic acid reached 43.3%, and the conversion rate of lignin conversion into 9-octadecenoic acid reached 41.4%. The sum of conversion rates exceeded 80%. Under the conditions of the group 29 (current intensity: 0.3 A, reaction time: 40 min), molarity and volume ratio of NaCl: 0.2 mol/L, mass/volume ratio of the particle electrodes in the electrolyte: 2%), the conversion rate of lignin conversion into palmitic acid reached 43.7%, and the conversion rate of lignin conversion into 9-octadecenoic acid reached 41.0%.

Embodiment 8

With the method above, an experiment was carried out in the present invention by using the following conditions. current intensity: 0.5 A; reaction time; molarity and volume ratio of NaCl: 0.4 mol/L; mass/volume ratio of the particle electrodes in the electrolyte: 3%; mass/volume ratio of the lignin in the electrolyte: 5%; After different reaction time, samples were taken and extracted by ethyl acetate and n-hexane. Yields and conversion rates of every product were analyzed by GC-MS.

TABLE 9
conversion ratios of two products in the present embodiment
		hexadecanoic	9-octadecenoic
	product	acid	acid
	conversion rate (120 min)	45.1%	40.2%

Embodiment 9

With the method above, an experiment was carried out in the present invention by using the following conditions, current intensity: 0.5 A; reaction time; molarity and volume ratio of KCl: 0.02 mol/L; mass/volume ratio of the particle electrodes in the electrolyte: 3%; mass/volume ratio of the lignin in the electrolyte: 5%; After different reaction time, samples were taken and extracted by ethyl acetate and n-hexane. Yields and conversion rates of every product were analyzed by GC-MS, as shown in Table 10.

TABLE 10
conversion ratios of two products in the present embodiment
		hexadecanoic	9-octadecenoic
	product	acid	acid
	conversion rate (120 min)	20.4%	21.5%

Embodiment 10

With the method above, an experiment was carried out in the present invention by using the following conditions. current intensity: 0.5 A; reaction time; molarity and volume ratio of KCl: 2 mol/L; mass/volume ratio of the particle electrodes in the electrolyte: 2%. mass/volume ratio of the corn straw in the electrolyte: 2%; After different reaction time, samples were taken and extracted by ethyl acetate and n-hexane. Yields and conversion rates of every product were analyzed by GC-MS, as shown in Table 11.

TABLE 11
conversion ratios of two products in the present embodiment
		hexadecanoic	9-octadecenoic
	product	acid	acid
	conversion rate (90 min)	12.5%	18.5%

Embodiment 11

With the method above, an experiment was carried out in the present invention by using the following conditions. current intensity: 0.5 A; reaction time; molarity and volume ratio of KCl: 1.2 mol/L; mass/volume ratio of the particle electrodes in the electrolyte: 3%; mass/volume ratio of the lignin in the electrolyte: 20%; After different reaction time, samples were taken and extracted by ethyl acetate and n-hexane. Yields and conversion rates of every product were analyzed by GC-MS, as shown in Table 12.

TABLE 12
conversion ratios of two products in the present embodiment
		hexadecanoic	9-octadecenoic
	product	acid	acid
	conversion rate (120 min)	30.4%	20.5%

Embodiment 12

With the method above, an experiment was carried out in the present invention by using the following conditions. current intensity: 0.5 A; reaction time; molarity and volume ratio of KCl: 0.8 mol/L; mass/volume ratio of the particle electrodes in the electrolyte: 3%; mass/volume ratio of the lignin in the electrolyte: 2%; After different reaction time, samples were taken and extracted by ethyl acetate and n-hexane. Yields and conversion rates of every product were analyzed by GC-MS, as shown in Table 13.

TABLE 13
conversion ratios of two products in the present embodiment
		hexadecanoic	9-octadecenoic
	product	acid	acid
	conversion rate (120 min)	26.2%	32.4%

Biomass materials included cellulose, hemicellulose and lignin-similar substances. The present invention disclosed a process of translating biomass materials into soluble substances such as organic acids, sugars and aromatic compounds. Activated carbon-similar substances were well distributed in solution to produce a large number of free radicals. The biomass materials can be oxidized by the free radicals to crack. This process required two electrodes that needed to be energized.

The number and the processing scale described herein was used to simplify the description of the present invention. The applications, modifications and variations of the bipolar three-dimension-electrodes system of the present invention was obvious to those skilled in the art.

As described above, the present invention had the effect of realizing one-step conversion, having mild reaction conditions and needing no additional chemical reagents due to using the bipolar three-dimension electrode to convert the biomass materials.

Although the embodiments of the present invention have been disclosed above, but it is not limited to the use of the specification and embodiments listed. It can be applied to various fields suitable for the present invention. Those skilled in the art can easily modified. Therefore, without departing from the general concept of the scope defined by the claims and the equivalents, the present invention is not limited to the specific details and illustrations herein illustrated and described herein.

Claims

1. A method for converting biomass materials into soluble substances by one-step, characterized by comprising:

converting biomass materials into soluble substances by using a bipolar three-dimensional-electrodes system to electrolyzing the biomass materials at a certain time under the condition of constant current by one-step, wherein the bipolar three-dimension-electrodes system includes an anode, a cathode, particle electrodes and electrolyte, and in electrolyzing process, the particle electrodes and the biomass materials being suspended in the electrolyte.

2. The method for converting biomass materials into soluble substances by one-step of claim 1, characterized by, the constant current being 0.1˜0.9 A.

3. The method for converting biomass materials into soluble substances by one-step of claim 2, characterized by, the constant current being 0.3˜0.7 A.

4. The method for converting biomass materials into soluble substances by one-step of claim 1, characterized by, converting biomass materials into organic acids which are some kinds of soluble substances by using bipolar three-dimension-electrodes system to electrolyzing the biomass materials at 10˜190 minutes under the condition of constant current by one-step.

5. The method for converting biomass materials into soluble substances by one-step of claim 1, characterized by, the electrolyte containing NaCl or KCl with molarity and volume ratio of 20 mmol/L˜2 mol/L.

6. The method for converting biomass materials into soluble substances by one-step of claim 1, characterized by, the particle electrodes are activated carbon microparticles, the mass/volume ratio of the activated carbon microparticles in the electrolyte being 1%˜9%.

7. The method for converting biomass materials into soluble substances by one-step of claim 1, characterized by, the diameter of the activated carbon microparticle being 3˜5 mm.

8. The method for converting biomass materials into soluble substances by one-step of claim 1, characterized by, the biomass materials being lignin or corn stalks.

9. The method for converting biomass materials into soluble substances by one-step of claim 1, characterized by, the mass/volume ratio of the biomass materials in the electrolyte being 2%˜20%.

10. The method for converting biomass materials into soluble substances by one-step of claim 1, characterized by, both the anode and the cathode being graphite plate electrodes.

11. A container for converting biomass materials into soluble substances by one-step, characterized by, comprising:

A tank which holds electrolyte at the interior thereof, wherein the side wall of the tank is provided with an opening, the opening is provided with a permeable membrane, and the opening also communicates with a discharge pipe;

A pair of electrode plates which are immersed into the electrolyte by at least a part thereof, wherein the pair of electrode plates space from each other and connect to positive pole and negative pole of power supply respectively to form anode and cathode in energized state respectively; and,

Particle electrodes which are in granular form and are suspended in the electrolyte.

12. The container for converting biomass materials into soluble substances by one-step of claim 11, characterized by, the upper portions of the pair of electrode plates being level with the upper portion of the tank.

13. The container for converting biomass materials into soluble substances by one-step of claim 11, characterized by, the electrolyte containing NaCl or KCl with molarity and volume ratio of 20 mmol/L˜2 mol/L.

14. The container for converting biomass materials into soluble substances by one-step of claim 11, characterized by, the particle electrodes being activated carbon microparticles, the mass/volume ratio of the activated carbon microparticles in the electrolyte being 1%˜9%.

15. The container for converting biomass materials into soluble substances by one-step of claim 11, characterized by, the pair of electrode plates being graphite plate electrodes.

16. The container for converting biomass materials into soluble substances by one-step of claim 11, characterized by, further comprising: air sparger which is disposed at the bottom of the tank, and is communicated with an intake pipe, to blow air to make the electrode particles to be suspended in the electrolyte.

17. Uses of soluble substances which are obtained by the method in claim 1.