Method for reducing content of steroid hormones in mushroom dregs and method for preparing biomass fuel

Abstract

The invention provides a method for reducing the content of steroid hormones in mushroom dregs and a method for preparing biomass fuel, and particularly relates to a method for reducing the content of the steroid hormones in a water-containing sample, and the method comprises the step of carrying out irradiation treatment on the water-containing sample containing the steroid hormones by utilizing electron beams. By utilizing the method for reducing the content of the steroid hormones in the mushroom dregs, the steroid hormones in the mushroom dregs can be effectively degraded, so that the aim of effectively removing the steroid hormones is fulfilled. Moreover, the method is simple and convenient to operate, short in consumed time and suitable for large-scale application. The steroid hormone mushroom dregs treated by the method can be used for preparing biomass fuel, the purposes of harmless treatment and resource utilization are achieved, and the application value is high.

Description

Technical Field

[0001] The present application relates to the technical field of hazardous solid waste utilization, and in particular to a method for reducing the steroid hormone content in fungus residue and a method for preparing biomass fuel. Background Art

[0002] Steroid hormones mainly include estrogen, androgen, progesterone and adrenal cortex hormone. They are the second class of drugs after antibiotics and are widely used in medical fields such as anti-inflammatory, contraception, treatment of endocrine disorders and cardiovascular diseases, and anti-tumor. The large-scale use of steroid hormones poses potential hazards to the ecological environment and human health. Steroid hormones are an important class of endocrine disrupting chemicals (EDCs). Even at extremely low concentrations, they can cause hermaphroditism, reproduction, and immune system disorders in aquatic organisms, and accumulate through the food chain to affect human health.

[0003] Among them, steroidal androgens (Androgens) androstenedione (including androst-4-ene-3,17-dione (AD), 9α-hydroxy-androstenedione (OHAD)) are important raw materials and key intermediates for the synthesis of steroid hormone drugs, and the market size is huge. The production methods of androstenedione mainly include chemical synthesis and microbial fermentation. The chemical synthesis method has complex processes, high raw material costs, low yields, and serious environmental pollution, and has been gradually eliminated. At present, microbial fermentation has become the mainstream technology for the production of androstenedione. This method uses cholesterol or plant sterols as raw materials and converts them into androstenedione through microbial fermentation reactions. When the fermentation is completed, the target product androstenedione is extracted and purified, leaving a large amount of fungus residue waste.

[0004] The main components of fungus residue are mycelium, fermentation medium and residual androstenedione. It has a high content of organic components and is very easy to deteriorate and rot if left for a long time. Moreover, the residual androstenedione enters the environment and threatens ecological safety. If it is not properly handled, it will cause serious environmental pollution. The harmless treatment and resource utilization of steroid hormone fungus residue has become one of the problems that plague the development of pharmaceutical companies.

[0005] Biomass fuel refers to solid fuel made by burning biomass materials. Common biomass materials include agricultural and forestry waste, wood processing waste, and animal manure. Making steroid hormone residue into biomass fuel can not only solve the environmental pollution problem caused by the residue, but also realize the recycling of resources, bringing certain economic benefits to the enterprise. However, androstenedione has good thermal stability, and it is difficult to completely remove androstenedione pollutants in the residue by a simple pyrolysis carbonization process. In addition, the residue does not contain cellulose and hemicellulose, not only has poor molding performance, but also has a high content of fuel oil produced by direct pyrolysis carbonization, and the yield of solid fuel is low.

[0006] Therefore, there is an urgent need for an effective method for harmless treatment and resource utilization of steroid hormone bacterial residues. Summary of the invention

[0007] The present application aims to solve at least one of the technical problems existing in the prior art to a certain extent. To this end, one purpose of the present application is to propose a method for reducing the content of steroid hormones in an aqueous sample, a method for reducing the content of steroid hormones in aqueous steroid hormone bacterial residues and increasing the content of extracellular polysaccharides in the bacterial residues, a method for preparing biomass fuels and biomass fuels. The method for reducing the content of steroid hormones in an aqueous sample of the present application can effectively degrade the steroid hormones in the aqueous sample, thereby effectively removing the steroid hormones. In addition, the method is simple to operate, takes a short time, and is suitable for large-scale application. The steroid hormone bacterial residues treated by the method can be used to prepare biomass fuels, achieve the purpose of harmless treatment, and have high application value.

[0008] In one aspect of the present application, the present application provides a method for reducing the content of steroid hormones in an aqueous sample. According to an embodiment of the present application, the method comprises: irradiating the aqueous sample containing steroid hormones with an electron beam.

[0009] Therefore, after water molecules are irradiated by electron beams, they produce strong oxidizing hydroxyl radicals (·OH) and strong reducing hydrated electrons (e aq - ) and other active particles, and the steroid hormone molecules can undergo oxidation-reduction reactions with these active particles and be degraded, thereby effectively removing the steroid hormones and achieving the purpose of harmless treatment. In addition, the method is simple to operate, takes a short time, and is suitable for large-scale application.

[0010] According to an embodiment of the present application, the electron beam is generated by an electron accelerator.

[0011] According to an embodiment of the present application, the irradiation absorbed dose of the electron beam is 50 kGy to 100 kGy.

[0012] In another aspect of the present application, the present application proposes a method for reducing the steroid hormone content in fungus residue containing steroid hormones and increasing the exopolysaccharide content in the fungus residue. According to an embodiment of the present application, the method comprises: irradiating the fungus residue containing steroid hormones using the above method.

[0013] According to an embodiment of the present application, the moisture content of the mushroom residue is 37% to 80%.

[0014] In another aspect of the present application, the present application proposes a method for preparing biomass fuel. According to an embodiment of the present application, the method comprises: irradiating the steroid hormone-containing fungus residue using any of the above methods, drying, and obtaining pre-treated fungus residue; uniformly mixing the pre-treated fungus residue with straw to obtain mixed fungus residue; and pyrolyzing and carbonizing the mixed fungus residue to obtain the biomass fuel.

[0015] According to an embodiment of the present application, the steroid hormone includes androst-4-ene-3,17-dione or 9α-hydroxyandrostenedione.

[0016] According to an embodiment of the present application, the drying includes drying at 100° C. to 110° C. to constant weight.

[0017] According to an embodiment of the present application, the straw includes: corn straw.

[0018] According to an embodiment of the present application, the mass ratio of the pretreated fungus residue to the straw is 1:(1-2).

[0019] According to an embodiment of the present application, the temperature of the pyrolysis carbonization treatment is 500°C to 800°C.

[0020] In another aspect of the present application, the present application provides a biomass fuel, which is obtained by any of the above methods according to the embodiments of the present application.

[0021] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0023] Figure 1 These are the samples in Example 1 of the present application, wherein (left) is a sample formed by mixing OHAD fungus residue and straw in a ratio of 1:1 and pressing them into tablets; (right) is the biomass fuel obtained therefrom. DETAILED DESCRIPTION

[0024] The embodiments of the present application are described in detail below. The embodiments described below are exemplary and are only used to explain the present application, and cannot be understood as limiting the present application.

[0025] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. Further, in the description of this application, unless otherwise specified, the meaning of "plurality" is two or more.

[0026] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0027] In this document, the terms "include" or "comprising" are open expressions, that is, including the contents specified in the present application but not excluding other contents.

[0028] As used herein, the terms "optionally", "optional" or "optionally" generally mean that the subsequently described event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0029] Method for reducing the content of steroid hormones in aqueous samples

[0030] In one aspect of the present application, the present application provides a method for reducing the content of steroid hormones in an aqueous sample. According to an embodiment of the present application, the method comprises: irradiating the aqueous sample containing steroid hormones with an electron beam.

[0031] Electron beams are generated by electron accelerators. They are dense, high-speed electron streams with extremely high energy. Electron beam irradiation is an ionizing irradiation technology. When water molecules are excited by high-energy electron beam radiation, they produce highly oxidizing hydroxyl radicals (·OH) and highly reducing hydrated electrons (e aq - ) and other active particles (as shown in Formula 1, the values ​​in brackets are the radiochemical yield G value of each active particle). Steroid hormone molecules can undergo oxidation-reduction reactions with these active particles and be degraded. Thus, steroid hormones are effectively removed to achieve the purpose of harmless treatment. In addition, the method is simple to operate, takes a short time, and is suitable for large-scale application.

[0032]

[0033] According to an embodiment of the present application, the electron beam is generated by an electron accelerator, thereby forming an electron beam flow with high energy density, providing the required high-energy electron source for subsequent irradiation treatment.

[0034] According to an embodiment of the present application, the radiation absorption dose of the electron beam is 50 kGy to 100 kGy. Thus, the steroid hormones in the aqueous sample can be effectively degraded. Specifically, different radiation absorption doses can be obtained by controlling the beam intensity of the electron beam and the transmission speed of the sample.

[0035] Method for reducing steroid hormone content in fungus residue containing steroid hormone and increasing exopolysaccharide content in the fungus residue

[0036] On the other hand, the present application proposes a method for reducing the steroid hormone content in fungus residue containing steroid hormones and increasing the extracellular polysaccharide content in the fungus residue. According to an embodiment of the present application, the method includes: irradiating the fungus residue containing steroid hormones using the above method. Thus, the strong oxidizing active particles generated by electron beam irradiation efficiently degrade the steroid hormones in the fungus residue, significantly reducing its content and achieving the purpose of harmless treatment; at the same time, irradiation can also increase the soluble extracellular polysaccharide content, enhance the adhesion and molding properties of the fungus residue, and provide favorable conditions for subsequent resource utilization.

[0037] According to an embodiment of the present application, the moisture content of the mushroom residue is 37% to 80%. Thus, active particles are generated through water molecules.

[0038] According to the embodiments of the present application, electron beam irradiation has a good removal effect on androstenedione in fungus residue. When the absorbed dose is 100 kGy, the removal rate of androstenedione in fungus residue can reach more than 90%. Moreover, ionizing irradiation has little effect on the polysaccharide content of fungus residue. When the absorbed dose is 100 kGy, the polysaccharide content of the fungus residue mixture is basically unchanged, but the soluble extracellular polysaccharide content can be significantly increased by more than 2.5 times.

[0039] Method for preparing biomass fuel

[0040] In another aspect of the present application, the present application proposes a method for preparing biomass fuel. According to an embodiment of the present application, the method comprises: irradiating the fungus residue containing steroid hormones by any of the above methods, drying, and obtaining pretreated fungus residue; uniformly mixing the pretreated fungus residue with straw to obtain mixed fungus residue; pyrolysis and carbonization of the mixed fungus residue to obtain the biomass fuel. Thus, the steroid hormones in the fungus residue can be effectively degraded and the extracellular polysaccharide content can be increased by electron beam irradiation, the adhesion and molding properties of the fungus residue can be enhanced, and then the fungus residue can be mixed with straw, and the cellulose and hemicellulose of the straw can be used to improve the molding and combustion properties of the mixture. Finally, the mixed fungus residue can be converted into biomass fuel by pyrolysis and carbonization, so as to achieve harmless treatment and resource utilization of the fungus residue, bring economic benefits, and reduce environmental pollution.

[0041] According to an embodiment of the present application, the steroid hormone includes androst-4-ene-3,17-dione or 9α-hydroxyandrostenedione. Therefore, the two hormones are important raw materials and key intermediates for synthesizing steroid hormone drugs. The method of the present application can be used to harmlessly treat the steroid hormones in the fungus residue and utilize the fungus residue to form biomass fuel.

[0042] According to an embodiment of the present application, the drying includes drying at 100° C. to 110° C. to a constant weight. Thus, the moisture in the pre-treated fungus residue is removed, making it suitable for subsequent mixing and pyrolysis carbonization treatment.

[0043] According to an embodiment of the present application, the straw includes: corn straw. Therefore, corn straw is a common waste in agricultural production. Mixing it with pre-treated fungus residue can not only realize the resource utilization of agricultural waste and reduce environmental pollution, but also reduce the production cost of biomass fuel.

[0044] According to the embodiment of the present application, the mass ratio of the pretreated mushroom residue to the straw is 1:(1-2). As a result, the mushroom residue contains high organic matter and calorific value, while the straw provides good molding and combustion performance. Within this ratio range, the biomass fuel has good combustion characteristics and stability.

[0045] According to an embodiment of the present application, the temperature of the pyrolysis carbonization treatment is 500° C. to 800° C. Thus, within this range, the bonding between the polysaccharide in the fungus residue and the components such as the straw cellulose is promoted, thereby forming biomass fuel.

[0046] According to the embodiments of the present application, the biomass fuel made from steroid hormone fungus residue as raw material has a high calorific value, and the high calorific value can reach 30MJ / kg, which is equivalent to the calorific value of lignite (25-35MJ / kg). However, the fuel oil content produced by pyrolysis and carbonization of fungus residue is high, and the yield of solid fuel is low. The yield of solid fuel is low, less than 10%. After the fungus residue is mixed with straw and then pyrolyzed and carbonized, the fuel oil produced during the pyrolysis process can be absorbed by the straw, and the yield of solid fuel can be increased to more than 30%. In addition, the polysaccharides in the fungus residue help the straw to bond and form, and the solid fuel produced has better stability. The increase in the extracellular polysaccharide content after irradiation is more conducive to the bonding of straw.

[0047] Biomass fuel

[0048] In another aspect of the present application, the present application provides a biomass fuel, which is obtained by any of the above methods according to the embodiments of the present application.

[0049] Those skilled in the art will appreciate that the features and advantages described in the foregoing method are also applicable to the biomass fuel and will not be elaborated herein.

[0050] The scheme of the present application will be explained below in conjunction with the embodiments. It will be appreciated by those skilled in the art that the following embodiments are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If no specific technology or conditions are indicated in the embodiments, the technology or conditions described in the literature in this area or the product specification are carried out. The reagents used or the instruments that do not indicate the manufacturer are all conventional products that can be obtained commercially.

[0051] Example 1

[0052] In this embodiment, 9α-hydroxy-androstenedione (OHAD) residue was taken from a pharmaceutical company in central China, with a moisture content of 37%, a total solid (TS) content of 332 g / kg, a volatile solid (VS) / TS ratio of 99%, a polysaccharide content of 85 g / kg, of which the soluble extracellular polysaccharide content was 2.9 g / kg, and the concentration of residual OHAD was about 1000 mg / kg.

[0053] 1. Take a certain amount of OHAD residue and put it into a sample bag, and send it to the irradiation room of the electron accelerator by a conveyor belt for irradiation. The irradiation absorbed dose is 50kGy and 100kGy respectively.

[0054] 2. Dry the original fungus residue and the irradiated fungus residue at 105°C to constant weight to obtain dry fungus residue.

[0055] 3. Crush corn stalks to 100 mesh, mix dry fungus residue and stalks in a ratio of 1:1 or 1:2, and squeeze them into sheets using a tablet press. Then, pyrolysis and carbonization were carried out under nitrogen protection, with a heating rate of 5°C / min, and the temperature was maintained at 550°C for 60 minutes to obtain fungus residue biomass solid fuel. The dry fungus residue alone was used as a control.

[0056] 4. Detection

[0057] The detection indicators include: 1) OHAD concentration in original fungus residue, fungus residue after electron beam irradiation and fungus residue biomass fuel; 2) soluble extracellular polysaccharide content of fungus residue after electron beam irradiation; 3) yield (Y), high heating value (HHV), comprehensive combustion characteristics index (S) and stability (DU) of biomass fuel.

[0058] The residual OHAD content in the fungus residue and solid fuel was first extracted with acetonitrile and then detected by liquid chromatography. The specific steps are as follows:

[0059] Take about 0.2g of sample and put it in a 15mL polypropylene centrifuge tube, add 5mL acetonitrile, vortex for 3min, and perform ultrasonic assisted extraction for 20min. Centrifuge at 10000rpm for 10min, take the supernatant and filter it with a 0.22μm filter membrane. After filtration, dilute the solution to an appropriate multiple for HPLC detection.

[0060] The high performance liquid chromatograph used was Agilent 1200, the chromatographic column was XDB-C18 reverse phase column, the column temperature was 30°C, the mobile phase was 0.1% formic acid aqueous solution and acetonitrile (mixing ratio 30:70), the detector was an ultraviolet detector, and the OHAD detection wavelength was 254nm.

[0061] Polysaccharide content: determined by phenol-sulfuric acid method. The detection method of extracellular polysaccharide is: centrifuge the fungus residue at 10000 rpm for 10 minutes, and detect the polysaccharide content in the obtained supernatant.

[0062] Solid fuel yield: Weigh the mass of biomass fuel before and after combustion, and calculate according to the following formula: Yield (%) = (mass before combustion / mass after combustion) × 100%

[0063] High Heating Value (HHV): High Heating Value refers to the heat released when a unit mass of fuel is completely burned. It is the main indicator for evaluating fuel quality and is measured using an oxygen bomb calorimeter.

[0064] Combustion characteristic comprehensive index (S): calculated based on the data of thermogravimetric analyzer. Thermogravimetric analysis test conditions are: temperature range: room temperature-850℃, heating rate: 10℃ / min, test atmosphere: air. The calculation formula of S is as follows:

[0065]

[0066] V max is the maximum fuel rate (% / min); V a is the average burning rate (% / min); T i is the ignition temperature (℃); T e is the burnout temperature (℃). The comprehensive combustion index represents the comprehensive combustion capacity of biomass fuel. The larger the value, the better the combustion characteristics.

[0067] Stability (DU): It is expressed by anti-crushing strength. The test method is: drop the biomass fuel molded sample from a height of 2m onto a stainless steel plate, and use the ratio of the mass measured before and after the drop to express its stability.

[0068] DU = (mass after falling / mass before falling) × 100

[0069] 5. Results and Analysis

[0070] Table 1 shows the OHAD concentration before and after OHAD irradiation. Electron beam irradiation can effectively degrade OHAD in the fungus residue. When the absorbed dose is 50 kGy to 100 kGy, the removal rate of OHAD can reach more than 80%, and most of the steroid hormone pollutants in the fungus residue are removed by irradiation.

[0071] Table 1 OHAD content of OHAD residue before and after irradiation (mg / kg)

[0072]

[0073] Note: Table 1 is the result of mixing dry mushroom residue and straw in a ratio of 1:1.

[0074] Table 2 shows the OHAD concentration detected in OHAD residue biomass fuel. When the residue is directly made into biomass fuel without irradiation, OHAD residue of about 8.1 mg / L can still be detected. Steroidal androgens have good thermal stability. When the irradiated residue is made into biomass fuel, the OHAD concentration can be reduced to a level that cannot be detected by liquid chromatography, meeting the harmless requirements.

[0075] Table 2 OHAD content of biomass fuels obtained from OHAD residue treated under different conditions (mg / kg)

[0076]

[0077] Note: ND: Not Detected

[0078] Table 3 shows the performance of OHAD residue biomass fuel made under different conditions. It can be seen that the yield of biomass fuel made by mixing residue with straw and then burning and carbonizing can be significantly increased from 9.2% to more than 30%. The increase in the proportion of straw slightly increased the yield of solid fuel. The yield of biomass fuel made from irradiated residue is slightly higher than that of unirradiated residue.

[0079] The calorific value of biomass fuel made from OHAD residue alone is high, with a HHV of 30.2MJ / kg. After the residue is mixed with straw, its calorific value decreases. The higher the proportion of straw, the greater the decrease. The HHV of biomass fuel made from irradiated residue and straw (25.5MJ / kg) is higher than that of unirradiated residue (24.1MJ / kg).

[0080] Mixing mushroom residue with straw can improve the combustion performance of mushroom residue biomass fuel. Compared with biomass fuel made from mushroom residue alone, the S value of biomass fuel mixed with mushroom residue and straw increased by 1.3 to 1.7 times. The S value of biomass fuel made from irradiated mushroom residue and straw increased by 1.2 times compared with unirradiated mushroom residue.

[0081] In addition, it is difficult to press the fungus residue into tablets alone, but it is easy to press the fungus residue into tablets when mixed with straw. Furthermore, the extracellular polysaccharide content of the fungus residue increased significantly after irradiation. After irradiation of OHAD fungus residue with 100kGy, its extracellular polysaccharide can be increased from 2.9g / L to about 7.3g / L, which is conducive to the bonding of the fungus residue and straw mixture, and the stability of the generated fuel is better. As can be seen from Table 3, the stability parameter of the biomass solid fuel made by mixing the irradiated fungus residue and straw in a ratio of 1:1 is 98%, which is higher than the 92% of the biomass solid fuel made by mixing the original fungus residue and straw in a ratio of 1:1. Figure 1 These are photos of the biomass fuel produced by pressing irradiated mushroom residue and straw in a 1:1 ratio.

[0082] Table 3 Performance indicators of OHAD fungus residue biomass fuel

[0083]

[0084] Example 2

[0085] In this embodiment, androst-4-ene-3,17-dione (AD) residue was taken from a pharmaceutical company in North China, with a moisture content of 80%, a TS content of 212 g / kg, a VS / TS ratio of 85%, a polysaccharide content of 18 g / kg, of which the soluble extracellular polysaccharide content was 1.8 g / kg, and the concentration of residual AD was about 230 mg / kg.

[0086] 1. Take a certain amount of AD bacterial residue and put it into a sample bag, and use a conveyor belt to send it to the irradiation room of the electron accelerator for irradiation. The irradiation absorbed dose is 50kGy and 100kGy.

[0087] 2. Dry the original fungus residue and the irradiated fungus residue at 105°C to constant weight to obtain dry fungus residue.

[0088] 3. Crush corn stalks to 100 mesh, mix dry fungus residue and stalks in a ratio of 1:1 or 1:2, and squeeze them into sheets using a tablet press. Then, pyrolysis and carbonization were carried out under nitrogen protection, with a heating rate of 5℃ / min, and the temperature was maintained at 700℃ for 60min to obtain fungus residue biomass solid fuel. In addition, the experiment of directly making biomass fuel from dry fungus residue was also carried out at the same time.

[0089] 4. The detection index and detection method are the same as those in Example 1, except that the liquid chromatography detection wavelength of AD is 245 nm.

[0090] 5. The experimental results are as follows:

[0091] Table 4 shows the AD concentration before and after AD irradiation. Electron beam irradiation can effectively degrade AD in fungus residue. When the absorbed dose is 50 kGy to 100 kGy, the removal rate of AD can reach more than 82%, and most of the steroid hormone pollutants in fungus residue are removed by irradiation.

[0092] Table 4 AD content of AD fungus residue before and after irradiation (mg / kg)

[0093]

[0094] Table 5 shows the AD concentration detected in the biomass fuel of fungus residue. Steroidal androgens have good thermal stability. When the fungus residue is directly made into biomass fuel without irradiation, AD residue of about 3.6 mg / L can still be detected. When the irradiated fungus residue is made into biomass fuel again, the AD concentration can be reduced to a level that cannot be detected by liquid chromatography, meeting the requirements for harmlessness.

[0095] Table 5 AD content in biomass fuels obtained from AD fungus residue treated under different conditions (mg / kg)

[0096]

[0097] ND: Not Detected

[0098] Table 6 shows the properties of AD slag biomass fuels made under different conditions. It can be seen that the yield of biomass fuel made by mixing slag with straw and then burning and carbonizing it can be significantly increased from 12.2% to more than 30%. The yield of solid fuel increases slightly with the increase of the proportion of straw. The yield of biomass fuel made from irradiated slag is slightly higher than that of unirradiated slag.

[0099] The calorific value of biomass fuel made from AD residue alone is high, with an HHV of 29.0 MJ / kg. After the residue is mixed with straw, its calorific value decreases. The higher the proportion of straw, the greater the decrease. The HHV of biomass fuel made from irradiated residue and straw (24.0 MJ / kg) is higher than that of unirradiated residue (23.3 MJ / kg).

[0100] Mixing mushroom residue with straw can improve the combustion performance of mushroom residue biomass fuel. Compared with biomass fuel made from mushroom residue alone, the S value of the mixed biomass fuel of mushroom residue and straw increased by 1.5 to 1.7 times. The S value of the biomass fuel made from the mixture of irradiated mushroom residue and straw increased by 1.2 times compared with the unirradiated mushroom residue.

[0101] In addition, AD fungus residue alone is difficult to be pressed into tablets, but the mixture of fungus residue and straw is easy to be pressed into tablets. Furthermore, the extracellular polysaccharide content of the fungus residue increased significantly after irradiation. After AD fungus residue was irradiated with 50kGy, its extracellular polysaccharide content increased from 1.8g / L to about 4.7g / L, which is conducive to the bonding of the fungus residue and straw mixture, and the stability of the generated fuel is better. As can be seen from Table 6, the stability parameter of the biomass solid fuel made by mixing the irradiated fungus residue and straw in a ratio of 1:1 is 97%, which is higher than the 90% of the biomass solid fuel made by mixing the original fungus residue and straw in a ratio of 1:1.

[0102] Table 6 Performance indicators of AD fungus residue biomass fuel

[0103]

[0104] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0105] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. A method for reducing the content of steroid hormones in an aqueous sample, characterized in that: include: An aqueous sample containing steroid hormones is irradiated using an electron beam.

2. The method according to claim 1, characterized in that The irradiation absorbed dose of the electron beam is 50 kGy to 100 kGy.

3. A method for reducing the steroid hormone content in aqueous steroid hormone bacterial residue and increasing the exopolysaccharide content in the bacterial residue, characterized in that: include: Irradiating aqueous steroid hormone bacterial residue using the method described in any one of claims 1 to 2; Optionally, the moisture content of the mushroom residue is 37% to 80%.

4. A method for preparing biomass fuel, characterized in that: include: irradiating the steroid hormone bacterial residue using the method according to any one of claims 1 to 3, and drying to obtain pretreated bacterial residue; uniformly mixing the pretreated fungus residue with straw to obtain mixed fungus residue; The mixed fungus residue is subjected to pyrolysis and carbonization treatment to obtain the biomass fuel.

5. The method according to claim 4, characterized in that The steroid hormone includes androst-4-ene-3,17-dione or 9α-hydroxyandrostenedione.

6. The method according to claim 4, characterized in that The drying comprises drying at 100° C. to 110° C. to a constant weight.

7. The method according to claim 4, characterized in that The straw includes: corn straw.

8. The method according to claim 4, characterized in that The mass ratio of the pretreated fungus residue to the straw is 1:(1-2).

9. The method according to claim 4, characterized in that The temperature of the pyrolysis carbonization treatment is 500°C to 800°C.

10. A biomass fuel, characterized in that: Obtained by the method according to any one of claims 4 to 9.

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