A method for converting multi-source waste biomass into clean energy

Abstract

The present invention discloses a method for converting multi-source waste biomass into clean energy, including catalyst preparation, multi-source waste biomass mixing and clean energy conversion. The conversion method of the present invention skillfully mixes multi-source biomass including residual sludge, agricultural and forestry waste, livestock and poultry manure, and restaurant waste, adds a homemade catalyst, and effectively realizes the simultaneous conversion of multi-source biomass into clean energy by adjusting the lighting conditions to obtain bioethanol, biodiesel and by-product glycerol; during the reaction process, due to the flexible change of lighting conditions, the lignocellulosic biomass in the multi-source biomass is effectively broken down.

Description

Technical Field

[0001] The invention relates to a clean energy conversion method, in particular to a multi-source waste biomass clean energy conversion method. Background Art

[0002] Waste biomass is the waste consumed or generated by people in the process of production and life due to the application of biomass. It has the characteristics of wide sources, various types, and serious environmental pollution. However, it is far from enough to only solve the collection of these solid wastes. At present, when traditional energy is increasingly exhausted, making full use of these "misplaced resources" and turning them into treasures is the ultimate way to solve the problem.

[0003] At present, a lot of research has been carried out on the resource utilization of waste biomass, and significant progress has been made. The more mature technologies developed mainly include: biomass fermentation technology, biomass carbonization technology, biomass composting technology, etc. Kou Mengtian et al. used corn stalks as substrates, and co-cultured rumen fungi and brewer's yeast at 39°C for 72 hours to investigate the effects of fermentation conditions on substrate degradation and metabolites. The results showed that under the action of rumen fungi, the ethanol conversion rate was the highest when 5 mL of brewer's yeast was added. Compared with the control group without brewer's yeast, the ethanol conversion rate increased by 23.04% (Kou Mengtian et al., Transactions of the Chinese Society of Agricultural Engineering. 2022, 38(05)). Wang Haihou et al. used static composting and high-temperature aerobic fermentation methods to investigate the humification characteristics of sheep manure compost under the condition of adding biochar. Through a 43-day composting test, combined with humification characteristics such as compost temperature, seed germination index, humic acid and its composition, it was concluded that adding biochar can promote the decomposition of compost and improve the stability of humic acid, but has no effect on the absolute content of humic acid and its components (Wang Haihou et al., Journal of Agricultural Resources and Environment. 2022, 39(04)).

[0004] The above technologies mainly realize resource recycling through chemical conversion, biological conversion, or physical conversion in biomass conversion. During the implementation process, experimental research is mainly carried out on single-source biomass. These technologies have enhanced the resource utilization rate of biomass to a certain extent, but these technologies have been difficult to promote and apply on a large scale due to more or less reasons such as low energy conversion rate, high cost, poor controllability, cumbersome sorting process, and secondary pollution. Therefore, in order to meet the requirements of low-cost clean energy conversion of waste biomass, there are still great challenges in researching and developing clean, efficient, and easy-to-operate multi-source biomass mixed resource technology. Summary of the invention

[0005] Purpose of the invention: The present invention aims to provide a multi-source waste biomass clean energy conversion method that can effectively convert waste biomass into clean energy and obtain bioethanol, biodiesel and by-product glycerol.

[0006] Technical solution: The multi-source waste biomass clean energy conversion method of the present invention comprises the following steps:

[0007] (1) Preparation of catalyst: soak the gasified slag in a hydrofluoric acid solution, transfer the gasified filter residue to a HNO3 solution after sealed stirring, and conduct a water bath heating reaction. After the reaction is completed, filter the filter residue, add the filter residue to a solvent, and then add nano-cobalt, ammonia water and tetraethoxysilane to the liquid in sequence, stir and react to obtain catalyst A; add catalyst A to a solvent, and add n-butyl titanate dropwise, dry the liquid, roast the dried product and cool it to room temperature to obtain catalyst B;

[0008] (2) Mixing of waste biomass from multiple sources: Mix residual sludge, livestock and poultry manure, absolutely dry agricultural and forestry waste, and restaurant waste to obtain waste biomass from multiple sources, immerse it in deionized water, and add the above-mentioned catalysts A and B;

[0009] (3) Clean energy conversion: The above reactants are heated in a water bath and the reaction is carried out under alternating light. After the reaction is completed, cellulase is added to the slurry in the dark to carry out enzymatic hydrolysis. Yeast is then added to the slurry in batches to carry out the reaction. After the reaction is completed, the ethanol is recovered by reducing the pressure, the catalyst is separated, and the biodiesel and the by-product glycerol are recovered.

[0010] Furthermore, in step (1), the temperature during the sealed stirring is 40-45°C, and the stirring time is 20-25 min; the temperature of the water bath heating reaction is 66-73°C, and the reaction time is 0.5-0.8 h; the mass fraction of the nano-cobalt relative to the gasified slag is 0.12-0.15%; the solid-liquid mass ratio of the catalyst A after adding the solvent is 1:5-8; after adding n-butyl titanate, the reaction is continued for 3-3.8 h; the drying temperature is 50-55°C, the roasting temperature is 500-535°C, and the roasting time is 3-4.5 h. The specific steps of sequentially adding nano cobalt, ammonia and tetraethoxysilane to the feed liquid are as follows: first, adding 0.12-0.15% nano cobalt relative to the mass fraction of gasified slag to the feed liquid, stirring at a constant temperature of 30-35°C for 45-50 minutes, then adding 2-3 mL of ammonia to the feed liquid and stirring for 10-20 minutes, then slowly dripping 1 mL of tetraethoxysilane into the feed liquid, rapidly stirring for 6-7 hours, and after the reaction is completed, cooling, filtering out the liquid phase, and drying the solid phase to obtain solid A.

[0011] Furthermore, the composition of the multi-source biomass in step (2) and the mass fraction of each component are: residual sludge 45-64%, livestock and poultry manure 16-9%, dry agricultural and forestry waste 28-20% and restaurant waste 11-7%.

[0012] Furthermore, the specific process of the multi-source biomass mixing in step (2) is as follows: the agricultural and forestry waste is crushed through a 30-50 mesh sieve, and then a catalyst B with a mass fraction of 5.5-8.3% is added to the agricultural and forestry waste, and the two are immersed in deionized water together, and irradiated with sunlight for 0.8-1.5 hours while stirring; then the prepared residual sludge and livestock and poultry manure are added to the slurry, and the slurry is irradiated with sunlight for 30-50 minutes while stirring; then the catering waste is continued to be added to the slurry, and the catalyst A is added to the slurry at the same time, and the addition amount is 5-11% of the total mass of the slurry.

[0013] Furthermore, the water bath heating temperature in step (3) is 35-38°C, the alternating illumination is 5 minutes of illumination followed by 30-60 seconds of light avoidance, and the alternating illumination time is 0.5-2.2 hours; the enzymatic hydrolysis reaction is carried out in a constant temperature shaking incubator at a rotation speed of 150-180 r / min, a temperature of 35-42°C, and a reaction time of 2.5-3 hours.

[0014] Furthermore, the specific steps of adding yeast to the slurry in batches for reaction in step (3) are as follows: first, adding 0.1-0.3% of the mass of the absolute dry agricultural and forestry waste to the yeast, reacting in a water bath at 35-42° C. for 1-1.5 hours, then raising the water bath temperature to 65-88° C., and continuing the reaction for 1-2.5 hours; after the reaction is completed, lowering the temperature to 35-42° C., and then adding 0.08-0.25% of the mass of the absolute dry agricultural and forestry waste to the solution, reacting for 1-1.3 hours, and then raising the water bath temperature to 65-88° C. again, and reacting for 3-3.5 hours; after the reaction is completed, lowering the temperature to 35-42° C. again, and adding 0.15-0.3% of the mass of the absolute dry agricultural and forestry waste to the solution, reacting for 2-3 hours, and then recovering the ethanol under reduced pressure, separating the catalyst, and recovering the biodiesel and by-product glycerol.

[0015] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) It can effectively realize the conversion of waste biomass into clean energy and obtain bioethanol, biodiesel and by-product glycerol. The method of the present invention cleverly mixes multi-source biomass including residual sludge, agricultural and forestry waste, livestock and poultry manure, and catering waste, adds a homemade catalyst, and effectively realizes the simultaneous conversion of multi-source biomass into clean energy by adjusting the lighting conditions to obtain bioethanol, biodiesel and by-product glycerol; during the reaction process, due to the flexible change of lighting conditions, the lignocellulosic biomass in the multi-source biomass is effectively broken down; (2) It is beneficial to reduce the amount of enzyme used and reduce costs. During the enzymatic saccharification process, a small amount of sludge protein and other surfactants derived from the breaking process can effectively reduce the cellulase from lignin. The loss caused by non-specific absorption and interface effect saves the amount of cellulase used; (3) The reaction conversion rate is high. The present invention changes the reaction conditions to timely promote the ester exchange reaction between the fermentation product ethanol and oil to generate biodiesel; the reduction due to the conversion of bioethanol effectively improves the conversion rate of the fermentation process and makes the reaction more thorough; (4) The multi-source waste biomass after the reaction is effectively reduced and resourced, effectively controlling the environmental pollution of these wastes and solving the problem of waste biomass treatment and disposal; (5) The method is simple and the reaction time is short. The present invention effectively shortens the reaction time by reasonably arranging the experimental sequence and adding the catalyst. As for the enzymatic hydrolysis reaction in the process alone, most of the existing research reports require more than 90 hours or even 100 hours to obtain the same enzymatic hydrolysis rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The conversion rate of reducing sugar and ethanol and the recycling of catalyst in Example 1;

[0017] Figure 2 The conversion rate of reducing sugar and ethanol and the recycling of catalyst in Example 2;

[0018] Figure 3 This is the reducing sugar and ethanol conversion rate and catalyst reuse situation of Example 3. DETAILED DESCRIPTION

[0019] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and embodiments.

[0020] Example 1

[0021] (1) Raw material sampling:

[0022] The residual sludge was taken from the urban sewage treatment plant, the agricultural and forestry waste biomass was taken from the surrounding area of ​​a city, the catering waste was taken from a school canteen, the livestock and poultry manure was taken from the livestock farm, and the gasification slag was taken from the waste slag produced during the production process of the gasifier. The agricultural and forestry waste was dried to absolute dryness and crushed through a 30-50 mesh sieve.

[0023] (2) Preparation of catalyst:

[0024] Take a certain amount of gasified slag to remove the coarse impurities, soak it in a container filled with 1M hydrofluoric acid solution, ensure that the gasified slag can always be completely immersed in the solution, seal the container, and stir it magnetically at 40°C for 20min; then move the gasified filter residue to 0.5MHNO3 solution, the amount of HNO3 solution ensures that the gasified slag can always be completely immersed in the solution, seal it, stir it magnetically at a water bath temperature of 66°C for 0.5h, then filter and dry it. Immerse the dry residue in anhydrous ethanol, the amount of anhydrous ethanol ensures that the gasified slag can always be completely in the liquid phase, and add 0.12% nano-cobalt relative to the mass fraction of the gasified slag, stir it at a constant temperature of 30°C for 45min, then add 2mL of ammonia water to the feed liquid and stir it for 10min, then slowly drip 1mL of tetraethoxysilane into the feed liquid, stir it rapidly for 6h, after the reaction is completed, cool, filter out the liquid phase, and dry the solid phase to obtain catalyst A. Catalyst A was added to anhydrous ethanol at a solid-liquid mass ratio of 1:5, and the mixture was rapidly stirred in a constant temperature water bath at 48°C. Meanwhile, 3 mL of n-butyl titanate was added dropwise to the solution, and stirring was continued for 3 h. The liquid was then dried at 50°C. Finally, the dried material was placed in a muffle furnace at 500°C and calcined for 3 h, then taken out and cooled to room temperature to obtain catalyst B.

[0025] (3) Multi-source biomass blending:

[0026] According to the mass fraction, 45% of residual sludge, 16% of livestock and poultry manure, 28% of absolutely dry agricultural and forestry waste, and 11% of catering waste are taken; then, 5.5% of catalyst B relative to its mass is added to the agricultural and forestry waste, and the two are immersed in deionized water together. The amount of water ensures that the solids are completely immersed in the entire reaction process, and the mixture is stirred and irradiated with sunlight for 0.8h; then, the prepared residual sludge and livestock and poultry manure are added to the liquid, and the mixture is stirred and irradiated with sunlight for 30min; then, the prepared catering waste is continued to be added to the liquid, and catalyst A is added to the liquid at the same time, and the addition amount is 5% of the total mass of the liquid.

[0027] (4) Clean energy conversion:

[0028] The final feed solution of step 3 is heated in a water bath at 35°C, and the reaction is carried out under the alternating light and dark for 0.5h, and the light is kept away from light for 30s every 5min of light exposure; after the reaction is completed, 5FPU / g of cellulase is added to the feed solution under the condition of keeping away from light, and the mixture is fully mixed. The enzymatic hydrolysis reaction is carried out in a constant temperature shaking incubator (150r / min) at a temperature of 35°C for 2.5h. Then, 0.1% of yeast relative to the mass of absolute dry agricultural and forestry waste is added to the feed solution, and after heating in a water bath at 35°C for 1h, the water bath temperature is increased to 65°C, and the reaction is continued for 1h; after the reaction is completed, the temperature is reduced to 35°C, and 0.08% of yeast relative to the mass of absolute dry agricultural and forestry waste is added to the solution, and after the reaction is carried out for 1h, the water bath temperature is increased to 65°C again, and the reaction is carried out for 3h; after the reaction is completed, the temperature is further reduced to 35°C, and 0.15% of yeast relative to the mass of absolute dry agricultural and forestry waste is added to the solution, and after the reaction is carried out for 2h, the ethanol is recovered under reduced pressure, the catalyst is separated, and the biodiesel and by-product glycerol are recovered.

[0029] Effect analysis:

[0030] After the catalyst reaction in the above embodiment is completed, the conversion rate of biodiesel (relative to restaurant waste oil) reducing sugar (relative to absolute dry agricultural and forestry waste biomass), ethanol (relative to absolute dry agricultural and forestry waste biomass) and the catalyst reuse effect are shown in Table 1-1 and Figure 1 Table 1-1 Experimental details of the control group (CK): After heating the reactor to 85°C and maintaining a constant temperature, common sodium hydroxide catalyst, catering waste equivalent to the amount of the embodiment, and ethanol were added to the reactor and stirred. The total mass ratio of the catalyst to the reactants was 5% (wt / wt). After reacting for 6 hours, the biodiesel was recovered. Figure 1 Experimental details of the control group (CK): the same amount of absolutely dry agricultural and forestry waste biomass as in the example, the addition amount of catalyst Ca(OH)2 was 5% (w / v), the pretreatment temperature was 150°C, the pretreatment time was 4h, the enzyme loading was 80FPU / g, and the enzymatic hydrolysis time was 100h.

[0031] Table 1-1 Biodiesel conversion rate and catalyst reuse

[0032]

[0033] From the data in the table, we can see that the homemade catalyst still has good catalytic activity when it is reused for the third time.

[0034] Product performance testing:

[0035] The main physical and chemical properties of the product biodiesel were analyzed and the results are shown in Table 1-2.

[0036] Table 1-2 Main physical and chemical properties of homemade biodiesel

[0037]

[0038] From the data in Table 1-2, it can be seen that biodiesel products meet the EN14214 standard.

[0039] In the above examples, the cellulase activity was effectively improved and the waste biomass was significantly reduced.

[0040] Example 2

[0041] (1) Raw material sampling is the same as in Example 1.

[0042] (2) Catalyst preparation:

[0043] Take a certain amount of gasified slag to remove the coarse impurities, soak it in a container filled with 1M hydrofluoric acid solution, ensure that the gasified slag can always be completely immersed in the solution, seal the container, and stir it magnetically at 41°C for 21min; then move the gasified filter residue to 0.5MHNO3 solution, the amount of HNO3 solution ensures that the gasified slag can always be completely immersed in the solution, seal it, stir it magnetically at a water bath temperature of 67°C for 0.55h, then filter and dry it. Immerse the dry residue in anhydrous ethanol, the amount of anhydrous ethanol ensures that the gasified slag can always be completely in the liquid phase, and add 0.125% nano-cobalt relative to the mass fraction of the gasified slag, stir it at a constant temperature of 31°C for 46min, then add 2.2mL of ammonia water to the feed liquid and stir it for 12min, then slowly drip 1mL of tetraethoxysilane into the feed liquid, stir it rapidly for 6.2h, after the reaction is completed, cool it, filter out the liquid phase, and dry the solid phase to obtain catalyst A. Catalyst A was added to anhydrous ethanol with a solid-liquid mass ratio of 1:5.5, and the mixture was rapidly stirred in a constant temperature water bath at 49°C. Meanwhile, 3.5 mL of n-butyl titanate was added dropwise to the solution, and stirring was continued for 3.1 h. The liquid was then dried at 51°C. Finally, the dried material was placed in a muffle furnace and calcined for 3.2 h at 505°C, and then taken out and cooled to room temperature to obtain catalyst B.

[0044] (3) Multi-source biomass blending:

[0045] Take 50% of residual sludge, 15% of livestock and poultry manure, 26% of absolutely dry agricultural and forestry waste, and 9% of catering waste according to mass fraction. Then add 6% of catalyst B relative to its mass to the agricultural and forestry waste, and immerse the two together in deionized water. The amount of water ensures that the solid is completely immersed during the entire reaction process, and irradiate with sunlight for 1 hour while stirring; then add the prepared residual sludge and livestock and poultry manure to the liquid, and irradiate with sunlight for 35 minutes while stirring; then continue to add the prepared catering waste to the liquid, and at the same time add catalyst A to the liquid, and the addition amount is 6% of the total mass of the liquid.

[0046] (4) Clean energy conversion:

[0047] The final feed solution of step 3 was heated in a water bath at 35.5°C, and the reaction was carried out under alternating light and dark for 1 hour, with 40 seconds of light protection for every 5 minutes of illumination; after the reaction was completed, 7FPU / g of cellulase was added to the feed solution under light-proof conditions, and the mixture was fully mixed. The enzymatic hydrolysis reaction was carried out in a constant temperature shaking incubator (155r / min) at 36°C for 2.6 hours. Then, 0.15% of yeast relative to the mass of absolute dry agricultural and forestry waste was added to the liquid, and after heating in a water bath at 36°C for 1.1 hours, the water bath temperature was increased to 70°C, and the reaction was continued for 1.2 hours; after the reaction was completed, the temperature was lowered to 36°C, and 0.1% of yeast relative to the mass of absolute dry agricultural and forestry waste was added to the solution. After the reaction was completed for 1.05 hours, the water bath temperature was increased to 70°C again, and the reaction was continued for 3.1 hours; after the reaction was completed, the temperature was further lowered to 36°C, and 0.2% of yeast relative to the mass of absolute dry agricultural and forestry waste was added to the solution. After the reaction was completed for 2.2 hours, the ethanol was recovered under reduced pressure, the catalyst was separated, and the biodiesel and by-product glycerol were recovered.

[0048] Effect analysis:

[0049] The analysis items and the control group (CK) are the same as in Example 1, and the results are shown in Table 2-1 and Figure 2 .

[0050] Table 2-1 Biodiesel conversion rate and catalyst reuse

[0051]

[0052] From the data in the table, we can see that the homemade catalyst still has good catalytic activity when it is reused for the third time.

[0053] The main physical and chemical properties of the product biodiesel were analyzed and the results are shown in Table 2-2.

[0054] Table 2-2 Main physical and chemical properties of homemade biodiesel

[0055]

[0056] From the data in Table 2-2, it can be seen that biodiesel products meet the EN14214 standard.

[0057] In the above examples, the cellulase activity was effectively improved and the waste biomass was significantly reduced.

[0058] Example 3

[0059] (1) Raw material sampling is the same as in Example 1.

[0060] (2) Catalyst preparation:

[0061] Take a certain amount of gasified slag to remove the coarse impurities, soak it in a container filled with 1M hydrofluoric acid solution, ensure that the gasified slag can always be completely immersed in the solution, seal the container, and stir it magnetically at 42°C for 22 minutes; then move the gasified filter residue to 0.5MHNO3 solution, the amount of HNO3 solution ensures that the gasified slag can always be completely immersed in the solution, seal it, stir it magnetically at a water bath temperature of 68°C for 0.6h, then filter and dry it. Immerse the dry residue in anhydrous ethanol, the amount of anhydrous ethanol ensures that the gasified slag can always be completely in the liquid phase, and add 0.13% nano-cobalt relative to the mass fraction of the gasified slag, stir it at a constant temperature of 32°C for 47 minutes, then add 2.5mL of ammonia water to the feed liquid and stir it for 15 minutes, then slowly drip 1mL of tetraethoxysilane into the feed liquid, stir it rapidly for 6.5h, after the reaction is completed, cool it, filter out the liquid phase, and dry the solid phase to obtain catalyst A. Catalyst A was added to anhydrous ethanol with a solid-liquid mass ratio of 1:6, and the mixture was rapidly stirred in a constant temperature water bath at 50°C. At the same time, 4 mL of n-butyl titanate was added dropwise to the solution, and stirring was continued for 3.5 h. The liquid was then dried at 53°C. Finally, the dried material was placed in a muffle furnace at 515°C and calcined for 3.5 h, then taken out and cooled to room temperature to obtain catalyst B.

[0062] (3) Multi-source biomass blending:

[0063] According to the mass fraction, 55% of residual sludge, 13% of livestock and poultry manure, 24% of absolutely dry agricultural and forestry waste, and 8% of catering waste were taken. Then, 7% of the mass of catalyst B was added to the agricultural and forestry waste, and the two were immersed in deionized water. The amount of water ensured that the solid was completely immersed during the entire reaction process, and the mixture was stirred and exposed to sunlight for 1.1 hours; then, the prepared residual sludge and livestock and poultry manure were added to the liquid, and the mixture was stirred and exposed to sunlight for 40 minutes; then, the prepared catering waste was continued to be added to the liquid, and catalyst A was added to the liquid at the same time, and the addition amount was 8% of the total mass of the liquid.

[0064] (4) Clean energy conversion:

[0065] The final feed solution of step 3 was heated in a water bath at 36.5°C, and the reaction was carried out under alternating light and dark conditions for 1.5 hours, with 50 seconds of light protection for every 5 minutes of illumination. After the reaction was completed, 10 FPU / g of cellulase was added to the feed solution under light-protected conditions, and the mixture was fully mixed. The enzymatic hydrolysis reaction was carried out in a constant temperature shaking incubator (165 r / min) at 38°C for 2.7 hours. Then, 0.2% of the mass of yeast relative to the absolute dry agricultural and forestry waste was added to the liquid, and after heating in a water bath at 38°C for 1.3 hours, the water bath temperature was increased to 75°C, and the reaction was continued for 1.8 hours; after the reaction was completed, the temperature was lowered to 38°C, and 0.17% of the mass of yeast relative to the absolute dry agricultural and forestry waste was added to the solution. After the reaction was completed for 1.2 hours, the water bath temperature was increased to 75°C again, and the reaction was continued for 3.3 hours; after the reaction was completed, the temperature was further lowered to 38°C, and 0.22% of the mass of yeast relative to the absolute dry agricultural and forestry waste was added to the solution. After the reaction was completed for 2.5 hours, the ethanol was recovered under reduced pressure, the catalyst was separated, and the biodiesel and by-product glycerol were recovered.

[0066] Effect analysis:

[0067] The analysis items and the control group (CK) are the same as those in Example 1, and the results are shown in Table 3-1 and Figure 3 .

[0068] Table 3-1 Biodiesel conversion rate and catalyst reuse

[0069]

[0070] From the data in the table, we can see that the homemade catalyst still has good catalytic activity when it is reused for the third time.

[0071] The main physical and chemical properties of the product biodiesel were analyzed and the results are shown in Table 3-2.

[0072] Table 3-2 Main physical and chemical properties of homemade biodiesel

[0073]

[0074] From the data in Table 3-2, we can see that biodiesel products meet the EN14214 standard.

[0075] In the above examples, the cellulase activity was effectively improved and the waste biomass was significantly reduced.

[0076] Example 4

[0077] (1) Raw material sampling is the same as in Example 1.

[0078] (2) Preparation of catalyst: Take a certain amount of gasified slag to remove the impurities, soak it in a container filled with 1M hydrofluoric acid solution, ensure that the gasified slag can always be completely immersed in the solution, seal the container, and stir it magnetically at 44°C for 24 minutes; then move the gasified filter residue to 0.5M HNO3 solution, the amount of HNO3 solution ensures that the gasified slag can always be completely immersed in the solution, seal it, stir it magnetically at a water bath temperature of 70°C for 0.75h, then filter and dry it. Immerse the dry residue in anhydrous ethanol, the amount of anhydrous ethanol ensures that the gasified slag can always be completely in the liquid phase, and add 0.14% nano-cobalt relative to the mass fraction of the gasified slag, stir it at a constant temperature of 34°C for 49 minutes, then add 2.8mL of ammonia water to the feed liquid and stir it for 18 minutes, then slowly drip 1mL of tetraethoxysilane into the feed liquid, stir it rapidly for 6.8h, after the reaction is completed, cool it, filter out the liquid phase, and dry the solid phase to obtain catalyst A. Catalyst A was added to anhydrous ethanol with a solid-liquid mass ratio of 1:7, and the mixture was rapidly stirred in a constant temperature water bath at 51°C. At the same time, 4.5 mL of n-butyl titanate was added dropwise to the solution, and stirring was continued for 3.6 h. The liquid was then dried at 54°C. Finally, the dried material was placed in a muffle furnace at 530°C and calcined for 4.4 h, then taken out and cooled to room temperature to obtain catalyst B.

[0079] (3) Mixing of multiple sources of biomass: Take 60% of residual sludge, 10% of livestock and poultry manure, 22.5% of absolutely dry agricultural and forestry waste, and 7.5% of catering waste according to mass fraction. Then add 8% of catalyst B to the agricultural and forestry waste, and immerse the two together in deionized water. The amount of water ensures that the solids are completely immersed during the entire reaction process. Stir and irradiate with sunlight for 1.4 hours; then add the prepared residual sludge and livestock and poultry manure to the liquid, stir and irradiate with sunlight for 45 minutes; then continue to add the prepared catering waste to the liquid, and at the same time add catalyst A to the liquid, the addition amount is 10% of the total mass of the liquid.

[0080] (4) Clean energy conversion: The final feed liquid obtained in the second step was heated in a 37°C water bath, and the reaction was carried out for 2 h under the alternating light and dark conditions, with 55 s of light exposure for every 5 min of light exposure. After the reaction was completed, 13 FPU / g of cellulase was added to the feed liquid under light-proof conditions, and the mixture was fully mixed. The enzymatic hydrolysis reaction was carried out in a constant temperature shaking incubator (175 r / min) at 40°C for 2.9 h. Then, 0.25% of yeast relative to the mass of absolute dry agricultural and forestry waste was added to the liquid, and after heating in a water bath at 40°C for 1.4 hours, the water bath temperature was increased to 85°C, and the reaction was continued for 2.2 hours; after the reaction was completed, the temperature was lowered to 40°C, and 0.23% of yeast relative to the mass of absolute dry agricultural and forestry waste was added to the solution, and after the reaction was carried out for 1.25 hours, the water bath temperature was increased to 85°C again, and the reaction was carried out for 3.4 hours; after the reaction was completed, the temperature was further lowered to 40°C, and 0.27% of yeast relative to the mass of absolute dry agricultural and forestry waste was added to the solution, and after the reaction was carried out for 2.8 hours, the ethanol was recovered under reduced pressure, the catalyst was separated, and the biodiesel and by-product glycerol were recovered.

[0081] Example 5

[0082] (1) Raw material sampling is the same as in Example 1.

[0083] (2) Preparation of catalyst: Take a certain amount of gasified slag to remove the impurities, soak it in a container filled with 1M hydrofluoric acid solution, ensure that the gasified slag can always be completely immersed in the solution, seal the container, and stir it magnetically at 45°C for 25 minutes; then move the gasified filter residue to 0.5M HNO3 solution, the amount of HNO3 solution ensures that the gasified slag can always be completely immersed in the solution, seal it, stir it magnetically at a water bath temperature of 73°C for 0.8h, then filter and dry it. Immerse the dry residue in anhydrous ethanol, the amount of anhydrous ethanol ensures that the gasified slag can always be completely in the liquid phase, and add 0.15% nano-cobalt relative to the mass fraction of the gasified slag, stir it at a constant temperature of 35°C for 50 minutes, then add 3mL of ammonia water to the feed liquid and stir it for 20 minutes, then slowly drip 1mL of tetraethoxysilane into the feed liquid, stir it rapidly for 7h, after the reaction is completed, cool it, filter out the liquid phase, and dry the solid phase to obtain catalyst A. Catalyst A was added to anhydrous ethanol with a solid-liquid mass ratio of 1:8, and the mixture was rapidly stirred in a constant temperature water bath at 52°C. At the same time, 5 mL of n-butyl titanate was added dropwise to the solution, and stirring was continued for 3.8 h. The liquid was then dried at 55°C. Finally, the dried material was placed in a muffle furnace at 535°C and calcined for 4.5 h, then taken out and cooled to room temperature to obtain catalyst B.

[0084] (3) Mixing of multiple sources of biomass: Take a certain amount of residual sludge, agricultural and forestry waste, livestock and poultry manure, and catering waste respectively, of which agricultural and forestry waste is dried to absolute dryness and crushed to pass through a 50-mesh sieve. Take 64% residual sludge, 9% livestock and poultry manure, 20% absolute dry agricultural and forestry waste, and 7% catering waste according to mass fraction. Then add 8.3% of catalyst B relative to its mass to the agricultural and forestry waste, and immerse the two together in deionized water. The amount of water ensures that the solid is completely immersed during the entire reaction process, and the mixture is stirred and exposed to sunlight for 1.5 hours; then add the prepared residual sludge and livestock and poultry manure to the liquid, and stir and expose to sunlight for 50 minutes; then continue to add the prepared catering waste to the liquid, and at the same time add catalyst A to the liquid, with the addition amount being 11% of the total mass of the liquid.

[0085] (4) Clean energy conversion: The final feed solution of the second step was heated in a water bath at 38°C, and the reaction was carried out for 2.2 hours under the alternating light and dark conditions, with 60 seconds of light protection for every 5 minutes of light exposure. After the reaction was completed, 15 FPU / g of cellulase was added to the feed solution under light-protected conditions, and the mixture was fully mixed. The enzymatic hydrolysis reaction was carried out in a constant temperature shaking incubator (180 r / min) at 42°C for 3 hours. Then, 0.3% of the mass of yeast relative to the absolute dry agricultural and forestry waste was added to the liquid, and after heating in a water bath at 42°C for 1.5 hours, the water bath temperature was increased to 88°C, and the reaction was continued for 2.5 hours; after the reaction was completed, the temperature was lowered to 42°C, and 0.25% of the mass of yeast relative to the absolute dry agricultural and forestry waste was added to the solution, and after the reaction was carried out for 1.3 hours, the water bath temperature was increased to 88°C again, and the reaction was carried out for 3.5 hours; after the reaction was completed, the temperature was further lowered to 42°C, and 0.3% of the mass of yeast relative to the absolute dry agricultural and forestry waste was added to the solution, and after the reaction was carried out for 3 hours, the ethanol was recovered under reduced pressure, the catalyst was separated, and the biodiesel and by-product glycerol were recovered.

[0086] The above method realizes the resource utilization and reduction of various waste biomass at the same time through self-made multifunctional catalysts and appropriate regulation of experimental conditions at each stage, and improves enzyme activity, reduces enzyme dosage, and saves costs in the process; the intermediate product is transferred away in time because it participates in the next reaction, which improves the reaction kinetics in the positive direction, and significantly improves the final clean fuel conversion rate. The present invention fully considers the composition characteristics and physicochemical properties of residual sludge, agricultural and forestry waste, livestock and poultry manure, and catering waste. Through appropriate mixing, timely addition of additives, and flexible changes in reaction conditions, it simultaneously realizes efficient energy conversion of multi-source biomass, and has the characteristics of unique novelty, economic efficiency, etc.

Claims

1. A method for converting multi-source waste biomass into clean energy, characterized in that: The method comprises the following steps: (1) Preparation of catalyst: soak the gasified slag in a hydrofluoric acid solution, transfer the gasified filter residue to a HNO3 solution after sealed stirring, and conduct a water bath heating reaction. After the reaction is completed, filter the filter residue, add the filter residue to a solvent, and then add nano-cobalt, ammonia water and tetraethoxysilane to the liquid in sequence, stir and react to obtain catalyst A; add catalyst A to the solvent, and add n-butyl titanate dropwise, dry the liquid, roast the dried material and cool it to room temperature to obtain catalyst B; (2) Mixing of waste biomass from multiple sources: Mixing waste biomass from multiple sources by taking residual sludge, livestock and poultry manure, absolutely dry agricultural and forestry waste, and restaurant waste, immersing the biomass in deionized water and adding the above-mentioned catalysts A and B; (3) Clean energy conversion: The above reactants are heated in a water bath and the reaction is carried out under alternating light. After the reaction is completed, cellulase is added to the feed liquid under light-proof conditions to carry out enzymatic hydrolysis, and then yeast is added to the feed liquid in batches to carry out the reaction. After the reaction is completed, the ethanol is recovered by reducing the pressure, the catalyst is separated, and the biodiesel and the by-product glycerol are recovered; The specific process of the multi-source biomass mixing in step (2) is as follows: crush the agricultural and forestry waste through a 30-50 mesh sieve, then add 5.5-8.3% by mass of catalyst B to the agricultural and forestry waste, and immerse the two together in deionized water, stirring and irradiating with sunlight for 0.8-1.5 hours; then add the prepared residual sludge and livestock and poultry manure to the feed liquid, stirring and irradiating with sunlight for 30-50 minutes; then continue to add catering waste to the feed liquid, and at the same time add catalyst A to the feed liquid, the addition amount is 5-11% of the total mass of the feed liquid; The specific steps of adding yeast to the slurry in batches for reaction in step (3) are as follows: first, adding 0.1-0.3% of the mass of the absolute dry agricultural and forestry waste to the yeast, reacting in a water bath at 35-42°C for 1-1.5 hours, then raising the water bath temperature to 65-88°C, and continuing the reaction for 1-2.5 hours; after the reaction is completed, lowering the temperature to 35-42°C, and then adding 0.08-0.25% of the mass of the absolute dry agricultural and forestry waste to the solution, reacting for 1-1.3 hours, and then raising the water bath temperature to 65-88°C again, and reacting for 3-3.5 hours; after the reaction is completed, lowering the temperature to 35-42°C again, and adding 0.15-0.3% of the mass of the absolute dry agricultural and forestry waste to the solution, reacting for 2-3 hours, and recovering ethanol under reduced pressure, separating the catalyst, and recovering biodiesel and by-product glycerol.

2. The method for converting multi-source waste biomass into clean energy according to claim 1, characterized in that: The temperature during the sealed stirring in step (1) is 40-45°C, and the stirring time is 20-25 min; the temperature of the water bath heating reaction is 66-73°C, and the reaction time is 0.5-0.8 h.

3. The method for converting multi-source waste biomass into clean energy according to claim 1, characterized in that: The mass fraction of the nano-cobalt relative to the gasified slag in step (1) is 0.12-0.15%.

4. The method for converting multi-source waste biomass into clean energy according to claim 1, characterized in that: In step (1), the solid-liquid mass ratio of the catalyst A after adding the solvent is 1:5-8; after adding n-butyl titanate, the reaction is continued for 3-3.8 hours.

5. The method for converting multi-source waste biomass into clean energy according to claim 1, characterized in that: The drying temperature in step (1) is 50-55°C, the roasting temperature is 500-535°C, and the roasting time is 3-4.5h.

6. The method for converting multi-source waste biomass into clean energy according to claim 1, characterized in that: The composition of the multi-source biomass in step (2) and the mass fraction of each component are: residual sludge 45-64%, livestock and poultry manure 16-9%, dry agricultural and forestry waste 28-20% and catering waste 11-7%.

7. The method for converting multi-source waste biomass into clean energy according to claim 1, characterized in that: The water bath heating temperature in step (3) is 35-38° C., the alternating illumination is 5 minutes of illumination followed by 30-60 seconds of dark avoidance, and the alternating illumination time is 0.5-2.2 hours.

8. The method for converting multi-source waste biomass into clean energy according to claim 1, characterized in that: The enzymatic hydrolysis reaction in step (3) is carried out in a constant temperature shaking incubator at a rotation speed of 150-180 r / min, a temperature of 35-42°C, and a reaction time of 2.5-3 h.

Images