A biological enzyme catalyst, a preparation method and application thereof

Abstract

The application discloses a kind of biological enzyme catalyst and its preparation method and application, belong to biological catalysis and energy-saving environmental protection technical field, the biological enzyme catalyst is composed of composite biological enzyme 15~35 parts, non-ionic surfactant 3~12 parts, enzyme stabilizer 1~8 parts and deionized water 45~80 parts;Composite biological enzyme is compounded by lipase, cellulase, laccase and catalase according to enzyme activity unit proportion;The viscosity of catalyst is 5~25 mPa·s at 25 DEG C, and pH is 6.0~8.5, preparation method adopts low-temperature step-by-step mixing process, enzyme liquid is mixed in turn, stabilizer solution is added, and surfactant is added dropwise, and homogeneous filtration is obtained after brown transparent liquid, when application, catalyst is added to industrial fuel oil according to 0.03%~0.8% of oil quality, after mixing activation, it is sent into combustion equipment, the application realizes fuel oil molecule enzymatic micro-cracking and chemical rearrangement by the synergistic effect of four enzymes, promotes complete combustion, achieves the purpose of energy saving, reduces and discharges, it is simple and easy to operate and does not need to change existing combustion system.

Description

Technical Field

[0001] This invention relates to the fields of biocatalysis and industrial energy conservation and environmental protection, specifically to a bio-enzyme catalyst, a method for preparing the catalyst, and the application of the catalyst in industrial oil combustion treatment, applicable to energy-saving and emission-reduction operation of industrial boilers, kilns, diesel generator sets, marine engines, and various fuel burners. Background Technology

[0002] Bioenzymes, as a class of highly efficient biocatalysts, can significantly lower the activation energy of chemical reactions at room temperature and pressure, enabling specific chemical reactions to be completed at extremely high speeds. The production process of enzymes involves microorganisms initiating gene secretion of enzyme groups when targeting a specific substrate. Enzymes can lower the energy barrier required for biochemical reactions, allowing specific chemical reactions to occur at a rate of one biochemical reaction per millionth of a second, without requiring high temperature and pressure conditions, and to be completed rapidly. Therefore, enzymes possess characteristics of high catalytic efficiency, mild reaction conditions, and strong specificity, and are currently receiving significant attention from various industries.

[0003] In the field of industrial combustion, the combustion process of fuel oil (such as diesel, heavy oil, fuel oil, etc.) is essentially a series of complex oxidation reactions. Complete combustion requires sufficient oxygen. In the design of various combustion equipment, the supply of air is considered from a macroscopic perspective. However, at the microscopic level, insufficient oxygen supply often occurs during combustion, leading to incomplete combustion and the generation of large amounts of pollutants such as sulfur oxides (SOx), nitrogen oxides (NOx), and particulate matter. This not only wastes energy but also causes serious environmental pollution.

[0004] Traditional solutions often focus on improving the burner structure or adding exhaust gas treatment devices. These methods involve large investments, high maintenance costs, and often require modifications to existing equipment. Summary of the Invention

[0005] The purpose of this invention is to provide a bio-enzyme catalyst that, through the synergistic action of lipase, cellulase, laccase and catalase, performs micro-cracking, isomerization and chemical rearrangement of fuel molecules at room temperature, thereby promoting complete combustion.

[0006] Another objective of this invention is to provide a method for preparing the catalyst, which employs a low-temperature stepwise mixing process to effectively maintain the activity of the multi-enzyme system and obtain a uniform and stable liquid catalyst product.

[0007] Another objective of this invention is to provide a method for applying the catalyst in industrial oil combustion treatment, specifying the addition ratio, mixing conditions, activation parameters, etc., to achieve seamless integration with existing oil supply systems and achieve significant oil saving and emission reduction effects.

[0008] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: In a first aspect, the present invention provides a bio-enzyme catalyst, comprising, by weight, 15-35 parts of a composite bio-enzyme, 3-12 parts of a nonionic surfactant, 1-8 parts of an enzyme stabilizer, and 45-80 parts of deionized water. The composite bio-enzyme comprises lipase, cellulase, laccase, and catalase, with an enzyme activity unit ratio of (2-5):(1-3):(1-4):(1-2). The catalyst is prepared by a method including the following steps: mixing the enzyme solutions at 10-20°C, adding a pre-prepared stabilizer solution, then adding the nonionic surfactant dropwise, homogenizing, and filtering to obtain the catalyst. The resulting catalyst has a viscosity of 5-25 mPa·s at 25°C, a pH value of 6.0-8.5, and is a transparent liquid. Preferably, the nonionic surfactant is at least one of polyoxyethylene sorbitan monooleate, alkylphenol polyoxyethylene ether, and coconut oil fatty acid diethanolamide; the enzyme stabilizer is at least one of trehalose, glycerol, sorbitol, and polyethylene glycol 400.

[0009] Preferably, the ratio of enzyme activity units of the composite bioenzyme is lipase: cellulase: laccase: catalase = 3.5: 2: 2.5: 1.2.

[0010] Preferably, the bio-enzyme catalyst has a viscosity of 8~20 mPa·s at 25°C and a pH value of 6.5~7.8; the single enzyme activity of the lipase solution, cellulase solution, laccase solution and catalase solution is not less than 5000 U / mL.

[0011] Secondly, the present invention provides a method for preparing the catalyst, the specific steps of which are: Step S1: Under aseptic conditions, add lipase solution, cellulase solution, laccase solution and catalase solution to the mixing tank in the ratio of enzyme activity units (2~5):(1~3):(1~4):(1~2), control the temperature at 10~20℃, and stir at 80~150 rpm for 10~20 minutes to obtain a compound enzyme mixture. Step S2: Dissolve the enzyme stabilizer in a portion of deionized water to prepare a stabilizer solution with a mass concentration of 15% to 35%, and slowly add it to the complex enzyme mixture in step S1, and continue stirring for 15 to 30 minutes. Step S3: Keep the temperature at 10~20℃, add the nonionic surfactant dropwise, adjust the stirring speed to 60~100 rpm, and continue stirring for 20~40 minutes until the system is homogeneous and transparent; Step S4: Add the remaining deionized water to the target weight, continue stirring at 60-80 rpm for 10-15 minutes, let stand to defoam, and then filter through a 0.45μm filter membrane to obtain the bio-enzyme catalyst.

[0012] Thirdly, the present invention provides a method for applying the catalyst in the combustion treatment of industrial oil products, comprising the following steps: Step S1: Add the bio-enzyme catalyst to the fuel to be treated at a ratio of 0.03% to 0.8% of the industrial oil mass; Step S2: Mix the bio-enzyme catalyst evenly in the fuel at a temperature of 10℃~45℃ for 10~60 minutes by mechanical stirring, pump circulation or static mixer; Step S3: Let the mixed fuel stand for 15-120 minutes to activate it, so that the complex bio-enzyme in the bio-enzyme catalyst can carry out enzymatic micro-cleavage and chemical rearrangement reaction on the fuel molecules. Step S4: The activated fuel is fed into the combustion equipment for combustion.

[0013] Preferably, the industrial oil is at least one of diesel oil, heavy oil, fuel oil, marine fuel oil, or boiler oil.

[0014] Preferably, the proportion of the bio-enzyme catalyst added in step S1 is 0.05% to 0.3% of the oil mass.

[0015] Preferably, the settling and activation time in step S3 is 30 to 90 minutes, and the fuel temperature is maintained at 20°C to 40°C during the settling process.

[0016] Preferably, the method further includes injecting the bio-enzyme catalyst into the fuel pipeline in proportion by an online metering pump before the fuel enters the combustion equipment, and then directly supplying it for combustion after mixing by a static mixer; the combustion equipment is an industrial boiler, kiln, diesel generator set, marine engine or fuel burner.

[0017] Enzyme-catalyzed reaction mechanism: After the bio-enzyme catalyst enters the fuel, lipase catalyzes the hydrolysis of ester bonds and transesterification, generating oxygen-containing active intermediates at the oil-water micro-interface; cellulase assists in the degradation of gums and macromolecular impurities that may be present in the fuel, improving fuel fluidity; laccase, as a multi-copper oxidase, catalyzes the oxidative transformation of aromatic compounds and nitrogen / sulfur-containing compounds, promoting the conversion of sulfur-containing compounds to a stable oxidation state (SO4²⁻), and nitrogen-containing compounds to form a stable state via the NH3→NO→NO2→NO3 pathway; catalase, in conjunction with laccase, decomposes trace amounts of hydrogen peroxide and generates oxygen-rich free radicals, enhancing overall oxidation activity. Through the synergistic action of these four enzymes, fuel molecules undergo micro-cracking and chemical rearrangement, long-chain hydrocarbons break down to produce more branched-chain hydrocarbons and cycloalkanes, and some dehydrogenates generate aromatics, thereby significantly improving the combustion characteristics of the fuel. In the presence of water molecules, a water-gas reaction (C+H2O→CO+H2) can also occur during high-temperature combustion, producing hydrogen (H2), which is a clean fuel, making combustion more complete and increasing energy efficiency.

[0018] The second aspect of this invention provides a method for preparing the catalyst, employing a low-temperature stepwise mixing process: first, four enzyme solutions are mixed at 10-20°C, then a stabilizer solution is added, and finally, a surfactant is added dropwise. The key to this process is that the low-temperature operation effectively protects enzyme activity; the stabilizer is pre-dissolved and added slowly, which non-specifically protects the liquid enzyme protein from denaturation and inactivation [reference:2]; and the surfactant is added dropwise at the end, ensuring sufficient dispersion at the oil-water interface without damaging the enzyme structure. Through the above stepwise control, a brown transparent liquid catalyst with moderate viscosity (5-25 mPa·s) and neutral pH (6.0-8.5) is obtained.

[0019] The third aspect of this invention provides a method for applying the catalyst in industrial oil combustion treatment, specifying key operating parameters such as the addition ratio (0.03%~0.8%), mixing temperature (10~45℃), and activation time (15~120 minutes), which can be seamlessly integrated with existing oil supply systems.

[0020] Compared with the prior art, the present invention has the following beneficial effects: 1. Significant fuel saving effect: Actual tests on industrial boilers and diesel engines show a fuel saving rate of 3% to 12%, directly reducing fuel costs.

[0021] 2. Outstanding emission reduction capabilities: SOx emissions are reduced by 20% to 60%, NOx emissions by 20% to 55%, while reducing particulate matter and CO emissions, fundamentally alleviating combustion pollution.

[0022] 3. Easy to use and operate: No modifications are required to any existing combustion system equipment. Simply add the catalyst in proportion and mix and activate it before the fuel enters the combustion equipment. It can be used for intermittent batch processing or for continuous online addition via a metering pump.

[0023] 4. Equipment protection benefits: Complete combustion reduces the generation of acidic substances (sulfuric acid and nitric acid precursors), slows down low-temperature corrosion of the combustion chamber and tail flue; reduced carbon deposits extend the equipment maintenance cycle.

[0024] 5. Green and environmentally friendly: The enzyme catalyst itself is biodegradable, and the combustion process does not produce secondary pollution, which meets the requirements of green chemistry.

[0025] 6. Good catalyst stability: Through low-temperature stepwise mixing and the use of specific stabilizers, the enzyme activity retention rate is high, and the product can have a shelf life of more than 12 months at room temperature. Attached Figure Description

[0026] Figure 1 This is a flowchart illustrating the preparation process of the bio-enzyme catalyst of this invention. Figure 2This is a flowchart illustrating the application of the bio-enzyme catalyst of the present invention in the combustion treatment of industrial oil products. Detailed Implementation

[0027] The present invention will now be described in further detail with reference to the accompanying drawings, but the scope of protection of the present invention is not limited to these embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0028] Example 1, Catalyst formulation: 25 parts by weight of compound biological enzyme, wherein lipase solution (enzyme activity 8000 U / mL), cellulase solution (6000 U / mL), laccase solution (7000 U / mL), and catalase solution (5200 U / mL) are prepared in an enzyme activity unit ratio of 3.5:2:2.5:1.2; 8 parts of Tween-80; 3 parts of trehalose; 2 parts of glycerol; and 62 parts of deionized water.

[0029] like Figure 1 As shown, the catalyst preparation process is as follows: In a sterile room at 15℃, the four enzyme solutions mentioned above were added to a mixing tank in proportion and stirred at 120 rpm for 15 minutes; trehalose and glycerol were dissolved in 25 parts of deionized water to prepare a stabilizer solution (concentration approximately 16.7%), which was slowly added to the mixed enzyme solution under stirring, and stirring continued for 20 minutes; while maintaining 15℃, Tween-80 was added dropwise, and the stirring speed was adjusted to 80 rpm, and stirring continued for 30 minutes until the system became homogeneous and transparent; the remaining deionized water was added to a total volume of 100 parts, stirred at 70 rpm for 12 minutes, allowed to stand for defoaming for 2 hours, and filtered through a 0.45 μm polypropylene filter membrane to obtain a brown transparent liquid catalyst. Tests: viscosity at 25℃ 18 mPa·s, pH 7.2.

[0030] like Figure 2 As shown, the application of bio-enzyme catalysts in the combustion treatment of industrial oil products involves adding the bio-enzyme catalyst to the fuel oil to be treated at a ratio of 0.03% to 0.8% of the industrial oil weight. The mixture is then stirred for 10 to 60 minutes at a temperature of 10℃ to 45℃ using mechanical stirring, pump circulation, or a static mixer to ensure uniform dispersion of the bio-enzyme catalyst in the fuel oil. The mixed fuel oil is then allowed to stand for activation for 15 to 120 minutes, allowing the composite bio-enzymes in the catalyst to perform enzymatic micro-cleavage and chemical rearrangement reactions on the fuel oil molecules. The activated fuel oil is then fed into a combustion device for combustion. After 72 hours of continuous operation, compared with the blank control without catalyst, the average fuel saving rate was 8.5%, SOx emission concentration decreased by 46%, NOx emission concentration decreased by 39%, boiler flue gas temperature decreased by approximately 12℃, and furnace carbon deposits were significantly reduced.

[0031] Example 2, catalyst formulation: 30 parts by weight of compound bio-enzyme (lipase:cellulase:laccase:catalase enzyme activity ratio = 4:1.5:3:1); 6 parts of alkylphenol polyoxyethylene ether (OP-10); 4 parts of sorbitol; 59 parts of deionized water.

[0032] Preparation process: At 18℃, the enzyme solutions were mixed and stirred at 100 rpm for 18 minutes; sorbitol and PEG400 were dissolved in 20 parts of deionized water to prepare a stabilizer solution, which was slowly added and stirred for 25 minutes; OP-10 was added dropwise and stirred at 70 rpm for 35 minutes until clear; deionized water was added to make up the volume, and the mixture was stirred at 65 rpm for 15 minutes. After standing to remove foam, it was filtered through a 0.45 μm filter. The catalyst viscosity was 22 mPa·s, and the pH was 7.5.

[0033] Application Testing: Catalyst was added at a ratio of 0.15% to 180cSt marine heavy fuel oil, the oil temperature was maintained at 35℃, and the mixture was circulated and mixed for 40 minutes using a cargo oil pump. After standing and activation for 90 minutes, it was applied to a 6500kW marine main engine. After 240 hours of continuous operation, the average fuel saving rate was 6.8%, SOx emissions were reduced by 53%, visible black smoke on the chimney was significantly reduced, carbon deposits in the cylinder were significantly reduced, and the piston ring wear rate decreased.

[0034] Example 3, Catalyst formulation: 25 parts by weight of compound biological enzyme, wherein lipase solution (enzyme activity 8000 U / mL), cellulase solution (6000 U / mL), laccase solution (7000 U / mL), and catalase solution (5200 U / mL) are prepared in an enzyme activity unit ratio of 3.5:2:2.5:1.2; 8 parts of Tween-80; 3 parts of trehalose; 2 parts of glycerol; and 62 parts of deionized water.

[0035] Preparation process: In a sterile room at 15℃, the four enzyme solutions mentioned above were added to the mixing tank in proportion and stirred at 120 rpm for 15 minutes. Trehalose and glycerol were dissolved in 25 parts of deionized water to prepare a stabilizer solution (concentration approximately 16.7%), which was slowly added to the mixed enzyme solution while stirring, and stirring was continued for 20 minutes. While maintaining 15℃, Tween-80 was added dropwise, and the stirring speed was adjusted to 80 rpm, and stirring was continued for 30 minutes until the system became homogeneous and transparent. The remaining deionized water was added to a total volume of 100 parts, stirred at 70 rpm for 12 minutes, allowed to stand for defoaming for 2 hours, and filtered through a 0.45 μm polypropylene filter membrane to obtain a brown transparent liquid catalyst. Testing: Viscosity at 25℃: 18 mPa·s; pH: 7.2.

[0036] Application method: Install a metering pump and a static mixer on the heavy oil supply pipeline of an industrial kiln. Set the metering pump to continuously inject the catalyst at a ratio of 0.08% of the fuel oil flow rate, and after online mixing by the static mixer, supply it directly to the burner.

[0037] Application testing: After 30 days of continuous operation on a 2t / h aluminum melting kiln, compared with the same period without catalyst, the average oil saving rate was 7.2%, NOx emissions were reduced by 48%, and SOx emissions were reduced by 41%. Coking on the surface of the kiln refractory material was significantly reduced, and the furnace cleaning cycle was extended from the original 15 days to more than 30 days, significantly reducing maintenance costs.

[0038] Example 4, catalyst formulation: 20 parts of compound bio-enzyme (enzyme activity ratio 2.5:3:1.5:2); 10 parts of coconut oil fatty acid diethanolamide; 2 parts of trehalose; 2 parts of glycerol; 66 parts of deionized water.

[0039] Preparation process: The enzyme solution was mixed at 150 rpm for 12 minutes at 12℃; a 25% stabilizer solution was added and stirred for 30 minutes; a surfactant was added dropwise and stirred at 60 rpm for 40 minutes; water was added and stirred at 80 rpm for 10 minutes, then filtered through a 0.45 μm filter. The catalyst viscosity was 15 mPa·s, and the pH was 6.9.

[0040] Application testing: Added to boiler fuel oil at a ratio of 0.1%, stirred at 30℃ for 20 minutes, activated for 45 minutes, and then used in industrial boilers. After 168 hours of continuous operation, the fuel oil saving rate was 9.2%, NOx was reduced by 55%, and SOx was reduced by 48%.

[0041] Comparative Example 1 used a single lipase (25 portions, enzyme activity 8000 U / mL) instead of the composite biological enzyme, with the remaining components and preparation process the same as in Example 1. Under the same boiler conditions, the oil saving rate was only 2.1%, SOx decreased by 12%, and NOx decreased by 8%. This indicates that the synergistic effect of the four enzymes is key to achieving efficient oil saving and emission reduction.

[0042] Comparative Example 2 used the same formulation as Example 1, but the preparation process was changed to mixing all components at room temperature (25°C) in a single step. The resulting catalyst had a viscosity of 35 mPa·s and contained trace amounts of precipitate. Under the same application conditions, the oil saving rate was only 4.3%, SOx was reduced by 28%, and NOx was reduced by 21%. This indicates that the low-temperature stepwise mixing process is crucial for maintaining enzyme activity and product stability.

[0043] The above examples and comparative examples fully demonstrate the synergistic advantages of the catalyst composition, preparation method, and application method of the present invention. Through the rational combination of four enzymes, the low-temperature stepwise preparation process, and standardized application operations, the present invention achieves significant energy-saving and emission-reduction effects in industrial oil combustion treatment. Furthermore, it is simple to operate, highly adaptable, and has good prospects for industrial promotion.

[0044] The catalyst raw materials for this invention are all commercially available industrial-grade products, and the preparation conditions are mild, requiring no special equipment. The application method can be flexibly adopted in intermittent or continuous online manner, and it is fully compatible with existing fuel supply systems. This technology is applicable to various industrial boilers, kilns, ships, and generator sets, and can be rapidly deployed without modifying equipment, offering significant economic and environmental benefits and promising broad industrialization prospects.

[0045] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A bio-enzyme catalyst, characterized in that, By weight, it consists of the following components: 15-35 parts of compound bio-enzyme; 3-12 parts of nonionic surfactant; 1-8 parts enzyme stabilizer; 45-80 parts deionized water; The complex bio-enzyme is composed of lipase, cellulase, laccase and catalase, and its complex bio-enzyme activity unit ratio is (2~5):(1~3):(1~4):(1~2).

2. The bio-enzyme catalyst according to claim 1, characterized in that: The nonionic surfactant is at least one of polyoxyethylene sorbitan monooleate, alkylphenol polyoxyethylene ether, and coconut oil fatty acid diethanolamide; the enzyme stabilizer is at least one of trehalose, glycerol, sorbitol, and polyethylene glycol 400.

3. The bio-enzyme catalyst according to claim 1, characterized in that: The ratio of enzyme activity units of the composite bioenzyme is lipase: cellulase: laccase: catalase = 3.5: 2: 2.5: 1.

2.

4. The bio-enzyme catalyst according to claim 1, characterized in that: The bio-enzyme catalyst has a viscosity of 8~20 mPa·s at 25℃ and a pH value of 6.5~7.8; the single enzyme activity of the lipase solution, cellulase solution, laccase solution and catalase solution is not less than 5000 U / mL.

5. A method for preparing a bio-enzyme catalyst as described in claim 1, characterized in that, Includes the following steps: Step S1: Under aseptic conditions, add lipase solution, cellulase solution, laccase solution and catalase solution to the mixing tank in the ratio of enzyme activity units (2~5):(1~3):(1~4):(1~2), control the temperature at 10~20℃, and stir at 80~150 rpm for 10~20 minutes to obtain a compound enzyme mixture. Step S2: Dissolve the enzyme stabilizer in a portion of deionized water to prepare a stabilizer solution with a mass concentration of 15% to 35%, and slowly add it to the complex enzyme mixture in step S1, and continue stirring for 15 to 30 minutes. Step S3: Keep the temperature at 10~20℃, add the nonionic surfactant dropwise, adjust the stirring speed to 60~100 rpm, and continue stirring for 20~40 minutes until the system is homogeneous and transparent; Step S4: Add the remaining deionized water to the target weight, continue stirring at 60-80 rpm for 10-15 minutes, let stand to defoam, and then filter through a 0.45μm filter membrane to obtain the bio-enzyme catalyst.

6. A method for applying a bio-enzyme catalyst in the combustion treatment of industrial oil products, characterized in that, The bio-enzyme catalyst is the bio-enzyme catalyst according to claim 1; the application method includes the following steps: Step S1: Add the bio-enzyme catalyst to the fuel to be treated at a ratio of 0.03% to 0.8% of the industrial oil mass; Step S2: Mix the bio-enzyme catalyst evenly in the fuel at a temperature of 10℃~45℃ for 10~60 minutes by mechanical stirring, pump circulation or static mixer; Step S3: Let the mixed fuel stand for 15-120 minutes to activate it, so that the complex bio-enzyme in the bio-enzyme catalyst can carry out enzymatic micro-cleavage and chemical rearrangement reaction on the fuel molecules. Step S4: The activated fuel is fed into the combustion equipment for combustion.

7. The application method according to claim 6, characterized in that: The industrial oil product is at least one of diesel oil, heavy oil, fuel oil, marine fuel oil, or boiler oil.

8. The application method according to claim 6, characterized in that: The proportion of the bio-enzyme catalyst added in step S1 is 0.05% to 0.3% of the oil mass.

9. The application method according to claim 6, characterized in that: In step S3, the settling and activation time is 30 to 90 minutes, and the fuel temperature is maintained at 20°C to 40°C during the settling process.

10. The application method according to claim 6, characterized in that: The method further includes injecting the bio-enzyme catalyst into the fuel pipeline in proportion by an online metering pump before the fuel enters the combustion equipment, and then directly supplying it for combustion after mixing by a static mixer; the combustion equipment is an industrial boiler, kiln, diesel generator set, marine engine or fuel burner.

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