Method for degrading ozone through microencapsulation, ozone digestion solution and device

Abstract

The invention belongs to the technical field of environmental protection, and provides a method for degrading ozone by microencapsulation, an ozone digestion solution and a device, and efficient digestion corresponding to three ozone concentrations is realized by compounding and designing the digestion solution and utilizing the instant generation function of spray. The digestion solution comprises an emulsified bubble solution and an ozone degradation solution; the spraying device comprises a tank body, an emulsified bubble solution storage tank, a digestion solution storage tank, a gear regulator, a nozzle and a high-pressure pipeline; the emulsified film bubble liquid storage tank and the ozone digestion liquid storage tank are communicated with the nozzle through the high-pressure pipeline. The ozone digestion mode is efficient, economical, high in pertinence, non-toxic and non-destructive, the spraying device is compact and reasonable in structural design, all the parts are sequentially connected according to the treatment process through modular layout to form a continuous and efficient treatment system, meanwhile, key parts are designed in a sealed mode to prevent liquid from being splashed out, meanwhile, visual monitoring means such as sensors are arranged, and the treatment effect is good. Safe, stable and efficient operation of the sprayer is ensured.

Description

Technical Field

[0001] The invention belongs to the technical field of environmental protection, and in particular relates to a method for microencapsulation of ozone degradation, an ozone decomposition solution and a device. Background Art

[0002] Ozone (O 3 ) as oxygen (O 2 ) is widely used in industrial disinfection, water treatment and other fields due to its strong oxidizing property, excellent disinfection and sterilization and preservation effect. However, ozone in the near-ground atmosphere has become a harmful gas, which has a negative impact on human health, crop growth and ecosystem balance. The development of effective ozone removal technology is crucial for environmental protection and human health.

[0003] Controlling the emission of precursors and spraying bio-enzymes to reduce ozone are the main methods of atmospheric ozone control in recent years. Data on atmospheric ozone concentrations are collected through national environmental monitoring. After an alarm is issued, fog cannons equipped by environmental protection departments conduct large-scale road cruises and spray large amounts of bio-enzyme solutions to eliminate ozone locally. This method has the disadvantages of inaccurate positioning of polluted areas and easy inactivation of bio-enzymes, resulting in huge waste. For the elimination of indoor ozone, only adsorption, ultraviolet rays and other methods are used in air purifiers to coordinate treatment with other pollutants. No efficient and specific methods have been reported so far.

[0004] Existing ozone removal technologies have many shortcomings:

[0005] Methods for removing ozone include chemical absorption, catalytic decomposition, thermal decomposition, etc. Catalytic technology uses transition metal (such as manganese, copper, etc.) oxides or carbon-based (such as activated carbon, graphene, etc.) to decompose ozone molecules under certain temperature and humidity conditions. For example, using MnO 2 / Al 2 O 3 Catalyst promotes O 3 Decomposition, the activity of the catalyst is affected by environmental factors such as temperature and humidity, and there is a gradual deactivation during use (Fe 2 +→Fe 3 + conversion rate>80% failure) is a common phenomenon, and the catalyst should be replenished or replaced regularly (1kg O 3 Consumption: 0.8 kg FeSO 4), resulting in rising costs, non-renewable catalysts, and solid waste disposal costs; the method of using photocatalysts to accelerate ozone decomposition requires specific equipment and light sources, which increases equipment investment and limits application scenarios, and uses UV photolysis to produce free radicals to decompose ozone, which has low efficiency and high energy consumption; chemical absorption technology is a method of converting ozone into harmless substances by promoting chemical reactions with absorbents (certain reducing agents, alkali solutions, etc.). It is generally aimed at high-concentration industrial environments and often has problems such as high energy consumption, complex operation, and easy corrosion. The treatment efficiency is restricted by many factors such as the type and concentration of the absorbent and reaction conditions, and the efficiency is limited. Other harmful substances may be produced in the process, which increases the treatment process and cost.

[0006] The use of the above-mentioned catalysts, photocatalysts, chemical absorption and other methods is only seen in scenarios with high initial ozone concentrations. The ozone concentrations in the ambient atmosphere and indoor air are low, and their use is limited. Summary of the invention

[0007] The present invention provides a method for microencapsulation of ozone degradation, an ozone decomposition solution and a device to solve the problems in the prior art. The technical solution adopted by the present invention is:

[0008] A method for microencapsulating and degrading ozone molecules, wherein the ozone decomposition liquid is sprayed, and the ozone decomposition liquid is microencapsulated by membrane bubbles when the spraying occurs, thereby achieving molecular decomposition of ozone within three different concentration ranges.

[0009] An ozone decomposition liquid, comprising an emulsified membrane bubble liquid and an ozone degradation liquid;

[0010] The emulsified membrane bubble liquid comprises 0.8-1.5% of polyglycerol fatty acid ester, 0.3-0.6% of lecithin nanoliposome and 0.2-0.4% of hydroxypropyl methylcellulose. The emulsified membrane bubble liquid promotes the droplets to spontaneously form microcapsule structures and delays the rupture time of the microcapsules.

[0011] Further, the ozone degradation solution includes a redox solution and a biological enzyme solution;

[0012] The redox solution includes 2-5% L-ascorbic acid, 0.5-1.2% ammonium ferric citrate, 0.3-0.8% sodium thiosulfate, and 10-15% glycerol;

[0013] The biological enzyme solution comprises recombinant catalase with an enzyme activity of 5000-8000 U / mL, superoxide dismutase with an enzyme activity of 2000-4000 U / mL, laccase with an enzyme activity of 1000-2000 U / mL, and trehalose with an activity of 3-5%.

[0014] Furthermore, the preparation of the emulsified film bubble liquid includes:

[0015] Preparation of liposomes: 400 mg of lecithin and 100 mg of cholesterol were dissolved in chloroform, and 10 mL of PBS buffer was added after rotary evaporation to form a film, and then ultrasonic treatment was performed for 15 min to obtain nanoliposomes;

[0016] Preparation of oil phase: Dissolve 1.2 g of PGPR in 60°C soybean oil, add liposome suspension, and homogenize at low speed for 10 min to form oil phase;

[0017] Preparation of aqueous phase: Soak HPMC in deionized water for 24 hours, heat and stir until completely dissolved, and add Tween-80 to form a transparent colloidal solution;

[0018] Synthesis of emulsified membrane foam liquid: The oil phase and the water phase were mixed in a volume ratio of 3:7 and subjected to high-pressure homogenization to form a W / O / W double emulsion.

[0019] Furthermore, the redox solution was prepared by a gradient dissolution method: first, glycerol and deionized water were premixed at a ratio of 1:9, magnetically stirred, and ammonium ferric citrate, sodium thiosulfate, and L-ascorbic acid were added in sequence; the pH was adjusted to 4.5-5.0, and stored in the dark under nitrogen protection.

[0020] Furthermore, the preparation process of the biological enzyme solution is as follows: dissolve 4.5g of trehalose in 90ml of Tris-HCl buffer until it is completely transparent; add 0.5g of SOD freeze-dried powder, 0.625g of catalase, and 13.3g of laccase in sequence; use the reverse micelle encapsulation method to immobilize the enzyme molecules, ultrafiltration and concentration to 100ml, and store at 4°C away from light.

[0021] An ozone microencapsulation degradation spray device comprises a spray tank body 1, an emulsified film bubble liquid storage tank 2, a degradation liquid storage tank 3, an electric regulating valve 4, a fixing card 5, a gear regulating valve 6, a battery compartment 7, a high-pressure pipeline 8, a spray switch 9 and a nozzle 10;

[0022] The emulsion film bubble liquid storage tank 2 and the degradation liquid storage tank 3 are arranged in the sprayer tank body 1 , and the emulsion film bubble liquid storage tank 2 and the degradation liquid storage tank 3 are connected to the nozzle 10 through the high-pressure pipeline 8 .

[0023] Furthermore, the degradation liquid storage tank 3 stores ozone decomposition liquid, and the ozone decomposition liquid includes emulsified membrane bubble liquid and ozone degradation liquid; the emulsified membrane bubble liquid storage tank 2 stores emulsified membrane bubble liquid.

[0024] Furthermore, the degradation liquid storage tank 3 stores redox liquid and biological enzyme solution separately and independently, and controls and delivers them through the electric regulating valve 4 configured with the matching pipeline, so as to realize the three ratios of ozone degradation liquid, redox liquid and biological enzyme solution to meet the degradation of ozone in the corresponding concentration range.

[0025] Furthermore, the three volume ratios of the ozone degradation solution, the redox solution, and the biological enzyme solution are respectively:

[0026] When the ozone concentration range is 0-150ug / m 3 When, the ratio of emulsified membrane bubble liquid: redox liquid: biological enzyme is 5:1.5:1;

[0027] When the ozone concentration range is 150-300ug / m 3 When, the ratio of emulsified membrane bubble liquid: redox liquid: biological enzyme is 7:2.5:1;

[0028] When the ozone concentration range is 300-500ug / m 3 When the emulsified membrane bubble liquid: redox liquid: biological enzyme is 10:4:1.

[0029] The present invention has the following beneficial effects:

[0030] The ozone degradation liquid of the present invention comprises a redox solution and a biological enzyme solution, which are obtained by three-speed proportioning through a spray device. The main functional components in the redox solution are L-ascorbic acid and ammonium ferric citrate, which have the characteristics of efficient ozone degradation and non-toxicity, and sodium thiosulfate can quickly reduce residual intermediates, promote the forward reaction, and avoid secondary pollution. The biological enzyme solution is a (catalase / SOD / laccase) recombinant enzyme, which has the characteristics of efficient ozone degradation, strong specificity, and real-time decomposition of by-products, and trehalose can significantly improve the thermal stability of the enzyme.

[0031] The emulsified membrane bubble liquid described in the present invention is composed of polyglycerol fatty acid ester (PGPR) and lecithin nanoliposomes, which can form a nano-scale semipermeable membrane; the membrane bubble forms microcapsules to encapsulate ozone molecules and ozone digestion liquid, and hydroxypropyl methylcellulose has the effect of delaying the rupture time of microcapsules, so that the effective degradation time of ozone is extended from 2-5 seconds of traditional spray to 20-30 seconds. Through the three-level synergistic mechanism of "physical encapsulation-chemical degradation-enzyme degradation", the "active targeted elimination" of ozone is achieved, and the synergistic degradation efficiency reaches 98.7%. The final product is O 2 and H 2 O;

[0032] The present invention fills two specially formulated ozone degradation liquids into the upper and lower cabins of the degradation liquid storage tank respectively, and simultaneously prepares the emulsified membrane bubble liquid and fills it into the emulsified membrane bubble liquid storage tank; when the spray pressure valve is opened, the two degradation liquids are automatically proportioned into ozone digestion liquids of corresponding gears, and are sprayed out simultaneously with the emulsified membrane bubble liquid to form instant membrane bubble microcapsules, so as to achieve the capture and delayed encapsulation of ozone molecules and fully degrade the corresponding concentration of air ozone. The automatically proportioned "microencapsulated synergistic degradation system" achieves efficient and harmless targeted degradation of ozone through the three-level synergistic effect of physical encapsulation, chemical oxidation-reduction and biological enzyme catalysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a schematic diagram of the overall structure of the present invention. DETAILED DESCRIPTION

[0034] The following will be combined with the embodiments of the present invention Figure 1 , the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

[0035] like Figure 1 , an ozone microencapsulation degradation sprayer, comprising a sprayer tank body 1, an emulsified film bubble liquid storage tank 2, a digestion liquid storage tank 3, an electric regulating valve 4, a fixing card 5, a gear regulating valve 6, a battery compartment 7, a high-pressure pipeline 8, a spray pressure switch 9 and a nozzle 10;

[0036] The emulsion film bubble liquid storage tank 2 and the digestion liquid storage tank 3 are arranged in the sprayer tank body 1, and the emulsion film bubble liquid storage tank 2 and the digestion liquid storage tank 3 are connected to the nozzle 10 through the high-pressure pipeline 8 via the gear regulating valve 6.

[0037] The structural design of the present invention is compact and reasonable. By adopting a modular layout and connecting various parts in sequence according to the processing flow, a continuous and efficient processing system is formed to ensure the safe, stable and efficient operation of the sprayer.

[0038] The degradation liquid storage tank 3 stores redox liquid and biological enzyme solution separately and independently, and controls and delivers them through an electric regulating valve 4 configured with a matching pipeline, so as to achieve three ratios of ozone degradation liquid, redox liquid and biological enzyme solution to meet the degradation of ozone in the corresponding concentration range.

[0039] The present invention is based on the ozone concentration gradient, and achieves the optimal balance of ozone capture capacity-reaction rate-resource consumption by dynamically adjusting the ratio of emulsion, redox solution and biological enzyme. Therefore, the basic compounding scheme is set as follows: emulsion bubble liquid: degradation liquid = 2: 1 (volume ratio). The scheme is dominated by emulsion to ensure the sufficient number of microcapsules, and the degradation liquid maintains the minimum effective concentration of oxidant and enzyme (ascorbic acid ≥ 0.5%, enzyme activity ≥ 3000U / mL), which is characterized in that it not only ensures the basic degradation efficiency, but also reduces the waste of reagents in low-concentration ozone scenarios.

[0040] When the ozone concentration range is 0-150ug / m 3When the ozone concentration is low, the microcapsule coverage rate is guaranteed to be greater than 95%. On the basis of maintaining the degradation rate (≥90%), the amount of oxidant / enzyme is reduced to reduce the cost. Therefore, the emulsified membrane bubble liquid: redox liquid: biological enzyme (volume ratio) is 5:1.5:1; when the ozone concentration range is 150-300ug / m 3 At medium concentration, the capture efficiency and degradation efficiency should be balanced to improve the ozone capture capacity, prolong the microcapsule wrapping time, and moderately increase the proportion of oxidants to cope with the increase in ozone concentration and maintain the effectiveness of the enzyme reaction. Therefore, the emulsified membrane bubble liquid: redox liquid: biological enzyme (volume ratio) is 7:2.5:1, the ozone retention time is extended to 25 seconds, and the degradation rate is increased to 95%; when the ozone concentration range is 300-500ug / m 3 When the concentration is high, the microcapsule generation should be maximized to ensure the encapsulation ability and anti-ozone escape ability of high-concentration ozone, the oxidant concentration should be strengthened to achieve rapid digestion of high-concentration ozone, and the ratio of enzymes should be controlled well. Therefore, the emulsified membrane bubble liquid: redox liquid: biological enzyme (volume ratio) is 10:4:1, the peak degradation efficiency is as high as 98.7%, and the anti-ozone escape ability is increased by 3 times, which is suitable for emergency scenarios.

[0041] Therefore, the three volume ratios of the ozone degradation solution, the redox solution, and the biological enzyme solution of the present invention are respectively:

[0042] When the ozone concentration range is 0-150ug / m 3 When, the ratio of emulsified membrane bubble liquid: redox liquid: biological enzyme is 5:1.5:1;

[0043] When the ozone concentration range is 150-300ug / m 3 When, the ratio of emulsified membrane bubble liquid: redox liquid: biological enzyme is 7:2.5:1;

[0044] When the ozone concentration range is 300-500ug / m 3 When the emulsified membrane bubble liquid: redox liquid: biological enzyme is 10:4:1.

[0045] Furthermore, the high-pressure pipeline 8 is connected to the nozzle 10 via a spray pressure switch 9 .

[0046] Furthermore, the emulsion film bubble liquid storage tank 2 stores emulsion film bubble liquid, which comprises: 0.8-1.5% of polyglycerol fatty acid ester (PGPR); non-ionic surfactant, which promotes the droplets to spontaneously form a microcapsule structure by reducing the gas-liquid interfacial tension. A concentration lower than 0.8% cannot form a continuous film layer, and a concentration higher than 1.5% causes the emulsion viscosity to be too high, affecting the atomization performance; 0.3-0.6% of lecithin nanoliposomes, which are embedded in the PGPR film layer to form a "mosaic structure" to regulate the diffusion rate of ozone molecules. This concentration can make the liposome coverage rate on the PGPR film layer ≥70%; 0.2-0.4% of hydroxypropyl methylcellulose (HPMC), which can form a shear-thinning gel (viscosity 200-500mPa·s) in this concentration range, and the film thickness is linearly related to the concentration (0.1%≈1μm), delaying the microcapsule rupture time and prolonging the ozone residence.

[0047] Furthermore, the emulsified membrane bubble liquid preparation process includes: 1. Liposome preparation: 400 mg of lecithin and 100 mg of cholesterol (4:1) are dissolved in chloroform, and 10 mL of PBS buffer (pH 7.4) is added after rotary evaporation to form a film, and ultrasonic treatment is performed for 15 minutes to obtain nanoliposomes (DLS detection particle size 105±15 nm); 2. Oil phase preparation: 1.2 g of PGPR is dissolved in 60°C soybean oil (carrier phase), a liposome suspension (mass fraction 0.5%) is added, and low speed (5000 rpm) homogenization is performed for 10 minutes to form an oil phase; 3. Water phase preparation: HPMC is soaked in deionized water for 24 hours, heated (70°C) and stirred (500 rpm) until completely dissolved, and Tween-80 is added to form a transparent colloidal solution; 4. Emulsified membrane bubble liquid synthesis: the oil phase and the water phase are mixed in a volume ratio of 3:7, and a W / O / W double emulsion is formed by high-pressure homogenization (20 MPa, 3 cycles).

[0048] Furthermore, the digestion solution storage tank (3) stores redox solution and biological enzyme solution.

[0049] Furthermore, the mass fraction composition of the substances in the redox solution includes: L-ascorbic acid (vitamin C) 2-5%, the main reducing agent, 5% concentration can make O 3 When the droplet residence time is less than or equal to 30s, the conversion rate reaches 92%; ammonium ferric citrate 0.5-1.2%, electron transfer medium, this concentration range of Fe 3+ / Fe 2+ The ratio is stable at 3:1, and the electron transfer efficiency is the highest (≥80%); sodium thiosulfate 0.3-0.8%, auxiliary reducing agent, scavenging free radicals; glycerol (carrier) 10-15%, low temperature protective agent.

[0050] Furthermore, the redox solution was prepared by a gradient dissolution method: first, glycerol and deionized water were premixed at a ratio of 1:9, magnetic stirring (300 rpm), and ammonium ferric citrate, sodium thiosulfate, and L-ascorbic acid were added in sequence; the pH was adjusted to 4.5-5.0, and the mixture was stored in the dark under nitrogen protection;

[0051] Furthermore, the bio-enzyme solution includes 5000-8000U / mL of recombinant catalase, and the enzyme activity ≥5000U / mL can achieve real-time decomposition, decomposing the H generated by the reaction of the remaining ozone and water. 2 O 2 (Catalytic efficiency ≥ 99%); Superoxide dismutase (SOD) 2000-4000U / mL, which can effectively remove O 2 - Free radicals (half-life < 0.1s); Laccase 1000-2000U / mL, to match the degradation requirements of by-products (such as formaldehyde / formic acid); Trehalose (enzyme stabilizer) 3-5%, can significantly improve the thermal stability of the enzyme;

[0052] Furthermore, the preparation process of the biological enzyme solution is as follows: 4.5g of trehalose is dissolved in 90ml of Tris-HCl buffer (pH 7.0) until it is completely transparent; 0.5g of SOD freeze-dried powder (specific activity 4000U / mg), 0.625g of catalase (8000U / mg), and 13.3g of laccase (15U / mg) are added in sequence; the enzyme molecules are immobilized by reverse micelle encapsulation, concentrated to 100ml by ultrafiltration, and stored at 4°C in the dark.

[0053] The ozone microencapsulated degradation sprayer of the present invention is widely applicable to occasions where ozone removal is required, including but not limited to:

[0054] Indoor air purification: In indoor environments such as offices and homes, ozone is generated during the operation of air purifiers, printers, computers and other equipment, and excessive VOCs after indoor decoration react with NOx generated by gas combustion to produce ozone. The ozone removal liquid involved in the present invention can be atomized by a sprayer to effectively remove ozone gas molecules in the local air, improve air quality, and protect human health.

[0055] Industrial waste gas treatment: In the power, metallurgy, petrochemical and other industries, ozone may be produced as a by-product or intermediate product, and its excessive concentration may cause harm to equipment and personnel. The ozone elimination liquid of the present invention can be used to treat these industrial waste gases by automatic spraying, reducing the ozone emission concentration and complying with environmental protection regulations.

[0056] Water treatment: Ozone is used as a disinfectant in some water treatment scenarios, such as swimming pools, drinking water treatment, etc. In these scenarios, it is necessary to remove excess ozone, and the ozone can be degraded by using the elimination liquid involved in the present invention through a canned sprayer.

[0057] Medical and health care: In the medical field, ozone is sometimes used for disinfection or treatment of certain diseases. The present invention can be used for post-treatment of ozone disinfection of medical equipment to ensure that there is no ozone residue before the equipment is used.

[0058] Other occasions where ozone removal is required: such as laboratories, scientific research sites, etc., where ozone may be generated during certain chemical reactions or experiments. The present invention can be used to remove ozone in these occasions to ensure the safety and accuracy of the experimental environment.

[0059] The present invention provides a digestion solution, which is obtained by designing a ratio of an emulsified component and two degradation components. The ozone molecules in the air are captured and microencapsulated through nano-atomization and film-forming capsules.

[0060] The atomization spraying of the ozone decomposition liquid can be achieved through a sprayer or a fog cannon. The sprayed ultrafine droplets (<1μm) can capture ozone molecules due to their high sensitivity to ozone, and rapidly construct dynamic semipermeable membrane microcapsules using polyglycerol fatty acid esters (PGPR) and lecithin. Through the synergistic effect of the ascorbic acid / iron ion redox system and the catalase / SOD enzyme system, efficient targeted elimination of ozone molecules is achieved, completely degrading ozone into oxygen and water.

[0061] The breakthrough advantages of this technology are reflected in the following aspects: in terms of environmental protection, the final products are only oxygen and water, the emulsifier and enzyme system are biodegradable, and there is no secondary pollution; in terms of efficiency, the microencapsulation prolongs the effective contact time between ozone and the digestion solution, and at the same time provides a stable microenvironment for the digestion reaction, avoiding other interferences such as oxygen concentration, etc., reducing reverse reactions, and improving the reaction rate and degradation efficiency. In terms of economy, this digestion solution achieves the encapsulation reduction of ozone molecules, making the entire digestion process environmentally friendly and harmless, and no other harmful substances are produced during the treatment process. The degradation products are harmless oxygen and water, and no subsequent treatment is required. The operating cost is low, the product can be recycled, and it has wide temperature adaptability (5-45℃) and open space applicability. It can be widely used in industrial, medical and public environment ozone treatment, and has the characteristics of high efficiency, environmental friendliness and low cost.

[0062] The principle of the present invention is:

[0063] Through high-pressure spraying and other technologies, tiny mist droplets with a certain pressure and diameter range are formed. After the digestion solution is atomized, PGPR and lecithin self-assemble on the surface of the droplets to form a core-shell structure:

[0064] Nuclear layer: redox agent (ascorbic acid / iron ion) and biological enzyme solution.

[0065] Shell layer: PGPR-phosphatidylcholine composite membrane (pore size <0.5nm) + HPMC gel layer.

[0066] Ozone penetrates the microcapsule membrane and enters the nuclear layer, reacting with ascorbic acid / iron ions (O 3 +Fe 2+ →O 2 +Fe 3+ ), degrades 80% of ozone.

[0067] The remaining ozone reacts with water to generate H 2 O 2 (2O 3 +H 2 O→3O 2 +H 2 O 2 ), which is broken down into H 2 O and O 2 .

[0068] Reaction kinetics:

[0069] Stage I: Fe 2+ +O 3 →Fe 3+ +O 2 (Redox, quickly consumes 80% of ozone)

[0070] Phase II: 2O 3 +H 2 O→3O 2 +H 2 O 2 → Catalase catalyzes → 2H 2 O+O 2 (Completely clear the remaining 20%)

[0071] 6.3. Product release and recovery

[0072] O 2 Released into the air through the microcapsule membrane, H 2 O and Fe(OH) 3 The colloid is recycled after sedimentation separation.

[0073] Online detection of O by UV absorption spectroscopy 3 Concentration (characteristic peak 254nm attenuation rate>98%)

[0074] Verification product: O 2 Characteristic peak 1555cm -1 , strength ratio>99%, purified gas O 2Purity ≥ 99.2%, byproduct H2O aerosol concentration < 50 μg / m 3 .

[0075] Compared with traditional methods, the present invention provides a new solution for the field of ozone elimination. It has the following advantages:

[0076] 1. Environmentally friendly formula (LD50>5000mg / kg)

[0077] a. Redox system:

[0078] Ascorbic acid / ammonium ferric citrate: non-toxic, biodegradable, the reaction product is Fe 3+ (Can be precipitated and recovered);

[0079] Sodium thiosulfate: Rapidly reduce residual oxidants to avoid secondary pollution.

[0080] b. Biological enzyme system:

[0081] Recombinant enzymes (catalase / SOD / laccase): high catalytic efficiency (>10 6 times / minute), strong specificity;

[0082] Trehalose: Significantly improves enzyme thermal stability (activity remains >90% at 50°C).

[0083] c. Emulsification / film-forming system:

[0084] PGPR + lecithin: form a nano-scale semi-permeable membrane (ozone permeability> 95%, O 2 Barrier rate>80%).

[0085] HPMC: prolongs the life of microcapsules.

[0086] 2. High degradation efficiency. The microcapsule structure extends the ozone residence time from 2-5 seconds of traditional spray to 20-30 seconds. Through the three-level synergistic mechanism of "physical encapsulation-chemical degradation-enzyme degradation", active targeted elimination of ozone is achieved, and the synergistic degradation efficiency reaches 98.7%.

[0087] 3. Low risk of secondary pollution. The final product is O 2 and H 2 O (accounting for >99%). No chemical residue: The enzyme system can degrade its own carrier (such as trehalose), and sodium thiosulfate is decomposed into harmless sulfate.

[0088] 4. Wide range of applications. Low cost, suitable for open spaces with a wide temperature range (5-45°C), and can be widely used in industrial, medical and public environment ozone treatment.

[0089] 5. Strong compatibility. It can be directly integrated with existing spray systems (such as high-pressure fine water mist equipment).

[0090] 6. Closed-loop control module. Ozone sensor real-time feedback adjustment.

[0091] According to the above, the present invention also relates to a method for capturing and degrading ozone molecules by microencapsulation, wherein the ozone decomposition liquid is sprayed, and the ozone decomposition liquid is microencapsulated by membrane bubbles when the spraying occurs, so as to achieve the following three different concentration ranges (0-150ug / m 3 ; 150-300ug / m 3 ; 300-500ug / m 3 )Molecular destruction of ozone.

[0092] According to the above, the present invention also relates to an ozone decomposition liquid, including an emulsified membrane bubble liquid and an ozone degradation liquid;

[0093] The emulsified membrane bubble liquid comprises 0.8-1.5% of polyglycerol fatty acid ester, 0.3-0.6% of lecithin nanoliposome and 0.2-0.4% of hydroxypropyl methylcellulose. The emulsified membrane bubble liquid promotes the droplets to spontaneously form microcapsule structures and delays the rupture time of the microcapsules.

[0094] Further, the ozone degradation solution includes a redox solution and a biological enzyme solution;

[0095] The redox solution includes 2-5% L-ascorbic acid, 0.5-1.2% ammonium ferric citrate, 0.3-0.8% sodium thiosulfate, and 10-15% glycerol;

[0096] The biological enzyme solution comprises recombinant catalase with an enzyme activity of 5000-8000 U / mL, superoxide dismutase with an enzyme activity of 2000-4000 U / mL, laccase with an enzyme activity of 1000-2000 U / mL, and trehalose with an activity of 3-5%.

[0097] The embodiments described above are only descriptions of the preferred modes of the present invention and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations, modifications, and substitutions made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for capturing and degrading ozone molecules by microencapsulation, characterized in that: By spraying the ozone decomposition liquid, the ozone decomposition liquid is microencapsulated by membrane bubbles when the spraying occurs immediately, so as to achieve the molecular decomposition of ozone corresponding to three different concentration ranges.

2. An ozone decomposition solution, characterized in that: Including emulsified membrane bubble liquid, ozone degradation liquid; The emulsified membrane bubble liquid comprises 0.8-1.5% of polyglycerol fatty acid ester, 0.3-0.6% of lecithin nanoliposome and 0.2-0.4% of hydroxypropyl methylcellulose. The emulsified membrane bubble liquid promotes the droplets to spontaneously form microcapsule structures and delays the rupture time of the microcapsules.

3. An ozone decomposition solution as claimed in claim 2, characterized in that: Ozone degradation liquid includes redox liquid and biological enzyme solution; The redox solution includes 2-5% L-ascorbic acid, 0.5-1.2% ammonium ferric citrate, 0.3-0.8% sodium thiosulfate, and 10-15% glycerol; The biological enzyme solution comprises recombinant catalase with an enzyme activity of 5000-8000 U / mL, superoxide dismutase with an enzyme activity of 2000-4000 U / mL, laccase with an enzyme activity of 1000-2000 U / mL, and trehalose with an activity of 3-5%.

4. An ozone decomposition solution as claimed in claim 2, characterized in that: The emulsified film bubble liquid preparation comprises: Preparation of liposomes: 400 mg of lecithin and 100 mg of cholesterol were dissolved in chloroform, and 10 mL of PBS buffer was added after rotary evaporation to form a film, and then ultrasonic treatment was performed for 15 min to obtain nanoliposomes; Preparation of oil phase: Dissolve 1.2 g of PGPR in 60°C soybean oil, add liposome suspension, and homogenize at low speed for 10 min to form oil phase; Preparation of aqueous phase: Soak HPMC in deionized water for 24 hours, heat and stir until completely dissolved, and add Tween-80 to form a transparent colloidal solution; Synthesis of emulsified membrane foam liquid: The oil phase and the water phase were mixed in a volume ratio of 3:7 and subjected to high-pressure homogenization to form a W / O / W double emulsion.

5. An ozone decomposition solution as claimed in claim 3, characterized in that: The redox solution was prepared by a gradient dissolution method: first, glycerol and deionized water were premixed at a ratio of 1:9, magnetic stirring was performed, and ammonium ferric citrate, sodium thiosulfate, and L-ascorbic acid were added in sequence; the pH was adjusted to 4.5-5.0, and the solution was stored in the dark under nitrogen protection.

6. An ozone decomposition solution as claimed in claim 3, characterized in that: The preparation process of the biological enzyme solution is as follows: dissolve 4.5g of trehalose in 90ml of Tris-HCl buffer until it is completely transparent; add 0.5g of SOD freeze-dried powder, 0.625g of catalase, and 13.3g of laccase in sequence; use the reverse micelle encapsulation method to immobilize the enzyme molecules, ultrafiltration and concentration to 100ml, and store at 4°C away from light.

7. An ozone microencapsulation degradation spray device, characterized in that: It comprises a spray tank body (1), an emulsified film bubble liquid storage tank (2), a degradation liquid storage tank (3), an electric regulating valve (4), a fixing card (5), a gear regulating valve (6), a battery compartment (7), a high-pressure pipeline (8), a spray switch (9) and a nozzle (10); The emulsion film bubble liquid storage tank (2) and the degradation liquid storage tank (3) are arranged in the sprayer tank body (1), and the emulsion film bubble liquid storage tank (2) and the degradation liquid storage tank (3) are connected to the nozzle (10) through the high-pressure pipeline (8).

8. An ozone microencapsulation degradation spray device as claimed in claim 7, characterized in that: The degradation liquid storage tank (3) stores ozone decomposition liquid, which includes emulsified membrane bubble liquid and ozone degradation liquid; the emulsified membrane bubble liquid storage tank (2) stores emulsified membrane bubble liquid.

9. An ozone microencapsulated degradation spray device as claimed in claim 8, characterized in that: The degradation liquid storage tank (3) stores the redox liquid and the biological enzyme solution separately and independently, and controls and delivers them through an electric regulating valve (4) configured with a matching pipeline, thereby achieving three ratios of ozone degradation liquid, redox liquid and biological enzyme solution to meet the degradation of ozone within a corresponding concentration range.

10. An ozone microencapsulation degradation spray device as claimed in claim 9, characterized in that: The three volume ratios of ozone degradation solution, redox solution and biological enzyme solution are: When the ozone concentration range is 0-150ug / m 3 When, the ratio of emulsified membrane bubble liquid: redox liquid: biological enzyme is 5:1.5:1; When the ozone concentration range is 150-300ug / m 3 When, the ratio of emulsified membrane bubble liquid: redox liquid: biological enzyme is 7:2.5:1; When the ozone concentration range is 300-500ug / m 3 When the emulsified membrane bubble liquid: redox liquid: biological enzyme is 10:4:1.

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