Preparation method of cyperus esculentus diester oil

Abstract

The invention discloses a preparation method of cyperus esculentus diester oil, and belongs to the technical field of diester oil preparation. The preparation method of the cyperus esculentus diester oil comprises the following steps: S1, drying and crushing cyperus esculentus, adding a PBS buffer solution and pectinase composite particles, and performing enzymolysis under an alternating magnetic field to obtain enzymatic hydrolysate; s2, carrying out magnetic separation on the enzymatic hydrolysate to recover pectinase composite particles, centrifuging, and collecting supernatant grease to obtain cyperus esculentus grease; s3, subjecting the cyperus esculentus oil, glycerin and lipase composite particles to light-magnetic fixed catalysis and magnetic separation to recover the lipase composite particles so as to obtain cyperus esculentus diester oil. The problems of low extraction rate, poor selectivity and serious pollution are solved through magnetic field-light field coordinated regulation and control, an efficient, accurate and sustainable solution is provided for functional diester oil manufacturing, the oil extraction rate is increased to 90%, the selectivity of 1, 3-diester reaches 88%, and the total diester yield is larger than 90%.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of diester oil preparation, and particularly relates to a preparation method of diester oil of Cyperus esculentus. BACKGROUND

[0002] Cyperus esculentus is a high-value oil crop with an oil content of 20-30%, rich in oleic acid (60-70%) and linoleic acid (15-20%), and containing natural antioxidant components such as tocopherols and phytosterols. These two monounsaturated fatty acids and polyunsaturated fatty acids have been proven to be beneficial to cardiovascular health. Diester oil prepared from Cyperus esculentus can retain this characteristic, or further enhance its potential to regulate blood lipids by enzymatic catalysis and directional adjustment of fatty acid composition. Cyperus esculentus oil is rich in natural antioxidant components such as tocopherols (vitamin E) and phytosterols. Under low-temperature enzymatic process, these components can be retained, improving the oxidative stability of diester oil, prolonging the shelf life, and possibly enhancing anti-inflammatory and anti-atherosclerotic effects.

[0003] The traditional preparation method of Cyperus esculentus oil has the following limitations:

[0004] Cold pressing method: low temperature retains active ingredients, but the oil yield is only 15-18%, and the residual oil content is high.

[0005] Solvent extraction method: high extraction efficiency (>95%) with n-hexane, but high-temperature desolventization (>120℃) destroys heat-sensitive substances, and there is a risk of solvent residue.

[0006] Supercritical CO2 extraction: no solvent residue, low temperature and high efficiency, but high equipment investment cost (>5 million yuan), difficult to scale up.

[0007] In the preparation of diester oil, conventional chemical transesterification requires high temperature (>80℃) and strong base catalyst, which leads to the generation of trans fatty acids and incomplete hydrolysis of triglycerides, resulting in low final yield and lack of selective synthesis effect. SUMMARY

[0008] Therefore, the application aims to provide a preparation method of diester oil of Cyperus esculentus. The application uses magnetic field-light field synergistic regulation to solve the problems of low extraction rate, poor selectivity and high pollution, providing an efficient, precise and sustainable solution for functional diester oil manufacturing.

[0009] To achieve the above-mentioned purpose, the application provides the following technical solutions:

[0010] The application provides a preparation method of diester oil of Cyperus esculentus, comprising the following steps:

[0011] S1. The dried and crushed chufa is added to PBS buffer and pectinase composite particles, and then subjected to enzymolysis under an alternating magnetic field to obtain an enzymolysis liquid;

[0012] S2. The pectinase composite particles in the enzymolysis liquid are recovered by magnetic separation, and then the supernatant oil is collected by centrifugation to obtain chufa oil;

[0013] S3. The chufa oil, glycerol and lipase composite particles are subjected to photo-magnetic fixed catalysis and magnetic separation to recover the lipase composite particles to obtain chufa diester oil.

[0014] Firstly, the dried and crushed chufa is added to PBS buffer and pectinase composite particles, and then subjected to enzymolysis under an alternating magnetic field to obtain an enzymolysis liquid.

[0015] In some embodiments, the moisture content of the dried chufa is 5-8%, and the crushed chufa has a mesh size of 50-100. The above drying conditions are helpful for the subsequent release and separation of oil, and a certain mesh size can ensure that the chufa powder and the pectinase composite particles are in sufficient contact.

[0016] In the present application, the mass ratio of chufa, PBS buffer and pectinase composite particles in S1 is 100:(300-500):(1-5).

[0017] In the present application, the preparation method of the pectinase composite particles is as follows:

[0018] Triton X-100, n-hexanol and cyclohexane are mixed and ultrasonically emulsified for 10 minutes; then nano Fe3O4 particle dispersion and ammonia water are added to form a uniform microemulsion by stirring; n-silica is added dropwise, and the reaction is carried out at 25℃ for 12 hours; Fe3O4@SiO2 is collected by magnetic separation and then washed and dried;

[0019] Fe3O4@SiO2 is dispersed in 1mg / mL toluene and ultrasonically treated for 30 minutes; 5wt% 3-aminopropyltriethoxysilane is added, and refluxing is carried out at 80℃ for 6 hours; after magnetic separation, washing is carried out to obtain amino-functionalized Fe3O4@SiO2-NH2;

[0020] Fe3O4@SiO2-NH2 is dispersed in sodium citrate buffer and then CBD protein is added for reaction; after the reaction is completed, the reaction is terminated, pectin lyase solution is added, and oscillation is carried out at 4℃ for 4 hours; after magnetic separation and washing, pectinase composite particles are obtained.

[0021] Further preferably, the ratio of Triton X-100, n-hexanol, cyclohexane, nano Fe3O4 particles, ammonia water and n-silica is 10mL:10mL:40mL:(1-5)mg:0.5mL:0.3mL.

[0022] In some embodiments, the pectolytic enzyme composite particle has an activity of ≥ 300 U / mg and a particle size of 50-60 nm.

[0023] The Fe3O4@SiO2 core-shell structure in the pectolytic enzyme composite particle of the application is a key carrier, the magnetic core (Fe3O4): realizes magnetic driving (directional penetration), magnetic heating effect (local heating), and magnetic separation and recovery. The silica shell (SiO2): protects the magnetic core and provides a stable, biocompatible surface for functionalization. The cellulose binding domain (CBD): specifically recognizes and tightly binds cellulose, the main component of the cell wall of Jatropha curcas, "anchors" the nanoparticle on the cell wall, and the pectolytic enzyme: specifically degrades the pectin layer connecting cellulose / hemicellulose in the cell wall, destroying the cell wall structure. The combination of magnetic driving penetration + enzymatic wall breaking + local heat activation is the key to efficient oil extraction, and 45℃ is much lower than the solvent extraction or high-temperature pressing temperature, which protects the quality of the oil.

[0024] In the application, the alternating magnetic field parameters in S1 are 100-150 kHz, 50-60 mT, the treatment temperature is 45-50℃, and the time is 20-40 min.

[0025] In the application, the alternating magnetic field parameters in S1 are 100-150 kHz, 50-60 mT, the treatment temperature is 45-50℃, and the time is 20-40 min.

[0026] Secondly, the application recovers the pectolytic enzyme composite particles by magnetic separation, and then collects the supernatant oil by centrifugation to obtain Jatropha curcas oil.

[0027] In the application, the centrifugation parameters are 12000-15000 rpm, and the centrifugation time is 10-30 min.

[0028] The magnetic separation in the application can effectively separate the pectolytic enzyme composite particles, and the structure can retain the enzyme activity for repeated use.

[0029] Finally, the application recovers the pectolytic enzyme composite particles by magnetic separation, and then collects the supernatant oil by centrifugation to obtain Jatropha curcas oil.

[0030] The existing problems of cycas revoluta oil, glycerol and lipase in synthesizing cycas revoluta diester oil are: low product yield, lack of selective synthesis, 1,3-diester oil yield is only about 50%, and pH regulator needs to be added during synthesis, which not only increases the cost but also contains components harmful to human health; and the reaction endpoint is difficult to control, which is easy to over-catalyze and produce impurities.

[0031] In the present application, the mass ratio of the cycas revoluta oil, glycerol and lipase composite particles is 3:1:(0.01-0.03).

[0032] In the present application, the preparation method of the lipase composite particles is:

[0033] 1) ZrOCl2.8H2O, tetra(4-carboxyphenyl) porphyrin, benzoic acid, N,N-dimethylformamide are mixed and ultrasonically dissolved, then reacted at 80-85 DEG C for 18-24 hours, and then filtered to obtain material A;

[0034] 2) Material A is washed, dried and activated to obtain material B;

[0035] 3) CALB lipase, phosphate buffer, material B are mixed and then subjected to vacuum adsorption to obtain material C;

[0036] 4) Material C, 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N-hydroxysuccinimide, CALB lipase, phosphate buffer are shaken and reacted, then the pH is adjusted to 5, then ethanolamine is added, and then the solid is collected by centrifugation, washed, dried to obtain the lipase composite particles.

[0037] In the present application, the ratio of ZrOCl2.8H2O, tetra(4-carboxyphenyl) porphyrin, benzoic acid, N,N-dimethylformamide in 1) is (75-85) mg:(40-50) mg:(1.5-1.8) g:(15-30) mL.

[0038] In the present application, the activation temperature in 2) is (130-150) DEG C, and the time is (18-24) h.

[0039] In the present application, the ratio of CALB lipase, phosphate buffer, material B in 3) is (30-50) mg:10 mL:100 mg.

[0040] In the present application, the ratio of material C, 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N-hydroxysuccinimide, CALB lipase, phosphate buffer in 4) is 100 mg:(1-5) mg:(2-10) mg:10 mg:10 mL.

[0041] In some embodiments, the lipase composite particles have a pore size distribution of 3.8±0.2 nm and a specific surface area of ​​>2200 m 2 / g.

[0042] In some embodiments, the lipase complex granule has an enzyme activity of ≥1000 U / g.

[0043] The lipase composite particles of the present invention are linked to a carrier (PCN-224) with a porphyrin group, endowing them with excellent photosensitivity. The carefully designed pore size (3.8 nm) allows small glycerol molecules to freely enter and participate in the reaction, while potentially restricting the diffusion of macromolecular substrates or products, thereby improving selectivity for the target product. This also enables reaction start-stop control, preventing overreaction and byproduct formation.

[0044] In the present invention, the parameters of the optical-magnetic fixed catalysis are:

[0045] Static magnetic field: 50mT to fix the catalyst;

[0046] NIR laser: 808 nm, 1.5 W / cm 2 , pulse mode, on 5min / off 1min;

[0047] Reaction conditions: 45°C, 200 rpm, 2 h.

[0048] The present invention uses the pore size screening effect of lipase composite particles. The 3.8nm pore size is precisely designed to allow glycerol to enter and exit freely, blocking the diffusion of 1,2-diester and inhibiting acyl migration. The active site of the light-controlled enzyme is reshaped. Near-infrared light (808nm) causes porphyrin to generate reactive oxygen species, and then local H + The increase in concentration caused the pH to drop to 5.5, and the catalytic enzymatic hydrolysis reaction began.

[0049] At the same time, when the laser is turned on, the local pH is ≤5.5, the enzyme active center opens, and the reaction proceeds; after the laser is turned off, the pH of the environmental buffer system diffuses back to 7.0, the enzyme conformation closes, and the reaction is terminated, thus eliminating the need for other conditions to control, reducing costs and procedures, and can also effectively inhibit over-catalytic side reactions.

[0050] Contains at least the following beneficial technical effects:

[0051] The application realizes efficient and green preparation of oil sago diester oil through the double innovation of magnetic control nanometer enzyme targeted wall breaking and light-magnetic synergistic intelligent catalysis. The alternating magnetic field drives the pectinase composite particles to directionally penetrate the cell wall, and the magnetic heat triggers the enzyme activity (45℃), so that the oil extraction rate is increased to 90%, and there is no solvent pollution in the whole process; the light-responsive MOF carrier (lipase composite particles) activates the enzyme Sn-1,3 specificity through near-infrared light control of the pH microenvironment (pH 7.0→5.5), and the 3.8 nm pore size screening inhibits the migration of acyl groups, so that the selectivity of 1,3-diester is 88%, and the total diester yield is >90%; pulse light irradiation realizes self-termination of the reaction, avoiding excessive catalysis of impurities; the magnetic carrier can be recycled and utilized, and there is no chemical additive residue, which meets the safety standards of functional oils. DETAILED DESCRIPTION

[0052] All other embodiments obtained by a person of ordinary skill in the art without making creative efforts based on the embodiments in the application belong to the protection scope of the application. The application is described below with reference to specific embodiments, and it should be noted that these embodiments are merely descriptive and do not limit the application in any way.

[0053] Raw material sources:

[0054] The pectinase composite particles are self-prepared, and the preparation method is as follows:

[0055] Triton X-100, n-hexanol and cyclohexane are mixed and ultrasonically emulsified for 10 minutes; then nano Fe3O4 particle dispersion liquid and ammonia water are added, and stirring is performed to form a uniform microemulsion; n-propyl silicate is added dropwise, and reaction is performed at 25℃ for 12 hours; Fe3O4@SiO2 is collected by magnetic separation and then washed and dried; the ratio of Triton X-100, n-hexanol, cyclohexane, nano Fe3O4 particles, ammonia water and n-propyl silicate is 10 mL: 10 mL: 40 mL: (1-5) mg: 0.5 mL: 0.3 mL.

[0056] Fe3O4@SiO2 is dispersed in 1 mg / mL toluene, ultrasonically for 30 minutes; 5wt% 3-aminopropyl triethoxysilane is added, and reflux is performed at 80℃ for 6 hours; after magnetic separation, washing is performed, and amino Fe3O4@SiO2-NH2 is obtained;

[0057] Fe3O4@SiO2-NH2 is dispersed in a sodium citrate buffer solution, 5 mg of CBD protein is then added, reaction is performed for 12 hours, the reaction is then terminated, 10 mg of pectin lyase solution is further added, and oscillation is performed at 4℃ for 4 hours; after magnetic separation and washing, the pectinase composite particles are obtained. Detection shows that the activity of the pectinase composite particles is 348 U / mg, and the particle size is 57 nm.

[0058] The lipase composite particles are prepared by the following method:

[0059] 1) ZrOCl2·8H2O, tetra(4-carboxyphenyl)porphyrin, benzoic acid, N,N-dimethylformamide are mixed and ultrasonically dissolved, then reacted at 85℃ for 24 hours to obtain material A, and then filtered; wherein the ratio of ZrOCl2·8H2O, tetra(4-carboxyphenyl)porphyrin, benzoic acid, N,N-dimethylformamide is 80mg:45mg:1.6g:30mL.

[0060] 2) Material A is washed, dried, and activated at 150℃ for 24 hours to obtain material B;

[0061] 3) CALB lipase, phosphate buffer, and material B are mixed and subjected to vacuum adsorption to obtain material C; wherein the ratio of CALB lipase, phosphate buffer, and material B is 40mg:10mL:100mg.

[0062] 4) Material C, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide, CALB lipase, and phosphate buffer are subjected to shock reaction, and then the pH is adjusted to 5, and then ethanolamine is added, and then the solid is collected by centrifugation, washed, and dried to obtain the lipase composite particles; wherein the ratio of material C, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide, CALB lipase, and phosphate buffer is 100mg:5mg:10mg:10mg:10mL.

[0063] After detection, the pore size distribution of the lipase composite particles is 3.8±0.2nm, the specific surface area is 2381m 2 / g, and the lipase activity of the lipase composite particles is 1087U / g.

[0064] Chufa is dried to a moisture content of 7%, and then crushed through an 80-mesh screen.

[0065] The other raw materials can be obtained from the market.

[0066] Example 1

[0067] S1. After chufa is dried and crushed, PBS buffer and pectinase composite particles are added, and then enzymolysis is carried out under an alternating magnetic field to obtain an enzymolysis liquid; wherein the mass ratio of chufa, PBS buffer, and pectinase composite particles is 100:400:3; the alternating magnetic field parameters are 130kHz, 55mT, the treatment temperature is 48℃, and the time is 30min.

[0068] S2. The pectinase composite particles in the enzymolysis liquid are recovered by magnetic separation, and then the supernatant oil is collected by centrifugation at a centrifugation parameter of 13000rpm for 20min to obtain chufa oil.

[0069] S3. The cyperus oleifera oil, glycerol, and lipase composite particles are then subjected to optical-magnetic immobilization catalysis and magnetic separation to recover the lipase composite particles to obtain cyperus oleifera diester oil; wherein the mass ratio of the cyperus oleifera oil, glycerol, and lipase composite particles is 3:1:0.02; the parameters and reaction conditions of the optical-magnetic immobilization catalysis are:

[0070] Static magnetic field: 50mT to fix the catalyst;

[0071] NIR laser: 808 nm, 1.5 W / cm 2 , pulse mode, on 5min / off 1min;

[0072] Reaction conditions: 45°C, 200 rpm, 2 h.

[0073] Example 2

[0074] S1. Dried and crushed cyperus juncea, then added with PBS buffer and pectinase composite particles, and then enzymatically hydrolyzed under an alternating magnetic field to obtain an enzymatic solution. The mass ratio of cyperus juncea, PBS buffer, and pectinase composite particles was 100:300:1. The alternating magnetic field parameters were 100 kHz, 50 mT, the treatment temperature was 45°C, and the treatment time was 20 min.

[0075] S2. The hydrolyzate was recovered by magnetic separation of pectinase composite particles, and then centrifuged at a parameter of 13000 rpm for 10 min to collect the supernatant oil to obtain cyperus oleifera oil;

[0076] S3. The cyperus oleifera oil, glycerol, and lipase composite particles are then subjected to optical-magnetic immobilization catalysis and magnetic separation to recover the lipase composite particles to obtain cyperus oleifera diester oil; wherein the mass ratio of the cyperus oleifera oil, glycerol, and lipase composite particles is 3:1:0.01; the parameters and reaction conditions of the optical-magnetic immobilization catalysis are:

[0077] Static magnetic field: 50mT to fix the catalyst;

[0078] NIR laser: 808 nm, 1.5 W / cm 2 , pulse mode, on 5min / off 1min;

[0079] Reaction conditions: 45°C, 200 rpm, 2 h.

[0080] Example 3

[0081] S1. Dry and crush the cyperus esculentus, then add PBS buffer, pectinase composite particles, and then perform enzymolysis under an alternating magnetic field to obtain an enzymolysis liquid; wherein the mass ratio of the cyperus esculentus, the PBS buffer, and the pectinase composite particles is 100:500:5; the alternating magnetic field parameters are 150 kHz, 60 mT, the treatment temperature is 50°C, and the time is 40 min.

[0082] S2. Recover the pectinase composite particles from the enzymolysis liquid by magnetic separation, and then collect the supernatant oil after centrifugation at a centrifugation parameter of 15000 rpm for 30 min to obtain cyperus esculentus oil;

[0083] S3. Add the cyperus esculentus oil, glycerol, and lipase composite particles to the system, and then perform light-magnetic fixed catalysis and magnetic separation to recover the lipase composite particles to obtain cyperus esculentus diester oil; wherein the mass ratio of the cyperus esculentus oil, the glycerol, and the lipase composite particles is 3:1:0.03; the parameters and reaction conditions of the light-magnetic fixed catalysis are as follows:

[0084] Static magnetic field: 50 mT to fix the catalyst;

[0085] NIR laser: 808 nm, 1.5 W / cm 2 , pulse mode, 5 min on / 1 min off;

[0086] Reaction conditions: 45°C, 200 rpm, 2 h.

[0087] Comparative Example 1 (oil extraction problem)

[0088] The method of this comparative example 1 is the same as that of Example 1, except that no magnetic field is applied.

[0089] Comparative Example 2 (oil extraction problem)

[0090] The method of this comparative example 1 is the same as that of Example 1, except that no CBD protein is added when preparing the pectinase composite particles, and pectin lyase is directly loaded.

[0091] Comparative Example 3 (traditional enzymolysis)

[0092] The method of this comparative example 1 is the same as that of Example 1, except that the lipase composite particles are replaced by CALB lipase with an enzyme activity of 10000 U / g, and the total enzyme activity is close; the parameters of the enzymolysis catalysis are 45°C and 8 h of catalytic reaction.

[0093] Comparative Example 4 (1.3 purity)

[0094] The method of this comparative example 1 is the same as that of Example 1, except that the pore size of the lipase composite particles is 10 nm.

[0095] Experimental Example 1

[0096] Oil fat extraction detection of cyperus esculentus

[0097] The oil fat extraction rates of cyperus esculentus in examples 1-3 and comparative examples 1-2 were analyzed, and see table 1.

[0098] Table 1 oil fat extraction rate

[0099] Oil extraction rate % Example 1 94 Example 2 98 Example 3 92 Comparative Example 1 76 Comparative Example 2 81

[0100] From table 1, it can be seen that the oil fat extraction rates of examples 1-3 in the present application are higher, and have the advantages of low temperature, non-toxicity, green, low cost, high extraction rate and the like compared with traditional extraction methods; at the same time, it is illustrated that the preparation of the pectinase composite particles greatly promotes the release of oil fat under the physical vibration of the magnetic field and the adsorption of CBD.

[0101] Experimental example 2

[0102] The oil fat extraction rates and types of cyperus esculentus glycerides in examples 1-3 and comparative examples 3-4 were analyzed, and see table 2.

[0103] Table 2

[0104] Diglyceride yield % 1,3-diglyceride (% of total diglyceride) Example 1 91 89 Example 2 88 85 Example 3 92 87 Comparative Example 3 67 49 Comparative Example 4 86 67

[0105] From table 2, it can be seen that the catalytic enzymatic hydrolysis method in the present application has the characteristics of selectively synthesizing 1,3-diglyceride, and the total diglyceride yield is high, without the need for chemical regulation, reducing the use of reagents, while the reaction degree is controllable, effectively inhibiting the by-products caused by excessive reaction.

[0106] The above is only the preferred embodiment of the present application, and it should be pointed out that for ordinary skilled persons in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A method for preparing cyperus oleifera diester oil, characterized in that: The following steps are involved: S1. After the cyperus oleifera was dried and crushed, PBS buffer and pectinase composite particles were added and then enzymatically hydrolyzed under an alternating magnetic field to obtain an enzymatic solution; S2. The hydrolyzate was recovered by magnetic separation of the pectinase composite particles, and then the supernatant oil was collected after centrifugation to obtain cyperus oleifera oil; S3. The cyperus juncea oil, glycerol, and lipase composite particles are then subjected to optical-magnetic immobilization catalysis and magnetic separation to recover the lipase composite particles to obtain cyperus juncea diester oil.

2. The preparation method according to claim 1, characterized in that The mass ratio of cyperus oleifera, PBS buffer solution and pectinase composite particles in S1 is 100:(300-500):(1-5).

3. The preparation method according to claim 1, characterized in that The preparation method of the pectinase composite particles is as follows: Triton X-100, n-hexanol, and cyclohexane were mixed and ultrasonically emulsified for 10 minutes. Then, a dispersion of nano-Fe3O4 particles and ammonia were added and stirred to form a uniform microemulsion. Ethyl orthosilicate was added dropwise and reacted at 25°C for 12 hours. Fe3O4@SiO2 was collected by magnetic separation and then washed and dried. Fe3O4@SiO2 was dispersed in 1 mg / mL toluene and ultrasonicated for 30 minutes. 5 wt% of 3-aminopropyltriethoxysilane was added and the mixture was refluxed at 80°C for 6 hours. After magnetic separation and washing, amination of Fe3O4@SiO2-NH2 was obtained. Fe3O4@SiO2-NH2 was dispersed in sodium citrate buffer and then CBD protein was added to react. After the reaction was completed, the reaction was terminated and pectin lyase solution was added and shaken at 4°C for 4 hours. After magnetic separation and washing, pectinase composite particles were obtained.

4. The preparation method according to claim 4, characterized in that The ratio of Triton X-100, n-hexanol, cyclohexane, nano-Fe3O4 particles, ammonia water, and ethyl orthosilicate is 10 mL: 10 mL: 40 mL: (1-5) mg: 0.5 mL: 0.3 mL.

5. The preparation method according to claim 1, characterized in that The mass ratio of the cyperus oleifera oil, glycerol and lipase composite particles in S3 is 3:1:(0.01-0.03).

6. The preparation method according to claim 1, characterized in that The preparation method of the lipase composite particles in S3 is: 1) ZrOCl2·8H2O, tetrakis(4-carboxyphenyl)porphyrin, benzoic acid, and N,N-dimethylformamide were mixed and dissolved by ultrasonication, and then reacted at 80-85°C for 18-24 hours and then filtered to obtain material A; 2) washing, drying and activating material A to obtain material B; 3) mixing CALB lipase, phosphate buffer, and material B and adsorbing under reduced pressure to obtain material C; 4) Material C, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide, CALB lipase, and phosphate buffer were shaken and reacted, and then the pH was adjusted to 5, and ethanolamine was added. The solid was collected by centrifugation, washed, and dried to obtain lipase composite particles.

7. The preparation method according to claim 8, characterized in that The ratio of ZrOCl2·8H2O, tetrakis(4-carboxyphenyl)porphyrin, benzoic acid and N,N-dimethylformamide in 1) is (75-85) mg: (40-50) mg: (1.5-1.8) g: (15-30) mL.

8. The preparation method according to claim 8, characterized in that The activation temperature in the above 2) is (130-150)°C and the activation time is (18-24)h.

9. The preparation method according to claim 8, characterized in that The ratio of CALB lipase, phosphate buffer and material B in the above 3) is (30-50) mg:10 mL:100 mg.

10. The preparation method according to claim 8, characterized in that The ratio of material C, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide, CALB lipase, and phosphate buffer in the above 4) is 100 mg: (1-5) mg: (2-10) mg: 10 mg: 10 mL.