CN114672371B - Preparation method of epoxidized oil - Google Patents
Preparation method of epoxidized oil Download PDFInfo
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- CN114672371B CN114672371B CN202210263978.1A CN202210263978A CN114672371B CN 114672371 B CN114672371 B CN 114672371B CN 202210263978 A CN202210263978 A CN 202210263978A CN 114672371 B CN114672371 B CN 114672371B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011973 solid acid Substances 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003921 oil Substances 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008157 edible vegetable oil Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 235000019198 oils Nutrition 0.000 claims description 16
- 239000003549 soybean oil Substances 0.000 claims description 16
- 235000012424 soybean oil Nutrition 0.000 claims description 16
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 14
- 235000019253 formic acid Nutrition 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000011363 dried mixture Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000010419 fine particle Substances 0.000 abstract description 3
- 238000005728 strengthening Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 description 5
- 239000008158 vegetable oil Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
Abstract
The invention relates to a preparation method of epoxidized oil, which comprises the following steps: (1) Weighing Na 2 SiO 3 、Al(NO 3 ) 3 With Zr (NO) 3 ) 4 Mixing, adding into water, adding ammonia water to adjust pH, stirring to completely precipitate, standing and aging; (2) Drying the solid obtained by ageing, adding sulfuric acid solution, mixing and soaking, and drying; (3) Calcining, cooling, and grinding into fine particles to obtain a solid acid catalyst; (4) The edible oil is taken to be subjected to catalytic reaction by solid acid in a hydrodynamic cavitation device, and the like. The method applies the hydrodynamic cavitation strengthening technology to the solid acid catalytic oil oxidation process, adopts a method of combining hydrodynamic cavitation and a solid acid catalyst in the process of preparing epoxidized oil, improves the yield and the production efficiency of an epoxidized product by the method, and reduces the damage to equipment and the environment.
Description
Technical Field
The invention relates to a preparation method of epoxidized oil.
Background
The epoxidized vegetable oil is used as a plasticizer and has the characteristics of good compatibility, low volatility, no toxicity, oil resistance and the like, and simultaneously, renewable resources are used as raw materials, so that the pressure brought by resource exhaustion can be relieved, and the pressure of the environment can be relieved, so that the epoxidized vegetable oil has great application value and market competitiveness.
In the industrial preparation of epoxy vegetable oil, liquid acid is usually selected as a catalyst, the epoxy oil produced by the method has complicated process in the subsequent acid removal process due to the difficulty in separating the liquid acid, and the acidity of strong acid can cause certain corrosion to equipment, so that the search of a novel catalytic epoxidation method is widely focused by people. The hydrodynamic cavitation energy can generate mechanical effect, activation effect, thermal effect and optical effect, has outstanding advantages in terms of improving yield and product quality, reducing energy consumption, shortening time and the like, is currently applied to various industries and environments, has the advantages of easy separation of solid acid, recycling, low requirement on equipment and small environmental pollution, meets the requirement of an environment-friendly green catalyst, and has a certain significance in promoting the development of the catalysis field to the green environment-friendly direction. At present, the preparation process of the epoxidized oil by combining solid acid catalysis and hydrodynamic cavitation is not known.
Disclosure of Invention
The invention aims to solve the technical problems that: the method applies the hydrodynamic cavitation strengthening technology to the solid acid catalytic oil oxidation process, and adopts a method of combining hydrodynamic cavitation with a solid acid catalyst in the process of preparing the epoxidized oil.
The technical scheme for solving the technical problems is as follows: the preparation method of the epoxidized oil comprises the following steps:
(1) Weighing Na 2 SiO 3 、Al(NO 3 ) 3 With Zr (NO) 3 ) 4 Mixing and adding the mixture into water, adding ammonia water to adjust the pH value to 8-9, stirring until the mixture is completely precipitated, and standing and aging the precipitate for 20-30 hours at the temperature of minus 16 ℃ to minus 20 ℃; na (Na) 2 SiO 3 、Al(NO 3 ) 3 With Zr (NO) 3 ) 4 The mass ratio is 1 (4.9-5.1), the water dosage is 1g Na 2 SiO 3 Add 9-13mL water meter.
(2) Drying the solid obtained by water washing at 105-115 ℃ to constant weight after aging, adding 2.5-3.5mol/L sulfuric acid solution into the dried mixture, mixing and soaking for 20-40 min, and drying at 105-115 ℃ to constant weight; the addition amount of the sulfuric acid solution was 1g Na 2 SiO 3 Add 15-25mL sulfuric acid solution.
(3) Calcining the dried solid at 300-500 ℃ for 2-5h, cooling, and grinding into particles with the particle size smaller than 1mm to obtain the solid acid catalyst.
(4) Adding proper amount of formic acid with mass concentration of 86-90% and solid acid catalyst into edible oil to obtain mixture, wherein the addition amount of formic acid is calculated according to mole number of formic acid and edible oilThe molar ratio of the medium double bonds is 1-2:1, the solid acid catalyst is added according to the amount of 3.5-4.5g solid acid catalyst added per 100g edible oil, then the mixture is preheated to 43-48 ℃, and the mass concentration of H is 28-32% 2 O 2 Dropwise addition to the mixture, wherein H 2 O 2 The addition amount is H 2 O 2 Starting to dropwise add H according to the mol ratio of 2-3:1 of the double bonds in the edible oil 2 O 2 Immediately circulating the mixture and passing through a hydrodynamic cavitation device, and setting the circulating flow to be 5-7L/min.
(5) H is added within 10-20min 2 O 2 Then circularly reacting for 1-3h at 52-58 ℃, separating after the reaction is finished, collecting a sample at the upper layer, washing the sample with 2-4% NaOH solution until the pH value is 5-6, washing the sample with 52-58 ℃ distilled water until the sample is neutral, and finally performing rotary evaporation to obtain the epoxidized oil.
The device used in the step (4) is a hydrodynamic cavitation device, the hydrodynamic cavitation device comprises a heater, a storage container, a centrifugal pump and a hydrodynamic cavitation device, the storage container is communicated with the centrifugal pump through a pipeline, the centrifugal pump is communicated with the hydrodynamic cavitation device through a pipeline, the hydrodynamic cavitation device is communicated with the storage container through a pipeline, and a thermometer is arranged in the storage container. Adding mixture of edible oil, formic acid and solid acid catalyst into storage container, preheating to 43-48 deg.C by heater, and heating to H 2 O 2 Dropwise adding the mixture, and simultaneously starting a centrifugal pump to enable the mixture to circularly flow in the hydrodynamic cavitation device.
The hydrodynamic cavitation device is a venturi tube.
The edible oil is soybean oil, rapeseed oil, castor oil, palm oil or peanut oil.
By adopting the technical scheme, the invention has the following beneficial effects:
1. in the process for preparing the epoxidized vegetable oil, a solid acid catalyst alone or a hydrodynamic cavitation alone is used, but a process of combining the two is not known. Hydrodynamic cavitation is widely applied to the strengthening of chemical reaction processes as a novel efficient treatment technology, and in the hydrodynamic cavitation process, cavitation bubble collapse causes various physicochemical effects similar to ultrasonic cavitation, such as generation of shearing force, shock wave, extremely high temperature, pressure and active free radicals, and simultaneously hydrodynamic cavitation breaks liquid drops into smaller sizes by reducing interfacial tension so as to enhance mixing of immiscible two phases. In the experimental process, it is found that the catalytic effect can not be improved by combining any solid acid with hydrodynamic cavitation, but the catalytic effect can be improved by combining the solid acid catalyst prepared by the method with hydrodynamic cavitation, and the relative conversion rate of the epoxy value of the prepared epoxy vegetable oil can be improved; but also can improve the production efficiency.
2. The preparation process of combining the solid acid catalyst and the hydrodynamic cavitation is adopted, so that the acid content in the reaction solution is low, the damage to equipment and environment can be reduced, the requirements of green development are met, and the preparation process is suitable for the production of various epoxidized oil.
3. The solid acid catalyst prepared by the invention can recover the repeated interest rate, has simple solid-liquid separation operation and easy recovery, and can simplify the subsequent acid removal process and the process flow compared with the liquid acid catalysis process.
The technical features of the method for producing epoxidized oil according to the present invention will be further described with reference to the accompanying drawings and examples.
Drawings
Fig. 1: schematic diagram of hydrodynamic cavitation device used in example 1 of the present invention.
Fig. 2: schematic diagram of hydrodynamic cavitation device used in example 1 of the present invention.
In the figure: 1-a constant-temperature water bath kettle, 2-a three-neck flask, 3-a centrifugal pump, 4-a condensing tube, 5-a thermometer, 6-a venturi tube and 7-a pressure gauge.
Detailed Description
Example 1: the preparation method of the epoxidized oil comprises the following steps:
(1) 10g of Na was weighed 2 SiO 3 50g of Al (NO) 3 ) 3 With Zr (NO) 3 ) 4 （Al(NO 3 ) 3 :Zr(NO 3 ) 4 Mass ratio = 5:2) is mixed into 100mL of water, ammonia is addedAdjusting pH to 8.5 with water, stirring with glass rod to completely precipitate, and aging at-18deg.C for 25 hr.
(2) And (3) drying the solid obtained by water washing in an oven at 110 ℃ until the weight is constant after ageing is finished, adding 200mL of 3mol/L sulfuric acid solution into the dried mixture, mixing and soaking for 30min, and then drying in the oven at 110 ℃ until the weight is constant.
(3) And (3) placing the dried solid into a muffle furnace to calcine for 3.5h at 400 ℃, cooling, and grinding into fine particles with the particle size smaller than 1mm to obtain the solid acid catalyst.
(4) This step uses hydrodynamic cavitation device (as shown in fig. 1-2), and this hydrodynamic cavitation device includes heater (thermostat water bath), storing container (three-neck flask), centrifugal pump and hydrodynamic cavitation ware (venturi tube), in thermostat water bath was placed in to three-neck flask, the right side mouth of three-neck flask was passed through the pipeline and is linked together with the centrifugal pump, and the centrifugal pump passes through pipeline and venturi tube intercommunication, installs the manometer on this pipeline, and hydrodynamic cavitation ware passes through the pipeline and is linked together with the middle mouth of three-neck flask, is provided with the thermometer in the three-neck flask, installs the condenser pipe on the right side mouth of three-neck flask.
The geometrical parameters of the venturi are shown in table 1.
Table 1: geometrical parameters of the venturi.
Note that: alpha: an inlet cone angle; beta: an outlet cone angle; l: throat length; d, d 0 : the diameter of the throat; d, d 1 : an inlet diameter; d, d 2 : outlet diameter.
Based on the added amount of formic acid n (formic acid) and n (soybean oil double bond) of 1.5:1 (mole ratio), adding solid acid catalyst in an amount of 4g solid acid catalyst per 100g soybean oil, adding proper amount of 88% formic acid and solid acid catalyst into 120g soybean oil, mixing in a three-neck flask of a hydrodynamic cavitation device, preheating the mixture to 45 ℃, and adding 30% H 2 O 2 Is added dropwise into the reaction system, wherein n (H 2 O 2 ) N (soybean oil double bond) is 2.5:1 (molar ratio), and beginning to dropwise add H 2 O 2 When the centrifugal pump is started immediately, the mixture flows through the hydrodynamic cavitation device to generate hydrodynamic cavitation, and the circulation flow is set to be 6.5L/min.
(5) H was added within 15min 2 O 2 And (3) carrying out post-circulation hydrodynamic cavitation reaction for 2 hours (the reaction temperature is 55 ℃), centrifuging after the reaction is finished, collecting a sample at the upper layer, washing the sample with 3% NaOH until the pH value is 5.5, washing the sample with distilled water at the temperature of 55 ℃ until the sample is neutral (the water temperature used in the washing process is similar to the temperature of a reaction system), and finally carrying out rotary evaporation to obtain the epoxidized soybean oil.
Example 2: the preparation method of the epoxidized oil comprises the following steps:
(1) 10g of Na was weighed 2 SiO 3 50g of Al (NO) 3 ) 3 With Zr (NO) 3 ) 4 (mass ratio Al (NO) 3 ) 3 :Zr(NO 3 ) 4 =5:4) was mixed into 100mL of water, pH was adjusted to 8 by adding ammonia water, stirred with a glass rod until complete precipitation, and the precipitate was aged in a-18 ℃ refrigerator for 20h.
(2) And (3) drying the solid obtained by water washing in an oven at 110 ℃ until the weight is constant after ageing is finished, adding 250mL of 3mol/L sulfuric acid solution into the dried mixture, mixing and soaking for 40min, and then drying in the oven at 110 ℃ until the weight is constant.
(3) And (3) placing the dried solid into a muffle furnace, calcining for 4 hours at 450 ℃, cooling, and grinding into fine particles with the particle size smaller than 1mm to obtain the solid acid catalyst.
(4) The hydrodynamic cavitation apparatus used in this step was the same as in example 1. Based on the added amount of formic acid n (formic acid) and n (soybean oil double bond) of 1.8:1 (mole ratio), adding solid acid catalyst in an amount of 4g solid acid catalyst per 100g soybean oil, adding proper amount of 88% formic acid and solid acid catalyst into 120g soybean oil, mixing in a three-neck flask of a hydrodynamic cavitation device, preheating the mixture to 45 ℃, and adding 30% H 2 O 2 Is added dropwise into the reaction system, wherein n (H 2 O 2 ) N (soybean oil double bond) is 2:1 (molar ratio), and beginning to dropwise add H 2 O 2 When the centrifugal pump is started immediately, the circulating flow is set to be 7L/min.
(5) H was added within 10min 2 O 2 And (3) carrying out post-circulation hydrodynamic cavitation reaction for 3 hours (the reaction temperature is 55 ℃), centrifuging after the reaction is finished, collecting a sample at the upper layer, washing the sample with 3% NaOH until the pH is 6, washing the sample with distilled water at the temperature of 55 ℃ until the sample is neutral (the water temperature used in the water washing process is similar to the temperature of a reaction system), and finally carrying out rotary evaporation to obtain the epoxidized soybean oil.
Comparative experiments
Comparative experiment 1: the procedure was essentially the same as in example 1, steps (4) and (5), except that no solid acid was added in step (4).
Comparative experiment 2: the procedure is substantially the same as in example 1, except that the centrifugal pump is not started in step (4), i.e., hydrodynamic cavitation is not generated.
Comparative experiment 3: the procedure was essentially the same as in example 2, steps (4) and (5), except that no solid acid was added in step (4).
Comparative experiment 4: the procedure is substantially the same as in example 2, except that the centrifugal pump is not started in step (4), i.e., hydrodynamic cavitation is not generated.
Table 2: the experimental results are collated.
As can be seen from Table 2, the epoxidized soybean oil is produced by combining hydrodynamic cavitation with the solid acid catalyst, so that the production efficiency of the epoxidized soybean oil can be effectively improved, and meanwhile, compared with the liquid acid catalyst, the adopted solid acid catalyst is easy to separate, so that the corrosion to equipment is reduced.
Solid acid catalyst recovery and utilization experiment:
recovery and use of experimental example 1: the solid acid catalyst used in example 1 was taken out from the reaction system, centrifugally filtered, washed with cyclohexane and methanol, dried, and then epoxidized soybean oil was prepared from the recovered solid acid catalyst according to the process parameters of example 1.
Recovery and use experiment example 2: the solid acid catalyst used in example 2 was taken out from the reaction system, centrifugally filtered, washed with cyclohexane and methanol, dried, and then epoxidized soybean oil was prepared from the recovered solid acid catalyst according to the process parameters of example 2.
Table 3: the solid acid catalyst recovery and utilization experimental results are shown in the table.
From the above table, the catalytic effect of the solid acid catalyst is not greatly reduced after the solid acid catalyst is recycled for 2 times, which indicates that the solid acid catalyst prepared by the invention can be recycled.
Claims (2)
1. A preparation method of epoxidized oil is characterized in that: the method comprises the following steps:
(1) Weighing Na 2 SiO 3 、Al(NO 3 ) 3 With Zr (NO) 3 ) 4 Mixing and adding the mixture into water, adding ammonia water to adjust the pH value to 8-9, stirring until the mixture is completely precipitated, and standing and aging the precipitate for 20-30 hours at the temperature of minus 16 ℃ to minus 20 ℃; na (Na) 2 SiO 3 、Al(NO 3 ) 3 With Zr (NO) 3 ) 4 The mass ratio is 1 (4.9-5.1), the water dosage is 1g Na 2 SiO 3 Adding 9-13mL of water into the reactor;
(2) Drying the solid obtained by water washing at 105-115 ℃ to constant weight after aging, adding 2.5-3.5mol/L sulfuric acid solution into the dried mixture, mixing and soaking for 20-40 min, and drying at 105-115 ℃ to constant weight; the addition amount of the sulfuric acid solution was 1g Na 2 SiO 3 Adding 15-25mL sulfuric acid solution;
(3) Calcining the dried solid at 300-500 ℃ for 2-5h, cooling, and grinding into particles with the particle size smaller than 1mm to obtain a solid acid catalyst;
(4) Adding proper amount of 86-90% formic acid and solid into edible oilThe acid catalyst is a mixture, wherein the addition amount of formic acid is calculated according to the proportion of 1-2:1 of the mole number of formic acid to the mole number of double bonds in the edible oil, the addition amount of the solid acid catalyst is calculated according to the addition amount of 3.5-4.5g of solid acid catalyst per 100g of edible oil, then the mixture is preheated to 43-48 ℃, and the mass concentration of H with 28-32% is obtained 2 O 2 Dropwise addition to the mixture, wherein H 2 O 2 The addition amount is H 2 O 2 Starting to dropwise add H according to the mol ratio of 2-3:1 of the double bonds in the edible oil 2 O 2 Immediately enabling the mixture to circularly flow and pass through a hydrodynamic cavitation device, and setting the circulation flow to be 5-7L/min;
(5) H is added within 10-20min 2 O 2 Then circularly reacting for 1-3h at 52-58 ℃, separating after the reaction is finished, collecting a sample at the upper layer, washing the sample with 2-4% NaOH solution until the pH value is 5-6, washing the sample with 52-58 ℃ distilled water until the sample is neutral, and finally performing rotary evaporation to obtain epoxidized oil;
the device used in the step (4) is a hydrodynamic cavitation device, the hydrodynamic cavitation device comprises a heater, a storage container, a centrifugal pump and a hydrodynamic cavitation device, the storage container is communicated with the centrifugal pump through a pipeline, the centrifugal pump is communicated with the hydrodynamic cavitation device through a pipeline, the hydrodynamic cavitation device is communicated with the storage container through a pipeline, and a thermometer is arranged in the storage container;
adding mixture of edible oil, formic acid and solid acid catalyst into storage container, preheating to 43-48 deg.C by heater, and heating to H 2 O 2 Dropwise adding the mixture, and simultaneously starting a centrifugal pump to enable the mixture to circularly flow in the hydrodynamic cavitation device;
the hydrodynamic cavitation device is a venturi tube.
2. The method for producing epoxidized oil according to claim 1, characterized in that: the edible oil is soybean oil, rapeseed oil, castor oil, palm oil or peanut oil.
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