Method for catalytically synthesizing captan by using supergravity equipment

Abstract

The invention discloses a method for catalytically synthesizing captan by using supergravity equipment, which comprises the following step: by taking tetrahydrophthalimide sodium salt and perchloromethyl mercaptan as raw materials, water as a solvent and supported solid acid as a catalyst, reacting in a supergravity reactor to obtain the captan. The supergravity reactor and the supported solid acid catalyst have a synergistic effect, the supergravity reactor strengthens reactant mass transfer on the surface of the catalyst, acid sites of the catalyst accelerate reaction kinetics, and the supergravity reactor and the supported solid acid catalyst synergistically improve reaction selectivity. Compared with a traditional water-phase synthesis method with sodium hydroxide as a catalyst, the captan yield is increased by 7.5-10%, the catalyst can be recycled, wastewater COD is reduced, and the method is more environmentally friendly.

Description

Technical Field

[0001] This invention relates to a method for synthesizing captan, specifically a method for catalytic synthesis of captan using a hypergravity device. Background Technology

[0002] Captan, also known as N-(trichloromethylthio)cyclohexyl-4-ene-1,2-dicarboximide, is a low-toxicity, broad-spectrum organosulfur fungicide developed by Chevron Chemicals. It can be used to control various diseases on crops such as barley, rice, corn, cotton, vegetables, fruit trees, melons, and tobacco, including wheat rust, rice blast, tobacco black rot, apple rot, powdery mildew, and black spot. It can also be mixed with various pesticides. Captan remains a best-selling fungicide in Europe and parts of Asia. Its chemical structure is shown in formula (I). .

[0003] A hypergravity reactor is a reactor that uses a high-magnitude gravitational field to induce a hypergravity state in matter, thereby controlling the structure and properties of the matter in a very short time. This unique working principle can greatly improve the reaction rate and reaction occupancy rate, and has important application value for the rapid synthesis of new materials and catalytic reactions.

[0004] The traditional synthesis method for captan is the aqueous phase method, which involves the condensation reaction of tetrahydrophthalimide or its salt (such as sodium salt) with perchloromethanethiol (ClSCCl3) under alkaline conditions. However, this method has the following drawbacks: 1. Low mass transfer efficiency: In traditional homogenizers or stirred tanks, the contact area of ​​the reactants is limited, resulting in a low mass transfer rate and prolonged reaction time; 2. Residue problem: Unreacted perchloromethanethiol has a strong pungent odor and is easily retained in the product, requiring additional purification steps, increasing costs and environmental burden; 3. High energy consumption: The process requires long-term heat preservation reaction (2-3 hours), resulting in high energy consumption; 4. Catalyst limitations: Using homogeneous alkaline catalysts (such as NaOH) presents problems such as wastewater generation after neutralization, non-recoverable wastewater, and easy side reactions, and also has poor compatibility with perchloromethanethiol, affecting reaction selectivity. Summary of the Invention

[0005] To address the shortcomings of current aqueous phase methods for preparing captan, this invention provides a method for catalytic synthesis of captan using a hypergravity device. The hypergravity reactor (such as a rotating packed bed reactor) has highly efficient mass transfer characteristics, improving mass transfer efficiency. At the same time, when combined with a supported solid acid catalyst, the reaction time is shortened, the reaction selectivity is improved, and the catalyst is easy to recover and recycle, reducing costs and environmental burden.

[0006] The specific technical solution of this invention is as follows: A method for catalytic synthesis of captan using a hypergravity device, wherein the method uses sodium tetrahydrophthalimide and perchloromethanethiol as raw materials, water as solvent, and a supported solid acid as catalyst, and reacts in a hypergravity reactor to obtain captan.

[0007] Furthermore, the sodium tetrahydrophthalimide is obtained by reacting tetrahydroimide (1,2,3,6-tetrahydrophthalimide) with sodium hydroxide, wherein the molar ratio of tetrahydroimide to sodium hydroxide is 1:1 to 1.2, for example, 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09, 1:1.10, 1:1.11, 1:1.12, 1:1.13, 1:1.14, 1:1.15, 1:1.16, 1:1.17, 1:1.18, 1:1.19, or 1:1.2. The sodium tetrahydrophthalimide can be mixed with perchloromethanethiol in aqueous solution form, or it can be mixed with perchloromethanethiol and water in solid form. Preferably, tetrahydroimine is reacted with an aqueous solution of sodium hydroxide to obtain an aqueous solution of sodium tetrahydrophthalimide, which is then mixed with perchloromethanethiol.

[0008] Furthermore, there are no special requirements for the order in which the raw materials are added. For example, an aqueous solution of sodium tetrahydrophthalimide, perchloromethanethiol, and supported solid acid can be added to the hypergravity reactor, and the temperature and time can be controlled for the reaction.

[0009] Furthermore, the molar ratio of sodium tetrahydrophthalimide to perchloromethanethiol is 1:0.95 to 1.2, for example, 1:0.95, 1:1.0, 1:1.05, 1:1.1, 1:1.15, 1:1.2.

[0010] Furthermore, in the reaction system of sodium tetrahydrophthalimide, perchloromethanethiol, catalyst and water, the mass ratio of sodium tetrahydrophthalimide to all the water in the system is 1:3-8, for example 1:3, 1:4, 1:5, 1:6, 1:7, 1:8.

[0011] Furthermore, in the reaction system of sodium tetrahydrophthalimide, perchloromethanethiol, catalyst, and water, the pH of the reaction system is approximately between 10.3 and 10.7. Within this pH range, the supported solid acid catalyst is stable and exhibits excellent catalytic performance. This pH can be achieved by adding a pH adjuster, which can be an inorganic base such as sodium hydroxide or potassium hydroxide, or an aqueous solution thereof, preferably an aqueous solution of sodium hydroxide. When preparing the aqueous solution of sodium tetrahydrophthalimide, the pH of the resulting aqueous solution can be controlled by adjusting the amount of sodium hydroxide added to maintain it within a suitable pH range.

[0012] Furthermore, the supported solid acid used in this invention is sulfonic acid-functionalized HZSM-5 molecular sieve (HZSM-5@SO3H). The specific surface area of ​​this HZSM-5@SO3H is ≥400 m² / g, for example, 400 m² / g, 450 m² / g, 500 m² / g, 550 m² / g, 600 m² / g, 650 m² / g, etc.; the acid density is ≥1.2 mmol / g, for example, 1.2 mmol / g, 1.3 mmol / g, 1.4 mmol / g, 1.5 mmol / g, 1.6 mmol / g, 1.7 mmol / g, 1.8 mmol / g, 1.9 mmol / g, 2.0 mmol / g, 2.1 mmol / g, 2.2 mmol / g, 2.3 mmol / g, 2.4 mmol / g, 2.5 mmol / g, 2.6 mmol / g, 2.7 mmol / g, 2.8 mmol / g, 2.9 mmol / g, 3.0 mmol / g, etc.

[0013] Furthermore, the sulfonic acid-functionalized HZSM-5 molecular sieve (HZSM-5@SO3H) can be prepared according to methods disclosed in the prior art, such as calcining the HZSM-5 molecular sieve to remove the template agent, then immersing it in sulfuric acid, followed by drying and calcination. The silica-alumina ratio (the ratio of silicon oxide to aluminum oxide) of the HZSM-5 molecular sieve can be 23-25:1, and the calcination to remove the template agent can be carried out at 500-800℃. The concentration of sulfuric acid can be 0.5-1 mol / L, the immersion temperature can be 70-90℃, and the immersion time can be 5-8 h. Calcination is carried out under gas protection at a temperature of 270-350℃ for 2-5 h.

[0014] Furthermore, the catalyst dosage is 1-3.5% of the total mass of sodium tetrahydrophthalimide and perchloromethanethiol, for example, 1%, 2%, 3%, 3.5%.

[0015] Furthermore, the reaction is carried out in a hypergravity reactor. The hypergravity reactor, in conjunction with a supported solid acid catalyst, significantly improves the reaction selectivity and increases the reaction yield. The hypergravity reactor is a reactor that uses a high-magnitude gravitational field to induce a hypergravity state in substances, thereby controlling the structure and properties of substances in a very short time. It can be a rotating packed bed reactor, etc., and is commercially available. During the reaction, the hypergravity factor (the ratio of actual gravitational acceleration to standard gravitational acceleration) of the hypergravity reactor is 50-200, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200.

[0016] Furthermore, after all materials are mixed, the reaction temperature of the hypergravity reactor is adjusted to 0-25℃ for the reaction, for example, 0℃, 1℃, 2℃, 3℃, 4℃, 5℃, 6℃, 7℃, 8℃, 9℃, 10℃, 11℃, 12℃, 13℃, 14℃, 15℃, 16℃, 17℃, 18℃, 19℃, 20℃, 21℃, 22℃, 23℃, 24℃, and 25℃. The reaction time is generally 0.5-1.5 hours, for example, 0.5 hours, 1.0 hour, and 1.5 hours.

[0017] Furthermore, after the reaction, the reaction solution is centrifuged and filtered to recover the solid acid catalyst. The solid acid catalyst is then washed with ethanol, dried, and de-alcoholized, allowing for recycling. The catalyst can be recycled more than five times. The removed ethanol can be reused to wash the catalyst.

[0018] Furthermore, the reaction solution after catalyst separation is heated to 50-100℃ and kept at that temperature for 0.5-4 hours to decompose the residual perchloromethyl mercaptan. Then, it is cooled to 10-25℃ for crystallization. The resulting crystals are washed and dried to obtain captan crystals.

[0019] Furthermore, the mother liquor and washing water after crystallization can be treated with activated carbon and then directly reused or discharged.

[0020] The present invention has the following beneficial effects: 1. This invention employs a synergistic effect of a supergravity reactor and a supported solid acid catalyst. The supergravity reactor enhances the mass transfer of reactants on the catalyst surface, and the acidic sites of the catalyst accelerate the reaction kinetics. The synergistic effect of the two improves the reaction selectivity, and the yield of captan is increased by 7.5-10% compared with the traditional aqueous synthesis method using sodium hydroxide as a catalyst.

[0021] 2. In this invention, the supported solid acid HZSM-5@SO3H is selected as a catalyst, which can promote the directional condensation of sodium tetrahydrophthalimide salt and perchloromethanethiol through acidic sites and suppress side reactions.

[0022] 3. The catalyst of this invention exhibits strong stability under alkaline conditions. The HZSM-5@SO3H catalyst covalently bonds the -SO3H groups to the molecular sieve framework through high-temperature sulfonation (calcination under gas protection at 270-350℃). This chemical anchoring significantly enhances the stability of the -SO3H groups in alkaline environments. XPS analysis shows that after five cycles of catalyst recycling, the sulfur (S) content on its surface only decreases by 3%, indicating that the -SO3H groups have not undergone significant hydrolysis and exhibit strong stability. After calcination to remove the template and high-temperature sulfonation, the HZSM-5 molecular sieve framework has a higher silicon-to-aluminum ratio (SiO2 / Al2O3), resulting in a more stable silicon-oxygen network under alkaline conditions, inhibiting aluminum dissolution, and also enhancing the corrosion resistance of the molecular sieve framework.

[0023] 4. This invention avoids catalyst deactivation by controlling reaction conditions. During the reaction, the pH is adjusted in real time between 10.3 and 10.7 using an online pH probe to avoid localized over-alkalinity (e.g., pH > 11) which would lead to rapid hydrolysis of sulfonic acid groups; the low reaction temperature significantly reduces the hydrolysis rate of the molecular sieve framework and sulfonic acid groups under alkaline conditions; and the short reaction time minimizes the time the catalyst is exposed to the alkaline environment, greatly reducing the risk of catalyst deactivation.

[0024] 5. The catalyst of this invention can be recycled through simple filtration and can be reused more than 5 times, reducing waste emissions.

[0025] 6. This invention uses less catalyst, has a lower reaction temperature, a shorter reaction time, and a higher product yield, thus improving production efficiency. Attached Figure Description

[0026] Figure 1 The image shows the high-performance liquid chromatogram of captan obtained during catalyst recycling in Example 2. Detailed Implementation

[0027] The following description illustrates exemplary embodiments of the present invention, including various details to aid understanding, and should be considered merely exemplary. Therefore, those skilled in the art will recognize that various changes and modifications can be made to the embodiments described herein without departing from the scope and spirit of the invention. Similarly, for clarity and brevity, descriptions of well-known functions, operations, and structures are omitted in the following description.

[0028] Unless otherwise defined, the technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. While similar or identical methods and materials may be applied in experimental or practical applications, the present invention describes materials and methods hereinafter. In case of conflict, the definitions included herein shall prevail.

[0029] Unless otherwise specified, all concentrations mentioned in the following examples and comparative examples are mass percentage concentrations.

[0030] In the following examples and comparative examples, the HZSM-5 molecular sieve used was purchased from Zhengzhou Xiangpai New Material Technology Co., Ltd. The tetrahydrophthalimide used was from Shandong Weifang Runfeng Chemical Co., Ltd. The centrifugal reactor used was purchased from Lianyungang Shengyuan Technology Co., Ltd.

[0031] In the following examples and comparative examples, the formula for calculating the yield of captan is: Yield = Actual mass of captan product / Theoretical mass of captan * 100%.

[0032] Example 1 HZSM-5 molecular sieve (silicon-to-aluminum ratio 25:1) was calcined at 550℃ for 4 hours to remove the template agent. The calcined molecular sieve was then completely impregnated in a 0.5 mol / L sulfuric acid solution and stirred at 80℃ for 6 hours. The sulfuric acid-impregnated molecular sieve was removed, washed with deionized water until neutral, and dried at 110℃ for 12 hours. Under nitrogen protection, the dried molecular sieve was calcined at 300℃ for 3 hours to obtain the HZSM-5@SO3H catalyst. The acid density of the catalyst was determined to be 1.5 mmol / g and the specific surface area was 420 m² / g by titration and BET methods.

[0033] Example 2 A method for synthesizing captan includes the following steps: 1. Mix 20g of 1,2,3,6-tetrahydrophthalimide (THPI) with 18.4g of 30% sodium hydroxide aqueous solution, add 100g of tap water, and stir at room temperature for 20 minutes to obtain a tetrahydrophthalimide sodium salt (THPI-Na) solution (pH≈10.5).

[0034] 2. The tetrahydrophthalimide sodium salt solution from step 1, 24.7 g of liquid perchloromethanethiol (ClSCCl3, purity ≥99.5%), and 1.65 g of the HZSM-5@SO3H catalyst prepared in Example 1 were added to the hypergravity reactor. The temperature was controlled at 20±2℃ (temperature controlled by the circulating water cooling system), and the hypergravity factor was 150 (achieved by adjusting the rotor speed to 2800 rpm). The reaction was carried out for 1 h.

[0035] 3. After the reaction, the reaction solution is centrifuged at 3000 rpm for 10 minutes, filtered, and the solid catalyst is recovered. The solid catalyst recovery rate is ≥98%. The recovered catalyst is washed three times with ethanol, dried at 80℃, and can be recycled. The ethanol used for washing is recovered by distillation and can be recycled.

[0036] 4. Transfer the liquid after catalyst recovery to a purification vessel, heat to 80℃ and hold for 2 hours to decompose residual perchloromethanethiol, then cool to 10℃ for crystallization. After filling with analytical crystals, filter, wash the crystals three times with cold water (10-15℃), and dry under vacuum at 60℃ to obtain white captan crystals. The yield of captan, calculated as tetrahydrophthalimide, is 96.5%, and the purity is (HPLC, Figure 1 99.5%, with a total chloromethanethiol residue of 0.006 wt% (HPLC).

[0037] 5. Combine the washing water and the crystallization mother liquor, with a COD of 3500 mg / L. Then, treat the mixed wastewater in an activated carbon adsorption tower. After treatment, the COD of the wastewater is ≤500 mg / L, and it can be directly reused or discharged.

[0038] The HZSM-5@SO3H catalyst recovered in this embodiment was recycled using the same preparation process and recovery conditions as in this embodiment. The results of the catalyst recycling are shown in Table 1 below: Table 1 Note: Catalyst recovery rate = mass of recovered catalyst / mass of catalyst added initially.

[0039] Example 3 Captan was prepared according to the procedure in Example 2, except that the hypergravity factor of the hypergravity reactor in step 2 was 50, 100, 200, and 250. The results of the obtained captan are shown in Table 2 below. The purity of the product and the residual amount of perchloromethanethiol were determined by HPLC.

[0040] Table 2 Example 4 Captan was prepared according to the procedure in Example 2, except that the temperature of the centrifugal reactor was 0°C in step 2. The yield of the obtained captan, based on tetrahydrophthalimide, was 95.7%, the purity was 99.2% (HPLC), and the residual perchloromethanethiol was 0.007 wt% (HPLC).

[0041] Example 5 Captan was prepared according to the procedure in Example 2, except that the temperature of the centrifugal reactor was 10°C in step 2. The yield of the obtained captan, based on tetrahydrophthalimide, was 96.1%, the purity was 99.4% (HPLC), and the residual perchloromethanethiol was 0.008 wt% (HPLC).

[0042] Example 6 Captan was prepared according to the procedure in Example 2, except that the reaction time was 0.5 h in step 2. The yield of the obtained captan, based on tetrahydrophthalimide, was 95.2%, the purity was 98.9% (HPLC), and the residual perchloromethanethiol was 0.006 wt% (HPLC).

[0043] Example 7 Captan was prepared according to the procedure in Example 2, except that the reaction time was 1.5 h in step 2. The yield of the obtained captan, based on tetrahydrophthalimide, was 96.4%, the purity was 99.4% (HPLC), and the residual perchloromethanethiol was 0.006 wt% (HPLC).

[0044] Comparative Example 1 1. Mix 20g of 1,2,3,6-tetrahydrophthalimide (THPI) with 18.4g of 30% sodium hydroxide aqueous solution, add 100g of tap water, and stir at room temperature for 20 minutes to obtain a tetrahydrophthalimide sodium salt (THPI-Na) solution (pH≈10.5).

[0045] 2. The sodium tetrahydrophthalimide solution from step 1 and 24.7g of liquid perchloromethanethiol (ClSCCl3, purity ≥99.5%) were stirred and reacted using a homogenizer. A 20wt% sodium hydroxide solution was used as a catalyst, with a feed amount of 7.1g. The temperature was controlled at 25℃ (temperature controlled by a circulating water cooling system), and the reaction was carried out for 2 hours.

[0046] 3. After the reaction, the reaction solution was transferred to a purification vessel, heated to 80℃ and held for 2 hours to decompose the residual perchloromethanethiol. Then, it was cooled to 10℃ to crystallize. After passing through the analytical filtration tank, the crystals were washed three times with cold water (10-15℃) and dried under vacuum at 60℃ to obtain white captan crystals. The yield of captan, calculated as tetrahydrophthalimide, was 88.7%, the purity was 96% (HPLC), and the residual perchloromethanethiol content was 0.023 wt% (HPLC).

[0047] 4. Combine the washing water and the mother liquor of crystal precipitation, and its COD is 12000 mg / L.

[0048] A comparison of Example 2 and Comparative Example 1 shows that the present invention utilizes a synergistic effect of a hypergravity reactor and a solid acid catalyst, reducing catalyst usage by 60%, lowering the reaction temperature by 5°C, shortening the reaction time by at least half, and increasing the yield by 7.8%, demonstrating significant improvement. Furthermore, the product yield of the present invention remains >95% after five cycles of catalyst recycling, while the catalyst in Comparative Example 1 cannot be recycled. The COD of the wastewater in Example 2 of the present invention is only 3500 mg / L, a 70.8% reduction compared to Comparative Example 1, indicating a significant improvement in the environmental friendliness of the method of the present invention.

[0049] Comparative Example 2 Captan was prepared according to the procedure in Example 2, except that step 2 involved adding the sodium tetrahydrophthalimide solution from step 1, 24.7 g of liquid perchloromethanethiol (ClSCCl3, purity ≥99.5%), and 1.65 g of unmodified HZSM-5 molecular sieve catalyst to a hypergravity reactor. The temperature was controlled at 20 ± 2 °C (temperature controlled by a circulating water cooling system), and the hypergravity factor was 150 (achieved by adjusting the rotor speed to 2800 rpm). The reaction was carried out for 1.5 h. The yield of captan based on tetrahydrophthalimide was 91.2%, the purity was 96.2% (HPLC), and the residual amount of perchloromethanethiol was 0.015 wt% (HPLC). A comparison between Example 2 and Comparative Example 2 shows that modifying the molecular sieve with sulfonic acid improves the selectivity of the reaction and shortens the reaction time.

[0050] Comparative Example 3 Captan was prepared according to the procedure in Example 2, except that 1.65 g of HZSM-5@SO3H was replaced with 1.65 g of solid sodium hydroxide. The yield of the obtained captan, based on tetrahydrophthalimide, was 89.3%, the purity was 97.5% (HPLC), and the residual amount of perchloromethanethiol was 0.015 wt% (HPLC).

[0051] Comparative Example 4 Captan was prepared according to the procedure in Example 2, except that 1.65 g of HZSM-5@SO3H was replaced with 1.65 g of tetrabutylammonium bromide. The yield of the obtained captan, based on tetrahydrophthalimide, was 86.2%, the purity was 95.2% (HPLC), and the residual amount of perchloromethanethiol was 0.105 wt% (HPLC).

[0052] Comparative Example 5 Captan was prepared according to the procedure in Example 2, except that HZSM-5@SO3H was not added. The yield of the obtained captan, calculated as sodium tetrahydrophthalimide, was 86.9%, the purity was 95.7% (HPLC), and the residual amount of perchloromethanethiol was 0.118 wt% (HPLC).

[0053] Comparative Example 6 Captan was prepared according to the procedure in Example 2, except that in step 2, the reactor was replaced with a conventional reaction flask, and the hypergravity factor was maintained at 1. The yield of the obtained captan, calculated as tetrahydrophthalimide, was 87.5%, the purity was 96.7% (HPLC), and the residual amount of perchloromethanethiol was 0.10 wt% (HPLC).

[0054] Comparative Example 7 Captan was prepared according to the procedure in Example 2, except that 1.65 g of HZSM-5@SO3H was replaced with 2.5 mmol of 1 mol / L sulfuric acid solution. The yield of the obtained captan was 80% based on tetrahydrophthalimide, the purity was 92.3% (HPLC), and the residual amount of perchloromethanethiol was 0.35 wt% (HPLC).

Claims

1. A method for catalytic synthesis of captan using a centrifugal device, characterized in that: Captan was obtained by reacting sodium tetrahydrophthalimide and perchloromethanethiol as raw materials, water as solvent, and supported solid acid as catalyst in a supergravity reactor.

2. The method according to claim 1, characterized in that: The sodium tetrahydrophthalimide salt is obtained by reacting 1,2,3,6-tetrahydrophthalimide with sodium hydroxide, wherein the molar ratio of 1,2,3,6-tetrahydrophthalimide to sodium hydroxide is 1:1 to 1.

2.

3. The method according to claim 1, characterized in that: The molar ratio of sodium tetrahydrophthalimide to perchloromethanethiol is 1:0.95~1.

2.

4. The method according to claim 1, characterized in that: The supported solid acid is a sulfonic acid-functionalized HZSM-5 molecular sieve with a specific surface area ≥400 m² / g and an acid density ≥1.2 mmol / g.

5. The method according to claim 4, characterized in that: The sulfonic acid-functionalized HZSM-5 molecular sieve is obtained by calcining HZSM-5 molecular sieve to remove the template agent, then immersing it in sulfuric acid, drying it, and calcining it under gas protection. Preferably, the silicon-to-aluminum ratio of the HZSM-5 molecular sieve is 23-25:1, the calcination temperature for removing the template agent is preferably 500-800℃, the sulfuric acid concentration is preferably 0.5-1 mol / L, the immersion temperature in sulfuric acid is preferably 70-90℃, the immersion time in sulfuric acid is preferably 5-8 h, the calcination temperature is preferably 270-350℃, and the calcination time is preferably 2-5 h.

6. The method according to any one of claims 1-5, characterized in that: The catalyst dosage is 1-3.5% of the total mass of sodium tetrahydrophthalimide and perchloromethanethiol.

7. The method according to any one of claims 1-5, characterized in that: The mass ratio of sodium tetrahydrophthalimide to all the water in the reaction system is 1:3-8.

8. The method according to any one of claims 1-5, characterized in that: The reaction was carried out at pH 10.3–10.

7.

9. The method according to any one of claims 1-5, characterized in that: The hypergravity factor of the hypergravity reactor is 50-200.

10. The method according to any one of claims 1-5, characterized in that: The reaction temperature is 0-25℃, and the reaction time is 0.5-1.5 hours.

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