Continuous production device and production method of chlorobenzyl cyanide
Through continuous production equipment and mild reaction conditions, the problem of changes in product concentration and sodium cyanide concentration in the traditional preparation of o-chlorobenzonitrile is solved, and the production of o-chlorobenzonitrile with high purity and high yield is achieved, reducing production costs.
Patent Information
- Application Number
- CN202510666863.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-22
- Publication Date
- 2025-10-10
AI Technical Summary
In the traditional method for preparing o-chlorobenzonitrile, as the reaction proceeds, the product concentration increases and the sodium cyanide concentration decreases, resulting in a decrease in the main reaction rate and an acceleration of the side reaction rate. In addition, the use of expensive catalysts leads to high production costs.
A continuous production device, including a continuous reactor and a continuous phase separation device, is used to achieve efficient continuous reaction, separation and purification of o-chlorophenylacetonitrile by adjusting the material molar ratio and temperature. Mild reaction conditions are used to reduce side reactions and improve product purity and yield.
The highly selective synthesis of o-chlorophenylacetonitrile is achieved, with product purity and yield greater than 95%, thus reducing production costs and being suitable for industrial production.
Smart Images
Figure HDA0005415338910000011 
Figure HDA0005415338910000012
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of organic intermediate preparation, in particular, relates to a continuous production device and method of o-chlorobenzyl cyanide. BACKGROUND
[0002] O-chlorobenzyl cyanide is also known as o-chlorobenzyl cyanide, 2-chlorobenzyl cyanide, which is an important fine chemical and organic synthesis intermediate. It is an important intermediate for the production of pesticides, medicines, high molecular polymers, dyes, pigments, etc. O-chlorobenzyl cyanide is used for the synthesis of new antimalarial drug nitroquine, antihypertensive drug valsartan, uracil herbicide, etc. The traditional batch preparation method is that o-chlorobenzyl cyanide is subjected to substitution reaction with sodium cyanide aqueous solution under the action of phase transfer catalyst, thereby preparing o-chlorobenzyl cyanide. However, in the actual production process, as the reaction proceeds, the concentration of the product o-chlorobenzyl cyanide increases, and the concentration of sodium cyanide decreases, resulting in a decrease in the main reaction rate and an increase in the side reaction rate.
[0003] Chinese invention patent CN114349660B discloses a synthesis method of o-chlorobenzyl cyanide, which adopts a special composite catalyst of ferric chloride and 4-dimethylaminopyridine. Ferric chloride can easily form a compound with Lewis base, thereby activating the organic substrate, and the catalytic effect is good. The structure of 4-dimethylaminopyridine has electron-donating dimethylamino and resonance with the mother ring pyridine ring, which can strongly activate the nitrogen atom on the ring for nucleophilic substitution, and significantly catalyze the acylation reaction of high steric hindrance and low reactivity alcohol and amine. However, the invention needs to use expensive composite catalyst, and the reaction temperature is greater than 130℃, so the production cost is high. SUMMARY
[0004] The first aspect of the present application provides a continuous production device of o-chlorophenylacetonitrile, comprising: an o-chlorobenzyl chloride storage tank, a sodium cyanide aqueous solution storage tank, a first tower type continuous reactor, a first continuous phase separation device, a low-content sodium cyanide aqueous layer storage tank, an o-chlorophenylacetonitrile crude product storage tank, a first continuous rectifying column, a condenser, an o-chlorophenylacetonitrile finished product storage tank, a second tower type continuous reactor, a second continuous phase separation device, a to-be-broken cyanide aqueous layer storage tank, an intermediate storage tank, a preparation kettle, a catalyst feeding bin, a solution A storage tank, a solution B storage tank and a second continuous rectifying column; the preparation kettle is connected with the sodium cyanide aqueous solution storage tank, the catalyst feeding bin and the solution A storage tank respectively; the first tower type continuous reactor is connected with the o-chlorobenzyl chloride storage tank, the first continuous phase separation device and the solution A storage tank respectively; one end of the first continuous phase separation device is sequentially connected with the o-chlorophenylacetonitrile crude product storage tank, the first continuous rectifying column, the condenser and the o-chlorophenylacetonitrile finished product storage tank, and the other end is sequentially connected with the low-content sodium cyanide aqueous layer storage tank, the second tower type continuous reactor, the second continuous phase separation device, the solution B storage tank, the second continuous rectifying column and the condenser; the condenser is connected with the o-chlorophenylacetonitrile crude product storage tank; the second continuous phase separation device is further connected with the to-be-broken cyanide aqueous layer storage tank; the second continuous rectifying column is further connected with the condenser and the intermediate storage tank; the first tower type continuous reactor and the second tower type continuous reactor are both packed columns.
[0005] The present application researches and finds that by adjusting the molar ratio of the materials in the first tower type continuous reactor and the second tower type continuous reactor, the purity and yield of the product can be improved, which may be that the sufficient contact of the reaction raw materials is promoted and the reaction is fast: in the first stage of the reaction, the sodium cyanide is excessive, so that the o-chlorobenzyl chloride can be efficiently converted into o-chlorophenylacetonitrile, and the excessive sodium cyanide enters the second stage; in the second stage of the reaction, the o-chlorobenzyl chloride is excessive, so that the excessive sodium cyanide in the first stage can be efficiently converted into o-chlorophenylacetonitrile, and the excessive o-chlorobenzyl chloride is recovered by rectification and reused, thereby improving the utilization rate of raw materials, reducing side reactions, and effectively improving the reaction yield and purity.
[0006] The second aspect of the present application provides a method for producing o-chlorophenylacetonitrile, comprising the following steps:
[0007] S1, the sodium cyanide aqueous solution and the phase transfer catalyst are respectively input into the preparation kettle from the sodium cyanide aqueous solution storage tank and the catalyst feeding bin, and are transferred into the solution A storage tank;
[0008] S2, the o-chlorobenzyl chloride in the o-chlorobenzyl chloride storage tank and the materials in the solution A storage tank are input into the first tower type continuous reactor for reaction, the reaction liquid overflows to the first continuous phase separation device, the separated aqueous phase enters the low-content sodium cyanide aqueous layer storage tank, and the organic phase sequentially enters the o-chlorophenylacetonitrile crude product storage tank, the first continuous rectifying column, the condenser and is collected into the o-chlorophenylacetonitrile finished product storage tank;
[0009] S3, the water phase in the low-content sodium cyanide water layer storage tank and the material in the intermediate storage tank are input into the second tower continuous reactor for reaction, the reaction solution overflows to the second continuous phase-splitting device, the separated water phase is stored to the end of the water layer storage tank to be broken cyanide, the organic phase enters the solution B storage tank and the second continuous distillation tower in sequence, and is rectified in the second continuous distillation tower, the light component is collected in the intermediate storage tank after cooling by the condenser, and the heavy component is rectified in the first continuous distillation tower through the o-chlorophenylacetonitrile crude product storage tank.
[0010] The material in the intermediate storage tank includes o-chlorobenzyl chloride or a mixture of o-chlorophenylacetonitrile and o-chlorobenzyl chloride.
[0011] The mass ratio of the chlorobenzeneacetonitrile to o-chlorobenzyl chloride is 1:20-100.
[0012] Optionally, the mass ratio of the chlorobenzeneacetonitrile to o-chlorobenzyl chloride is 1:20-80.
[0013] The content of the phase transfer catalyst in the preparation kettle is 0.05-0.8 wt%.
[0014] Optionally, the content of the phase transfer catalyst in the preparation kettle is 0.1-0.4 wt%.
[0015] Optionally, the content of the phase transfer catalyst in the preparation kettle is 0.15-0.3 wt%.
[0016] The temperature of the first tower continuous reactor is 50-80°C, and the temperature of the second tower continuous reactor is 60-90°C.
[0017] Optionally, the temperature of the first tower continuous reactor is 65-80°C, and the temperature of the second tower continuous reactor is 75-90°C.
[0018] The molar ratio of o-chlorobenzyl chloride to sodium cyanide in the first tower continuous reactor is 1:1.1-3.5.
[0019] Optionally, the molar ratio of o-chlorobenzyl chloride to sodium cyanide in the first tower continuous reactor is 1:1.3-2.5.
[0020] Optionally, the molar ratio of o-chlorobenzyl chloride to sodium cyanide in the first tower continuous reactor is 1:1.5-2.2.
[0021] The molar ratio of sodium cyanide to o-chlorobenzyl chloride in the second tower continuous reactor is 1:1.5-5.
[0022] Optionally, the molar ratio of sodium cyanide to o-chlorobenzyl chloride in the second tower continuous reactor is 1:2-4.
[0023] Optionally, the molar ratio of sodium cyanide to o-chlorobenzyl chloride in the second tower continuous reactor is 1:2-3.
[0024] The residence time of the material in the first tower continuous reactor is 0.25 to 3 hours.
[0025] Optionally, the residence time of the material in the first tower continuous reactor is 0.5 to 1.5 hours.
[0026] Optionally, the residence time of the material in the first tower continuous reactor is 1 to 1.5 hours.
[0027] The residence time of the material in the second tower continuous reactor is 0.25 to 2 hours.
[0028] Optionally, the residence time of the material in the second tower continuous reactor is 0.25 to 1 hour.
[0029] Optionally, the residence time of the material in the second tower continuous reactor is 0.5 to 1 h.
[0030] Beneficial effects
[0031] 1. The continuous production device of the present invention includes a continuous tower reactor, a continuous phase separation device, a continuous distillation tower and various storage tanks, which realizes efficient continuous reaction, separation and purification of o-chlorophenylacetonitrile.
[0032] 2. By adjusting the molar ratio of raw materials in the first tower continuous reactor and the second tower continuous reactor, the purity and yield of the product can be improved.
[0033] 3. The molar ratio of o-chlorobenzyl chloride to sodium cyanide in the first tower continuous reactor is 1:1.1-3.5; the molar ratio of sodium cyanide to o-chlorobenzyl chloride in the second tower continuous reactor is 1:1.5-5, and the product purity and yield are both greater than 95%.
[0034] 4. The method for producing o-chlorophenylacetonitrile of the present invention has mild reaction conditions and can effectively reduce production costs.
[0035] 5. The present invention achieves highly selective synthesis (yield greater than 98%) by combining the device with specific process parameters
[0036] With industrialized and stable production. BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Figure 1 This is a continuous production device for o-chlorophenylacetonitrile in Example 1.
[0038] Figure 2 The GC-MASS (gas chromatography-mass spectrometry) spectrum of the product in Example 1 is shown.
[0039] Wherein: 1. o-chlorobenzyl chloride storage tank; 2. sodium cyanide aqueous solution storage tank; 3. first tower-type continuous reactor; 4. first continuous phase-separation device; 5. low-content sodium cyanide aqueous layer storage tank; 6. o-chlorobenzeneacetonitrile crude product storage tank; 7. first continuous distillation tower; 8. condenser; 9. o-chlorobenzeneacetonitrile finished product storage tank; 10. second tower-type continuous reactor; 11. second continuous phase-separation device; 12. storage tank for the cyanide-to-be-broken aqueous layer; 13. intermediate storage tank; 14. preparation kettle; 15. catalyst feeding bin; 16. solution A storage tank; 17. solution B storage tank; 18. second continuous distillation tower. DETAILED DESCRIPTION
[0040] Example 1
[0041] A continuous production device for o-chlorophenylacetonitrile, such as Figure 1 As shown, it includes: an o-chlorobenzyl chloride storage tank 1, a sodium cyanide aqueous solution storage tank 2, a first tower continuous reactor 3, a first continuous phase separation device 4, a low-content sodium cyanide water layer storage tank 5, an o-chlorophenylacetonitrile crude product storage tank 6, a first continuous distillation tower 7, a condenser 8, an o-chlorophenylacetonitrile finished product storage tank 9, a second tower continuous reactor 10, a second continuous phase separation device 11, a cyanide water layer storage tank to be broken 12, an intermediate storage tank 13, a preparation kettle 14, a catalyst feeding bin 15, a solution A storage tank 16, a solution B storage tank 17, and a second continuous distillation tower 18; the preparation kettle 14 is respectively connected to the sodium cyanide aqueous solution storage tank 2, the catalyst feeding bin 15, and the solution A storage tank 16; the first tower continuous reactor 3 is respectively connected to the o-chlorobenzyl chloride storage tank 1, the first continuous reactor 10, and the second continuous phase separation device 11. The continuous phase-separation device 4 is connected to the solution A storage tank 16; one end of the first continuous phase-separation device 4 is connected in sequence to the o-chlorobenzeneacetonitrile crude product storage tank 6, the first continuous distillation tower 7, the condenser 8, and the o-chlorobenzeneacetonitrile finished product storage tank 9, and the other end is connected in sequence to the low-content sodium cyanide water layer storage tank 5, the second tower continuous reactor 10, the second continuous phase-separation device 11, the solution B storage tank 17, the second continuous distillation tower 18, and the condenser 8; the condenser 8 is connected to the o-chlorobenzeneacetonitrile crude product storage tank 6; the second continuous phase-separation device 11 is also connected to the cyanide water layer storage tank 12 to be broken; the second continuous distillation tower 18 is also connected to the condenser 8 and the intermediate storage tank 13; the first tower continuous reactor 3 and the second tower continuous reactor 10 are both packed towers.
[0042] A method for producing o-chlorophenylacetonitrile comprises the following steps:
[0043] S1, 30wt% sodium cyanide aqueous solution and phase transfer catalyst are respectively fed from sodium cyanide aqueous solution storage tank 2 and catalyst feeding bin 15 into preparation kettle 14 at a mass ratio of 1:0.0015, and then transferred to solution A storage tank 16;
[0044] S2, at 70-75°C, 1500 kg of o-chlorobenzyl chloride in o-chlorobenzyl chloride storage tank 1 and 2263 kg of material in solution A storage tank 16 are fed into the first tower continuous reactor 3 for reaction, with the o-chlorobenzyl chloride flow rate being 25 kg / min and the solution A flow rate being 37.7 kg / min. The reaction materials reside in the first tower continuous reactor 3 for 1 hour, and the reaction liquid overflows into the first continuous phase separation device 4. The separated 2347 kg of aqueous phase enters the low-content sodium cyanide aqueous layer storage tank 5, wherein the sodium cyanide content is 9.3 wt%. The organic phase enters the o-chlorophenylacetonitrile crude product storage tank 6, the first continuous distillation tower 7, the condenser 8, and is collected in the o-chlorophenylacetonitrile finished product storage tank 9;
[0045] S3, at 75 ~ 80 ℃, the aqueous phase in the low-content sodium cyanide water layer storage tank 5 and 1449 kg of o-chlorobenzyl chloride in the intermediate storage tank 13 are input into the second tower continuous reactor 10 for reaction, the low-content sodium cyanide water layer flow rate is 78.2 kg / min, the o-chlorobenzyl chloride flow rate is 48.3 kg / min, the reaction material stays in the second tower continuous reactor 10 for 0.5 h, the reaction solution overflows to the second continuous phase separation device 11, the separated aqueous phase is stored in the cyanide water layer storage tank 12, and the separated aqueous phase is separated. 1379 kg of organic phase sequentially enters the solution B storage tank 17 and the second continuous distillation tower 18, and is distilled in the second continuous distillation tower 18. 726.2 kg of light components are cooled by a condenser and collected in the intermediate storage tank 13, wherein the o-chlorophenylacetonitrile content in the light component is 2.25 wt %, and the o-chlorobenzyl chloride content is 97.75 wt %. The heavy components are passed through the o-chlorophenylacetonitrile crude product storage tank 6 and the crude product in the crude product storage tank 6 in step S2, and are combined and distilled in the first continuous distillation tower 7 to obtain 2063 kg of o-chlorophenylacetonitrile finished product.
[0046] Example 2
[0047] The specific implementation method is the same as that in Example 1; except that, the method for producing o-chlorophenylacetonitrile described in Example 2 is the following steps:
[0048] S1, 30wt% sodium cyanide aqueous solution and phase transfer catalyst are respectively fed from sodium cyanide aqueous solution storage tank 2 and catalyst feeding bin 15 into preparation kettle 14 at a mass ratio of 1:0.003, and then transferred to solution A storage tank 16;
[0049] S2, at 75-80 ° C, 1500 kg of o-chlorobenzyl chloride in the o-chlorobenzyl chloride storage tank 1 and 3022 kg of material in the solution A storage tank 16 are fed into the first tower continuous reactor 3 for reaction, the o-chlorobenzyl chloride flow rate is 16.7 kg / min, the solution A flow rate is 33.6 kg / min, the reaction materials reside in the first tower continuous reactor 3 for 1.5 h, the reaction liquid overflows into the first continuous phase separation device 4, the separated 3100 kg of aqueous phase enters the low-content sodium cyanide aqueous layer storage tank 5, wherein the sodium cyanide content is 14.1 wt %. The organic phase enters the o-chlorophenylacetonitrile crude product storage tank 6, the first continuous distillation tower 7, the condenser 8 and is collected in the o-chlorophenylacetonitrile finished product storage tank 9;
[0050] S3, at 80-85 ° C, the aqueous phase in the low-content sodium cyanide water layer storage tank 5 and 4309 kg of o-chlorobenzyl chloride in the intermediate storage tank 13 are input into the second tower continuous reactor 10 for reaction, the low-content sodium cyanide water layer flow rate is 103.3 kg / min, the o-chlorobenzyl chloride flow rate is 143.6 kg / min, the reaction material stays in the second tower continuous reactor 10 for 0.5 h, the reaction solution overflows to the second continuous phase separation device 11, the separated aqueous phase is stored in the cyanide water layer storage tank 12, and the separation The 4177 kg organic phase is sequentially fed into the solution B storage tank 17 and the second continuous distillation tower 18, and is distilled in the second continuous distillation tower 18. The 2834.5 kg light component is cooled by the condenser and collected in the intermediate storage tank 13, wherein the o-chlorophenylacetonitrile content in the light component is 1.35 wt %, and the o-chlorobenzyl chloride content is 98.65 wt %. The heavy component is passed through the o-chlorophenylacetonitrile crude product storage tank 6 and the crude product in the crude product storage tank 6 in step S2 and is combined and distilled in the first continuous distillation tower 7 to obtain 2790.5 kg of o-chlorophenylacetonitrile finished product.
[0051] Example 3
[0052] The specific implementation method is the same as that in Example 1; except that, the method for producing o-chlorophenylacetonitrile described in Example 3 is the following steps:
[0053] S1, 30wt% sodium cyanide aqueous solution and phase transfer catalyst are respectively fed from sodium cyanide aqueous solution storage tank 2 and catalyst feeding bin 15 into preparation kettle 14 at a mass ratio of 1:0.003, and then transferred to solution A storage tank 16;
[0054] S2, 1500 kg of o-chlorobenzyl chloride in o-chlorobenzyl chloride storage tank 1 and 3312 kg of material in solution A storage tank 16 were input into the first continuous reactor 3 at 75-80 °C for reaction, the flow rate of o-chlorobenzyl chloride was 16.7 kg / min, the flow rate of solution A was 36.8 kg / min, the residence time of the reaction material in the first continuous reactor 3 was 1.5 h, the reaction liquid overflowed to the first continuous phase separation device 4, 3390 kg of the separated water phase entered the low content sodium cyanide water layer storage tank 5, wherein the content of sodium cyanide was 15.13 wt%, the organic phase entered the o-chlorobenzyl cyanide crude product storage tank 6, the first continuous rectifying column 7, the condenser 8 in sequence and was collected into the o-chlorobenzyl cyanide product storage tank 9;
[0055] S3, the water phase in the low content sodium cyanide water layer storage tank 5 and 5055.7 kg of o-chlorobenzyl chloride in the intermediate storage tank 13 were input into the second continuous reactor 10 at 80-85 °C for reaction, the flow rate of the low content sodium cyanide water layer was 75.3 kg / min, the flow rate of o-chlorobenzyl chloride was 112.3 kg / min, the residence time of the reaction material in the second continuous reactor 10 was 0.75 h, the reaction liquid overflowed to the second continuous phase separation device 11, the separated water phase was stored in the cyanide breaking water layer storage tank 12, and the separated 4866.8 kg of organic phase entered the solution B storage tank 17, the second continuous rectifying column 18 in sequence and was distilled in the second continuous rectifying column 18, 3307.7 kg of light components were collected in the intermediate storage tank 13 after being cooled by the condenser, wherein the content of o-chlorobenzyl cyanide in the light components was 1.83 wt%, the content of o-chlorobenzyl chloride was 98.17 wt%, and the heavy components were combined with the crude product in the crude product storage tank 6 in step S2 and were distilled in the first continuous rectifying column 7 to obtain 3051.8 kg of o-chlorobenzyl cyanide product.
[0056] Example 4
[0057] The specific implementation is the same as that in Example 1, except that the method for producing o-chlorobenzyl cyanide in Example 3 is as follows:
[0058] S1, 30 wt% of sodium cyanide aqueous solution and phase transfer catalyst were input into the preparation kettle 14 from the sodium cyanide aqueous solution storage tank 2 and the catalyst feed bin 15 in a mass ratio of 1:0.003, respectively, and were transferred to the solution A storage tank 16;
[0059] S2, at 65-70°C, 600 kg of o-chlorobenzyl chloride in o-chlorobenzyl chloride storage tank 1 and 1208.8 kg of material in solution A storage tank 16 were input into the first continuous reactor 3 for reaction, the flow rate of o-chlorobenzyl chloride was 10 kg / min, the flow rate of solution A was 20.1 kg / min, the residence time of the reaction material in the first continuous reactor 3 was 1 h, the reaction liquid overflowed to the first continuous phase separation device 4, 1240.3 kg of the separated water phase entered the low content sodium cyanide water layer storage tank 5, wherein the content of sodium cyanide was 14.27 wt%, the organic phase entered the o-chlorobenzyl cyanide crude product storage tank 6, the first continuous rectifying column 7, the condenser 8 in sequence and was collected into the o-chlorobenzyl cyanide product storage tank 9;
[0060] S3, at 75-80°C, the water phase in the low content sodium cyanide water layer storage tank 5 and 1296.8 kg of mixture in the intermediate storage tank 13 in Example 2 were input into the second continuous reactor 10 for reaction, wherein the content of chlorobenzyl cyanide in the mixture was 1.35 wt%, the content of o-chlorobenzyl chloride was 98.65 wt%, the flow rate of the low content sodium cyanide water layer was 27.56 kg / min, the flow rate of o-chlorobenzyl chloride was 28.82 kg / min, the residence time of the reaction material in the second continuous reactor 10 was 0.75 h, the reaction liquid overflowed to the second continuous phase separation device 11, the separated water phase was stored in the to-be-broken cyanide water layer storage tank 12, and 1232.9 kg of the separated organic phase entered the solution B storage tank 17, the second continuous rectifying column 18 in sequence and was rectified in the second continuous rectifying column 18, 702 kg of light components were collected in the intermediate storage tank 13 after being cooled by the condenser, wherein the content of o-chlorobenzyl cyanide in the light components was 3.35 wt%, the content of o-chlorobenzyl chloride was 96.65 wt%, and the heavy components were combined with the crude product in the crude product storage tank 6 in step S2 and the crude product in the crude product storage tank 6 in step S2 and were rectified in the first continuous rectifying column 7 to obtain 1097.3 kg of o-chlorobenzyl cyanide product.
[0061] Example 5
[0062] The specific implementation is the same as that in Example 1, except that the method for producing o-chlorobenzyl cyanide in Example 3 is as follows:
[0063] S1, 30 wt% of sodium cyanide aqueous solution and phase transfer catalyst were input into the preparation kettle 14 from the sodium cyanide aqueous solution storage tank 2 and the catalyst feed bin 15 respectively according to a mass ratio of 1:0.002, and were transferred to the solution A storage tank 16;
[0064] S2, 1200 kg of o-chlorobenzyl chloride in o-chlorobenzyl chloride storage tank 1 and 2155.5 kg of the material in solution A storage tank 16 were input into the first continuous reactor 3 at 65-70°C to react, the flow rate of o-chlorobenzyl chloride was 20 kg / min, the flow rate of solution A was 35.9 kg / min, the residence time of the reaction material in the first continuous reactor 3 was 1 h, the reaction liquid overflowed into the first continuous phase separation device 4, 2220.7 kg of the separated water phase entered the low content sodium cyanide water layer storage tank 5, the content of sodium cyanide in the water phase was 12.49 wt%, and the organic phase entered the o-chlorobenzyl cyanide crude product storage tank 6, the first continuous rectifying column 7, the condenser 8 and was collected into the o-chlorobenzyl cyanide product storage tank 9 in sequence;
[0065] S3, the water phase in the low content sodium cyanide water layer storage tank 5 and 1856.3 kg of the mixture in the intermediate storage tank 13 were input into the second continuous reactor 10 at 75-80°C to react, the flow rate of the low content sodium cyanide water layer was 37 kg / min, the flow rate of o-chlorobenzyl chloride was 30.9 kg / min, the residence time of the reaction material in the second continuous reactor 10 was 1 h, the reaction liquid overflowed into the second continuous phase separation device 11, the separated water phase was stored in the to-be-broken cyanide water layer storage tank 12, and 1738.4 kg of the separated organic phase entered the solution B storage tank 17 and the second continuous rectifying column 18 in sequence and was rectified in the second continuous rectifying column 18, 881.8 kg of light components were collected in the intermediate storage tank 13 after being cooled by the condenser, the content of o-chlorobenzyl cyanide in the light components was 1.17 wt%, and the content of o-chlorobenzyl chloride was 98.83 wt%, and the heavy components were combined with the crude product in the crude product storage tank 6 in step S2 and were rectified in the first continuous rectifying column 7 to obtain 1517.8 kg of o-chlorobenzyl cyanide product.
[0066] Comparative Example 1
[0067] 2259.7 kg of 30 wt% sodium cyanide aqueous solution and 10 kg of phase transfer catalyst were placed in a reaction kettle, the temperature was raised to 70-75°C, then 1500 kg of o-chlorobenzyl chloride was added dropwise, the dropwise addition was completed in 2 h, and the temperature was maintained until the control was qualified (o-chlorobenzyl chloride area normalization <1%), then the temperature was lowered to room temperature, and the organic layer was separated, and o-chlorobenzyl cyanide product 1266.6 kg was obtained by rectification.
[0068] Comparative Example 2
[0069] 3013 kg of 30 wt% sodium cyanide aqueous solution and 20 kg of phase transfer catalyst were placed in a reactor and heated to 75-80 ° C. Then, 1500 kg of o-chlorobenzyl chloride was added dropwise for 2 hours. After the addition was completed, the temperature was kept constant until the control was qualified (the area normalization of o-chlorobenzyl chloride was <1%). After cooling to room temperature, the layers were separated and the organic layer was distilled to obtain 1259.3 kg of o-chlorobenzeneacetonitrile product.
[0070] Performance testing methods
[0071] 1. The o-chlorophenylacetonitrile finished products obtained in the embodiments and comparative examples were subjected to purity and yield tests. The test data are listed in Table 1.
[0072] 2. Example 1 The o-chlorophenylacetonitrile finished product was subjected to GC-MASS (gas chromatography-mass spectrometry) test. Figure 2 As shown, except for o-chlorophenylacetonitrile, the analysis spectrum shows that the ion information of the by-product is: m / z=275.0 (M + ), 125.0([M-C7H5ClCN] + ).
[0073] Performance test data
[0074] Table 1
[0075] purity% Yield % Example 1 98.42 96.3 Example 2 98.83 97.2 Example 3 98.26 96.85 Example 4 98.52 97.05 Example 5 98.67 96.75 Comparative Example 1 98.47 89.2 Comparative Example 2 98.14 88.7
Claims
1. A continuous production device for o-chlorophenylacetonitrile, characterized in that, include: o-chlorobenzyl chloride storage tank (1), sodium cyanide aqueous solution storage tank (2), first tower continuous reactor (3), first continuous phase separation device (4), low-content sodium cyanide water layer storage tank (5), o-chlorophenylacetonitrile crude product storage tank (6), first continuous distillation tower (7), condenser (8), o-chlorophenylacetonitrile finished product storage tank (9), second tower continuous reactor (10), second continuous phase separation device (11), to-be-broken cyanide water layer storage tank (12), intermediate storage tank (13), preparation kettle (14), catalyst feeding bin (15), solution A storage tank (16), solution B storage tank (17), second continuous distillation tower (18); the preparation kettle (14) is connected to the sodium cyanide aqueous solution storage tank (2), catalyst feeding bin (15), solution A storage tank (16), respectively; the first tower continuous reactor (3) The first continuous phase separation device (4) is connected to the o-chlorobenzyl chloride storage tank (1), the first continuous phase separation device (4), and the solution A storage tank (16) respectively; one end of the first continuous phase separation device (4) is connected in sequence to the o-chlorophenylacetonitrile crude product storage tank (6), the first continuous distillation tower (7), the condenser (8), and the o-chlorophenylacetonitrile finished product storage tank (9), and the other end is connected in sequence to the low-content sodium cyanide water layer storage tank (5), the second tower continuous reactor (10), the second continuous phase separation device (11), the solution B storage tank (17), the second continuous distillation tower (18), and the condenser (8); the condenser (8) is connected to the o-chlorophenylacetonitrile crude product storage tank (6); the second continuous phase separation device (11) is also connected to the cyanide-destroying water layer storage tank (12); the second continuous distillation tower (18) is also connected to the condenser (8) and the intermediate storage tank (13).
2. The continuous production device of o-chlorophenylacetonitrile according to claim 1, wherein The first tower continuous reactor (3) and the second tower continuous reactor (10) are both packed towers.
3. A method for producing o-chlorophenylacetonitrile according to the device of claim 2, characterized in that, The following steps are involved: S1, sodium cyanide aqueous solution and phase transfer catalyst are respectively inputted from sodium cyanide aqueous solution storage tank (2) and catalyst feeding bin (15) into preparation kettle (14), and then transferred to solution A storage tank (16); S2, the o-chlorobenzyl chloride in the o-chlorobenzyl chloride storage tank (1) and the material in the solution A storage tank (16) are fed into the first tower continuous reactor (3) for reaction, the reaction liquid overflows into the first continuous phase separation device (4), the separated water phase enters the low-content sodium cyanide water layer storage tank (5), and the organic phase enters the o-chlorophenylacetonitrile crude product storage tank (6), the first continuous distillation tower (7), the condenser (8) and is collected into the o-chlorophenylacetonitrile finished product storage tank (9); S3, the aqueous phase in the low-content sodium cyanide water layer storage tank (5) and the material in the intermediate storage tank (13) are input into the second tower continuous reactor (10) for reaction, the reaction solution overflows to the second continuous phase separation device (11), the separated aqueous phase is stored in the cyanide-to-be-broken aqueous layer storage tank (12), the organic phase enters the solution B storage tank (17) and the second continuous distillation tower (18) in sequence, and is distilled in the second continuous distillation tower (18), the light component is cooled by the condenser and collected in the intermediate storage tank (13), and the heavy component is distilled in the first continuous distillation tower (7) through the o-chlorophenylacetonitrile crude product storage tank (6).
4. The method for producing o-chlorophenylacetonitrile according to claim 3, wherein The material in the intermediate storage tank (13) includes a mixture of o-chlorophenylacetonitrile and o-chlorobenzyl chloride or o-chlorobenzyl chloride.
5. The method for producing o-chlorophenylacetonitrile according to claim 3, wherein The content of the phase transfer catalyst in the preparation kettle (14) is 0.05-0.8 wt%.
6. The method for producing o-chlorophenylacetonitrile according to claim 3, wherein The temperature of the first tower continuous reactor (3) is 50-80°C, and the temperature of the second tower continuous reactor (10) is 60-90°C.
7. The method for producing o-chlorophenylacetonitrile according to claim 3, wherein The molar ratio of o-chlorobenzyl chloride to sodium cyanide in the first tower continuous reactor (3) is 1:1.1-3.
5.
8. The method for producing o-chlorophenylacetonitrile according to claim 4, wherein The molar ratio of sodium cyanide to o-chlorobenzyl chloride in the second tower continuous reactor (10) is 1:1.5-5.
9. The method for producing o-chlorophenylacetonitrile according to claim 8, wherein The residence time of the material in the first tower continuous reactor (3) is 0.25 to 3 hours.
10. The method for producing o-chlorophenylacetonitrile according to claim 8, wherein The residence time of the material in the second tower continuous reactor (10) is 0.25 to 2 hours.
Citation Information
Patent Citations
A method for synthesizing o-chlorobenzonitrile
CN114349660B