CN113072555A - Synthesis method and device of diquat dichloride - Google Patents
Synthesis method and device of diquat dichloride Download PDFInfo
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- CN113072555A CN113072555A CN202110372235.3A CN202110372235A CN113072555A CN 113072555 A CN113072555 A CN 113072555A CN 202110372235 A CN202110372235 A CN 202110372235A CN 113072555 A CN113072555 A CN 113072555A
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- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
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Abstract
The invention discloses a method and a device for synthesizing diquat dichloride, which comprise the following steps: loading the catalyst into a fixed bed reactor, activating for 4-6h at the temperature of 300-550 ℃ and under the nitrogen flow rate of 50-150ml/min, and then cooling to the reaction temperature; adding dichloroethane and 2, 2-bipyridine into a mixer for mixing; the mixed liquid in the mixer is pumped into a gasification chamber for gasification at a certain speed through a centrifugal pump, the fixed bed reactor enters a condensation pipe for condensation, water is continuously fed into the condensation pipe for extracting dichlorphenate, then the extract liquid and the raffinate liquid enter a standing kettle for liquid separation, the upper-layer aqueous solution enters a concentration kettle for concentration, the lower-layer dichloroethane phase enters a film evaporator for recovering dichloroethane and bipyridyl, and the concentrated mixed liquid can be prepared into a mother liquor of the dichlorphenate or a mother medicine of the dichlorphenate as required. The invention adopts a continuous production method, which not only greatly improves the production efficiency, but also has simple process, convenient solvent recovery and low requirement on equipment for reaction.
Description
Technical Field
The invention relates to the technical field of herbicide synthesis, in particular to a method and a device for synthesizing diquat dichloride.
Background
The diquat has the chemical name of 1,1' -ethylene-2, 2' -bipyridyl di-onium salt, is an important pyridine herbicide, is a colorless to faint yellow crystal in a pure product, is developed by Zusanhuanda company, and often exists in the form of a monohydrate compound of a dibromo salt, and at present, the production method of the diquat in China mainly adopts 2,2' -bipyridyl and dibromoethane to carry out cyclization reaction in a kettle type intermittent reactor.
The existing industrialized method for synthesizing diquat is mainly characterized in that 2,2' -bipyridine reacts with dibromoethane to prepare the diquat, the preparation of other counter ion salts of the diquat is difficult, and the dichloronium salt of the diquat is most economical in terms of atom economy, but due to the low activity of dichloroethane, the preparation method of the dichloroquat which is similar to the preparation method of the dibromosalt of the diquat needs high pressure and temperature, seriously corrodes equipment, and industrial production cannot be realized. In a series of patent documents of ICI company, the preparation of diquat dichloride is not finally industrialized. The synthesis of diquat dichloride is mainly prepared by adopting an ion exchange method, and Chinese patent CN201811318062.1 discloses a preparation method of 1,1 '-ethylene-2, 2' -bipyridine dichloride, wherein diquat dibromo salt aqueous solution is mixed with hydrochloric acid and then is dripped into a mixed solution of an organic solvent, a bromine absorbent and an oxidant for reaction to prepare the diquat dichloride; chinese patent CN201710760340.8 discloses a green preparation method of diquat anion salt, in the presence of hydrochloric acid or sulfuric acid, diquat dibromide mother liquor reacts with an oxidant to obtain reaction liquid containing diquat dichloride or diquat bisulfate, and acetylene is added to recover bromine.
The two patents adopt an ion exchange method to prepare the diquat dichloride, but the method has complex process and complicated operation, and simultaneously is an intermittent reaction with lower efficiency; in addition, the method also relates to the recovery of bromine atoms, the solvent recovery is troublesome in the reaction process, and the corrosion to equipment is serious, thus being not beneficial to industrial production.
In conclusion, the problems of the synthesis of the dichlormate at present are as follows:
1. the diquat dichloride is mainly prepared by ion exchange by diquat dibromo salt, and has the advantages of complex process, complex operation and high equipment requirement.
2. Since the activity of dichloroethane is lower than that of dibromoethane, the dichloroethane can not be directly cyclized with pyridine to prepare diquat dichloride.
3. At present, the synthesis of diquat is mainly intermittent reaction, and the production efficiency is low.
Disclosure of Invention
The invention aims to provide a method and a device for synthesizing diquat dichloride, which are used for solving the problems of complex process, complex operation and low production efficiency in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a synthetic method of diquat dichloride comprises the following steps:
step 1: catalyst activation
Loading the catalyst into a fixed bed reactor, activating for 4-6h at the temperature of 300-;
step 2: mixing of raw materials
Adding dichloroethane and 2, 2-bipyridine into a mixer for mixing, wherein the temperature of the mixer is between 50 and 100 ℃;
and step 3: cyclization reaction
The mixed solution in the mixer is pumped into a gasification chamber for gasification at a certain speed through a centrifugal pump, the gasified gas enters a fixed bed reactor from the top of the fixed bed for reaction, the fixed bed reactor then enters a condenser pipe for condensation, water is continuously fed into the condenser pipe for extracting diquat dichloride, then the extract and raffinate enter a standing kettle for liquid separation, the upper-layer aqueous solution enters a concentration kettle for concentration, and the water is recycled and reused; the dichloroethane phase at the lower layer enters a film evaporator to recover the dichloroethane and the bipyridyl, and the concentrated mixed solution can be prepared into diquat mother liquor or diquat mother medicine according to requirements.
Further, the catalyst in the step 1 is CuO/gamma-Al2O3The catalyst in the step 1 contains 0.2 to 10 percent of CuO.
Further, CuO/gamma-Al described in step 12O3The catalyst is prepared by an impregnation method.
Further, the reaction temperature in step 3 is 120-350 ℃, preferably 140-300 ℃, and the reaction pressure in step 3 is 0.1-5MPa, preferably 1-3 MPa.
Further, the molar ratio of 2,2' -bipyridine to dichloroethane in step 2 is 1:1.1 to 5.3, and the feed rate of the raw material is 0.02 to 10ml/min, preferably 0.5 to 5 ml/min.
Further, the cyclization reagent and the solvent in the step 3 are dichloroethane, and the gasification temperature of the raw material is 150-300 ℃.
The invention also provides another technical scheme: the utility model provides a device that synthetic method of diquat dichloride utilized, includes blender, vaporizer, fixed bed reactor, condenser pipe, stilling cauldron, concentration cauldron, film evaporator, connect the centrifugal pump between blender and the vaporizer, the feed end of fixed bed reactor is connected to the discharge end of vaporizer, the feed end of condenser pipe is connected to the discharge end of fixed bed reactor, fresh water is poured into to the upper end of condenser pipe, and stilling cauldron feed end is connected to the discharge end of condenser pipe, and film evaporator is connected to the bottom of stilling cauldron, and film evaporator still is connected with the blender and makes dichloroethane and 2,2 ally oneself with the pyridine cover and apply mechanically, stilling cauldron is connected with the filter, and the pipeline connection of stilling cauldron and fresh water.
Furthermore, the fixed bed reactor consists of three catalyst bed layers, each catalyst bed layer is provided with three layers, the upper layer and the lower layer are screens, and the middle layer is a catalyst.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts the catalyst to synthesize the diquat dichloride for the first time, and the product yield can reach more than 90 percent.
2. The diquat dichloride is prepared by adopting a fixed bed reactor to carry out cyclization, so that the continuity of the diquat dichloride is realized, and the production efficiency is greatly improved.
3. And in the post-treatment stage, two-stage continuous extraction and a thin film evaporator are adopted, so that the production efficiency is improved.
4. Realizes the reutilization of the raw materials and the solvent and saves the cost of the raw materials.
Drawings
FIG. 1 is a schematic diagram of an apparatus for synthesizing diquat dichloride according to the present invention.
In the figure: 1. a mixer; 2. a centrifugal pump; 3. a gasification chamber; 4. a fixed bed reactor; 5. a condenser tube; 6. standing the mixture in a kettle; 7. a concentration kettle; 8. a thin film evaporator; 9. and (3) a filter.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, a method for synthesizing diquat dichloride comprises the following steps:
step 1: catalyst activation
Loading the catalyst into a fixed bed reactor 4, activating for 4-6h at the temperature of 300-550 ℃ and the nitrogen flow rate of 50-150ml/min, then cooling to the reaction temperature, and simultaneously adjusting the pressure to the reaction pressure;
step 2: mixing of raw materials
Adding dichloroethane and 2, 2-bipyridyl into a mixer 1 for mixing, wherein the temperature of the mixer 1 is between 50 and 100 ℃;
and step 3: cyclization reaction
The mixed solution in the mixer 1 is pumped into a gasification chamber 3 for gasification at a certain speed through a centrifugal pump 2, the gasified gas enters a fixed bed reactor 4 from the top of the fixed bed for reaction, the fixed bed reactor 4 then enters a condenser pipe 5 for condensation, water-extracted diquat dichloride continuously enters the condenser pipe 5, then the extract and raffinate enter a standing kettle 6 for liquid separation, the upper-layer aqueous solution enters a concentration kettle 7 for concentration, and water is recycled and reused; the dichloroethane phase at the lower layer enters a film evaporator 8 to recover the dichloroethane and the bipyridyl, and the concentrated mixed solution can be prepared into diquat mother liquor or diquat mother medicine according to requirements.
A synthesizer of diquat dichloride comprises a mixer 1, a gasification chamber 3, a fixed bed reactor 4, a condenser pipe 5, a standing still 6, a concentration still 7 and a film evaporator 8, wherein a centrifugal pump 2 is connected between the mixer 1 and the gasification chamber 3, the mixer 1 is used for mixing 2, 2-bipyridyl and dichloroethane solution, the mixed solution is sent into the gasification chamber 3 through the centrifugal pump 2 for gasification, the discharge end of the gasification chamber 3 is connected with the feed end of the fixed bed reactor 4, the gasified mixed solution enters the fixed bed reactor 4, the discharge end of the fixed bed reactor 4 is connected with the feed end of the condenser pipe 5, the mixed solution enters the condenser pipe 5 for condensation after the full reaction of the fixed bed reactor 4, fresh water is injected into the upper end of the condenser pipe 5, the mixed solution is condensed by using the temperature difference of water, the discharge end of the condenser pipe 5 is connected with the feed end of the standing still 6, the standing still 6 is beneficial to, the bottom end of the still standing kettle 6 is connected with a thin film evaporator 8, the thin film evaporator 8 is also connected with the mixer 1 to enable dichloroethane and 2, 2-bipyridyl to be applied mechanically, the still standing kettle 6 is connected with a filter 9, and the still standing kettle 6 is connected with a pipeline of fresh water.
The fixed bed reactor 4 consists of three catalyst bed layers, each catalyst bed layer has three layers, the upper layer and the lower layer are screens, and the middle layer is a catalyst. The fixed bed adopts three catalyst layers, the catalyst is uniformly distributed and is convenient to disassemble, and side reactions are obviously reduced.
Example 1:
mixing CuO/gamma-Al2O3(CuO content is 1%) catalyst is loaded into a fixed bed reactor, activated for 4h under the conditions of 300 ℃ and 100ml/min of nitrogen flow, cooled to 140 ℃, the reaction pressure is 1MPa, the raw materials enter the reactor at the speed of 0.5ml/min for reaction, and then the product of diquat dichloride is obtained through cooling, extraction, separation, distillation and filtration, with the yield of 93.5%。
Example 2:
mixing CuO/gamma-Al2O3(the content of CuO is 1%) catalyst is loaded into a fixed bed reactor, activated for 6h under the conditions of 550 ℃ and nitrogen flow rate of 150ml/min, cooled to 300 ℃, the reaction pressure is 3MPa, raw materials enter the reactor at the speed of 2.5ml/min for reaction, and then the product of diquat dichloride is obtained through cooling, extraction, separation, distillation and filtration, with the yield of 91.2%.
Example 3:
mixing CuO/gamma-Al2O3(the content of CuO is 5%) catalyst is loaded into a fixed bed reactor, activated for 4h under the conditions of 450 ℃ and 100ml/min of nitrogen flow, cooled to 250 ℃ and the reaction pressure is 2MPa, raw materials enter the reactor at the speed of 1ml/min for reaction, and then the product of diquat dichloride is obtained through cooling, extraction, separation, distillation and filtration, and the yield is 92.3%.
Example 4:
mixing CuO/gamma-Al2O3(the content of CuO is 5%) catalyst is loaded into a fixed bed reactor, activated for 6h under the conditions of 350 ℃ and nitrogen flow rate of 50ml/min, cooled to 200 ℃, the reaction pressure is 3MPa, raw materials enter the reactor at the speed of 5ml/min for reaction, and then the product of diquat dichloride is obtained through cooling, extraction, separation, distillation and filtration, and the yield is 90.5%.
Example 5:
mixing CuO/gamma-Al2O3(the content of CuO is 10%) catalyst is loaded into a fixed bed reactor, activated for 5h under the conditions of 400 ℃ and 50ml/min of nitrogen flow, cooled to 300 ℃, the reaction pressure is 0.5MPa, the raw material enters a reactor at the speed of 1.5ml/min for reaction, and then the product of diquat dichloride is obtained through cooling, extraction, separation, distillation and filtration, and the yield is 94.2%.
Example 6:
mixing CuO/gamma-Al2O3(CuO content is 10%) catalyst is loaded into a fixed bed reactor, activated for 5h under the conditions of 250 ℃ and 100ml/min of nitrogen flow rate, cooled to 140 ℃, the reaction pressure is 0.2MPa, and the raw material velocity is 2.5The mixture enters a reactor for reaction at a concentration of ml/min, and then is cooled, extracted, separated, distilled and filtered to obtain a diquat dichloride product with a yield of 91.2 percent.
Example 7:
mixing CuO/gamma-Al2O3(the content of CuO is 7%) catalyst is loaded into a fixed bed reactor, activated for 5.5h under the conditions of 300 ℃ and nitrogen flow rate of 70ml/min, cooled to 180 ℃, the reaction pressure is 1.3MPa, raw materials enter the reactor at the speed of 3.2ml/min for reaction, and then the product of diquat dichloride is obtained through cooling, extraction, separation, distillation and filtration, with the yield of 90.1%.
Example 8:
mixing CuO/gamma-Al2O3(the content of CuO is 3%) catalyst is loaded into a fixed bed reactor, activated for 4.5h under the conditions of 350 ℃ and nitrogen flow rate of 80ml/min, cooled to 270 ℃, the reaction pressure is 2.3MPa, raw materials enter the reactor at the speed of 0.3ml/min for reaction, and then the product of diquat dichloride is obtained through cooling, extraction, separation, distillation and filtration, with the yield of 90.2%.
The invention takes pyridine and dichloroethane as raw materials, adopts a continuous production method, not only greatly improves the production efficiency, but also has simple process, convenient solvent recovery and low requirement on equipment for reaction, solves the problems existing in the prior diquat dichloride synthesis process, and realizes the process for directly synthesizing the diquat dichloride from the pyridine and the dichloroethane; the method conforms to the atom economy principle in chemical production, does not produce pollution harmful to the environment, and is a green chemical intermediate production technology.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (8)
1. A synthetic method of diquat dichloride is characterized by comprising the following steps:
step 1: catalyst activation
The catalyst is loaded into a fixed bed reactor (4), activated for 4-6h at the temperature of 300-;
step 2: mixing of raw materials
Adding dichloroethane and 2, 2-bipyridyl into a mixer (1) for mixing, wherein the temperature of the mixer (1) is between 50 and 100 ℃;
and step 3: cyclization reaction
The mixed solution in the mixer (1) is pumped into a gasification chamber (3) for gasification at a certain speed through a centrifugal pump (2), the gasified gas enters a fixed bed reactor (4) from the top of the fixed bed for reaction, the fixed bed reactor (4) then enters a condensation pipe (5) for condensation, water-extracted diquat dichloride continuously enters the condensation pipe (5), then the extract and raffinate enter a standing kettle (6) for liquid separation, the upper-layer aqueous solution enters a concentration kettle (7) for concentration, and water is recycled and reused; the dichloroethane phase at the lower layer enters a film evaporator (8) to recover dichloroethane and bipyridyl, and the concentrated mixed solution can be prepared into diquat mother liquor or diquat mother medicine according to requirements.
2. The method of claim 1, wherein the catalyst in step 1 is CuO/γ -Al2O3The catalyst in the step 1 contains 0.2 to 10 percent of CuO.
3. The method of claim 1, wherein the CuO/γ -Al is used in step 12O3The catalyst is prepared by an impregnation method.
4. The method for synthesizing diquat dichloride as claimed in claim 1, wherein the reaction temperature in step 3 is 120-350 ℃, preferably 140-300 ℃, and the reaction pressure in step 3 is 0.1-5MPa, preferably 1-3 MPa.
5. The method for synthesizing a diquat dichloride as claimed in claim 1, wherein the molar ratio of 2,2' -bipyridine to dichloroethane in step 2 is 1:1.1-5.3, and the raw material is fed at a rate of 0.02-10ml/min, preferably 0.5-5 ml/min.
6. The method as claimed in claim 1, wherein said cyclization agent and solvent in step 3 are dichloroethane, and the gasification temperature of raw material is 150-300 ℃.
7. The device for utilizing the synthesis method of diquat dichloride as claimed in claim 1, which comprises a mixer (1), a gasification chamber (3), a fixed bed reactor (4), a condenser pipe (5), a still standing kettle (6), a concentration kettle (7) and a thin film evaporator (8), wherein a centrifugal pump (2) is connected between the mixer (1) and the gasification chamber (3), the discharge end of the gasification chamber (3) is connected with the feed end of the fixed bed reactor (4), the discharge end of the fixed bed reactor (4) is connected with the feed end of the condenser pipe (5), fresh water is injected into the upper end of the condenser pipe (5), the discharge end of the condenser pipe (5) is connected with the feed end of the still standing kettle (6), the bottom end of the still standing kettle (6) is connected with the thin film evaporator (8), and the thin film evaporator (8) is also connected with the mixer (1) to ensure that dichloroethane and 2 are mixed, the 2-bipyridyl is used mechanically, the still standing kettle (6) is connected with the filter (9), and the still standing kettle (6) is connected with a pipeline of fresh water.
8. The apparatus for synthesizing aquacide dichlorosalt according to claim 7, wherein the fixed bed reactor (4) is composed of three catalyst beds, each catalyst bed has three layers, the upper and lower layers are screens, and the middle layer is catalyst.
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