CN109053454B - Preparation method of nitromethane and application of poly (4-vinylpyridine) - Google Patents
Preparation method of nitromethane and application of poly (4-vinylpyridine) Download PDFInfo
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- CN109053454B CN109053454B CN201810833081.1A CN201810833081A CN109053454B CN 109053454 B CN109053454 B CN 109053454B CN 201810833081 A CN201810833081 A CN 201810833081A CN 109053454 B CN109053454 B CN 109053454B
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- vinylpyridine
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- nitromethane
- nitrite
- dimethyl sulfate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/10—Preparation of nitro compounds by substitution of functional groups by nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
Abstract
A preparation method of nitromethane relates to the field of organic synthesis, and comprises the step of carrying out mixed reaction on dimethyl sulfate, nitrite, alkali and poly (4-vinylpyridine). The addition of poly (4-vinylpyridine) can reduce harmful gas in the production process and greatly improve the yield and purity of the product. Meanwhile, the poly (4-vinylpyridine) is easy to separate, and is beneficial to recovering the sulfate as a byproduct. The preparation method has mild conditions and simple operation, and is suitable for industrial large-scale production. The application of poly (4-vinylpyridine) in the synthesis reaction of nitromethane can improve the yield and purity of nitromethane and does not affect the recovery of by-products.
Description
Technical Field
The invention relates to the field of organic synthesis, and particularly relates to a preparation method of nitromethane and application of poly (4-vinylpyridine).
Background
Nitromethane is an important organic chemical product and an organic synthesis intermediate, is colorless and transparent oily liquid with aromatic flavor and certain volatility, has melting point of-28.5 ℃, boiling point of 100.8 ℃, relative density of 1.1371(20/4 ℃), refractive index of 1.3817, flash point of 35 ℃, is partially soluble with water, is acidic in water solution, and is dissolved in ethanol, ether, dimethylformamide and caustic alkali solution; the explosive is easy to ignite, can cause explosion under strong force impact or detonator detonation, and the steam and the air can form an explosive mixture, the lower explosion limit is 7.3 percent (V), the toxicity is high, and the explosive mixture has irritation to conjunctiva, respiratory tract and skin. The maximum allowable concentration in air is 100 ppm.
Nitromethane is miscible with most organic compounds and is a good solvent for aromatic hydrocarbons, alcohols, ketones, ethers, esters and carboxylic acid-based compounds. The catalyst has the characteristics of good selectivity, low viscosity, low volatility and the like, is widely used for synthesizing high polymer materials, and can also be used for preparing industries such as explosives, rocket fuels, pesticides, gasoline additives, coatings, textiles, foods, paints and the like. Nitromethane is also ー liquid explosive with good performance, and can be used as a fuel additive to improve the combustion value of the fuel and reduce pollution. The nitromethane is used as a raw material to synthesize a plurality of important organic chemical products, such as nitroalcohol and the like, and thus, the nitromethane is also an important raw material in the industries of medicine, pesticide, dye and the like.
In recent years, market demand has increased, and export volume has increased year by year. The domestic process routes for producing nitromethane mainly comprise two types: one is a methane gas phase nitration method: spraying nitric acid into mist state, gasifying the nitric acid, mixing the nitric acid and methane (natural gas) in proportion, directly nitrifying the mixture in a tubular reactor at the normal pressure of 450-550 ℃, and condensing, absorbing, roughly distilling and rectifying the mixture to obtain a finished product. The raw material methane (natural gas) used in the method is flammable and explosive, is not beneficial to safe production, and has the advantages of multiple side reactions, low product purity, high energy consumption and high cost. The other method is a dimethyl sulfate nitroso substitution method: the method is prepared by replacing dimethyl sulfate and sodium nitrite, rough distillation and rectification, and has the advantages of simple process operation, easily obtained raw materials, low production cost, easy industrial production and the like. At present, most domestic manufacturers adopt the method, but the yield is less than 70 percent, and the product purity is difficult to reach 99 percent.
The reaction formula for producing nitromethane by replacing dimethyl sulfate and sodium nitrite is as follows:
(CH3)2SO4+2NaNO2→2CH3NO2+Na2SO4
the by-product of the reaction is methyl nitrite with a chemical formula of CH3ONO。
Thus, the off-gas from the production contains the isomer methyl nitrite of the by-product nitromethane. The boiling point is-17.3 ℃, colorless, toxic and irritant gas is generated at normal temperature, the gas is not dissolved in water, and low-boiling gas methyl nitrite is generated, so that environmental and safety hazards such as sparks and the like are easily generated in the rectification process.
In small-scale laboratory preparations, small amounts of by-products are not yet to be of significant importance. However, in the industrial mass production process, the reaction temperature is difficult to control, a large amount of harmful gas is generated, the surrounding environment is affected, the purity of the final product is difficult to reach more than 99%, and the later purification cost is increased.
In the prior art, the yield and purity of the reaction can be improved by adding an appropriate adjuvant such as N, N-dimethylaniline, N-diethylaniline, N-dimethyl-N-propylamine during the reaction, but these adjuvants have been found to be difficult to remove from the system when recovery of by-product sodium sulfate is required, and to cause trouble in separation of sodium sulfate.
Disclosure of Invention
The invention aims to provide a preparation method of nitromethane, which has mild reaction conditions and simple operation, can obtain high-purity nitromethane with high yield, and can conveniently recover byproducts.
It is another object of the present invention to provide the use of poly (4-vinylpyridine) which increases the yield and purity of nitromethane without affecting the recovery of by-products.
The embodiment of the invention is realized by the following steps:
a method for preparing nitromethane, comprising:
dimethyl sulfate, nitrite, alkali and poly (4-vinylpyridine) are mixed and reacted.
An application of poly (4-vinylpyridine) in synthesizing nitromethane.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a preparation method of nitromethane, which comprises the step of mixing dimethyl sulfate, nitrite, alkali and poly (4-vinylpyridine) for reaction. The addition of poly (4-vinylpyridine) can reduce harmful gas in the production process and greatly improve the yield and purity of the product. Meanwhile, the poly (4-vinylpyridine) is easy to separate, and is beneficial to recovering the sulfate as a byproduct. The preparation method has mild conditions and simple operation, and is suitable for industrial large-scale production.
The embodiment of the invention also provides application of the poly (4-vinylpyridine), which can improve the yield and purity of the nitromethane and does not influence the recovery of byproducts by applying the poly (4-vinylpyridine) to the synthesis reaction of the nitromethane.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of a method for preparing nitromethane and the application of poly (4-vinylpyridine) according to an embodiment of the present invention.
The embodiment of the invention provides a preparation method of nitromethane, which comprises the following steps:
dimethyl sulfate, nitrite, alkali and poly (4-vinylpyridine) are mixed and reacted.
Nitromethane is an important organic chemical product and an organic synthesis intermediate, is colorless and transparent oily liquid with aromatic flavor and certain volatility, has melting point of-28.5 ℃, boiling point of 100.8 ℃, relative density of 1.1371(20/4 ℃), refractive index of 1.3817, flash point of 35 ℃, is partially soluble with water, is acidic in water solution, and is dissolved in ethanol, ether, dimethylformamide and caustic alkali solution; the explosive is easy to ignite, can cause explosion under strong force impact or detonator detonation, and the steam and the air can form an explosive mixture, the lower explosion limit is 7.3 percent (V), the toxicity is high, and the explosive mixture has irritation to conjunctiva, respiratory tract and skin. The maximum allowable concentration in air is 100 ppm.
The domestic process routes for producing nitromethane mainly comprise two types: one is methane gas phase nitration and the other is dimethyl sulfate nitroso substitution. Compared with the prior art, the dimethyl sulfate nitroso substitution method has the advantages of simple process operation, easily obtained raw materials, low production cost, easy industrial production and the like.
Taking dimethyl sulfate and sodium nitrite as an example for replacing and producing nitromethane, the reaction formula is as follows:
(CH3)2SO4+2NaNO2→2CH3NO2+Na2SO4
the nitroso group can serve as both nitrogen and oxygen as the reaction center during the substitution reaction. The nitroso can generate nitrogen nucleophilic reaction to obtain nitromethane and can also generate oxygen nucleophilic reaction to obtain byproduct methyl nitrite with the chemical formula of CH3ONO. Meanwhile, the yield of nitromethane is usually not more than 70% because the nitrogen and the oxygen are in the same period and have little difference in nucleophilicity, which leads to little difference in the amounts of main products and byproducts.
Furthermore, methyl nitrite has a boiling point of-17.3 ℃, is colorless, toxic and irritant gas at normal temperature, is insoluble in water, and generates low-boiling gas methyl nitrite which can be mixed in produced tail gas, so that environmental and safety hazards such as sparks are easily generated in the rectification process. At the same time, by-product Na is generated2SO4As an important working raw material, the material also needs to be recycled, so that the waste of the material is avoided. Therefore, in the post-treatment process of the above reaction, the removal of methyl nitrite and the recovery of sodium sulfate are important two points.
For the reasons, the embodiment of the invention inventively adds poly (4-vinylpyridine) as an auxiliary agent in the synthesis of nitromethane to inhibit oxygen nucleophilic reaction, thereby improving the yield and purity of nitromethane. Meanwhile, the poly (4-vinylpyridine) is solid and can be very simply separated from the sodium sulfate, thereby being beneficial to the recovery of the sodium sulfate.
Further, in the present examples, the molar ratio of dimethyl sulfate to nitrite was 1: 2.0 to 2.3. Wherein the nitrite comprises at least one of sodium nitrite, potassium nitrite and magnesium nitrite. According to the reaction formula for synthesizing nitromethane, the molar ratio of dimethyl sulfate to nitrite is 1: 2, in actual production, the nitrite can be in proper excess to ensure that the dimethyl sulfate is completely reacted. Excess nitrite can be recovered in the post-treatment, avoiding waste of materials.
Further, in the present examples, the molar ratio of dimethyl sulfate to base was 1: 0.05 to 0.2. Wherein the base comprises at least one of sodium carbonate, potassium carbonate and lithium carbonate. The base may be reacted with methyl nitrite to produce dimethyl carbonate. Dimethyl carbonate is generally a neutral colorless liquid, has mild smell and low toxicity, and can reduce the toxicity of reaction tail gas. Meanwhile, dimethyl carbonate is an important chemical raw material, and can be further converted into dimethyl sulfate for use, so that the dimethyl carbonate can be recycled in post-treatment.
Further, in the present example, the mass ratio of dimethyl sulfate to poly (4-vinylpyridine) was 1: 0.01 to 0.02. The inventors have found through creative work that when the above-mentioned ratio is added, the inhibition effect on the oxygen nucleophilic reaction is better, and the yield and purity of nitromethane are improved.
Further, dimethyl sulfate, nitrite, alkali and poly (4-vinylpyridine) are mixed and reacted for 3-5 hours at the temperature of 30-35 ℃. When the reaction is carried out at the above temperature, the effect of suppressing the side reaction is good, and the amount of the by-product can be effectively reduced.
Optionally, mixing the alkali, the nitrite and the poly (4-vinylpyridine) to obtain a mixed solution; and then dimethyl sulfate is dropwise added into the mixed solution. The dropwise adding mode is adopted, so that the amount of dimethyl sulfate participating in the reaction at the same time can be reduced, and the occurrence of side reaction is reduced.
Further, after the reaction was completed, the solid phase component was removed by filtration, and the liquid phase component was subjected to rectification. The solid phase component contains sulfate and poly (4-vinylpyridine), and after the solid phase component is washed by water, the sulfate enters into a water phase, so that the poly (4-vinylpyridine) can be quickly separated.
The embodiment of the invention also provides application of the poly (4-vinylpyridine) in nitromethane synthesis. The poly (4-vinylpyridine) is applied to the synthesis reaction of nitromethane, can improve the yield and the purity of the nitromethane, and does not influence the recovery of byproducts.
The features and properties of the present invention are described in further detail below with reference to examples. It is noted that in the following examples, the purity of nitromethane was measured on a 103 GC, a thermal conductivity detector, a CDMC-2A chromatograph data processor, a phi 3mm X2 m stainless steel column for the column, and a filler of 150-180 μm filled with three X-502.
Example 1
The embodiment provides a preparation method of nitromethane, which comprises the following steps:
s1, respectively adding 63g (0.5mmol) of dimethyl sulfate, 69g (1.0mmol) of sodium nitrite, 1.0g of poly (4-vinylpyridine), 4.0g of sodium carbonate and 30mL of water into a three-mouth bottle provided with an electric stirrer, a reflux condenser tube and a thermometer to obtain reaction liquid;
s2, stirring and heating the reaction liquid to 30 ℃ and reacting for 3 h.
S3, filtering and separating, and rectifying the liquid phase component to obtain 24.5g of nitromethane, wherein the yield is 80%, and the purity is 99.9%.
Example 2
The embodiment provides a preparation method of nitromethane, which comprises the following steps:
s1, respectively adding 63g (0.5mmol) of dimethyl sulfate, 93.6g (1.1mmol) of potassium nitrite, 0.7g of poly (4-vinylpyridine), 10.0g of sodium carbonate and 40mL of water into a three-mouth bottle provided with an electric stirrer, a reflux condenser tube and a thermometer to obtain reaction liquid;
s2, stirring and heating the reaction liquid to 35 ℃ and reacting for 3 h.
S3, filtering and separating, and rectifying the liquid phase component to obtain 25.0g of nitromethane, wherein the yield is 82% and the purity is 99.9%.
Example 3
The embodiment provides a preparation method of nitromethane, which comprises the following steps:
s1, respectively adding 63g (0.5mmol) of dimethyl sulfate, 76g (1.1mmol) of sodium nitrite, 1.2g of poly (4-vinylpyridine), 8.2g of potassium carbonate and 50mL of water into a three-necked bottle provided with an electric stirrer, a reflux condenser tube and a thermometer to obtain a reaction solution;
s2, stirring and heating the reaction liquid to 35 ℃ to react for 5 hours.
S3, filtering and separating, and rectifying the liquid phase component to obtain 23.5g of nitromethane, wherein the yield is 77%, and the purity is 99.9%.
Example 4
The embodiment provides a preparation method of nitromethane, which comprises the following steps:
s1, respectively adding 63g (0.5mmol) of dimethyl sulfate, 79g (1.15mmol) of sodium nitrite, 0.8g of poly (4-vinylpyridine), 4.0g of potassium carbonate and 30mL of water into a three-necked bottle provided with an electric stirrer, a reflux condenser tube and a thermometer to obtain a reaction solution;
s2, stirring and heating the reaction liquid to 30 ℃ and reacting for 5 hours.
S3, filtering and separating, and rectifying the liquid phase component to obtain 23.8g of nitromethane, wherein the yield is 79 percent, and the purity is 99.9 percent.
Example 5
The embodiment provides a preparation method of nitromethane, which comprises the following steps:
s1, respectively adding 69g (1.0mmol) of sodium nitrite, 1.0g of poly (4-vinylpyridine), 4.0g of sodium carbonate and 30mL of water into a three-necked flask provided with an electric stirrer, a reflux condenser tube and a thermometer to obtain reaction liquid;
s2, stirring and heating the reaction liquid to 30 ℃, dropwise adding 63g (0.5mmol) of dimethyl sulfate, and continuing to react for 3 hours after dropwise adding is finished.
S3, filtering and separating, and rectifying the liquid phase component to obtain 25.6g of nitromethane, wherein the yield is 84%, and the purity is 99.9%.
In summary, the embodiments of the present invention provide a method for preparing nitromethane, which comprises mixing dimethyl sulfate, nitrite, alkali and poly (4-vinylpyridine) for reaction. The addition of poly (4-vinylpyridine) can reduce harmful gas in the production process and greatly improve the yield and purity of the product. Meanwhile, the poly (4-vinylpyridine) is easy to separate, and is beneficial to recovering the sulfate as a byproduct. The preparation method has mild conditions and simple operation, and is suitable for industrial large-scale production.
The embodiment of the invention also provides application of the poly (4-vinylpyridine), which can improve the yield and purity of the nitromethane and does not influence the recovery of byproducts by applying the poly (4-vinylpyridine) to the synthesis reaction of the nitromethane.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing nitromethane is characterized by comprising the following steps:
dimethyl sulfate, nitrite, alkali and poly (4-vinylpyridine) are mixed and reacted.
2. The method of claim 1, wherein the molar ratio of dimethyl sulfate to nitrite is 1: 2 to 2.3.
3. The production method according to claim 2, wherein the nitrite includes at least one of sodium nitrite, potassium nitrite, and magnesium nitrite.
4. The method according to claim 1, wherein the molar ratio of the dimethyl sulfate to the base is 1: 0.05 to 0.2.
5. The method of claim 4, wherein the base comprises at least one of sodium carbonate, potassium carbonate, and lithium carbonate.
6. The method according to claim 1, wherein the mass ratio of the dimethyl sulfate to the poly (4-vinylpyridine) is 1: 0.01 to 0.02.
7. The method according to claim 1, wherein the dimethyl sulfate, the nitrite, the alkali and the poly (4-vinylpyridine) are mixed and reacted at 30-35 ℃ for 3-5 hours.
8. The method of claim 7, wherein the base, the nitrite, and the poly (4-vinylpyridine) are first mixed to obtain a mixed solution; and dropwise adding the dimethyl sulfate into the mixed solution.
9. The method according to claim 1, wherein after completion of the reaction, the solid phase component is removed by filtration, and the liquid phase component is rectified.
10. An application of poly (4-vinylpyridine) in synthesizing nitromethane.
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| CN115124427A (en) * | 2021-03-26 | 2022-09-30 | 湖北富博化工有限责任公司 | Method for reducing peroxide value in nitromethane crude product |
Citations (3)
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| CN102659602A (en) * | 2012-04-13 | 2012-09-12 | 湖北远大富驰医药化工股份有限公司 | Novel method for producing nitromethane |
| CN103553924A (en) * | 2013-10-21 | 2014-02-05 | 石家庄铁道大学 | Method for synthesizing nitromethane |
| CN107857703A (en) * | 2017-09-14 | 2018-03-30 | 北京凯瑞英科技有限公司 | A kind of reactor and method of continuous production nitromethane |
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| CN102659602A (en) * | 2012-04-13 | 2012-09-12 | 湖北远大富驰医药化工股份有限公司 | Novel method for producing nitromethane |
| CN103553924A (en) * | 2013-10-21 | 2014-02-05 | 石家庄铁道大学 | Method for synthesizing nitromethane |
| CN107857703A (en) * | 2017-09-14 | 2018-03-30 | 北京凯瑞英科技有限公司 | A kind of reactor and method of continuous production nitromethane |
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