CN107986971A - A kind of preparation method of cyclohexyl nitrate - Google Patents
A kind of preparation method of cyclohexyl nitrate Download PDFInfo
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- CN107986971A CN107986971A CN201711313381.9A CN201711313381A CN107986971A CN 107986971 A CN107986971 A CN 107986971A CN 201711313381 A CN201711313381 A CN 201711313381A CN 107986971 A CN107986971 A CN 107986971A
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- organic phase
- cyclohexyl nitrate
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- nitric acid
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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
- C07C201/02—Preparation of esters of nitric acid
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation method of cyclohexyl nitrate, comprises the following steps：Step 1, add a certain amount of 98% concentrated sulfuric acid in the four-hole boiling flask equipped with blender, low-reading thermometer, air set pipe and dropping funel, 65% concentrated nitric acid is added dropwise under high degree of agitation, then a certain amount of cyclohexanol is added dropwise --- chloroformic solution, after adding, reacts 20 25min；Reaction mixture, be poured into frozen water by step 2, separates organic phase, and water is mutually extracted, merged with above-mentioned organic phase at twice with 45 55mL chloroforms again；Step 3, organic phase are washed with water to neutrality, are finally dried with anhydrous sodium sulfate after aqueous sodium carbonate washs；Chloroform is steamed under step 4, normal pressure and obtains crude product, then is evaporated under reduced pressure to obtain pure cyclohexyl nitrate.This method yield and purity are higher, and technique is simple, raw material is easy to get, cost is relatively low, it is of high cost in overcoming the drawbacks of.
Description
Technical field
The present invention relates to cyclohexyl nitrate technology, more particularly to a kind of preparation method of cyclohexyl nitrate.
Background technology
At present, each oil plant in China generally uses catalytic cracking secondary operation technique, to improve the yield of light oil.Use this
The octane number of gasoline is higher in the light oil of kind technique productions, but the Cetane number of diesel oil is very low, and generally only 20~25, only
It can allocate and use with straight-run diesel oil.But due to the limits throughput of straight-run diesel oil, along with the crude oil in oil field newly developed is heavier,
So that China's market available diesel oil Cetane number does not reach requirement generally.Therefore, it is in the urgent need to address to improve diesel cetane-number
Problem.The Cetane number of diesel oil can be improved with the method for solvent extraction and hydrogenation, but it is costly, it is economically uneconomical, and
Production cetane number improver cost is low, and technique is simple, and can effectively improve Cetane number, so cetane number improver is just
Increasingly it is valued by people.
The different pungent vinegar of nitric acid is the cetane number improver being widely used, and China is every year from the substantial amounts of nitric acid of imported from America
Different pungent vinegar improves the Cetane number of diesel oil.As cetane number improver, also someone reports nitric acid hexamethylene vinegar already, and generally
Additive amount is 1.5% (volume fraction), and Cetane number can improve about 20 units, and pungent cruel additive effect more different than nitric acid is good,
It is a potential cetane number improver, but does not put into production also in the world at present.It is proposed using cyclohexanol and nitric acid as
Raw material, liquor-saturated acetic acid is solvent, is added according to a certain ratio in reaction flask, nitric acid synthesis hexamethylene vinegar.The reaction of this method is more steady, production
Rate and purity are all higher, easily grasp, but solvent acetic acid is too big with dosage, it is impossible to recycle, it is of high cost, and without actual
Industrial production is worth.
The content of the invention
It is it is an object of the present invention to too big with dosage for the preparation method solvent acetic acid of current cyclohexyl nitrate, it is impossible to
Recycling, it is of high cost, the problem of value without actual industrial production, propose a kind of preparation method of cyclohexyl nitrate,
This method yield and purity are higher, and technique is simple, raw material is easy to get, cost is relatively low, it is of high cost in overcoming the drawbacks of.
To achieve the above object, the technical solution adopted by the present invention is：A kind of preparation method of cyclohexyl nitrate, including with
Lower step：
Step 1, add one in the four-hole boiling flask equipped with blender, low-reading thermometer, air set pipe and dropping funel
The 98% quantitative concentrated sulfuric acid, 65% concentrated nitric acid is added dropwise under high degree of agitation, a certain amount of cyclohexanol is then added dropwise --- and chloroform is molten
Liquid, after adding, reacts 20-25min；
Reaction mixture, be poured into frozen water by step 2, separates organic phase, and water is mutually extracted at twice with 45-55mL chloroforms again
Take, merge with above-mentioned organic phase；
Step 3, organic phase are washed with water to neutrality, are finally dried with anhydrous sodium sulfate after aqueous sodium carbonate washs；
Chloroform is steamed under step 4, normal pressure and obtains crude product, then is evaporated under reduced pressure to obtain pure cyclohexyl nitrate.
Further, the ratio of sulfuric acid and nitric acid is 2:l(m ol/m ol).Known by reaction mechanism, sulfuric acid before the reaction after
Do not consume, only serve the effect of catalyst.In the reaction, catalyst sulfuric acid dosage is bigger.If dosage is excessive, just
The recycling of nitration mixture after reacting can be given to bring difficulty, cause to waste, and cost also improves；As sulfuric acid amount is very few, then it is unfavorable for shape
Into NO2+Ion, the reaction time is long, is also easy to produce emulsion, is unfavorable for separating, and can also reduce yield and purity.
Further, the optimum molar proportioning of the nitric acid and cyclohexanol is 1.28：1.
Further, the esterification temperature is more than -8 DEG C, less than 0 DEG C.
The concentrated sulfuric acid is stirred by the present invention at low temperature with concentrated nitric acid, then reacts to obtain nitre with the chloroformic solution of cyclohexanol
Sour cyclohexyl ester, has the following advantages compared with prior art：
1) herein using nitric acid and cyclohexanol as raw material, sulfuric acid is catalyst, and urea is stabilizer, has synthesized nitric acid hexamethylene
Ester, yield and purity are also all higher.
2) in present invention reaction, chloroform is solvent, can be recycled.
3) this method technique is simple, raw material is easy to get, cost is relatively low, it is of high cost in overcoming the drawbacks of.
Embodiment
The present invention is further described with reference to embodiments：
Embodiment 1
Present embodiment discloses a kind of preparation method of cyclohexyl nitrate, comprise the following steps：
Step 1, add one in the four-hole boiling flask equipped with blender, low-reading thermometer, air set pipe and dropping funel
The 98% quantitative concentrated sulfuric acid, 65% concentrated nitric acid is added dropwise under high degree of agitation, a certain amount of cyclohexanol is then added dropwise --- and chloroform is molten
Liquid, after adding, reacts 20-25min；
Reaction mixture, be poured into frozen water by step 2, separates organic phase, and water is mutually extracted at twice with 45-55mL chloroforms again
Take, merge with above-mentioned organic phase；
Step 3, organic phase are washed with water to neutrality, are finally dried with anhydrous sodium sulfate after aqueous sodium carbonate washs；
Chloroform is steamed under step 4, normal pressure and obtains crude product, then is evaporated under reduced pressure to obtain pure cyclohexyl nitrate.
The ratio of sulfuric acid and nitric acid is 2:l(m ol/m ol).To be known by reaction mechanism, sulfuric acid does not consume afterwards before the reaction,
Only serve the effect of catalyst.In the reaction, catalyst sulfuric acid dosage is bigger.If dosage is excessive, reaction will be given
The recycling of nitration mixture brings difficulty afterwards, causes to waste, and cost also improves；As sulfuric acid amount is very few, then it is unfavorable for forming NO2+From
Son, the reaction time is long, is also easy to produce emulsion, is unfavorable for separating, and can also reduce yield and purity.
The optimum molar proportioning of the nitric acid and cyclohexanol is 1.28：1.
The esterification temperature is more than -8 DEG C, less than 0 DEG C.
The concentrated sulfuric acid is stirred by the present invention at low temperature with concentrated nitric acid, then reacts to obtain nitre with the chloroformic solution of cyclohexanol
Sour cyclohexyl ester, has the following advantages compared with prior art：Herein using nitric acid and cyclohexanol as raw material, sulfuric acid is catalyst,
Urea is stabilizer, has synthesized cyclohexyl nitrate, and yield and purity are also all higher.In present invention reaction, chloroform is solvent, can be with
Recycling.This method technique is simple, raw material is easy to get, cost is relatively low, it is of high cost in overcoming the drawbacks of.
1278cm in spectrogram-1And 1321cm-1For the characteristic absorption peak (bimodal) of secondary alkyl vinegar；1623cm-1 is-NO2
Asymmetric vibration absorption peak, 869cm-1And 759cm-1It is mono- O stretching vibrations of N and NO respectively2Out-of-plane bending vibration absworption peak
(weaker).2964cm-1And 2864cm1-1It is a CH2Asymmetry and symmetric vibration absworption peak；1452cm-1It is CH2Scissors
Vibration.1025cm-1It is the flexural vibrations absworption peak of mono- C of C.759cm-1It is the breathing absworption peak of ring in nitric acid hexamethylene vinegar.By dividing
From the point of view of analysing result, the structure of product is nitric acid hexamethylene vinegar.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to
Can so modify to the technical solution described in foregoing embodiments, either to which part or all technical characteristic into
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (4)
1. a kind of preparation method of cyclohexyl nitrate, it is characterised in that comprise the following steps：
Step 1, add in the four-hole boiling flask equipped with blender, low-reading thermometer, air set pipe and dropping funel it is a certain amount of
98% concentrated sulfuric acid, be added dropwise under high degree of agitation 65% concentrated nitric acid, a certain amount of cyclohexanol is then added dropwise --- chloroformic solution, adds
After complete, 20-25min is reacted；
Reaction mixture, be poured into frozen water by step 2, separates organic phase, and water is mutually extracted at twice with 45-55mL chloroforms again, with
Above-mentioned organic phase merges；
Step 3, organic phase are washed with water to neutrality, are finally dried with anhydrous sodium sulfate after aqueous sodium carbonate washs；
Chloroform is steamed under step 4, normal pressure and obtains crude product, then is evaporated under reduced pressure to obtain pure cyclohexyl nitrate.
2. the preparation method of cyclohexyl nitrate according to claim 1, it is characterised in that the ratio of sulfuric acid and nitric acid is 2:l
(mol/mol)。
3. the preparation method of cyclohexyl nitrate according to claim 1, it is characterised in that the nitric acid and cyclohexanol it is optimal
Mol ratio is 1.28：1.
4. the preparation method of cyclohexyl nitrate according to claim 1, it is characterised in that the esterification temperature is more than -8 DEG C,
Less than 0 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711313381.9A CN107986971A (en) | 2017-12-12 | 2017-12-12 | A kind of preparation method of cyclohexyl nitrate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711313381.9A CN107986971A (en) | 2017-12-12 | 2017-12-12 | A kind of preparation method of cyclohexyl nitrate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511144A (en) * | 2019-09-16 | 2019-11-29 | 山东益丰生化环保股份有限公司 | A kind of preparation method of cetane number improver |
| CN114276250A (en) * | 2020-09-27 | 2022-04-05 | 中石化南京化工研究院有限公司 | Synthesis method of cyclohexyl nitrate |
-
2017
- 2017-12-12 CN CN201711313381.9A patent/CN107986971A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511144A (en) * | 2019-09-16 | 2019-11-29 | 山东益丰生化环保股份有限公司 | A kind of preparation method of cetane number improver |
| CN114276250A (en) * | 2020-09-27 | 2022-04-05 | 中石化南京化工研究院有限公司 | Synthesis method of cyclohexyl nitrate |
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| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180504 |
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| WW01 | Invention patent application withdrawn after publication |