CN101665434B - Safe separation and purification method of nitrate ester - Google Patents
Safe separation and purification method of nitrate ester Download PDFInfo
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- CN101665434B CN101665434B CN200910307026A CN200910307026A CN101665434B CN 101665434 B CN101665434 B CN 101665434B CN 200910307026 A CN200910307026 A CN 200910307026A CN 200910307026 A CN200910307026 A CN 200910307026A CN 101665434 B CN101665434 B CN 101665434B
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Abstract
The invention discloses a safe separation and purification method of nitrate ester, comprising the steps: organic solvent is distilled from the organic solution of nitrate ester by distillation; in distillation, distilled water is added into the organic solution of nitrate ester; and the organic solvent and water can form azeotropy, azeotrope formed by the distilled water and the organic solvent is distilled out, distillate is collected, the organic solvent is completely distilled out, then residue is obtained and divided into liquid-liquid two phases after standing, and the nitrate ester product phase at a lower layer is covered by the water phase. Compared with the method for removing the organic solvent from the nitrate ester by direct atmospheric and vacuum distillation, the safe separation and purification method of nitrate ester is simple in operation, safe and clean in process and high in product purity and yield, and leads the obtained nitrate ester to be safely protected by water, avoid dangers, and be stored for a long time.
Description
Technical field
The present invention relates to nitrate compound highly effective and safe separating and purifying method, belong to the nitric ether purification technique.
Background technology
Nitric ether is a kind of important organic cpds, in medicine, agricultural chemicals, commercial explosives and military field purposes is very widely arranged.In nitric ether was synthetic, traditional method was starting raw material mostly with the polyvalent alcohol, adopted nitre-sulphur nitration mixture, nitric acid etc. to prepare as nitrating agent.At present, with the nitrogen pentoxide be the research focus that the novel nitrated technology of the nitrated epoxy compounds of nitrating agent becomes the nitric acid synthesis ester compound.Yet the nitric ether product through above-mentioned preparation method obtains normally exists with the organic solution form of nitric ether, in order to obtain pure nitric ether product, need separate purification to the nitric ether organic solution that obtains, and removes organic solvent.
People such as patent EP0223440 and Golding (Tetrahedron Letters 1 988,29 (22): 2731-2734; Tetrahedron1993; 49 (32): 7051-70 62) obtain corresponding dinitrate with nitrated oxa-ring of the organic solution of nitrogen pentoxide and nitrogen heterocyclic, adopt direct underpressure distillation mode to steam organic solvent down at 30 ℃ and obtain pure nitric ether product.Patent GB2352239 and GB6072071 then adopt vacuum-drying to remove the organic solvent in the product to nitrated glycerin dinitrate for preparing of nitrogen pentoxide and polyvalent alcohol nitric ether organic solution, obtain pure nitric ether.People such as Hu Zhihua (Speciality Petrochemicals, 2004,2:1-3) the nitrated ethoxylated dodecyl alcohol nitric ether organic solvent for preparing of nitric-sulfuric acid is adopted air distillation mode refined product, reclaim solvent simultaneously.People such as Ma Qing (synthetic chemistry; 2008; 16 (6): 628-631) adopt the mode of two step underpressure distillation that the nitrated Racemic glycidol nitric ether for preparing of concentrated nitric acid is separated purification with the poly epihydric alcohol nitric ether; Adopt 40 ℃ of underpressure distillation 1h respectively, remove organic solvent at 55 ℃ of underpressure distillation 2h then and obtain the nitric ether product.
By on can know that the nitric ether organic solution that at present both at home and abroad nitration reaction is obtained adopts normal decompression straight run distillation mode to remove organic solvent usually and obtains pure nitric ether product.It is very unstable that yet most of pure nitric ether products are heated, and in above-mentioned still-process, especially very easily blasts in the distillation later stage and wait danger.
Summary of the invention
In order to solve the problem that exists in the prior art, the present invention provides a kind of safe separating method of purification of nitric ether, solves in the prior art and receives the easy explosion caused dangerous problem that waits of thermally labile because of pure nitric ether product.
The present invention realizes through following technical scheme: a kind of safe separating method of purification of nitric ether; Comprise the organic solution of nitric ether is steamed the step of organic solvent with the distillation mode, during distillation, in the organic solution of said nitric ether, add zero(ppm) water; The volume ratio of the organic solution of zero(ppm) water and said nitric ether was controlled at 1: 1 ~ 100: 1; Control pressure adds thermal rectification under 0.01MPa ~ 0.1MPa, said organic solvent can form azeotropic with water, and the azeotrope that zero(ppm) water and organic solvent are formed distills away; Collect overhead product; After organic solvent distills away fully, be divided into liquid-liquid two phases after the still liquid that obtains leaves standstill, lower floor's nitric ether product is covered by water.
Said nitric ether is wherein a kind of of monohydroxy-alcohol nitric ether, divalent alcohol nitric ether, polyvalent alcohol nitric ether or nitrous acid ester.
Said organic solvent is wherein a kind of of halohydrocarbon, other alkane or aromatic hydroxy compound.
The volume ratio of the organic solution of said zero(ppm) water and said nitric ether preferably was controlled at 1: 1 ~ 50: 1.
Said distillation pressure is preferably 0.03MPa ~ 0.1MPa.
Said overhead product boiling point control is at 20 ~ 90 ℃.
Said overhead product boiling point preferably is controlled at 20 ~ 60 ℃.
(j) preparing an oil-based drilling mud comprising the combined oil of step (g). the safe separating method of purification of nitric ether provided by the invention and normal decompression straight run distillation mode remove in the nitric ether method of organic solvent and compare; Simple to operate; Process safety, cleaning; Product purity and yield are high, and solvent recovering rate is high.The nitric ether that obtains is under the safeguard protection of water, avoids causing danger, and can deposit for a long time.Nitric ether organic solution sepn process involved in the present invention is that nitric ether is separated the pure nitric ether that obtains being in the stored safely state from its organic solution, and yield and purity are high, process safety, and the sample that obtains can directly be stored.The meeting natural layering can reclaim organic solvent after the azeotrope that distills out left standstill after simple separation.
Embodiment
Below in conjunction with specific embodiment the present invention is done to describe in detail.
The organic solution of nitric ether is joined in the distillation tower, add a certain amount of zero(ppm) water, the volume ratio of water and organic solution was controlled at 100: 1 ~ 1: 1.Under 0.01MPa ~ 0.1MPa, add thermal rectification, the azeotrope that water and organic solvent are formed distills away; After organic solvent distills away fully, be divided into liquid-liquid two phases after the still liquid that obtains leaves standstill, lower floor's nitric ether product is covered by water.
The mentioned nitric ether of the present invention can be monohydroxy-alcohol nitric ether, divalent alcohol nitric ether or polyvalent alcohol nitric ether, also can be nitrous acid ester.
The organic solvent that the present invention carried is the organism that can form azeotrope with water; Can be halohydrocarbon such as methylene dichloride, trichloromethane, tetracol phenixin, ethylene dichloride, 2 cbloropropane isopropyl chloride, Butyryl Chloride etc., also can be other alkane or aromatic hydroxy compound such as acetonitrile, benzene,toluene,xylene, hexanaphthene, pentane, heptane, nonane etc.
The water add-on is that the volume ratio of water and organic solution preferably was controlled at 1: 1 ~ 50: 1 in the said process; Distillation pressure should be regulated according to the boiling point of azeotrope, preferably is controlled at 0.03MPa ~ 0.1MPa; The overhead product boiling point control preferably is controlled at 20 ~ 60 ℃ at 20 ~ 90 ℃.
Embodiment 1
Propylene oxide and nitrogen pentoxide are carried out nitration reaction in dichloromethane solution; Obtain the divalent alcohol nitric ether as 1; 2-Ucar 35 dinitrate (PGDN))/dichloromethane solution 40mL (gross weight 57g, wherein the PGDN mass content 7%) joins in the 1000mL still kettle, adds 400mL zero(ppm) water.Under 0.1MPa, add thermal distillation, collect 38 ℃ ~ 40 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the PGDN product, the water of upper strata for not steaming.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 398.5g in the weighing still kettle, and the purity of stratographic analysis nitric ether is 99.9%; Steaming the cut gross weight is 56.5g, separates, and reclaiming lower floor's organism weight is 51.5g, the recovery 97%.
Embodiment 2
Propylene oxide and nitrogen pentoxide are carried out nitration reaction in chloroform soln; Obtain 1; 2-Ucar 35 dinitrate (PGDN)/chloroform soln 40mL (gross weight 63.2g, wherein the PGDN mass content 6.3%) joins in the 500mL still kettle, adds 200mL zero(ppm) water.Under 0.1MPa, add thermal distillation, collect 55 ℃ ~ 61 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the PGDN product, the water of upper strata for not steaming.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 202g in the weighing still kettle, and the purity of stratographic analysis nitric ether is 99.8%; Steam cut and be divided into two-layerly automatically, gross weight is 59.5g, and Separation and Recovery lower floor organism weight is 57.6g, the recovery 97.3%.
Embodiment 3
Propylene oxide and nitrogen pentoxide are carried out nitration reaction in tetrachloromethane solution; Obtain 1; 2-Ucar 35 dinitrate (PGDN)/tetrachloromethane solution 40mL (gross weight 67.6g, wherein the PGDN mass content 5.9%) joins in the 100mL still kettle, adds 40mL zero(ppm) water.Under 0.1MPa, add thermal distillation, collect 65 ℃ ~ 68 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the PGDN product, the water of upper strata for not steaming.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 41.3g in the weighing still kettle, and the purity of stratographic analysis nitric ether is 99.8%; Steam cut and be divided into two-layerly automatically, gross weight is 65.3g, and Separation and Recovery lower floor organism weight is 62.7g, the recovery 98.6%.
Embodiment 4
Propylene oxide and nitrogen pentoxide are carried out nitration reaction in n-propyl chloride solution; Obtain 1; 2-Ucar 35 dinitrate (PGDN)/n-propyl chloride solution 40mL (gross weight 39.7g, wherein the PGDN mass content 10%) joins in the 100mL still kettle, adds 40mL zero(ppm) water.Under 0.1MPa, add thermal distillation, collect 43 ℃ ~ 46 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the PGDN product, the water of upper strata for not steaming.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 43g in the weighing still kettle, and the purity of stratographic analysis nitric ether is 99.9%; Steam cut and be divided into two-layerly automatically, gross weight is 35.5g, and Separation and Recovery upper strata organism weight is 34.6g, the recovery 97%.
Embodiment 5
Propylene oxide and nitrogen pentoxide 1, are carried out nitration reaction in the 2-dichloroethane solution, obtain 1; 2-Ucar 35 dinitrate (PGDN)/1; 2-dichloroethane solution 40mL (gross weight 54g, wherein the PGDN mass content 7.4%) joins in the 100mL still kettle, adds 40mL zero(ppm) water.Under 0.1MPa, add thermal distillation, collect 70 ℃ ~ 73 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the PGDN product, the water of upper strata for not steaming.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 39.5 in the weighing still kettle, and the purity of stratographic analysis nitric ether is 99.8%; Steam cut and be divided into two-layerly automatically, gross weight is 53.8g, and Separation and Recovery lower floor organism weight is 49.3g, the recovery 98.6%.
Embodiment 6
With USP Kosher or soup and nitrogen pentoxide 1; Carry out nitration reaction in the 2-dichloroethane solution, obtain soup (NG)/1,2-dichloroethane solution 40mL (gross weight 54g; Wherein the NG mass content 7.4%) join in the 100mL still kettle, add 40mL zero(ppm) water.Under 0.1MPa, add thermal distillation, collect 70 ℃ ~ 73 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the NG product, the water of upper strata for not steaming.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 39.5g in the weighing still kettle, and the purity of stratographic analysis NG is 99.6%; Steam cut and be divided into two-layerly automatically, gross weight is 53.8g, and Separation and Recovery lower floor organism weight is 49.1g, the recovery 98%.
Embodiment 7
With 1; 2-butylene oxide ring and nitrogen pentoxide carry out nitration reaction in dichloromethane solution, obtain 1,2-butyleneglycol dinitrate (BTDN)/dichloromethane solution 40mL (gross weight 57g; Wherein the BTDN mass content 7%) join in the 100mL still kettle, add 40mL zero(ppm) water.Under 0.1MPa, add thermal distillation, collect 38 ℃ ~ 40 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the BTDN product, the water of upper strata for not steaming.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 38.6g in the weighing still kettle, and the purity of stratographic analysis nitric ether is 99.9%; Steaming the cut gross weight is 56.6g, separates, and reclaiming lower floor's organism weight is 51.6g, the recovery 97.3%.
Embodiment 8
Racemic glycidol and nitrogen pentoxide are carried out nitration reaction in dichloromethane solution, obtain soup Mononitrate (GLYN)/dichloromethane solution 40mL (gross weight 57g, wherein the GLYN mass content 7%) and join in the 100mL still kettle, add 40mL zero(ppm) water.Under 0.1MPa, add thermal distillation, collect 38 ℃ ~ 40 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the GLYN product, the water of upper strata for not steaming.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 38.6g in the weighing still kettle, and the purity of stratographic analysis nitric ether is 99.9%; Steaming the cut gross weight is 56.5g, separates, and reclaiming lower floor's organism weight is 51.5g, the recovery 97%.
Embodiment 9
Epoxy chloropropane and nitrogen pentoxide 1, are carried out nitration reaction in the 2-dichloroethane solution, obtain 3-chloro-1; 2-Ucar 35 dinitrate (CPDN)/1; 2-dichloroethane solution 40mL (gross weight 54g, wherein the CPDN mass content 7.4%) joins in the 100mL still kettle, adds 40mL zero(ppm) water.Under 0.1MPa, add thermal distillation, collect 70 ℃ ~ 73 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the CPDN product, the water of upper strata for not steaming.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 39.6g in the weighing still kettle, and the purity of stratographic analysis NG is 99.7%; Steam cut and be divided into two-layerly automatically, gross weight is 53.9g, and Separation and Recovery lower floor organism weight is 49.2g, the recovery 98.4%.
Embodiment 10
Propylene oxide and nitrogen pentoxide are carried out nitration reaction in benzole soln; Obtain the divalent alcohol nitric ether as 1; 2-Ucar 35 dinitrate (PGDN))/benzole soln 40mL (gross weight 39.2g, wherein the PGDN mass content 10.2%) joins in the 100mL still kettle, adds 40mL zero(ppm) water.Under 0.03MPa, add thermal distillation, collect 60 ℃ ~ 65 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the PGDN product, the water of upper strata for not steaming.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 38.8g in the weighing still kettle, and the purity of stratographic analysis nitric ether is 99.5%; Steaming the cut gross weight is 40.0g, separates, and reclaiming upper strata organism weight is 34.5g, the recovery 98%.
Embodiment 11
Propylene oxide and nitrogen pentoxide are carried out nitration reaction in acetonitrile solution; Obtain the divalent alcohol nitric ether as 1; 2-Ucar 35 dinitrate (PGDN))/acetonitrile solution 40mL (gross weight 35g, wherein the PGDN mass content 11.4%) joins in the 100mL still kettle, adds 40mL zero(ppm) water.Under 0.01MPa, add thermal distillation, collect 20 ℃ ~ 25 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the PGDN product, and the water that the upper strata is not steamed covers.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 38.8g in the weighing still kettle, and the purity of stratographic analysis nitric ether is 99.8%; Steaming the cut gross weight is 36.0g, separates, and reclaiming lower floor's organism weight is 30.5g, the recovery 98%.
Embodiment 12
Propylene oxide and nitrogen pentoxide are carried out nitration reaction in pentane solution; Obtain the divalent alcohol nitric ether as 1; 2-Ucar 35 dinitrate (PGDN))/pentane solution 40mL (gross weight 29.2g, wherein the PGDN mass content 13.7%) joins in the 100mL still kettle, adds 40mL zero(ppm) water.Under 0.1MPa, add thermal distillation, collect 33 ℃ ~ 35 ℃ cut, in receiving flask, be divided into two-layer after cut is cooled automatically.When the cut temperature raises suddenly, stop heating, leave standstill, gained still liquid is liquid-liquid two phase states, and lower floor is the PGDN product, and the water that the upper strata is not steamed covers.Product and overhead product are cooled to room temperature, and the weight of nitric ether and water is 43.5g in the weighing still kettle, and the purity of stratographic analysis nitric ether is 99.8%; Steaming the cut gross weight is 26.0g, separates, and reclaiming lower floor's organism weight is 24.9g, the recovery 98.8%.
Claims (6)
1. the safe separating method of purification of a nitric ether comprises the organic solution of nitric ether is steamed the step of organic solvent with the distillation mode, it is characterized in that; During distillation, in the organic solution of said nitric ether, add zero(ppm) water, the volume ratio of the organic solution of zero(ppm) water and said nitric ether was controlled at 1: 1～100: 1; Control pressure adds thermal rectification under 0.01MPa～0.1MPa; Said organic solvent can form azeotropic with water, and the azeotrope that zero(ppm) water and organic solvent are formed distill away, the collection overhead product; After organic solvent distills away fully; Be divided into liquid-liquid two phases after the still liquid that obtains leaves standstill, lower floor's nitric ether product is covered by water, and said nitric ether is wherein a kind of of monohydroxy-alcohol nitric ether, divalent alcohol nitric ether, polyvalent alcohol nitric ether.
2. according to the safe separating method of purification of the said nitric ether of claim 1, it is characterized in that said organic solvent is wherein a kind of of halohydrocarbon or aromatic hydroxy compound.
3. according to the safe separating method of purification of the said nitric ether of claim 1, it is characterized in that the volume ratio of the organic solution of said zero(ppm) water and said nitric ether was controlled at 1: 1～50: 1.
4. according to the safe separating method of purification of the said nitric ether of claim 1, it is characterized in that said distillation pressure is 0.03MPa～0.1MPa.
5. according to the safe separating method of purification of the said nitric ether of claim 1, it is characterized in that said overhead product boiling point control is at 20～90 ℃.
6. according to the safe separating method of purification of the said nitric ether of claim 5, it is characterized in that said overhead product boiling point control is at 20～60 ℃.
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| WO2001002336A1 (en) * | 1999-07-03 | 2001-01-11 | Qinetiq Limited | Process for the production of glycerol dinitrates |
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| WO2001002336A1 (en) * | 1999-07-03 | 2001-01-11 | Qinetiq Limited | Process for the production of glycerol dinitrates |
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| Title |
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| 胡智华等.月桂醇聚氧乙烯醚硝酸酯的合成工艺.《精细石油化工》.2004,(第2期),1-3. * |
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