CN101712588B - Method for preparing high-purity liquid chromatographic grade N-alkanes - Google Patents
Method for preparing high-purity liquid chromatographic grade N-alkanes Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity liquid chromatographic grade normal paraffin, in particular to a high-purity liquid chromatographic grade paraffin such as normal pentane, normal hexane, normal heptane, normal octane and the like with low ultraviolet absorption within the range of 195-280nm. The process flow is as follows: utilizing a given amount of ionic liquid and concentrated sulfuric acid to process industrial grade normal paraffin, and rectifying after multi-time sulfonation and desulfuration to obtain the liquid chromatographic grade paraffin. The method has the following advantage that ionic liquid is utilized to selectively extract sulfate and sulfocompound to carry out sulfonation and desulfuration simultaneously, thereby having simple flow, low energy consumption and high product purity.
Description
Technical field
The invention relates to the preparation method of high purity normal paraffin, particularly prepare the processing method of high-purity liquid chromatographic grade normal paraffin, belong to chemical production field.
Background technology
High-purity liquid chromatographic grade normal paraffin mainly is used as the positive liquid chromatography solvents, also be used as thinner and the senior solvent of medical building-up reactions as the high purity normal paraffin, as prepare the aseptic level of steroid class, hormones, cephalosporin etc. such as acetyl 2-ethoxyethyl acetate medicine, all use normal hexane to make solubility promoter.Along with the fast development of domestic and international pharmaceutical engineering, biological gene engineering and association area, the high-purity liquid chromatographic grade normal paraffin market requirement will increase in the coming years greatly, and market outlook are wide.
The normal hexane industrial production mainly is to reform from mink cell focus--separate raffinate oil (the containing normal hexane 11～13%) of aromatic extraction unit, generally adopt rectifying---the hydrogenation production technique.Normal hexane purity is one of most important control index in its production process, how to improve yield and the purity of product, reduces production costs, and to improve the competitive power of normal hexane product on market, becomes the emphasis of producing normal hexane research.In patent CN100441118C, introduce a kind of method of normal hexane and methylcyclopentane (the two boiling point is close to 68.7 ℃ and 71.8 ℃).With raw material and extraction distillation solvent dimethyl phthalate with 1: the mass flow rate of 3-5 is sent into rectifying tower, can obtain purity greater than 98% normal hexane, and recyclable 90% methylcyclopentane.Patent RU2128517 has introduced the mixture separation of benzene and Skellysolve A, continuously through 2 rectifying tower rectifying, and in first column overhead normal pressure separate light hydrocarbons, second column overhead pressurization separates normal hexane, further handles the product that can get purity 99% with zeolite or oleum.In patent CN101148390A, utilize the multitower continuous adsorption normal hexane that loads sorbent material, and carry out all voltage rise and all pressure drop operations between tower simultaneously, last desorb is to improve the purity of normal hexane, the simple level of automation height of this method equipment.By containing the fixed-bed reactor of ruthenium catalyst, can remove fully and contain a spot of benzene in the normal hexane by this process with certain linear velocity for mixture among the patent JP61289048.At 108-240 ℃, hydrogenation under the 30-60kg/cm2 mild condition, and rectifying again after handling with atlapulgite obtain product aromatic hydrocarbon less than 0.3% to patent JP5107671 with reformate, and the alkene bromine index is less than 30mg/100g.
The technology that these documents are reported all is only limited in the high-purity normal paraffin of preparation, is not the technology that special phase chromatography-use normal paraffin prepares.The phase chromatography-use normal paraffin except requiring its content height, reaches beyond 99.0% the high purity, also requires to have extremely low uv-absorbing.
Summary of the invention
The objective of the invention is to from the technical grade normal paraffin, utilize full glass reaction rectifying device, use gentle sulfonation desulfurization system, with safety, efficient, the mode that is easy to industrial operation, remove water, organism (alcohol, aldehyde, ketone, ether, ester, isomeric hydrocarbon, unsaturated hydrocarbons etc.), the ion impurity such as (metal ion, acid ions) of trace in the raw material, particularly remove the impurity that absorption is arranged in the near ultraviolet region, preparation has the method for the high-purity liquid chromatographic grade normal paraffin of low uv-absorbing in 195～280nm interval.
The objective of the invention is to be achieved through the following technical solutions:
1, a kind of is raw material with technical grade C5-C8 normal paraffin, in full glass reaction rectifier, remove the impurity such as water, organism, ion of trace in the raw material by rectifying after the sulfonation desulfurization repeatedly, the method for preparing high-purity liquid chromatographic grade normal paraffin, its idiographic flow is:
1. add a certain amount of ionic liquid and the vitriol oil in stirred reactor, under 25～40 ℃, fed raw material reaction while stirring 20～300 minutes.
2. after reaction is finished, will be taken out to second sulfonation desulphurization reactor with the upper strata alkane that ionic liquid separates automatically from stirred reactor top and repeat reaction process 1..
3. repeat 1. 2. repeatedly.
4. the alkane after the sulfonation desulfurization is sent into dehydrogenation, is taken off heavy, finished product three rectifying tower and carry out rectifying, obtains high-purity liquid chromatographic grade normal paraffin.
2, according to the above-mentioned method for preparing high-purity liquid chromatographic grade normal paraffin, C5-C8 normal paraffin make a comment or criticism pentane, normal hexane, normal heptane, octane.
3, according to the above-mentioned method for preparing high-purity liquid chromatographic grade normal paraffin, the input amount that it is characterized in that ionic liquid is 1/30～1/5 of stirred reactor effective volume, its preferred value is 1/20～1/10, the input amount of the vitriol oil is 1/10～1/3 of ionic liquid volume, and its preferred value is 1/8～1/5.
4, according to the method for the high-purity liquid chromatographic grade normal paraffin of above-mentioned preparation, the preferred value that it is characterized in that temperature of reaction is 25～30 ℃.The preferred value in reaction times is 30～50 minutes.
5, according to the above-mentioned method for preparing high-purity liquid chromatographic grade normal paraffin, it is characterized in that ionic liquid is but is not limited only to: the N-Methyl pyrrolidone hydrosulfate, the N-Methyl pyrrolidone dihydrogen phosphate, N-methylsulfonic acid base pyrrolidone hydrosulfate, N-ethyl sulfonic acid base pyrrolidone hydrosulfate, N-propanesulfonic acid base hydrosulfate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate, 1-butyl-3-N-Methylimidazoleacetic salt, 1-hexyl-3-methyl imidazolium tetrafluoroborate, one or more of 1-hexyl-3-Methylimidazole hexafluorophosphate combine.The concentration of the vitriol oil is 90%～98%.
6, according to the above-mentioned method for preparing high-purity liquid chromatographic grade normal paraffin, it is characterized in that raw materials used normal paraffin is technical grade, purity is more than 95.0%; Used ionic liquid and the vitriol oil are chemically pure reagent.
7, according to the above-mentioned method for preparing high-purity liquid chromatographic grade normal paraffin, it is characterized in that repeating repeatedly sulfonation desulfurization process, to guarantee to remove fully easy sulfonated bodies and sulfocompound.Multiplicity is determined by the analyzing and testing result.
8, according to the method for above-mentioned liquid high purity phase chromatographic grade normal paraffin, it is characterized in that rectifying obtains liquid chromatographic grade alkane and carries out UV detection (1cm colorimetric pool, water are reference) through UV2550.Through Agilent 7890 carry out GC detect (chromatographic column model: BP-5, column length 50m, internal diameter 0.32mm, thickness of liquid film 0.5 μ m. testing conditions: column temperature: starting temperature kept 15 minutes for 35 ℃, 2 ℃/minute rise to 160 ℃ after constant temperature 20 minutes; 220 ℃ of sampler temperature; 200 ℃ of detector temperatures .), its normal paraffin content is greater than 99.0%.
The advantage that this technology has:
(1) selected ionic liquid has the selective dissolution performance, and is insoluble to Skellysolve A, normal hexane, normal heptane and octane, but can dissolve the vitriol oil and reaction product sulfuric ester etc.
(2) ionic liquid has selective extraction capacity to sulfocompound.
(3) the sulfonation desulfurization system of this technology utilization ionic liquid and vitriol oil composition in the easy sulfonated bodies of sulfonation, utilizes ionic liquid to the selective extraction of sulfuric ester and sulfocompound, has reached the purpose that sulfonation and desulfurization are carried out simultaneously.
Embodiment
Further elaborate preparation method of the present invention below by embodiment
Embodiment 1
In 2L glass stirred reactor, drop into the N-Methyl pyrrolidone hydrosulfate ionic liquid 0.2L of raw material volume 1/10, and drop into 98% vitriol oil 0.02L of the ionic liquid scale of construction 1/10, feed 1.03 kilograms of (1.5L of industrial normal heptane raw material while stirring, 220nm place absorbancy is 0.1832), temperature control is left standstill and is made the reactant layering 25.0 ℃ of reaction 30 minutes.
Take out alkane to the second a 2L sulfonation desulphurization reactor from the stirred reactor upper strata, the same N-Methyl pyrrolidone hydrosulfate ionic liquid 0.2L that drops into raw material volume 1/10 in second reactor, and drop into 98% vitriol oil 0.02L of the ionic liquid scale of construction 1/10,25.0 ℃ of reactions of temperature of reaction 30 minutes, standing demix.
Repeat above reaction, carry out the sulfonation desulphurization reaction altogether 3 times, get the water that 2 milliliters of alkane add equal volume from stirred reactor top, fully shake the back and placed 5 minutes, the upper strata is the alkane of clear, and lower floor is the water of clear.Alkane is taken out from the 3rd sulfonation desulphurization reactor top, deliver to lightness-removing column, add thermal rectification and take off light constituent in reflux temperature is 92.0 ℃ lightness-removing column, entering reflux temperature then is to add thermal rectification in 105.0 ℃ of weight-removing columns to take off heavy constituent; From cat head extraction material normal heptane to finishing column rectifying again, feeding temperature is 90.0 ℃ in the finishing column, tower top temperature is 98.5 ℃, reflux ratio is 2.5, and reflux temperature is 96.0 ℃, and front-end volatiles are deviate from from gas phase, after cut separates at the bottom of by still, the front and back cut is sent reactive system back to and is recycled, and obtains 0.92 kilogram of liquid chromatographic grade level normal heptane finished product, yield 89.3% from the cat head extraction.Detect through UV, its 220nm place absorbancy is 0.0811.It is 99.5% that GC detects purity.
Embodiment 2
In 2L glass stirred reactor, drop into the N-Methyl pyrrolidone dihydrogen phosphate ionic liquid 0.3L of raw material volume 1/5, and drop into 98% vitriol oil 0.03L of the ionic liquid scale of construction 1/10, feed 0.94 kilogram of (1.5L of industrial Skellysolve A raw material while stirring, 220nm place absorbancy is 0.1483), temperature control is left standstill and is made the reactant layering 30.0 ℃ of reaction 100 minutes.
Take out alkane to the second a 2L sulfonation desulphurization reactor from the stirred reactor upper strata, the same N-Methyl pyrrolidone dihydrogen phosphate ionic liquid 0.3L that drops into raw material volume 1/5 in second reactor, and drop into 98% vitriol oil 0.03L of the ionic liquid scale of construction 1/10,30.0 ℃ of reactions of temperature of reaction 100 minutes, standing demix.
Repeat above reaction, carry out the sulfonation desulphurization reaction altogether 4 times, get the water that 2 milliliters of alkane add equal volume then from stirred reactor top, fully shake the back and placed 5 minutes, the upper strata is the alkane of clear, and lower floor is the water of clear.Alkane is taken out from last sulfonation desulphurization reactor top, deliver to lightness-removing column, add thermal rectification and take off light constituent in reflux temperature is 30.0 ℃ lightness-removing column, entering reflux temperature then is to add thermal rectification in 40.0 ℃ of weight-removing columns to take off heavy constituent; From cat head extraction material Skellysolve A to finishing column rectifying again, feeding temperature is 30.0 ℃ in the finishing column, tower top temperature is 36.1 ℃, reflux ratio is 4.0, and reflux temperature is 33.0 ℃, and front-end volatiles are deviate from from gas phase, after cut separates at the bottom of by still, the front and back cut is sent reactive system back to and is recycled, and obtains 0.83 kilogram of liquid chromatographic grade level Skellysolve A finished product, yield 88.3% from the cat head extraction.Detect through UV, its 220nm place absorbancy is 0.0758.It is 99.7% that GC detects purity.
Embodiment 3
In 2L glass stirred reactor, drop into the N-methylsulfonic acid base pyrrolidone hydrosulfate ionic liquid 0.1L of raw material volume 1/20, and drop into 98% vitriol oil 0.02L of the ionic liquid scale of construction 1/5, feed 1.05 kilograms of (1.5L of industrial octane raw material while stirring, place's absorbancy is 0.2004), temperature control is left standstill and is made the reactant layering 25.0 ℃ of reaction 300 minutes.
Take out alkane to the second a 2L sulfonation desulphurization reactor from the stirred reactor upper strata, the same N-methylsulfonic acid base pyrrolidone hydrosulfate ionic liquid 0.1L that drops into raw material volume 1/20 in second reactor, and drop into 98% vitriol oil 0.02L of the ionic liquid scale of construction 1/5,25.0 ℃ of reactions of temperature of reaction 300 minutes, standing demix.
Repeat above reaction, carry out the sulfonation desulphurization reaction altogether 4 times, get the water that 2 milliliters of alkane add equal volume from stirred reactor top, fully shake the back and placed 5 minutes, the upper strata is the alkane of clear, and lower floor is the water of clear.Alkane is taken out from last sulfonation desulphurization reactor top, deliver to lightness-removing column, add thermal rectification and take off light constituent in reflux temperature is 110.0 ℃ lightness-removing column, entering reflux temperature then is to add thermal rectification in 135.0 ℃ of weight-removing columns to take off heavy constituent; From cat head extraction material octane to finishing column rectifying again, feeding temperature is 110.0 ℃ in the finishing column, tower top temperature is 125.8 ℃, reflux ratio is 2.0, and reflux temperature is 123.0 ℃, and front-end volatiles are deviate from from gas phase, after cut separates at the bottom of by still, the front and back cut is sent reactive system back to and is recycled, and obtains 0.92 kilogram of liquid chromatographic grade level octane finished product, yield 87.6% from the cat head extraction.Detect through UV, its 220nm place absorbancy is 0.0742.It is 99.7% that GC detects purity.
Embodiment 4
In 2L glass stirred reactor, drop into the 1-butyl-3-Methylimidazole hexafluorophosphate ionic liquid 0.2L of raw material volume 1/10, and drop into 98% vitriol oil 0.04L of the ionic liquid scale of construction 1/5, feed 1.03 kilograms of (1.5L of industrial normal heptane raw material while stirring, 220nm place absorbancy is 0.1832), temperature control is left standstill and is made the reactant layering 25.0 ℃ of reaction 40 minutes.
Take out alkane to the second a 2L sulfonation desulphurization reactor from the stirred reactor upper strata, the same 1-butyl-3-Methylimidazole hexafluorophosphate ionic liquid 0.2L that drops into raw material volume 1/10 in second reactor, and drop into 98% vitriol oil 0.04L of the ionic liquid scale of construction 1/5,25.0 ℃ of reactions of temperature of reaction 40 minutes, standing demix.
Repeat above reaction, carry out the sulfonation desulphurization reaction altogether 5 times, get the water that 2 milliliters of alkane add equal volume from stirred reactor top, fully shake the back and placed 5 minutes, the upper strata is the alkane of clear, and lower floor is the water of clear.Alkane is taken out from last sulfonation desulphurization reactor top, deliver to lightness-removing column, add thermal rectification and take off light constituent in reflux temperature is 91.0 ℃ lightness-removing column, entering reflux temperature then is to add thermal rectification in 110.0 ℃ of weight-removing columns to take off heavy constituent; From cat head extraction material normal heptane to finishing column rectifying again, feeding temperature is 90.0 ℃ in the finishing column, tower top temperature is 98.5 ℃, reflux ratio is 2.5, and reflux temperature is 96.0 ℃, and front-end volatiles are deviate from from gas phase, after cut separates at the bottom of by still, the front and back cut is sent reactive system back to and is recycled, and obtains 0.90 kilogram of liquid chromatographic grade level normal heptane finished product, yield 87.4% from the cat head extraction.Detect through UV, its 220nm place absorbancy is 0.0725.It is 99.7% that GC detects purity.
Embodiment 5
In 2L glass stirred reactor, drop into the 1-butyl-3-N-Methylimidazoleacetic salt ion liquid 0.075L of raw material volume 1/20, and drop into 98% vitriol oil 0.0094L of the ionic liquid scale of construction 1/8, feed 1.03 kilograms of (1.5L of industrial normal heptane raw material while stirring, 220nm place absorbancy is 0.1832), temperature control is left standstill and is made the reactant layering 25.0 ℃ of reaction 45 minutes.
Take out alkane to the second a 2L sulfonation desulphurization reactor from the stirred reactor upper strata, the same 1-butyl-3-N-Methylimidazoleacetic salt ion liquid 0.075L that drops into raw material volume 1/20 in second reactor, and drop into 98% vitriol oil 0.0094L of the ionic liquid scale of construction 1/8,25.0 ℃ of reactions of temperature of reaction 45 minutes, standing demix.
Repeat above reaction, carry out the sulfonation desulphurization reaction altogether 3 times, get the water that 2 milliliters of alkane add equal volume from stirred reactor top, fully shake the back and placed 5 minutes, the upper strata is the alkane of clear, and lower floor is the water of clear.Alkane is taken out from last sulfonation desulphurization reactor top, deliver to lightness-removing column, add thermal rectification and take off light constituent in reflux temperature is 92.0 ℃ lightness-removing column, entering reflux temperature then is to add thermal rectification in 105.0 ℃ of weight-removing columns to take off heavy constituent; From cat head extraction material normal heptane to finishing column rectifying again, feeding temperature is 90.0 ℃ in the finishing column, tower top temperature is 98.5 ℃, reflux ratio is 2.5, and reflux temperature is 96.0 ℃, and front-end volatiles are deviate from from gas phase, after cut separates at the bottom of by still, the front and back cut is sent reactive system back to and is recycled, and obtains 0.92 kilogram of liquid chromatographic grade level normal heptane finished product, yield 89.3% from the cat head extraction.Detect through UV, its 220nm place absorbancy is 0.0854.It is 99.5% that GC detects purity.
Embodiment 6
In 2L glass stirred reactor, drop into the N-ethyl sulfonic acid base pyrrolidone hydrosulfate ionic liquid 0.2L of raw material volume 1/10, and drop into 98% vitriol oil 0.02L of the ionic liquid scale of construction 1/10, feed 0.99 kilogram of (1.5L of industrial normal hexane raw material while stirring, 220nm place absorbancy is 0.2113), temperature control is left standstill and is made the reactant layering 25.0 ℃ of reaction 45 minutes.
Take out alkane to the second a 2L sulfonation desulphurization reactor from the stirred reactor upper strata, the same N-ethyl sulfonic acid base pyrrolidone hydrosulfate ionic liquid 0.2L that drops into raw material volume 1/10 in second reactor, and drop into 98% vitriol oil 0.02L of the ionic liquid scale of construction 1/10,25.0 ℃ of reactions of temperature of reaction 45 minutes, standing demix.
Repeat above reaction, carry out the sulfonation desulphurization reaction altogether 3 times, get the water that 2 milliliters of alkane add equal volume from stirred reactor top, fully shake the back and placed 5 minutes, the upper strata is the alkane of clear, and lower floor is the water of clear.Alkane is taken out from the 3rd sulfonation desulphurization reactor top, deliver to lightness-removing column, add thermal rectification and take off light constituent in reflux temperature is 62.0 ℃ lightness-removing column, entering reflux temperature then is to add thermal rectification in 78.0 ℃ of weight-removing columns to take off heavy constituent; From cat head extraction material normal hexane to finishing column rectifying again, feeding temperature is 60.0 ℃ in the finishing column, tower top temperature is 68.7 ℃, reflux ratio is 3.5, and reflux temperature is 65.0 ℃, and front-end volatiles are deviate from from gas phase, after cut separates at the bottom of by still, the front and back cut is sent reactive system back to and is recycled, and obtains 0.90 kilogram of liquid chromatographic grade level normal hexane finished product, yield 90.9% from the cat head extraction.Detect through UV, its 220nm place absorbancy is 0.0569.It is 99.9% that GC detects purity.
Embodiment 7
In 2L glass stirred reactor, drop into the N-propanesulfonic acid base hydrosulfate ionic liquid 0.05L of raw material volume 1/30, and drop into 98% vitriol oil 0.017L of the ionic liquid scale of construction 1/3, feed 0.99 kilogram of (1.5L of industrial normal hexane raw material while stirring, 220nm place absorbancy is 0.2113), temperature control is left standstill and is made the reactant layering 40.0 ℃ of reaction 20 minutes.
Take out alkane to the second a 2L sulfonation desulphurization reactor from the stirred reactor upper strata, the same N-propanesulfonic acid base hydrosulfate ionic liquid 0.05L that drops into raw material volume 1/30 in second reactor, and drop into 98% vitriol oil 0.017L of the ionic liquid scale of construction 1/3,40.0 ℃ of reactions of temperature of reaction 20 minutes, standing demix.
Repeat above reaction secondary, carry out the sulfonation desulphurization reaction altogether 5 times, get the water that 2 milliliters of alkane add equal volume from stirred reactor top, fully shake the back and placed 5 minutes, the upper strata is the alkane of clear, and lower floor is the water of clear.Alkane is taken out from last sulfonation desulphurization reactor top, deliver to lightness-removing column, add thermal rectification and take off light constituent in reflux temperature is 61.0 ℃ lightness-removing column, entering reflux temperature then is to add thermal rectification in 75.0 ℃ of weight-removing columns to take off heavy constituent; From cat head extraction material normal hexane to finishing column rectifying again, feeding temperature is 60.0 ℃ in the finishing column, tower top temperature is 68.7 ℃, reflux ratio is 3.5, and reflux temperature is 65.0 ℃, and front-end volatiles are deviate from from gas phase, after cut separates at the bottom of by still, the front and back cut is sent reactive system back to and is recycled, and obtains 0.87 kilogram of liquid chromatographic grade level normal hexane finished product, yield 87.9% from the cat head extraction.Detect through UV, its 220nm place absorbancy is 0.0584.It is 99.8% that GC detects purity.
Embodiment 8
In 2L glass stirred reactor, drop into the 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid 0.25L of raw material volume 1/8, and drop into 98% vitriol oil 0.05L of the ionic liquid scale of construction 1/5, feed 0.94 kilogram of (1.5L of industrial Skellysolve A raw material while stirring, 220nm place absorbancy is 0.1483), temperature control is left standstill and is made the reactant layering 25.0 ℃ of reaction 45 minutes.
Take out alkane to the second a 2L sulfonation desulphurization reactor from the stirred reactor upper strata, the same 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid 0.25L that drops into raw material volume 1/8 in second reactor, and drop into 98% vitriol oil 0.05L of the ionic liquid scale of construction 1/5,25.0 ℃ of reactions of temperature of reaction 45 minutes, standing demix.
Repeat above reaction, carry out the sulfonation desulphurization reaction altogether 4 times, get the water that 2 milliliters of alkane add equal volume from stirred reactor top, fully shake the back and placed 5 minutes, the upper strata is the alkane of clear, and lower floor is the water of clear.Alkane is taken out from last sulfonation desulphurization reactor top, deliver to lightness-removing column, add thermal rectification and take off light constituent in reflux temperature is 30.0 ℃ lightness-removing column, entering reflux temperature then is to add thermal rectification in 40.0 ℃ of weight-removing columns to take off heavy constituent; From cat head extraction material Skellysolve A to finishing column rectifying again, feeding temperature is 30.0 ℃ in the finishing column, tower top temperature is 36.1 ℃, reflux ratio is 4.0, and reflux temperature is 33.0 ℃, and front-end volatiles are deviate from from gas phase, after cut separates at the bottom of by still, the front and back cut is sent reactive system back to and is recycled, and obtains 0.87 kilogram of liquid chromatographic grade level Skellysolve A finished product, yield 90.4% from the cat head extraction.Detect through UV, its 220nm place absorbancy is 0.0721.It is 99.7% that GC detects purity.
Embodiment 9
In 2L glass stirred reactor, drop into the 1-hexyl-3-methyl imidazolium tetrafluoroborate ionic liquid 0.1L of raw material volume 1/20, and drop into 98% vitriol oil 0.02L of the ionic liquid scale of construction 1/5, feed 0.99 kilogram of (1.5L of industrial normal hexane raw material while stirring, 220nm place absorbancy is 0.2113), temperature control is left standstill and is made the reactant layering 25.0 ℃ of reaction 45 minutes.
Take out alkane to the second a 2L sulfonation desulphurization reactor from the stirred reactor upper strata, the same 1-hexyl-3-methyl imidazolium tetrafluoroborate ionic liquid 0.1L that drops into raw material volume 1/20 in second reactor, and drop into 98% vitriol oil 0.02L of the ionic liquid scale of construction 1/5,25.0 ℃ of reactions of temperature of reaction 45 minutes, standing demix.
Repeat above reaction, carry out 4 sulfonation desulphurization reactions altogether and get the water that 2 milliliters of alkane add equal volume from stirred reactor top, fully shake the back and placed 5 minutes, the upper strata is the alkane of clear, and lower floor is the water of clear.Alkane is taken out from last sulfonation desulphurization reactor top, deliver to lightness-removing column, add thermal rectification and take off light constituent in reflux temperature is 63.0 ℃ lightness-removing column, entering reflux temperature then is to add thermal rectification in 78.0 ℃ of weight-removing columns to take off heavy constituent; From cat head extraction material normal hexane to finishing column rectifying again, feeding temperature is 60.0 ℃ in the finishing column, tower top temperature is 68.7 ℃, reflux ratio is 3.5, and reflux temperature is 65.0 ℃, and front-end volatiles are deviate from from gas phase, after cut separates at the bottom of by still, the front and back cut is sent reactive system back to and is recycled, and obtains 0.87 kilogram of liquid chromatographic grade level normal hexane finished product, yield 87.4% from the cat head extraction.Detect through UV, its 220nm place absorbancy is 0.0545.It is 99.8% that GC detects purity.
Embodiment 10
In 2L glass stirred reactor, drop into the 1-hexyl-3-Methylimidazole hexafluorophosphate ionic liquid 0.15L of material quantity 1/10, and drop into 98% vitriol oil 0.019L of the ionic liquid scale of construction 1/8, feed 1.05 kilograms of (1.5L of industrial octane raw material while stirring, 220nm place absorbancy is 0.2004), temperature control is left standstill and is made the reactant layering 25.0 ℃ of reaction 30 minutes.
Take out alkane to the second a 2L sulfonation desulphurization reactor from the stirred reactor upper strata, the same 1-hexyl-3-Methylimidazole hexafluorophosphate ionic liquid 0.15L that drops into raw material volume 1/10 in second reactor, and drop into 98% vitriol oil 0.019L of the ionic liquid scale of construction 1/8,25.0 ℃ of reactions of temperature of reaction 30 minutes, standing demix.
Repeat above reaction, carry out the sulfonation desulphurization reaction altogether 5 times, get the water that 2 milliliters of alkane add equal volume from stirred reactor top, fully shake the back and placed 5 minutes, the upper strata is the alkane of clear, and lower floor is the water of clear.Alkane is taken out from last sulfonation desulphurization reactor top, deliver to lightness-removing column, add thermal rectification and take off light constituent in reflux temperature is 115.0 ℃ lightness-removing column, entering reflux temperature then is to add thermal rectification in 145.0 ℃ of weight-removing columns to take off heavy constituent; From cat head extraction material octane to finishing column rectifying again, feeding temperature is 110.0 ℃ in the finishing column, tower top temperature is 125.8 ℃, reflux ratio is 2.0, and reflux temperature is 123.0 ℃, and front-end volatiles are deviate from from gas phase, after cut separates at the bottom of by still, the front and back cut is sent reactive system back to and is recycled, and obtains 0.89 kilogram of liquid chromatographic grade level octane finished product, yield 84.8% from the cat head extraction.Detect through UV, its 220nm place absorbancy is 0.0563.It is 99.9% that GC detects purity.
Claims (5)
1. one kind is raw material with technical grade C5～C8 normal paraffin, in full glass reaction rectifier, remove the impurity such as water, organism, ion of trace in the raw material by rectifying after the sulfonation desulfurization repeatedly, the method for preparing high-purity liquid chromatographic grade normal paraffin, it is characterized in that normal paraffin content greater than 99.0%, its idiographic flow is:
1. add a certain amount of ionic liquid and the vitriol oil in stirred reactor, under 25～40 ℃, fed raw material reaction while stirring 20～300 minutes, wherein the input amount of ionic liquid is 1/30～1/5 of stirred reactor volume, and the input amount of the vitriol oil is 1/10～1/3 of ionic liquid volume;
2. after reaction is finished, will be taken out to second sulfonation desulphurization reactor with the upper strata alkane that ionic liquid separates automatically from stirred reactor top and repeat reaction process 1.;
3. repeat 1. 2. repeatedly, to guarantee to remove fully easy sulfonated bodies and sulfocompound, multiplicity is determined by the analyzing and testing result;
4. the alkane after the sulfonation desulfurization is sent into dehydrogenation, is taken off heavy, finished product three rectifying tower and carry out rectifying, obtains high-purity liquid chromatographic grade normal paraffin.
2. according to the described method for preparing high-purity liquid chromatographic grade normal paraffin of claim 1, the input amount that it is characterized in that ionic liquid is 1/20～1/10 of stirred reactor volume, and the input amount of the vitriol oil is 1/8～1/5 of ionic liquid volume.
3. according to the described method for preparing high-purity liquid chromatographic grade normal paraffin of claim 1, it is characterized in that temperature of reaction is 25～30 ℃, the reaction times is 30～50 minutes.
4. according to the described method for preparing high-purity liquid chromatographic grade normal paraffin of claim 1, it is characterized in that ionic liquid is: the N-Methyl pyrrolidone hydrosulfate, the N-Methyl pyrrolidone dihydrogen phosphate, N-methylsulfonic acid base pyrrolidone hydrosulfate, N-ethyl sulfonic acid base pyrrolidone hydrosulfate, N-propanesulfonic acid base hydrosulfate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate, 1-butyl-3-N-Methylimidazoleacetic salt, 1-hexyl-3-methyl imidazolium tetrafluoroborate, one or more of 1-hexyl-3-Methylimidazole hexafluorophosphate combine, and the concentration of the vitriol oil is 90%～98%.
5. according to the described method for preparing high-purity liquid chromatographic grade normal paraffin of claim 1, it is characterized in that rectifying obtains liquid chromatographic grade alkane and detects through UV, its 220nm place absorbancy satisfies the liquid chromatography requirement.
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| CN105085140B (en) * | 2014-05-16 | 2018-03-06 | 上海星可高纯溶剂有限公司 | The method of purification of liquid chromatography mass combined instrument n-hexane |
| CN106278783A (en) * | 2016-08-17 | 2017-01-04 | 太仓沪试试剂有限公司 | A kind of purification process of normal hexane |
| CN107652155A (en) * | 2017-10-25 | 2018-02-02 | 广东工业大学 | A kind of method for producing the residual level n-hexane of agriculture |
| CN109160870A (en) * | 2018-09-14 | 2019-01-08 | 成都市科隆化学品有限公司 | A kind of production method of chromatograph-grade normal heptane |
| CN114276206A (en) * | 2020-09-27 | 2022-04-05 | 太仓沪试试剂有限公司 | Method for preparing high-purity liquid chromatographic grade normal paraffin |
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Non-Patent Citations (3)
| Title |
|---|
| 刘冉等.硫酸酯类离子液体对FCC汽油萃取脱硫性能的研究.《石油与天然气化工》.2007,第36卷(第05期), * |
| 张永新等.磺化反应机理的探讨.《黄淮学刊》.1993,第9卷(第2期), * |
| 胡松青等.离子液体萃取脱硫的探索性研究.《石油学报(石油加工)》.2007,第23卷(第01期), * |
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