CN101397231B - Method for preparing straight-chain odd number normal alkane - Google Patents
Method for preparing straight-chain odd number normal alkane Download PDFInfo
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- CN101397231B CN101397231B CN 200710061283 CN200710061283A CN101397231B CN 101397231 B CN101397231 B CN 101397231B CN 200710061283 CN200710061283 CN 200710061283 CN 200710061283 A CN200710061283 A CN 200710061283A CN 101397231 B CN101397231 B CN 101397231B
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Abstract
The invention relates to a preparation method of straight-chain odd-numbered n-alkane, the steps of the method are as follows: (1) low-grade odd-numbered halon and the corresponding n-halon are evenly mixed for forming alkyl bromide mixed liquid; (2) metal sodium is weighed for standby; (3) petroleum ether, the alkyl bromide mixed liquid and the metal sodium are added in a reactor for stirring, the temperature is increased to 50 to 60 DEG C, the heat release is carried out by relying on the reaction; (4) the alkyl bromide mixed liquid is slowly dripped for reaction for 1 to 2 hours; and (5) anhydrous ethanol and water are sequentially slowly dripped, anhydrous magnesium sulfate is used for drying, distillation is carried out, fractions are collected and washed by adding concentrated sulfuric acid till an acid layer is colorless or light yellow, the drying and the collection by an absorption column are carried out, then the distillation is further carried out, and the collected n-fraction is the straight-chain odd-numbered n-alkane. The preparation method breaks through the bottlenecks that by-products which are generated by using the Wurtz method for synthesizing asymmetric n-alkane are of great amount and the purification is difficult, thereby providing an effective raw material for developing a standard sample of the straight-chain odd-numbered n-alkane which is needed by the future atmospheric crude oil and geological analysis.
Description
Technical field
The invention belongs to the chemical reagent field, relate to a kind of preparation method of straight-chain odd number normal alkane.
Background technology
Normal paraffin as one of environmental protection liquid fuel composition key ingredient, and one of the component of diesel oil at low-temperature improving agent be used widely, simultaneously the normal paraffin monomer in the analysis field such as organism, also has very important function in geology, crude oil and Atmospheric particulates.But owing to differ in the source of normal paraffin, cause the composition of its all kinds of normal paraffins different, thereby make product form the difference that has in varying degrees, thereby be badly in need of some special normal paraffin monomer adjustment prescriptions so that its quality can access maximum the assurance.Through the data at home and abroad investigation, the method that is summed up for the preparation of normal paraffin has following three kinds: 1. the mixture that adopts the standby n-alkane of molecular sieve or urea dewaxing legal system, carry out the method for segmentation subzero fractionation n-alkane monomer, typical process has the independently developed IUDW technique of Molex technique and China of VOP company again; 2. adopt the Woertz reaction to prepare the method for symmetry even normal paraffin, such as Arthur I.Vogel: " A textbook of Practial organic Chemistry ", 4
ThEd., London, 324,1978.3. adopt the idoalkane method of reducing, such as A H Blatt: " OrganicSyntheses ", Coll, Vol.II, 1st ed., Queen ' s College, Flushing, N.Y., 320,1955.In above three kinds of methods, the first method processing condition are complicated, and some device structure and material are required height, only are suitable for extensive petrochemical industry production; Other two kinds of methods all exist and are only suitable for symmetry even normal paraffin preparation, and the defective such as raw material supply existing problems.
In view of above situation, seek a kind of simple, easy-operating in C11～C25 scope preparation and the method for purification of straight-chain odd number normal alkane, be that researcher is paid attention to.At present by literature search, there be not to find the report identical with the present invention.
Summary of the invention
The objective of the invention is to overcome the weak point of prior art and equipment, the preparation method of the higher straight-chain odd number normal alkane of a kind of purity in C11～C25 scope is provided.
The technical scheme that the present invention takes is:
A kind of preparation method of straight-chain odd number normal alkane, the step of its preparation method is:
(1). rudimentary odd number haloalkane is mixed with corresponding positive structure haloalkane, form the bromoalkane mixed solution, for subsequent use;
(2). take by weighing sodium Metal 99.5, and be cut into little slice, for subsequent use;
(3). drop into 60～90 ℃ of sherwood oils and bromoalkane mixed solution in reactor, and sodium Metal 99.5 stirs and be warming up to 50～60 ℃, remove thermal source, rely on exothermic heat of reaction, keep 70～90 ℃ of temperature of reaction, keep reflux state;
(4). slowly drip the bromoalkane mixed solution and also constantly add, sodium Metal 99.5 remains backflow, and is reinforced complete, keeps weak and refluxes, and reacts 1～2 hour;
(5). slowly drip successively dehydrated alcohol and water, tell organic phase, be washed to neutrality, use anhydrous magnesium sulfate drying, distill and collect 190～400 ℃ of fractions, this fraction enriching sulfuric acid scrubbing is colourless or light yellow to the acid layer for several times, the washing organic phase is to neutral, drying is collected rear distillation by the adsorption column of in-built solid adsorbent, collects positive fraction and namely obtains straight-chain odd number normal alkane.
And described odd number normal alkane is the straight-chain odd number normal alkane in C11～C25 scope.
And described rudimentary odd number haloalkane is 1: 1 with the mol ratio of corresponding positive structure haloalkane.
And the sodium Metal 99.5 in reaction process in the reaction solution should excessive 5%-30%.
And described solid adsorbent is one of them of gac, atlapulgite and molecular sieve.
Advantage of the present invention and positively effect are:
1. the present invention adopts the rudimentary odd number haloalkane of ample supply of commodities on the market and corresponding positive structure haloalkane, in the presence of the low saturated alkane that boils, carry out the corresponding odd number normal alkane of Woertz reaction preparation, the synthetic n-undecane in the presence of 60～90 ℃ of sherwood oils such as n-propyl bromide and n-octane bromide; Bromo pentane and bromo positive flow silane be synthetic Pentadecane in the presence of 90～120 ℃ of sherwood oils; Bromo heptane and bromo Octadecane synthesize pentacosane etc. in the presence of 90～120 ℃ of sherwood oils.
2. the present invention uses strong oxide compound (such as the vitriol oil, acid potassium permanganate etc.) that unsaturated compounds in the reactant and alcohols impurity are carried out oxygenizement, reaches the removal of impurities effect.
3. the present invention carries out removal of impurities, and distills by the adsorption of solid adsorbent (such as gac, atlapulgite, molecular sieve etc.), cuts the cut of wanting, and is applicable to the required chemical reagent of various experiments and produce.
4. the invention provides the preparation method of straight-chain odd number normal alkane monomer, the particularly important is to have broken through utilizes the synthetic asymmetry by product that normal paraffin produces of Woertz a lot, the bottleneck that is difficult for purification is for the from now on development of the required straight-chain odd number normal alkane standard model of large gas crude oil and geological analysis provides effective raw material.
Embodiment
Below in conjunction with embodiment technology contents of the present invention is described further; Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
The reactor that following embodiment adopts is a there-necked flask with reflux exchanger, agitator and minute dropping funnel.
Embodiment 1:
The preparation of n-undecane:
(1). at first n-propyl bromide 1229.9g (10mol) and n-octane bromide 1931.3g (10mol) are mixed, form the bromoalkane mixed solution, for subsequent use;
(2). take by weighing sodium Metal 99.5 551.76g (24mol), and be cut into little slice, for subsequent use;
(3). reach in the there-necked flask of minute dropping funnel with reflux exchanger, agitator one, drop into 450g, 60～90 ℃ of sherwood oils and 100g bromoalkane mixed solution, the 50g sodium Metal 99.5 stirs and is warming up to 60 ℃, remove thermal source, rely on exothermic heat of reaction, keep temperature of reaction more than 70 ℃, keep reflux state;
(4). slowly drip remaining mixed solution and also constantly add, sodium Metal 99.5 remains backflow, and the sodium Metal 99.5 in the reaction process in the reaction solution is answered excessive 5%-30%, and is reinforced complete, keeps weak backflow, reacts 1.5 hours;
(5). slowly drip successively the 400g dehydrated alcohol, and 1000g water, tell organic phase, washed several times with water is to neutral, use anhydrous magnesium sulfate drying, distillation is also collected 190～220 ℃ of fractions, and it is colourless or light yellow to the acid layer for several times that this fraction adds the washing of the 600g vitriol oil, and the washing organic phase is to neutral, dry, collect rear distillation by the adsorption column of in-built gac, collect positive fraction and obtain about 470g n-undecane, yield about 30%.
Embodiment 2:
The preparation of Pentadecane:
1. at first bromo pentane 1510.5g (10mol) and bromo positive flow silane 2211.8g (10mol) are mixed, for subsequent use;
2. take by weighing sodium Metal 99.5 551.76g (24mol), and be cut into little slice, for subsequent use;
3. in a there-necked flask with reflux exchanger, agitator and minute dropping funnel, drop into 450g, 90～120 ℃ of sherwood oils and 100g bromoalkane mixed solution, the 50g sodium Metal 99.5 stirs and is warming up to 60 ℃, remove thermal source, rely on exothermic heat of reaction, keep temperature of reaction more than 70 ℃, keep reflux state;
4. slowly drip remaining bromoalkane mixed solution and also constantly add, sodium Metal 99.5 remains backflow, and the sodium Metal 99.5 in the reaction process in the reaction solution should be excessive, and is reinforced complete, keeps weak and refluxes, and reacts 2 hours;
5. slowly drip successively the 400g dehydrated alcohol, and 1000g water, tell organic phase, washed several times with water is to neutral, use anhydrous magnesium sulfate drying, 260～280 ℃ of fractions are collected in distillation, and it is colourless or light yellow to the acid layer for several times that this fraction adds the washing of the 600g vitriol oil, and the washing organic phase is to neutral, dry, collect rear distillation by the adsorption column of in-built atlapulgite, collect positive fraction and obtain about 600g Pentadecane, yield about 30%.
Embodiment 3:
The preparation of pentacosane:
1. at first bromo heptane 895.5g (5mol) and bromo Octadecane 1667g (5mol) are mixed, for subsequent use;
2. take by weighing sodium Metal 99.5 275.99g (12mol), and be cut into little slice, for subsequent use;
3. in a there-necked flask with reflux exchanger, agitator and minute dropping funnel, drop into 450g, 90～120 ℃ of sherwood oils and 100g bromoalkane mixed solution, the 50g sodium Metal 99.5 stirs and is warming up to 60 ℃, remove thermal source, rely on exothermic heat of reaction, keep temperature of reaction more than 70 ℃, keep reflux state;
4. slowly drip remaining bromoalkane mixed solution and also constantly add, sodium Metal 99.5 remains backflow, and the sodium Metal 99.5 in the reaction process in the reaction solution should be excessive, and is reinforced complete, keeps weak and refluxes, and reacts 2 hours;
5. slowly drip successively the 400g dehydrated alcohol, and 1000g water, tell organic phase, washed several times with water is to neutral, use anhydrous magnesium sulfate drying, 210～230 ℃/5mmHg fraction is collected in distillation, and it is colourless or light yellow to the acid layer for several times that this fraction adds the washing of the 600g vitriol oil, and the washing organic phase is to neutral, dry, collect rear distillation by the adsorption column of in-built molecular sieve, collect positive fraction and obtain about 500g pentacosane, yield about 30%.
The product purity of above-mentioned three embodiment can reach 95～98%.
Among the present invention, the employed low saturated alkane that boils also can be normal hexane, normal heptane, reaches 60～90 ℃ of sherwood oils, 90～120 ℃ of sherwood oils etc.
Claims (1)
1. the preparation method of a straight-chain odd number normal alkane is characterized in that:
The step of its preparation method is:
(1). rudimentary odd number bromoalkane is mixed with corresponding positive structure bromoalkane, form the bromoalkane mixed solution, for subsequent use;
(2). take by weighing sodium Metal 99.5, and be cut into little slice, for subsequent use;
(3). in reactor, drop into 60～90 ℃ of sherwood oils and bromoalkane mixed solution, and sodium Metal 99.5 stirs and to be warming up to 50～60 ℃, remove thermal source, rely on exothermic heat of reaction, keep 70～90 ℃ of temperature of reaction, keep reflux state;
(4). slowly drip the bromoalkane mixed solution and also constantly add, sodium Metal 99.5 remains backflow, and is reinforced complete, keeps weak and refluxes, and reacts 1～2 hour;
(5). slowly drip successively dehydrated alcohol and water, tell organic phase, be washed to neutrality, use anhydrous magnesium sulfate drying, distill and collect 190～400 ℃ of fractions, this fraction enriching sulfuric acid scrubbing is colourless or light yellow to the acid layer for several times, the washing organic phase is to neutral, drying is collected rear distillation by the adsorption column of in-built solid adsorbent, collects positive cut and namely obtains straight-chain odd number normal alkane;
Described odd number normal alkane is the straight-chain odd number normal alkane in C11～C25 scope;
Described rudimentary odd number bromoalkane is 1: 1 with the mol ratio of corresponding positive structure bromoalkane;
Sodium Metal 99.5 in reaction process in the reaction solution is answered excessive 5%-30%;
Described solid adsorbent is one of them of gac, atlapulgite and molecular sieve.
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| CN101906008A (en) * | 2010-07-17 | 2010-12-08 | 天津市化学试剂研究所 | Method for preparing high-purity linear-chain symmetrical even normal paraffins |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1525950A (en) * | 2001-05-21 | 2004-09-01 | Oxidative halogenation of C* hydrocarbons to halogenated C* hydrocarbons and integrated processes related thereto | |
| CN101041609A (en) * | 2006-03-20 | 2007-09-26 | 微宏科技（湖州）有限公司 | Process for synthesizing hydrocarbon from three to thirteen carbon from methane by non-synthesis gas method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1525950A (en) * | 2001-05-21 | 2004-09-01 | Oxidative halogenation of C* hydrocarbons to halogenated C* hydrocarbons and integrated processes related thereto | |
| CN101041609A (en) * | 2006-03-20 | 2007-09-26 | 微宏科技（湖州）有限公司 | Process for synthesizing hydrocarbon from three to thirteen carbon from methane by non-synthesis gas method |
Non-Patent Citations (1)
| Title |
|---|
| 焦明杰等，.武兹反应.《有机化学》.1990,第34页. * |
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