CN113336227B - Benzene-free carbon disulfide and preparation method thereof - Google Patents
Benzene-free carbon disulfide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses benzene-free carbon disulfide and a preparation method thereof, wherein the preparation method comprises the following steps: s1, adding a 10X molecular sieve into industrial carbon disulfide, stirring, standing for layering, and filtering, and repeating the steps for 0-3 times; s2, adding a nitrating agent into the carbon disulfide solution, stirring for reaction, standing for layering, and repeating the steps for 0-3 times; s3, adding an acidity regulator into the carbon disulfide solution, stirring, and standing for layering; s4, adding pure water into the carbon disulfide solution, stirring, standing for layering, and repeating the steps for 1-5 times; s5, putting the carbon disulfide solution into a distiller for distillation, and collecting distillate within the temperature range of 46-47 ℃ to obtain the carbon disulfide solution. According to the invention, the industrial-grade carbon disulfide is subjected to preliminary benzene removal through a 10X molecular sieve, then deep benzene removal is performed through nitration reaction, and finally, the qualified benzene-free carbon disulfide product is obtained through acidity adjustment, pure water washing and rectification.
Description
Technical Field
The invention relates to the technical field of carbon disulfide purification, and particularly relates to benzene-free carbon disulfide and a preparation method thereof.
Background
Carbon disulfide is a colorless liquid, is mainly used as a raw material for manufacturing viscose fibers and cellophane, can be used as an ore flotation agent in the metallurgical industry, can be used for producing agricultural pesticides, can be used as a solvent of sulfur chloride, an anticorrosive agent, and can also be used as a solvent for detecting primary amine, secondary amine and alpha-amino acid, measuring a refractive index and carrying out chromatographic analysis. The carbon disulfide is an intermediate of bactericides such as isoprothiolane, captan, mancozeb, zineb, amobam, thiram, ziram, asomate and the like, and is also a raw material of artificial fiber and a rubber vulcanization accelerator.
Technical grade carbon disulfide is obtained by reacting sulfur vapor with hot coal mainly in the absence of oxygen, and thus has a yellowish color mixed with impurities such as sulfide (e.g., carbonyl sulfide), benzene, etc. The industrial-grade carbon disulfide is limited in use due to the mixing of a certain amount of benzene, cannot meet the requirement of customers on benzene-free carbon disulfide, and is detected by a standard method, the benzene content in the general industrial-grade carbon disulfide is in the range of 1000-. For the removal of benzene from carbon disulfide, the treatment methods currently exist are: 1. distilling and extracting; 2. adding a certain amount of concentrated sulfuric acid into carbon disulfide for washing for several times, then washing with water and distilling; 3. concentrated sulfuric acid and concentrated nitric acid are sequentially added into carbon disulfide to convert benzene into nitrobenzene, and then the nitrobenzene is washed, dried and distilled (refer to the prior document, a plurality of suggestions for measuring benzene in air by using a carbon disulfide extraction gas chromatography, Chengjiang Italy and the like, engineering quality, 2007). Because of the difficulties of these methods, for example, for distillation and extraction, the benzene boiling point is 80.1 ℃, the carbon disulfide boiling point is 46.5 ℃, and the distillation and extraction mode can not be completely removed; for the washing mode by using concentrated sulfuric acid, the purification process is complicated and troublesome, and the use amount of concentrated sulfuric acid is too large (the volume ratio is about 1: 5), so that the method is not suitable for industrial production; the concentrated sulfuric acid and concentrated nitric acid method can effectively remove trace benzene in the carbon disulfide, but the method still needs to use a large amount of concentrated sulfuric acid and concentrated nitric acid, and when the carbon disulfide is industrially purified, the large amount of concentrated sulfuric acid and concentrated nitric acid can release a large amount of heat, so that not only is the whole reaction system not easy to control and is safety accidents easy to cause, but also the nitration reaction is influenced by temperature and is easy to generate side reaction (sulfonation reaction) so as to further influence the purity.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the invention provides benzene-free carbon disulfide and a preparation method thereof, the invention firstly carries out preliminary benzene removal on industrial-grade carbon disulfide through a 10X molecular sieve, then carries out deep benzene removal through nitration reaction, and finally obtains a qualified benzene-free carbon disulfide product through acidity adjustment, pure water washing and rectification.
The technical scheme adopted by the invention is as follows: a preparation method of benzene-free carbon disulfide is characterized by comprising the following steps:
s1, adding a 10X molecular sieve in a certain proportion into industrial carbon disulfide, stirring for a certain time, standing for layering and filtering, collecting the upper carbon disulfide solution, and repeating the process for 1-5 times;
s2, adding a nitrating agent into the carbon disulfide solution obtained in the step S1 according to a certain proportion, stirring for reaction, standing for layering, collecting the carbon disulfide solution on the upper layer, and repeating the carbon disulfide solution for 1-4 times (according to experiments, the repetition frequency is preferably not more than 4 times, otherwise, the nitrating agent reacts with the carbon disulfide to generate impurities due to too many repetition frequencies, so that the effect is influenced), wherein the nitrating agent is prepared by mixing sulfuric acid and ammonium nitrate according to the volume ratio of (1-2): (1-2) mixing in proportion;
s3, adding a certain amount of acidity regulator into the carbon disulfide solution obtained in the step S2 to regulate the acidity of the carbon disulfide solution, stirring, standing for layering, and collecting the carbon disulfide solution on the lower layer;
s4, adding a certain amount of pure water into the carbon disulfide solution obtained in the S3 to clean acidic substances and impurities in the carbon disulfide, stirring for a certain time, standing for layering, collecting the carbon disulfide solution on the lower layer, and repeating the step for 1-5 times;
and S5, putting the carbon disulfide solution obtained in the S4 into a distiller for distillation, collecting distillate within the temperature range of 46-47 ℃, and condensing to obtain the carbon disulfide solution.
In the preparation method, experiments show that the benzene content in the industrial-grade carbon disulfide is relatively high, and if the industrial-grade carbon disulfide is directly treated by the nitrating agent, a large amount of heat is generated to cause uncontrollable reaction, in order to overcome the problem, technicians can remove a large amount of benzene in the industrial-grade carbon disulfide by using the 10X molecular sieve, and experiments show that the 10X molecular sieve cannot completely remove benzene, so that the benzene is further removed by the nitrating agent, and at the moment, the benzene content is reduced to a trace amount, the use amount of the nitrating agent is very small, so that the benzene removal process is controllable, the problem that the benzene is easily removed by nitration is further avoided, and finally the qualified benzene-free carbon disulfide can be obtained. The preparation method has the advantages of simple process flow, convenient and controllable operation and outstanding benzene removal effect, and is particularly suitable for large-scale industrial production.
Further, the volume ratio of the 10X molecular sieve to the industrial-grade carbon disulfide is 2-4: 100.
further, the volume ratio of the nitrating agent to the carbon disulfide solution is 0.5-2: 100. in the present invention, the volume ratio of concentrated sulfuric acid and ammonium nitrate in the nitrating agent, and the volume ratio of nitrating agent to carbon disulfide solution, are preferably within the ranges specified in the present invention, and if the ranges are exceeded, for example, an excess of acid, it is likely that the acid reacts with carbon disulfide to produce impurities, and eventually, the carbon disulfide content is unacceptable.
Further, the acidity is adjusted to be a weak alkaline solution with the mass fraction of 15% -30%, and the volume ratio of the weak alkaline solution to the carbon disulfide solution is 1: (3-5). The weakly alkaline solution may be weakly alkaline substances such as sodium carbonate, sodium bicarbonate, potassium carbonate, etc., preferably sodium bicarbonate.
Further, the volume ratio of the pure water to the carbon disulfide is 1: (3-5).
Further, when the nitrating agent is prepared by mixing, the mass fraction of the sulfuric acid is more than 97%, the mass fraction of the nitric acid is more than 67%, the sulfuric acid and the nitric acid are uniformly mixed according to the proportion, and then the mixture is stood and cooled for later use.
Preferably, the volume ratio of the sulfuric acid to the nitric acid is 1: 1.
the invention also comprises benzene-free carbon disulfide prepared by the preparation method.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that: according to the preparation method, the industrial-grade carbon disulfide is subjected to preliminary benzene removal through a 10X molecular sieve, then deep benzene removal is performed through nitration reaction, and finally a qualified benzene-free carbon disulfide product is obtained through acidity adjustment, pure water washing and rectification.
Drawings
Figure 1 is a chromatogram of a carbon disulfide product obtained in example 2 of the present invention;
FIG. 2 is a report of the area percentage calculation of the chromatogram of FIG. 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of benzene-free carbon disulfide comprises the following steps:
s1, mixing the components in a 30L three-neck flask according to the volume ratio of 3: adding a 10X molecular sieve and industrial carbon disulfide in a ratio of 100, stirring for 3 hours, standing for layering, filtering, collecting an upper carbon disulfide solution, and repeating the treatment for 1 time;
s2, adding 1/100 mixed acid (nitric acid: sulfuric acid volume ratio is 1:1, sulfuric acid content is 98%, nitric acid content is 68%) into the filtered carbon disulfide solution according to volume ratio, starting stirring, stirring for 4 hours, layering, collecting the upper layer carbon disulfide solution, and repeating the process for 1 time;
s3, adding a 20% sodium bicarbonate solution (the volume ratio of the carbon disulfide to the sodium bicarbonate solution is 4: 1) into the carbon disulfide solution, stirring for 3 hours, standing for layering, and collecting the lower-layer carbon disulfide solution;
s4, adding a certain amount of pure water (the volume ratio of carbon disulfide to pure water is 4: 1) into the carbon disulfide solution, stirring for 4 hours, standing for layering, collecting the lower carbon disulfide solution, and repeating the above steps for 3 times;
and S5, adding the treated carbon disulfide into a 20L evaporator, carrying out electric distillation, and collecting the carbon disulfide within the temperature range of 46-47 ℃ to obtain the carbon disulfide.
Example 2
A preparation method of benzene-free carbon disulfide comprises the following steps:
s1, adding the mixture into a 30L three-neck flask according to the volume ratio of 2: adding a 10X molecular sieve and industrial carbon disulfide in a ratio of 100, stirring for 3 hours, standing for layering, filtering, collecting an upper carbon disulfide solution, and repeating the treatment for 1 time;
s2, adding 2/100 mixed acid (nitric acid: sulfuric acid volume ratio is 1:1, sulfuric acid content is 98%, nitric acid content is 68%) into the filtered carbon dichloride solution according to volume ratio, starting stirring, stirring for 4 hours, layering, collecting the upper carbon disulfide solution, and repeating the process for 1 time;
s3, adding a 20% sodium bicarbonate solution (the volume ratio of the carbon disulfide to the sodium bicarbonate solution is 5: 1) into the carbon disulfide solution, stirring for 3 hours, standing for layering, and collecting the lower-layer carbon disulfide solution;
s4, adding a certain amount of pure water (the volume ratio of carbon disulfide to pure water is 5: 1) into the carbon disulfide solution, stirring for 4 hours, standing for layering, collecting the lower carbon disulfide solution, and repeating the above steps for 2 times;
and S5, adding the treated carbon disulfide into a 20L evaporator, carrying out electric distillation, and collecting the carbon disulfide within the temperature range of 46-47 ℃ to obtain the carbon disulfide.
Example 3
A preparation method of benzene-free carbon disulfide comprises the following steps:
s1, adding the components in a 30L three-neck flask according to the volume ratio of 4: adding a 10X molecular sieve and industrial carbon disulfide in a ratio of 100, stirring for 3 hours, standing for layering, filtering, collecting an upper carbon disulfide solution, and repeating the treatment for 1 time;
s2, adding 1/200 mixed acid (nitric acid: sulfuric acid volume ratio is 1: 2, sulfuric acid content is 98%, nitric acid content is 68%) into the filtered carbon dichloride solution according to volume ratio, starting stirring, stirring for 4 hours, layering, collecting the upper layer of carbon disulfide solution, and repeating the process for 2 times;
s3, adding a 25% sodium bicarbonate solution (the volume ratio of carbon disulfide to the sodium bicarbonate solution is 3: 1) into the carbon disulfide solution, stirring for 3 hours, standing for layering, and collecting the lower-layer carbon disulfide solution;
s4, adding a certain amount of pure water (the volume ratio of carbon disulfide to pure water is 3: 1) into the carbon disulfide solution, stirring for 4 hours, standing for layering, collecting the lower carbon disulfide solution, and repeating the treatment for 5 times;
and S5, adding the treated carbon disulfide into a 20L evaporator, carrying out electric distillation, and collecting the carbon disulfide within the temperature range of 46-47 ℃ to obtain the carbon disulfide.
The carbon disulfide obtained in examples 1-3 was detected by standard gas chromatography as follows (using example 2 as an example):
detection conditions
A detection instrument: a gas chromatograph; a detector: flame Ionization Detector (FID);
carrier gas and flow rate: nitrogen gas; hydrogen flow rate: 30 ml/min; air flow rate: 400 ml/min;
a chromatographic column: BD-1 (30m < 450um > m < 1.1.27 um);
column temperature: the initial temperature is 70 ℃, the temperature is kept for 3min, the temperature rise rate is 10 ℃/min, the temperature is raised to 120 ℃, and the temperature is kept for 12 min.
Sample inlet temperature: 200 ℃; detection chamber temperature: 300 ℃;
sample introduction amount: 5 ul; the split ratio is as follows: 30: 1; column flow rate: 2 ml/min.
The content is calculated by a common area normalization method.
The result of the detection
The detection report results are shown in fig. 1 and fig. 2, and are obtained from fig. 1 and fig. 2, and the benzene content of example 2 is below 0.5ppm, so that the invention achieves the purpose of removing benzene impurity in industrial-grade carbon disulfide, and the benzene removal is complete, thereby meeting the requirements of commercial customers for carbon-free carbon disulfide.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A preparation method of benzene-free carbon disulfide is characterized by comprising the following steps:
s1, adding a 10X molecular sieve into industrial carbon disulfide, wherein the volume ratio of the 10X molecular sieve to the industrial carbon disulfide is (2-4): 100, stirring for a certain time, standing for layering, filtering, collecting the carbon disulfide solution on the upper layer, and repeating the carbon disulfide solution for 1-5 times;
s2, adding a nitrating agent into the carbon disulfide solution obtained in the step S1, wherein the volume ratio of the nitrating agent to the carbon disulfide solution is 0.5-2:100, stirring for reaction, standing for layering, collecting the upper layer of the carbon disulfide solution, and repeating the step 1-4 times on the carbon disulfide solution, wherein the nitrating agent is prepared from sulfuric acid and nitric acid according to the volume ratio of (1-2): (1-2) mixing in proportion;
s3, adding a certain amount of acidity regulator into the carbon disulfide solution obtained in the step S2 to regulate the acidity of the carbon disulfide solution to pH 6-7, stirring, standing for layering, and collecting the carbon disulfide solution on the lower layer;
s4, adding a certain amount of pure water into the carbon disulfide solution obtained in the S3, stirring for a certain time, standing for layering, collecting the carbon disulfide solution on the lower layer, and repeating the step for 1-5 times;
and S5, putting the carbon disulfide solution obtained in the S4 into a distiller for distillation, collecting distillate within the temperature range of 46-47 ℃, and condensing to obtain the carbon disulfide solution.
2. The method for preparing carbon disulfide benzene as claimed in claim 1, wherein the acidity is adjusted to 15-30% by mass of a weakly alkaline solution, and the volume ratio of the weakly alkaline solution to the carbon disulfide solution is 1 (3-5).
3. The process for producing carbon disulfide benzene according to claim 1, wherein the volume ratio of pure water to carbon disulfide is from 1 (3) to 5.
4. The method for preparing carbon disulfide benzene as claimed in claim 1, wherein the mass fraction of sulfuric acid and the mass fraction of nitric acid are respectively 97% and 67%, respectively, and the sulfuric acid and the nitric acid are uniformly mixed in proportion, and then the mixture is allowed to stand and cool for later use.
5. The method of claim 4, wherein the volume ratio of sulfuric acid to nitric acid is 1: 1.
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| CN102992323A (en) * | 2011-09-15 | 2013-03-27 | 上海安谱科学仪器有限公司 | CS2 reagent purification method |
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| CN102718621B (en) * | 2012-07-03 | 2014-08-13 | 北京旭阳化工技术研究院有限公司 | Method for selectively desorbing carbon disulfide in coarse benzene |
| CN104230619B (en) * | 2013-06-17 | 2016-12-28 | 中国石油化工股份有限公司 | The method of aromatic hydrocarbons deep purifying |
| CN105905901A (en) * | 2016-03-29 | 2016-08-31 | 江阴秋毫检测有限公司 | Carbon disulfide purification method |
| CN107572483B (en) * | 2017-01-16 | 2020-04-21 | 赵西营 | Process for simultaneously producing carbon disulfide, sulfur and insoluble sulfur |
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| GB207594A (en) * | 1922-08-25 | 1923-11-26 | William Henry Ponter | A new or improved preparation for removing paint, varnish and the like |
| GB416404A (en) * | 1933-03-06 | 1934-09-06 | Nat Benzole Company Ltd | Improvements in the recovery of carbon disulphide and methyl alcohol from aqueous solutions obtained in the purification of benzole with methyl alcohol and caustic alkali |
| CN102992323A (en) * | 2011-09-15 | 2013-03-27 | 上海安谱科学仪器有限公司 | CS2 reagent purification method |
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