CN113956179A - Acetonitrile refining method and application thereof - Google Patents
Acetonitrile refining method and application thereof Download PDFInfo
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Abstract
The invention provides an acetonitrile refining method, which comprises the following steps: (1) adsorbing the water-containing crude acetonitrile by using an inorganic carbon material to prepare water-containing acetonitrile; (2) and dehydrating the water-containing acetonitrile to obtain the finished product of high-purity acetonitrile. The invention also provides application of the prepared high-purity acetonitrile. The invention has the beneficial effects that: the method creatively realizes effective adsorption treatment on the water-containing crude acetonitrile with the water content of 10-90%, can control the impurity content in the acetonitrile at an extremely low level, and effectively avoids the adverse effect of impurities on the subsequent rectification and purification of the acetonitrile; the method can effectively simplify the intermediate refining processes such as oxidation, reduction and the like, reduce the energy consumption by 10-30%, and simultaneously can effectively keep the high yield of acetonitrile, wherein the yield of acetonitrile reaches more than 95%; the prepared finished product of high-purity acetonitrile has the acetonitrile content of more than 99.9 percent and the 200nm light transmittance of more than 90 percent.
Description
Technical Field
The invention relates to the field of refining in acetonitrile production, in particular to an acetonitrile refining method and application thereof.
Background
Acetonitrile is a colorless transparent liquid, and the most important application is as a solvent, such as a solvent for extracting butadiene and a solvent for organic synthesis. Meanwhile, acetonitrile is an important raw material of medicines (vitamin B1) and perfume intermediates, and high-purity acetonitrile can be used as a mobile phase of liquid chromatography or an important solvent for preparing and purifying medicines such as insulin, paclitaxel and the like. Although the purity of the industrial-grade acetonitrile can reach 99.9 percent, the industrial-grade acetonitrile still contains various trace impurities, such as propionitrile, acetone, allyl alcohol, acrylic acid, toluene and the like, and the industrial-grade acetonitrile can be purified into chromatographic-grade high-purity acetonitrile by removing the impurities through processes of water removal, oxidation reduction, adsorption, rectification and the like, and is used in high-end application fields such as analytical chemistry, pharmaceutical synthesis and the like.
The acetonitrile production technology is mainly divided into two types: direct synthesis and indirect synthesis. The direct synthesis method comprises the following steps: acetic acid with ammonia, propane with ammonia, ethanol with ammonia, and the like. The indirect method mainly synthesizes acrylonitrile and simultaneously produces acetonitrile as a byproduct. The acetonitrile impurity of the direct synthesis method has definite types and small quality fluctuation, and is more suitable to be used as a raw material of high-purity acetonitrile. In the traditional acetonitrile refining process, the crude acetonitrile product prepared in the synthesis procedure needs to pass through a multistage rectifying tower to prepare industrial acetonitrile.
The applicant has found that the conventional refining process for acetonitrile production has the following problems: the steam consumption is high, and the energy consumption is high; the refining equipment is more, the process flow is long, the material liquid circulation amount is large, the material circulation period is long, the operation is complex, and the occupied area of the equipment is large; the acetonitrile quality is not high and can only reach industrial grade indexes. Further, a technology that water-containing crude acetonitrile is pretreated by using activated carbon and then purified is disclosed, but the applicant finds that the pretreatment of the water-containing crude acetonitrile by using the activated carbon in the prior art cannot reach an expected quality standard, and after the pretreatment of the activated carbon is completed, a large number of impurities still exist in the water-containing acetonitrile, and the existence of the impurities can form adverse effects of azeotrope and the like in the subsequent acetonitrile rectification and purification process, so that the purification and impurity removal capability of the water-containing acetonitrile through rectification and other refining methods is seriously affected, and the subsequent acetonitrile purification and purification process directly needs high processing energy consumption, complex process flows and more processing equipment to achieve high acetonitrile purity, and has adverse effects on the aspects of efficiency, cost and the like.
Chinese patent CN101830829A discloses a method for synthesizing acetonitrile by acetic acid one-step ammoniation, which comprises the steps of carrying out deammoniation rectification, normal-pressure rectification, reduced-pressure rectification and pressurized rectification on crude acetonitrile prepared by acetic acid ammoniation reaction to obtain finished acetonitrile. The disadvantages of the patent are that: in the refining process, multiple times of rectification are needed, the steam consumption is high, and the energy consumption is high; meanwhile, impurities in the crude acetonitrile can form binary or multi-component azeotrope with water and acetonitrile, so that the separation effect is low, the acetonitrile quality can only reach the industrial grade standard, and the high-purity acetonitrile can be prepared by adopting the combination of processes such as oxidation, reduction, rectification and the like so as to meet the high-purity application.
Japanese patent WO2016068068A1 discloses a method for producing acetonitrile, in which crude acetonitrile containing water is purified with activated carbon and then subjected to purification post-treatment such as rectification. However, the applicant finds that the pretreatment of the crude acetonitrile containing water by the activated carbon adopted in the patent cannot reach the expected quality standard, after the pretreatment of the activated carbon is completed, the content of impurities at a certain level still exists in the crude acetonitrile containing water, and the existence of the impurities can cause adverse effects on the subsequent rectification and purification of the acetonitrile, so that the high purification of the acetonitrile containing water is seriously affected, and the subsequent rectification and purification process of the acetonitrile needs to consume high treatment energy consumption, complicated process flows such as oxidation and reduction, more treatment equipment and adverse effects on the aspects of efficiency, cost and the like to achieve higher acetonitrile purity.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides an acetonitrile refining method, which aims to realize the following purposes:
(1) the crude acetonitrile in the production process of synthesizing acetonitrile is adsorbed and refined, and chemical refining processes such as oxidation reduction and the like are not needed, so that high-purity acetonitrile with the purity of over 99.9 percent can be prepared, the energy consumption is low, and the yield is high.
(2) The method can simplify the refining process flow of the crude acetonitrile, omit the refining processes such as oxidation reduction and the like in the prior art, reduce refining equipment, and reduce the material circulation amount and cycle period.
(3) Can prepare high-purity acetonitrile with the purity of over 99.9 percent, effectively improve the quality of the synthetic acetonitrile and meet the application requirements of high-end fields such as analysis and detection, preparative chromatography and the like.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for refining acetonitrile, the method comprising the steps of: (1) adsorbing the water-containing crude acetonitrile by using an inorganic carbon material to prepare water-containing acetonitrile; (2) and dehydrating the water-containing acetonitrile to obtain the finished product of high-purity acetonitrile.
Preferably, the inorganic carbon material is an inorganic carbon-rich material which is approximately amorphous, easily graphitized and has a micro mesoporous structure and is composed of SP2 hybridized carbon atoms and SP3 hybridized carbon atoms.
Preferably, the inorganic carbon material is at least one of: carbon fiber, active carbon, graphitized carbon black, carbon microspheres and carbon molecular sieves.
Preferably, the carbon content of the inorganic carbon material is more than 99.9%, and the specific surface area is 950-1250 m2(ii)/g, the average pore diameter is 1 to 10 nm.
Preferably, in the inorganic carbon material, the particle size of the activated carbon is 100 μm; the particle size of the graphitized carbon black is 250 mu m; the particle size of the carbon molecular sieve is 60 mu m; the grain diameter of the carbon microsphere is 80 μm; the carbon fiber has a length of 3 to 5mm and a diameter of 15 to 25 μm
Preferably, the inorganic carbon material has a graphitization degree G parameter value of 30-85% as measured by XRD.
Further, in the adsorption treatment, the contact time of the water-containing crude acetonitrile and the inorganic carbon material is not less than 5 min.
Further, the water content of the water-containing crude acetonitrile is 10-90%.
Furthermore, the inorganic carbon material is prepared by using polyvinylidene chloride, carbon powder and an auxiliary agent as raw materials through the steps of hot melting, sizing and carbonizing.
Further, the auxiliary agent comprises: dimethyl phthalate, dibutyl maleate, dioctyl adipate and di-sec-octyl phthalate.
Furthermore, the prepared finished product of high-purity acetonitrile has the acetonitrile content of more than 99.9 percent and the 200nm light transmittance of more than 90 percent.
The application of the prepared high-purity acetonitrile is to be used as a reagent for analysis and detection or a mobile phase for preparing chromatogram.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method for refining the acetonitrile provided by the invention has the essential characteristics that the carbon material with a specific purification effect on the water-containing crude acetonitrile is provided in a breakthrough manner, the inorganic carbon adsorption material with a specific structure, a specific crystal form and a specific graphitization degree is adopted, the effective adsorption treatment on the water-containing crude acetonitrile with the water content of 10-90% is creatively realized, the targeted adsorption of the inorganic carbon material on impurities in the water-containing crude acetonitrile is realized, the impurity content in the acetonitrile can be controlled at an extremely low level, and impurities except water are effectively removed; meanwhile, the inorganic carbon adsorption material has the advantages of wide working interval, high adsorption efficiency and strong working applicability.
(2) According to the acetonitrile refining method, the inorganic carbon adsorption material with a specific structure, a specific crystal form and a specific graphitization degree is used for effectively adsorbing the water-containing crude acetonitrile with the water content of 10-90%, the process flow of crude acetonitrile refining can be effectively simplified, the complex refining processes of oxidation, reduction and the like after acetonitrile adsorption treatment in the prior art are omitted, the acetonitrile high-purity process of direct dehydration treatment after adsorption treatment is realized in a breakthrough manner, and further, the method is distinguished from the prior art by only adsorption treatment and dehydration treatment, so that the high-purity acetonitrile with the purity of more than 99.9% and the light transmittance of 200nm of more than 90% can be prepared.
(3) The acetonitrile product prepared by the acetonitrile refining method has the acetonitrile content of more than 99.9 percent, the water content of less than 0.1 percent and the 200nm light transmittance of more than 90 percent.
(4) The method for refining acetonitrile provided by the invention breakthroughs the essential characteristics of a carbon material with a purification effect, adopts an inorganic carbon adsorption material with a specific structure, a specific crystal form and a specific graphitization degree, can effectively simplify the process flows of oxidation, reduction and the like, reduces the energy consumption, and can effectively keep the high yield of acetonitrile, wherein the yield of acetonitrile reaches more than 95%.
(5) The acetonitrile refining method provided by the invention breakthroughs the essential characteristics of a carbon material with a purification effect, and the adopted inorganic carbon adsorption material with a specific structure, a specific crystal form and a specific graphitization degree effectively reduces the reflux ratio in the subsequent rectification and dehydration process, effectively reduces the consumption of required steam, and effectively reduces the energy consumption by about 10-30%.
(6) The acetonitrile refining method provided by the invention has the advantages of less required equipment, simple process flow, short material circulation period and simplicity in operation, effectively reduces the occupied area of the equipment, and can effectively ensure the refining efficiency while ensuring high acetonitrile yield.
(7) The high-purity acetonitrile prepared by the acetonitrile refining method has good quality, and can meet the application requirements of high-end fields such as analysis and detection, preparative chromatography and the like.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
The acetonitrile refining method comprises the following steps:
(1) adsorbing the water-containing crude acetonitrile by using an inorganic carbon material to prepare water-containing acetonitrile;
(2) and dehydrating the water-containing acetonitrile to obtain the finished product of high-purity acetonitrile.
The inorganic carbon material is an inorganic carbon-rich material which is approximately amorphous, easy to graphitize and has a micro-mesoporous structure and is formed by SP2 hybridized carbon atoms and SP3 hybridized carbon atoms.
The carbon content of the inorganic carbon material is more than 99.9%, and the specific surface area is 100-1500 m2(G), the average pore diameter is 1-10 nm, and the graphitization degree G parameter value measured by XRD is 30-85%.
Wherein, the dehydration can be the prior acetonitrile purification dehydration technology.
The invention provides the essential characteristics of the carbon material with specific purification effect on the water-containing crude acetonitrile in a breakthrough manner, and the inorganic carbon adsorption material with specific carbon content, specific structure, specific crystal form and specific graphitization degree is adopted to creatively realize the effective adsorption treatment on the water-containing crude acetonitrile with the water content of 10-90%, so that the impurity content in the acetonitrile can be controlled at an extremely low level, and the adverse effect of impurities on the subsequent rectification and purification of the acetonitrile can be effectively avoided; the prepared high-purity acetonitrile product has acetonitrile content of more than 99.9 percent and 200nm light transmittance of more than 90 percent. Meanwhile, the inorganic carbon adsorption material has the advantages of wide working range, good treatment compatibility and strong treatment applicability.
On the basis of the technical scheme, in the preferable inorganic carbon material, the particle size of optional activated carbon, graphitized carbon black, carbon microspheres and carbon molecular sieves is 50-500 μm; the carbon fiber has a length of 3 to 5mm and a diameter of 15 to 25 μm. According to the invention, the particle size of the inorganic carbon material is further selected in a targeted manner according to the characteristics of each impurity in the crude acetonitrile, and the adsorption of the inorganic carbon material on the impurities in the acetonitrile is effectively enhanced through a proper pore size range, so that the content of the impurities in the acetonitrile is favorably controlled.
In addition to the above technical solution, the preferred inorganic carbon material of the present invention is at least one of the following materials: carbon fiber, active carbon, graphitized carbon black, carbon microspheres and carbon molecular sieves. Although the inorganic carbon adsorption material meeting the specific structure, the specific crystal form and the specific graphitization degree can achieve an ideal treatment effect, in order to further meet refined treatment standards and requirements and simultaneously consider the conditions and characteristics of various impurities in crude acetonitrile, the inorganic carbon material is preferably selected, the inorganic carbon material is further subjected to specific researches such as model selection, mixing and the like, the adsorption of the inorganic carbon material on the impurities in the acetonitrile is further enhanced, the selective adsorption of the impurities in the acetonitrile is achieved, and the content of the impurities in the acetonitrile is favorably controlled to be extremely low.
On the basis of the technical scheme, in the adsorption treatment, the contact time of the water-containing crude acetonitrile and the inorganic carbon material is not less than 5 min. The inorganic carbon adsorption material with specific carbon content, specific structure, specific crystal form and specific graphitization degree is used for creatively realizing effective adsorption treatment on the water-containing crude acetonitrile with the water content of 10-90%, and the impurity content in the acetonitrile can be controlled at an extremely low level by adopting the shortest treatment time of 5 min.
On the basis of the technical scheme, the prepared finished product of high-purity acetonitrile has the acetonitrile content of more than 99.9 percent and the 200nm light transmittance of more than 90 percent. According to the invention, the crude acetonitrile is treated by adopting the inorganic carbon adsorption material with a specific structure, a specific crystal form and a specific graphitization degree, so that the process flow can be effectively simplified, the energy consumption is reduced, and the process flow is simple.
The technical scheme of the invention specifically adopts a porous inorganic carbon-rich material to carry out adsorption treatment on the water-containing crude acetonitrile, and the method specifically comprises the following steps:
a. selecting an inorganic carbon-rich material which is approximately amorphous, easy to graphitize and has a micro mesoporous structure and consists of SP2 hybridized carbon atoms and SP3 hybridized carbon atoms as an adsorbent;
b. the adsorbent is densely filled in a sealing device with a certain volume and capable of keeping higher pressure;
c. the water content of the aqueous crude acetonitrile should not be less than 10% (mass fraction), and the aqueous crude acetonitrile must be maintained in contact with the adsorbent for an effective contact time during the adsorption treatment.
According to the technical scheme, the dehydration can be conventional acetonitrile purification dehydration treatment such as rectification, pervaporation membrane treatment or brine displacement distillation, and the like, and comprises the following specific steps:
d. and (3) carrying out differential pressure rectification or pervaporation membrane treatment or brine replacement distillation on the water-containing acetonitrile subjected to adsorption treatment, and further dehydrating to obtain the finished product of high-purity acetonitrile.
Furthermore, the water content of the water-containing crude acetonitrile is 10-90%.
Further, in the purification method, the inorganic carbon material may be: carbon-rich materials with micro-mesoporous structures such as carbon fibers, activated carbon, graphitized carbon black, carbon microspheres, carbon molecular sieves and the like.
Further, in the refining method, the carbon content of the inorganic carbon material is more than 99.9%, and the specific surface area is 100-1500 m2The average pore diameter is 1-10 nm, and the graphitization degree G parameter value measured by XRD is 30-85%.
Further, in the refining method, the particle size of optional activated carbon, graphitized carbon black, carbon microspheres and carbon molecular sieves in the inorganic carbon material is 50-500 μm; the carbon fiber has a length of 3 to 5mm and a diameter of 15 to 25 μm.
Further, the inorganic carbon material can be prepared by adopting polyvinylidene chloride, carbon powder and an auxiliary agent as raw materials through the following preparation method:
wherein the weight part ratio of the polyvinylidene chloride, the carbon powder and the auxiliary agent is 70-90:5-10: 5-20.
The auxiliary agent is at least one of the following components: dimethyl phthalate (DMP), dioctyl maleate (DOM), dibutyl maleate (DBM), dioctyl adipate (DOA), di-sec-octyl phthalate (DCP), dibutyl phthalate (DBP).
Specifically, the preparation method of the inorganic carbon material comprises the following steps: hot melting, shaping and carbonizing.
And in the step of hot melting, polyvinylidene chloride, carbon powder and an auxiliary agent in a predetermined part are mixed, smashed into powder, and heated to ensure that the solid-phase powder raw material is hot melted into a liquid phase.
The shaping is carried out, under the condition of preset pressure, the liquid phase raw material prepared in the hot melting step is sprayed, so that the sprayed liquid phase raw material is uniformly sprayed downwards in a foggy shape; meanwhile, cold air blown upwards is arranged below the spray; forming the atomized liquid phase raw material and cold air in a convection way, and shaping into 50-1.0 mm spherical objects.
And in the carbonization step, the spherical object prepared in the shaping step is heated to 1000-1500 ℃ for carbonization under the vacuum condition, so that the inorganic carbon material with the specific surface area and the specific pore diameter is prepared.
According to the specific preparation method of the inorganic carbon material, the specific inorganic carbon material raw material combination is set, the specific preparation process is combined, the inorganic carbon material meeting the performance indexes such as the required specific surface area and pore diameter is prepared in a targeted manner, and the selective adsorption of the inorganic carbon material on impurities in acetonitrile is further optimized.
Furthermore, the finished product of high-purity acetonitrile prepared by the refining method has the acetonitrile content of more than 99.9 percent and the 200nm light transmittance of more than 90 percent.
The technical scheme of the invention, in particular to an acetonitrile refining method, which comprises the following steps: adsorption treatment, rectification and dehydration.
And the adsorption treatment is to adopt an inorganic carbon material to adsorb the water-containing crude acetonitrile. Specifically, the water-containing crude acetonitrile flows through an adsorption column filled with an inorganic carbon material, the water-containing crude acetonitrile is fully contacted with the inorganic carbon material in the adsorption column, and after the water-containing crude acetonitrile stays for a short time, the adsorption treatment is completed, so that the water-containing acetonitrile subjected to the adsorption treatment is prepared. The water-containing acetonitrile is subjected to two-stage rectification dehydration treatment to prepare the finished high-purity acetonitrile with the acetonitrile purity of more than 99.9 percent and the 200nm light transmittance of more than 90 percent.
And in the adsorption treatment, the inorganic carbon material is filled into a pressure-resistant adsorption column made of stainless steel or polytetrafluoroethylene with the length-diameter ratio of 10-35, the filling compactness is ensured by full vibration, and the two ends of a column tube are sealed by sieve plates with the pore diameters smaller than the particle diameters of the inorganic carbon material. And (3) under the temperature of 5-35 ℃ and the pressure of 2-15 MPa, the water-containing crude acetonitrile flows through the adsorption column in the counter-gravity direction, and the contact time of the water-containing crude acetonitrile and the inorganic carbon material is ensured to be more than 5 min.
The water content of the water-containing crude acetonitrile is 10-90%.
The inorganic carbon material can be one or a combination of several of carbon materials such as carbon fiber, graphitized carbon black, carbon microspheres, activated carbon, carbon molecular sieves and the like.
The inorganic carbon material is a granular or fibrous inorganic carbon material which is approximately amorphous and easy to graphitize and consists of SP2 hybridized carbon atoms and SP3 hybridized carbon atoms. The carbon content is more than 99.9%, and the specific surface area is 100-1500 m2The average pore diameter is 1-10 nm, and the graphitization degree G parameter value measured by XRD is 30-85%.
The inorganic carbon material must be washed with high purity acetonitrile or otherwise cleaned prior to use to remove organic impurities from the inorganic carbon material.
The inorganic carbon material is preferably a fine particle material having a graphitization degree G parameter value of 50% or more. The graphitized carbon atom is hybridized by SP2, has a single electron pair and active ions, has a hexagonal microstructure, has extremely strong hydrophobicity, and can strongly adsorb non-polar and weakly polar compounds; and with the increase of the graphitization degree, the specific surface area of the material is sharply reduced, and the adsorption capacity is influenced. Therefore, the inorganic carbon material with specific graphitization degree is selected, and the adsorption capability of the inorganic carbon material is improved by efficiently adsorbing nonpolar and low-polarity compounds.
The inorganic carbon material preferably has a carbon content of more than 99.9% and a particle size of 50-100 um,the specific surface area is 900-1300 m2(iv) an inorganic carbon material having an average pore diameter of 1 to 5nm and a graphitization degree G parameter value of 50% or more.
Further, the dehydration can be rectification dehydration, namely, the acetonitrile obtained in the adsorption treatment step is subjected to rectification dehydration.
The rectification dehydration can be a dehydration process method such as differential pressure rectification and/or pervaporation treatment. Taking differential pressure rectification as an example, the differential pressure rectification comprises primary rectification and secondary rectification.
The first-stage rectification, wherein acetonitrile prepared by the adsorption treatment step enters a first rectification tower, when the liquid level of the first rectification tower reaches 35-45%, the first rectification tower starts to heat, and distillate enters a first reflux tank; when the liquid level in the first reflux tank reaches 30%, starting reflux; stopping feeding acetonitrile when the liquid level in the first reflux tank reaches 50-60%, and simultaneously keeping the temperature of a tower kettle of the first rectification tower at 65-99 ℃ to perform total reflux operation; and after the total reflux is carried out for 1-2 h, sampling and detecting the material in the first reflux tank, and if the acetonitrile content is 50-95% and the water content is less than 50%, feeding the second rectifying tower by the first reflux tank, and simultaneously starting the first rectifying tower for feeding again.
And refluxing the rectification tower in a reflux ratio of 0.2-0.8.
Performing secondary rectification, namely heating and boosting the pressure of the fed rectifying tower, and starting reflux; after the temperature and the pressure of the second rectifying tower reach set values and are stabilized for 20-30 min, starting a lateral line to extract reflux; and opening the finished product to be extracted when the temperature of the temperature measuring point of the finished product extracted from the second rectifying tower reaches 140 ℃ to prepare the finished product of high-purity acetonitrile.
The rectifying tower is heated and pressurized, and the reflux is started: the top pressure of the rectification second tower is 0.6-0.8 MPa, the temperature of the top of the rectification second tower is controlled to be 100-135 ℃, the temperature of the bottom of the rectification second tower is controlled to be 110-140 ℃, the reflux pressure is 0.9-1.0 MPa, and the reflux ratio is 2.2-2.7.
And the side stream is extracted and reflows, the extraction position is the middle upper part of the rectifying second tower body, and the side stream reflows to the middle lower part of the rectifying first tower body.
And the temperature measuring point for finished product extraction is positioned at the middle lower part of the rectifying second tower body.
The finished product of high-purity acetonitrile has acetonitrile content of more than 99.9 percent, water content of less than 0.1 percent and 200nm light transmittance of more than 90 percent.
Example 1
The water-containing crude acetonitrile is subjected to adsorption treatment and rectification dehydration by using graphitized carbon black (the graphitization degree of which is 83.5 percent by XRD test).
Specifically, a stainless steel adsorption column tube with an inner diameter of 10mm and a height of 200mm is filled with a filler with a particle size of 250 μm and a specific surface area of 1130m2Per gram of particulate graphitized carbon black. Wetting with organic-free clean water for many times during filling, compacting with clean high-pressure gas, sealing two ends of the adsorption column tube with stainless steel sieve plates with 5 μm pore diameter, pumping crude acetonitrile containing 50% water (mass fraction) at a flow rate of 2 ml/min under a pressure of 5MPa, collecting the water-containing acetonitrile with corresponding water content after adsorption treatment from the upper part of the adsorption column tube, and rectifying.
Wherein the contact time of the water-containing crude acetonitrile and the adsorption filler (graphitized carbon black) in the adsorption column is 8 minutes.
And the rectification dehydration comprises primary rectification and secondary rectification.
The first-stage rectification, namely feeding the water-containing acetonitrile obtained by the adsorption treatment step into a first rectification tower, heating the first rectification tower when the liquid level of the first rectification tower reaches 40%, and feeding the distillate into a first reflux tank; when the liquid level in the first reflux tank reaches 30%, starting reflux; when the liquid level in the first reflux tank reaches 55%, stopping feeding acetonitrile, and simultaneously keeping the temperature of a rectifying tower kettle at 80 ℃ to perform total reflux operation; and after the total reflux is carried out for 2 hours, sampling and detecting the material in the first reflux tank, and if the acetonitrile content is 50-95% and the water content is less than 50%, feeding the second rectifying tower by the first reflux tank, and simultaneously starting the first rectifying tower again for feeding.
The first rectification tower refluxes, and the reflux ratio is 0.5.
Performing secondary rectification, namely heating and boosting the pressure of the fed rectifying tower, and starting reflux; after the temperature and the pressure of the second rectifying tower reach set values and are stabilized for 30min, starting a side line to collect reflux; and opening the finished product to be extracted when the temperature of the temperature measuring point of the finished product extracted from the second rectifying tower reaches 140 ℃ to prepare the finished product of high-purity acetonitrile.
The rectifying tower is heated and pressurized, and the reflux is started: the top pressure of the rectifying second tower is 0.7MPa, the temperature of the top of the rectifying second tower is controlled to be 125 ℃, the temperature of the bottom of the rectifying second tower is controlled to be 140 ℃, the reflux pressure is 0.9MPa, and the reflux ratio is 2.3.
And the side stream is extracted and reflows, the extraction position is the middle upper part of the rectifying second tower body, and the side stream reflows to the middle lower part of the rectifying first tower body.
And the temperature measuring point for finished product extraction is positioned at the middle lower part of the rectifying second tower body.
The finished product of high-purity acetonitrile has acetonitrile content of more than 99.9 percent and 200nm light transmittance of more than 90 percent.
The ultraviolet transmittance of the finished high-purity acetonitrile product prepared by the embodiment is detected, and the specific data are shown in the following table:
according to the test data, the high-purity acetonitrile prepared by the embodiment has excellent indexes, and can fully meet the quality standard requirement of an analysis detection reagent; meanwhile, the high-purity acetonitrile can also meet the quality standard requirement of a mobile phase in a preparative chromatogram.
Example 2
The crude acetonitrile containing 60% of water (mass fraction) is subjected to adsorption treatment and rectification dehydration by adopting a carbon molecular sieve (the graphitization degree of which is 67.1% by XRD test). The particle size of the carbon molecular sieve is 60 mu m, and the specific surface area is 1050m2(ii) in terms of/g. The operation of packing the carbon molecular sieve was carried out as in example 1, followed by rectification purification.
The adsorption treatment of the water-containing crude acetonitrile, wherein the liquid passing pressure of the crude acetonitrile into an adsorption column tube is 8MPa, the flow rate is 3 ml/min, and the contact time of the water-containing crude acetonitrile and a carbon molecular sieve is 7 min.
And the rectification dehydration comprises primary rectification and secondary rectification.
The first-stage rectification, namely feeding the water-containing acetonitrile obtained by the adsorption treatment step into a first rectification tower, heating the first rectification tower when the liquid level of the first rectification tower reaches 40%, and feeding the distillate into a first reflux tank; when the liquid level in the first reflux tank reaches 30%, starting reflux; when the liquid level in the first reflux tank reaches 55%, stopping feeding acetonitrile, and simultaneously keeping the temperature of a rectifying tower kettle at 80 ℃ to perform total reflux operation; and after the total reflux is carried out for 2 hours, sampling and detecting the material in the first reflux tank, and if the acetonitrile content is 50-95% and the water content is less than 50%, feeding the second rectifying tower by the first reflux tank, and simultaneously starting the first rectifying tower again for feeding.
The first rectification tower refluxes, and the reflux ratio is 0.5.
Performing secondary rectification, namely heating and boosting the pressure of the fed rectifying tower, and starting reflux; after the temperature and the pressure of the second rectifying tower reach set values and are stabilized for 30min, starting a side line to collect reflux; and opening the finished product to be extracted when the temperature of the temperature measuring point of the finished product extracted from the second rectifying tower reaches 140 ℃ to prepare the finished product of high-purity acetonitrile.
The rectifying tower is heated and pressurized, and the reflux is started: the top pressure of the rectifying second tower is 0.7MPa, the temperature of the top of the rectifying second tower is controlled to be 125 ℃, the temperature of the bottom of the rectifying second tower is controlled to be 140 ℃, the reflux pressure is 0.9MPa, and the reflux ratio is 2.3.
And the side stream is extracted and reflows, the extraction position is the middle upper part of the rectifying second tower body, and the side stream reflows to the middle lower part of the rectifying first tower body.
And the temperature measuring point for finished product extraction is positioned at the middle lower part of the rectifying second tower body.
The finished product of high-purity acetonitrile has acetonitrile content of more than 99.9 percent and 200nm light transmittance of more than 94 percent.
The ultraviolet transmittance of the finished high-purity acetonitrile product prepared by the embodiment is detected, and the specific data are shown in the following table:
according to the test data, the high-purity acetonitrile prepared by the embodiment has excellent indexes, and can fully meet the quality standard requirement of an analysis detection reagent; meanwhile, the high-purity acetonitrile can also meet the quality standard requirement of a mobile phase in a preparative chromatogram.
Example 3
Activated carbon (the graphitization degree is 50.6 percent by XRD test) is adopted for 50 percent of crude acetonitrile containing water (mass fraction)Performing adsorption treatment and dehydration. The grain diameter of the carbon molecular sieve is 100 mu m, and the specific surface area is 1250m2(ii) in terms of/g. The operation of packing the carbon molecular sieve was carried out as in example 1, followed by rectification purification.
Wherein, the adsorption treatment of the water-containing crude acetonitrile, the liquid passing pressure of the crude acetonitrile into an adsorption column tube is 10MPa, the flow rate is 5 ml/min, and the contact time of the water-containing crude acetonitrile and the active carbon is 6 min.
The dehydration was a combined rectification and conventional pervaporation purification as described in example 1 above.
The finished product of high-purity acetonitrile prepared after dehydration has acetonitrile content of more than 99.9 percent and 200nm light transmittance of more than 92 percent.
The ultraviolet transmittance of the finished high-purity acetonitrile product prepared by the embodiment is detected, and the specific data are shown in the following table:
according to the test data, the high-purity acetonitrile prepared by the embodiment has excellent indexes, and can fully meet the quality standard requirement of an analysis detection reagent; meanwhile, the high-purity acetonitrile can also meet the quality standard requirement of a mobile phase in a preparative chromatogram.
Example 4
Crude acetonitrile containing 50% of water (mass fraction) is subjected to adsorption treatment and rectification dehydration by adopting carbon fibers (the graphitization degree of the carbon fibers is 32.3% by XRD test). The carbon fiber has a length of 3-5 mm, a diameter of 15-25 μm, and a specific surface area of 950m2(ii) in terms of/g. The carbon fiber packing operation was carried out as in example 1, followed by rectification purification.
The adsorption treatment of the water-containing crude acetonitrile, wherein the liquid passing pressure of the crude acetonitrile entering an adsorption column tube is 8MPa, the flow rate is 5 ml/min, and the contact time of the water-containing crude acetonitrile and the carbon fiber is 6 min.
And the rectification dehydration comprises primary rectification and secondary rectification.
The first-stage rectification, namely feeding the water-containing acetonitrile obtained by the adsorption treatment step into a first rectification tower, heating the first rectification tower when the liquid level of the first rectification tower reaches 35%, and feeding the distillate into a first reflux tank; when the liquid level in the first reflux tank reaches 30%, starting reflux; when the liquid level in the first reflux tank reaches 50%, stopping feeding acetonitrile, and simultaneously keeping the temperature of the tower bottom of the first rectification tower at 90 ℃ to perform total reflux operation; and after the total reflux is carried out for 1.5h, sampling and detecting the material in the first reflux tank, and if the acetonitrile content is 50-95% and the water content is less than 50%, feeding the second rectifying tower by the first reflux tank, and simultaneously starting the first rectifying tower again for feeding.
The first rectification tower refluxes, and the reflux ratio is 0.6.
Performing secondary rectification, namely heating and boosting the pressure of the fed rectifying tower, and starting reflux; after the temperature and the pressure of the second rectifying tower reach set values and are stabilized for 30min, starting a side line to collect reflux; and opening the finished product to be extracted when the temperature of the temperature measuring point of the finished product extracted from the second rectifying tower reaches 140 ℃ to prepare the finished product of high-purity acetonitrile.
The rectifying tower is heated and pressurized, and the reflux is started: the top pressure of the rectification second tower is 0.8MPa, the temperature of the top of the rectification second tower is controlled to be 120 ℃, the temperature of the bottom of the rectification second tower is controlled to be 135 ℃, the reflux pressure is 1.0MPa, and the reflux ratio is 2.5.
And the side stream is extracted and reflows, the extraction position is the middle upper part of the rectifying second tower body, and the side stream reflows to the middle lower part of the rectifying first tower body.
And the temperature measuring point for finished product extraction is positioned at the middle lower part of the rectifying second tower body.
The finished product of high-purity acetonitrile has acetonitrile content of more than 99.9 percent and 200nm light transmittance of more than 93 percent.
The ultraviolet transmittance of the finished high-purity acetonitrile product prepared by the embodiment is detected, and the specific data are shown in the following table:
according to the test data, the high-purity acetonitrile prepared by the embodiment has excellent indexes, and can fully meet the quality standard requirement of an analysis detection reagent; meanwhile, the high-purity acetonitrile can also meet the quality standard requirement of a mobile phase in a preparative chromatogram.
Example 5
Crude acetonitrile containing 60% of water (mass fraction) is subjected to adsorption treatment and rectification dehydration by using carbon microspheres (the graphitization degree of the carbon microspheres is 73.3% by XRD test). The particle size of the carbon microsphere is 80 mu m, and the specific surface area is 1200m2(ii) in terms of/g. The operation of loading the carbon microspheres was carried out as in example 1, followed by rectification and purification.
The adsorption treatment of the water-containing crude acetonitrile, wherein the liquid passing pressure of the crude acetonitrile into an adsorption column tube is 8MPa, the flow rate is 3 ml/min, and the contact time of the water-containing crude acetonitrile and the carbon microspheres is 7 min.
The carbon microsphere is prepared by adopting polyvinylidene chloride, carbon powder and an auxiliary agent as raw materials. Wherein the weight part ratio of the polyvinylidene chloride, the carbon powder and the auxiliary agent is 80:10: 7.
The auxiliary agent comprises: dimethyl phthalate (DMP), dibutyl maleate (DBM), dioctyl adipate (DOA), di-sec-octyl phthalate (DCP). The dimethyl phthalate (DMP): dibutyl maleate (DBM): dioctyl adipate (DOA): the ratio of parts by weight of di-sec-octyl phthalate (DCP) to parts by weight of di-sec-octyl phthalate (DCP) is 3:1:5: 3.
The preparation method of the carbon microsphere comprises the following steps: hot melting, shaping and carbonizing.
And in the hot melting step, polyvinylidene chloride, carbon powder and an auxiliary agent in a predetermined part are uniformly mixed, and are crushed into powder, and then the powder is heated and melted to ensure that the solid-phase powder raw material is hot-melted into a liquid phase.
The sizing step is that under the pressure condition of 750Pa, the liquid phase raw material prepared in the hot melting step is sprayed out through a spray nozzle, and the size and the spraying direction of a discharge port of the spray nozzle are adjusted to ensure that the sprayed liquid phase raw material is uniformly sprayed out downwards in a foggy shape; meanwhile, cold air blown upwards is arranged below the spray nozzle, and the atomized liquid phase raw material and the cold air are shaped into the resin microspheres after convection.
And carbonizing, namely heating the resin microspheres prepared in the shaping step to 1500 ℃ by adopting a vacuum tube type muffle furnace under a vacuum condition, and carbonizing the resin microspheres to prepare the carbon microspheres.
And the rectification dehydration comprises primary rectification and secondary rectification.
The first-stage rectification, namely feeding the water-containing acetonitrile obtained by the adsorption treatment step into a first rectification tower, heating the first rectification tower when the liquid level of the first rectification tower reaches 40%, and feeding the distillate into a first reflux tank; when the liquid level in the first reflux tank reaches 30%, starting reflux; when the liquid level in the first reflux tank reaches 55%, stopping feeding acetonitrile, and simultaneously keeping the temperature of a rectifying tower kettle at 80 ℃ to perform total reflux operation; and after the total reflux is carried out for 2 hours, sampling and detecting the material in the first reflux tank, and if the acetonitrile content is 50-95% and the water content is less than 50%, feeding the second rectifying tower by the first reflux tank, and simultaneously starting the first rectifying tower again for feeding.
The first rectification tower refluxes, and the reflux ratio is 0.5.
Performing secondary rectification, namely heating and boosting the pressure of the fed rectifying tower, and starting reflux; after the temperature and the pressure of the second rectifying tower reach set values and are stabilized for 30min, starting a side line to collect reflux; and opening the finished product to be extracted when the temperature of the temperature measuring point of the finished product extracted from the second rectifying tower reaches 140 ℃ to prepare the finished product of high-purity acetonitrile.
The rectifying tower is heated and pressurized, and the reflux is started: the top pressure of the rectifying second tower is 0.7MPa, the temperature of the top of the rectifying second tower is controlled to be 125 ℃, the temperature of the bottom of the rectifying second tower is controlled to be 140 ℃, the reflux pressure is 0.9MPa, and the reflux ratio is 2.3.
And the side stream is extracted and reflows, the extraction position is the middle upper part of the rectifying second tower body, and the side stream reflows to the middle lower part of the rectifying first tower body.
And the temperature measuring point for finished product extraction is positioned at the middle lower part of the rectifying second tower body.
The finished product of high-purity acetonitrile has acetonitrile content of more than 99.9 percent and 200nm light transmittance of more than 94 percent.
The ultraviolet transmittance of the finished high-purity acetonitrile product prepared by the embodiment is detected, and the specific data are shown in the following table:
according to the test data, the high-purity acetonitrile prepared by the embodiment has excellent indexes, and can fully meet the quality standard requirement of an analysis detection reagent; meanwhile, the high-purity acetonitrile can also meet the quality standard requirement of a mobile phase in a preparative chromatogram.
Comparative example 1
The technical solution of example 1 is adopted, with the difference that the adsorption treatment step is eliminated, and only the secondary rectification step is adopted to treat the crude acetonitrile.
The ultraviolet transmittance of the finished product acetonitrile prepared by the comparative example is detected, and the specific data are shown in the following table:
all percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The acetonitrile refining method is characterized by comprising the following steps: s01, adsorbing the water-containing crude acetonitrile by using an inorganic carbon material to obtain the water-containing acetonitrile; s02, dehydrating the water-containing acetonitrile to obtain a finished product of high-purity acetonitrile;
the inorganic carbon material is an inorganic carbon-rich material which is approximately amorphous, easy to graphitize and has a micro-mesoporous structure and consists of SP2 hybridized carbon atoms and SP3 hybridized carbon atoms;
the carbon content of the inorganic carbon material is more than 99.9%, and the specific surface area is 950-1250 m2(ii)/g, the average pore diameter is 1-10 nm;
the graphitization degree G parameter value measured by XRD of the inorganic carbon material is 30-85%;
the inorganic carbon material is at least one of: carbon fiber, active carbon, graphitized carbon black, carbon microspheres and carbon molecular sieves;
the finished product of high-purity acetonitrile prepared by the method has the acetonitrile content of more than 99.9 percent and the 200nm light transmittance of more than 90 percent.
2. The acetonitrile purification method according to claim 1, wherein the particle diameter of the activated carbon is 100 μm; the particle size of the graphitized carbon black is 250 mu m; the particle size of the carbon molecular sieve is 60 mu m; the grain diameter of the carbon microsphere is 80 μm; the carbon fiber has a length of 3-5 mm and a diameter of 15-25 μm.
3. The acetonitrile purification method according to claim 1, wherein in the adsorption treatment, the contact time of the crude acetonitrile containing water with the inorganic carbon material is not less than 5 min.
4. The acetonitrile purification method according to claim 1, wherein the water content of the water-containing acetonitrile is 10 to 90%.
5. The acetonitrile refining method according to claim 1, wherein the inorganic carbon material is prepared by using polyvinylidene chloride, carbon powder and an auxiliary agent as raw materials and performing the steps of hot melting, sizing and carbonization.
6. The acetonitrile purification method according to claim 5, wherein the auxiliary agent comprises: dimethyl phthalate, dibutyl maleate, dioctyl adipate and di-sec-octyl phthalate.
7. Use of the high-purity acetonitrile produced by the acetonitrile purification method according to any one of claims 1 to 6, wherein the high-purity acetonitrile is used as a reagent for analytical detection or a mobile phase for preparative chromatography.
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Denomination of invention: A Method for Refining Acetonitrile and Its Application Effective date of registration: 20230918 Granted publication date: 20220329 Pledgee: Postal Savings Bank of China Limited by Share Ltd. Weifang branch Pledgor: WEIFANG ZHONGHUI CHEMICAL Co.,Ltd. Registration number: Y2023980057325 |