CN115028510A - Synthetic preparation method of high-purity carbon tetrachloride - Google Patents
Synthetic preparation method of high-purity carbon tetrachloride Download PDFInfo
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 63
- 239000003463 adsorbent Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 27
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 9
- 239000007859 condensation product Substances 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- 150000004698 iron complex Chemical class 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 229910001220 stainless steel Inorganic materials 0.000 claims description 24
- 239000010935 stainless steel Substances 0.000 claims description 24
- 238000001179 sorption measurement Methods 0.000 claims description 22
- 238000005070 sampling Methods 0.000 claims description 15
- 239000002808 molecular sieve Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- -1 iron amino acid Chemical class 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229920002253 Tannate Polymers 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 29
- 238000004817 gas chromatography Methods 0.000 description 13
- 238000001514 detection method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LPOSZYSKJWFIQH-UHFFFAOYSA-N 2-aminoacetic acid;iron Chemical compound [Fe].NCC(O)=O LPOSZYSKJWFIQH-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007038 hydrochlorination reaction Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/007—Preparation of halogenated hydrocarbons from carbon or from carbides and halogens
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthetic preparation method of high-purity carbon tetrachloride, which comprises the following steps: mixing high-purity carbon disulfide and high-purity chlorine liquid to obtain a mixed reactant, adding an iron complex to obtain a reaction system, placing the reaction system in a reactor for heating reaction, continuously introducing dry inert gas into the reactor in the reaction process to continuously blow the mixed gas generated in the reaction process into a rectifying column for rectifying treatment, filling filler and phosphorus pentoxide into the rectifying column, retaining intermediate fraction, leading out the intermediate fraction for condensation, and collecting a condensation product; removing organic impurities from the condensation product by adopting an adsorbent, and finally distilling and collecting middle distillate in an inert atmosphere to further remove inorganic trace impurities introduced by the adsorbent to obtain high-purity carbon tetrachloride with the purity of 6N.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthetic preparation method of high-purity carbon tetrachloride.
Background
Carbon tetrachloride, also known as tetrachloromethane (tetrachloromethane), is a colorless, volatile, nonflammable liquid. Has the slightly sweet smell of chloroform. Slightly soluble in water, molecular weight 153.84, density 1.595g/cm 3 (20/4 ℃ C.), a boiling point of 76.8 ℃ and a vapor pressure of 15.26kPa (25 ℃ C.), and a vapor density of 5.3 g/L. Can be mixed with ethanol, diethyl ether, chloroform and petroleum ether. The substances which meet fire or incandescence can be decomposed into carbon dioxide, hydrogen chloride, phosgene, chlorine and the like. At present, the carbon tetrachloride comprises a methane thermal chlorination method, a carbon disulfide chlorination method, a co-production tetrachloroethylene method, a phosgene catalysis method, a methane oxychlorination method, a high-pressure chlorination method, a methanol hydrochlorination method and the like. Among them, methane thermal chlorination and carbon disulfide chlorination are the most commonly used, but the carbon tetrachloride preparation process has the defects of low purity of finished products, complex purification process, great harm of byproducts and the like. The domestic commercial carbon tetrachloride generally contains impurities such as dichloromethane, dichloroethane, trichloromethane, carbon disulfide, methanol, tetrachloroethylene and derivatives, water and the like, cannot meet the purity requirement of high-purity carbon tetrachloride, and limits the use of the carbon tetrachloride in the field of semiconductors.
Disclosure of Invention
Technical problem to be solved
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a method for synthesizing high purity carbon tetrachloride, which realizes the direct preparation of anhydrous high purity carbon tetrachloride with reduced cost, and the preparation method has simple operation and high efficiency.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the invention provides a method for synthesizing high-purity carbon tetrachloride, which comprises the following steps:
s1, mixing carbon disulfide with the purity of more than 97% and chlorine liquid with the purity of more than 99% according to the weight ratio of 1-1.1: 2-2.1 to obtain a mixed reactant, adding an iron complex with the mass of 0.8-1.2% of the total mass of the mixed reactant to obtain a reaction system, and placing the reaction system in a reactor for heating reaction at the reaction temperature of 95-100 ℃;
in the reaction process, continuously introducing dry inert gas into the reactor to continuously blow the mixed gas generated in the reaction process into a rectifying column for rectifying treatment, wherein the rectifying column is filled with filler and phosphorus pentoxide, the temperature of the rectifying column is controlled at 80-85 ℃ to remove impurities with low boiling point and high boiling point, and middle distillate is reserved; leading out the middle fraction for condensation, and collecting a condensation product;
s2, adding an adsorbent into the condensed product, and slightly stirring to enhance the adsorption and impurity removal effects; in the adsorption process, sampling and detecting the content of organic impurities at intervals until no organic impurities are detected; if organic impurities can be detected after 24 hours, continuously adding an adsorbent to perform enhanced adsorption, and sampling and detecting until no organic impurities are detected;
s3, separating the adsorbent, distilling in an inert atmosphere and collecting middle fraction to further remove inorganic trace impurities introduced by the adsorbent to obtain high-purity carbon tetrachloride with the purity of 6N. The carbon tetrachloride product can meet the use requirement of the semiconductor industry.
According to a preferred embodiment of the present invention, in step S1, the amount of the iron complex added is 1% of the total mass of the mixed reactants.
Preferably, the iron complex is one or more of an iron amino acid complex, an iron tannate complex, and an iron acetate complex.
According to a preferred embodiment of the present invention, in step S1, the rectifying column is a stainless steel rectifying column filled with a theta-type stainless steel filler and phosphorus pentoxide.
According to a preferred embodiment of the present invention, in step S2, the adsorbent comprises 4A molecular sieve and activated carbon.
According to the preferred embodiment of the present invention, in step S2, the 4A molecular sieve and activated carbon are activated and regenerated by a vacuum oven before being put into the condensed product. Wherein, in step S2, the speed of the gentle stirring is 55-65 rpm.
According to the preferred embodiment of the present invention, in step S2, 20 wt% of the adsorbent is added to the condensed product for the first time, and if organic impurities can be detected by sampling after stirring and adsorbing for 24 hours, 5-10 wt% of the adsorbent is added for enhanced adsorption.
According to the preferred embodiment of the present invention, in steps S2-S3, the sampling detection is performed by GC for organic impurities and ICP-OES for inorganic impurities, and the 6N high-purity carbon tetrachloride is detected by ICP-OES.
(III) advantageous effects
The final product prepared by the method has the inorganic impurity content less than 1ppm through ICP-OES full element detection; GC detection shows that the effective components are 100 percent, and high-purity carbon tetrachloride with the purity of more than 99.9999 percent is successfully obtained. The method can directly prepare the high-purity carbon tetrachloride through normal-pressure synthesis and purification, meets the use requirements of the semiconductor industry, has low cost, simple operation and less needed labor, and is suitable for industrial mass production.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail below with reference to specific embodiments.
The scheme provides a preparation method of high-purity carbon tetrachloride, which comprises the following steps:
the method comprises the following steps: mixing carbon disulfide with purity of more than 97% and chlorine liquid with purity of more than 99% according to the weight ratio of 1-1.1: 2-2.1, adding the mixture into a round bottom glass flask, then adding an iron complex compound with the total weight of 0.8-1.2 wt%, placing the glass flask in water, controlling the water temperature at 95-100 ℃, introducing reaction steam after reaction into a stainless steel rectifying column for rectification, wherein the stainless steel rectifying column is filled with theta-shaped stainless steel filler and phosphorus pentoxide; the reaction equation is: CS 2 +3Cl 2 →CCl 4 +S 2 Cl 2 。
Step two: the gas generated in the reaction was blown into the stainless steel rectifying column by continuously feeding dry inert gas into the round bottom glass flask.
Step three: the temperature of the stainless steel rectifying column is controlled at 80-85 ℃ to remove low boiling point impurities (discharged from the top of the stainless steel rectifying column or from the top of the stainless steel rectifying column) and high boiling point impurities (remained in a distillation bottle connected with the lower end of the stainless steel rectifying column), and middle distillate (located at the middle section of the stainless steel rectifying column and led out through an outlet at the middle section of the rectifying column) is reserved. And connecting the stainless steel rectifying column with a spherical condensing pipe to lead the middle fraction out of the spherical condensing pipe to generate condensation, and collecting the condensation product.
Step four: after a plurality of 4A molecular sieves and activated carbon are activated, regenerated and cooled by a vacuum oven, the activated and cooled molecular sieves and the activated carbon are directly put into a condensation product to be used as an adsorbent, and residual trace organic impurities are removed by an adsorption method, wherein the residual trace organic impurities are generally added into the reaction product by 20wt percent of the total weight of the reaction.
Step five: and (3) enhancing the adsorption effect by using a stirring adsorption mode so as to adsorb and remove the residual trace organic impurities. The adsorption effect of stirring is better than that of standing, and the stirring speed is 55-65 rpm.
Step six: sampling and detecting at intervals, if organic impurities are still detected after 24 hours and are not removed, adding an adsorbent for reinforced adsorption.
Step seven: separating adsorbent, collecting middle fraction by distillation in inert atmosphere (such as nitrogen) to remove inorganic trace impurities introduced by using adsorbent, and detecting by ICP-OES to obtain high purity carbon tetrachloride with purity of 6N. The separated adsorbent desorbs organic matters and carbon tetrachloride in the adsorbent in a decompression pumping and drying mode, and the organic matters and the carbon tetrachloride are reused after being dried and activated, so that the cost of the adsorbent is saved.
Wherein about 15 wt% of low boiling point fraction and about 15 wt% of high boiling point impurities can be removed by controlling the temperature at 80-85 ℃ in a stainless steel rectifying column, and 70 wt% fraction of the middle section is collected. The purity of the carbon tetrachloride is improved to about 99.6 percent and the organic impurities account for 0.4 percent through GC detection. This impurity cannot be removed by rectification.
Then removing residual trace organic impurities by using the activated 4A molecular sieve and activated carbon through an adsorption method, wherein the molecular size of the organic impurities is basically smaller than that of the organic impurities
Can be adsorbed by 4A sodium type molecular sieve
Organic impurities below a size above which organic impurities are adsorbed by activated carbon effective to adsorb organic impurities having a molecular size below
Organic impurities in between. The effect of removing organic impurities by singly using the 4A molecular sieve or the activated carbon is not as good as the effect of jointly using the 4A molecular sieve and the activated carbon.
Wherein the adsorption time is determined by the ambient temperature (room temperature), the organic impurity content and the mixing mode, and the sample is sampled and detected after 24 hours of adsorption until the organic impurities can not be detected by GC.
The following are preferred embodiments of the present invention.
Example 1
500g of carbon disulfide having a purity of 97% or more and 1000g of chlorine solution having a purity of 99% or more were mixed and charged into a round-bottomed glass flask, 15g of a total weight of glycine iron complex was then added, and the glass flask was placed in water with the water temperature controlled at 95 ℃. A rectifying column containing a theta-type stainless steel filler and 20g of AR-grade phosphorus pentoxide was heated at 80 ℃. In the reaction process, continuously introducing dry nitrogen into the flask for continuously purging, blowing gas generated in the reaction into the stainless steel rectifying column, removing 15% of low-boiling-point fraction and 15% of high-boiling-point impurities through the stainless steel rectifying column, collecting fraction of which the middle section is 70% and condensing to obtain a condensed product. The GC detection shows that the effective content of the carbon tetrachloride is increased to 99.6 wt%, and the carbon tetrachloride simultaneously contains 6 organic impurities which account for 0.4 wt%. This 0.4 wt% impurity cannot be removed by the rectification method.
Activating and regenerating a plurality of 4A molecular sieves and activated carbon in a vacuum oven at the high temperature of 130 ℃ during 12-stage pumping, mixing the molecular sieves and the activated carbon in a mass ratio of 1: 1 to obtain an adsorbent, putting 300g of the adsorbent into a condensation product, and removing the residual trace organic impurities by an adsorption method. And (3) adsorbing for 24 hours at least at the temperature of the environment for 24 hours for sampling, if organic impurities are still detected by the GC, continuously adding an adsorbent for adsorption, and sampling every 0.5 hour until no organic impurities are detected. The adsorption effect by stirring is better than that by standing, and the stirring speed is preferably 55-65 rpm.
Separating the adsorbent, and distilling and collecting the middle fraction in nitrogen atmosphere to remove inorganic trace impurities brought by the adsorbent. The finally obtained fraction is subjected to ICP-OES full element detection, and the content of all inorganic impurities is less than 1 ppm; GC detection shows that the effective components are 100 percent, and high-purity carbon tetrachloride with the purity of more than 99.9999 percent is successfully obtained. The separated adsorbent is subjected to desorption of organic matters and carbon tetrachloride in a decompression pumping and drying mode, and is dried and regenerated for reuse.
Example 2
500g of carbon disulfide having a purity of 97% or more and 1000g of chlorine solution having a purity of 99% or more were mixed and charged into a round-bottomed glass flask, 18g of a total weight of an iron glycine complex was then added, and the glass flask was placed in water with the water temperature controlled at 99 ℃. A rectifying column containing a theta-type stainless steel filler and 25g of AR-grade phosphorus pentoxide was heated at 83 ℃. And in the reaction process, continuously introducing dry nitrogen into the flask for continuous purging, blowing the gas generated by the reaction into the stainless steel rectifying column, removing low-boiling fraction and high-boiling impurities through the stainless steel rectifying column, collecting middle-section fraction, and condensing to obtain a condensed product.
A plurality of 4A molecular sieves and activated carbon are activated and regenerated when being pumped and dried in a vacuum oven at the high temperature of 130 ℃ for 12 ℃, mixed according to the mass ratio of 1: 1 to be used as an adsorbent, 290g of the adsorbent is added into a condensation product, and residual trace organic impurities are removed by an adsorption method. Sampling, detecting and sampling every 0.5h in the adsorption process, and detecting organic impurities by GC (gas chromatography) until no organic impurities are detected.
Separating the adsorbent, and distilling and collecting the middle fraction in nitrogen atmosphere to remove inorganic trace impurities brought by the adsorbent. The finally obtained fraction is subjected to ICP-OES all-element detection, and the content of all inorganic impurities is less than 1 ppm; GC detection shows that the effective components are 100 percent, and high-purity carbon tetrachloride with the purity of more than 99.9999 percent is successfully obtained.
Example 3
500g of carbon disulfide having a purity of 97% or more and 1000g of chlorine solution having a purity of 99% or more were mixed and charged into a round-bottomed glass flask, 15g of ethylenediamine, which is an iron acetate complex, was then added thereto, and the glass flask was placed in water with the water temperature being controlled at 96 ℃. A rectifying column containing a theta-type stainless steel filler and 28g of AR-grade phosphorus pentoxide was heated at 84 ℃. And in the reaction process, continuously introducing dry nitrogen into the flask for continuous purging, blowing the gas generated by the reaction into the stainless steel rectifying column, removing low-boiling fraction and high-boiling impurities through the stainless steel rectifying column, collecting middle-section fraction, and condensing to obtain a condensed product.
A plurality of 4A molecular sieves and activated carbon are activated and regenerated when being pumped and dried in a vacuum oven at the high temperature of 120 ℃ for 12 ℃, mixed according to the mass ratio of 1: 2 to be used as an adsorbent, 310g of the adsorbent is added into a condensation product, and residual trace organic impurities are removed by an adsorption method. Sampling, detecting and sampling every 0.5h in the adsorption process, and detecting organic impurities by GC (gas chromatography) until no organic impurities are detected.
Separating the adsorbent, and distilling and collecting the middle fraction in nitrogen atmosphere to remove inorganic trace impurities brought by the adsorbent. The finally obtained fraction is subjected to ICP-OES full element detection, and the content of all inorganic impurities is less than 1 ppm; the GC detection shows that the effective component is 100 percent, and the high-purity carbon tetrachloride with the purity of 99.9998 percent is successfully obtained.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A synthetic preparation method of high-purity carbon tetrachloride is characterized by comprising the following steps:
s1, mixing carbon disulfide with the purity of more than 97% and chlorine liquid with the purity of more than 99% according to the weight ratio of 1-1.1: 2-2.1 to obtain a mixed reactant, adding an iron complex with the mass of 0.8-1.2% of the total mass of the mixed reactant to obtain a reaction system, and placing the reaction system in a reactor for heating reaction at the reaction temperature of 95-100 ℃;
in the reaction process, continuously introducing dry inert gas into the reactor to continuously blow the mixed gas generated in the reaction process into a rectifying column for rectifying treatment, wherein the rectifying column is filled with filler and phosphorus pentoxide, the temperature of the rectifying column is controlled to be 80-85 ℃ to remove impurities with low boiling point and high boiling point, middle fraction is reserved, the middle fraction is led out for condensation, and a condensation product is collected;
s2, adding an adsorbent into the condensed product, stirring, sampling and detecting the content of organic impurities at intervals in the adsorption process until no organic impurities are detected, if organic impurities can be detected after 24 hours, continuously adding the adsorbent to perform enhanced adsorption, and sampling and detecting until no organic impurities are detected;
s3, separating the adsorbent, distilling in an inert atmosphere and collecting middle fraction to further remove inorganic trace impurities introduced by the adsorbent, and obtaining high-purity carbon tetrachloride with the purity of 6N.
2. The method according to claim 1, wherein the iron complex is added in an amount of 1% by mass based on the total mass of the mixed reactants in step S1.
3. The method according to claim 1 or 2, wherein in step S1, the iron complex includes one or more of an iron amino acid complex, an iron tannate complex, and ethylenediamine is an iron acetate complex.
4. The production method according to claim 1, wherein in step S1, the rectification column is a stainless steel rectification column filled with a theta type stainless steel filler and phosphorus pentoxide.
5. The method according to claim 1, wherein in step S2, the adsorbent comprises 4A molecular sieve and activated carbon.
6. The method of claim 1, wherein in step S2, the 4A molecular sieve and the activated carbon are activated and regenerated by a vacuum oven before being put into the condensed product.
7. The production method according to claim 1, wherein the stirring speed used in step S2 is 55 to 65 rpm.
8. The method according to any one of claims 1 to 7, wherein 20 wt% of the adsorbent is added to the condensed product in step S2 for the first time, and if organic impurities can be detected by sampling after stirring and adsorbing for 24 hours, 5 to 10 wt% of the adsorbent is added for enhanced adsorption.
9. The method of claim 1, wherein in steps S2-S3, the sampling test is performed to detect organic impurities by GC and inorganic impurities by ICP-OES.
10. The method of claim 1, wherein the 6N high purity carbon tetrachloride is detected by ICP-OES.
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| CN107353178A (en) * | 2017-06-26 | 2017-11-17 | 江苏南大光电材料股份有限公司 | The preparation method of ultra-pure carbon tetrachloride |
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| CN107353178A (en) * | 2017-06-26 | 2017-11-17 | 江苏南大光电材料股份有限公司 | The preparation method of ultra-pure carbon tetrachloride |
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