CN115385772A - Purification method of electronic-grade monofluoromethane - Google Patents
Purification method of electronic-grade monofluoromethane Download PDFInfo
- Publication number
- CN115385772A CN115385772A CN202210781212.2A CN202210781212A CN115385772A CN 115385772 A CN115385772 A CN 115385772A CN 202210781212 A CN202210781212 A CN 202210781212A CN 115385772 A CN115385772 A CN 115385772A
- Authority
- CN
- China
- Prior art keywords
- monofluoromethane
- tower
- methanol
- light component
- component removal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000000746 purification Methods 0.000 title description 8
- 239000012535 impurity Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 24
- NYGZKMXIYAFNRM-UHFFFAOYSA-N methanol;zinc Chemical compound [Zn].OC NYGZKMXIYAFNRM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 12
- 239000002910 solid waste Substances 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 239000007789 gas Substances 0.000 claims description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- -1 ethylene, propylene Chemical group 0.000 claims description 6
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 5
- 229940007718 zinc hydroxide Drugs 0.000 claims description 5
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000005587 bubbling Effects 0.000 abstract description 8
- 239000012043 crude product Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 18
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 238000003682 fluorination reaction Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- BFNXPMYZRJXOIV-UHFFFAOYSA-N fluoridochlorine(1+) Chemical compound [Cl+]F BFNXPMYZRJXOIV-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000006042 reductive dechlorination reaction Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
Abstract
The invention discloses a method for purifying electronic grade monofluoromethane, which comprises the following steps: respectively introducing a crude product monofluoromethane raw material and the methanol-zinc powder slurry into inlet pipelines at the lower end and the upper end of a bubbling reactor for pre-reaction, obtaining mixed gas after pre-reaction, discharging solid waste, and performing primary and secondary rectification through a light component removal tower and a heavy component removal tower to respectively remove light component impurities and heavy component impurities, thereby finally obtaining the electronic grade monofluoromethane with the purity of more than 99.999%. The crude product monofluoromethane raw material and the methanol-zinc powder slurry are firstly treated by the bubbling reactor, so that the yield of monofluoromethane is improved, the difficulty of subsequent rectification is effectively reduced, and the number of tower plates and the reflux ratio are reduced.
Description
Technical Field
The invention belongs to the technical field of gas purification, and particularly relates to a purification method of electronic-grade monofluoromethane.
Background
Monofluoromethane (HFC-41) having the molecular formula CH 3 F, colorless inflammable gas, easy to dissolve in ethanol and ether, low potential value of greenhouse effect (GWP 100= 116) and zero ozone depletion potential value (ODP), and is a few of products meeting European Union use standards (GWP 100)<150 ) of a saturated hydrofluorocarbon. In addition, the high-purity fluoromethane is a green and efficient electronic special gas, is used for etching semiconductors and electronic products, has good etching selectivity on silicide films, and can dissolve fluorine ions under a radio frequency field to perform reactive ion etching. Therefore, the demand of electronic grade monofluoromethane is more and more increased, which is the guarantee of manufacturing high-level and high-quality semiconductor products and electronic products, and the purity requirement of the products is more than or equal to 99.997 percent.
The synthesis method of monofluoromethane mainly has two methods: the esterification of methanol and hydrogen fluoride and the fluorination of chloromethane are both completed under the action of catalyst. In the industrial synthesis of monofluoromethane by the chloromethane fluorination method, a large amount of impurities are produced, which mainly comprise nitrogen, oxygen, carbon dioxide, carbon monoxide, hydrogen fluoride, water and the like.
A monofluoromethane purification process (CN 201811296975.8) discloses the steps of: (1) primary adsorption: primarily removing impurities from the monofluoromethane to be purified by using an adsorbent; (2) feeding and purifying: and (3) introducing the primarily adsorbed monofluoromethane to be purified into a cooled rectifying tower, removing light components in the monofluoromethane to be purified, discharging the substances in the rectifying tower, and filling the substances into a storage container, wherein the heavy components are remained in the tower, and the substances filled into the container are the monofluoromethane. Wherein, step (2) comprises two substeps: a. introducing the primarily adsorbed fluoromethane to be purified into a cooled rectifying tower A for rectification, discharging a crude product containing light components from a gas phase, and stopping discharging until the content of the light components in the gas phase is qualified; b. cooling the rectifying tower B, pressing the materials in the rectifying tower A to the rectifying tower B in a gas phase, stopping pressing when 1/12-1/8 of the mass of the residual total mass of the materials in the rectifying tower A is 1/12-1/8, wherein the residual materials in the rectifying tower A contain heavy components, and the materials in the rectifying tower B are high-purity monofluoromethane. The operation method is complicated, an adsorption method is used for removing impurities, the adsorbent is easily saturated, multiple times of activation are easily failed, and the product is unqualified. A method for preparing monofluoromethane (CN 201610942390.3) comprises the steps of carrying out gas-phase catalytic fluorination reaction on monochloromethane and hydrogen fluoride in the presence of a fluorination catalyst, wherein a product stream comprises methane, monofluoromethane, monochloromethane, hydrogen fluoride and hydrogen chloride, and obtaining monofluoromethane through distillation, wherein the distillation step comprises the following steps: (1) first distillation: the tower bottom components of the first distillation tower comprise methyl fluoride, methyl chloride, hydrogen fluoride and hydrogen chloride, the tower top components comprise methane, the tower bottom components can enter the second distillation tower for separation, and the tower top components are extracted out of the system; (2) second distillation: the tower kettle components of the second distillation tower comprise methane chloride and hydrogen fluoride, the tower top components comprise methyl fluoride and hydrogen chloride, and the tower top components enter a hydrogen chloride absorption tower for separation; the tower bottom of the hydrogen chloride absorption tower is filled with water, the hydrogen chloride is absorbed, the components at the tower top are subjected to deacidification, dehydration and distillation to obtain a fluoromethane product, and the components at the tower bottom are circulated to the gas phase catalytic fluorination reactor for continuous reaction. The patent uses a complex method for removing impurities, the product purity is low, the gas impurities are more, the subsequent purification method is complex, and the application value is low.
The purity of the monofluoromethane product can reach 99.9 percent by performing two-tower rectification by the traditional method, and if an electronic grade product with the mass fraction of more than 99.997 percent is desired to be obtained, the difficulty lies in that: the impurity water entering the low-temperature rectification system can be solidified, which is not beneficial to the operation of equipment; in addition, the impurity hydrogen fluoride is acid gas and is easy to corrode equipment. Therefore, it is important to develop a method for purifying electronic grade monofluoromethane.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for purifying electronic grade monofluoromethane, which comprises the steps of pre-reacting a crude monofluoromethane raw material with methanol-zinc powder slurry, removing impurities such as hydrogen fluoride and the like, and respectively removing light component impurities and heavy component impurities through primary rectification and secondary rectification to finally obtain the electronic grade monofluoromethane with the purity of more than 99.999 percent.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for purifying electronic grade monofluoromethane, comprising the steps of:
s1, introducing methanol-zinc powder slurry from an inlet at the upper end of a bubble reactor, introducing a crude monofluoromethane raw material from an inlet at the lower end of the bubble reactor, carrying out pre-reaction under the conditions that the operating temperature at the top of the bubble reactor is 80-110 ℃ and the pressure is 0.5-1.0 MPa, obtaining mixed gas after the pre-reaction is finished, and discharging solid waste from an outlet at the bottom of the bubble reactor;
s2, introducing the mixed gas obtained in the S1 into a light component removal tower for primary rectification, wherein light component impurities are extracted from the tower top of the light component removal tower, and the mixed gas after light component removal is extracted from a tower kettle; the operating temperature of the lightness-removing tower is-45 ℃ to-30 ℃, and the operating pressure is 0.3MPa to 0.8MPa;
s3, introducing the mixed gas obtained in the step S2 after light component removal into a heavy component removal tower for secondary rectification, wherein electronic grade monofluoromethane is extracted from the tower top of the heavy component removal tower, and heavy component impurities are extracted from a tower kettle; the operating temperature of the de-heavy tower is-25 ℃ to-15 ℃, and the operating pressure is 0.8MPa to 1.2MPa.
Preferably, the dosage ratio of the crude monofluoromethane raw material to the methanol-zinc powder slurry in S1 is 1: (2-5), wherein the using amount ratio of methanol to zinc powder in the methanol-zinc powder slurry is 1: (5-15).
Preferably, the mixed gas in S1 comprises monofluoromethane, nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propylene, hydrogen fluoride, hydrogen chloride, methanol and water, and the solid waste comprises zinc chloride and zinc hydroxide.
Preferably, the theoretical plate number of the light component removal tower in the S2 is 60 to 70, and the reflux ratio is 200 to 300.
Preferably, the theoretical plate number of the heavy component removing tower in the S3 is 40-50, and the reflux ratio is 25-35.
Preferably, the purity of the electronic grade monofluoromethane in S3 is 99.999% or more.
The invention uses methanol-zinc powder slurry to pretreat crude product monofluoromethane, and the reaction principle of the pre-reaction in S1 is as follows:
(1) Methanol reacts with hydrogen fluoride to convert the hydrogen fluoride to the desired product, monofluoromethane, as follows:
CH 3 OH+HF＝CH 3 F+H 2 O
(2) Zinc powder is subjected to reduction dechlorination to remove chlorofluoromethane with a boiling point close to that of monofluoromethane, and the reaction is as follows:
2CH 2 ClF+2Zn+2H 2 O＝2CH 3 F+ZnCl 2 +Zn(OH) 2
converting the monofluoromethane which is difficult to rectify and separate into the product monofluoromethane through zinc powder dechlorination reaction; the methanol plays the role of Lewis base in the reaction, is complexed with zinc chloride generated by the reaction, is separated from the surface of the zinc powder, and the exposed zinc inside continues to be subjected to reductive dechlorination;
impurities which are difficult to remove by a rectification method are removed after the pre-reaction, the yield of the product monofluoromethane is improved, the impurities in the mixed gas obtained after the pre-reaction are easier to remove by primary and secondary rectification, and the reaction conditions of the primary and secondary rectification are a better reaction condition range obtained through a large number of experiments according to the components of the mixed gas.
Compared with the prior art, the invention has the following advantages:
1. the invention removes impurities such as hydrogen fluoride, monofluoromethane and the like through the pre-reaction of a crude monofluoromethane raw material and methanol-zinc powder slurry, and the methanol treats the acid gas hydrogen fluoride to convert the hydrogen fluoride into the product monofluoromethane and avoid the washing process.
2. The invention converts the monofluoro-chloromethane which is difficult to rectify and separate into the product monofluoro-methane by zinc powder reduction dechlorination, effectively reduces the number of theoretical plates and reflux ratio required for separating the monofluoro-chloromethane, simultaneously, the methanol plays the role of Lewis base in the reaction, is complexed with the zinc chloride generated by the reaction, is separated from the surface of the zinc powder, and the zinc inside the zinc powder is exposed to continue reduction dechlorination.
3. The invention introduces methanol into the system to reduce the freezing point of water, prevent the water from freezing in the low-temperature light component removal tower, realize low-temperature rectification dehydration and avoid the adsorption dehydration process.
4. The product obtained by the method is easy to separate, and the electronic grade monofluoromethane product with the purity of more than 99.999 percent, the nitrogen content of less than 6ppm, the oxygen content of less than 1.5ppm and the water content of less than 2ppm can be obtained.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic flow diagram of the process for the purification of electronic grade monofluoromethane according to the present invention.
Description of reference numerals:
1-crude monofluoromethane feed; 2-methanol-zinc dust slurry; 3-solid waste; 4, mixing gas; 5-light component impurities; 6-mixed gas after light component removal; 7-electronic grade monofluoromethane; 8-heavy component impurities; r01 — bubble reactor; t01-light component removal tower; t02-heavy component removal tower.
Detailed Description
The mass fraction of the crude monofluoromethane starting material used in examples 1 to 3 was 99.37%, and the mass fractions of impurities in the crude monofluoromethane starting material were 0.01% nitrogen, 0.01% oxygen, 0.01% carbon monoxide, 0.05% carbon dioxide, 0.01% methane, 0.1% hydrogen fluoride, 0.01% ethane, 0.01% ethylene, 0.01% propylene, 0.01% hydrogen chloride, 0.2% monochloromethane and 0.2% water.
Example 1
The method for purifying electronic grade monofluoromethane of the present embodiment comprises the following steps:
s1, introducing methanol-zinc powder slurry 2 from an upper end inlet of a bubble reactor R01, introducing a crude fluoromethane raw material 1 from a lower end inlet, carrying out pre-reaction under the conditions that the operation temperature at the top of the bubble reactor R01 is 80 ℃ and the pressure is 1.0MPa, obtaining mixed gas 4 after the pre-reaction is finished, and discharging solid waste 3 from a bottom outlet of the bubble reactor R01; the dosage ratio of the crude product monofluoromethane raw material 1 to the methanol-zinc powder slurry 2 is 1:2; the mass flow of the methanol-zinc powder slurry 2 introduced into the bubbling reactor R01 is 45kg/hr, the mass flow of the crude fluoromethane raw material 1 introduced into the bubbling reactor is 100kg/hr, and the dosage ratio of zinc powder to methanol in the methanol-zinc powder slurry 2 is 1:8;
the purity of monofluoromethane in the mixed gas 4 is 99.56%, the content of hydrogen fluoride is lower than 0.1ppm, the content of monofluoromethane is lower than 0.1ppm, the content of nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propylene and hydrogen chloride is 0.01%, the content of water is 0.1%, and the content of methanol is 0.25%; the solid waste 3 comprises zinc chloride and zinc hydroxide;
s2, introducing the mixed gas 4 obtained in the S1 into a light component removal tower T01 for primary rectification to remove light component impurities 5, wherein the light component impurities 5 are extracted from the gas phase at the top of the light component removal tower T01, and the mixed gas 6 after light component removal is extracted from the tower kettle; the operating temperature of the lightness-removing tower T01 is-45 ℃, the operating pressure is 0.8MPa, the number of theoretical plates is 60, and the reflux ratio is 200;
the light component impurities 5 include nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethane, and ethylene; the mixed gas 6 after light component removal comprises monofluoromethane, propylene, methanol and water; the mass flow of the mixed gas 6 after the light component removal is 98kg/hr, and the purity of the monofluoromethane in the mixed gas 6 after the light component removal is 99.77 percent;
s3, introducing the mixed gas 6 subjected to light component removal obtained in the S2 into a heavy component removal tower T02 for secondary rectification to remove heavy component impurities 8, wherein electronic-grade monofluoromethane 7 is extracted from a gas phase at a tower top outlet of the heavy component removal tower T02, and heavy component impurities 8 are extracted from a tower kettle; the operation temperature of the de-weighting tower T02 is-25 ℃, the operation pressure is 0.8MPa, the number of theoretical plates is 40, and the reflux ratio is 25;
the mass flow of the produced electronic-grade monofluoromethane 7 is 90kg/hr, the purity of the electronic-grade monofluoromethane 7 reaches more than 99.999%, the nitrogen content is less than 6ppm, the oxygen content is less than 1.5ppm, and the water content is less than 2ppm; the heavy ends impurities 8 include propylene, methanol, and water.
Example 2
The method for purifying electronic grade monofluoromethane of the present embodiment comprises the following steps:
s1, introducing methanol-zinc powder slurry 2 from an upper end inlet of a bubble reactor R01, introducing a crude fluoromethane raw material 1 from a lower end inlet, carrying out pre-reaction under the conditions that the operation temperature at the top of the bubble reactor R01 is 100 ℃ and the pressure is 0.8MPa, obtaining mixed gas 4 after the pre-reaction is finished, and discharging solid waste 3 from a bottom outlet of the bubble reactor R01; the dosage ratio of the crude product monofluoromethane raw material 1 to the methanol-zinc powder slurry 2 is 1:5; the mass flow of the methanol-zinc powder slurry 2 introduced into the bubbling reactor R01 is 45kg/hr, the mass flow of the crude fluoromethane raw material 1 introduced into the bubbling reactor is 100kg/hr, and the dosage ratio of zinc powder to methanol in the methanol-zinc powder slurry 2 is 1:5;
the purity of monofluoromethane in the mixed gas 4 is 99.51%, the content of hydrogen fluoride is lower than 0.1ppm, the content of monofluoromethane is lower than 0.1ppm, the content of nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propylene and hydrogen chloride is 0.01%, the content of water is 0.1%, and the content of methanol is 0.3%; the solid waste 3 comprises zinc chloride and zinc hydroxide;
s2, introducing the mixed gas 4 obtained in the S1 into a light component removal tower T01 for primary rectification to remove light component impurities 5, wherein the light component impurities 5 are extracted from the gas phase at the top of the light component removal tower T01, and the mixed gas 6 after light component removal is extracted from the tower kettle; the operating temperature of the lightness-removing column T01 is-40 ℃, the operating pressure is 0.5MPa, the number of theoretical plates is 65, and the reflux ratio is 250;
the light component impurities 5 include nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethane, and ethylene; the mixed gas 6 after light component removal comprises monofluoromethane, propylene, methanol and water; the mass flow of the mixed gas 6 after the light component removal is 98kg/hr, and the purity of the monofluoromethane in the mixed gas 6 after the light component removal is 99.56 percent;
s3, introducing the mixed gas 6 subjected to light component removal obtained in the S2 into a heavy component removal tower T02 for secondary rectification to remove heavy component impurities 8, wherein electronic-grade monofluoromethane 7 is extracted from a gas phase at a tower top outlet of the heavy component removal tower T02, and heavy component impurities 8 are extracted from a tower kettle; the operation temperature of the de-weighting tower T02 is-20 ℃, the operation pressure is 1.0Mpa, the number of theoretical plates is 45, and the reflux ratio is 30;
the mass flow of the produced electronic-grade monofluoromethane 7 is 90kg/hr, the purity of the electronic-grade monofluoromethane 7 reaches more than 99.999 percent, the nitrogen content is less than 6ppm, the oxygen content is less than 1.5ppm, and the water content is less than 2ppm; the heavy ends impurities 8 include propylene, methanol and water.
Example 3
The method for purifying electronic grade monofluoromethane of the present embodiment comprises the following steps:
s1, introducing methanol-zinc powder slurry 2 from an upper end inlet of a bubble reactor R01, introducing a crude fluoromethane raw material 1 from a lower end inlet, carrying out pre-reaction under the conditions that the operation temperature at the top of the bubble reactor R01 is 110 ℃ and the pressure is 0.5MPa, obtaining mixed gas 4 after the pre-reaction is finished, and discharging solid waste 3 from a bottom outlet of the bubble reactor R01; the dosage ratio of the crude product monofluoromethane raw material 1 to the methanol-zinc powder slurry 2 is 1:3; the mass flow of the methanol-zinc powder slurry 2 introduced into the bubbling reactor R01 is 45kg/hr, the mass flow of the crude fluoromethane raw material 1 introduced into the bubbling reactor is 100kg/hr, and the dosage ratio of zinc powder to methanol in the methanol-zinc powder slurry 2 is 1:15;
the purity of monofluoromethane in the mixed gas 4 is 99.46%, the content of hydrogen fluoride is lower than 0.1ppm, the content of monofluoromethane is lower than 0.1ppm, the content of nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propylene and hydrogen chloride is 0.01%, the content of water is 0.1%, and the content of methanol is 0.25%; the solid waste 3 comprises zinc chloride and zinc hydroxide;
s2, introducing the mixed gas 4 obtained in the S1 into a light component removal tower T01 for primary rectification to remove light component impurities 5, wherein the light component impurities 5 are extracted from the gas phase at the top of the light component removal tower T01, and the mixed gas 6 after light component removal is extracted from the tower kettle; the operating temperature of the lightness-removing tower T01 is-30 ℃, the operating pressure is 0.3MPa, the number of theoretical plates is 70, and the reflux ratio is 300;
the light component impurities 5 include nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethane, and ethylene; the mixed gas 6 after light component removal comprises monofluoromethane, propylene, methanol and water; the mass flow of the mixed gas 6 after the light component removal is 98kg/hr, and the purity of the monofluoromethane in the mixed gas 6 after the light component removal is 99.81 percent;
s3, introducing the mixed gas 6 subjected to light component removal obtained in the S2 into a heavy component removal tower T02 for secondary rectification to remove heavy component impurities 8, extracting electronic-grade monofluoromethane 7 from a gas phase at an outlet of the tower top of the heavy component removal tower T02, and extracting heavy component impurities 8 from a tower kettle; the operation temperature of the de-weighting tower T02 is-15 ℃, the operation pressure is 1.2Mpa, the number of theoretical plates is 50, and the reflux ratio is 35;
the mass flow of the produced electronic-grade monofluoromethane 7 is 90kg/hr, the purity of the electronic-grade monofluoromethane 7 reaches more than 99.999 percent, the content of nitrogen is less than 6ppm, the content of oxygen is less than 1.5ppm, and the content of water is less than 2ppm; the heavy ends impurities 8 include propylene, methanol and water.
In examples 1-3, the apparatus used for the purification of electronic grade monofluoromethane comprises a bubble reactor R01, a lightness-removing column T01 and a heavies-removing column T02 connected in series.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (6)
1. A method for purifying electronic grade monofluoromethane, comprising the steps of:
s1, introducing methanol-zinc powder slurry from an inlet at the upper end of a bubble reactor, introducing a crude monofluoromethane raw material from an inlet at the lower end of the bubble reactor, carrying out pre-reaction under the conditions that the operating temperature at the top of the bubble reactor is 80-110 ℃ and the pressure is 0.5-1.0 MPa, obtaining mixed gas after the pre-reaction is finished, and discharging solid waste from an outlet at the bottom of the bubble reactor;
s2, introducing the mixed gas obtained in the S1 into a light component removal tower for primary rectification, wherein light component impurities are extracted from the tower top of the light component removal tower, and the mixed gas after light component removal is extracted from a tower kettle; the operating temperature of the lightness-removing tower is-45 ℃ to-30 ℃, and the operating pressure is 0.3MPa to 0.8MPa;
s3, introducing the mixed gas obtained in the step S2 after light component removal into a heavy component removal tower for secondary rectification, wherein electronic grade monofluoromethane is extracted from the tower top of the heavy component removal tower, and heavy component impurities are extracted from a tower kettle; the operation temperature of the de-weighting tower is-25 ℃ to-15 ℃, and the operation pressure is 0.8MPa to 1.2MPa.
2. The method of claim 1, wherein the ratio of the crude monofluoromethane feed to the methanol-zinc dust slurry in S1 is 1: (2-5), wherein the using amount ratio of methanol to zinc powder in the methanol-zinc powder slurry is 1: (5-15).
3. The method of claim 1, wherein the mixture gas in S1 comprises monofluoromethane, nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propylene, hydrogen fluoride, hydrogen chloride, methanol, and water, and the solid waste comprises zinc chloride and zinc hydroxide.
4. The method for purifying electronic grade monofluoromethane according to claim 1, wherein the number of theoretical plates of the lightness-removing column in S2 is 60 to 70, and the reflux ratio is 200 to 300.
5. The method for purifying electronic grade monofluoromethane according to claim 1, wherein the theoretical plate number of the de-weighting column in S3 is 40 to 50, and the reflux ratio is 25 to 35.
6. The method of claim 1, wherein the purity of the electronic grade monofluoromethane in S3 is 99.999% or greater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210781212.2A CN115385772A (en) | 2022-07-04 | 2022-07-04 | Purification method of electronic-grade monofluoromethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210781212.2A CN115385772A (en) | 2022-07-04 | 2022-07-04 | Purification method of electronic-grade monofluoromethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115385772A true CN115385772A (en) | 2022-11-25 |
Family
ID=84116298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210781212.2A Pending CN115385772A (en) | 2022-07-04 | 2022-07-04 | Purification method of electronic-grade monofluoromethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115385772A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735683A (en) * | 2021-09-27 | 2021-12-03 | 中船重工（邯郸）派瑞特种气体有限公司 | Purification device and purification method for electronic-grade difluoromethane |
| CN113816827A (en) * | 2021-09-27 | 2021-12-21 | 中船重工（邯郸）派瑞特种气体有限公司 | Purification method of electronic-grade trifluoromethane |
| WO2022016631A1 (en) * | 2020-07-23 | 2022-01-27 | 山东海益化工科技有限公司 | Rectification separation process for d-d mixture |
| CN114570051A (en) * | 2022-03-03 | 2022-06-03 | 中船(邯郸)派瑞特种气体股份有限公司 | Device and method for purifying trifluoromethanesulfonyl fluoride by continuous rectification |
| WO2022127018A1 (en) * | 2020-12-16 | 2022-06-23 | 浙江天采云集科技股份有限公司 | Ftrpsa separation and purification method for refinement of electronic-grade hf from industrial-grade high-concentration hf |
-
2022
- 2022-07-04 CN CN202210781212.2A patent/CN115385772A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022016631A1 (en) * | 2020-07-23 | 2022-01-27 | 山东海益化工科技有限公司 | Rectification separation process for d-d mixture |
| WO2022127018A1 (en) * | 2020-12-16 | 2022-06-23 | 浙江天采云集科技股份有限公司 | Ftrpsa separation and purification method for refinement of electronic-grade hf from industrial-grade high-concentration hf |
| CN113735683A (en) * | 2021-09-27 | 2021-12-03 | 中船重工（邯郸）派瑞特种气体有限公司 | Purification device and purification method for electronic-grade difluoromethane |
| CN113816827A (en) * | 2021-09-27 | 2021-12-21 | 中船重工（邯郸）派瑞特种气体有限公司 | Purification method of electronic-grade trifluoromethane |
| CN114570051A (en) * | 2022-03-03 | 2022-06-03 | 中船(邯郸)派瑞特种气体股份有限公司 | Device and method for purifying trifluoromethanesulfonyl fluoride by continuous rectification |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110606490B (en) | Synthesis and purification method of high-purity silicon tetrafluoride | |
| CN113735683B (en) | Purification device and purification method of electronic grade difluoromethane | |
| CN114920630B (en) | Continuous production process and equipment for ethylene glycol monovinyl ether | |
| CN113816827B (en) | Purification method of electronic grade trifluoromethane | |
| CN113563151A (en) | 4N electronic-grade acetylene purification device and purification process | |
| CN110922292B (en) | Preparation method of chloromethane | |
| CN113816826B (en) | Purification method of electronic grade monofluoromethane | |
| CN111018660A (en) | Separation method of chloromethane material | |
| CN115385772A (en) | Purification method of electronic-grade monofluoromethane | |
| CN107266285B (en) | Method for preparing tetrafluoroethane from trichloroethylene | |
| CN110922296B (en) | Separation method of chloromethane | |
| CN111484389A (en) | Production process for co-producing high-purity electronic grade hydrogen fluoride and carbon fluoride | |
| CN112827319B (en) | Chlorine-based SiC-CVD epitaxial tail gas full-temperature-range pressure swing adsorption hydrogen extraction and recycling method containing low-concentration silane and light hydrocarbons above carbon two | |
| CN109970509A (en) | A kind of method of purification of technical grade perfluoroethane | |
| TW201119998A (en) | Process for the distillative purification of fluoroethylene carbonate | |
| CN115073261A (en) | Purification method of electronic-grade tetrafluoromethane | |
| CN114591158B (en) | Method and device for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene | |
| CN111018656A (en) | Preparation method of chloromethane | |
| CN115403011B (en) | Preparation and purification method of high-purity diborane | |
| CN117534082A (en) | Boron trifluoride purification method with high recovery rate | |
| CN112778128B (en) | Treatment method, treatment system and application of mixed material flow containing dimethyl oxalate | |
| CN112279234B (en) | Azeotropic compositions of carbonyl fluoride and carbon dioxide | |
| JP4498152B2 (en) | Method for purifying trimethylsilane | |
| CN101759616B (en) | Method for producing and purifying triocarbamate liquid compound | |
| CN108997156B (en) | Method for continuously producing N, N-diethylformamide by one-step method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221125 |