CN113582800B - Purification method of high-purity electronic grade ethylene - Google Patents
Purification method of high-purity electronic grade ethylene Download PDFInfo
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- 239000005977 Ethylene Substances 0.000 title claims abstract description 94
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000000746 purification Methods 0.000 title claims abstract description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002808 molecular sieve Substances 0.000 claims abstract description 60
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 33
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010457 zeolite Substances 0.000 claims abstract description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 30
- 239000012043 crude product Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000002161 passivation Methods 0.000 claims abstract description 18
- 239000003507 refrigerant Substances 0.000 claims abstract description 14
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 150000001721 carbon Chemical class 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 238000010408 sweeping Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- -1 ethane Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a purification method of high-purity electronic grade ethylene, and relates to the technical field of ethylene purification. The purification method of the high-purity electronic grade ethylene comprises the following steps: the industrial grade ethylene is treated by two-stage low-temperature rectification with liquid nitrogen as a refrigerant to prepare a primary ethylene crude product, the temperatures of the two-stage low-temperature rectification are respectively T1 and T2, the pressures are respectively P1 and P2, the mass flow rate of the liquid nitrogen is respectively N1 and N2, and the reflux is respectively R1 and R2; wherein, T2 is less than or equal to minus 100 ℃ and less than or equal to minus 83 ℃, P2 is less than or equal to 0.1MPa and less than or equal to P2 and less than or equal to 0.5MPa, R1 is less than or equal to 40 and less than or equal to 50, R2 is less than or equal to 40 and less than or equal to 50, and N1 is not equal to N2; performing pressure swing adsorption on the primary ethylene crude product to obtain a secondary ethylene crude product; and (3) dehydrating the secondary ethylene crude product by adopting a special zeolite molecular sieve subjected to passivation treatment. The purification method realizes the purification of industrial grade ethylene through two-stage low-temperature rectification, pressure swing adsorption and dehydration by taking liquid nitrogen as a refrigerant, and the prepared ethylene has high purity.
Description
Technical Field
The invention relates to the technical field of ethylene purification, in particular to a purification method of high-purity electronic grade ethylene.
Background
Ethylene (C 2H4) is one of important basic raw materials in petrochemical industry, chemical products using ethylene as raw materials plays an important role in national economy, and the yield of ethylene is taken as one of important marks for measuring the national petrochemical industry and the economic development level in the world. The high-purity ethylene is widely applied to the fields of metallurgy, electronics, chemical industry, petroleum industry and the like, basic research, atmospheric pollution monitoring, aviation, atomic energy and the like. The purity of the ethylene used as the standard gas, the standard gas of the on-line instrument, the calibration gas and the special mixed gas needs to reach 4N5 (99.995%).
In the field of semiconductor wafer manufacturing, particularly in the 3D memory (3D-NAND) manufacturing process, high-purity electronic grade ethylene may be used in the deposition stage of amorphous carbon layer, hard mask carbon layer and silicon carbide (silicon carbide) under deep ultraviolet special photoresist according to different process and equipment choices. The purity requirements are extremely stringent, and a purity of 5N5 (99.9995%) is required. Particularly, the content of ethane, acetylene, methane, oxygen, carbon dioxide and water is required to avoid the influence of other hydrocarbon impurities on the thickness, uniformity, skeleton density and geometric morphology of the deposited amorphous carbon layer under the same Chemical Vapor Deposition (CVD) operation condition.
The method is a good means for obtaining high-purity electronic grade ethylene by separating and purifying industrial grade ethylene raw materials. However, the conventional process from industrial ethylene raw materials to industrial process of purifying high-purity electronic grade ethylene by rectification still needs to solve the following technical problems:
(1) The separation difficulty of ethylene and ethane is high, and the tower is extremely high or has huge energy consumption. The separation factor between ethylene and ethane is about 2.67, from 99.5% purification to about 150-180 theoretical plates of 5N 5.
(2) Molecules of the same polarity are readily entrained in constant boiling in ppm-level trace amounts, such as acetylene, carbon dioxide. And thus are difficult to separate by means of rectification.
(3) Trace amounts of water are difficult to remove to within 1ppm due to the reaction of the deeply dehydrated molecular sieve with ethylene.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a purification method of high-purity electronic grade ethylene, which realizes purification of industrial grade ethylene by two-stage low-temperature rectification, pressure swing adsorption and dehydration with liquid nitrogen as a refrigerant, and the purity of the prepared ethylene reaches 5N5 (99.9995%).
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a purification method of high-purity electronic grade ethylene, which comprises the following steps:
S1, step: removing heavy components and light components from industrial grade ethylene by adopting two-stage low-temperature rectification with liquid nitrogen as a refrigerant to prepare a primary grade ethylene crude product, wherein the temperatures of the two-stage low-temperature rectification are respectively T1 and T2, the pressures are respectively P1 and P2, the mass flow of the liquid nitrogen is respectively N1 and N2, and the reflux is respectively R1 and R2; wherein, T2 is less than or equal to minus 100 ℃ and less than or equal to minus 83 ℃, P2 is less than or equal to 0.1MPa and less than or equal to P2 and less than or equal to 0.5MPa, R1 is less than or equal to 40 and less than or equal to 50, R2 is less than or equal to 40 and less than or equal to 50, and N1 is not equal to N2;
s2, step: carrying out pressure swing adsorption on the primary ethylene crude product to obtain a secondary ethylene crude product;
S3, step: and (3) dehydrating the secondary ethylene crude product by adopting a special zeolite molecular sieve subjected to passivation treatment.
Preferably, in the step S1, when N1 is greater than N2, the first rectifying tower of the two-stage cryogenic rectification removes heavy components, and the second rectifying tower removes light components.
Preferably, in step S1, when N1< N2, the first rectification column of the two-stage cryogenic rectification removes light components and the second rectification column removes heavy components.
Preferably, in the step S2, the adsorbent used in the pressure swing adsorption is a modified carbon molecular sieve impregnated with acetone.
Preferably, in the step S2, the pressure swing adsorption adopts low pressure 0.08-0.12 MPa and high pressure 0.64-0.96MPa for conversion, and the conversion frequency is 24-36S.
Preferably, in step S2, the temperature of the pressure swing adsorption is 300 ℃.
Preferably, in step S3, the particular zeolite molecular sieve is a mixture of 5A molecular sieve and 4A molecular sieve.
Preferably, in the step S3, the dehydration operation is carried out at a pressure of 0.1-0.4MPa, a temperature of room temperature to 80 ℃ and a space velocity of 200-300/h.
Preferably, in the step S3, the passivation process includes the steps of:
S301, step: passivating the special zeolite molecular sieve by using gas with the volume fraction of 0.01% SO 2 as passivating gas;
s302, step: and (3) after the nitrogen high-temperature sweeping and activating the special zeolite molecular sieve, vacuumizing and replacing.
Preferably, in the step S301, the mass ratio of the sulfur content in the passivation gas to the specific zeolite molecular sieve is (0.01-0.05): 1.
Preferably, the operating temperature of step S301 is 300 ℃ for 30min.
The purification method of the high-purity electronic grade ethylene has the beneficial effects that:
(1) The invention adopts liquid nitrogen as refrigerant to separate ethane by two-stage low-temperature rectification, thereby reducing equipment investment and improving separation effect.
(2) And the pressure swing adsorption system is adopted to separate constant boiling substances, so that the effective separation of acetylene and carbon dioxide is realized.
(3) The special zeolite molecular sieve subjected to passivation treatment is adopted for dehydration, so that the technical effect of removing trace water to be within 1ppm is realized.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Ethylene (Ethylene), having a chemical formula of C 2H4 and a molecular weight of 28.06, is a compound consisting of two carbon atoms and four hydrogen atoms. The melting point is-169.4 ℃ and the boiling point is-103.9 ℃.
The embodiment of the invention provides a purification method of high-purity electronic grade ethylene, which comprises the following steps:
S1, step: removing heavy components and light components from industrial grade ethylene by adopting two-stage low-temperature rectification with liquid nitrogen as a refrigerant to prepare a primary grade ethylene crude product, wherein the temperatures of the two-stage low-temperature rectification are respectively T1 and T2, the pressures are respectively P1 and P2, the mass flow of the liquid nitrogen is respectively N1 and N2, and the reflux is respectively R1 and R2; wherein, T2 is less than or equal to minus 100 ℃ and less than or equal to minus 83 ℃, P2 is less than or equal to 0.1MPa and less than or equal to P2 and less than or equal to 0.5MPa, R1 is less than or equal to 40 and less than or equal to 50, R2 is less than or equal to 40 and less than or equal to 50, and N1 is not equal to N2; the industrial grade ethylene can be used for separating and purifying other hydrocarbons, mainly ethane, by a two-stage low-temperature rectification mode taking liquid nitrogen as a refrigerant in the step S1. By controlling T2< T1 and P2< P1, the materials in the first rectifying tower can be smoothly pressed into the second rectifying tower. The mass flow rates of liquid nitrogen in the first rectifying tower and the second rectifying tower of the two-stage cryogenic rectification are respectively N1 and N2, and whether heavy components (C 2H6 and hydrocarbons with carbon number more than 3) or light components (N 2、CO、O2、Ar、CH4 ) are removed can be adjusted. By this step, N 2、CO、O2、Ar、CH4、C2H6 and hydrocarbons with carbon number greater than 3 in technical grade ethylene) are all removed. The liquid nitrogen is adopted as a refrigerant, so that the temperature of rectification operation can be effectively reduced, the reflux ratio is reduced to 40-50, and the separation efficiency is greatly improved, therefore, the energy consumption and the number of tower plates of a rectification tower are reduced, and the equipment investment cost (about 60-70 m high temperature and high pressure rectification tower, 20-30 m short time) and the production cost (the reflux ratio is reduced to 40-50 at the original 70-80) are greatly reduced. The reflux ratio is adjusted according to the actual conditions of production.
Further, in the preferred embodiment of the present invention, when N1> N2, the first rectification column of the two-stage cryogenic rectification removes heavy components and the second rectification column removes light components.
Further, in the preferred embodiment of the present invention, when N1< N2, the first rectification column of the two-stage cryogenic rectification removes the light components and the second rectification column removes the heavy components.
S2, step: carrying out pressure swing adsorption on the primary ethylene crude product to obtain a secondary ethylene crude product; and separating constant boiling substances in the primary ethylene crude product by pressure swing adsorption. Mainly acetylene and carbon dioxide.
Further, in the preferred embodiment of the present invention, the adsorbent used for pressure swing adsorption is a carbon molecular sieve modified by acetone impregnation. The carbon molecular sieve has no oxygen and aluminum, no active center, and ethylene double bond can not be opened in the adsorption process, polymerization and adsorption with the carbon molecular sieve can not occur. Carbon dioxide is easily polarized (polarization rate a=2.76×10 -24 cm3), the negative charge of oxygen is high, and the positive charge of carbon is high; acetylene is very easily ionized in organic matter (ionization coefficient pka=25), and hc≡c-and h+ are easily ionized. The two gas molecules show a Knudsen diffusion mechanism in the pore canal of the adsorbent, are easy to polarize and ionize, so that the polarity is strong, and the two gas molecules are compatible with impregnated acetone molecules similarly, therefore, the carbon molecular sieve modified by the impregnation of acetone can effectively adsorb CO 2 and acetylene, and the technical effect of removing CO 2 and acetylene is achieved.
Further, in the preferred embodiment of the present invention, the pressure swing adsorption is performed using a low pressure of 0.08-0.12 MPa and a high pressure of 0.64-0.96MPa for a frequency of 24-36s.
Further, in the preferred embodiment of the present invention, the temperature of the pressure swing adsorption is 300 ℃.
S3, step: and (3) dehydrating the secondary ethylene crude product by adopting a special zeolite molecular sieve subjected to passivation treatment. The activity of the molecular sieve can be effectively reduced by passivating the molecular sieve.
Further, in a preferred embodiment of the present invention, the particular zeolite molecular sieve is a mixture of 5A molecular sieve and 4A molecular sieve.
Further, in the preferred embodiment of the present invention, the dehydration operation is performed at a pressure of 0.1-0.4MPa, a temperature of room temperature to 80℃and a space velocity of 200-300/h.
Further, in a preferred embodiment of the present invention, the passivation process includes the steps of:
s301, step: passivating the special zeolite molecular sieve by using SO 2 with the volume fraction of 0.01% as passivating gas;
s302, step: and (3) after the nitrogen high-temperature sweeping and activating the special zeolite molecular sieve, vacuumizing and replacing.
Further, in the preferred embodiment of the present invention, the mass ratio of sulfur content in the passivation gas to the specific zeolite molecular sieve is (0.01-0.05): 1.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a purification method of high-purity electronic grade ethylene, which comprises the following steps:
S1, step: the first rectifying tower and the second rectifying tower which take liquid nitrogen as refrigerant form a two-stage low-temperature rectifying section, and industrial grade ethylene is treated to remove heavy components and light components so as to prepare a primary ethylene crude product. Wherein the temperatures of the first rectifying tower and the second rectifying tower are respectively-83 ℃ and-100 ℃. The pressures are respectively 0.5MPa and 0.1 MPa. The liquid nitrogen mass flow rates are respectively 0.01m 3/s、0.02m3/s, and the reflux ratios are all 43. At this time, the first rectifying tower of the two-stage low-temperature rectification removes light components, and the second rectifying tower removes heavy components. In this embodiment, the mass flow rate N1 of the first rectifying tower is smaller than the mass flow rate N2 of the second rectifying tower, the first rectifying tower of the two-stage cryogenic rectification removes light components, and the second rectifying tower removes heavy components. In other embodiments, the mass flow rate N1 of the first rectifying tower may be greater than the mass flow rate N2 of the second rectifying tower, the first rectifying tower for low-temperature rectification removing heavy components, and the second rectifying tower removing light components. It is within the scope of the present embodiment as long as the effect of the combined removal of the light component and the heavy component by the first rectifying tower and the second rectifying tower can be achieved.
S2, step: carrying out pressure swing adsorption on the primary ethylene crude product at 300 ℃ to obtain a secondary ethylene crude product; the adsorbent used in the pressure swing adsorption is a carbon molecular sieve which is impregnated and modified by acetone. The pressure swing adsorption adopts low pressure 0.10 MPa and high pressure 0.80MPa conversion, and the conversion frequency is 30s.
S3, step:
S301, step: passivating the special zeolite molecular sieve for 30min at a high temperature of 300 ℃ by adopting gas with volume fraction of 0.01% SO 2 (the rest is N 2) as passivating gas; the mass ratio of the sulfur content in the passivation gas to the mass ratio of the special zeolite molecular sieve is 0.03:1. the particular zeolite molecular sieve in this example is a mixture of 5A molecular sieve and 4A molecular sieve. In other embodiments, other molecular sieves are also possible, and are within the scope of this embodiment as long as the dehydration of this embodiment is achieved and no reaction with ethylene occurs.
S302, step: and (3) after the nitrogen high-temperature sweeping and activating the special zeolite molecular sieve, vacuumizing and replacing.
The special zeolite molecular sieve after the passivation treatment by the steps is dehydrated under the conditions of the pressure of 0.3MPa, the temperature of 50 ℃ and the airspeed of 250/h.
Example 2
The embodiment provides a purification method of high-purity electronic grade ethylene, which comprises the following steps:
S1, step: the first rectifying tower and the second rectifying tower which take liquid nitrogen as refrigerant form a two-stage low-temperature rectifying section, and industrial grade ethylene is treated to remove heavy components and light components so as to prepare a primary ethylene crude product. Wherein the temperatures of the first rectifying tower and the second rectifying tower are respectively-88 ℃ and-95 ℃. The pressures are respectively 0.4MPa and 0.2 MPa. The liquid nitrogen mass flow rates were 0.01m 3/s、0.15m3/s and the reflux ratios were 40 and 45, respectively. At this time, the first rectifying tower of the two-stage low-temperature rectification removes light components, and the second rectifying tower removes heavy components. In this embodiment, the mass flow rate N1 of the first rectifying tower is smaller than the mass flow rate N2 of the second rectifying tower, the first rectifying tower of the two-stage cryogenic rectification removes light components, and the second rectifying tower removes heavy components. In other embodiments, the mass flow rate N1 of the first rectifying tower may be greater than the mass flow rate N2 of the second rectifying tower, the first rectifying tower for low-temperature rectification removing heavy components, and the second rectifying tower removing light components. It is within the scope of the present embodiment as long as the effect of the combined removal of the light component and the heavy component by the first rectifying tower and the second rectifying tower can be achieved.
S2, step: carrying out pressure swing adsorption on the primary ethylene crude product at 300 ℃ to obtain a secondary ethylene crude product; the adsorbent used in the pressure swing adsorption is a carbon molecular sieve which is impregnated and modified by acetone. The pressure swing adsorption adopts low pressure 0.08 MPa and high pressure 0.96MPa conversion, and the conversion frequency is 24s.
S3, step:
S301, step: passivating the special zeolite molecular sieve for 30min at a high temperature of 300 ℃ by adopting gas with volume fraction of 0.01% SO 2 (the rest is N 2) as passivating gas; the mass ratio of the sulfur content in the passivation gas to the mass ratio of the special zeolite molecular sieve is 0.01:1. the particular zeolite molecular sieve in this example is a mixture of 5A molecular sieve and 4A molecular sieve. In other embodiments, other molecular sieves are also possible, and are within the scope of this embodiment as long as the dehydration of this embodiment is achieved and no reaction with ethylene occurs.
S302, step: and (3) after the nitrogen high-temperature sweeping and activating the special zeolite molecular sieve, vacuumizing and replacing.
The special zeolite molecular sieve after the passivation treatment by the steps is dehydrated under the conditions of 0.4MPa of pressure, room temperature and 300/h of airspeed.
Example 3
The embodiment provides a purification method of high-purity electronic grade ethylene, which comprises the following steps:
S1, step: the first rectifying tower and the second rectifying tower which take liquid nitrogen as refrigerant form a two-stage low-temperature rectifying section, and industrial grade ethylene is treated to remove heavy components and light components so as to prepare a primary ethylene crude product. Wherein the temperatures of the first rectifying tower and the second rectifying tower are respectively-83 ℃ and-100 ℃. The pressures are respectively 0.5MPa and 0.1 MPa. The liquid nitrogen mass flow rates are respectively 0.01m 3/s、0.15m3/s, and the reflux ratios are 50. At this time, the first rectifying tower of the two-stage low-temperature rectification removes light components, and the second rectifying tower removes heavy components. In this embodiment, the mass flow rate N1 of the first rectifying tower is smaller than the mass flow rate N2 of the second rectifying tower, the first rectifying tower of the two-stage cryogenic rectification removes light components, and the second rectifying tower removes heavy components. In other embodiments, the mass flow rate N1 of the first rectifying tower may be greater than the mass flow rate N2 of the second rectifying tower, the first rectifying tower for low-temperature rectification removing heavy components, and the second rectifying tower removing light components. It is within the scope of the present embodiment as long as the effect of the combined removal of the light component and the heavy component by the first rectifying tower and the second rectifying tower can be achieved.
S2, step: carrying out pressure swing adsorption on the primary ethylene crude product at 300 ℃ to obtain a secondary ethylene crude product; the adsorbent used in the pressure swing adsorption is a carbon molecular sieve which is impregnated and modified by acetone. The pressure swing adsorption adopts low pressure 0.12 MPa and high pressure 0.64MPa conversion, and the conversion frequency is 36s.
S3, step:
S301, step: passivating the special zeolite molecular sieve for 30min at a high temperature of 300 ℃ by adopting gas with volume fraction of 0.01% SO 2 (the rest is N 2) as passivating gas; the mass ratio of the sulfur content in the passivation gas to the mass ratio of the special zeolite molecular sieve is 0.05:1. the particular zeolite molecular sieve in this example is a mixture of 5A molecular sieve and 4A molecular sieve. In other embodiments, other molecular sieves are also possible, and are within the scope of this embodiment as long as the dehydration of this embodiment is achieved and no reaction with ethylene occurs.
S302, step: and (3) after the nitrogen high-temperature sweeping and activating the special zeolite molecular sieve, vacuumizing and replacing.
The special zeolite molecular sieve after the passivation treatment by the steps is dehydrated under the conditions of 0.1MPa of pressure, room temperature and space velocity of 200/h.
Test example 1
The raw materials of the technical grade ethylene comprise the following components:
TABLE 1 raw material composition of technical grade ethylene and target content of high purity electronic grade ethylene
| Industrial grade ethylene raw material composition | Boiling point (. Degree. C.) | Raw material content | Target content of high purity electronic grade ethylene | Unit (B) |
| C2H4 | -104 | 99.5 | 99.9995 | % |
| N2 | -196 | 80 | <1 | 10-6(ppmv) |
| CO | -191 | 10 | <1 | 10-6(ppmv) |
| O2+Ar | -183 | 20 | <1 | 10-6(ppmv) |
| CH4 | -161 | 500 | <1 | 10-6(ppmv) |
| C2H6 | -89 | 1000 | <1 | 10-6(ppmv) |
| C2H2 | -84 | 5 | <1 | 10-6(ppmv) |
| CO2 | -78 | 50 | <1 | 10-6(ppmv) |
| Other hydrocarbons (e.g. propylene having more than 3 carbon atoms, etc.) | <4000 | <4 | 10-6(ppmv) | |
| H2O | 5 | <1 | 10-6(ppmv) | |
| Total impurities | <5000 ppm | <5 | 10-6(ppmv) |
This test example is used to explain the method of evaluating the purity of ethylene. The experimental example uses Agilent 7820 as equipment, adopts a gas chromatography method for measuring hydrocarbon impurities in industrial ethylene of GB/T3391-2002, a gas chromatography method for measuring trace water in industrial ethylene and propylene of GB/T3727-2003, a gas chromatography method for measuring trace carbon monoxide, carbon dioxide and acetylene in industrial ethylene and propylene of GB/T3394-2009, and a gas chromatography method for measuring trace hydrogen in industrial ethylene and propylene of GB/T3393-2009 to measure H2O、N2、CO、O2、Ar、CH4、C2H6、C2H2、CO2 and hydrocarbon with carbon number more than 3 in the high-purity electronic grade ethylene purified in the examples 1-3.
Pre-separation column: A316L stainless steel column with a length of about 5m and an inner diameter of 2mm is internally provided with Porapak Q (high molecular polymer) with a particle size of 0.18-0.25 mm.
Chromatographic column I: A316L stainless steel column with the length of about 2m and the inner diameter of 2mm is internally provided with a 5A molecular sieve with the particle size of 0.18-0.25 mm and is used for analyzing water, oxygen, argon and nitrogen.
Chromatographic column II: A316L stainless steel column with a length of about 2m and an inner diameter of 2mm is internally provided with HayeSep DB (high-molecular polymer) with a grain diameter of 0.18-0.25 mm and is used for analyzing the content of carbon monoxide, methane, carbon dioxide, ethane, acetylene and hydrocarbons with carbon number of more than 3.
Standard sample: the volume fraction of the component content was 2 x 10 -6, and the balance gas was helium.
Ethylene purity calculation formula:
A=100-（A1+ A2+ A3+ A4+ A5+ A6+ A7）*10-4
Wherein:
a: nitrogen content (volume fraction), 10 -2;
a1: carbon monoxide content (volume fraction), 10 -6;
A2: oxygen + argon content (volume fraction), 10 -6;
A3: methane content (volume fraction), 10 -6;
A4: ethane content (volume fraction), 10 -6;
A5: the content (volume fraction) of carbon dioxide, 10 -6;
A6: a hydrocarbon content (volume fraction) of greater than 3 carbon atoms, 10 -6;
A7: water content (volume fraction), 10 -6;
The results of test example 1 are shown in Table 2 below
TABLE 2 purity of high purity electronic grade ethylene purified in examples 1-3
| Purity of ethylene (%) | |
| Example 1 | 99.9998% |
| Example 2 | 99.9996% |
| Example 3 | 99.9995% |
In summary, the purification method of high-purity electronic grade ethylene provided by the invention realizes the purification of industrial grade ethylene through two-stage low-temperature rectification, pressure swing adsorption and dehydration by taking liquid nitrogen as a refrigerant, and the purity of the prepared ethylene reaches 5N5 (99.9995%). As shown in Table 2, the ethylene prepared in examples 1-3 has a purity of 5N5, and the ethylene prepared in example 1 has the highest purity, and the above purification process solves the technical problem of difficult ethylene purification in practical production. The invention adopts liquid nitrogen as refrigerant to separate ethane by two-stage low-temperature rectification, thereby reducing equipment investment and improving separation effect. And the pressure swing adsorption system is adopted to separate constant boiling substances, so that the effective separation of acetylene and carbon dioxide is realized. The special zeolite molecular sieve subjected to passivation treatment is adopted for dehydration, so that the technical effect of removing trace water to be within 1ppm is realized.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (2)
1. The purification method of the high-purity electronic grade ethylene is characterized by comprising the following steps of:
s1, step: removing heavy components and light components from industrial grade ethylene by adopting two-stage low-temperature rectification with liquid nitrogen as a refrigerant to prepare a primary grade ethylene crude product, wherein the temperatures of the two-stage low-temperature rectification are respectively T1 and T2, the pressures are respectively P1 and P2, the mass flow of the liquid nitrogen is respectively N1 and N2, and the reflux ratio is respectively R1 and R2; wherein, T2 is less than or equal to minus 100 ℃ and less than or equal to minus 83 ℃, P2 is less than or equal to 0.1MPa and less than or equal to P2 and less than or equal to 0.5MPa, R1 is less than or equal to 40 and less than or equal to 50, R2 is less than or equal to 40 and less than or equal to 50, and N1 is not equal to N2;
S2, step: the primary ethylene crude product is subjected to pressure swing adsorption to obtain a secondary ethylene crude product;
s3, step: dehydrating the secondary ethylene crude product by adopting a special zeolite molecular sieve subjected to passivation treatment;
in the step S1, when N1 is larger than N2, the heavy components are removed by a first rectifying tower of the two-stage low-temperature rectification, and the light components are removed by a second rectifying tower;
In the step S1, when N1 is less than N2, the light component is removed by a first rectifying tower of the two-stage low-temperature rectification, and the heavy component is removed by a second rectifying tower;
S2, the adsorbent adopted by the pressure swing adsorption is a modified carbon molecular sieve impregnated by acetone;
In the step S2, the pressure swing adsorption adopts low pressure of 0.08-0.12 MPa and high pressure of 0.64-0.96MPa for conversion, and the conversion frequency is 24-36S;
in the step S2, the temperature of the pressure swing adsorption is 300 ℃;
In the step S3, the special zeolite molecular sieve is a mixture of a 5A molecular sieve and a 4A molecular sieve;
In the step S3, the pressure of the dehydration operation is 0.1-0.4MPa, the temperature is room temperature to 80 ℃, and the airspeed is 200-300/h;
in step S3, the passivation process includes the following steps:
s301, step: passivating the special zeolite molecular sieve by using gas with the volume fraction of 0.01% SO 2 as passivating gas;
s302, step: and (3) after the special zeolite molecular sieve is activated by high-temperature nitrogen purging, vacuumizing and replacing.
2. The method for purifying high purity electronic grade ethylene according to claim 1, wherein in step S301, the mass ratio of sulfur content in the passivation gas to the specific zeolite molecular sieve is (0.01-0.05): 1.
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