CN114618429A - Surface modification modified ZSM-5 molecular sieve and application thereof - Google Patents
Surface modification modified ZSM-5 molecular sieve and application thereof Download PDFInfo
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- CN114618429A CN114618429A CN202011454915.1A CN202011454915A CN114618429A CN 114618429 A CN114618429 A CN 114618429A CN 202011454915 A CN202011454915 A CN 202011454915A CN 114618429 A CN114618429 A CN 114618429A
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- molecular sieve
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- organic impurities
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- modified zsm
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 95
- 230000004048 modification Effects 0.000 title claims abstract description 32
- 238000012986 modification Methods 0.000 title claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 49
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 239000004341 Octafluorocyclobutane Substances 0.000 claims abstract description 25
- 235000019407 octafluorocyclobutane Nutrition 0.000 claims abstract description 25
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 16
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 9
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- WSJULBMCKQTTIG-OWOJBTEDSA-N (e)-1,1,1,2,3,4,4,4-octafluorobut-2-ene Chemical compound FC(F)(F)C(/F)=C(\F)C(F)(F)F WSJULBMCKQTTIG-OWOJBTEDSA-N 0.000 claims description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 claims description 3
- DAFIBNSJXIGBQB-UHFFFAOYSA-N perfluoroisobutene Chemical group FC(F)=C(C(F)(F)F)C(F)(F)F DAFIBNSJXIGBQB-UHFFFAOYSA-N 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 42
- 230000000694 effects Effects 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 perfluoro compound Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 1
- 239000004340 Chloropentafluoroethane Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003058 plasma substitute Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28095—Shape or type of pores, voids, channels, ducts
-
- 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
Abstract
The invention discloses a surface modification ZSM-5 molecular sieve and application thereof in removing azeotropic organic impurities in octafluorocyclobutane, wherein the preparation method of the surface modification ZSM-5 molecular sieve comprises the following steps: adding a ZSM-5 molecular sieve with the silica-alumina ratio of 25-100 into a nonpolar organic solvent, adding a surface modifier, reacting for 2-10 hours at 20-80 ℃, drying at 50-200 ℃, and roasting at 300-800 ℃ to obtain the surface modified ZSM-5 molecular sieve, wherein the surface modifier is methyl orthosilicate and/or silicon tetrachloride. The invention has the advantages of controllable pore diameter of the pore channel window, mild adsorption condition, good adsorption effect and the like.
Description
Technical Field
The invention relates to the field of fluorine chemical industry, and in particular relates to a surface modification ZSM-5 molecular sieve and application of the surface modification ZSM-5 molecular sieve in removing azeotropic organic impurities in octafluorocyclobutane.
Background
The octafluorocyclobutane has stable chemical performance, no toxicity and harm, zero ozone consumption index value and low greenhouse effect potential, and is a green environment-friendly special gas. In recent years, octafluorocyclobutane has been widely used in the semiconductor industry, and is often used as an etching gas or a cleaning gas in the fields of IC integrated circuits and optical fibers. However, impurities in octafluorocyclobutane affect product performance and yield, so that octafluorocyclobutane needs to be purified, but conventional rectification can only remove conventional impurities, and azeotropic organic impurities such as perfluoroisobutylene, octafluoro-2-butene, hydrogen trichloride, difluorodichloromethane, difluorochloromethane, difluoromethane, pentafluoroethane, hexafluoropropylene and the like cannot be removed.
In order to remove azeotropic organic impurities, extractive distillation, chemical conversion, adsorption, etc. are often used. However, the extractive distillation method is easy to introduce new impurities, increases the production cost and has complex operation; the chemical conversion process is complex and has high requirements on equipment; the adsorption method has low cost and convenient operation, and is the most ideal purification method. The core of the adsorption method lies in an adsorbent, and the adsorbents which can remove azeotropic organic impurities are reported to comprise:
1) activated carbon
Patent CN1455699A discloses a method for effectively adsorbing impurities such as hexafluoropropylene, chloropentafluoroethane, heptafluoropropane and the like in octafluorocyclobutane by using activated carbon, and patent JP20043391187A discloses a purification method for reducing hydrogen fluoride and water in a perfluoro compound to 1ppm or less by contacting the activated carbon with the perfluoro compound. However, the active carbon adopted as the adsorbent generally has the defects of small impurity adsorption capacity, easy desorption and difficulty in meeting the requirements of industrial production.
2) Metal oxides
The patent CN107694509A discloses an adsorbent for removing hexafluoropropylene in octafluorocyclobutane, which comprises 10-25% by mass of iron oxide, 5-20% by mass of copper oxide, 60-80% by mass of tin oxide, 0.05-0.5% by mass of gallium, 0.05-0.3% by mass of platinum, 0.1-1.5% by mass of cadmium and 0.1-3% by mass of molybdenum. The modified metal oxide can effectively remove azeotropic impurities, but the pore channels of the metal oxide exist in micro-mesopores, and the heterogeneity of the pore channels causes that the adsorption depth and the adsorption capacity are lower.
3) Molecular sieves
Patent US20050183573A discloses a process for adsorbing fluorinated hydrocarbons by contacting a gas mixture containing partially fluorinated and/or perfluorinated hydrocarbons and an inert gas with a hydrophobic molecular sieve having a silica to alumina ratio of 80 or more and
but the partially fluorinated and/or perfluorinated hydrocarbons do not include octafluorocyclobutane, it is not disclosed that the process can remove azeotropic organic impurities in octafluorocyclobutane.
JP2011136955A discloses a modified molecular sieve for removing organic impurities from perfluorocarbons, wherein at least 20% of ions in the modified molecular sieve are Ca-coated2+、Mg2+、Ba2+、Li+Plasma substitution. However, the pore size of the modified molecular sieve cannot be effectively controlled, and impurities are difficult to effectively separate.
Disclosure of Invention
In order to solve the technical problems, the invention provides a surface modification ZSM-5 molecular sieve which has controllable pore diameter of a pore channel window, mild adsorption conditions and good adsorption effect.
Generally, the adsorption capacity of unmodified molecular sieves for azeotropic organic impurities is very small, while the pore diameter of the modified molecular sieves cannot be effectively controlled, and the requirements of adsorption capacity and selective adsorption of the azeotropic organic impurities cannot be met at the same time. The invention provides the surface modification ZSM-5 molecular sieve through a great deal of research, and the surface modification agent is adopted to modify and modify the surface of the molecular sieve under the condition of not influencing the internal pore passage of the molecular sieve, so that the modulation of the surface aperture of the molecular sieve is effectively realized.
The modification method of the molecular sieve comprises a chemical vapor deposition method and a chemical liquid deposition method, and the invention adopts the chemical liquid deposition method with simpler operation and better effect.
The purpose of the invention is realized by the following technical scheme:
a surface modification ZSM-5 molecular sieve is prepared by the following steps:
adding a raw material ZSM-5 molecular sieve with the silicon-aluminum ratio of 25-500 into a nonpolar organic solvent, adding a surface modifier, reacting for 2-10 hours at 20-80 ℃, drying at 50-200 ℃, and roasting at 300-800 ℃ to obtain the surface modified ZSM-5 molecular sieve, wherein the surface modifier is methyl orthosilicate and/or silicon tetrachloride.
As a preferred embodiment, the surface modification modified ZSM-5 molecular sieve is prepared by reacting at 25-30 ℃ for 2-5 hours, drying at 100-110 ℃ and roasting at 550-600 ℃.
Furthermore, the silica-alumina ratio of the ZSM-5 molecular sieve is 25-100.
The molecular kinetic diameter of the methyl orthosilicate and/or silicon tetrachloride surface modifier is
The pore diameter is larger than that of the ZSM-5 molecular sieve as the raw material, the molecular sieve can not enter the pore canal of the molecular sieve and only contacts with the outer surface of the ZSM-5 molecular sieveAnd the pore-opening hydroxyl reacts, and is roasted in the air to form a silicon dioxide coating which is deposited on the outer surface and the pore opening of the ZSM-5 molecular sieve, so that the pore size of the pore channel window on the outer surface of the surface modified ZSM-5 molecular sieve is reduced.
Furthermore, the pore size of the pore channel window on the outer surface of the ZSM-5 molecular sieve after surface modification can be further adjusted by adjusting the dosage of the surface modifier.
In a specific embodiment, in the preparation process of the surface modification modified ZSM-5 molecular sieve, the mass ratio of the surface modifier to the raw material ZSM-5 molecular sieve is 1-50: 10 to 100. Preferably, the mass ratio of the surface modifier to the ZSM-5 molecular sieve is 1-5: 10 to 20.
Further, in the preparation process of the surface modification modified ZSM-5 molecular sieve, the concentration of the surface modifier is 0.1-2.0 mol/L, preferably 0.5-1.0 mol/L.
Furthermore, the pore diameter of the pore canal window on the outer surface of the surface modified ZSM-5 molecular sieve is
More preferably
According to the surface modification modified ZSM-5 molecular sieve, in the preparation process of the surface modification modified ZSM-5 molecular sieve, the nonpolar organic solvent is selected from at least one of cyclohexane, n-heptane and n-propanol, and is preferably cyclohexane and/or n-heptane.
The invention also provides application of any one of the surface modification ZSM-5 molecular sieves in removing azeotropic organic impurities.
The application of the modified molecular sieve in removing azeotropic organic impurities in different products can be realized by adjusting the pore diameter of the pore channel on the outer surface of the surface modification ZSM-5 molecular sieve.
The invention also provides a method for removing azeotropic organic impurities from octafluorocyclobutane, which adopts any one of the surface modification ZSM-5 molecular sieves for 20 hours at the temperature of between 20 and 100 DEG C-1～100h-1The octafluorocyclobutane gas containing azeotropic organic impurities is introduced at the space velocity of (A). Preferably, any one of the surface modification modified ZSM-5 molecular sieves is adopted, and the temperature is between 20 and 60 ℃ for 20 hours-1～40h-1The octafluorocyclobutane gas containing azeotropic organic impurities is introduced at the space velocity of (A).
In order to further improve the removal effect of azeotropic organic impurities, the surface modification modified ZSM-5 molecular sieve is activated and then subjected to adsorption removal of the organic impurities, wherein the activation temperature is 100-900 ℃, and preferably 300-600 ℃.
In a preferred embodiment, the azeotropic organic impurities are selected from at least one of perfluoroisobutylene, octafluoro-2-butene, hydrogen trichloride, difluorodichloromethane, difluorochloromethane, difluoromethane, pentafluoroethane, and hexafluoropropylene, at a concentration of 100ppm to 2000ppm, more preferably at a concentration of 100ppm to 500 ppm. After azeotropic organic impurities are removed by the surface modification ZSM-5 molecular sieve, the purity of the octafluorocyclobutane gas is more than or equal to 99.999 percent.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, methyl orthosilicate and/or silicon tetrachloride are used as a surface modifier to modify the surface of the ZSM-5 molecular sieve, and the amount of the surface modifier is adjusted to adjust the pore size of a pore channel window on the outer surface of the ZSM-5 molecular sieve, so that when azeotropic organic impurities in octafluorocyclobutane are removed from the surface modified ZSM-5 molecular sieve, the azeotropic organic impurity molecules effectively enter the pore channel, while the octafluorocyclobutane is blocked outside the pore channel and cannot enter the pore channel, and the purpose of separation is achieved.
2. The method adopts the surface modification ZSM-5 molecular sieve to remove the azeotropic organic impurities, has mild adsorption conditions, good adsorption effect, low requirement on adsorption equipment, convenient operation and low cost, and is suitable for industrial application.
3. The surface modification ZSM-5 molecular sieve is formed by crossing two channels with different results, namely a straight channel and a zigzag channel, and the special channel structure can increase the diffusion resistance of azeotropic organic impurity molecules and improve the removal effect.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
Adding a ZSM-5 molecular sieve (50g) serving as a raw material with a silica-alumina ratio of 25 into cyclohexane, adding silicon tetrachloride (5g and the concentration of 0.5mol/L), reacting at room temperature (about 25 ℃) for 5 hours, drying at 110 ℃ for 8 hours, and roasting at 550 ℃ for 5 hours to obtain the surface modification ZSM-5 molecular sieve, which is marked as molecular sieve No. 1.
Examples 2 to 4
Examples 2-4 were performed as in example 1, except that: the raw material ZSM-5 molecular sieve with the silica-alumina ratio of 38, 60 and 100 is respectively adopted to prepare the obtained molecular sieve which is marked as molecular sieve No. 2, molecular sieve No. 3 and molecular sieve No. 4.
Examples 5 to 7
Examples 5-7 were performed as in example 1, except that: the concentration of the silicon tetrachloride is changed to 0.1mol/L, 1mol/L and 2mol/L, and the prepared molecular sieves are marked as molecular sieve No. 5, molecular sieve No. 6 and molecular sieve No. 7.
Examples 8 to 9
Examples 8-9 were performed as in example 1, except that: the surface modifier is methyl orthosilicate, a mixture of silicon tetrachloride and methyl orthosilicate (silicon tetrachloride: methyl orthosilicate is 1:1), and the prepared molecular sieve is marked as molecular sieve 8# and molecular sieve 9 #.
Comparative examples 1 to 3
Comparative examples 1-3 were conducted as in example 1 except that: the ZSM-5 molecular sieves are replaced by the 4A molecular sieve, the NaY molecular sieve and the 13X molecular sieve respectively, and the prepared molecular sieves are marked as molecular sieves B1#, B2# and B3 #.
Example 10
Activating the prepared molecular sieve No. 1 at 600 ℃. Loading 5g of activated molecular sieve No. 1 into adsorption column for 20 hr-1Introducing octafluorocyclobutane gas containing azeotropic organic impurities with the concentration of 500ppm at the adsorption temperature of 40 ℃, collecting the octafluorocyclobutane gas after removing the impurities at the outlet of the adsorption column for gas chromatography analysis, and calculating to obtain the penetrating adsorption capacity of the azeotropic organic impurities of 10.56 mL/g.
Examples 11 to 21
The operation of this example is the same as example 10 except that: activating and adsorbing by using the activated molecular sieve 2# to 9# and the activated molecular sieve B1# to B3# to calculate the penetrating adsorption capacity of the azeotropic organic impurities, which is specifically shown in the following table 1:
TABLE 1 breakthrough adsorption capacities of different molecular sieves
| Examples | Activated molecular sieve | Breakthrough adsorption capacity/mL/g |
| 10 | Molecular sieve 1# | 10.56 |
| 11 | Molecular sieve 2# | 9.87 |
| 12 | Molecular sieve 3# | 6.51 |
| 13 | Molecular sieve 4# | 2.65 |
| 14 | Molecular sieve 5# | 5.64 |
| 15 | Molecular sieve 6# | 10.45 |
| 16 | Molecular sieve 7# | 7.36 |
| 17 | Molecular sieve 8# | 6.87 |
| 18 | Molecular sieve 9# | 8.90 |
| 19 | Molecular sieve B1# | 3.29 |
| 20 | Molecular sieve B2# | 7.81 |
| 21 | Molecular sieve B3# | 8.90 |
Examples 22 to 24
The operation of this example is the same as example 10 except that: changing the activation temperature of the molecular sieve 1#, respectively carrying out activation and adsorption at 100 ℃, 300 ℃ and 900 ℃, and calculating to obtain the breakthrough adsorption capacity of the azeotropic organic impurities, wherein the breakthrough adsorption capacity is specifically shown in the following table 2:
TABLE 2 breakthrough adsorption capacities at different activation temperatures
| Examples | Activation temperature/. degree.C | Breakthrough adsorption capacity/mL/g |
| 22 | 100 | 2.54 |
| 23 | 300 | 10.41 |
| 24 | 900 | 6.76 |
Examples 25 to 28
The operation of this example is the same as example 10 except that: respectively at different sampling airspeeds: 20h-1、60h-1、80h-1、100h-1Introducing azeotropic organic impurities, and calculating to obtain the penetration absorption of the azeotropic organic impuritiesThe attached capacity is specifically shown in the following table 3:
TABLE 3 breakthrough adsorption capacities at different space velocities
| Examples | Space velocity/h-1 | Breakthrough adsorption capacity/mL/g |
| 25 | 20 | 10.54 |
| 26 | 60 | 8.97 |
| 27 | 80 | 7.75 |
| 28 | 100 | 5.32 |
Examples 29 to 32
The operation of this example is the same as example 10 except that: the adsorption temperature was varied, adsorption was carried out at 20 ℃, 60 ℃, 80 ℃ and 100 ℃ respectively, and the breakthrough adsorption capacity of the azeotropic organic impurities was calculated and obtained as shown in table 4 below:
TABLE 4 breakthrough adsorption capacities at different adsorption temperatures
| Examples | Adsorption temperature/. degree.C | Breakthrough adsorption capacity/mL/g |
| 29 | 20 | 8.65 |
| 30 | 60 | 10.10 |
| 31 | 80 | 8.64 |
| 32 | 100 | 5.61 |
Examples 33 to 36
The operation of this example is the same as example 10 except that: changing the content of the azeotropic organic impurities in the octafluorocyclobutane gas, respectively adopting the octafluorocyclobutane gas with the azeotropic organic impurities of 100ppm, 1000ppm, 1500ppm and 2000ppm for adsorption, and calculating to obtain the penetrating adsorption capacity of the azeotropic organic impurities, which is specifically shown in the following table 5:
TABLE 5 breakthrough adsorption capacity at different impurity concentrations
| Examples | Impurity concentration/ppm | Breakthrough adsorption capacity/mL/g |
| 33 | 100 | 10.26 |
| 34 | 1000 | 10.35 |
| 35 | 1500 | 8.65 |
| 36 | 2000 | 5.62 |
Claims (10)
1. A surface modification ZSM-5 molecular sieve is characterized in that: the preparation method of the surface modification modified ZSM-5 molecular sieve comprises the following steps:
adding a raw material ZSM-5 molecular sieve with the silicon-aluminum ratio of 25-500 into a nonpolar organic solvent, adding a surface modifier, reacting for 2-10 hours at 20-80 ℃, drying at 50-200 ℃, and roasting at 300-800 ℃ to obtain the surface modified ZSM-5 molecular sieve, wherein the surface modifier is methyl orthosilicate and/or silicon tetrachloride.
2. The surface modified ZSM-5 molecular sieve of claim 1, wherein: in the preparation process of the surface modification modified ZSM-5 molecular sieve, the mass ratio of the surface modifier to the ZSM-5 molecular sieve as the raw material is as follows: 1-50: 10 to 100.
3. The surface modified ZSM-5 molecular sieve of claim 1 or 2, wherein: the pore diameter of the pore canal window on the outer surface of the surface modification ZSM-5 molecular sieve is
4. The surface modified ZSM-5 molecular sieve of claim 1, wherein: the nonpolar organic solvent is selected from at least one of cyclohexane, n-heptane and n-propanol.
5. The surface modified ZSM-5 molecular sieve of claim 1 or 2, wherein: the concentration of the surface modifier is 0.1-2.0 mol/L.
6. Use of the surface modified ZSM-5 molecular sieve as claimed in any of claims 1 to 5 in the removal of azeotropic organic impurities.
7. A method for removing azeotropic organic impurities in octafluorocyclobutane is characterized by comprising the following steps: the surface modification modified ZSM-5 molecular sieve of any one of claims 1 to 5 is adopted at 20 ℃ to 100 ℃ for 20h-1～100h-1The octafluorocyclobutane gas containing azeotropic organic impurities is introduced at the space velocity of (A).
8. The method for removing azeotropic organic impurities in octafluorocyclobutane according to claim 7, wherein: the surface modification modified ZSM-5 molecular sieve is used after being activated at the temperature of 100-900 ℃.
9. The method for removing azeotropic organic impurities in octafluorocyclobutane according to claim 7, wherein: the concentration of the azeotropic organic impurities is 100ppm to 5000 ppm.
10. The method for removing azeotropic organic impurities in octafluorocyclobutane according to claim 7, wherein: the azeotropic organic impurities are at least one of perfluoroisobutylene, octafluoro-2-butene, hydrogen trichloride, difluorodichloromethane, difluorochloromethane, difluoromethane, pentafluoroethane and hexafluoropropylene.
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