CN115957717A - Monolithic porous inorganic material adsorbent and application thereof - Google Patents
Monolithic porous inorganic material adsorbent and application thereof Download PDFInfo
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- CN115957717A CN115957717A CN202211639376.8A CN202211639376A CN115957717A CN 115957717 A CN115957717 A CN 115957717A CN 202211639376 A CN202211639376 A CN 202211639376A CN 115957717 A CN115957717 A CN 115957717A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 59
- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 14
- 239000011147 inorganic material Substances 0.000 title claims abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 84
- 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 84
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims description 15
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 241000269350 Anura Species 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
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- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 239000002594 sorbent Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 239000007789 gas Substances 0.000 description 37
- 239000011148 porous material Substances 0.000 description 23
- 238000005245 sintering Methods 0.000 description 13
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 12
- 229910001424 calcium ion Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000005922 Phosphane Substances 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 229910000064 phosphane Inorganic materials 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- -1 cesium ions Chemical class 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
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- 231100000331 toxic Toxicity 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
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- 231100001261 hazardous Toxicity 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
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- 239000012298 atmosphere Substances 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
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- 239000012159 carrier gas Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
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- 239000010959 steel Substances 0.000 description 2
- 229910001427 strontium ion Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000074 antimony hydride Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910000078 germane Inorganic materials 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 class [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
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- 229910001419 rubidium ion Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical compound [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
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- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 1
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Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a monolithic porous inorganic material adsorbent, wherein raw materials of the adsorbent comprise a molecular sieve and metal ions I, the addition amount of the molecular sieve in the raw materials of the adsorbent is not less than 50 percent, the addition amount of the metal ions I is not less than 0.001 percent, and the addition amount of the metal ions I does not contain the content of the metal ions carried by the molecular sieve, according to the total mass percentage of 100 percent of the adsorbent. The adsorbent improves the adsorption capacity of the molecular sieve adsorption material to the special gas by introducing new metal ions I into the molecular sieve.
Description
Technical Field
The invention relates to the technical field of semiconductor manufacturing, in particular to a monolithic porous inorganic material adsorbent for adsorbing and desorbing special gas in the preparation process of a semiconductor wafer.
Background
During the manufacture of very large scale semiconductor integrated circuits, hazardous and toxic specialty gases are often used. The special gas mainly refers to some chemical gases used in the processes of extending, ion injecting, blending, washing and film forming in the semiconductor production link, namely electronic gases, such as high-purity SiH 4 、PH 3 、AsH 3 、B 2 H 6 、N 2 O、NH 3 、SF 6 、NF 3 、CF 4 、BCl 3 、BF 3 、HCl、Cl 2 And the like, which have important roles in the performance, integration level, and yield of semiconductor integrated circuits.
In semiconductor manufacturing, these specialty gases are usually transported in a high density form in a specific container, such as a high pressure gas cylinder, by compression or liquefaction. However, in some unexpected situations, these hazardous and toxic gases may leak, such as accidental release of high pressure gas, leakage from the cylinder itself, etc. Accidental leakage of these toxic gases can cause serious injury or even death to nearby personnel. It is therefore desirable to provide a means of safely storing and transporting these highly toxic or hazardous specialty gases.
CN1132662C (storage and release system for gaseous compounds) mentions a negative pressure gas cylinder filled with molecular sieve adsorbent, which is used for safe and efficient operation of high toxicity specialty gas. The negative pressure gas steel cylinder utilizes the specific regular nano-pore structure of the molecular sieve to provide the adsorption force for gas molecules so as to adsorb special gas with high toxicity, thereby reducing the pressure in the steel cylinder and further reducing the chance of accidental gas leakage. The release of the adsorbed specialty gas from the molecular sieve adsorbent can be effected by a pressure differential, which is achieved by providing a pressure outside the vessel that is lower than the pressure inside the vessel. The release of the adsorbed specialty gas may also be accomplished by heating the physical adsorbent media to break the low association bond between the adsorbed gas and the physical adsorbent media. In addition, the release of the adsorbed specific gas can also be effected by a carrier gas flowing through the interior of the cylinder container, so that a concentration difference acts on the adsorbed gas, causing a large flow of adsorbed gas into the carrier gas flow.
US5704965 describes a negative pressure gas cylinder using a filled activated carbon adsorbent, which provides adsorbability to gas molecules using the high surface area and nano-sized rich pore structure of activated carbon to adsorb specialty gases with high toxicity. The activated carbon adsorbent has higher adsorption capacity to highly toxic special gases than the molecular sieve adsorbent.
CN1723072 (gas storage and dispensing system with monolithic carbon adsorbent) describes a method of forming pores in the shape of more than 20% micropores below 2nm and more than 30% cracks in the shape of 0.3 nm to 0.7 nm by pyrolysis and activation of some polymers using a negative pressure gas cylinder filled with monolithic carbon physical adsorbent. The adsorption material has a specific gas AsH of more than 50% calculated on the basis of the volume of the cylinder 3 The amount of adsorption of (2).
In these gas storage and dispensing systems based on molecular sieve or activated carbon physical adsorbents, the adsorption and desorption capacity of the adsorbent media for highly toxic specialty gases is a major limitation in practical applications. Therefore, how to increase the adsorption and desorption capacities of the physical adsorbent is the direction of research by those skilled in the art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a monolithic porous inorganic material adsorbent.
In order to achieve the purpose, the invention adopts the technical scheme that: a monolithic porous inorganic material adsorbent comprises a molecular sieve and metal ions I in raw materials, wherein the addition amount of the molecular sieve in the raw materials of the adsorbent is not less than 50%, the addition amount of the metal ions I is not less than 0.001%, and the addition amount of the metal ions I does not contain the content of the metal ions carried by the molecular sieve, wherein the raw materials of the adsorbent comprise the molecular sieve and the metal ions I according to 100% of the total mass of the adsorbent.
The molecular sieve material has the advantages of low relative density, high specific strength, large specific surface area, good permeability, strong adsorbability, large porosity, light weight and the like. The pore size of the molecular sieve material comprises microporous, mesoporous and macroporous materials. The microporous, mesoporous, and macroporous materials are in accordance with the general pore size classification, for example, materials with pore sizes below 2nm are called microporous materials; the material with the pore size of 2-50nm is called mesoporous material; materials with pore sizes larger than 50nm are called macroporous materials.
The molecular sieve material comprises a natural molecular sieve and an artificially synthesized molecular sieve. The most representative molecular sieve materials include a type a, X, Y, mordenite, ZSM and SAPO molecular sieves. The molecular sieves can have different pore structures and pore sizes. For example, a type a molecular sieve consisting of an LTA type framework structure, typically a type a molecular sieve having a main crystal pore structure of an eight-membered ring structure. Wherein the aperture of the A-type molecular sieve is 0.3 nanometer of 3A; 0.3 nm for 4A; pore size of 5A 0.5 nm; 0.9 nm for 13X; 0.8 nm at 10X. The Y-type molecular sieve has an oversized inner pore diameter, the pore diameter of the cavity in the cage is about 1.3nm, and the pore diameter of the inner ring is about 0.74nm and has a twelve-membered ring structure. MOR type molecular sieves or mordenites having different pore diameters, such as large pore type LPM type mordenite molecular sieves having a pore diameter of about 0.7 nm and small pore size SPM type mordenite having a pore diameter of about 0.4 nm.
The artificially synthesized molecular sieve comprises aluminosilicate zeolite ZSM-5 molecular sieve, silicoaluminophosphate SAPO type molecular sieve and the like with high silica-alumina ratio and three-dimensional through pore channel structure.
As a specific embodiment, the molecular sieve is preferably a 4A molecular sieve, a 5A molecular sieve, a 13X molecular sieve, a 10X molecular sieve; preferably a molecular sieve of type 5A and/or 13X; more preferably 5A molecular sieves.
As a specific embodiment, the molecular sieve is added in any range of 60-90%, 60-85%, 70-80%, 60-70%, preferably, the molecular sieve is added in an amount of 60-85%.
The molecular sieve is extruded and molded, and the finally molded integral monolithic molecular sieve material can be in the shapes of a cylinder, a square column, a polygonal column, a large sphere, a large square angle and the like. A cylindrical type and a square cylindrical type are preferable, and a cylindrical type is more preferable.
The cylindrical molecular sieve has a shape with a diameter of at least 5 mm and a height of at least 1 mm. The diameter of the cylindrical molecular sieve can be selected from the group consisting of 5 mm to 1000 mm, 10 mm to 500 mm, 10 mm to 400 mm, 10 mm to 300 mm, 10 mm to 200 mm, 10 mm to 100 mm, 10 mm to 50 mm, 20 mm to 500 mm, 20 mm to 400 mm, 20 mm to 300 mm, 20 mm to 200 mm, 20 mm to 100 mm, 20 mm to 50 mm, 40 mm to 500 mm, 40 mm to 400 mm, 40 mm to 300 mm, 40 mm to 200 mm, 40 mm to 100 mm, preferably 20 mm to 300 mm, 30 mm to 300 mm, more preferably 40 mm to 200 mm. The height of the cylindrical molecular sieve may be selected from the group consisting of 1 mm to 500 mm, 5 mm to 300 mm, 5 mm to 200 mm, 5 mm to 100 mm 50 mm to 50 mm, 5 mm to 40 mm, 5 mm to 30 mm, 5 mm to 20 mm, 5 mm to 10 mm 20 mm to 500 mm, 10 mm to 300 mm, 10 mm to 200 mm, 10 mm to 100 mm, 10 mm to 50 mm, 10 mm to 40 mm, 10 mm to 30 mm, 10 mm to 20 mm, preferably 5 mm to 40 mm, 5 mm to 20 mm, more preferably 5 mm to 30 mm.
In a specific embodiment, the metal ion I is a newly added metal ion, excluding metal ions carried by the molecular sieve itself, such as calcium ion and other metal ions which are not contained in about 10% of the calcium ion and other metal ions already existing in the 5A molecular sieve. The metal ions I are selected from at least one metal ion in a first main group, a second main group, a third main group, an IB subgroup and a IIB subgroup, and preferably at least one metal ion in lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, beryllium ions, magnesium ions, calcium ions, strontium ions, barium ions, aluminum ions and gallium ions; more preferably magnesium ion, calcium ion, strontium ion and barium ion; more preferably one or a mixture of magnesium ions and calcium ions.
Preferably, the metal ion I is selected from metal ions in the first and second main groups.
As a particular embodiment, the metal ion I is selected from magnesium ions and/or calcium ions.
As a specific embodiment, the metal ion I is added in an amount of 0.05-10%, preferably 0.05-5%, 0.05-2%, 0.1-2%. Preferably between 0.1 and 2%.
As a specific embodiment, the metal ion I is added to the mixture of the molecular sieve and the binder in the form of a metal ion salt, an oxide or a hydroxide. Preferably, the metal ion salt is added as an aqueous solution. The adding time can be added before the molecular sieve is formed or after the molecular sieve is formed.
The adding mode of the metal ions I comprises the steps of directly mixing metal ion salts with the molecular sieve, or exchanging the metal ions with the molecular sieve, or directly immersing metal ion solution in the molecular sieve, and the like. Direct immersion of the metal ion solution in the molecular sieve is preferred. In one embodiment, a repeated impregnation process may be used to increase the concentration of the desired metal ion I in the molecular sieve.
The activation of the added metal ion I needs to be carried out at a certain temperature and in a certain atmosphere, and the heating temperature comprises 50-500 ℃, preferably 50-400 ℃, 50-300 ℃, 50-200 ℃, 50-150 ℃ and 50-100 ℃, more preferably 100-200 ℃; the atmosphere here includes inert gases such as nitrogen, argon, helium and active gases such as air, oxygen, hydrogen, carbon dioxide, carbon monoxide or a mixture of two or more thereof. Nitrogen and carbon dioxide are preferred.
In a specific embodiment, the raw material of the adsorbent further comprises a binder, the addition amount of the binder is between 0 and 50%, and the binder is selected from at least one of halloysite, attapulgite, alumina, pseudoboehmite, silica, montmorillonite, rectorite, sepiolite, cellulose and sesbania powder.
As a specific embodiment, the addition amount of the binder is 5-40%, 5-30%, 5-20%, 10-40%, 20-40%, 30-40%, preferably 20-30%.
It is another object of the present invention to provide the use of the above monolithic porous inorganic material adsorbent in a specialty gas storage and dispensing system in a negative pressure gas cylinder. Gases adsorbed by the adsorbent include, but are not limited to: silane, diborane, arsine, phosphane, chlorine, boron trichloride, boron trifluoride, B2D6, (CH 3) 3Sb, tungsten hexafluoride, hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, germane, ammonia, stibine, hydrogen sulfide, nitrogen trifluoride.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the monolithic porous inorganic material adsorbent provided by the invention has the advantages that the adsorption capacity of the molecular sieve adsorption material to special gases is improved by introducing new metal ions I into the molecular sieve.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to specific examples.
The invention provides a monolithic porous inorganic material adsorbent, which comprises a molecular sieve, metal ions I and a binder in the raw materials, wherein the addition amount of the molecular sieve is not less than 50 percent, the addition amount of the metal ions I is not less than 0.05 percent, the addition amount of the binder is 0-50 percent, and the molecular sieve is selected from one or more of A-type, X-type, Y-type, mordenite, ZSM-type and SAPO-type molecular sieves, wherein the total mass percentage of the adsorbent is 100 percent. The metal ions I do not contain the original metal ion content of the molecular sieve.
In the following examples, monolithic porous inorganic adsorbents were formed by mixing the components in proportions under extrusion and activation conditions. The monolithic porous inorganic adsorbents in the examples were cylindrical, and monolithic cylindrical adsorbents of different volumes were prepared according to different experimental conditions, having a diameter of 10 mm to 100 mm and a height of 5 mm to 200 mm.
1. Effect of Binder concentration on monolithic molecular Sieve adsorbent Performance
In this example, the molecular sieve used was a 5A molecular sieve, mixed with the binders pseudo-boehmite and sesbania powder in a ratio shown in table 1, and uniformly mixed with an inorganic acid, which was hydrochloric acid or nitric acid, and then sintered at a temperature of 500 ℃ for 4 hours in a vacuum tube sintering furnace, and the specific surface area was measured in a nitrogen atmosphere, and the results are shown in table 1.
Here, the specific surface area was measured gravimetrically using a Kingonian V-Sorb 2800 specific surface area and pore size measuring apparatus.
TABLE 1
As can be seen from table 1, in samples 1 to 5, as the proportion of the pseudoboehmite gradually decreases, the density of the sintered product gradually decreases, the hardness also gradually decreases, and the specific surface area gradually increases, and sample 5 shows a larger specific surface area. In samples 6 to 10, the hardness was gradually increased by increasing the proportion of sesbania powder, and the specific surface area reached the maximum value in sample 8. In addition, it can be seen from Table 1 that when the binder used is pseudoboehmite and sesbania powder, the ratio of the two is best controlled between 0.2 and 0.75.
2. Effect of sintering conditions on the Performance of monolithic molecular sieves adsorbents
According to the ingredients of the sample 8, the performance of the adsorbent is tested at different sintering temperatures and sintering times, and the test results are shown in table 2.
TABLE 2
| Sample (I) | Sintering temperature | Sintering time | Density g/cm 3 | hardness/N | S BET /(m 2 /g) | Sv/(m 2 /ml) |
| 11 | 400℃ | 6 hours | 1.22 | 46.2 | 472.1 | 576.0 |
| 12 | 450℃ | 4 hours | 1.29 | 54.5 | 459.1 | 592.2 |
| 8 | 500℃ | 4 hours | 1.32 | 60.9 | 595.3 | 785.8 |
| 13 | 500℃ | 6 hours | 1.31 | 62.4 | 432.2 | 566.2 |
| 14 | 600℃ | 4 hours | 1.29 | 60.2 | 410.1 | 529.0 |
S BET /(m 2 /g) is the specific surface area by weight; sv/(m) 2 Per ml) is the specific surface area in terms of volume.
From table 2, it can be seen that when the sintering temperature is higher than 450 ℃ under the same sintering time, the density and hardness of the adsorbent are not significantly affected, but the specific surface area of the monolithic molecular sieve adsorbent is greatly different, and when the sintering temperature reaches 600 ℃, the specific surface area of the monolithic molecular sieve adsorbent is reduced. In addition, when the sintering temperature is the same, the specific surface area is reduced when the sintering time exceeds 4 hours. Therefore, the optimum sintering temperature is 500 ℃ and the sintering time is 4 hours.
3. Performance of calcium ion supported monolithic molecular sieve adsorbents
Sample 15 was prepared according to the formulation of sample 8 by different process conditions. Sample 15A was prepared by immersing sintered and molded sample 15 in 0.5M calcium nitrate aqueous solution at room temperature for 15 hours, taking out, then placing on a flat plate for 30 minutes to drain off excess liquid on the surface, and then baking at 110 ℃ for 3 hours to obtain sample 15A. The performance of the two materials was tested, and the test results are shown in Table 3.
TABLE 3
| Sample(s) | Density (g/mL) | S BET /(m 2 /g) | Sv/(m 2 /mL) |
| 15 | 1.025 | 539.4 | 545.7 |
| 15A | 1.02 | 444.2 | 462.7 |
From Table 3, it can be seen that sample 15A, impregnated with calcium nitrate, has an incorporated calcium ion content of 0.73% net weight in the monolithic molecular sieve adsorbent, and has an S content of BET The specific surface area is reduced by more than 17%, and the specific surface area of Sv is reduced by about 15%.
4. Adsorption performance of calcium ion supported monolithic molecular sieve adsorbent on ethanol and water
Samples 15 and 15A were immersed in pure water and pure ethanol liquid, respectively, at room temperature for 6 hours, and then placed on a flat plate for 40 minutes to drain the excess liquid on the surface, and then the weight was measured. The resulting adsorbed amounts of ethanol and water were converted to the calculated adsorbed amounts for sample 15 and sample 15A at 100 grams or one liter. The results are shown in Table 4.
TABLE 4
From table 4, we can see that sample 15A loaded with calcium ions has a reduced adsorption capacity for water and ethanol, indicating that the deposition of calcium ions in the pores of the monolithic molecular sieve adsorbent reduces the adsorption of ethanol and water.
5. Monolithic molecular sieve adsorbent supported by calcium ions for pH 3 Adsorption condition of (2)
A certain amount of sample 15 and sample 15A were taken and placed in a gas cylinder respectively and evacuated. The gas of phosphane is gradually fed into the cylinder under vacuum condition at room temperature until the equilibrium state. The monolithic molecular sieve adsorbent was then tested for adsorption weight gain on phosphane. The adsorption amount of the obtained phosphane was converted into the calculated adsorption amounts of the sample 15 and the sample 15A in 100 g or one liter, and the measurement results thereof are shown in Table 5.
TABLE 5
As can be seen from Table 5, in comparative sample 15, although sample 15A has a lower specific surface area than sample 15, the amount of adsorption of phosphane is significantly increased, and sample 15A has an increase in adsorption of phosphane of about 14% as calculated on 100 grams or one liter of molecular sieve adsorbent; considering the adsorption amount of a unit of specific surface area to phosphane, the adsorption amount of the sample 15A to phosphane is obviously increased by 38.93% compared with the sample 15.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The monolithic porous inorganic material adsorbent is characterized in that raw materials of the adsorbent comprise a molecular sieve and metal ions I, the adding amount of the molecular sieve in the raw materials of the adsorbent is not less than 50%, the adding amount of the metal ions I is not less than 0.001%, and the adding amount of the metal ions I does not contain the content of the metal ions carried by the molecular sieve, wherein the adding amount of the molecular sieve and the metal ions I is calculated according to 100% of the total mass of the adsorbent.
2. The monolithic porous inorganic material adsorbent of claim 1, wherein said molecular sieve is selected from at least one of type a, type X, type Y, mordenite, ZSM, and SAPO, preferably said molecular sieve is selected from type 5A and/or type 13X molecular sieves.
3. The monolithic porous inorganic adsorbent material of claim 1, wherein said molecular sieve is added in an amount of between 60-90%.
4. The monolithic porous inorganic material adsorbent of claim 1, wherein said metal ion i is selected from at least one metal ion of the first main group, the second main group, the third main group, the ib subgroup, and the ib subgroup, preferably said metal ion i is selected from metal ions of the first main group and the second main group.
5. The monolithic porous inorganic adsorbent material of claim 4 wherein said metal ion I is selected from the group consisting of magnesium and/or calcium.
6. The monolithic porous inorganic adsorbent material of claim 1 wherein said metal ion i is added in an amount of 0.05-10%, preferably 0.1-2%.
7. The monolithic porous inorganic adsorbent material of claim 1 further comprising a binder in the raw material, wherein the binder is added in an amount of 0-50%, and wherein the binder is selected from at least one of halloysite, attapulgite, alumina, pseudoboehmite, silica, montmorillonite, rectorite, sepiolite, cellulose, and sesbania powder.
8. The monolithic porous inorganic adsorbent material of claim 7 wherein said binder is added in an amount between 20-30%.
9. The monolithic porous inorganic material adsorbent of claim 1, wherein said metal ion I is added to the mixture of molecular sieve and binder in the form of a metal ion salt, oxide or hydroxide.
10. Use of the monolithic porous inorganic material sorbent of claim 1 in a specialty gas storage and dispensing system in a negative pressure gas cylinder.
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