CN115722189A - Adsorbent for removing oxygen-containing compounds in low-molecular hydrocarbons - Google Patents
Adsorbent for removing oxygen-containing compounds in low-molecular hydrocarbons Download PDFInfo
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- CN115722189A CN115722189A CN202111009059.3A CN202111009059A CN115722189A CN 115722189 A CN115722189 A CN 115722189A CN 202111009059 A CN202111009059 A CN 202111009059A CN 115722189 A CN115722189 A CN 115722189A
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- molecular sieve
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- 239000001301 oxygen Substances 0.000 title claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 33
- 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 33
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 24
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 7
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 3
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 3
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 3
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 3
- 150000003751 zinc Chemical class 0.000 claims abstract description 3
- 150000003754 zirconium Chemical class 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002048 multi walled nanotube Substances 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- -1 ethylene, propylene Chemical group 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims 1
- 239000002594 sorbent Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 5
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 239000003795 chemical substances by application Substances 0.000 description 18
- 239000011734 sodium Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000003814 drug Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 230000005484 gravity Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 238000005804 alkylation reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000008279 sol Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
An adsorbent for removing oxygen-containing compounds in low-molecular hydrocarbons is characterized by comprising a Y-type molecular sieve, aluminum oxide and/or silicon oxide and a modifying component, wherein the modifying component comprises one or more of sodium salt, potassium salt, magnesium salt, calcium salt, zirconium salt, molybdenum salt and zinc salt and carbon nano tubes. The adsorbent can effectively improve the adsorption quantity of the oxidized substances of the low-polarity macromolecules such as dimethyl ether, MTBE and the like, and can be used for adsorption purification industrial production for removing oxygen-containing compounds from various raw materials.
Description
Technical Field
The invention relates to an adsorbent, in particular to an adsorbent for removing oxygen-containing compounds in low molecular hydrocarbons.
Background
Since the eighties of the last century, many major oil companies and scientific research institutes around the world have been devoted to research and development of solid acid alkylation processes, in order to replace liquid acid alkylation processes with environment-friendly solid acid alkylation processes, and realize green alkylation processes.
Isobutane and butene are mainly obtained from processes of catalytic cracking in refineries, ethylene preparation through steam cracking, and mixed carbon four as a byproduct generated from natural gas. In recent years, with natural gas becoming the main source of fuel, carbon four begins to be used as the reaction raw material of high-octane gasoline blending components, including isobutylene and methanol etherification, isobutylene polymerization hydrogenation and carbon four alkylation reactions. The C four feedstock contains oxygenate impurities such as methanol, dimethyl ether, ethanol, t-butyl alcohol, and methyl t-butyl ether. In the alkylation reaction process catalyzed by solid acid, oxygen-containing compounds are easily adsorbed on acid centers, so that the service life of the catalyst is quickly reduced, and therefore, the pretreatment process of the raw materials of the oxygen-containing compounds has important influence on the alkylation reaction.
Adsorption of oxygenates by adsorbents is a common means of alkylation feed pretreatment processes. Common adsorbents include porous materials such as silica gel, alumina, and molecular sieves. For example, US6111162 discloses the use of silica gel as an adsorbent for the adsorptive removal of oxygenates from hydrocarbon feedstocks. US4371718 discloses alumina as an adsorbent for removing methanol from butene feedstocks. EP0229994 discloses the removal of C from the liquid state 3 ～C 5 Process for removing dimethyl ether from olefins in which the molecular sieve adsorbent has a faujasite structure, preferably the olefin stream is from the C of Fluid Catalytic Cracking (FCC) 3 ～C 5 An olefin stream. US4465870 discloses the adsorption removal of methanol, water and methyl tert-butyl ether from C4 using a 13X, 5A molecular sieve. CN1806029A discloses a method for removing dimethyl ether from olefin stream by using a solid adsorbent mainly composed of molecular sieve or metal oxide impregnated with Zn or Mg plasma, wherein the molecular sieve has a framework structure of 4-to 12-membered rings or larger poresMolecular sieves, but the adsorption capacity of the adsorbents is only 0.1 to 1.0%.
The oxygen-containing compounds in the low molecular weight hydrocarbon are generally dimethyl ether, methyl tert-butyl ether (MTBE), methanol, acetone, methyl ethyl ketone, butyraldehyde, tert-butyl alcohol and the like, wherein the dimethyl ether, the acetone and the methyl tert-butyl ether are weak in polarity, and the butyraldehyde, the methanol and the tert-butyl alcohol are strong in polarity. When a mixture of oxygen-containing compounds with different polarities is adsorbed, competitive adsorption occurs no matter silica gel, alumina or a molecular sieve is used as an adsorbent, and the adsorption amount of the oxygen-containing compounds with low polarity and large molecular size is low.
Disclosure of Invention
The invention aims to provide an adsorbent for improving the adsorption quantity of oxygen-containing compounds with weak polarity and large molecular size aiming at the defects of the adsorbent for removing the oxygen-containing compounds in low molecular hydrocarbons in the prior art.
In order to achieve the purpose of the invention, the adsorbent for removing oxygen-containing compounds in low molecular hydrocarbons is characterized by comprising a Y-type molecular sieve, alumina and/or silica and a modifying component, wherein the modifying component comprises one or more of sodium salt, potassium salt, magnesium salt, calcium salt, zirconium salt, molybdenum salt and zinc salt and carbon nano tubes.
The low molecular hydrocarbon is C2-C5 olefin or alkane, wherein the C2-C5 olefin is one or a mixture of ethylene, propylene, butene-1, butene-2, isobutene, pentene and isopentene.
The oxygen-containing compound comprises one or more of dimethyl ether, methanol, acetone, methyl ethyl ketone, butyraldehyde, tert-butyl alcohol and MTBE, wherein the dimethyl ether, the acetone and the methyl tert-butyl ether are weak in polarity, and the butyraldehyde, the methanol and the tert-butyl alcohol are strong in polarity.
The Y-type molecular sieve is preferably a Y-type molecular sieve having a crystal grain size with an average diameter of 200 to 1000nm, and may be, for example, a Y-type molecular sieve having a crystal grain size with an average diameter of 700 to 1000nm or a Y-type molecular sieve having a crystal grain size with an average diameter of 200 to 700nm. The grain size of the Y-type molecular sieve can be selectedSEM (scanning Electron microscope) measurement, for example, by JSM-5610LV type scanning electron microscope observation. The Y-type molecular sieve with the average diameter of 200-1000 nm is prepared by carrying out hydrothermal crystallization on a mixture A consisting of a directing agent, water, a silicon source and an aluminum source under the condition of synthesizing a NaY molecular sieve, recovering the obtained product, and carrying out ammonium sodium reduction, hydrothermal treatment and dealuminization and silicon supplementation processes, wherein the directing agent is obtained by mixing sodium metaaluminate and water glass to ensure that the molar concentration of aluminum elements in the water glass is gradually increased from zero to form Na with the molar ratio of (6-25) 2 O:A1 2 O 3 :(6～25)SiO 2 The mixture B is obtained by dynamic aging, standing aging and water supplementing in sequence, wherein the mixture A is obtained by sequentially adding a guiding agent, a silicon source, an aluminum source and water into a mixing tank in sequence.
The adsorbent of the invention preferably comprises the following components in percentage by weight based on the total amount of the adsorbent: 25-80 wt% of Y-type molecular sieve, 10-70 wt% of alumina and/or silica and 2-10 wt% of carbon nano tube.
The precursor of the alumina is from alumina sol and/or hydrated alumina, such as pseudo-boehmite, SB powder, etc.
The precursor of the silica is preferably derived from silica or silica sol.
The carbon nanotubes are preferably multi-walled carbon nanotubes, typically having a density of about 2.1g/cm 3 (at 20 ℃), the purity is more than or equal to 95%, the inner diameter is about 10-20 nm, and the length is about 10-30 μm.
The adsorbent is obtained by kneading and molding a mixed slurry of a Y-type molecular sieve, alumina and/or silica, a modifying component, an acid and water. Wherein the shaping comprises extruding strips or rolling balls. More specifically, the adsorbent of the present invention is prepared by suitably pre-kneading a Y-type molecular sieve with a mixture of hydrated alumina, alumina sol, silica sol, clay and acid. The water is added to the mixture, and the kneading is preferably performed for 30-40min. The length of kneading time can directly affect subsequent bar extrusion and rolling ball. The kneading is insufficient, the material is difficult to extrude, the extruded strips have more burrs, multiple white spots and easy breakage, and balls with undersized particle size tend to be generated during rolling; too long a kneading time may damage the pore structure and specific surface of the support. The control of the water adding amount is also important and is the most key factor for the smoothness of the subsequent rolling ball. Both too dry and too wet materials cannot be extruded into noodles and rolled balls. In order to avoid excessive water addition, the humidity of the materials needs to be observed in the kneading process, and the water content is suitable to be 35-40%. The bar extruding step is also a key step, and the operability of subsequent rolling balls can be well predicted according to the condition of the extruded bar, so that the best condition for the rolling balls can be created as far as possible during bar extruding. The extruded strands ideally are continuous in discharge, smooth in surface, tough, and non-curling and tacky. The speed of extruding the strips is controlled well in the process of extruding the strips, the speed of extruding the strips and the speed of rolling balls are balanced as much as possible, and excessive extruding of the strips is avoided. The rolling ball is the last key for forming the adsorbent, and directly influences the primary yield, the particle size distribution, the roundness and the like of the small ball. The proper parameters are selected in the rolling process, so that the generation probability of the small balls and the strips can be reduced. The means for regulating and controlling the rolling ball include rotating speed, blowing quantity, feeding quantity and rolling time. The balling condition should be monitored in good time during the balling process, and the operating parameters should be adjusted in time to ensure that the balling is carried out under the optimal condition.
When the adsorbent is used for adsorbing oxygen-containing compound mixtures with different polarities, competitive adsorption among oxides with different polarities can be weakened, and meanwhile, the prepared adsorbent has a larger pore diameter and a smooth pore structure, so that the oxides with the sizes of weak-polarity macromolecules still have higher adsorption capacity.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In each of the examples and comparative examples, the grain size of the Y-type molecular sieve was measured by means of SEM (scanning electron microscope) and observed by a JSM-5610LV type scanning electron microscope.
Example 1
The synthesis process of the NaY molecular sieve comprises the following steps: 50.39g of a high alkali sodium metaaluminate solution (Medium petrochemical Co., ltd.) was addedProvided by Ringzhao corporation, al 2 O 3 The content of Na is 40.2g/L 2 O content of 255g/L and specific gravity of 1.324) was added to 65.56g of water glass (supplied by ChangLing division of catalyst, zhongpetrochemical Co., ltd., siO 2 The content of Na is 260.6g/L 2 O content of 81.6g/L, specific gravity of 1.2655 and modulus of 3.3), stirring and aging at room temperature for 48 hours, then statically aging at 60 ℃ for 5 hours, and finally adding 15g of deionized water under stirring to obtain the final molar ratio of the directing agent of 15Na 2 O:A1 2 O 3 :15SiO 2 :320H 2 And (O). The prepared directing agent is totally used for preparing a reaction mixture, and the adding amount of the directing agent is calculated according to that the mole number of the aluminum element in the directing agent accounts for 3 percent of the total mole number of the aluminum element. Under stirring at room temperature and high speed, according to the guiding agent (prepared by the previous step), 1682.6g of water glass (same above), 134.19g of low alkali sodium metaaluminate solution (provided by Changjingtian catalyst, china petrochemical company, ltd., al) 2 O 3 The content of Na is 194g/L 2 286.2g/L of O, 1.413 of specific gravity), 448.02g of aluminum sulfate (provided by ChangLing division of catalyst of Zhongpetrochemical Co., ltd., al 2 O 3 88.9g/L, specific gravity 1.2829) and 150.4g of water are sequentially added into a mixing tank, and the total feeding molar ratio of the reaction mixture is 3Na 2 O:A1 2 O 3 :12SiO 2 :209H 2 And O. Stirring, placing into a stainless steel reaction kettle, statically crystallizing at 100 deg.C for 24 hr, filtering, washing, and drying to obtain NaY molecular sieve product with crystal grain size of 200-500nm and water content of 24% as shown by scanning electron microscope photograph.
Under stirring, mixing NaY19.5g of molecular sieve, 16.97g of pseudoboehmite (Zibocyclolin aluminum industry Co., ltd., water content of 19%), 20.42g of SB powder (Zibosin chemical industry Co., ltd., water content of 33%), 1.6g of nitric acid (analytically pure, national medicine group chemical reagent Co., ltd.), 1.96g of NaCl (analytically pure, national medicine group chemical reagent Co., ltd.), caCl 2 (analytically pure, national chemical group chemical reagent Co., ltd.) 0.74g, multi-walled carbon nanotubes (Xinao graphene technology Co., ltd., density of about 2.1 g/cm) 3 (at 20 ℃), the purity is more than or equal to 95%Inner diameter of about 10-20 nm and length of about 10-30 μm, the same below) 3g and 60g of water are mixed uniformly, premixed and kneaded for 0.5h, the obtained slurry is extruded into strips, the obtained strips are dried at 110 ℃ for 3h, roasted at 450 ℃ for 3h, and crushed particles are screened into 20-40 meshes to obtain an adsorbent sample, wherein the number is a.
Comparative example 1
19.5g of NaY molecular sieve (particle size of 1000-1300nm, water content of 25%) 16.97g of pseudoboehmite (Zibo Cyclolin aluminum Co., ltd., water content of 19%), 20.42g of SB powder (Zibo Senz chemical Co., ltd., water content of 33%), 1.6g of nitric acid (analytically pure, chemical reagent of national drug group Co., ltd.), 1.96g of NaCl (analytically pure, chemical reagent of national drug group Co., ltd.), caCl and stirring 2 0.74g of (analytically pure, chemical reagents of national drug group Co., ltd.), 3g of multi-walled carbon nano-tube (Xinao graphene technology Co., ltd., water content of 12%) and 60g of water are uniformly mixed, premixed and kneaded for 0.5h, the obtained slurry is extruded into strips, the obtained strips are dried at 110 ℃ for 3h and roasted at 450 ℃ for 3h, and crushed particles are sieved into 20-40 meshes to obtain an adsorbent sample, wherein the number is A.
Example 2
19.5g of NaY (same as example 1), 26.20g of pseudo-boehmite, 9.78g of SB powder, 1.6g of nitric acid, 1.96g of NaCl and ZnSO were mixed under stirring 4 (analytically pure, national medicine group chemical reagent Co., ltd.) 0.88g, multi-walled carbon nanotubes 3g and 60g water are mixed uniformly, premixed and kneaded for 0.5h, the obtained slurry is extruded into strips, the obtained strips are dried at 110 ℃ for 3h, roasted at 450 ℃ for 3h, crushed particles are screened into 20-40 meshes to obtain an adsorbent sample, and the number is b.
Comparative example 2
19.5g of small-grained NaY (same as example 1), 26.20g of pseudo-boehmite, 9.78g of SB powder, 1.6g of nitric acid (analytically pure, national chemical Co., ltd.), 1.96g of NaCl (analytically pure, national chemical Co., ltd.), and ZnSO 4 (analytically pure, national drug group chemical reagent Co., ltd.) 0.88g and 60g water are mixed uniformly, then premixed and kneaded for 0.5h, the obtained slurry is extruded into strips, the obtained strips are dried at 110 ℃ for 3h, roasted at 450 ℃ for 3h, and crushed particles are screened into 20-40 meshes to obtain an adsorbent comparison sample, wherein the number is B.
Example 3
The synthesis process of the NaY molecular sieve comprises the following steps: 50.39g of a high alkali sodium metaaluminate solution (supplied by ChangLing division, a catalyst of Zhongpetrochemical Co., ltd., al) 2 O 3 The content of Na is 40.2g/L 2 O content of 255g/L and specific gravity of 1.324) was added to 65.56g of water glass (provided by ChangLing division of catalyst of Zhongpetrochemical Co., ltd., siO 2 The content of Na is 260.6g/L 2 O content of 81.6g/L, specific gravity of 1.2655 and modulus of 3.3), stirring and aging at room temperature for 24 hours, then statically aging at 60 ℃ for 2 hours, and finally adding 15g of deionized water under stirring to obtain the final molar ratio of the directing agent of 15Na 2 O:A1 2 O 3 :15SiO 2 :320H 2 And O. The prepared directing agent is totally used for preparing a reaction mixture, and the adding amount of the directing agent is calculated according to that the mole number of the aluminum element in the directing agent accounts for 3 percent of the total mole number of the aluminum element. Under stirring at room temperature and high speed, according to the guiding agent (prepared by the previous step), 1682.6g of water glass (same above), 134.19g of low alkali sodium metaaluminate solution (provided by Changjingtian catalyst, china petrochemical company, ltd., al) 2 O 3 The content of Na is 194g/L 2 286.2g/L of O content, 1.413 of specific gravity), 448.02g of aluminum sulfate (provided by ChangLing division of catalyst of Zhongpetrochemical Co., ltd., al 2 O 3 88.9g/L, specific gravity of 1.2829) and 150.4g of water are added into a mixing tank in sequence, and the total feeding molar ratio of the reaction mixture is 3Na 2 O:A1 2 O 3 :12SiO 2 :209H 2 And O. After being stirred evenly, the mixture is put into a stainless steel reaction kettle and is statically crystallized for 24 hours at the temperature of 100 ℃, and then the NaY molecular sieve product is obtained by filtering, washing and drying, wherein the scanning electron microscope photo shows that the grain size is 400-700nm and the water content is 24 percent.
32.5g of NaY molecular sieve, 6.78g of pseudo-boehmite, 3.37g of SB powder, 10.00g of white carbon black (New Material Co., ltd., shandong Sertoli, with a Water content of 2%), 1.6g of nitric acid, 1.96g of NaCl and ZrCl were mixed under stirring 2 0.74g of O (analytically pure, chemical reagents of national medicine group Co., ltd.), 3g of multi-walled carbon nano-tube and 60g of water are uniformly mixed, premixed and kneaded for 0.5h, the obtained slurry is extruded into strips, and the obtained strips are preparedDrying at 110 ℃ for 3h, roasting at 450 ℃ for 3h, and sieving the crushed particles into 20-40 meshes to obtain an adsorbent sample with the number of c.
Comparative example 3
32.5g of NaY (same as example 3), 6.78g of pseudo-boehmite, 3.37g of SB powder, 10.00g of white carbon black (New Material Co., ltd., shandong Sertoli, moisture content: 2%), 1.6g of nitric acid, 1.96g of NaCl, zrCl 2 0.74g of O (analytically pure, national medicine group chemical reagent Co., ltd.) and 60g of water are uniformly mixed, premixed and kneaded for 0.5h, the obtained slurry is extruded into strips, the obtained strips are dried at 110 ℃ for 3h, roasted at 450 ℃ for 3h, crushed particles are screened into 20-40 meshes to obtain an adsorbent sample, and the number of the adsorbent sample is C.
Example 4
The synthesis process of the NaY molecular sieve comprises the following steps: 50.39g of a high alkali sodium metaaluminate solution (available from ChangLing division, a catalyst of Zhongpetrochemical Co., ltd., al) 2 O 3 The content of Na is 40.2g/L 2 O content of 255g/L and specific gravity of 1.324) was added to 65.56g of water glass (provided by ChangLing division of catalyst of Zhongpetrochemical Co., ltd., siO 2 The content of Na is 260.6g/L 2 O content of 81.6g/L, specific gravity of 1.2655 and modulus of 3.3), aging at 60 deg.C for 5 hr under stirring, statically aging at 60 deg.C for 5 hr, and adding 15g deionized water under stirring to obtain directing agent with final molar ratio of 15Na 2 O:A1 2 O 3 :15SiO 2 :320H 2 And (O). The prepared directing agent is totally used for preparing a reaction mixture, and the adding amount of the directing agent is calculated according to that the mole number of the aluminum element in the directing agent accounts for 3 percent of the total mole number of the aluminum element. Under stirring at room temperature and high speed, according to the guiding agent (prepared by the previous step), 1682.6g of water glass (same above), 134.19g of low alkali sodium metaaluminate solution (provided by Changjingtian catalyst, china petrochemical company, ltd., al) 2 O 3 The content of Na is 194g/L 2 286.2g/L of O content, 1.413 of specific gravity), 448.02g of aluminum sulfate (provided by ChangLing division of catalyst of Zhongpetrochemical Co., ltd., al 2 O 3 88.9g/L of water with a specific gravity of 1.2829) and 1419.4g of water are sequentially added into a mixing tank, and the total feeding molar ratio of the reaction mixture is 3Na 2 O:A1 2 O 3 :12SiO 2 :350H 2 And O. After being stirred evenly, the mixture is put into a stainless steel reaction kettle and is statically crystallized for 32 hours at the temperature of 100 ℃, and then the NaY molecular sieve product is obtained by filtering, washing and drying, and the scanning electron microscope photo shows that the grain size is 700-1000 nm.
39.5g of NaY (moisture content 24%), 13.86g of pseudo-boehmite, 6.68g of SB powder, 1.6g of nitric acid, 1.96g of NaCl and ZnSO were mixed under stirring 4 0.88g of (analytically pure, national medicine group chemical reagent Co., ltd.), 3g of multi-walled carbon nano-tube and 60g of water are uniformly mixed, premixed and kneaded for 0.5h, the obtained slurry is extruded into strips, the obtained strips are dried at 110 ℃ for 3h and roasted at 450 ℃ for 3h, and crushed particles are sieved into 20-40 meshes to obtain an adsorbent sample, wherein the serial number is d.
Comparative example 4
39.5g of NaY (particle size 1000-1300nm, water content 25%) 13.86g of pseudo-boehmite, 6.68g of SB powder, 1.6g of nitric acid, 1.96g of NaCl and ZnSO were mixed under stirring 4 (analytically pure, national medicine group chemical reagent Co., ltd.) 0.88g, multiwall carbon nanotube 3g and 60g water are mixed evenly, premixed and kneaded for 0.5h, the obtained slurry is extruded into strips, the obtained strips are dried at 110 ℃ for 3h, roasted at 450 ℃ for 3h, crushed particles are screened into 20-40 meshes to obtain an adsorbent sample, and the number is D.
Example 5
48.75g of NaY (same as example 1), 12.5g of alumina sol (80% water content, shandong Lier New materials Co., ltd.), 6.16g of SB powder, 1.6g of nitric acid, 0.49g of NaCl0, (NH) 4 ) 2 Mo 4 O 13 ·2H 2 1.29g of O (analytically pure, chemical reagents of national drug group Co., ltd.), 1.61g of multi-walled carbon nano-tube and 50g of water are uniformly mixed, premixed and kneaded for 0.5h, the obtained slurry is extruded into strips, the obtained strips are dried at 110 ℃ for 3h and roasted at 450 ℃ for 3h, and crushed particles are screened into 20-40 meshes to obtain an adsorbent sample, wherein the number is e.
Comparative example 5
48.75g of NaY (particle size 1000-1300nm, water content 25%) 12.5g of alumina sol (80% water content, new Material Ltd., shandong province) 6.16g of SB powder, 1.6g of nitric acid, 0.49g of NaCl0, (NH) were mixed under stirring 4 ) 2 Mo 4 O 13 ·2H 2 1.29g of O (analytically pure, chemical reagents of national drug group Co., ltd.), 1.61g of multi-walled carbon nano-tube and 50g of water are uniformly mixed, premixed and kneaded for 0.5h, the obtained slurry is extruded into strips, the obtained strips are dried at 110 ℃ for 3h and roasted at 450 ℃ for 3h, and crushed particles are screened into 20-40 meshes to obtain an adsorbent sample, wherein the number is E.
The mass fractions of the components of the adsorbents in the above examples and comparative examples are shown in Table 1.
TABLE 1
Test example
This test example demonstrates the adsorption performance of the adsorbent of the present invention for removing oxygenates from low molecular weight hydrocarbons.
The experimental conditions are as follows: the fixed bed is roasted for 2 hours at 500 ℃ under the nitrogen condition, and then is cooled to 30 ℃. The reaction conditions are that the reaction temperature is 30 ℃, the weight space velocity is 2h -1 The adsorbent is 10 g, and the raw material isobutane contains 1252ppm of dimethyl ether, 189.4ppm of MTBE, 686ppm of methanol, 90.2ppm of acetone, 4.96ppm of butyraldehyde and 9.88ppm of tertiary butanol.
Gas chromatography detection shows that more than 10ppm of any oxygen-containing compound in the purified raw material can be regarded as saturation of the adsorbent.
The results are shown in Table 2.
TABLE 2
| Adsorbent and process for producing the same | a | A | b | B | c | C | d | D | e | E |
| Dimethyl ether | 6.2 | 3.5 | 7.1 | 4.4 | 6.5 | 2.7 | 6.8 | 3.33 | 7.0 | 4.2 |
| MTBE | 0.9 | 0.5 | 1.1 | 0.7 | 1.0 | 0.4 | 1.0 | 0.49 | 1.1 | 0.66 |
| Methanol | 3.4 | 1.9 | 3.9 | 2.4 | 3.6 | 1.5 | 3.7 | 1.81 | 3.8 | 2.28 |
| Acetone (II) | 0.4 | 0.2 | 0.5 | 0.3 | 0.5 | 0.2 | 0.5 | 0.24 | 0.5 | 0.3 |
| Butyraldehyde | 0.02 | 0.01 | 0.03 | 0.02 | 0.02 | 0.01 | 0.03 | 0.01 | 0.03 | 0.02 |
| Tert-butyl alcohol | 0.05 | 0.03 | 0.06 | 0.03 | 0.05 | 0.02 | 0.05 | 0.02 | 0.05 | 0.03 |
As can be seen from the results in table 2, the adsorbent provided by the present invention has a higher saturated adsorption capacity for oxygen-containing compounds of low polarity and large molecular size, such as dimethyl ether and MTBE, than the comparative adsorbent.
Claims (10)
1. An adsorbent for removing oxygen-containing compounds in low-molecular hydrocarbons is characterized by comprising a Y-type molecular sieve, aluminum oxide and/or silicon oxide and a modifying component, wherein the modifying component comprises one or more of sodium salt, potassium salt, magnesium salt, calcium salt, zirconium salt, molybdenum salt and zinc salt and carbon nano tubes.
2. The adsorbent of claim 1 wherein said low molecular weight hydrocarbon is a C2-C5 olefin or alkane.
3. The adsorbent of claim 2 wherein said C2 to C5 olefin is a mixture of one or more of ethylene, propylene, butene-1, butene-2, isobutylene, pentene, and isoamylene.
4. The adsorbent of claim 1 wherein said oxygenate is one or more of the group consisting of dimethyl ether, methanol, acetone, methyl ethyl ketone, butyl aldehyde, t-butyl alcohol, and MTBE.
5. The adsorbent of claim 1 wherein said Y-type molecular sieve has a grain size with an average diameter of 200 to 1000nm.
6. The adsorbent of claim 1, wherein the Y-type molecular sieve has an average grain diameter of 200 to 700nm.
7. The adsorbent of claim 1, wherein the Y-type molecular sieve has an average grain diameter of 700 to 1000nm.
8. The adsorbent according to claim 1, wherein the adsorbent comprises the following components in percentage by weight based on the total amount of the adsorbent: 25-80 wt% of molecular sieve, 10-70 wt% of alumina and/or silicon oxide and 2-10 wt% of carbon nano tube.
9. The sorbent of claim 1, wherein the alumina is derived from an alumina sol and/or a hydrated alumina.
10. The adsorbent of claim 1 wherein said carbon nanotubes are multi-walled carbon nanotubes.
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