CN117582939A - Preparation method and application of purifying adsorbent for oxygen-containing compounds in olefin flow - Google Patents
Preparation method and application of purifying adsorbent for oxygen-containing compounds in olefin flow Download PDFInfo
- Publication number
- CN117582939A CN117582939A CN202311826918.7A CN202311826918A CN117582939A CN 117582939 A CN117582939 A CN 117582939A CN 202311826918 A CN202311826918 A CN 202311826918A CN 117582939 A CN117582939 A CN 117582939A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- adsorbent
- drying
- modified
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 73
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 52
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000001301 oxygen Substances 0.000 title claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 title claims description 24
- 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 116
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002808 molecular sieve Substances 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000001035 drying Methods 0.000 claims abstract description 49
- 238000009495 sugar coating Methods 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 26
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 20
- 238000000746 purification Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 12
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229960000892 attapulgite Drugs 0.000 claims description 9
- 229910052625 palygorskite Inorganic materials 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 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 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 68
- 230000008929 regeneration Effects 0.000 abstract description 23
- 238000011069 regeneration method Methods 0.000 abstract description 23
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000003883 substance clean up Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 36
- 238000005507 spraying Methods 0.000 description 27
- 238000005303 weighing Methods 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000011812 mixed powder Substances 0.000 description 14
- 238000007873 sieving Methods 0.000 description 13
- 238000009736 wetting Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
- -1 ethylene, propylene Chemical group 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 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
- 239000007788 liquid Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 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
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01D53/04—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 with stationary adsorbents
-
- 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
- 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
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3028—Granulating, agglomerating or aggregating
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
-
- 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
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of adsorbent preparation, in particular to a preparation method and application of an oxygen-containing compound purification adsorbent in olefin flow. The preparation method comprises the following steps of (1) firstly adding alumina into alkali metal solution, modifying the alumina, filtering and drying the modified alumina after modification to obtain modified alumina balls; (2) Adding a molecular sieve into a solution containing transition metal ions for ion exchange modification, and filtering, washing and drying after modification to obtain a modified molecular sieve; (3) Adding modified alumina balls into a sugar coating pan, adding the obtained modified molecular sieve, adding a binder and water, and performing ball forming; (4) And drying and activating the formed adsorbent to obtain the finished adsorbent. Compared with the existing adsorbent, the adsorbent has the advantages of simple preparation, high adsorption precision, low adsorption heat, simple regeneration operation, low energy consumption and the like.
Description
Technical Field
The invention relates to the technical field of adsorbent preparation, in particular to a preparation method and application of an oxygen-containing compound purification adsorbent in olefin flow.
Background
The alkene is an important basic material for national economy development, and main sources of the alkene such as ethylene, propylene and the like are naphtha cracking, alkane dehydrogenation, methanol conversion (MTO, MTP) in coal chemical industry and the like. Because of different raw materials and production processes, the prepared olefin has different impurity contents, but trace oxygen-containing compounds, especially the olefin prepared by converting coal chemical methanol, have more oxygen-containing compound types and higher content, the impurities can reach the requirements of polymerized olefin after purification, and along with continuous high-end functionalization of the polymerized material, the polymerized catalyst is continuously promoted to be new, and the higher requirements on the purity of the olefin are provided.
The current method for removing the main stream of the oxygen-containing compound is an adsorption method, and the key of the adsorption method is the selection of an adsorbent. Patent EP0229994 uses a crystalline molecular sieve adsorbent to remove dimethyl ether from C3-C5 olefins, patent US6111162 reports the use of silica gel as the adsorbent to remove oxygenates from a hydrocarbon gas stream, and patent US4371718 uses alumina as the adsorbent to remove methanol from a butene feedstock. CN102744035B adopts ion exchange molecular sieve and then adds binder to prepare solid adsorbent, which is used for removing oxygen-containing compound from olefin, and solves the problems of low adsorption precision, low adsorption capacity and higher adsorption heat in the prior art. CN103495378B uses kaolin as an inert matrix, alumina or an inorganic silicon-aluminum mixture as an adhesive, and a submicron molecular sieve as an active component, and is used for preparing microsphere adsorbents with certain particle size distribution, wherein the content of each component of the oxygen-containing compounds in the olefin flow is less than 1ppm (weight ratio). CN104549140B adopts ion exchange technology, modifies molecular sieve by introducing at least one metal cation in group IA or IIA and adding a small amount of other auxiliary agent, and prepares into particle adsorbent, which is used in adsorption purification industrial production for removing oxygen-containing compound from various olefin raw materials, and has the advantages of large adsorption capacity, good regeneration stability, etc. CN105585405a uses waste catalyst containing SAPO-34 molecular sieve alone or in combination with other adsorbents and method for removing methanol from olefins to reuse the waste. CN109482143a describes the use of rapid-granulation of adsorbents made from molecular sieves, alumina, activity modifiers, etc. for deep removal of various oxygenate impurities from low carbon olefins. CN102921373B describes a process for the preparation of adsorbents for impurities in olefin streams, zeolite molecular sieves are synthesized on activated alumina supports, and metal oxides are loaded onto the adsorbent by ion exchange. The adsorbent is used for removing carbon dioxide, hydrogen sulfide, carbonyl sulfide, methanol, mercaptan and ammonia from olefin streams such as ethylene or propylene. CN108246249a describes a process for removing polar molecules from olefins made of molecular sieves, metal oxides, rare earth oxides and activated alumina. CN103523796B describes a synthesis method and application of submicron X-type molecular sieve. The submicron X-type molecular sieve has small crystal grains, greatly shortens the synthesis time and reduces the production cost. The molecular sieve is applied to hydrocarbon separation and adsorption, and particularly has the technical characteristic of deeply removing the oxygen-containing compound impurities of the olefin in the process of preparing olefin (MTO) from methanol. CN105289477B describes an adsorbent for removing impurities from olefin streams in coal chemical industry and its use, wherein the adsorbent is prepared from modified zeolite molecular sieve, modified mesoporous material and metal component, and can reduce the content of oxygen-containing compounds in olefin streams to ppb level (weight ratio). CN106512926B describes a regenerable microporous-mesoporous composite adsorbent, a preparation method and application thereof, wherein the regenerable microporous-mesoporous composite adsorbent is prepared into an adsorbent with a certain particle size distribution through tabletting, extrusion molding or rolling ball molding. The method has better effect for removing alcohol ether in olefin flow. CN108126664a provides a modified molecular sieve for purifying olefins and a method for removing oxygen-containing impurities from olefins using the same. The modified molecular sieve is modified by using metal organic compounds, and olefin flow containing oxygen-containing impurities such as water, ether aldehyde, copper, alcohol and the like passes through a molecular sieve bed layer modified by the metal organic compounds to obtain high-purity olefin flow.
The prior art mainly faces the problems of large adsorption heat release amount, insufficient adsorption capacity, high regeneration temperature and the like in the adsorption removal of the oxygen-containing compounds in the olefin, and the problems of increasing the adsorption capacity, reducing the adsorption heat, improving the purification precision and reducing the regeneration energy consumption in the prior art are all realized by microscopically changing the pore canal of the adsorbent and the like without changing the preparation structure of the adsorbent in the above part of documents generally by adopting molecular sieve hybridized alumina or modified molecular sieve. In terms of adsorption principle, the adsorption process is divided into a diffusion stage, an adsorption stage and a desorption stage, wherein the diffusion is the first stage, adsorption molecules move from fluid to the surface of an adsorbent, the adsorption is the second stage of the adsorption process, adsorption molecules are adsorbed by the adsorbent, desorption is the third stage of the adsorption process, adsorbed substances are desorbed from the adsorbent, when the adsorbed molecules reach equilibrium when the molecular weight of the adsorbed substances is equivalent to that of desorption, the adsorbed molecules penetrate the adsorbent at the moment, the adsorbent needs to be regenerated and then is subjected to next adsorption, regeneration and adsorption are opposite processes, the stronger adsorption molecules need longer energy consumption and time, the adsorbent which is not deep on the surface or in the pore path is easy to regenerate, the adsorbed heat is easy to remove in time, the adsorbent which is adsorbed deep in the pore path and in the adsorbent is difficult to regenerate, the heat released by adsorption is difficult to diffuse, and the temperature is easy to fly.
Disclosure of Invention
The invention aims to overcome the defects of difficult diffusion of adsorption heat, high regeneration energy consumption, high regeneration temperature and the like in the prior art, and provides a preparation method of an adsorbent for purifying an oxygen-containing compound in an olefin stream.
In order to achieve the above object, the present invention has the following technical scheme:
a process for preparing an oxygenate purification adsorbent in an olefin stream comprising the steps of:
(1) Firstly, adding alumina into an alkali metal solution, modifying the alumina, and filtering and drying the modified alumina after modification to obtain modified alumina balls;
(2) Adding a molecular sieve into a solution containing transition metal ions for ion exchange modification, and filtering, washing and drying after modification to obtain a modified molecular sieve;
(3) Adding the modified alumina balls prepared in the step (1) into a sugar coating pan, then adding the modified molecular sieve obtained in the step (2), and then adding a binder and water to perform rolling ball forming;
(4) And (3) drying and activating the adsorbent molded in the step (3) to obtain the finished adsorbent.
As a preferred embodiment in the present application, the alumina described in step (1) is activated alumina having a specific surface area of > 200m 2 And/g, the particle size is 0.5-2mm, and the particle size can be selected according to the requirement.
As a preferred embodiment of the present application, the alkali metal solution in the step (1) is a solution formed by dissolving a salt or alkali of any one or more of sodium, potassium and calcium in water; the alkali metal salt or alkali is one or more of potassium chloride, sodium chloride, calcium chloride, sodium nitrate, potassium nitrate, calcium nitrate, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. The weight ratio of the alkali metal solution to the activated alumina balls is 1-2, and the mass fraction of the alkali metal contained in the alkali metal solution is 0.5% -10%. And (3) filtering and drying the modified alumina balls, wherein the drying temperature is 80-150 ℃, the drying time is 6-12 h, and the modified activated alumina balls are obtained after drying.
As a preferred embodiment of the present application, the molecular sieve in step (2) is one or more of 13X molecular sieve, naY molecular sieve, USY molecular sieve; the transition metal ion is Ni 2+ Can be one or more of nickel nitrate, nickel chloride and nickel sulfate, and Ni in the solution during molecular sieve ion exchange 2+ The concentration is 0.3-2 mol/L, the liquid-solid ratio of the salt solution and the molecular sieve is 1.5-10, the exchange temperature is 30-80 ℃, and the exchange time is 3-12 h.
As a preferred embodiment in the present application, the binder in step (3) is one or more of pseudo-boehmite, activated clay, kaolin, attapulgite, and alumina cement.
As a preferred embodiment in the present application, the adsorbent in step (3) is molded with a modified alumina content of 15 to 45% by mass, a modified molecular sieve content of 50 to 80% by mass, a binder content of 2 to 10% by mass, and a total mass percentage of 100%.
As a preferred embodiment of the present application, the drying temperature in step (4) is 80 to the upper
The drying time is 4-12 h at 150 ℃.
As a preferred embodiment in the application, the activation in the step (4) adopts a roasting mode, the roasting temperature is 350-500 ℃, and the roasting time is 4-12 h.
It is a further object of the present invention to protect the oxygenate purification adsorbent in an olefin stream obtained by the above method or combination of steps.
Another object of the present invention is the use of a protected oxygenate purification adsorbent for the removal of oxygenates from an olefin stream; the specific application method comprises the following steps: the adsorbent is arranged in a fixed bed adsorber, is adsorbed at low temperature and high pressure, and is desorbed at high temperature and low pressure, wherein the oxygen-containing compound is methanol, propionaldehyde or dimethyl ether, the volume concentration of the oxygen-containing compound is 2-1000 ppm, and the concentration of the oxygen-containing compound after the oxygen-containing compound is removed is less than 1ppm, so that the precision meets the requirements of polymerized olefin.
The adsorbent is contacted with an olefin flow containing an oxide compound, the oxide compound in the adsorbent is adsorbed and removed under the conditions of high pressure and low temperature, the precision of the removed olefin reaches the polymerization grade requirement, and inert gas is adopted to regenerate under the conditions of high temperature and low pressure after adsorption saturation. The regenerated adsorbent can be adsorbed for the next time. Preferred olefin streams are C4 and below olefins, preferred oxygenates are methanol, dimethyl ether, propionaldehyde, the concentration of the oxygenate is from 10 to 1000ppm, and the gas space velocity of the adsorption is from 500 to 3000 hours -1 The space velocity of the liquid phase is 0.5 to 6 hours -1 . The regeneration temperature is 180-250 ℃, and the regeneration airspeed is 500-2000 h -1 。
Compared with the prior art, the invention has the beneficial effects that:
high purification precision
Adopts transition metal nickel ion modified molecular sieve and uses Ni 2+ Partial Na in molecular sieve + Out of the way due to one N i 2+ Can exchange two Na + The active center of the cation is changed, the number of atoms is reduced, and meanwhile, due to Ni 2+ Radius less than Na + The radius of the pore canal is modified, and the pore canal and the pore volume are increased, so that the adsorption capacity and the precision of the adsorbent are improved.
(II) the adsorption is not easy to fly temperature, the regeneration temperature is low, and the energy consumption is low
Alkali metal modified active alumina is used as seed globule, transition metal Ni 2+ The modified molecular sieve powder is taken as a main adsorption component, and is wrapped outside the activated alumina balls, so that the molecular sieve with large adsorption capacity is arranged on the outer layer, the alumina with smaller adsorption capacity is arranged on the inner layer, heat released by adsorption is not easy to gather, and the heat is easy to be carried out along with air flow, and the adsorption is not easy to fly to warm. The alkali metal is used for modifying the activated alumina, so that the acid and alkali properties of the alumina are changed, the adsorption quantity of olefin is further reduced, and the adsorption heat is reduced. Simultaneously, because a large amount of adsorbed impurities are on the surface layer of the adsorbent, the regeneration and desorption are relatively easy, the adsorbent can be regenerated at a relatively low temperature, the energy consumption of desorption is reduced, and the adsorbent can be regenerated at a relatively low temperatureThe carbon deposition of the molecular sieve is reduced, and the service life is prolonged.
The adsorbent is simple to prepare and high in strength
The adsorbent is prepared by adopting rolling ball forming, wherein the step of rolling ball forming is to prepare small ball seeds firstly, then continuously adding powder and rolling the seeds to a proper particle size after the seeds are prepared, and the strength of the seeds directly influences the strength of a finished product.
Detailed Description
All of the features disclosed in this specification, or all of the steps in a method or process disclosed, may be combined in any combination, except for mutually exclusive features and/or steps.
Any feature disclosed in this specification (including any accompanying claims, abstract) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. That is, each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise.
The features and capabilities of the present invention are described in further detail below in connection with examples.
Example 1:
1kg of sodium carbonate is weighed and dissolved in 35kg of deionized water to obtain solution a, 20kg of activated alumina (0.5-1.2 mm) is weighed and poured into the solution a to be immersed for 6 hours at normal temperature, and then the solution is dried for 8 hours at 130 ℃ to obtain modified activated alumina balls. 28.7kg of nickel chloride hexahydrate is weighed and dissolved in 120kg of water to obtain a solution b, 20kg of 13X molecular sieve is weighed, 20kg of NaY molecular sieve is weighed and poured into the solution b, modified dipping is carried out for 6 hours at 60 ℃, then washing and filtering are carried out, and drying is carried out at 110 ℃ for 8 hours to obtain modified molecular sieve powder. Weighing 1.7kg of pseudo-boehmite and 0.8kg of attapulgite, and adding the pseudo-boehmite and the attapulgite into the modified molecular sieve powder for fully and uniformly mixing. Adding activated alumina balls into a sugar coating pan, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pan under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 120 ℃ for 8 hours, and roasting at 400 ℃ for 5 hours to obtain a sample S1.
Example 2:
weighing 0.6kg of sodium hydroxide and 0.6kg of potassium hydroxide, dissolving in 30kg of deionized water to obtain a solution a, weighing 25kg of activated alumina (0.5-1.2 mm), pouring into the solution a, soaking for 8 hours at normal temperature, and then drying for 7 hours at 130 ℃ to obtain modified activated alumina balls. 42.18kg of nickel chloride hexahydrate is weighed and dissolved in 176kg of water to obtain a solution b, 10kg of 13X molecular sieve is weighed, 34kg of NaY molecular sieve is weighed and poured into the solution b, modified dipping is carried out for 8 hours at 50 ℃, then washing and filtering are carried out, and drying is carried out at 130 ℃ for 9 hours to obtain modified molecular sieve powder. Weighing 2.2kg of activated clay, adding into the modified molecular sieve powder, and fully and uniformly mixing. Adding activated alumina balls into a sugar coating pan, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pan under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 120 ℃ for 8 hours, and roasting at 420 ℃ for 4 hours to obtain a sample S2.
Example 3:
1.6kg of sodium hydroxide is weighed and dissolved in 30kg of deionized water to obtain solution a, 25kg of activated alumina (0.5-1.2 mm) is weighed and poured into the solution a to be immersed for 8 hours at normal temperature, and then the solution is dried for 7 hours at 130 ℃ to obtain modified activated alumina balls. 52.2kg of nickel nitrate hexahydrate is weighed and dissolved in 180kg of water to obtain a solution b, 25kg of 13X molecular sieve is weighed, 10kg of NaY molecular sieve and 10kg of USY molecular sieve are weighed and poured into the solution b, modified dipping is carried out for 8 hours at 40 ℃, then washing and filtering are carried out, and drying is carried out at 130 ℃ for 8 hours to obtain modified molecular sieve powder. Weighing 1.8kg of high alumina cement, adding the high alumina cement into the modified molecular sieve powder, and fully and uniformly mixing. Adding activated alumina balls into a sugar coating pan, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pan under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 120 ℃ for 8 hours, and roasting at 430 ℃ for 6 hours to obtain a sample S3.
Example 4:
1.05kg of sodium hydroxide is weighed and dissolved in 35kg of deionized water to obtain solution a, 25kg of activated alumina (0.5-1.5 mm) is weighed and poured into the solution a to be immersed for 8 hours at normal temperature, and then the solution is dried for 8 hours at 130 ℃ to obtain modified activated alumina balls. 25.44kg of nickel nitrate hexahydrate and 20.92kg of nickel chloride hexahydrate are weighed and dissolved in 175kg of water to obtain a solution b, 50kg of 13X molecular sieve is weighed and poured into the solution b, modified dipping is carried out for 6 hours at 50 ℃, then washing and filtering are carried out, and drying is carried out at 130 ℃ for 8 hours to obtain modified molecular sieve powder. Weighing 4.28kg of pseudo-boehmite, adding the pseudo-boehmite into the modified molecular sieve powder, and fully and uniformly mixing. Adding activated alumina balls into a sugar coating pot, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pot under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 120 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain a sample S4.
Comparative example 1:
1.05kg of sodium hydroxide is weighed and dissolved in 35kg of deionized water to obtain solution a, 25kg of activated alumina (0.5-1.5 mm) is weighed and poured into the solution a to be immersed for 8 hours at normal temperature, and then the solution is dried for 8 hours at 130 ℃ to obtain modified activated alumina balls. 50kg of 13X molecular sieve is weighed, 4.28kg of pseudo-boehmite is weighed and fully and uniformly mixed. Adding activated alumina balls into a sugar coating pan, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pan under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 120 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain a sample D1.
Comparative example 2:
25.44kg of nickel nitrate hexahydrate and 20.92kg of nickel chloride hexahydrate are weighed and dissolved in 175kg of water to obtain a solution b, 50kg of 13X molecular sieve is weighed and poured into the solution b, modified dipping is carried out for 6 hours at 50 ℃, then washing and filtering are carried out, and drying is carried out at 130 ℃ for 8 hours to obtain modified molecular sieve powder. Weighing 4.28kg of pseudo-boehmite, adding the pseudo-boehmite into the modified molecular sieve powder, and fully and uniformly mixing. Weighing 25kg of unmodified active alumina balls (0.5-1.5 mm), adding into a sugar coating pot, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pot under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after finishing the adding, taking 2-3mm of balls as a finished product, drying at 120 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain a sample D2.
Comparative example 3:
50kg of 13X molecular sieve is weighed, 4.28kg of pseudo-boehmite is weighed and fully and uniformly mixed. Weighing 25kg of unmodified active alumina balls (0.5-1.5 mm), adding into a sugar coating pan, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pan under the condition of continuously spraying water, rolling the balls for molding, sieving after finishing the molding, taking 2-3mm balls as finished products, drying at 120 ℃ for 8h, and roasting at 450 ℃ for 4h to obtain a sample D3.
Comparative example 4:
75kg of 13X molecular sieve is weighed, 6.42kg of pseudo-boehmite is weighed and fully and uniformly mixed. Then, the mixed powder of the molecular sieve and the binder is slowly added into a sugar coating pan under the condition of continuously spraying water, the ball is formed, screening is carried out after the completion of the addition, the balls with the diameter of 2-3mm are taken as finished products, the products are dried at 120 ℃ for 8 hours, and the products are baked at 450 ℃ for 4 hours, thus obtaining a sample D4.
Example 5:
1.2kg of sodium carbonate and 1.2kg of potassium carbonate are weighed and dissolved in 36kg of deionized water to obtain solution a, 25kg of activated alumina (0.5-1.2 mm) is weighed and poured into the solution a to be immersed for 8 hours at normal temperature, and then the solution is dried for 8 hours at 130 ℃ to obtain modified activated alumina balls. Weighing 52.568kg of nickel sulfate hexahydrate, dissolving in 200kg of water to obtain a solution b, weighing 25kg of NaY molecular sieve and 25kg of USY molecular sieve, pouring into the solution b, modifying and impregnating for 6 hours at 50 ℃, washing and filtering, and drying at 130 ℃ for 8 hours to obtain modified molecular sieve powder. 1.5kg of activated clay and 1.5kg of kaolin are weighed and added into the modified molecular sieve powder to be fully and uniformly mixed. Adding activated alumina balls into a sugar coating pan, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pan under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 120 ℃ for 8 hours, and roasting at 430 ℃ for 6 hours to obtain a sample S5.
Example 6:
weighing 0.72kg of sodium hydroxide and 1.1kg of potassium hydroxide, dissolving in 36kg of deionized water to obtain a solution a, weighing 28kg of activated alumina (0.5-1.2 mm), pouring into the solution a, soaking for 9h at normal temperature, and drying at 140 ℃ for 8h to obtain modified activated alumina balls. Weighing 27.92kg of nickel nitrate hexahydrate and 25.2kg of nickel sulfate hexahydrate, dissolving in 240kg of water to obtain a solution b, weighing 30kg of 13X molecular sieve and 20kg of USY molecular sieve, pouring into the solution b, modifying and impregnating for 10 hours at 50 ℃, washing and filtering, drying at 140 ℃ for 8 hours, and obtaining modified molecular sieve powder. Weighing 4kg of kaolin, adding the kaolin into the modified molecular sieve powder, and fully and uniformly mixing. Adding activated alumina balls into a sugar coating pot, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pot under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 110 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain a sample S6.
Example 7:
weighing 0.8kg of sodium nitrate, 1kg of potassium nitrate and 0.8kg of calcium nitrate, dissolving in 40kg of deionized water to obtain a solution a, weighing 30kg of activated alumina (0.5-1.2 mm), pouring into the solution a, soaking for 8 hours at normal temperature, and drying at 140 ℃ for 8 hours to obtain modified activated alumina balls. 69.79kg of nickel nitrate hexahydrate is weighed and dissolved in 200kg of water to obtain solution b, 50kg of NaY molecular sieve is weighed and poured into the solution b, modified dipping is carried out for 8 hours at 40 ℃, then washing and filtering are carried out, and drying is carried out for 8 hours at 140 ℃, thus obtaining modified molecular sieve powder. Weighing 3kg of kaolin and 3kg of attapulgite, and adding the kaolin and the 3kg of attapulgite into the modified molecular sieve powder for fully and uniformly mixing. Adding activated alumina balls into a sugar coating pot, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pot under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 110 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain a sample S7.
Example 8:
weighing 0.8kg of sodium nitrate and 1kg of potassium hydroxide, dissolving in 40kg of deionized water to obtain a solution a, weighing 25kg of activated alumina (0.5-1.2 mm), pouring into the solution a, soaking for 8 hours at normal temperature, and drying for 8 hours at 140 ℃ to obtain modified activated alumina balls. Weighing 25.17kg of nickel chloride hexahydrate and 13.09kg of nickel nitrate hexahydrate, dissolving in 150kg of water to obtain a solution b, weighing 30kg of 13X molecular sieve, 10kg of NaY molecular sieve and 10kg of USY molecular sieve, pouring into the solution b, modifying and soaking for 8h at 40 ℃, washing and filtering, and drying at 140 ℃ for 8h to obtain modified molecular sieve powder. Weighing 1.5kg of high alumina cement and 2kg of attapulgite, and adding the high alumina cement and the 2kg of attapulgite into the modified molecular sieve powder for fully and uniformly mixing. Adding activated alumina balls into a sugar coating pot, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pot under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 110 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain a sample S8.
Example 9:
1kg of potassium chloride and 2.5kg of sodium hydroxide are weighed and dissolved in 42kg of deionized water to obtain solution a, 25kg of activated alumina (0.5-1.5 mm) is weighed and poured into the solution a to be immersed for 8 hours at normal temperature, and then the solution is dried for 8 hours at 140 ℃ to obtain modified activated alumina balls. 56.08kg of nickel chloride hexahydrate is weighed and dissolved in 165kg of water to obtain a solution b, 40kg of 13X molecular sieve and 15kg of NaY molecular sieve are weighed and poured into the solution b, modified dipping is carried out for 8 hours at 40 ℃, then washing and filtering are carried out, and drying is carried out at 140 ℃ for 8 hours to obtain modified molecular sieve powder. 3.92kg of pseudo-boehmite and 1.65kg of kaolin are weighed and added into the modified molecular sieve powder to be fully and uniformly mixed. Adding activated alumina balls into a sugar coating pot, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pot under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 110 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain a sample S9.
Example 10:
1.35kg of potassium carbonate and 0.9kg of sodium hydroxide are weighed and dissolved in 45kg of deionized water to obtain solution a, 25kg of activated alumina (0.5-1.5 mm) is weighed and poured into the solution a to be immersed for 9 hours at normal temperature, and then the solution is dried for 8 hours at 140 ℃ to obtain modified activated alumina balls. Weighing 57.57kg of nickel nitrate hexahydrate, dissolving in 220kg of water to obtain a solution b, weighing 25kg of 13X molecular sieve and 25kg of NaY molecular sieve, pouring into the solution b, modifying and soaking for 8h at 40 ℃, washing and filtering, and drying at 140 ℃ for 8h to obtain modified molecular sieve powder. 1.5kg of activated clay and 1.5kg of kaolin are weighed, and 1.5kg of attapulgite is added into the modified molecular sieve powder to be fully and uniformly mixed. Adding activated alumina balls into a sugar coating pot, spraying water for wetting, then slowly adding mixed powder of a molecular sieve and a binder into the sugar coating pot under the condition of continuously spraying water, enabling the molecular sieve powder to be wrapped outside the alumina balls, sieving after the adding is finished, taking 2-3mm balls as finished products, drying at 110 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain a sample S10.
Performance test of adsorbents
The samples prepared in the examples and comparative examples were tested for strength using an intelligent particle strength meter, 25 samples each were randomly tested, and the average strength results are shown in table 1 below.
Table 1 results table of strength test
The samples prepared in each of the examples and comparative examples were placed in a fixed bed reactor, and the temperature change during adsorption, the accuracy of removal of the oxygen-containing compound, the adsorption time, and repeated regeneration adsorption were continuously measured. The adsorbent loading was 50g, and the adsorbent gas composition was such that ethylene contained 100ppm of methanol, 100ppm of dimethyl ether, and 100ppm of propionaldehyde. The adsorption temperature is 40 ℃, the adsorption pressure is 0.5MPa, and the adsorption volume space velocity is 3000h -1 Because the dimethyl ether adsorption capacity is relatively small and the penetration time is short, the dimethyl ether penetration time is taken as an adsorption end point, the concentration in tail gas is analyzed on line by adopting gas chromatography, the regeneration temperature is 200 ℃, the regeneration time is 8h, and the nitrogen volume airspeed is 1000h for regeneration -1 . The gas phase ethylene adsorption performance results are shown in Table 2 below.
TABLE 2 adsorption Properties of oxygenates in gaseous ethylene
Several samples are selected for testing the oxidation and removal performance of liquid-phase propylene, wherein the composition of the adsorption liquid is that the propylene contains 100ppm of methanol, 100ppm of dimethyl ether and 100ppm of propionaldehyde, and the content is the mass ratio. Space velocity of adsorbed liquid volume 3h -1 The adsorption pressure is 2.0MPa, the dimethyl ether permeation time is taken as an adsorption end point, the concentration in tail gas is analyzed on line by adopting gas chromatography, the regeneration temperature is 200 ℃, the regeneration time is 8 hours, and the nitrogen volume space velocity is 1000 hours for regeneration -1 . The liquid propylene adsorption performance results are shown in Table 3 below.
TABLE 3 Table of the Properties of the oxygenates in liquid propylene
| Sample numbering | Adsorption maximum temperature rise DEG C | First adsorption time h | Adsorption time h after 5 times of continuous adsorption regeneration |
| S1 | 35 | 100 | 80 |
| S4 | 35 | 101 | 80 |
| D1 | 46 | 92 | 74 |
| D2 | 40 | 96 | 76 |
| D3 | 51 | 88 | 70 |
| D4 | 73 | 120 | 82 |
| S8 | 34 | 101 | 80 |
The sample S4 fixed bed reactor is used for carrying out the service life test of the adsorption performance of the oxygenated compounds in the ethylene, the loading amount of the adsorbent is 50g, and the composition of the adsorption gas is that the ethylene contains 150ppm of methanol, 150ppm of dimethyl ether and 150ppm of propionaldehyde. The adsorption temperature is 40 ℃, the adsorption pressure is 0.5MPa, and the adsorption volume space velocity is 3000h -1 The concentration in the tail gas is analyzed on line by adopting gas chromatography, the regeneration temperature is 200 ℃, the regeneration time is 8 hours, and the volume space velocity of nitrogen is 1000 hours -1 . The adsorption regeneration is carried out for more than 50 times, the adsorption precision of impurities still can meet the requirements of polymerization grade olefin, the adsorption time is not obviously reduced, and the adsorption operation time is shown in the following table 4.
TABLE 4 adsorption time schedule for successive multiple adsorption regenerations
The foregoing examples merely represent specific embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present application, which fall within the protection scope of the present application.
This background section is provided to generally present the context of the present invention and the work of the presently named inventors, to the extent it is described in this background section, as well as the description of the present section as not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present invention.
Claims (10)
1. A process for preparing an oxygenate purification adsorbent in an olefin stream, comprising the steps of:
(1) Firstly, adding alumina into an alkali metal solution, modifying the alumina, and filtering and drying the modified alumina after modification to obtain modified alumina balls;
(2) Adding a molecular sieve into a solution containing transition metal ions for ion exchange modification, and filtering, washing and drying after modification to obtain a modified molecular sieve;
(3) Adding the modified alumina balls prepared in the step (1) into a sugar coating pan, then adding the modified molecular sieve obtained in the step (2), and then adding a binder and water to perform rolling ball forming;
(4) And (3) drying and activating the adsorbent molded in the step (3) to obtain the finished adsorbent.
2. A process for the preparation of an oxygenate purification adsorbent in an olefin stream as claimed in claim 1, wherein: the alumina in the step (1) is active alumina with specific surface area more than 200m 2 And/g, the grain diameter is 0.5-2mm.
3. A process for the preparation of an oxygenate purification adsorbent in an olefin stream as claimed in claim 1, wherein: the alkali metal solution in the step (1) is a solution formed by dissolving any one or more of sodium, potassium and calcium salts or alkali into water; the weight ratio of the alkali metal solution to the activated alumina balls is 1-2, and the mass fraction of the alkali metal contained in the alkali metal solution is 0.5% -10%; the drying temperature is 80-150 ℃ and the drying time is 6-12 h.
4. A process for the preparation of an oxygenate purification adsorbent in an olefin stream as claimed in claim 1, wherein: the molecular sieve in the step (2) is one or a mixture of a 13X molecular sieve, a NaY molecular sieve and a USY molecular sieve; the transition metal ion is Ni 2+ The source is its soluble salts; ni in solution during molecular sieve ion exchange 2+ The concentration is 0.3-2 mol/L, the liquid-solid ratio of the salt solution to the molecular sieve is 1.5-10, the exchange temperature is 30-80 ℃, and the exchange time is 3-12 h; the drying temperature is 80-150 ℃ and the drying time is 4-12 h.
5. A process for the preparation of an oxygenate purification adsorbent in an olefin stream as claimed in claim 1, wherein: the binder in the step (3) is one or more of pseudo-boehmite, activated clay, kaolin, attapulgite and high alumina cement.
6. A process for the preparation of an oxygenate purification adsorbent in an olefin stream as claimed in claim 1, wherein: when the adsorbent in the step (3) is molded, the modified alumina accounts for 15-45% by mass, the modified molecular sieve accounts for 50-80% by mass, the binder accounts for 2-10% by mass, and the sum of the total mass percentages is 100%.
7. A process for the preparation of an oxygenate purification adsorbent in an olefin stream as claimed in claim 1, wherein: the drying temperature in the step (4) is 80-150 ℃ and the drying time is 4-12 h.
8. A process for the preparation of an oxygenate purification adsorbent in an olefin stream as claimed in claim 1, wherein: in the step (4), the activation adopts a roasting mode, the roasting temperature is 350-500 ℃, and the roasting time is 4-12 h.
9. An oxygenate purification adsorbent in an olefin stream obtained according to the process of any one of claims 1-8.
10. Use of an oxygenate purification adsorbent in an olefin stream according to claim 9, characterized in that the adsorbent is used for the removal of oxygenates in an olefin stream; the specific application method comprises the following steps: the adsorbent is arranged in a fixed bed adsorber, is adsorbed at low temperature and high pressure, and is desorbed at high temperature and low pressure, wherein the oxygen-containing compound is methanol, propionaldehyde or dimethyl ether, the volume concentration of the oxygen-containing compound is 2-1000 ppm, and the concentration of the oxygen-containing compound after the oxygen-containing compound is removed is less than 1ppm, so that the precision meets the requirements of polymerized olefin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311826918.7A CN117582939A (en) | 2023-12-28 | 2023-12-28 | Preparation method and application of purifying adsorbent for oxygen-containing compounds in olefin flow |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311826918.7A CN117582939A (en) | 2023-12-28 | 2023-12-28 | Preparation method and application of purifying adsorbent for oxygen-containing compounds in olefin flow |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117582939A true CN117582939A (en) | 2024-02-23 |
Family
ID=89913460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311826918.7A Pending CN117582939A (en) | 2023-12-28 | 2023-12-28 | Preparation method and application of purifying adsorbent for oxygen-containing compounds in olefin flow |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117582939A (en) |
-
2023
- 2023-12-28 CN CN202311826918.7A patent/CN117582939A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101597342B1 (en) | Agglomerated zeolite adsorbent and preparation method thereof | |
| CN100364658C (en) | Adsorption mass and method for removing carbon monoxide from flows of material | |
| US20120190900A1 (en) | Molecular sieve adsorbent blends and uses thereof | |
| JP5268310B2 (en) | Process for producing isobutene by decomposition of methyl-t-butyl ether in the gas phase | |
| CN1267185C (en) | Paraxylene sorbent and its preparing method | |
| US20020068843A1 (en) | Selective hydrogenation catalyst for selectively hydrogenating of unsaturated olefin, process for preparing the same and its use | |
| CN105582885B (en) | The method for preparing adsorbent and its methanol removal using dead catalyst containing molecular sieve | |
| JP2008056674A (en) | METHOD FOR DECOMPOSING ISOBUTENE BY DECOMPOSITION OF METHYL-t-BUTYL ETHER | |
| CN101885656B (en) | Adsorption purification method for hydrocarbon stream | |
| CN111420632B (en) | Composite molecular sieve, desulfurization adsorbent, preparation method and application thereof | |
| CN101472665A (en) | Adsorption composition and method of removing CO from streams | |
| CN109692659B (en) | Binder-free spherical paraxylene adsorbent and preparation method thereof | |
| CN107999118A (en) | A kind of aromatic hydrocarbons and synthesis gas alkylation catalyst and preparation method and application | |
| CN101884905B (en) | Solid adsorbent and preparation method thereof | |
| KR20140144146A (en) | Adsorbent based on a zeolite and a silica-rich clay, and process for purifying hydrocarbon feeds containing unsaturated molecules | |
| CN105732264A (en) | Selective hydrogenation method of trace amount of acetylene in methanol to olefin (MTO) apparatus | |
| CN109692658B (en) | Binder-free spherical 5A molecular sieve adsorbent and preparation method thereof | |
| CN114433172B (en) | Selective hydrogenation catalyst, preparation method and application thereof | |
| CN117582939A (en) | Preparation method and application of purifying adsorbent for oxygen-containing compounds in olefin flow | |
| RU2527573C1 (en) | Catalyst for processing heavy crude oil material and method of its preparation | |
| EP4219001A1 (en) | Adsorbent composition, and preparation method therefor and application thereof | |
| CN102372537A (en) | Method for preparing propylene and aromatic hydrocarbon through methanol conversion | |
| CN107774300B (en) | ZSM-11/SSZ-13 composite structure molecular sieve catalyst, preparation method and application thereof | |
| CN105732263A (en) | Selective hydrogenation method of trace amount of acetylene in methanol to olefin (MTO) apparatus | |
| CN104276924A (en) | Shape-selective disproportionation method of toluene and ethylbenzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |