CN106861614A - 5A adsorbent of molecular sieve containing n-alkane distillate adsorbing separation and preparation method thereof - Google Patents
5A adsorbent of molecular sieve containing n-alkane distillate adsorbing separation and preparation method thereof Download PDFInfo
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- CN106861614A CN106861614A CN201710220852.5A CN201710220852A CN106861614A CN 106861614 A CN106861614 A CN 106861614A CN 201710220852 A CN201710220852 A CN 201710220852A CN 106861614 A CN106861614 A CN 106861614A
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- preparation
- polyquaternium
- adsorbent
- alkane
- distillate
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 61
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003463 adsorbent Substances 0.000 title claims abstract description 48
- 238000000926 separation method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920000289 Polyquaternium Polymers 0.000 claims abstract description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000011324 bead Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000001110 calcium chloride Substances 0.000 claims description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 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 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229920000691 Poly[bis(2-chloroethyl) ether-alt-1,3-bis[3-(dimethylamino)propyl]urea] Polymers 0.000 claims description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 150000001924 cycloalkanes Chemical class 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 241000219782 Sesbania Species 0.000 claims description 4
- 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 claims description 4
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 4
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 229920003086 cellulose ether Polymers 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229920002553 poly(2-methacrylolyloxyethyltrimethylammonium chloride) polymer Polymers 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- KNMXNVMDTOAYBU-UHFFFAOYSA-N tert-butyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C KNMXNVMDTOAYBU-UHFFFAOYSA-N 0.000 claims description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 150000003672 ureas Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 230000008961 swelling Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 35
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 239000002594 sorbent Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000005287 template synthesis Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000003795 desorption Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 6
- -1 amine Salt Chemical class 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 125000000030 D-alanine group Chemical group [H]N([H])[C@](C([H])([H])[H])(C(=O)[*])[H] 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 3
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical class C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- IVOPCIDRGUFTCJ-UHFFFAOYSA-N C(C=C)(=O)N.[Cl-].C(=CC)[NH+](C)C Chemical compound C(C=C)(=O)N.[Cl-].C(=CC)[NH+](C)C IVOPCIDRGUFTCJ-UHFFFAOYSA-N 0.000 description 1
- BNWPKFSOJQJVSQ-UHFFFAOYSA-N C(C=C)(=O)N.[Cl-].C(C)[NH3+] Chemical compound C(C=C)(=O)N.[Cl-].C(C)[NH3+] BNWPKFSOJQJVSQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920000688 Poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- JFXWPUPGEROKLY-UHFFFAOYSA-N [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.CCO[Si](OCC)(OCC)OCC Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.CCO[Si](OCC)(OCC)OCC JFXWPUPGEROKLY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RISSOAQTPCDYBY-UHFFFAOYSA-N azanium;n-methylmethanamine;chloride Chemical compound [NH4+].[Cl-].CNC RISSOAQTPCDYBY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichlorine monoxide Inorganic materials ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KGAWPIXNSIYQPC-UHFFFAOYSA-N ethyl piperidine-2-carboxylate;hydrochloride Chemical compound Cl.CCOC(=O)C1CCCCN1 KGAWPIXNSIYQPC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 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
- B01J20/10—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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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Abstract
The invention discloses 5A adsorbent of molecular sieve containing n-alkane distillate adsorbing separation and preparation method thereof, preparation method is added in the sol system of silicon source and silicon source mixing using polyquaternium as crystallization synthesis soft template, and Hydrothermal Synthesiss have the multi-stage porous 4A molecular sieves of microporous mesoporous structure；By above-mentioned 4A molecular sieves remove after soft template with the bead that binding agent roller forming is 0.2~0.8mm particle diameters, obtain the 5A adsorbent of molecular sieve of microporous mesoporous structure by carrying out calcium ion-exchanged, activation after drying, roasting；The ratio of 5A molecular sieves is 90~97wt% in above-mentioned adsorbent, and the ratio of binding agent is 3~10%.In the sorbent preparation method that the present invention is provided, the multistage pore canal 5A molecular sieves of synthesis significantly improve diffusion coefficient of the n-alkane in molecular sieve, so as to improve the speed of adsorbing separation while keeping having equilibrium adsorption capacity higher to n-alkane.
Description
Technical field
The present invention relates to 5A adsorbent of molecular sieve containing n-alkane distillate adsorbing separation and preparation method thereof, tool
Say body, be to synthesize a kind of 4A molecular sieves of micropore-mesopore hierarchical porous structure, with binding agent roller forming, calcium ion-exchanged system
It is standby to obtain 5A adsorbent of molecular sieve, can be used for the separating-purifying from the distillate containing n-alkane and go out n-alkane.
Background technology
Separating-purifying goes out n-alkane and has great importance from oil refining product cut.Such as in naphtha positive structure
The separation of alkane and other hydro carbons (isoparaffin, cycloalkane and aromatic hydrocarbons) can improve downstream ethene and dress of reforming with optimizing raw material
The benefit put.The nC isolated from kerosene distillate10~nC14N-alkane is the raw material for preparing detergent.From gasoline fraction
Isolating n-alkane can significantly improve the octane number of gasoline.The nC isolated in diesel oil distillate14 +N-alkane can synthesize
The high value added products such as petroleum albumen, chlorinated paraffin, plasticizer and lube oil additive.
Usual oil product boiling range wider range, and boiling point difference is smaller between Isomers, it is difficult to separated with rectificating method
N-alkane.Uop Inc. of the U.S. exploitation Molex liquid phases simulated moving bed technology be used for adsorbing separation oil product in just,
Isohydrocarbon etc..Molex techniques with virgin kerosene as raw material, with moving-bed adsorption by n-alkane and isoparaffin, aromatic hydrocarbons
Separate.N-alkane is adsorbed, and desorbing agent is the mixture of pentane and isooctane, is finally returned from desorption product with rectification method
Desorbing agent is received to recycle.
Use Ca2+The 5A molecular sieves effective aperture for exchanging the acquisition of 4A molecular sieves is about 0.51nm.The minimum of n-alkane molecule
Diameter projected is about 0.49nm, and non-n-alkane is all in more than 0.55nm.The effective aperture of 5A molecular sieves is between n-alkane
Between molecule and minimum projection's diameter of non-n-alkane molecule, therefore, 5A molecular sieves have shape-selective adsorbing separation to n-alkane
Effect.
The 5A molecular sieves of conventional method synthesis only have a micropore canals structure, limited molecular diffusion rate in micropore, compared with
Diffusion path and relatively low activated centre utilization rate long significantly limit absorption/desorption rate so that absorption/de-adsorption cycle
Cycle is more long.Now can be by building the problem that mesoporous method overcomes diffusion to limit from molecular sieve crystal.Generally build and divide
The method of son sieve micropore-mesopore structure includes：Hard template method, soft template method, post processing go silicon to go the methods such as aluminium.Wherein soft template
Agent is easier to evenly spread in whole system, advantageously forms microporous molecular sieve-meso-hole structure.
The content of the invention
The present invention provides 5A adsorbent of molecular sieve containing n-alkane distillate adsorbing separation and preparation method thereof, with poly-
Quaternary ammonium salt is soft template, and the 4A molecular sieves with micropore-mesopore structure are synthesized with hydrothermal crystallizing synthetic method, is then passed through
Roller forming method prepares the multistage pore canal 5A adsorbent of molecular sieve for being remarkably improved n-alkane adsorbing separation speed.
5A molecular sieves synthesized by the present invention have with the mesopore orbit of 2~15nm of aperture and connect based on the micropore of 0.5nm
The general character, N-alkanes primary attachment is in the microchannel of molecular sieve.
The central synthetic steps of multistage pore canal 4A molecular sieves are：Raw material preparation, plastic and ageing, crystallization, washing, stripper plate
Agent is simultaneously activated, ion exchange, activation.
Preferably 0.1~1.0 μm of the grain size of 5A molecular sieves of the present invention, described 5A molecular sieves can be by 4A molecular sieves
In more than 67% Na ions obtained after Ca ion exchanges, now its structure cell composition is Ca4Na4[Al12Si12O48]·20H2O。
The present invention is realized especially by following technical scheme：
A kind of n-alkane adsorbing separation adsorbent that the present invention is provided and preparation method thereof, it is characterised in that：With poly- season
Ammonium salt is added in the sol system that silicon source, silicon source and NaOH mix as crystallization promoting agent synthesis, and hydrothermal crystallizing synthesis has micro-
The multi-stage porous 4A molecular sieves of hole-meso-hole structure；By above-mentioned 4A molecular sieves remove soft template after with binding agent roller forming be 0.2
The bead of~0.8mm particle diameters, the 5A molecules of micropore-mesopore structure are obtained by carrying out calcium ion-exchanged, activation after drying, roasting
Sieve adsorbant；The ratio of 5A molecular sieves is 90~97wt% in above-mentioned adsorbent, and the ratio of binding agent is 3~10%.
In the present invention crystallization synthesis 4A molecular sieves silicon-aluminum sol body in silicon source with SiO2Meter, silicon source is with Al2O3Meter, NaOH
With Na2O is counted, and in terms of PQA, crystallization feed molar proportioning is polyquaternium：Na2O：SiO2：Al2O3：PQA：H2O=1.5~
3.4：1.6~2.4：1：0.005~0.05：75~185.
The polyquaternium surfactant added in synthetic mixture of the present invention includes as crystallization additive synthesis：It is poly- [double
Double [3- (dimethylamino) propyl group] ureas of (2- chloroethyls) ether-alt-1,3-] quaternized (polyquaternium -2), polydiene dimethylamine
Ammonium chloride (polyquaternium -6), dimethyl diallyl ammonium chloride-acrylamide copolymer (polyquaternium -7), chlorination -2-
Hydroxyl -3- (dimethylamino) propyl group PEO cellulose ether (Polyquaternium-10), dimethyl diallyl ammonium chloride-the third
Olefin(e) acid copolymer (Merquat 280), 2- MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides-acrylamide copolymer (polyquaternary amine
Salt -32), N, the homopolymers (polyquaternary amine of N, N- trimethyl -2- [(2- methyl isophthalic acids-oxygen -2- acrylic) epoxide] ethylamine hydrochloride
Salt -37), dimethyl diallyl ammonium chloride-acrylamide and acrylic acid copolymer (polyquaternium -39), N- vinylpyrrolidones
With one or more in quartenized vinyl imidazoles copolymer (polyquaternium -44).
Polyquaternium PQA of the present invention, is the polymer of the degree of polymerization 10~100000, and the degree of polymerization refers to average polymerization
Degree, i.e., contained number of repeat unit purpose average value on polymer macromolecule chain.
Wherein, the polyquaternium -2 is poly- [double (2- chloroethyls) ether-alt-1,3- pairs [3- (dimethylamino) propyl group]
Urea] quaternized solution, molecular formula is (C11H26N4O)n.(C4H8Cl2O) n, n are positive integer；Structural formula is：
Wherein, the polyquaternium -6 is the copolymer of dimethyl diallyl ammonium chloride, and molecular formula is (C8H16ClN) n,
N is positive integer；Structural formula is：
Wherein, the polyquaternium -7 is propenyl dimethyl ammonium chloride-acrylamide solution, and molecular formula is
(C8H16ClN)n.(C3H5NO) m, n and m are positive integer, and structural formula is：
Wherein, the Polyquaternium-10 is chlorination -2- hydroxyls -3- (dimethylamino) propyl group PEO cellulose ether,
Structural formula is：
Wherein, the polyquaternium -11 is poly- [(2- dimethylaminoethyl ethyl sulfuric acid diethylester-co (1- second
Alkenyl -2-Pyrrolidone)], structural formula is：
Wherein, the Merquat 280 is dimethyl diallyl ammonium chloride-acrylic copolymer (C8H16ClN)n.
(C3H5NO) m, n and m are positive integer, and structural formula is：
Wherein, the polyquaternium -32 is 2- MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides-acrylamide copolymer
(C9H18ClNO2)n.(C3H5NO) m, n and m are positive integer, and structural formula is：
Wherein, the polyquaternium -33 be N, N, N- trimethyl -2- (1- oxo -2- acrylic epoxide) ethyl ammonium chloride -
Acrylamide copolymer, (C8H16ClNO2)n.(C3H5NO) m, n and m are positive integer, and structural formula is：
Wherein, the polyquaternium -44 is N- vinylpyrrolidones and quartenized vinyl imidazoles copolymer, (C6H9N2)x.
(C6H9NO)x.(CH3O4S) x, x are positive integer, and structural formula is：
Described silicon source is one kind of white carbon, active silica, sodium metasilicate, silester or methyl silicate.Crystallization
Reaction raw materials mol ratio is：Na2O：SiO2：Al2O3：PQA：H2O=1.5~3.4：1.6~2.4：1：0.005~0.05：75
~185.Wherein, Na2The content of O includes the Na contained in sodium metasilicate2The amount of O.
Described silicon source is aluminium isopropoxide, sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminium chloride, aluminium hydroxide or intends thin water aluminium
One kind of stone.
The 4A molecular sieves of the multistage pore canal that crystallization synthesis of the present invention is obtained, are characterised by that its duct exists<2nm, 2~5nm and 5
~15nm scopes have pore-size distribution, micro pore volume>0.20cm3/ g, mesopore volume>0.35cm3/ g, specific surface area>350m2/g。
Binding agent is in kaolin, bentonite, rectorite, montmorillonite, galapectite in heretofore described adsorbent
One or more.
During the roller forming sesbania powder or carboxymethylcellulose calcium are added in 4A molecular sieves and binder mixtures.
Adsorbent is used for the calcium ion source of ion exchange in calcium chloride, calcium nitrate, calcium bicarbonate, hydrogen sulfate in preparing
In calcium, calcium bromide solution one or more.
In the present invention adsorbing separation pair as if n-alkane distillate, be the C containing n-alkane5~C11Distillate,
C9~C21Distillate, C10~C15Distillate or C10~C23Distillate.
The non-n-alkane contained in the distillate is isoparaffin, cycloalkane and aromatic hydrocarbons.
Micropore-mesopore structure 5A adsorbent of molecular sieve after the activation that the present invention is provided 800 DEG C of loss on ignition for 1.0~
3.0%.
The non-n-alkane contained in the distillate is isoparaffin, cycloalkane and aromatic hydrocarbons.When evaporating containing n-alkane
Oil is divided to be the C containing n-alkane5~C11During distillate, raffinating oil for obtaining can be used as the raw material of catalytic reforming or high-octane rating
Gasoline ready-mixed oil.When the distillate containing n-alkane is the C containing n-alkane9~C21During distillate, the conduct of raffinating oil for obtaining
The raw material or chemical reagent raw material of Ethylene vapor cracking.
Adsorption separation process of the present invention is operated preferably under liquid phase state, is considered from adsorption capacity is increased, low temperature
Being conducive to increasing adsorption capacity, but low temperature is unfavorable for that mass transfer spreads, the operation temperature of adsorbing separation of the present invention is preferably 120~
200℃.To ensure that logistics at the operational is liquid phase, adsorbing separation pressure is preferably 0.5~2.0MPa.
Feed stream must include normal paraffin hydrocarbons and non-straight fatty mixture in the inventive method.The non-straight chain hydrocarbon can
With comprising cyclic compound and/or side chain hydro carbons.Preferably feed stream is purified, such as it is a large amount of to remove with hydrotreating
Sulphur, oxygen, nitrogen or olefin(e) compound.
Typical raw material is mixed for C10~C15 alkanes, the mixture of C9~C21 alkanes or C10~C23 alkanes
Compound and the non-straight fatty mixture of same boiling spread.Due to branched-chain hydrocarbons and alicyclic boiling point with same carbon atom
Several corresponding straight-chain hydrocarbons slightly difference, so while the scope of carbon number is changed slightly, but non-straight catenanes has
Similar boiling point.Aromatic hydrocarbon can also be present.
Adsorption separation process is preferably carried out in multiple adsorbent bed Simulation moving bed devices, and adsorbent is with solid
The form of fixed bed is seated in pillar container, and adsorbent bed can be that multiple adsorption columns are connected, or in an absorption
Multiple beds are divided into by screen cloth or grid inside post, liquid stream circulates between adsorbent bed from top to bottom.Into or
Leave adsorbent bed several logistics and adsorbent is at least divided into absorption, purification, three regions of desorption, preferably move simulation
Bed it is adsorbent bed be divided into absorption, purification, be desorbed and isolate four areas carry out adsorbing separation operation.
N-alkane in raw material experiences absorption, purification, desorption process respectively in different regions.Into adsorption chamber
Region referred to as adsorption zone between raw material and the suction extraction raffinate for leaving adsorption chamber, the raw material containing n-alkane is from the upstream of adsorption zone
Into adsorption chamber, contacted with adsorbent, the n-alkane in raw material is adsorbed into the geode of zeolite, form absorption phase, it is former
Adsorbed isoparaffin, cycloalkane, aromatic hydrocarbons do not flow out adsorption chamber shape with partial detachment agent from the downstream of adsorption zone in material
Into suction extraction raffinate；Leave the Extract of adsorption chamber and into the region referred to as purification section between the raw material of adsorption chamber, the Qu Zishang
Under logistics the non-n-alkane outside adsorbent micropore is flushed to downstream, the area upstream rich in n-alkane in raw material,
And the Extract containing desorbing agent leaves adsorption chamber.Into adsorption chamber desorbing agent and leave adsorption chamber Extract between
Region is referred to as being desorbed area, and desorbing agent enters from the area upstream, and the n-alkane in adsorbent micropore is cemented out makes adsorbent
Reuse.There can also be isolated area in desorbing agent and between inhaling extraction raffinate, the purpose in the area is to prevent anon-normal in adsorption zone
Structure alkane enters desorption zone and pollutes Extract.
Adsorbent is maintained static, each adsorption column or it is adsorbent bed be connected to a few logistic pipeline, be used to convey
Into or leave several logistics of adsorption separation device, this several logistics of periodic variation from top to bottom enter or leave absorption
The position of agent bed, you can reach downward liquid flow in adsorbent, the liquid-solid two-phase of adsorbent relative upward movement is relatively inverse
The effect of flow field simulation movement.The Extract and suction extraction raffinate for leaving adsorption chamber respectively enter fractionating column and isolate n-alkane and anon-normal
Structure alkane, and recycled desorbing agent.
Compared with micropore 5A adsorbent of molecular sieve, n-alkane is in adsorbent for multi-stage porous 5A adsorbent of molecular sieve of the invention
On reach adsorption equilibrium time it is shorter.The multistage pore canal 5A molecular sieves of micropore-mesopore interconnection can be inhaled with balance higher
While attached amount, the rate of adsorption of N-alkanes molecule is significantly improved, therefore n-alkane adsorption separation efficiency can be improved.
Brief description of the drawings
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
Fig. 1：Moving-bed adsorption piece-rate system schematic diagram
Fig. 2：Rotary valve type Simulation moving bed schematic flow sheet
Specific embodiment
Embodiment of the present invention and produced effect, but guarantor of the invention are further illustrated by embodiment and comparative example
Shield scope is not limited to the content listed by embodiment.
Embodiment 1
By the following raw material mol ratio：
nNa2O∶nSiO2∶nAl2O3∶nPQA∶nH2O=3: 2: 1: 0.010: 150
Weigh polyquaternium, silicon source solution, NaOH, silicon source solution and deionized water uniformly to mix, specific synthesis step is such as
Under：
1) a certain amount of polyquaternium solution is weighed according to proportioning, is dissolved in 100ml water, add sodium silicate solution and
NaOH stirring and dissolvings are used as silicon source.Sodium metaaluminate is dissolved in 50ml water as silicon source.Silicon source solution is added dropwise at 40 DEG C
To in silicon source solution, still aging 2h after 10min is stirred vigorously.By silicon-aluminum mixture move into crystallizing kettle in 99 ± 1 DEG C of crystallization
4h, natural cooling.Product suction filtration after crystallization is obtained into molecular sieve crystal, 3 times is washed with ethanol and is washed with deionized water to pH=7
~8.12h is dried at 120 DEG C, multi-stage porous 4A molecular sieves are obtained.
2) 4A molecular screen primary powders, kaolin and sesbania powder are pressed 92：7：1 mass ratio is well mixed to be made mixed powder,
It is put into coating pan rotating disk and sprays into appropriate deionized water when rolling, is rolled onto the bead of a diameter of 0.2~0.8mm, spin
When the water that sprays into be the 12wt% of solid powder.Shaping bead is dried into 8h at 80 DEG C, is warmed up to the speed of 2 DEG C/min
550 DEG C of roasting 4h.
3) at 60 DEG C, above-mentioned molecular sieve crystal is pressed into solid-to-liquid ratio 1：10 in 0.5mol/L CaCl295 DEG C of autoclaves in solution
Ion exchange twice, 2 hours every time, filtering and washing to neutrality, 105 DEG C of dryings 24 hours.450 DEG C of activation 3h, obtain multi-stage porous
5A molecular sieve spherical adsorbents, are designated as A.
Embodiment 2~18
The spherical sorbent preparation method step of multi-stage porous 5A molecular sieves is same as Example 1, the difference is that component in raw material
Mol ratio, polyquaternium, silicon source it is different with silicon source and the calcium salt species of exchange, specifically as shown in Tables 1 and 2.
Table 1
Table 2
| Embodiment is numbered | Adsorbent title | Silicon source species | Silicon source species | Polyquaternium species | Ionic calcium soln |
| Embodiment 1 | A | Waterglass | Sodium aluminate | Polyquaternium -2 | Calcium chloride |
| Embodiment 2 | B | White carbon | Aluminium chloride | Polyquaternium -6 | Calcium chloride |
| Embodiment 3 | C | Ludox | Sodium aluminate | Polyquaternium -7 | Calcium chloride |
| Embodiment 4 | D | Methyl silicate | Aluminum nitrate | Polyquaternium-10 | Calcium chloride |
| Embodiment 5 | E | Waterglass | Aluminum sulfate | Merquat 280 | Calcium chloride |
| Embodiment 6 | F | Ludox | Aluminium isopropoxide | Polyquaternium -32 | Calcium chloride |
| Embodiment 7 | G | White carbon | Sodium aluminate | Polyquaternium -37 | Calcium nitrate |
| Embodiment 8 | H | Ludox | Aluminium chloride | Polyquaternium -39 | Calcium nitrate |
| Embodiment 9 | I | White carbon | Boehmite | Polyquaternium -44 | Calcium nitrate |
| Embodiment 10 | J | Tetraethyl orthosilicate | Aluminum nitrate | Polyquaternium -2 | Calcium nitrate |
| Embodiment 11 | K | Methyl silicate | Aluminum sulfate | Polyquaternium -6 | Calcium nitrate |
| Embodiment 12 | L | Waterglass | Aluminium isopropoxide | Polyquaternium -7 | Calcium nitrate |
| Embodiment 13 | M | Ludox | Sodium aluminate | Polyquaternium-10 | Calcium bicarbonate |
| Embodiment 14 | N | White carbon | Aluminium chloride | Merquat 280 | Calcium bisulfate |
| Embodiment 15 | O | Ludox | Boehmite | Polyquaternium -32 | Calcium bromide |
| Embodiment 16 | P | White carbon | Aluminum nitrate | Polyquaternium -37 | Calcium bicarbonate |
| Embodiment 17 | Q | Tetraethyl orthosilicate | Aluminum sulfate | Polyquaternium -39 | Calcium bisulfate |
| Embodiment 18 | R | Methyl silicate | Aluminium isopropoxide | Polyquaternium -44 | Calcium bromide |
Embodiment 19
Micromeritics ASAP2020 type nitrogen things are used to 5A sample of sorbent prepared in embodiment 1~18
Reason adsorption instrument carries out phenetic analysis.The preprocess method of sample is as follows before analysis：Sieve sample is vacuumized at normal temperatures
Treatment, after vacuum condition is reached, 2h is processed at 130 DEG C；Afterwards 2h is processed at 350 DEG C.Nitrogen physisorption result shows, sample
The micropore size of product 1~20 is 0.3~0.5nm, contains mesoporous pore size distribution, mesoporous average pore size, mesopore volume and specific surface
Product is as shown in table 3.
Table 3
Comparative example 1
Take 90 grams of NaA molecular sieves original powder (Tianjin Nan Hua catalyst Co., Ltd), (Chinese kaolin has 9.5 grams of kaolin
Limit company produces) and 0.5g sesbania powders, it is put into rotating disk and sprays into appropriate deionized water in rolling, it is attached in order to solid powder
The bead that particle diameter is 0.3~0.8mm is polymerized to, the water sprayed into during spin is the 12wt% of solid powder.The shaping that will be obtained is small
Ball is calcined 4 hours at 540 DEG C.With 0.1mol/L calcium chloride solutions in 80 DEG C, volume space velocity 2.0 hours-1Under conditions of carry out post
Formula ion exchange 2 hours, then dried 24 hours in 200 DEG C, nitrogen stream, adsorbent is obtained, it is designated as VS-1.
Comparative example 2
Conventional NaA molecular sieve is prepared by the method for CN1087030A.
With sodium aluminate (Na2O·Al2O33H2O) with sodium metasilicate (Na2SiO3·5H2O) and sodium hydroxide solution for original
Material, by 3.165Na2O：Al2O3：1.926SiO2：128H2O mol ratios prepare synthesized gel rubber as follows：
(1) 82.58g sodium aluminates are taken to be added in the NaOH solution that 400ml concentration is 0.22mol/L, 30min is stirred at room temperature
Obtain settled solution；
(2) 154.80g sodium metasilicates are taken to be added in the NaOH solution that 400ml concentration is 0.22mol/L, is stirred at room temperature
30min obtains settled solution；
(3) solution obtained in (2) step is quickly poured into solution obtained in (1) step, stirring is until the life of thick shape homogeneous gel
Into；
(4) gel obtained in (3) is placed in hydrothermal crystallizing kettle into the crystallization cooling in 4 hours at 99 ± 1 DEG C to reclaim, is spent
PH is arrived in ion washing<9, obtain 2~3 μm of 4A molecular sieves of uniform cubic grain；
(5) above-mentioned 4A molecular sieves are carried out into ion exchange with 1.0mol/L calcium chloride solutions in 80 DEG C and obtains 5A molecules in 6 hours
Sieve, ground again, compression molding is designated as VS-2 as adsorbent after 120 DEG C of dryings.
Comparative example 3
1.0g APGs are added into 140m1 sodium aluminate solutions (Na2O：90g/L, Al2O3：60g/L) it is sufficiently stirred for, then presses
Al2O3/SiO2=1.8 amount adds sodium silicate solution (Na2O concentration is 45g/L, SiO2Concentration is 120g/L), use NaOH
Solution regulation material pH value is strong stirring 10 minutes after 10, obtains colloid.Above-mentioned colloid is loaded into crystallization device, 75 are warming up to
DEG C, static crystallization 30 minutes.Filtering, it is 8,200 DEG C of dryings 5 hours that gained solid is washed with water to cleaning solution pH value, obtains crystalline substance
Grain size is 1.2~2.0 μm of NaA molecular sieve.
NaA molecular sieve powder and kaolin are pressed 92：8 mass ratio is well mixed, and is put into rotating disk and is sprayed into when rolling
Appropriate deionized water, the bead that particle diameter is 0.3~0.8mm is agglomerated into order to solid powder, and the water sprayed into during spin is
The 12wt% of solid powder.
Above-mentioned bead is dried into 8h in 80 DEG C, 550 DEG C of roasting 4h, then with the NaOH aqueous solution that 100L concentration is 1.5mol/L
1h is soaked at 95 DEG C, makes kaolin in-situ crystallization, be then washed with deionized to washing lotion pH and be dried to obtain less than 10,100 DEG C
Turn the NaA beads after crystalline substance.
50L is turned into the NaA beads after crystalline substance, the CaC1 that 200L concentration is 1.0mol/L is immersed in2Enter in 95 DEG C in the aqueous solution
Row Ca2+4h is exchanged, is then washed with deionized, 100 DEG C dry 4h, 450 DEG C of activation 3h, obtain the spherical absorption of 5A molecular sieves
Agent, is designated as VS-3.
Embodiment 20~26
Moving-bed adsorption separation system as shown in Figure 1, naphtha cut is input to suction as charging by rotary valve
Attached bed, target product after adsorbing purification process, to be parsed with strippant and be input to Extract after obtaining Extract
Rectifying removes strippant in separator, obtains the n-alkane of high-purity；And the suction extraction raffinate obtained from adsorption bed is transported to suction
In extraction raffinate separator, carry out obtaining non-n-alkane component after rectifying removes strippant.As shown in Fig. 2 moving-bed adsorption
Separator main body is made up of 12 splitters (30mm × 800mm) and 1 rotary valve.12 each posts of splitter are connected in series,
Adsorbent 5A adsorbent of molecular sieve is loaded respectively, and raw material, desorbing agent import and desorption product, the remaining product exit of suction are by rotary valve
Allotment.12 posts are divided into four areas：Adsorption zone (I areas), purification section (II areas), desorption area (III areas) and isolated area (IV areas).Point
Use PID temperature controls from post and pipe temperature, rotary valve by Three-phase Induction Motor Control, by setting switching time, periodically
Change material import and export position, to realize the relative reverse flow of mobile phase and fixing phase, realize being continuously separated between component.
12 adsorption columns are built-in fill out embodiment in the 5A molecular sieve spheroidal adsorbents that prepare of method, absorption raw material is nC10
~nC15 stone brain distillates, desorbing agent makees desorption agent composition for the mixture of 60%n-C5 and 40%i-C8.4 posts of adsorption zone
Son, the pillar of purification section 3, desorption 4, area pillar, 1 pillar of isolated area.
170 DEG C of temperature, pressure 1.0MPa, feedstock flow (F)=712mL/h, desorption agent flux (D)=
2699mL/h, internal circulating load (Q)=8034mL/h, extraction flow quantity (E)=1671mL/h, suction extraction raffinate flow (R)=1740mL/h,
Stepping time carries out adsorbing separation under conditions of 90 seconds.Chromatography is calculated total n-alkane (n-C10~n- in Extract
C15 purity (deduction desorbing agent) and total n-alkane yield data) is as shown in table 4.
Comparative example 4~6
Tested with Small-Scale Simulated Moving Bed by the method for example 5, the difference is that in filling comparative example 1~3 used
The 5A adsorbents of preparation, 170 DEG C of temperature, pressure 1.0MPa, feedstock flow (F)=712mL/h, desorption agent flux (D)=
2719mL/h, internal circulating load (Q)=8346mL/h, extraction flow quantity (E)=1434mL/h, suction extraction raffinate flow (R)=1997mL/h,
Stepping time carries out adsorbing separation under conditions of 90 seconds.Chromatography is calculated total n-alkane (n-C10~n- in Extract
C15 purity (deduction desorbing agent)) and total n-alkane yield data are as shown in table 5~7.
Table 4
Table 5
Table 6
Table 7
The adsorbing separation result that consolidated statement 4~7 is obtained, to containing C10~C15 naphtha Cut raw materials, using embodiment 1
Adsorbent A~the H prepared in~7 well can separate n-alkane with non-n-alkane on Small-Scale Simulated Moving Bed, point
Total n-alkane product (nC10~nC15) purity for separating out>98.3%, yield>98.0%.And it is prepared in comparative example 1~3
Total n-alkane product purity for obtaining of adsorbent VS-1~VS-3 adsorbing separations<87%, yield<96%.This illustrates this hair
Multi-stage porous 5A adsorbent of molecular sieve prepared by bright method has outstanding effect for the adsorbing separation purification of n-alkane.
The embodiment only technology design and feature to illustrate the invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (13)
1. the preparation method of the 5A adsorbent of molecular sieve containing n-alkane distillate adsorbing separation, it is characterised in that：With poly- season
Ammonium surfactant is added in the sol system that silicon source, silicon source and NaOH mix as soft template, hydrothermal crystallizing synthesis
Multi-stage porous 4A molecular sieves with micropore-mesopore structure；By above-mentioned 4A molecular sieves remove soft template after with binding agent spin into
Type is the bead of 0.2~0.8mm particle diameters, and micropore-mesopore structure is obtained by carrying out calcium ion-exchanged, activation after drying, roasting
5A adsorbent of molecular sieve；The content of binding agent is 3~10wt% in the 5A adsorbent of molecular sieve.
2. preparation method according to claim 1, it is characterised in that：Silicon source is with SiO in silicon-aluminum sol body2Meter, silicon source with
Al2O3Meter, NaOH is with Na2O is counted, and in terms of PQA, crystallization feed molar proportioning is polyquaternium：Na2O：SiO2：Al2O3：
PQA：H2O=1.5~3.4：1.6~2.4：1：0.005~0.05：75~185.
3. preparation method according to claim 1, it is characterised in that：Polyquaternium surfactant, it is characterised in that bag
Include poly- [double [3- (dimethylamino) propyl group] ureas of double (2- chloroethyls) ether-alt-1,3-] quaternized (polyquaternium -2), polydiene
Diallyidimethylammonium chloride (polyquaternium -6), dimethyl diallyl ammonium chloride-acrylamide copolymer (polyquaternium -7),
Chlorination -2- hydroxyls -3- (dimethylamino) propyl group PEO cellulose ether (Polyquaternium-10), dimethyl diallyl chlorine
Change ammonium-acrylic copolymer (Merquat 280), 2- MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides-acrylamide copolymer
(polyquaternium -32), N, the homopolymers of N, N- trimethyl -2- [(2- methyl isophthalic acids-oxygen -2- acrylic) epoxide] ethylamine hydrochloride
(polyquaternium -37), dimethyl diallyl ammonium chloride-acrylamide and acrylic acid copolymer (polyquaternium -39), N- ethene
One or more in pyrrolidones and quartenized vinyl imidazoles copolymer (polyquaternium -44).
4. preparation method according to claim 1, it is characterised in that：Silicon source is white carbon, active silica, silicic acid
One kind of sodium, silester or methyl silicate.
5. preparation method according to claim 1, it is characterised in that：Silicon source be aluminium isopropoxide, sodium metaaluminate, aluminum nitrate,
One kind of aluminum sulfate, aluminium chloride, aluminium hydroxide or boehmite.
6. preparation method according to claim 1, it is characterised in that：The 4A molecular sieves of multistage pore canal, its duct exists<2nm、
2~5nm and 5~15nm scopes have pore-size distribution, micro pore volume>0.20cm3/ g, mesopore volume>0.35cm3/ g, specific surface area
>350m2/g。
7. preparation method according to claim 1, it is characterised in that：Binding agent derives from kaolin, swelling in adsorbent
In soil, rectorite, montmorillonite, galapectite one or more.
8. preparation method according to claim 1, it is characterised in that：4A molecular sieves and binding agent are mixed during roller forming
Sesbania powder or carboxymethylcellulose calcium are added in compound.
9. preparation method according to claim 1, it is characterised in that：Calcium ion source is in calcium chloride, calcium nitrate, bicarbonate
In calcium, calcium bisulfate, calcium bromide solution one or more.
10. preparation method according to claim 1, it is characterised in that the distillate containing n-alkane is containing N-alkanes
The C of hydrocarbon5~C11Distillate, C9~C21Distillate, C10~C15Distillate or C10~C23Distillate.
11. preparation methods according to claim 10, it is characterised in that the non-n-alkane contained in the distillate is
Isoparaffin, cycloalkane and aromatic hydrocarbons.
12. preparation methods according to claim 1, it is characterised in that the micropore-mesopore structure 5A molecular sieves after activation are inhaled
Attached dose is 1.0~3.0% in 800 DEG C of loss on ignition.
The 5A adsorbent of molecular sieve that 13. preparation method as described in claim 1~12 any one is obtained, with the micro- of 0.5nm
Based on hole, there is connectedness with the mesopore orbit of 2~15nm of aperture.
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