CN115805055B - Adsorbent for removing organic chlorine and preparation method and application thereof - Google Patents
Adsorbent for removing organic chlorine and preparation method and application thereof Download PDFInfo
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- CN115805055B CN115805055B CN202211574414.6A CN202211574414A CN115805055B CN 115805055 B CN115805055 B CN 115805055B CN 202211574414 A CN202211574414 A CN 202211574414A CN 115805055 B CN115805055 B CN 115805055B
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- adsorbent
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- organic chlorine
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 59
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000000460 chlorine Substances 0.000 title claims abstract description 52
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 15
- 150000004706 metal oxides Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000012686 silicon precursor Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 26
- 239000001301 oxygen Substances 0.000 abstract description 26
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 6
- 239000003921 oil Substances 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 230000000382 dechlorinating effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000012286 potassium permanganate Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000004045 organic chlorine compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to an adsorbent for removing organic chlorine, a preparation method and application thereof. The adsorbent utilizes the active composition and rich oxygen vacancy defects generated by the accelerator to form chemical adsorption with chlorine atoms in the organic chloride, so as to realize the removal of chloride impurities. The adsorbent not only realizes high dispersion of active components by virtue of the characteristics of high surface area of the silicon oxide carrier and rich mesoporous channel structure, but also improves the mass transfer efficiency of macromolecular organic chlorine impurities in the adsorbent. The adsorbent provided by the invention can realize the purpose of deeply removing trace organic chlorine in oil products, the removal precision reaches 0.1ppmwt, the service life of the adsorbent is prolonged by 50% compared with the existing industrial adsorbent, and the risk of metal ion loss is avoided.
Description
Technical Field
The invention belongs to the technical field of organic chloride removal, and relates to an adsorbent for removing organic chloride, and a preparation method and application thereof.
Background
Trace chloride impurities in liquid organic raw materials not only can influence the quality of the raw materials, but also can cause corrosion and blockage of process equipment. In order to eliminate the adverse effect caused by the chlorides, industry has been to remove the chlorides by providing a fixed bed adsorption tank and filling the adsorbent. The concentration of chloride in the feed must be tightly controlled to meet process related requirements. If the chloride content in the alkylate is required to be not more than 5ppm, and if the reformate is required to be not more than 0.5ppm. Through analysis of the types of chlorides in the raw materials, the impurities are discovered to contain not only HCl but also organic chlorine such as mono-substituted chloralkane, poly-substituted chloralkane and the like. The existing dechlorination technology has better effect on removing inorganic chlorine in liquid-phase organic raw materials. As disclosed in CN1081936A, an alkali metal promoted activated alumina is disclosed, the adsorbent contains at least 5wt% alkali metal oxide, and the adsorbent has a good removal effect on HCl. Even when the HCl content is only 2-4 ppm, the removal accuracy can be ensured to be less than 1 ppm. But the adsorbent has no removal effect on the organic chlorine. The service life of the existing liquid-phase dechlorinating agent in China is usually not more than 4 months, and only reaches 1/3 of the design value. The root of the method is that the removal effect on the organic chlorine is poor, and the practical service life of the adsorbent cannot be expected. For the removal of organic chlorides, different technical directions are proposed in the prior art.
US8551328B2 discloses a molecular sieve adsorbent, which improves the adsorption effect of the molecular sieve adsorbent on organic chlorine by effectively regulating and controlling the Si/Al ratio of a 13X molecular sieve. When the Si/Al ratio is less than 1.25, the removal effect of the 13X molecular sieve on the organic chlorine is obviously improved.
Chinese patent CN107876016B discloses a low-temperature liquid-phase dechlorinating agent, its preparation method and application. The dechlorinating agent consists of modified activated carbon and sodium acetate or sodium citrate adsorbed on the activated carbon. The adsorbent has the dual functions of converting organic chlorine into inorganic chlorine and absorbing inorganic chlorine. The modifier used for the activated carbon is hydroxide, nitrate and/or carbonate of the element of main group I.
Chinese patent CN109311783a discloses a process for hydrocarbon purification. By contacting the hydrocarbon mixture with a mixed metal oxide adsorbent. The mixed metal oxide is obtained by heat treatment of Layered Double Hydroxides (LDHs). At least one of the first metal or the second metal comprises a transition metal selected from Fe, co, ni, cu and mixtures thereof. The hydrocarbon mixture comprises organochlorine impurities such as polychlorinated benzene, polychlorinated toluene, and mixtures thereof.
Chinese patent CN110841591a discloses a normal temperature organic chlorine dechlorinating agent, preparation method and application. The dechlorinating agent consists of an active component precursor, an adsorbent, a pore-forming agent, a binder and a bonding hydration agent. The active component precursor comprises basic zinc carbonate, the adsorbent comprises active alumina powder, the pore-forming agent comprises sodium bicarbonate, potassium bicarbonate, sodium carbonate or potassium carbonate, the binder comprises pseudo-boehmite, sodium bentonite or sheep's bone, and the binder is sodium hydroxide or potassium hydroxide.
Chinese patent CN111013532a discloses a dechlorinating agent, its preparation method and application. The dechlorinating agent comprises 3.3-6.6wt% of copper oxide and 5-25wt% of potassium permanganate, and the carrier comprises clay and molecular sieve. The manganese atoms in the potassium permanganate contain a large number of empty orbitals, and the chlorine atoms in the organic chlorine have three pairs of lone electrons, so that the adsorption and removal of the organic chlorine are improved. The content of acidic groups and alkaline groups on the surface of the carrier can be changed due to the oxidizing property of the potassium permanganate, so that the chemical property of the surface of the carrier is changed, and the adsorption capacity of the carrier on organic chlorine and hydrogen chloride is improved; on the other hand, the potassium permanganate, the copper oxide and the binder produce synergistic effect, so that the affinity between each component and the carrier is improved, and the loss of each component in the using process is reduced.
Chinese patent CN1302834C discloses a method for dechlorinating an organic chlorine compound. The invention takes the mixture of calcium oxide and ferric oxide or the calcium-iron composite oxide as dechlorinating agent, and the mixture is mixed with hexachlorobenzene which is a representative substance in organic chlorine compounds in a closed container, and the mixture reacts at the temperature of more than 200 ℃ to realize dechlorination of the hexachlorobenzene.
Although the prior art for removing the organic chlorine improves the removal capacity of the organic chlorine, the prior art still has some defects, such as weak binding force to the organic chlorine molecules in a physical adsorption mode, and easy occurrence of a chlorine discharge phenomenon, and the removal effect of the organic chlorine is not obvious by simply improving the specific surface area. Finally, although potassium permanganate can provide a rich empty track to promote chemisorption of organic chlorine, its strong oxidizing property tends to adversely affect the raw materials, particularly in the presence of unsaturated hydrocarbon species, side reactions are more likely to occur, introducing new impurities.
Disclosure of Invention
The invention aims to provide an adsorbent for removing organic chlorine, and a preparation method and application thereof.
The adsorbent provided by the invention forms chemical adsorption on the organic chlorine by utilizing oxygen vacancies formed in the composite metal oxide, thereby realizing the deep removal of the organic chlorine impurities in the liquid-phase organic raw material. The high specific surface and rich mesoporous channels of the carrier are utilized, so that the utilization rate of active components is improved, and the mass transfer efficiency during liquid phase adsorption is optimized. Compared with the prior art, the removal precision of the adsorbent can reach below 0.1ppm, and the service life is prolonged by more than 50%.
So-called oxygen vacancies: that is, oxygen vacancy defects are defects formed by removing oxygen atoms in the synthesized metal oxide crystal lattice by controlling specific synthesis conditions during the preparation of the metal oxide. After oxygen vacancies are formed, the localized lattice defects carry 2 positive charges.
The aim of the invention can be achieved by the following technical scheme:
One of the technical schemes of the invention provides an adsorbent for removing organic chlorine, which comprises a composite metal oxide, an accelerator and a silicon dioxide carrier, wherein the content of the composite metal oxide is 5-20wt%, the content of the accelerator is 0.5-1.5wt% calculated by oxide, and the rest is the silicon dioxide carrier. Specifically, the content of the silica carrier is 78.5-94.5 wt%.
Further, the chemical composition of the composite metal oxide is represented by Zn xTiyOx+2y, and x: y=1 (0.1 to 1.0). That is, in the preparation of the composite metal oxide, the atomic composition of the formed composite metal oxide is made to fall within the above-described range by adjusting the synthesis ratio. As in the preparation, zn is controlled in terms of molar ratio: ti=1: 0.5, the composite oxide prepared is represented by ZnTi 0.5O2.
After the dechlorinating agent is treated in a certain temperature and a reducing atmosphere, part of oxygen in the zinc-titanium composite metal oxide is reduced to form oxygen holes. The formed oxygen hole has stronger positive charge and forms stronger interaction with the outer electron of the halogen element, thereby enriching the organic chlorine molecules around the oxygen hole and further removing the organic chlorine impurities.
Further, the accelerator is an oxide of a rare earth metal element, and may specifically be an oxide of cerium. By utilizing the excellent oxygen storage and release properties of cerium oxide, the active oxygen vacancies in the adsorbent can be further increased.
Further, the silica carrier has mesoporous pore distribution, the specific surface area is 700-1300 m 2/g, the pore volume is 0.7-2.1 cc/g, and the average mesoporous pore diameter is 2-15 nm. Preferably, the specific surface area of the carrier is greater than 850m 2/g, the pore volume is greater than 0.9cc/g, and the average mesoporous pore diameter is 4-10 nm. More preferably, the mesoporous silica is a silica molecular sieve with a regular pore structure, such as SBA-15, MCM-41 and the like. The carrier with the regular pore canal structure can better transfer the mass of the liquid phase of the adsorbent. Compared with microporous materials, mesoporous materials with larger pore sizes are familiar to those skilled in the art, the mesoporous materials have obvious promotion of macromolecular adsorption and catalytic performance, can greatly inhibit carbon deposition and side reactions, and prolong the operation period of the materials.
The second technical scheme of the invention provides a preparation method of the adsorbent for removing the organic chlorine, which comprises the following steps:
(1) The method comprises the steps of (1) dissolving precursors of zinc, titanium and an accelerator in a solvent to obtain a mixed solution A;
(2) Mixing a silicon precursor and a structural auxiliary agent to prepare a mixed solution B;
(3) Regulating the pH values of the mixed solution A and the mixed solution B by adopting an alkaline solution to respectively obtain a precursor precipitation solution A and a precursor precipitation solution B, stirring and mixing the precursor precipitation solution A and the precursor precipitation solution B, aging, and performing airtight hydrothermal crystallization;
(4) Washing, separating, drying and roasting the crystallized product obtained in the step (3), and finally, continuing the reduction treatment under the reducing atmosphere to obtain the target product.
Further, in the step (1), the zinc precursor is one of zinc oxide, zinc acetate, zinc nitrate, zinc chloride and zinc sulfate. Preferably one of zinc oxide and zinc acetate.
Further, in the step (1), the precursor of titanium is one of organic titanate, titanium trichloride and titanyl sulfate. Preferred are organic phthalates such as tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate. Since the hydrolysis rate of the organic titanate is high, the organic titanate is usually mixed with an organic solvent such as ethylene glycol or propanol in advance when the organic titanium salt is used as a precursor, so as to prevent the problem of too high hydrolysis.
Further, in the step (1), the precursor of the accelerator is one of nitrate, acetate or sulfate of the rare earth element. Cerium acetate is preferred.
Further, in terms of molar ratios, si in the silicon precursor: structural auxiliary agent: h 2 o=1: (0.1-0.4) and (50-100).
Further, in the step (2), the silicon precursor is one of ethyl orthosilicate, silica sol and sodium metasilicate. When silica sol is used as a silicon source, the content of silica in the silica sol is 25-28% wt, and the particle size of the silica oligomer is less than 1um. More preferably, the particle size of the silica oligomer is below 600nm.
Further, in the step (2), the structural auxiliary agent is one or a combination of several of a block copolymer and halogenated quaternary ammonium salt, and specifically can be selected from CTMAB, P123, dodecyl trimethyl ammonium chloride and the like. The construction aid is typically dissolved in water to provide a solution of a certain concentration. Generally, the concentration of the aqueous solution is 3 to 12% by weight, and from the viewpoint of cost control, the lower the concentration of the structural aid is, but for the purpose of achieving both the performance, the preferable concentration of the structural aid solution is 5 to 10% by weight, and the more preferable concentration is 6 to 8% by weight.
For mixing the silicon oxide precursor with the structural aid, a more suitable dosing sequence is to put the silicon precursor into the structural aid with vigorous stirring. The temperature is usually kept between 25 and 30 ℃ during feeding. In small experiments, the temperature rise of the solution is usually not significant, whereas in large-scale production it is often necessary to introduce cooling means to maintain a relatively low reaction temperature, typically below 50 ℃, when the precursor is mixed with the construction aid.
Further, in the step (3), the alkaline substance in the alkaline solution is hydroxide, alkali metal carbonate, ammonia water or organic amine, preferably ammonia water and hydroxide, and the number of carbon atoms in the organic amine is 3-12. Specifically, the pH of the mixed solution A and the mixed solution B is adjusted to 10 to 12.
Further, in the step (3), the aging temperature is 20-100 ℃, preferably 50-80 ℃, and the time is 1-24 hours, preferably 3-12 hours, so that the proper aging is more beneficial to the growth of crystal grains and the formation of mesoporous carriers.
Further, in the step (3), the hydrothermal crystallization is performed at a temperature of 100 to 150℃for 12 to 72 hours, preferably 24 to 48 hours, more preferably 24 to 36 hours.
In the step (4), the drying temperature is 100 ℃ and the drying time is 2-5 h.
Further, in the step (4), the baking temperature is 500 to 600 ℃, preferably 550 ℃, and the time is 2 to 4 hours, preferably 4 hours.
And separating, drying and roasting the mixed solution after crystallization to obtain the adsorbent. Wherein the roasting temperature is 550 ℃ and the roasting time is 4 hours, so as to thoroughly remove the structural auxiliary agent. Many separation methods include centrifugation and vacuum separation, and one recommended separation mode is in a spray form, and the separation and drying are integrated, so that the obtained adsorbent has finer particle size distribution and better final adsorption performance. The adsorbent after roasting is powder.
Further, in order to form the dechlorinating agent into a rich oxygen cavity, the calcined sample needs to be treated again in a reducing atmosphere, wherein in the step (4), the reducing atmosphere is a mixed gas of H 2 and N 2 with the concentration of H 2 being 1-5 vol%, and the reducing treatment temperature is 150-450 ℃ for 1-4 hours.
The reduced adsorbent can be tested for oxygen hole content by O 2 -plus. The higher the oxygen pulse frequency the more oxygen holes are formed at the surface. In general, zinc oxide or titanium oxide alone can form oxygen vacancies in a reducing atmosphere, but the requirements for material preparation are relatively high, and finer synthesis conditions are required to obtain oxides grown along specific crystal planes or having specific crystal phase structures to have higher activity. When zinc and titanium are simultaneously introduced, because the composite metal oxide similar to a spinel phase structure can be formed, the synthesis process is more controllable, the large-scale generation is facilitated, the structure is stable, and the performance is more excellent than that of zinc oxide or titanium oxide alone.
In order to meet the industrial application requirements, the adsorbent is usually molded and processed into adsorbents with different properties and different sizes. Such as spherical, bar-shaped, clover-shaped, hollow cylindrical, etc. One recommended specification for the adsorbent after molding is spherical particles with a particle size in the range of 1.6 to 2.5 mm. The formation of the adsorbent is familiar to those skilled in the art and will not be described in detail herein.
The third technical scheme of the invention provides application of the adsorbent for removing the organic chlorine, and the adsorbent is used for removing trace organic chlorine impurities in liquid-phase organic raw materials. Specifically, the liquid phase organic raw material is naphtha, alkylate or reformed oil, etc., and the content of organic chlorine impurity is 2-50 ppm; the removal accuracy of the adsorbent is better than 0.1ppm wt.
Compared with the prior art, the invention has the following advantages:
1) The removal precision is higher, and the service life is prolonged by 50%.
2) Compared with the prior art, the dechlorination mechanism is also obviously different, the formed oxygen vacancy defect is utilized to enable the composite metal oxide and the organic chlorine to form chemical adsorption, the binding force between the adsorbed chloride and the adsorbent is stronger, and the phenomenon of chlorine discharge in the application process is avoided, namely the chlorine content in the raw material is higher than the original chlorine content after passing through the adsorbent.
3) Because the composite metal oxide is highly dispersed on the carrier, not only the utilization of the active composition is greatly improved, but also the loss condition of the active composition is obviously improved.
Drawings
FIG. 1 is a schematic diagram of an adsorbent dynamic evaluation apparatus;
FIGS. 2 and 3 are dynamic chlorine capacity evaluation results of examples and comparative examples, respectively;
FIG. 4 is a graph of X-ray small angle diffraction patterns of examples and example 2;
FIG. 5 shows the oxygen pulse results of example 2.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the examples below, the reagents used were purchased from the sea division company of the national drug reagent group.
The schematic diagram of the adsorbent dynamic evaluation device can be seen in fig. 1, and the whole device comprises a raw material tank 1, a switch valve 2, a liquid phase pump 3, an adsorption bed 4, a back pressure valve 5, a storage tank 6, a sampling valve 7 and a detector 8 which are sequentially connected. And the organic chlorine removal performance is evaluated by taking reformed oil as a raw material, feeding the reformed oil through a microcoulomb method and a liquid phase pump, wherein the loading amount of the adsorbent is 5.0g, the particle size is 20-30 mesh, the feeding flow is 0.5ml/min, the temperature is room temperature, the system pressure is 2.0MPa, the inlet organic chlorine content is 50ppmwt, and the adsorbent is considered to be penetrated and deactivated after the outlet concentration is more than 0.1 ppmwt.
Example 1
I) According to the molar weight of each substance, 0.225mol of zinc oxide, 0.009mol of cerium nitrate and 0.0225mol of titanium trichloride are weighed and mixed with 35mol of water to obtain a mixed solution A;
ii) 1.23mol of tetraethyl orthosilicate, 0.3mol of CTMAB and 30mol of water are weighed and mixed to obtain a solution B;
iii) The solutions A, B were each adjusted to a pH of between 10 and 11 with strong stirring with concentrated aqueous ammonia, followed by mixing of the pH-adjusted A, B precipitate solutions with stirring, and then aging of the resulting white mixture at 20℃for 24h. And finally transferring the solution into a crystallization kettle for crystallization for 24 hours at 150 ℃.
Iv) filtering the crystallized mixed solution, drying for 5h at 110 ℃, roasting for 4h at 550 ℃, and removing the structure auxiliary agent and the precursor to obtain the oxide.
V) samples, labeled SA-1, were pre-treated for 4H at 300℃in a 2% H 2/N2 atmosphere for performance testing.
Example 2
I) Weighing 0.05mol of zinc acetate, 0.003mol of cerium acetate according to the molar amount of each substance, mixing with 30mol of water, and adding a mixed solution of 0.035mol of tetrabutyl titanate and 20mL of ethylene glycol to obtain a mixed solution A;
ii) weighing 1.48mol of sodium metasilicate, mixing 0.59mol of P123 with 35mol of water to obtain a solution B; to dissolve P123 sufficiently, an appropriate amount of hydrochloric acid was added to solution B.
Iii) The solutions A, B were each vigorously stirred with n-butylamine to adjust the pH between 10 and 11, then A, B precipitate solutions with adjusted pH were mixed under stirring, and then the resulting white mixture was aged at 60℃for 5h. And finally transferring the solution into a crystallization kettle for crystallization for 72 hours at the temperature of 100 ℃.
Iv) filtering the crystallized mixed solution, drying for 4h at 110 ℃, roasting for 3h at 550 ℃, and removing the structure auxiliary agent and the precursor to obtain the oxide.
V) samples, labeled SA-2, were pre-treated for 1H at a temperature of 450℃in a 1.5% H 2/N2 atmosphere for performance testing.
Example 3
I) According to the molar weight of each substance, 0.17mol of zinc acetate, 0.007mol of cerium acetate, 0.05mol of titanyl sulfate, 70mol of water and 100ml of glycol are weighed to obtain a mixed solution A;
ii) weighing 1.27mol of sodium metasilicate, mixing 0.15mol of dodecyl trimethyl ammonium chloride with 60mol of water to obtain a solution B;
iii) The solutions A, B were each adjusted to a pH of between 10 and 11 with vigorous stirring at 1.0mol/LNaOH, then A, B precipitate solutions with adjusted pH were mixed under stirring, and the resulting white mixture was aged at 60℃for 24h. And finally transferring the solution into a crystallization kettle for crystallization for 12 hours at the temperature of 100 ℃.
Iv) filtering the crystallized mixed solution, drying for 4h at 110 ℃, roasting for 3h at 550 ℃, and removing the structure auxiliary agent and the precursor to obtain the oxide.
V) samples, labeled SA-3, were pre-treated for 1H at a temperature of 450℃in a 1.5% H 2/N2 atmosphere for performance testing.
Example 4
I) According to the molar weight of each substance, 0.1mol of zinc sulfate, 0.005mol of cerium acetate, 0.05mol of titanyl sulfate, 70mol of water and 100ml of glycol are weighed to obtain a mixed solution A;
ii) weighing 1.36mol of sodium metasilicate, mixing 0.34mol of dodecyl trimethyl ammonium chloride with 60mol of water to obtain a solution B;
iii) The solutions A, B were each adjusted to a pH of between 11 and 12 with vigorous stirring at 1.0mol/LNaOH, followed by mixing of the pH-adjusted A, B precipitate solutions under stirring, and then aging of the resulting white mixture at 60℃for 5h. And finally transferring the solution into a crystallization kettle for crystallization for 12 hours at 150 ℃.
Iv) filtering the crystallized mixed solution, drying for 4h at 110 ℃, roasting for 3h at 550 ℃, and removing the structure auxiliary agent and the precursor to obtain the oxide.
V) the samples, labeled SA-4, were pre-treated for 4H at 150℃in a 5% H 2/N2 atmosphere, for performance testing.
Example 5
I) According to the molar weight of each substance, 0.123mol of zinc acetate, 0.009mol of cerium acetate, 0.123mol of titanium trichloride and 35mol of water are weighed and mixed to obtain a mixed solution A
Ii) 1.23mol of tetraethyl orthosilicate, 0.49mol of CTMAB and 30mol of water are weighed and mixed to obtain a solution B
Iii) The solutions A, B were each adjusted to a pH between 11 and 12 with 25% tetrapropylamine hydroxide under vigorous stirring, then A, B precipitate solutions with adjusted pH were mixed under stirring, and the resulting white mixture was aged at 20℃for 24h. And finally transferring the solution into a crystallization kettle for crystallization for 48 hours at 150 ℃.
Iv) filtering the crystallized mixed solution, drying for 4h at 110 ℃, roasting for 3h at 550 ℃, and removing the structure auxiliary agent and the precursor to obtain the oxide.
V) the samples, labeled SA-5, were pre-treated for 4H at 150℃in a 5% H 2/N2 atmosphere, for performance testing.
Example 6
The oxygen pulse verifies the amount of oxygen vacancies contained in the sample. The pulse program function of the chemical adsorption instrument is adopted, oxygen is used as a probe, pulse oxygen is introduced at a proper temperature, and the oxygen introduction is stopped when the signal value of the residual oxygen is tested each time until the signal value difference of the continuous three pulse oxygen is not more than 1%, so that the oxygen cavity in the sample is evaluated.
The test conditions are that the pulse gas composition is 1%O 2/He, the quantitative ring volume is 0.5mL, the sample loading amount is 0.5g, the detector TCD and the test temperature is 75 ℃.
Comparative example 1
The 13X molecular sieve Si/al=1.15 was used as an adsorbent as comparative example 1, and the capability of removing organic chlorine was measured under the same conditions and is denoted as DB-1.
Comparative example 2
Referring to patent US4047195, MCM-41 pure silicon molecular sieve was prepared as comparative example 2, and the capability of removing organic chlorine was tested under the same conditions and recorded as DB-2.
Comparative example 3
Referring to patent CN 110841591A, example 1, an organic dechlorinating agent was prepared as comparative example 3, and the capability of removing organic chlorine was tested under the same conditions and is noted as DB-3.
Comparative example 4
Referring to patent CN 107876016B, example 1, an organic dechlorinating agent was prepared as comparative example 4, and the capability of removing organic chlorine was tested under the same conditions and is noted as DB-4.
Comparative example 5
The capability of removing organic chlorine was measured under the same conditions using commercially available active zinc oxide as an adsorbent, as comparative example 5, and was designated as DB-5.
TABLE 1 preparation of examples and comparative examples samples and pore Structure data
Examples 7 to 10:
Most of the same as in example 1, except that zinc oxide was replaced with equal molar amounts of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, respectively.
Examples 11 to 13:
the procedure was as in example 1, except that titanium trichloride was replaced with an equimolar amount of tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate, and the organic titanate was previously mixed with an organic solvent such as ethylene glycol and propanol.
Example 14:
Most of the same as in example 1, except that titanium trichloride was replaced with an equimolar amount of titanyl sulfate.
Example 15:
Most of the same as in example 1, except that the silicon precursor ethyl orthosilicate was replaced with a silica sol of equimolar silicon content.
Example 16:
the process was the same as in example 1 except that the aging temperature was adjusted to 100℃and the aging time was adjusted to 1h.
Example 18:
The process was the same as in example 1 except that the aging temperature was adjusted to 50℃and the aging time was adjusted to 18 hours.
Example 19:
The process was the same as in example 1 except that the aging temperature was adjusted to 80℃and the aging time was adjusted to 12 hours.
Example 20:
The procedure was the same as in example 1, except that the temperature of the calcination was adjusted to 500℃and the time was adjusted to 4 hours.
Example 21:
the procedure was the same as in example 1, except that the temperature of the calcination was adjusted to 600℃and the time was adjusted to 2 hours.
Example 22:
Most of the same as in example 1 except that the reducing atmosphere was adjusted to a mixture of H 2 and N 2 having a concentration of H 2% by volume.
Example 23:
Most of the same as in example 1 except that the reducing atmosphere was adjusted to a mixed gas of H 2 and N 2 having a concentration of H 2 of 10 vol%.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (7)
1. The adsorbent for removing the organic chlorine is characterized by comprising a composite metal oxide, an accelerator and a silicon dioxide carrier, wherein the content of the composite metal oxide in the adsorbent is 5-20% by weight, the content of the accelerator is 0.5-1.5% by weight based on the oxide, and the balance is the silicon dioxide carrier;
the chemical composition of the composite metal oxide is represented by Zn xTiyOx+2y, and x: y=1 (0.1 to 1.0);
the accelerator is oxide of rare earth metal element cerium;
The silicon dioxide carrier is provided with mesoporous pore canal distribution, the specific surface area is 700-1300 m 2/g, the pore volume is 0.7-2.1 cc/g, and the average mesoporous pore diameter is 2-15 nm;
the adsorbent is prepared by the following steps:
(1) The method comprises the steps of (1) dissolving precursors of zinc, titanium and an accelerator in a solvent to obtain a mixed solution A;
(2) Mixing a silicon precursor and a structural auxiliary agent to prepare a mixed solution B;
(3) Regulating the pH values of the mixed solution A and the mixed solution B by adopting an alkaline solution to respectively obtain a precursor precipitation solution A and a precursor precipitation solution B, stirring and mixing the precursor precipitation solution A and the precursor precipitation solution B, aging, and performing airtight hydrothermal crystallization;
(4) Washing, separating, drying and roasting the crystallized product obtained in the step (3), and finally, continuing the reduction treatment under the reducing atmosphere to obtain the adsorbent;
the structural auxiliary agent is one or a combination of a plurality of block copolymers and halogenated quaternary ammonium salts;
The temperature of hydrothermal crystallization is 100-150 ℃ and the time is 12-72 h;
The reducing atmosphere is mixed gas of H 2 and N 2 with the concentration of H 2 being 1-5 vol%, the temperature of the reduction treatment is 150-450 ℃, and the time is 1-4H.
2. The method for preparing the adsorbent for removing organic chlorine as claimed in claim 1, wherein the method comprises the following steps:
(1) The method comprises the steps of (1) dissolving precursors of zinc, titanium and an accelerator in a solvent to obtain a mixed solution A;
(2) Mixing a silicon precursor and a structural auxiliary agent to prepare a mixed solution B;
(3) Regulating the pH values of the mixed solution A and the mixed solution B by adopting an alkaline solution to respectively obtain a precursor precipitation solution A and a precursor precipitation solution B, stirring and mixing the precursor precipitation solution A and the precursor precipitation solution B, aging, and performing airtight hydrothermal crystallization;
(4) Washing, separating, drying and roasting the crystallized product obtained in the step (3), and finally, continuing the reduction treatment under the reducing atmosphere to obtain the adsorbent.
3. The method for preparing the adsorbent for removing organic chlorine according to claim 2, wherein in the step (1), the zinc precursor is one of zinc oxide, zinc acetate, zinc nitrate, zinc chloride and zinc sulfate;
The precursor of titanium is one of organic titanate, titanium trichloride and titanyl sulfate;
the precursor of the accelerator is one of nitrate, acetate or sulfate containing rare earth element cerium.
4. The method for preparing an adsorbent for removing organic chlorine according to claim 2, wherein in the step (2), the silicon precursor is one of ethyl orthosilicate, silica sol and sodium metasilicate.
5. The method for preparing the adsorbent for removing organic chlorine according to claim 2, wherein in the step (3), the alkaline substance in the alkaline solution is hydroxide, alkali metal carbonate, ammonia water or organic amine, and the pH of the mixed solution a and the mixed solution B are adjusted to 10-12;
The aging temperature is 20-100 ℃ and the aging time is 1-24 hours.
6. The method for preparing the adsorbent for removing organic chlorine according to claim 2, wherein in the step (4), the drying temperature is 100 ℃ and the time is 2-5 hours;
the roasting temperature is 500-600 ℃ and the roasting time is 2-4 hours.
7. Use of an adsorbent for removal of organochlorine impurities as defined in claim 1, wherein said adsorbent is used for removal of trace organochlorine impurities from liquid phase organic feedstock.
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| CN102343250A (en) * | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Monolene desulphurization adsorbent, preparation method thereof, and application thereof |
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| CN115805055A (en) | 2023-03-17 |
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