CN1702157A - Method for refining catalytic liquefied petroleum gas - Google Patents
Method for refining catalytic liquefied petroleum gas Download PDFInfo
- Publication number
- CN1702157A CN1702157A CN200510072353.3A CN200510072353A CN1702157A CN 1702157 A CN1702157 A CN 1702157A CN 200510072353 A CN200510072353 A CN 200510072353A CN 1702157 A CN1702157 A CN 1702157A
- Authority
- CN
- China
- Prior art keywords
- liquefied petroleum
- petroleum gas
- catalyst
- catalytic liquefied
- catalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003915 liquefied petroleum gas Substances 0.000 title claims abstract description 243
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 240
- 238000000034 method Methods 0.000 title claims abstract description 94
- 238000007670 refining Methods 0.000 title claims abstract description 32
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims abstract description 218
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 112
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 96
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 92
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 90
- 239000001301 oxygen Substances 0.000 claims abstract description 90
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 84
- 230000007062 hydrolysis Effects 0.000 claims abstract description 83
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 68
- 230000008569 process Effects 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 330
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 114
- 239000000047 product Substances 0.000 claims description 107
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 100
- 239000011656 manganese carbonate Substances 0.000 claims description 74
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 74
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 72
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 70
- 235000006748 manganese carbonate Nutrition 0.000 claims description 68
- 229940093474 manganese carbonate Drugs 0.000 claims description 65
- 230000003009 desulfurizing effect Effects 0.000 claims description 63
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 39
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 37
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 34
- 229910052717 sulfur Inorganic materials 0.000 claims description 34
- 239000011593 sulfur Substances 0.000 claims description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 31
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims description 30
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 24
- 239000000292 calcium oxide Substances 0.000 claims description 22
- 238000011049 filling Methods 0.000 claims description 22
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 229910052925 anhydrite Inorganic materials 0.000 claims description 18
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 18
- 150000002697 manganese compounds Chemical class 0.000 claims description 18
- 230000009471 action Effects 0.000 claims description 15
- -1 alcohol amine Chemical class 0.000 claims description 14
- 239000013589 supplement Substances 0.000 claims description 13
- 229910000859 α-Fe Inorganic materials 0.000 claims description 12
- 230000003301 hydrolyzing effect Effects 0.000 claims description 11
- 238000005194 fractionation Methods 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 150000004687 hexahydrates Chemical class 0.000 claims description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 44
- 230000000694 effects Effects 0.000 abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009466 transformation Effects 0.000 abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012190 activator Substances 0.000 abstract 4
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 abstract 1
- 229940099349 liquefied petroleum gas Drugs 0.000 description 191
- 238000004519 manufacturing process Methods 0.000 description 111
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 91
- 239000000920 calcium hydroxide Substances 0.000 description 91
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 91
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 30
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 30
- 235000011130 ammonium sulphate Nutrition 0.000 description 30
- 229910052602 gypsum Inorganic materials 0.000 description 28
- 238000002156 mixing Methods 0.000 description 27
- 239000003513 alkali Substances 0.000 description 26
- 229910002588 FeOOH Inorganic materials 0.000 description 23
- 239000007788 liquid Substances 0.000 description 20
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 16
- 238000004898 kneading Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 12
- 238000009740 moulding (composite fabrication) Methods 0.000 description 12
- BVJRIMBTLVPCFB-UHFFFAOYSA-N [Fe+2].[O-2].[Ca+2].[O-2] Chemical compound [Fe+2].[O-2].[Ca+2].[O-2] BVJRIMBTLVPCFB-UHFFFAOYSA-N 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- 230000001706 oxygenating effect Effects 0.000 description 9
- 238000010099 solid forming Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 230000001502 supplementing effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 8
- 230000023556 desulfurization Effects 0.000 description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 150000003573 thiols Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 206010021143 Hypoxia Diseases 0.000 description 4
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 4
- 238000004332 deodorization Methods 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- KANHTMXMAWADED-UHFFFAOYSA-N 3-methylthietan-2-one Chemical compound CC1CSC1=O KANHTMXMAWADED-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000010811 mineral waste Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a method for refining catalytic liquefied petroleum gas, in which catalyzed liquefied petroleum gas by alconol-amine method removing hydrogen sulfide process is operated by hydrolysis carbonyl sulfur process by passing through carbonyl sulfur hydrolysis activator bed layer, such that carbonyl sulfur hydrolysis generates sulfureted hydrogen and carbon dioxide; then it passes through the desulfurizer bed layer to operate hydrogen sulfide removing process, the preparation of reaction of the hydrogen sulfide and the desulfurizer is chemically absorbed on the desulfurizer; at last, liquid oxygen supplying agent having effective component of tert-butyl hydroperoxide is applied into the catalyzed liquefied petroleum gas, then it is processed by transformation mercaptan by passing through the double effects activator bed layer, under the effect of the double effects activator, the tert-butyl hydroperoxide is hydrogen peroxide decomposed to release fresh state oxygen, and the mercaptan is oxygenated to bisulfide; the activate component of the double effects activator is compound of manganic.
Description
Technical Field
The invention belongs to the field of refining processing of liquefied petroleum gas, and particularly relates to a method for removing organic sulfur compounds in catalytic liquefied petroleum gas.
Background
In refining sulfur-containing petroleum, liquefied petroleum gas obtained by catalytic cracking (hereinafter referred to as catalytic liquefied petroleum gas) contains sulfur compounds such as hydrogen sulfide, carbonyl sulfide and mercaptan, and thus it is necessary to remove the catalytic liquefied petroleum gas and refine the converted sulfur compounds. When the catalytic liquefied petroleum gas is refined, firstly, hydrogen sulfide in the catalytic liquefied petroleum gas is removed by adopting an alcohol amine method, and then, the catalytic liquefied petroleum gas is subjected to deodorization treatment to convert and remove mercaptan and partial carbonyl sulfide contained in the catalytic liquefied petroleum gas. The alcohol amine solvent adopted by the hydrogen sulfide removal by the alcohol amine method is monoethanolamine, diethanolamine, N-methyldiethanolamine or diisopropanolamine, and when the operation condition and the solvent performance are better, the hydrogen sulfide can be removed to trace. In the deodorization treatment, the catalytic liquefied petroleum gas after hydrogen sulfide removal is generally subjected to a preliminary alkali washing method (mixing a sodium hydroxide solution with the catalytic liquefied petroleum gas) to further remove hydrogen sulfide and part of carbonyl sulfide (also called fine desulfurization, in which sodium hydroxide reacts with hydrogen sulfide to generate sodium sulfide and water, carbonyl sulfide undergoes a hydrolysis reaction under the catalysis of sodium hydroxide to generate hydrogen sulfide and carbon dioxide, carbon dioxide is dissolved in the sodium hydroxide solution to form sodium carbonate, the sodium hydroxide solution in which the sodium sulfide and the sodium carbonate are dissolved is separated from the catalytic liquefied petroleum gas in a preliminary alkali washing tank), then on one hand, the catalytic liquefied petroleum gas after preliminary alkali washing is subjected to a mercaptan removal treatment, on the other hand, the sodium hydroxide solution in which the sodium sulfide and the sodium carbonate are dissolved is sent back to a preliminary alkali washing device for use, when the concentration of the sodium hydroxide solution is reduced to a certain degree and cannot be recycled, the sodium hydroxide solution is discharged as waste alkali liquor (commonly called caustic sludge), so the sodium hydroxide solution for pre-alkali washing must be frequently replaced, and sometimes needs to be replaced once for several days; therefore, although the residual hydrogen sulfide and part of carbonyl sulfide in the catalytic liquefied petroleum gas can be removed by the pre-alkali washing, a large amount of waste alkali liquor is generated, and the carbonyl sulfide is difficult to completely remove.
The method for removing mercaptan from liquefied petroleum gas by catalysis is originally proposed by the American ring oil product company (UOP) in 1958, and a mature liquid-liquid extraction and oxidation regeneration process is developed to date. The most basic process of the process is that poly-cobalt phthalocyanine or sulfonated cobalt phthalocyanine catalyst is dissolved in sodium hydroxide solution, then the dissolved poly-cobalt phthalocyanine or sulfonated cobalt phthalocyanine catalyst and catalytic liquefied petroleum gas are fully mixed and reacted in a tower or a container, and mercaptan in the catalytic liquefied petroleum gas and sodium hydroxide are reacted to generate sodium mercaptan, and the sodium mercaptan enters alkali liquor. Mixing the alkali solution carrying sodium mercaptide with air, and then feeding the mixture into a regeneration tower for reaction, sedimentation and separation to generate disulfide, wherein the disulfide is insoluble in the alkali solution, and the disulfide and the alkali solution are separated to regenerate the alkali solution. In the mercaptan removal treatment, part of the carbonyl sulfide is also converted. Generally, 10 to 40ppm of carbonyl sulfide remains in the catalytic liquefied petroleum gas after deodorization treatment. When the refined catalytic liquefied petroleum gas is fractionated to obtain chemical products such as propylene, carbonyl sulfide is enriched in propylene due to the fact that the boiling point of carbonyl sulfide is close to that of propylene, and the quality of the propylene product is affected.
In addition, in the mercaptan removal treatment, the quality of the catalytic liquefied petroleum gas product is greatly influenced by the dissolving condition of mercaptan in alkali liquor, the catalytic oxidation reaction degree of mercaptan sodium salt in a regeneration tower and the separation efficiency of disulfide and catalyst alkali liquor, and the product is unqualified because the total sulfur in the catalytic liquefied petroleum gas product exceeds the standard in actual production, so that the alkali liquor and/or the catalyst alkali liquor has to be recycled or frequently replaced, and chemical raw materials are wasted and more alkali residues are generated. The consumption of alkali liquor and catalyst in the process is large, and the discharge treatment of waste alkali liquor not only has complex process and high cost, but also can cause secondary pollution, and is a main pollution source of the odor of an oil refinery.
As an improvement, chinese patent application 00109633.8 discloses a method for converting mercaptan contained in liquefied petroleum gas. The method is that the liquefied petroleum gas passes through a catalyst bed layer which is arranged in a fixed bed reactor and used for converting mercaptan, and under the action of a catalyst, dissolved oxygen in the liquefied petroleum gas and the liquefied petroleum gasMercaptan contained in the petroleum gas is oxidized to generate disulfide; the active component of the adopted catalyst is nano-grade transition metal oxide, perovskite type rare earth composite oxide or spinel type oxide or iron calcium oxide Ca2Fe2O5. Chinese patent application 00129724.4 discloses a method for refining liquefied petroleum gas under completely alkali-free conditions. The method adopts a desulfurizer which takes iron-calcium oxide as an active component to carry out fine hydrogen sulfide removal on the liquefied petroleum; then, deodorizing the liquefied petroleum gas by adopting a catalyst which takes a nano-scale transition metal element oxide or a perovskite type rare earth composite oxide or a spinel type oxide as an active component, namely converting mercaptan into disulfide by utilizing dissolved oxygen in the liquefied petroleum gas; and then separating the disulfide from the liquefied petroleum gas or natural gas through fractional distillation to obtain a qualified finished product of the liquefied petroleum gas or natural gas. Chinese patent application 01134688.4 discloses a method for industrially refining liquefied petroleum gas under alkali-free conditions. The method comprises the steps of sequentially carrying out fine hydrogen sulfide removal treatment and mercaptan conversion treatment on liquefied petroleum gas after alcohol amine treatment by adopting a desulfurizing agent and a mercaptan removal catalyst which are arranged in a fixed bed reactor, wherein a product generated by reaction of hydrogen sulfide and the desulfurizing agent is attached to the desulfurizing agent, and mercaptan is oxidized into disulfide by dissolved oxygen in the liquefied petroleum gas under the action of the mercaptan removal catalyst, wherein active ingredients of the desulfurizing agent and the mercaptan removal catalyst are iron calcium oxide or hydrated iron calcium oxide; then rectifying the liquefied petroleum gas to obtain a mixture rich in disulfide from the bottom of the tower and a finished liquefied petroleum gas product from the top of the tower.
In the technology disclosed in the above patent application, mercaptan is converted by oxidizing mercaptan into neutral disulfide with dissolved oxygen in liquefied petroleum gas under the action of a mercaptan removal catalyst disposed in a fixed bed reactor, and if the dissolved oxygen in the liquefied petroleum gas is sufficient enough to satisfy the amount of oxygen required for mercaptan conversion, the above method for converting mercaptan is feasible. However, in practice, the inventors of the present patent application found that: the amount of dissolved oxygen in the catalytic liquefied petroleum gas is very small, generally less than 50ppm, some are even below 0.2ppm, and the content of mercaptan is generally tens to hundreds ppm, so in the implementation of the mercaptan conversion method, the residual dissolved oxygen of the catalytic liquefied petroleum gas alone cannot meet the required oxygen amount for converting mercaptan, and the mercaptan in the catalytic liquefied petroleumgas cannot be completely converted, or even cannot be converted. In addition, the processes of 00129724.4 and 01134688.4 do not have a specific step for removal of carbonyl sulfide.
Some documents relating to the carbonyl sulfide hydrolysis catalyst and the preparation method thereof are as follows: chinese patent application 00119385.6 discloses a carbonyl sulfide hydrolysis catalyst and a preparation method thereof. The desulfurizer comprises the following components in percentage by weight: gamma-Al2O383 to 97%, K22-15% of O and 0.1-2% of BaO. Chinese patent application 92104524.7 discloses a carbonyl sulfide hydrolysis catalyst, which is prepared from gamma-Al2O3Dipping 2-25% of potassium carbonate on the pellet carrier, drying and roasting to obtain the final product. At 50 ℃, the carbonyl sulfide concentration is 5mg/m3Volume space velocity of 2000h-1Under the condition, the conversion rate of COS is more than 95 percent. Chinese patent application 00122946.X discloses a sulfur carbonyl desulfurizer and a preparation method thereof, wherein the desulfurizer contains 1-20% by weight of metal oxide, 4-12% by weight of modifying agent, 0.01-0.1% by weight of mass transfer promoter, and the balance of activated carbon; wherein the metal oxide is selected from one of aluminum oxide, titanium dioxide, copper oxide, zirconium dioxide and alkaline earth metal oxide, the modifier is selected from one or more of potassium carbonate, sodium hydroxide and potassium hydroxide, and the mass transfer promoter is one of phosphate, sulfonate and alcohol amine. Chinese patent application 95111160.4 discloses a hydrolysis catalyst and its preparation method, the catalyst is prepared from gamma-Al2O3And titanium dioxide, wherein the content of the titanium dioxide is 4-20%.
The desulfurizing agent mentioned in the present invention is a desulfurizing agent for removing hydrogen sulfide. Chinese patent application 98117729.8 proposes a desulfurizing agent for removing hydrogen sulfide, which uses iron-calcium oxide as an active component, and the document firstly proposes to remove hydrogen sulfide in gaseous or liquid materials, including liquid hydrocarbons. In the background section of this patent application, it is also mentioned that the existing desulfurizing agents are mainly activated carbon type desulfurizing agents or desulfurizing agents containing zinc oxide and iron oxide as main components. The active carbon type desulfurizer removes hydrogen sulfide by adsorbing the hydrogen sulfide on the desulfurizer by the physical adsorption principle, and the desulfurizer taking zinc oxide and ferric oxide as main components is subjected to neutralization reaction with the hydrogen sulfide to enable the generated product to be chemically adsorbed on the desulfurizer. The substance whose active ingredient is iron calcium oxide or hydrated iron calcium oxide disclosed in the method of the above-mentioned chinese patent application 01134688.4 can be used not only as a desulfurizing agent but also as a catalyst for converting mercaptan. The desulfurizing agent using the iron calcium oxide or hydrated iron calcium oxide as the active component and the desulfurizing agent using zinc oxide and ferric oxide as the main components are chemical adsorption desulfurizing agents.
Disclosure of Invention
The invention aims to provide a method for refining catalytic liquefied petroleum gas with high efficiency when the amount of dissolved oxygen in the catalytic liquefied petroleum gas is insufficient or the content of mercaptan is too high without alkali liquor.
The general technical concept of the invention is as follows: hydrolyzing carbonyl sulfide on the catalytic liquefied petroleum gas subjected to hydrogen sulfide removal treatment by an alcohol amine method, and converting the carbonyl sulfide in the catalytic liquefied petroleum gas into hydrogen sulfide under the action of a hydrolysis catalyst; then removing hydrogen sulfide generated by hydrolyzing carbonyl sulfide in the catalytic liquefied petroleum gas and hydrogen sulfide remained in the catalytic liquefied petroleum gas after the hydrogen sulfide is removed by an alcohol ammonium method; then the catalytic liquefied petroleum gas which is treated by removing hydrogen sulfide and is in a flowing state is subjected to mercaptan conversion treatment, namely, firstly adding a liquid oxygenating agent of which the effective component is tert-butyl hydroperoxide into the catalytic liquefied petroleum gas in a flowing state in a conveying pipeline, when the catalytic liquefied petroleum gas dissolved with the tert-butyl hydroperoxide passes through a bed layer of a double-effect catalyst which is arranged in a fixed bed reactor and has the catalytic performance of decomposing the tert-butyl hydroperoxide and the catalytic performance of converting mercaptan, under the action of the double-effect catalyst, tert-butyl hydroperoxide in the catalytic liquefied petroleum gas is decomposed to release nascent active oxygen, and the released oxygen oxidizes mercaptan in the catalytic liquefied petroleum gas into disulfide.
① hydrolyzes carbonyl sulfide in the catalytic liquefied petroleum gas in a flowing state after hydrogen sulfide is removed by an alcohol amine method, namely when the catalytic liquefied petroleum gas passes through a bed layer of a carbonyl sulfide hydrolysis catalyst arranged in a first fixed bed reactor, carbonyl sulfide in the catalytic liquefied petroleum gas and water in the catalytic liquefied petroleum gas react to generate hydrogen sulfide and carbon dioxide under the action of the carbonyl sulfide hydrolysis catalyst, ② desulfurizes the catalytic liquefied petroleum gas in a flowing stateafter the carbonyl sulfide hydrolysis treatment, namely when the catalytic liquefied petroleum gas passes through a bed layer of a desulfurizing agent arranged in a second fixed bed reactor, the generated product generated by the reaction of hydrogen sulfide in the catalytic liquefied petroleum gas and a chemical adsorption desulfurizing agent is chemically adsorbed on the desulfurizing agent, ③ converts the catalytic liquefied petroleum gas in a flowing state after the hydrogen sulfide removal treatment of the second fixed bed reactor into mercaptan, namely when the catalytic liquefied petroleum gas in a flowing state after the hydrogen sulfide removal treatment of the second fixed bed reactor is firstly released into a catalytic liquefied petroleum gas, an effective component of tertiary butyl hydroperoxide is added into the catalytic liquefied petroleum gas, and when the catalytic liquefied petroleum gas in a tertiary butyl hydroperoxide catalytic liquefied petroleum gas with the tertiary butyl hydroperoxide, the catalytic liquefied petroleum gas is released, the catalytic liquefied petroleum gas has double-catalyzed by a tertiary butyl hydroperoxide-catalyzed active catalyst, namely, the tertiary butyl hydroperoxide-catalyzed active catalyst, and the tertiary butyl hydroperoxide-catalyzed active catalyst is dissolved in a tertiary butyl hydroperoxide-catalyzed active catalyst, and the tertiary butyl hydroperoxide-catalyzed active catalyst, namely, the tertiary butyl catalyst is dissolved tertiary butyl catalyst, and the tertiary butyl catalyst, namely the tertiary butyl catalyst is used for the tertiary butyl catalyst, and the tertiary butyl catalyst is used for catalyzing liquefied petroleum gas, wherein the tertiary butyl catalyst, and the.
The manganese compound is manganese dioxide, manganomanganic oxide or manganese carbonate, preferably manganese dioxide.
The active component of the carbonyl sulfide hydrolysis catalyst used in the step ① is sodium hydroxide, potassium hydroxide, or sodium hydroxide and potassium hydroxide, and the carrier of the carbonyl sulfide hydrolysis catalyst is gamma-Al2O3Preferably gamma-Al produced by a rapid exfoliation method2O3The catalytic liquefied petroleum gas after hydrogen sulfide removal treatment by alcohol amine method is treated by hydrolyzing carbonyl sulfide in ①, the temperature of the catalytic liquefied petroleum gas is 0-60 ℃, the pressure is 0.8 MPa-1.4 MPa, and the catalytic liquefied petroleum gas is catalyzed by hydrolyzing carbonyl sulfide to catalyze the carbonyl sulfideThe volume space velocity of the catalyst bed layer is 1h-1～4h-1(ii) a The filling height-diameter ratio of the carbonyl sulfide hydrolysis catalyst is 3-6: 1.
The specific surface area of the carbonyl sulfide hydrolysis catalyst is 150m2/g～200m2Per g, the pore volume is 0.3 ml/g-0.4 ml/g, and the bulk density is 0.75g/cm3～0.9g/cm3. The method for producing the carbonyl sulfide hydrolysis catalyst comprises the following steps: mixing gamma-Al2O3Pellets (preferably gamma-Al produced by a rapid desorption method)2O3) Soaking in sodium hydroxide solution or potassium hydroxide solution or sodium hydroxide and potassium hydroxide solution, taking out the pellet, drying and roasting to obtain the carbonyl sulfide hydrolysis catalyst.
The carbonyl sulfide hydrolysis catalyst used in step ① can also be a carbonyl sulfide hydrolysis catalyst of the prior art, such as those disclosed in chinese patent applications 00119385.6, 92104524.7, 00122946.X and 95111160.4.
The chemical adsorption desulfurizing agent used in the step ② is a desulfurizing agent whose active component is dicalcium ferrite, tricalcium ferrite hexahydrate or iron oxyhydroxide(the molecular formula is FeOOH, commonly called as iron monooxide).
When the active component of the desulfurizing agent used in step ② is iron oxyhydroxide, the desulfurizing agent may further have CaSO as a support4·2H2O, and iron oxyhydroxide and CaSO in the desulfurizing agent4·2H2The molar ratio of O is 1: 1; the preparation method of the desulfurizer comprises the steps of weighing a proper amount of 7-hydrated ferrous sulfate and calcium hydroxide, adding a proper amount of water, stirring, kneading uniformly, extruding and forming on a strip extruding machine, generally extruding into strips, and standing and drying in the air for about 24 hours to obtain the finished product of the desulfurizer. The performance specifications are as follows: the specific surface area is 80m2/g～150m2Per g, the pore volume is 0.3 ml/g-0.4 ml/g, and the bulk density is 0.8g/cm3～0.9g/cm3The lateral pressure strength is 100N/cm-150N/cm. when the chemical adsorption desulfurizer adopted in the step ② is a chemical adsorption desulfurizer with an active component of dicalcium ferrite or tricalcium ferrite hexahydrate, the desulfurizer can also comprise calcium oxide as a carrier, the weight percentage of the active component in the desulfurizer is 85-95%, and the desulfurizer is strip-shaped or cylindrical and has a specific surface area of 1.8m2/g～10m2Per g, pore volume of 0.2-0.3 ml/g, and bulk density of 1.0g/cm3～1.1g/cm3The lateral pressure intensity is 80N/cm-150N/cm. The desulfurizer can also be the desulfurizer with the active component of dicalcium ferrite disclosed in Chinese patent applications 01134688.4 and 98117729.8, or the desulfurizer with the active component of tricalcium ferrite hexahydrate disclosed in Chinese patent application 01134688.4.
When the catalytic liquefied petroleum gas after the carbonyl sulfide hydrolysis treatment is subjected to hydrogen sulfide removal treatment in the step ②, the temperature of the catalytic liquefied petroleum gas is 0-60 ℃, the pressure is 0.8-1.4 MPa, and the volume space velocity of the catalytic liquefied petroleum gas passing through a desulfurizer bed layer is 1h-1～4h-1(ii) a The packing height-diameter ratio of the desulfurizer is 3-6: 1.
The double-effect catalyst described in the above-mentioned step ③ may be composed of all the compounds of active component manganese, and the double-effect catalyst is the compound of manganese pressed into cylindrical or strip formSurface area of 40m2/g～60m2Per g, the pore volume is 0.2 ml/g-0.3 ml/g, and the bulk density is 0.8g/cm3～1.0g/cm3The lateral pressure intensity is 100N/cm-170N/cm. It is to be emphasized that: the double-effect catalyst is a solid forming object obtained by compression forming by a tablet machine or a tablet machine, so that the double-effect catalyst has the good physical properties, and can be used as the double-effect catalyst. The preparation method of the double-effect catalyst is to directly press the powdery manganese compound into a solid forming object by a tablet machine or a tablet machine to obtain the finished product of the double-effect catalyst.
The components of the double-effect catalyst can also be provided with CaSO as a support body of an active component4·2H2The weight percentage of the O and manganese compounds in the double-effect catalyst is 5 to 90 percent. The double-effect catalyst is in the shape of a strip or a cylinder, and the specific surface area of the double-effect catalyst is 150m2/g～250m2Per g, the pore volume is 0.2 ml/g-0.35 ml/g, and the bulk density is 0.8g/cm3～0.9g/cm3The lateral pressure intensity is 90N/cm-150N/cm. The preparation method of the double-effect catalyst comprises the steps of weighing 74 parts by weight of powdery calcium hydroxide, 132 parts by weight of powdery ammonium sulfate and 9-1548 parts by weight of powdery manganese compound, adding the powdery calcium hydroxide, 132 parts by weight of powdery ammonium sulfate and 9-1548 parts by weight of powdery manganese compound into a kneader, adding water accounting for 3% -10% of the total weight of the weighed powdery calcium hydroxide, ammonium sulfate and manganese compound into the kneader, kneading the materials uniformly in the kneader, carrying out extrusion forming in a strip extruder, and finally putting the obtained solid forming object in air to be dried to obtain the finished double-effect catalyst.
The components of the double-effect catalyst can also have ferric oxyhydroxide besides active components and a support body, and the molecular formula of the ferric oxyhydroxide is FeOOH, namely the double-effect catalyst is a manganese compound, the ferric oxyhydroxide and CaSO4·2H2Mixtures of O, iron oxyhydroxide and CaSO4·2H2The molar ratio of O is 1: 1. The double-effect catalyst is in a strip shape or a cylindrical shape, and the specific surface area of the double-effect catalyst is 150m2/g～250m2Per g, the pore volume is 0.2 ml/g-0.35 ml/g, and the bulk density is 0.8g/cm3～0.9g/cm3The lateral pressure intensity is 90N/cm-150N/cm. When manufacturing a groupDivided into manganese carbonate, iron oxyhydroxide and CaSO4·2H2The preparation method of the O double-effect catalyst can be as follows: weighing 278 parts by weight of powdery 7 parts of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide and 14-2349 parts by weight of powdery manganese carbonate as raw materials, kneading the three raw materials uniformly in a kneader, then carrying out extrusion forming in a stripextruding machine, and then placing the obtained solid forming product in the air for airing to obtain the finished product of the double-effect catalyst. Wherein when the raw materials are kneaded in the kneader, water accounting for 5-20 percent of the total weight of the three raw materials can be added, and after uniform kneading, the subsequent molding and airing operation is carried out. When the manufacturing components are manganese dioxide, iron oxyhydroxide and CaSO4·2H2The preparation method of the O double-effect catalyst can be as follows: 278 parts by weight of powdery 7 parts of hydrated ferrous sulfate, 74 parts by weight of powdery calcium hydroxide and 14-2349 parts by weight of powdery manganese dioxide are taken as raw materials, then the three raw materials are uniformly kneaded in a kneader, then are extruded and formed in a strip extruding machine, and the obtained solid forming object is placed in the air to be dried to obtain the finished product of the double-effect catalyst. Wherein when the raw materials are kneaded in the kneader, water accounting for 5-20 percent of the total weight of the three raw materials can be added, and after uniform kneading, the subsequent molding and airing operation is carried out. When the manufacturing components are mangano-manganic oxide, iron oxyhydroxide and CaSO4·2H2The preparation method of the O double-effect catalyst can be as follows: weighing 278 parts by weight of powdery 7 parts of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide and 21-3554 parts by weight of powdery manganese carbonate as raw materials, kneading the three raw materials uniformly in a kneader, carrying out extrusion forming in a strip extruder, placing the obtained solid forming product in air for drying, roasting for about 1 hour at 300-320 ℃ under the condition of oxygen deficiency, and taking the solid forming product as a finished product of the double-effect catalyst after the manganese carbonate isdecomposed to generate manganous manganic oxide. Wherein when the raw materials are kneaded in the kneader, water accounting for 5-20% of the total weight of the three raw materials can be added, and after uniform kneading, the subsequent operations of forming, airing and roasting are carried out.
In the manufacturing method of the double-effect catalyst, when the double-effect catalyst is formed, the pressure of a tablet press, a tablet machine or a strip extruding machine can be adjusted to obtain the finished product of the double-effect catalyst with the corresponding lateral pressure. The higher the general pressure is, the higher the lateral pressure strength is; the bulk density of the catalyst is mainly related to the length of the catalyst forming product, the compactness degree during stacking and the density of the catalyst forming product; the specific surface area and pore volume of the catalyst are then related to the properties of the object itself and the accuracy of the measuring tool. For a two-way catalyst having more than one component, the side pressure strength is mainly related to the pressure of a tablet press, a tablet press or a bar press, and also related to the content of the support, and generally, when the content of the support is higher, the side pressure strength is higher under the same conditions.
In addition, when a double-effect catalyst bed layer is filled, the selection standard of the size of the used double-effect catalyst is as follows: the ratio of the diameter of the double-effect catalyst bed layer to the diameter of the used double-effect catalyst is more than or equal to 40, so that the liquefied petroleum gas is fully contacted with the double-effect catalyst when passing through the double-effect catalyst bed layer.
The flow direction of the catalytic liquefied petroleum gas with the tert-butyl hydroperoxide dissolved in the step ③ is frombottom to top when the catalytic liquefied petroleum gas passes through the two-way catalyst bed layer arranged in the third fixed bed reactor.
The molar ratio of the effective oxygen contained in the oxygen supplementing agent added into the catalytic liquefied petroleum gas in the step ③ to the mercaptan sulfur contained in the catalytic liquefied petroleum gas is 0.5-2: 1, preferably 1-1.5: 1, when the catalytic liquefied petroleum gas dissolved with the tert-butyl hydroperoxide passes through a catalyst bed, the temperature of the catalytic liquefied petroleum gas is 0-60 ℃, preferably 20-40 ℃, the pressure is 0.8-1.4 MPa, and the volume space velocity of the catalytic liquefied petroleum gas passing through the double-effect catalyst bed is 1h-1～4h-1Preferably 1.5h-1～3h-1(ii) a The filling height-diameter ratio of the double-effect catalyst is 3-6: 1.
Under the action of a double-effect catalyst taking a manganese compound as an active component, the tert-butyl hydroperoxide undergoes the following decomposition reaction to release available oxygen, which is also called nascent active oxygen. The mol number n (mol) of the available oxygen contained in 1kg of the oxygen supplying agent can be calculated by the reaction formula: the value of n can be obtained by decomposing each mole of tert-butyl hydroperoxide to generate 1 mole of available oxygen and then obtaining the value of n according to the mass concentration a% of tert-butyl hydroperoxide contained in the oxygenating agent and the formula n ═ a/9.
In addition, mercaptan sulfur refers to sulfur atoms in mercapto groups (-SH) in mercaptan, and the content (ppm) of mercaptan sulfur in catalytic liquefied petroleum gas can be measured by instruments such as a WDL-94 microcomputer multifunctionalsulfur analyzer (produced by chemical research institute, southwest, chemical engineering department); therefore, the mole number of the mercaptan sulfur contained in the catalytic liquefied petroleum gas can be calculated, so that the mole ratio of the effective oxygen contained in the oxygen supplementing agent added into the catalytic liquefied petroleum gas to the mercaptan sulfur contained in the catalytic liquefied petroleum gas can be a specific numerical value by controlling the addition amount of the oxygen supplementing agent.
The effective component of the oxygenating agent is tert-butyl hydroperoxide, and the requirement of the needed supplemented effective oxygen can be met as long as the tert-butyl hydroperoxide reaches a certain amount, so that no special requirement is imposed on the concentration of the effective component of the oxygenating agent; therefore, the oxygen supplement agent can be all tert-butyl hydroperoxide or a solution containing a certain weight percentage of tert-butyl hydroperoxide; however, since high-purity t-butyl hydroperoxide is difficult to prepare in industrial production, commercially available t-butyl hydroperoxide contains di-t-butyl peroxide, and the mass percent concentration of t-butyl hydroperoxide is generally 70% to 99%; therefore, the present invention preferably uses such commercially available t-butyl peroxide as an oxygen supplying agent used in the present invention.
When the liquid oxygen supplying agent is added to the catalytic liquefied petroleum gas in the step ③, in order to more accurately control the addition amount of the tert-butyl hydroperoxide, the oxygen supplying agent may be diluted by an organic solution such as n-hexane, and then the diluted oxygen supplying agent is added to the catalytic liquefied petroleum gas.
In the specific implementation of the invention, the pipeline for conveying the catalytic liquefied petroleum gas between the second fixed bed reactor and the third fixed bed reactor can be a single conveying pipeline, or a conveying pipeline for connecting a mixing device in series on the conveying pipeline, and the mixing device can be a mixing tank (for example, a mixing tank with a cavity inside or a mixing tank with a baffle plate inside) commonly used in the oil refining industry, or a mixing device with a stirrer; when the conveying pipeline with the mixing device is adopted, the access port of the oxygen supplement agent can be directly arranged on the mixing device and also can be arranged on a conveying pipeline positioned in front of the mixing device, so that the oxygen supplement agent and the catalytic liquefied petroleum gas can achieve a better mixing effect.
④ the method for refining catalytic liquefied petroleum gas can also comprise sequentially subjecting the catalytic liquefied petroleum gas after mercaptan conversion treatment to gas fractionation and rectification, i.e. obtaining C contained in the liquefied petroleum gas by gas fractionation3～C4And a catalytic liquefied petroleum gas enriched in disulfide heavy components; then rectifying the catalytic liquefied petroleum gas enriched with the heavy components of the disulfide, and separating the disulfide from the catalytic liquefied petroleum gas enriched with the heavy components of the disulfide through rectification treatment to obtain the ultralow-sulfur or sulfur-free catalytic liquefied petroleum gas and the disulfide.
Compared with the prior art, the invention has the following positive effects: (1) the method for refining the catalytic liquefied petroleum gas completely discards the traditional alkali liquor treatment process, and can achieve the purposes of completely removing carbonyl sulfide contained in the catalytic liquefied petroleum gas and converting mercaptan only by utilizing a hydrolysis catalyst, a desulfurizing agent, an oxygen supplement agent taking tert-butyl hydroperoxide as an effective component and a double-effect catalyst which has the catalytic performance of decomposing tert-butyl hydroperoxide and the catalytic performance of converting mercaptan, and sequentially performing hydrolysis carbonyl sulfide treatment, hydrogen sulfide removal treatment, oxygen supplement treatment and mercaptan conversion treatment on the catalytic liquefied petroleum gas subjected to alcohol amine desulfurization treatment, in the whole process of refining the catalytic liquefied petroleum gas, organic alkali solution or inorganic alkali solution is not needed to be added, so that the real complete alkali-free desulfurization and deodorization process is realized, and the process is free of alkali residue and secondary pollution and is beneficial to protecting the environment and human health. (2) The invention carries out the treatment of hydrolyzing carbonyl sulfide on the catalytic liquefied petroleum gas in a flowing state after the hydrogen sulfide removal treatment by an alcohol amine method, namely when catalyzingWhen the liquefied petroleum gas passes through the bed layer of carbonyl sulfide hydrolysis catalyst arranged in the first fixed bed reactor, the carbonyl sulfide in the catalytic liquefied petroleum gas and the water in the catalytic liquefied petroleum gas are reacted to generate hydrogen sulfide and carbon dioxide under the action of the carbonyl sulfide hydrolysis catalyst, and when the catalytic liquefied petroleum gas passes through the bed layer of desulfurizer arranged in the second fixed bed reactor again, the catalytic liquefied petroleum gas catalyzes the water in the liquefied petroleum gasThe product generated by the reaction of the hydrogen sulfide and the chemical adsorption type desulfurizing agent is chemically adsorbed on the desulfurizing agent, so that the carbonyl sulfide is thoroughly removed, and the hydrogen sulfide remained in the catalytic liquefied petroleum gas after the hydrogen sulfide is removed by the alcohol ammonium method. Compared with the traditional process for removing carbonyl sulfide by pre-alkali washing, the process for removing carbonyl sulfide in the invention has the advantages that the removal of carbonyl sulfide is more thorough, the removal of carbonyl sulfide can be reduced to below 0.1ppm, and propylene (namely C contained in catalytic liquefied petroleum gas) is prepared in the subsequent gas fractionation process3Olefins) can be obtained, a better quality propylene product can be obtained. (3) According to the invention, the tert-butyl hydroperoxide is decomposed by the double-effect catalyst to release nascent active oxygen, so that the defect that mercaptan cannot be completely converted into disulfide due to neglect of the shortage of dissolved oxygen in catalytic liquefied petroleum gas in the prior art is effectively overcome; the invention can control the oxygen content in the catalytic liquefied petroleum gas by accurately controlling the amount of the oxygen supplement agent added into the catalytic liquefied petroleum gas, so that the nascent active oxygen released by the tert-butyl hydroperoxide under the action of the double-effect catalyst reacts with mercaptan in the catalytic liquefied petroleum gas to oxidize the mercaptan into disulfide, thereby just meeting the safety requirement on the treatment of the catalytic liquefied petroleum gas and solving the problem which needs to be solved for a long time. (4) The catalyst used in the invention has the active component of manganese compound, and the catalyst taking the manganese compound as the active component not only has the catalytic performance of decomposing tert-butyl hydroperoxide, but also has the catalytic performance of converting mercaptan. When liquid oxygen supplying agent with tert-butyl hydroperoxide as effective component is added into catalytic liquefied petroleum gas containing mercaptan, the oxygen supplying agent follows the catalytic liquefied petroleum gas to makeits effective component tert-butyl hydroperoxide moveThe basic hydrogen peroxide and the catalytic liquefied petroleum gas are uniformly mixed, when the basic hydrogen peroxide and the catalytic liquefied petroleum gas pass through a double-effect catalyst bed layer arranged in a fixed bed reactor, the tert-butyl hydrogen peroxide is decomposed to release nascent oxygen with stronger activity under the catalysis of an active component manganese compound of a catalyst, and then the nascent active oxygen and mercaptan in the catalytic liquefied petroleum gas are oxidized under the catalysis of the catalyst, so that the mercaptan is converted into disulfide. The nascent oxygen has the advantage of higher reaction activity, can timely, effectively and thoroughly oxidize mercaptan into disulfide under the action of corresponding catalysts, and is completely dissolved in catalytic liquefied petroleum gas even if redundant oxygen exists, so that the safety is higher. (5) The invention can mix the manganese compound and the mercaptan removal catalyst used in the fixed bed to prepare the double-effect catalyst with the catalytic performance of decomposing tert-butyl hydroperoxide and the catalytic performance of converting mercaptan, for example, the active components disclosed in the prior art are nano-transition metal oxide, perovskite type rare earth composite oxide or spinel type oxide, iron calcium oxide Ca2Fe2O5Or the mercaptan-removing catalyst of hydrated iron-calcium oxide, then the catalyst and manganese compound are mixed by adding water, kneaded and extruded to form the catalyst, and the catalyst can also be used as a double-effect catalyst, which also belongs to the protection scope of the invention. (6) When the invention is implemented, the invention can be implemented only by simply modifying the existing equipment of an oil refinery, such as adding a pump for adding an oxygenating agent and removing a plurality of pieces of equipment which are redundant for implementing the invention, so that the invention has the advantages of convenience and low cost, and the running cost is greatly reduced because the number of the used equipment is less. (7) The invention adds oxygen-supplementing agent whose effective component is tert-butyl hydroperoxide into catalytic liquefied petroleum gas, and generates oxygen and tert-butyl alcohol under the action of double-effect catalyst, on one hand, it can provide enough oxygen, at the same time the generated tert-butyl alcohol also can be used as a portion of catalytic liquefied petroleum gas, i.e. it can be combusted and can provide heat, and said invented product can be used for producing liquefied petroleum gasThe tertiary butanol does not need to be separated from the catalytic liquefied petroleum gas. (8) When the components selected by the invention are calcium sulfate dihydrate, iron oxyhydroxide andwhen the solid formed product of the manganese compound is used as a double-effect catalyst, the raw material 7 hydrated ferrous sulfate and calcium hydroxide react to generate CaSO as a support4·2H2O, and the calcium sulfate dihydrate also has excellent water resistance and lateral pressure strength; and because the 7 hydrated ferrous sulfate can be obtained from the mineral waste in a large amount, the price is lower, and the cost is lower. When the double-effect catalyst is used for mercaptan conversion, the mercaptan sulfur content in the catalytic liquefied petroleum gas after the catalyst passes through the catalyst bed layer can be reduced to be below 0.1ppm, so that the solid molded product can be used as a preferable double-effect catalyst. (9) The invention adopts the chemical adsorption desulfurizer to remove the hydrogen sulfide, the removal effect is obvious, and when the desulfurizer taking the FeOOH as the active component is selected, the sulfur penetration capacity is larger. Because the FeOOH reacts with the hydrogen sulfide to generate the FeOOH, after the desulfurizer is used fora period of time, air can be introduced into the fixed bed to enable the FeOOH in the desulfurizer to react with oxygen to generate FeOOH and elemental sulfur, and although the elemental sulfur is absorbed in the desulfurizer, the newly generated FeOOH can better react with the hydrogen sulfide due to higher activity, so that the penetrating sulfur capacity of the desulfurizer can be greatly increased. (10) When the catalytic liquefied petroleum gas after mercaptan conversion treatment is subjected to gas fractionation and rectification treatment in sequence, C with high added value contained in the catalytic liquefied petroleum gas can be obtained through the gas fractionation3～C4And a catalytic liquefied petroleum gas enriched in disulfide heavy components; then rectifying the catalytic liquefied petroleum gas enriched with the heavy components of the disulfide, and separating the disulfide from the catalytic liquefied petroleum gas enriched with the heavy components of the disulfide through rectification treatment to obtain the ultralow-sulfur or sulfur-free catalytic liquefied petroleum gas and the disulfide with high added value.
Drawings
FIG. 1 is a schematic diagram of the process flow of example 1 of the present invention.
FIG. 2 is an X-ray diffraction spectrum of desulfurizing agent E11.
Detailed Description
1. And (5) manufacturing the double-effect catalyst.
Production examples 1 to 3
The active component is a cylindrical double-effect catalyst A1 of manganese dioxide, and the double-effect catalyst A1 is composed of manganese dioxide. The manufacturing method comprises the following steps: in each production example, a certain weight of powdery manganese dioxide was weighed, and the powdery manganese dioxide was pressed under a corresponding pressure by a tablet press or a tablet press to form a cylindrical solid molding having a certain lateral pressure strength, thereby obtaining a finished double-effect catalyst product a11 of production example 1, a finished double-effect catalyst product a12 of production example 2, and a finished double-effect catalyst product a13 of production example 3, respectively. The diameter of the finished product of the double-effect catalyst is 6.5mm, and the height of the finished product of the double-effect catalyst is 6.2 mm-6.5 mm. The parameters relating to the specification and performance of the catalyst of each production example are shown in Table 1. In production examples 1 to 3, the manufacturers of powdery manganese dioxide used in different production examples were different, or the same manufacturer but different production lots were used.
(production examples 4 to 6)
The active component is a cylindrical double-effect catalyst A2 of manganese carbonate, and the double-effect catalyst A2 is composed of manganese carbonate. The manufacturing method comprises the following steps: in each manufacturing example, a certain weight of powdery manganese carbonate is weighed, and the powdery manganese carbonate is pressed into a cylindrical solid forming object with a certain lateral pressure strength by a tablet machine or a tablet press under corresponding pressure, so that the finished double-effect catalyst product a21 of manufacturing example 4, the finished double-effect catalyst product a22 of manufacturing example 5 and the finished double-effect catalyst product a23 of manufacturing example 6 are obtained respectively. The diameter of the finished product of the double-effect catalyst is 6.5mm, and the height of the finished product ofthe double-effect catalyst is 6.2 mm-6.5 mm. The parameters relating to the specification and performance of the catalyst of each production example are shown in Table 1. In production examples 4 to 6, the manufacturers of powdery manganese carbonates used in different production examples were different, or the same manufacturer but different production lots were used.
Production examples 7 to 9
The active component is cylindrical double-effect catalyst A3 of mangano-manganic oxide, and the double-effect catalyst A3 is composed of mangano-manganic oxide. The manufacturing method comprises the following steps: in each manufacturing example, a certain weight of powdery trimanganese tetroxide is weighed, and is pressed into a cylindrical solid forming object with a certain lateral pressure strength by a tablet machine or a tablet press under corresponding pressure, so as to obtain the finished double-effect catalyst product a31 of manufacturing example 7, the finished double-effect catalyst product a32 of manufacturing example 8 and the finished double-effect catalyst product a33 of manufacturing example 9. The diameter of the finished product of the double-effect catalyst is 6.5mm, and the height of the finished product of the double-effect catalyst is 6.2 mm-6.5 mm. The parameters relating to the specification and performance of the catalyst of each production example are shown in Table 1. In production examples 7 to 9, the manufacturers of powdery trimanganese tetroxide used in different production examples were different, or the same manufacturer but different production lots were used.
TABLE 1
| Production example Serial number | Code number | Active component | Active component The content wt% | Specific surface area m/g | Pore volume ml/g | Bulk density g/cm3 | Lateral pressure strength N/cm |
| 1 | A11 | MnO2 | 100 | 50 | 0.25 | 0.85 | 175 |
| 2 | A12 | MnO2 | 100 | 40 | 0.2 | 1.0 | 200 |
| 3 | A13 | MnO2 | 100 | 60 | 0.3 | 0.8 | 100 |
| 4 | A21 | MnCO3 | 100 | 50 | 0.25 | 0.95 | 130 |
| 5 | A22 | MnCO3 | 100 | 40 | 0.2 | 1.0 | 170 |
| 6 | A23 | MnCO3 | 100 | 60 | 0.3 | 0.8 | 100 |
| 7 | A31 | Mn3O4 | 100 | 50 | 0.25 | 0.9 | 140 |
| 8 | A32 | Mn3O4 | 100 | 40 | 0.2 | 1.0 | 170 |
| 9 | A33 | Mn3O4 | 100 | 60 | 0.3 | 0.8 | 100 |
(production examples 10 to 12)
The active component is manganese carbonate, and the support body is CaSO4·2H2O, B1. The manufacturers of powdery manganese carbonates in the respective production examples were different.
Wherein the weight percentage of the manganese carbonate in the double-effect catalyst in the manufacturing example 10 is 50%, the shape of the manganese carbonate is cylindrical, the diameter of the finished product of the catalyst is 6.5mm, and the height of the finished product of the catalyst is 6.2 mm-6.5 mm. The manufacturing method comprises the following steps: 74 parts of powdery calcium hydroxide, 132 parts of powdery ammonium sulfate (even if the molar ratio of the calcium hydroxide to the ammonium sulfate is 1: 1), 172 parts of powdery manganese carbonate and 30 parts of water (in the manufacturing example, 3-10% of the total weight of the calcium hydroxide, the ammonium sulfate and the manganese carbonate can be weighed) are weighed, the powdery calcium hydroxide, the powdery manganese carbonate and the water are uniformly kneaded in a kneader, the mixture is pressed and formed in a tablet press or a tablet machine with corresponding pressure, the formed product is put in the air and dried to obtain the finished product double-effect catalyst B11, the lateral pressure strength of the catalyst B11 is mainly determined by the pressure of the tablet press or the tablet machine, and relevant parameters in the specification and the performance are shown in Table 2.
The manganese carbonate of preparation example 11 was 5% by weight of the double-effect catalyst, and was shaped like a bar, the diameter of the finished catalyst product was 3mm, and the length was 15mm to 20 mm. The manufacturing method comprises the following steps: 74 parts of powdery calcium hydroxide, 132 parts of powdery ammonium sulfate (even if the molar ratio of the calcium hydroxide to the ammonium sulfate is 1: 1), 9 parts of powdery manganese carbonate and 20 parts of deionized water (in the preparation example, 3-10% of the total weight of the calcium hydroxide, the ammonium sulfate and the manganese carbonate can be weighed) are weighed, kneaded uniformly in a kneader, then extruded and formed in a strip extruding machine with corresponding pressure, and then the obtained formed product is put in air to be dried to be used as a finished double-effect catalyst B12, wherein the lateral pressure strength of the double-effect catalyst B12 is mainly determined by the pressure of the strip extruding machine, and relevant parameters in specification and performance are shown in Table 2.
The manganese carbonate in the preparation example 12 accounts for 90 wt% of the double-effect catalyst, and the manganese carbonate is strip-shaped, and the diameter of the finished catalyst is 5mm, and the length of the finished catalyst is 15-20 mm. The manufacturing method comprises the following steps: 74 parts of powdery calcium hydroxide, 132 parts of powdery ammonium sulfate (even if the molar ratio of the calcium hydroxide to the ammonium sulfate is 1: 1), 1548 parts of powdery manganese carbonate and 150 parts of deionized water (in the preparation example, 3-10% of the total weight of the calcium hydroxide, the ammonium sulfate and the manganese carbonate can be weighed) are weighed, directly kneaded uniformly in a kneader, then extruded and formed in a bar extruder with corresponding pressure, and then the obtained formed product is put in the air to be dried to be used as a finished product double-effect catalyst B13, wherein the lateral pressure strength of the double-effect catalyst B13 is mainly determined by the pressure of the bar extruder, and relevant parameters in specification performance are shown in Table 2.
(production examples 13 to 15)
The active component is manganese dioxide, and the support body is CaSO4·2H2O, B2. The manufacturers of the powdery manganese dioxide in the respective production examples were different.
Wherein the manganese dioxide in the double-effect catalyst in the manufacturing example 13 accounts for 50% by weight, the shape is cylindrical, the diameter of the finished catalyst is 6.5mm, and the height is 6.2mm to 6.5 mm. The manufacturing method comprises the following steps: 74 parts of powdery calcium hydroxide, 132 parts of powdery ammonium sulfate (even if the molar ratio of the calcium hydroxide to the ammonium sulfate is 1: 1), 172 parts of powdery manganese dioxide and 25 parts of deionized water (in the preparation example, 3-10% of the total weight of the calcium hydroxide, the ammonium sulfate and the manganese dioxide can be weighed), the powdery calcium hydroxide, the powdery manganese dioxide and the deionized water are directly kneaded uniformly in a kneader, then the mixture is pressed and formed in a tablet press or a tablet machine with corresponding pressure, the formed product is placed in air and dried to obtain the finished product double-effect catalyst B21, the lateral pressure strength of the double-effect catalyst B21 is mainly determined by the pressure of the tablet press or the tablet machine, and relevant parameters in the specification and performance are shown in Table 2.
The manganese dioxide in the preparation example 14 accounts for 5 wt% of the double-effect catalyst, and the manganese dioxide is strip-shaped, and the diameter of the finished catalyst is 3mm, and the length of the finished catalyst is 15-20 mm. The manufacturing method comprises the following steps: 74 parts of powdery calcium hydroxide, 132 parts of powdery ammonium sulfate (even if the molar ratio of the calcium hydroxide to the ammonium sulfate is 1: 1), 9 parts of powdery manganese dioxide and 20 parts of deionized water (in the preparation example, 3-10% of the total weight of the calcium hydroxide, the ammonium sulfate and the manganese dioxide can be weighed) are weighed, kneaded uniformly in a kneader, then extruded and formed in a strip extruding machine with corresponding pressure, and then the formed product is put in air to be dried to obtain the finished double-effect catalyst B22, wherein the lateral pressure strength of the double-effect catalyst B22 is mainly determined by the pressure of the strip extruding machine, and relevant parameters in specification and performance are shown in Table 2.
The manganese dioxide in the preparation example 15 accounts for 90 wt% of the double-effect catalyst, and the manganese dioxide is strip-shaped, and the diameter of the finished catalyst is 5mm, and the length of the finished catalyst is 15-20 mm. The manufacturing method comprises the following steps: 74 parts of powdery calcium hydroxide, 132 parts of powdery ammonium sulfate (even if the molar ratio of the calcium hydroxide to the ammonium sulfate is 1: 1), 1548 parts of powdery manganese dioxide and 150 parts of deionized water (in the preparation example, 3-10% of the total weight of the calcium hydroxide, the ammonium sulfate and the manganese dioxide can be weighed) are weighed, are directly kneaded uniformly in a kneader, are extruded and formed in a strip extruding machine with corresponding pressure, and are dried in the air to obtain the finished double-effect catalyst B23, wherein the lateral pressure strength of the double-effect catalyst B23 is mainly determined by the pressure of the strip extruding machine, and relevant parameters in specification and performance are shown in Table 2.
Production examples 16 to 18
The active component is mangano-manganic oxide, and the support body is CaSO4·2H2O, B3. The manufacturers of the powdery trimanganese tetroxide in the respective production examples were different.
Wherein the weight percentage of the manganous-manganic oxide in the double-effect catalyst in the manufacturing example 16 is 50 percent, the shape is cylindrical, the diameter of the finished product of the catalyst is 6.5mm, and the height is 6.2 mm-6.5 mm. The manufacturing method comprises the following steps: 74 parts of powdery calcium hydroxide, 132 parts of powdery ammonium sulfate (even if the molar ratio of the calcium hydroxide to the ammonium sulfate is 1: 1), 172 parts of powdery manganous-manganic oxide and 30 parts of water (in the manufacturing example, 3-10% of the total weight of the calcium hydroxide, the ammonium sulfate and the manganous-manganic oxide can be weighed) are weighed, and are directly kneaded uniformly in a kneader, and then are pressed andformed in a tablet press or a tablet machine with corresponding pressure, and the formed product is put in the air to be dried to be used as a finished double-effect catalyst B31, wherein the lateral pressure strength of the double-effect catalyst B31 is mainly determined by the pressure of the tablet press or the tablet machine, and relevant parameters in the specification and performance are shown in Table 2.
The weight percentage of the manganous-manganic oxide in the double-effect catalyst in the preparation example 17 is 5%, the manganous-manganic oxide is in a strip shape, the diameter of a finished catalyst product is 3mm, and the length of the finished catalyst product is 15-20 mm. The manufacturing method comprises the following steps: 74 parts of powdery calcium hydroxide, 132 parts of powdery ammonium sulfate (even if the molar ratio of the calcium hydroxide to the ammonium sulfate is 1: 1), 9 parts of powdery manganous-manganic oxide and 20 parts of deionized water (in the manufacturing example, 3-10 percent of the total weight of the calcium hydroxide, the ammonium sulfate and the manganous-manganic oxide can be weighed) are weighed, kneaded uniformly in a kneader, extruded and formed in a strip extruding machine with corresponding pressure, and the formed product is put in the air to be dried to obtain the finished product double-effect catalyst B32, wherein the lateral pressure strength of the double-effect catalyst B32 is mainly determined by the pressure of the strip extruding machine, and relevant parameters in specification performance are shown in Table 2.
The weight percentage of the manganous-manganic oxide in the double-effect catalyst in the manufacturing example 18 is 90%, the manganous-manganic oxide is in a strip shape, the diameter of a finished catalyst product is 5mm, and the length of the finished catalyst product is 15-20 mm. The manufacturing method comprises the following steps: 74 parts of powdery calcium hydroxide, 132 parts of powdery ammonium sulfate (even if the molar ratio of the calcium hydroxide to the ammonium sulfate is 1: 1), 1548 parts of powdery manganous-manganic oxide and 150 parts of deionized water (in the preparation example, 3-10 percent of the total weight of the calcium hydroxide, the ammonium sulfate and the manganous-manganic oxide can be weighed) are weighed, directly kneaded uniformly in a kneader, then extruded and formed in a strip extruding machine with corresponding pressure, and the obtained formed product is put in air to be dried to obtain the finished product double-effect catalyst B33, wherein the lateral pressure strength of the double-effect catalyst B33 is mainly determined by the pressure of the strip extruding machine, and relevant parameters in specification and performance are shown in Table 2.
TABLE 2
| Production example Serial number | Code number | Activity of Components | Non-active ingredients | Active component The content wt% | Specific surface area Product m2/g | Pore volume ml/g | Bulk density g/cm3 | Lateral pressure strength N/cm |
| 10 | B11 | MnCO3 | CaSO4·2H2O | 50 | 200 | 0.25 | 0.85 | 120 |
| 11 | B12 | MnCO3 | CaSO4·2H2O | 5 | 150 | 0.2 | 0.8 | 150 |
| 12 | B13 | MnCO3 | CaSO4·2H2O | 90 | 250 | 0.35 | 0.9 | 90 |
| 13 | B21 | MnO2 | CaSO4·2H2O | 50 | 200 | 0.30 | 0.85 | 120 |
| 14 | B22 | MnO2 | CaSO4·2H2O | 5 | 150 | 0.2 | 0.8 | 150 |
| 15 | B23 | MnO2 | CaSO4·2H2O | 90 | 250 | 0.35 | 0.9 | 90 |
| 16 | B31 | Mn3O4 | CaSO4·2H2O | 50 | 200 | 0.25 | 0.85 | 120 |
| 17 | B32 | Mn3O4 | CaSO4·2H2O | 5 | 150 | 0.2 | 0.8 | 150 |
| 18 | B33 | Mn3O4 | CaSO4·2H2O | 90 | 250 | 0.35 | 0.9 | 90 |
(production examples 19 to 21)
The active component is manganese carbonate, and the support is iron oxyhydroxide (the molecular formula is FeOOH) and CaSO4·2H2O, C1. The manufacturers of powdery manganese carbonates in the respective production examples were different.
Among them, iron oxyhydroxide and CaSO in production example 194·2H2The molar ratio of O is 1: 1, and manganese carbonate is used as a double-effect catalystThe catalyst is 50 wt%, and the catalyst is cylindrical, and has a diameter of 6.5mm and a height of 6.2-6.5 mm. The manufacturing method comprises the following steps: weighing 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1) and 261 parts by weight of powdery manganese carbonate, directly kneading uniformly in a kneader, then pressing and molding in a tablet press or a tablet machine with corresponding pressure, and then putting the obtained molded product in air for airing to obtain a finished product of the double-effect catalyst C11, wherein the lateral pressure strength of the double-effect catalyst C11 is mainly determined by the pressure of the tablet press or the tablet machine; or 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1), 261 parts by weight of powdery manganese carbonate and 100 parts by weight of water (in the preparation example, 5-20% of the total weight of the calcium hydroxide, the 7 parts by weight of ferrous sulfate hydrate and the manganese carbonate can be weighed), the powdery manganese carbonate and the powdery calcium hydroxide are uniformly kneaded in a kneader, then the powdery manganese carbonate and the powdery calcium hydroxide are extruded in a strip extruder with corresponding pressure, the powdery manganese carbonate and the powdery manganese carbonate are put in the air to be dried, and the powdery manganese carbonate is used as the finished double-effect catalyst C11, wherein the lateral pressure strength of the double-effect catalyst C11 is mainly.
The manganese carbonate in the preparation example 20 accounts for 5 wt% of the double-effect catalyst, and the manganese carbonate is strip-shaped, and the diameter of the finished catalyst is 3mm, and the length of the finished catalyst is 15-20 mm. The manufacturing method comprises the following steps: weighing 278 parts by weight of powdery 7 parts of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts of ferrous sulfate hydrate to the calcium hydroxide is 1: 1) and 14 parts by weight of powdery manganese carbonate, directly kneading uniformly in a kneader, then carrying out extrusion molding in a strip extruder with corresponding pressure, and then putting the obtained molded product in the air for airing to obtain the finished product double-effect catalyst C12, wherein the lateral pressure strength of the double-effect catalyst C12 is mainly determined by the pressure of the strip extruder; or 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1), 14 parts by weight of powdery manganese carbonate and 50 parts by weight of water (in the preparation example, 5-20% of the total weight of the calcium hydroxide, the 7 parts by weight of ferrous sulfate hydrate and the manganese carbonate can be weighed), the powdery manganese carbonate and the powdery calcium hydroxide are uniformly kneaded in a kneader, then the powdery manganese carbonate and the powdery calcium hydroxide are extruded in a strip extruder with corresponding pressure, the powdery manganese carbonate and the powdery manganese carbonate are put in the air to be dried, and the powdery manganese carbonate is used as the finished double-effect catalyst C12, wherein the lateral pressure strength of the double-effect catalyst C12 is mainly.
The manganese carbonate in the preparation example 21 accounts for 90 wt% of the double-effect catalyst, and the manganese carbonate is strip-shaped, and the diameter of the finished catalyst is 5mm, and the length of the finished catalyst is 15-20 mm. The manufacturing method comprises the following steps: 278 parts by weight of powdery 7 parts of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts of ferrous sulfate hydrate to the calcium hydroxide is 1: 1) and 2349 parts by weight of powdery manganese carbonate are weighed, directly kneaded uniformly in a kneader, then extruded and formed in a strip extruding machine with corresponding pressure, and the obtained formed product is put in the air and dried to obtain the finished product of the double-effect catalyst C13, wherein the lateral pressure strength of the double-effect catalyst C13 is mainly determined by the pressure of the strip extruding machine; or 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1), 2349 parts by weight of powdery manganese carbonate and 300 parts by weight of water (in the manufacturing example, 5-20% of the total weight of the calcium hydroxide, the 7 parts by weight of ferrous sulfate hydrate and the manganese carbonate can be weighed), the powdery manganese carbonate and the powdery calcium hydroxide are uniformly kneaded in a kneader, then the powdery manganese carbonate and the powdery calcium hydroxide are pressed and formed in a tablet press or a tablet beater with corresponding pressure, the formed product is put in air and dried to obtain the finished product catalyst C13, the lateral pressure strength of the double-effect catalyst C13 is mainly determined by the pressure of the tablet press or the beater, and relevant parameters in the.
(production examples 22 to 24)
The active component is manganese dioxide and the support is CaSO4·2H2O and iron oxyhydroxide C2. The manufacturers of the powdery manganese dioxide in the respective production examples were different.
Among them, iron oxyhydroxide and CaSO in production example 194·2H2The molar ratio of O is 1: 1, the weight percentage of manganese dioxide in the double-effect catalyst is 50%, the manganese dioxide is cylindrical, the diameter of the finished catalyst is 6.5mm, and the height is 6.2 mm-6.5 mm. The manufacturing method comprises the following steps: weighing 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1) and 261 parts by weight of powdery manganese dioxide, directly kneading uniformly in a kneader, then pressing and molding in a tablet press or a tablet machine with corresponding pressure, and then putting the obtained molded product in air for airing to obtain a finished product of the double-effect catalyst C21, wherein the lateral pressure strength of the double-effect catalyst C21 is mainly determined by the pressure of the tablet press or the tablet machine; or 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1), 261 parts by weight of powdery manganese dioxide and 100 parts by weight of water (in the manufacturing example, 5-20% of the total weight of the calcium hydroxide, the 7 parts by weight of ferrous sulfate hydrate and the manganese dioxide can be weighed), the powdery manganese dioxide and the 100 parts by weight of water are uniformly kneaded in a kneader, then the mixture is extruded and formed in a strip extruding machine with corresponding pressure, and the formed product is placed in air and dried to obtain the finished product double-effect catalyst C21, wherein the lateral pressure strength of the double-effect catalyst C21 is mainly determined by the pressure of the strip extruding machine, and relevant.
The manganese dioxide of preparation example 23 was 5% by weight of the two-way catalyst, iron oxyhydroxide, and CaSO4·2H2The molar ratio of O is 1: 1, the catalyst is strip-shaped, the diameter of the finished catalyst is 3mm, and the length of the finished catalyst is 15-20 mm. Method for producing the sameThe method comprises the following steps: weighing 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1) and 14 parts by weight of powdery manganese dioxide, kneading uniformly in a kneader, then carrying out extrusion forming in a strip extruding machine with corresponding pressure, and then putting the obtained formed product in air for airing to obtain a finished product of the double-effect catalyst C22, wherein the lateral pressure strength of the double-effect catalyst C22 is mainly determined by the pressure of the strip extruding machine; or 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1), 14 parts by weight of powdery manganese dioxide and 50 parts by weight of water (in the preparation example, 5 to 20 percent of the total weight of the calcium hydroxide, the 7 parts by weight of ferrous sulfate hydrate and the manganese dioxide can be weighed) are uniformly kneaded in a kneader, then the mixture is extruded and formed in a strip extruding machine with corresponding pressure, and the formed product is placed in the air and dried to obtain the finished product double-effect catalyst C22, wherein the lateral pressure strength of the double-effect catalyst C22 is mainly determined by the pressure of the strip extruding machine, and relevant parameters in specification and performance are shown in Table 3.
The manganese dioxide of preparation example 24 was 90% by weight of the two-way catalyst, iron oxyhydroxide andCaSO4·2H2the molar ratio of O is 1: 1, the catalyst is strip-shaped, the diameter of the finished catalyst is 5mm, and the length of the finished catalyst is 15-20 mm. The manufacturing method comprises the following steps: weighing 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1) and 2349 parts by weight of powdery manganese dioxide, directly kneading uniformly in a kneader, then carrying out extrusion molding in a strip extruding machine with corresponding pressure, and then putting the obtained molded product in air for airing to obtain a finished product of the double-effect catalyst C23, wherein the lateral pressure strength of the double-effect catalyst C23 is mainly determined by the pressure of the strip extruding machine; or 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (i.e., the molar ratio of 7 parts by weight of ferrous sulfate hydrate to calcium hydroxide is 1: 1), 2349 parts by weight of powdery manganese dioxide and 300 parts by weight of water (in this production example, 5 to 20% by weight of the total weight of calcium hydroxide, 7 parts by weight of ferrous sulfate hydrate and manganese dioxide may be weighed),kneading in a kneader, extruding in a extruder with corresponding pressure, and air drying to obtain the final product, double-effect catalyst C23, wherein the lateral pressure strength of the double-effect catalyst C23 is determined mainly by the pressure of the extruder, and the relevant parameters of the specification and performance are shown in Table 3.
TABLE 3
| Production example Serial number | Code number | Activity of Components | Non-active ingredients | Active component The content wt% | Specific surface area Product m2/g | Pore volume ml/g | Bulk density Degree g/cm3 | Side pressure Degree N/cm |
| 19 | C11 | MnCO3 | CaSO4·2H2O、FeOOH | 50 | 200 | 0.25 | 0.85 | 120 |
| 20 | C12 | MnCO3 | CaSO4·2H2O、FeOOH | 5 | 150 | 0.2 | 0.8 | 150 |
| 21 | C13 | MnCO3 | CaSO4·2H2O、FeOOH | 90 | 250 | 0.35 | 0.9 | 90 |
| 22 | C21 | MnO2 | CaSO4·2H2O、FeOOH | 50 | 200 | 0.4 | 0.85 | 120 |
| 23 | C22 | MnO2 | CaSO4·2H2O、FeOOH | 5 | 150 | 0.3 | 0.8 | 150 |
| 24 | C23 | MnO2 | CaSO4·2H2O、FeOOH | 90 | 250 | 0.5 | 0.9 | 90 |
| 25 | C31 | Mn3O4 | CaSO4·2H2O、FeOOH | 50 | 200 | 0.4 | 0.85 | 120 |
| 26 | C32 | Mn3O4 | CaSO4·2H2O、FeOOH | 5 | 150 | 0.3 | 0.8 | 150 |
| 27 | C33 | Mn3O4 | CaSO4·2H2O、FeOOH | 90 | 250 | 0.5 | 0.9 | 90 |
(production examples 25 to 27)
The active component is mangano-manganic oxide, and the support body is CaSO4·2H2O and iron oxyhydroxide C3. The manufacturers of the powdery manganese carbonate used as the raw material for preparing thedouble-effect catalyst C3 in each manufacturing example are different.
Among them, iron oxyhydroxide and CaSO in production example 254·2H2The molar ratio of O is 1: 1, the weight percentage of the manganous-manganic oxide in the double-effect catalyst is 50 percent, the catalyst is cylindrical, the diameter of the finished catalyst is 6.5mm, and the height of the finished catalyst is 6.2 mm-6.5 mm. The manufacturing method comprises the following steps: 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate and 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1) and 395 parts by weight of powdery manganese carbonate are weighed, kneaded uniformly directly in a kneader, then pressed and formed in a tablet press or a flaker with corresponding pressure, and the obtained mixture is subjected to compression moldingThe obtained formed product is put in air for airing, and then is roasted for about 1 hour at the temperature of 300-310 ℃ under the condition of oxygen deficiency (such as in a closed furnace or in an inert gas atmosphere), namely, the manganese carbonate is decomposed to generate manganous-manganic oxide to be used as a finished product of the double-effect catalyst C31, wherein the lateral pressure strength of the double-effect catalyst C31 is mainly determined by the pressure of a tablet press or a tablet forming machine; or 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1), 395 parts by weight of powdery manganese carbonate and 100 parts by weight of water (in the present manufacturing example, 5-20% of the total weight of the calcium hydroxide, the 7 parts by weight of ferrous sulfate hydrate and the manganese carbonate can be weighed), the powdery manganese carbonate and the 100 parts by weight of water are uniformly kneaded in a kneader, then the mixture is extruded and formed in a bar extruder with corresponding pressure, the formed product is placed in the air to be dried, and then the dried product is roasted for about 1 hour under the condition of 300-310 ℃ and oxygen deficiency (for example, in a closed furnace or in an inert gas atmosphere), even if the manganese carbonate is decomposed to generate the trimanganese tetroxide, the finished product of the double-effect catalyst C31 can be. The relevant parameters of the specification properties are shown in Table 3.
Weight of trimanganese tetroxide in preparation example 26 in two-way catalystThe percentage is 5%, iron oxyhydroxide and CaSO4·2H2The molar ratio of O is 1: 1, the catalyst is strip-shaped, the diameter of the finished catalyst is 3mm, and the length of the finished catalyst is 15-20 mm. The manufacturing method comprises the following steps: weighing 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1) and 21 parts by weight of powdery manganese carbonate, directly kneading the materials uniformly in a kneader, then carrying out extrusion forming in a strip extruding machine with corresponding pressure, placing the obtained formed product in the air for drying, roasting for about 1 hour at the temperature of about 310-320 ℃ under the condition of oxygen deficiency, even if the manganese carbonate is decomposed to generate manganous manganic oxide, the manganous oxide can be used as a finished product of the double-effect catalyst C32, and the lateral pressure strength of the double-effect catalyst C32 is mainly determined by the pressure of the strip extruding machine; or 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1), 21 parts by weight of powdery manganese carbonate and 50 parts by weight of water (in this production example, 5 to 20% by weight of the total weight of the calcium hydroxide, the 7 parts by weight of ferrous sulfate hydrate and the manganese carbonate can be weighed), kneading in a kneader uniformly, extruding in a bar extruder with corresponding pressure, air drying, calcining at 300-310 deg.C under oxygen-deficient conditions (e.g. in a closed furnace or in an inert gas atmosphere) for about 1 hour, even if manganous carbonate is decomposed to generate manganous-manganic oxide, the manganous-manganic oxide can be used as a finished product of the double-effect catalyst C32, the lateral pressure strength of the double-effect catalyst C32 is mainly determined by the pressure of a bar extruder, and relevant parameters in specification and performance are shown in a table 3.
The weight percentage of trimanganese tetroxide in the two-way catalyst in preparation example 27 was 90%, iron oxyhydroxide and CaSO4·2H2The molar ratio of O is 1: 1, the catalyst is strip-shaped, the diameter of the finished catalyst is 5mm, and the length of the finished catalyst is 15-20 mm. The manufacturing method comprises the following steps: 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1) and 3554 parts by weight of powdery manganese carbonate are weighed, directly kneaded uniformly in a kneader, then extruded and molded in a bar extruder with corresponding pressure, and the obtained molded product is put in the airAfter air drying, roasting for about 1 hour under the condition of about 300 ℃ and insufficient oxygen, namely decomposing manganese carbonate to generate manganomanganic oxide to be used as a finished product of the double-effect catalyst C33, wherein the lateral pressure strength of the double-effect catalyst C33 is mainly formed by the pressure of a plodderForce determination; or 278 parts by weight of powdery 7 parts by weight of ferrous sulfate hydrate, 74 parts by weight of powdery calcium hydroxide (even if the molar ratio of the 7 parts by weight of ferrous sulfate hydrate to the calcium hydroxide is 1: 1), 3554 parts by weight of powdery manganese carbonate and 300 parts by weight of water (in this production example, 5 to 20% by weight of the total weight of the calcium hydroxide, the 7 parts by weight of ferrous sulfate hydrate and the manganese carbonate can be weighed), kneading in a kneader uniformly, extruding in a bar extruder with corresponding pressure, air drying, calcining at 300-310 deg.C under oxygen-deficient conditions (such as in a closed furnace or in an inert gas atmosphere) for about 1 hour, even if manganous carbonate is decomposed to generate manganous-manganic oxide, the manganous-manganic oxide can be used as a finished product of the double-effect catalyst C33, the lateral pressure strength of the double-effect catalyst C33 is mainly determined by the pressure of a bar extruder, and relevant parameters in specification and performance are shown in a table 3.
2. Production of carbonyl sulfide hydrolysis catalyst
(production examples 28 to 30)
The active component is sodium hydroxide, and the carrier is gamma-Al2O3The spherical carbonyl sulfide hydrolysis catalyst D1. The manufacturing method comprises the following steps: mixing gamma-Al2O3Pellets (gamma-Al made by quick-release method)2O3Purchased from Shandong aluminum works) in sodium hydroxide solution, then taken out and dried at 100-150 ℃ to obtain the finished carbonyl sulfide hydrolysis catalyst D1.
Wherein the finished cos hydrolysis catalyst of manufacturing example 28 was D11, where the weight percentage of sodium hydroxide in the cos hydrolysis catalyst was 4%; the finished cos hydrolysis catalyst of preparative example 29 was D12, where the weight percentage of sodium hydroxide in the cos hydrolysis catalyst was 1%; the finished cos hydrolysis catalyst of manufacturing example 30 was D13, where the weight percentage of sodium hydroxide in the cos hydrolysis catalyst was 7%. The relevant parameters for their specification properties are given in Table 4.
(production examples 31 to 33)
The active component is potassium hydroxide, and the carrier is gamma-Al2O3The spherical carbonyl sulfide hydrolysis catalyst D2. The manufacturing method comprises the following steps: mixing gamma-Al2O3Pellets (gamma-Al made by quick-release method)2O3Purchased from Shandong aluminum works) in potassium hydroxide solution, then taken out and dried at 100-150 ℃ to obtain the finished carbonyl sulfide hydrolysis catalyst D2.
Wherein the finished cos hydrolysis catalyst of manufacturing example 31 was D21, where the weight percentage of potassium hydroxide in the cos hydrolysis catalyst was 4%; the finished cos hydrolysis catalyst of preparative example 32 was D22, where the weight percentage of potassium hydroxide in the cos hydrolysis catalyst was 1%; the finished cos hydrolysis catalyst of manufacturing example 33 was D23, where the weight percentage of potassium hydroxide in the cos hydrolysis catalyst was 7%. The relevant parameters for their specification properties are given in Table 4.
Production examples 34 to 36
The active components are potassium hydroxide and sodium hydroxide, and the carrier is gamma-Al2O3The spherical carbonyl sulfide hydrolysis catalyst D2. The manufacturing method comprises the following steps: mixing gamma-Al2O3Pellets (gamma-Al made by quick-release method)2O3Purchased from Shandong aluminum works) in a mixed solution of potassium hydroxide and sodium hydroxide, wherein the molar ratio of the potassium hydroxide to the sodium hydroxide is 1: 1, and then the catalyst is taken out and dried at 100-150 ℃ to obtain the finished carbonyl sulfide hydrolysis catalyst D3.
Wherein the finished carbonyl sulfide hydrolysis catalyst of preparation example 34 is D31, wherein the weight percentage of the active component in the carbonyl sulfide hydrolysis catalyst is 4%, and the molar ratio of potassium hydroxide to sodium hydroxide is 1: 1; the finished cos hydrolysis catalyst of preparation 35 was D32, where the weight percentage of the active component in the cos hydrolysis catalyst was 1% and the molar ratio of potassium hydroxide to sodium hydroxide was 1: 1; the finished cos hydrolysis catalyst of preparative example 36 was D33 where the weight percent of active component in the cos hydrolysis catalyst was 7% and the molar ratio of potassium hydroxide to sodium hydroxide was 1: 1. The relevant parameters for their specification properties are given in Table 4.
TABLE 4
| Production example Serial number | Code number | Activity of Components | Is inactive Components | Active group In parts by weight wt％ | Specific surface area Product m2/g | Pore volume ml/g | Bulk density g/cm3 | Radial compression resistance Mean value of crushing force N/particle |
| 28 | D11 | NaOH | γ-Al2O3 | 4 | 175 | 0.35 | 0.80 | 40-50 |
| 29 | D12 | NaOH | γ-Al2O3 | 1 | 200 | 0.3 | 0.75 | 40-50 |
| 30 | D13 | NaOH | γ-Al2O3 | 7 | 150 | 0.4 | 0.9 | 40-50 |
| 31 | D21 | KOH | γ-Al2O3 | 4 | 175 | 0.35 | 0.80 | 40-50 |
| 32 | D22 | KOH | γ-Al2O3 | 1 | 200 | 0.3 | 0.75 | 40-50 |
| 33 | D23 | KOH | γ-Al2O3 | 7 | 150 | 0.4 | 0.9 | 40-50 |
| 34 | D31 | NaOH、KOH | γ-Al2O3 | 4 | 175 | 0.35 | 0.80 | 40-50 |
| 35 | D32 | NaOH、KOH | γ-Al2O3 | 1 | 200 | 0.3 | 0.75 | 40-50 |
| 36 | D33 | NaOH、KOH | γ-Al2O3 | 7 | 150 | 0.4 | 0.9 | 40-50 |
3. Producing the desulfurizing agent.
(production examples 37 to 39) the active ingredient was iron oxyhydroxide and the support was CaSO4·2H2Desulfurizing agent B1 of O, wherein iron oxyhydroxide and CaSO4·2H2The molar ratio of O is 1: 1, and the penetrating sulfur capacity can be more than or equal to (more than or equal to) 17 weight percent. The desulfurizer is strip-shapedThe diameter of the steel wire is 5mm, and the length of the steel wire is 15-25 mm. The manufacturing method comprises the following steps: FeSO is weighed according to the molar ratio of 1: 14·7H2O (7 iron sulfate hydrate) and Ca (OH)2(calcium hydroxide) is directly kneaded evenly in a kneader, then extruded and formed in a strip extruder, and then put in the air to be dried, thus obtaining the finished product of the strip-shaped desulfurizer B1.
Wherein the desulfurizing agent of preparation example 37 is E11, which is a mixture of iron oxyhydroxide and CaSO4·2H2The molar ratio of O is 1: 1, FIG. 2 is the X-ray diffraction spectrum of desulfurizing agent E11, the diffraction peak marked in the graph is CaSO4·2H2The characteristic peak of O, combined with the above reaction formula, shows that the composition of the phase of the desulfurizing agent E11 is amorphous FeOOH (i.e. iron oxyhydroxide) and crystal form CaSO4·2H2And O. (ii) a The desulfurizing agent prepared in preparation example 38 was E12, which was a mixture of iron oxyhydroxide and CaSO4·2H2The molar ratio of O is 1: 1; the desulfurizing agent prepared in preparation example 39 was E13, which was a mixture of iron oxyhydroxide and CaSO4·2H2The molar ratio of O is 1 to1. The relevant parameters for their specification properties are given in Table 5.
(production examples 40 to 42)
The effective component is 2 CaO. Fe2O3① mixing powder containing iron oxide and/or iron hydroxide and/or iron nitrate with powder of calcium oxide and/or calcium hydroxide and/or calcium bicarbonate and/or calcium carbonate, wherein the molar ratio of iron to calcium is 1: 1 to 1: 1.5, preferably 1: 1 to 1: 1.2, more preferably 1: 1 to 1: 1.05, ② adding water into the mixture, stirring, molding and drying, ③ roasting the product obtained in step ② in an oxidizing atmosphere at 850-950 ℃ for 2-3 hours, ④ cooling the product obtained in step ③ to obtain dicalcium ferrite 2 CaO. Fe2O3Is a strip-shaped desulfurizer E2 with the appearance of an active ingredient of tan or earthy yellow.
Wherein the system isThe final desulfurizing agent of preparation example 40 was E21, in which 2 CaO. Fe2O3The weight percentage in the desulfurizer is 90 percent; the desulfurizing agent prepared in preparation example 41 was E22 containing 2 CaO. Fe2O3The weight percentage in the desulfurizer is 85 percent; the desulfurizing agent prepared in preparation example 42 was E23 containing 2 CaO. Fe2O3The weight percentage in the desulfurizing agent is 95%. The relevant parameters for their specification properties are given in Table 5.
TABLE 5
| Production example Serial number | Code number | Active component | Non-active ingredients | Active group In parts by weight wt％ | Proportion table Area of m2/g | Pore volume ml/g | Bulk density Degree of rotation g/cm3 | Side pressure Degree of rotation N/cm |
| 37 | E11 | FeOOH | CaSO4·2H2O | 34 | 110 | 0.35 | 0.85 | 125 |
| 38 | E12 | FeOOH | CaSO4·2H2O | 34 | 80 | 0.3 | 0.9 | 150 |
| 39 | E13 | FeOOH | CaSO4·2H2O | 34 | 150 | 0.4 | 0.8 | 100 |
| 40 | E21 | 2CaO·Fe2O3 | CaO | 90 | 5 | 0.15 | 1.05 | 130 |
| 41 | E22 | 2CaO·Fe2O3 | CaO | 85 | 1.8 | 0.1 | 1.0 | 110 |
| 42 | E23 | 2CaO·Fe2O3 | CaO | 95 | 10 | 0.2 | 1.1 | 150 |
| 43 | E31 | 3CaO·Fe2O3·6H2O | CaO | 90 | 5 | 0.25 | 1.15 | 120 |
| 44 | E32 | 3CaO·Fe2O3·6H2O | CaO | 85 | 1.8 | 0.2 | 1.1 | 80 |
| 45 | E33 | 3CaO·Fe2O3·6H2O | CaO | 95 | 10 | 0.3 | 1.2 | 150 |
(production examples 43 to 45)
The effective component is 3 CaO. Fe2O3·6H2O, a desulfurizer E3. with a CaO supporting body, wherein the desulfurizer E3. has a strip shape, a diameter of 5mm, a length of 15-25 mm, and a penetrating sulfur capacity of 30 wt% or more, and the preparation method comprises thestep of mixing ① powder containing iron oxide and/or iron hydroxide and/or iron nitrate with powder of calcium oxide and/or calcium hydroxide and/or calcium bicarbonate and/or calcium carbonate, wherein the molar ratio of iron to calcium is 1: 1 to 1: 1.5, preferably 1: 11 to 1: 1.2, preferably 1: 1 to 1: 1.05, ② adding water into the mixture, stirring, forming and drying, ③ roasting the product obtained in the step ② in an oxidizing atmosphere at 850 to 950 ℃ for 2 to 3 hours, ④ cooling the product obtained in the step ③ to obtain the dicalcium ferrite 2 CaO. Fe2O3⑤ mixing the product obtained in step ④ with water and calcium oxide to react to obtain brown strip-shaped product, and air drying to obtain desulfurizer E3.
The desulfurizing agent of preparation example 43 was E31 containing 3 CaO. Fe2O3·6H2The weight percentage of O in the desulfurizer is 90 percent; the desulfurizing agent product of preparation example 44 was E32 containing 3 CaO. Fe2O3·6H2The weight percentage of O in the desulfurizer is 85 percent; the desulfurizing agent prepared in preparation example 45 was E33 containing 3 CaO. Fe2O3·6H2The weight percentage of O in the desulfurizing agent is 95%. The relevant parameters for their specification properties are given in Table 5.
4. Preparing an oxygen supplement agent.
The oxygenating agent F is purchased from Korean Industrial and trade company Limited liability company in Beijing, and the mass concentration of an effective component of tert-butyl hydroperoxide (TBHP) in the oxygenating agent F is 71 percent. If a relatively low rate of addition of t-butyl hydroperoxide is desired, the t-butyl hydroperoxide can be diluted with a liquid hydrocarbon such as n-hexane to provide better control of the amount of t-butyl hydroperoxideadded.
5. And refining the catalytic liquefied petroleum gas. The method for refining catalytic liquefied petroleum gas according to the present invention will be further described with reference to the following specific examples.
(example 1)
Referring to fig. 1, this example employs three-stage fixed bed reactors for refining catalytic liquefied petroleum gas.
In fig. 1, a is a first fixed bed reactor (tower) for performing a process of hydrolyzing carbonyl sulfide on the catalytic liquefied petroleum gas after the hydrogen sulfide removal process, that is, when the catalytic liquefied petroleum gas passes through a bed layer of a carbonyl sulfide hydrolysis catalyst disposed in the first fixed bed reactor (tower), the carbonyl sulfide in the catalytic liquefied petroleum gas reacts with water in the catalytic liquefied petroleum gas under the action of the carbonyl sulfide hydrolysis catalyst to generate hydrogen sulfide and carbon dioxide.
In fig. 1, B is a second fixed bed reactor (tower) for performing hydrogen sulfide removal treatment on the catalytic liquefied petroleum gas in a flowing state after the carbonyl sulfide hydrolysis treatment, that is, when the catalytic liquefied petroleum gas passes through a bed layer of a desulfurizing agent arranged in the second fixed bed reactor, a product of a reaction between hydrogen sulfide in the catalytic liquefied petroleum gas and the desulfurizing agent is chemically adsorbed on the desulfurizing agent.
In FIG. 1, C is a third fixed bed reactor (tower), D is a plunger metering pump (Sigma/2, model number, manufactured by Proming fluid control, Inc., Germany), and E is a transfer pipe located behind the second fixed bed reactor. The third fixed bed reactor (tower) is used for converting the catalytic liquefied petroleum gas in aflowing state which is subjected to the hydrogen sulfide removal treatment of the second fixed bed reactor (tower) into mercaptan, namely, liquid tert-butyl hydroperoxide is added into the catalytic liquefied petroleum gas in a flowing state in a conveying pipeline between the second fixed bed reactor and the third fixed bed reactor, when the catalytic liquefied petroleum gas dissolved with the liquid tert-butyl hydroperoxide passes through a double-effect catalyst bed layer which is arranged in a third fixed bed reactor and has the catalytic performance of decomposing the tert-butyl hydroperoxide and the catalytic performance of converting mercaptan, under the action of a double-effect catalyst, tert-butyl hydroperoxide in the catalytic liquefied petroleum gas is decomposed to release nascent active oxygen, and mercaptan in the catalytic liquefied petroleum gas is oxidized into disulfide by the released oxygen; the active component of the double-effect catalyst is a manganese compound. In addition, 1, 2, 3 and 4 shown in figure 1 are all catalytic liquefied petroleum gas sampling places.
The method for refining the catalytic liquefied petroleum gas of the embodiment comprises the following steps:
① Process for hydrolyzing carbonyl sulfide on flowing liquefied petroleum gas after dehydrosulfurization by alcohol amine method, i.e. reacting carbonyl sulfide in liquefied petroleum gas with water in liquefied petroleum gas to generate hydrogen sulfide and carbon dioxide under the action of carbonyl sulfide hydrolysis catalyst when the liquefied petroleum gas passes through the bed of carbonyl sulfide hydrolysis catalyst in the first fixed bed reactor, wherein the carbonyl sulfide hydrolysis catalyst used is the catalyst D11 obtained in preparation example 28, the specific surface area of catalyst D11 is 175m2Per g, pore volume of 0.35ml/g, bulk density of 0.80g/cm3The weight percentage of sodium hydroxide in the carbonyl sulfide hydrolysis catalyst D11 was 4%.
After the catalytic liquefied petroleum gas passes through the first fixed bed reactor, the catalytic liquefied petroleum gas is sampled and detected at the position 1 shown in fig. 1, the carbonyl sulfur content of the catalytic liquefied petroleum gas is detected by a WDL-94 type microcomputer multifunctional sulfur analyzer (produced by the southwest chemical research institute of the chemical industry department, the lowest detection line of the instrument is 0.02ppm), the detection result is 20ppm, the mercaptan sulfur content of the catalytic liquefied petroleum gas is detected by the WDL-94 type microcomputer multifunctional sulfur analyzer (produced by the southwest chemical research institute of the chemical industry department, the lowest detection line of the instrument is 0.02ppm) and is 400ppm, and the dissolved oxygen in the catalytic liquefied petroleum gas is detected by a CW-2000 fuel cell oxygen analyzer (produced by the Beijing Seikagai Ministry of development of the technology and oxygen measuring technology) and is 5.
The first fixed bed reactor (tower) is internally provided with1-2 layers of stainless steel wire meshes with the diameter smaller than 2mm are arranged on a baffle fixed in a tower, ceramic balls with the thickness of 200-300 mm and the particle size of 5-20mm are laid on the upper surface of the wire mesh, carbonyl sulfide hydrolysis catalyst is filled above the ceramic ball layers, 1-2 layers of upper layer ceramic balls with the thickness of 200-300 mm and the particle size of 5-20mm are laid above the carbonyl sulfide hydrolysis catalyst, and the stainless steel wire mesh is arranged on the upper layer ceramic balls to form a carbonyl sulfide hydrolysis catalyst bed layer. The filling height of the carbonyl sulfide hydrolysis catalyst is 7 m, and the height-diameter ratio is 5: 1. The catalytic liquefied petroleum gas after hydrogen sulfide removal by the alcohol aminemethod flows through a carbonyl sulfide hydrolysis catalyst bed layer from bottom to top, and the temperature of the catalytic liquefied petroleum gas is 20 ℃, the pressure is 1.1MPa, and the volume space velocity is 2.5h-1. The flow rate of the catalytic liquefied petroleum gas was 14.8 ton/hr.
The catalytic liquefied petroleum gas was sampled and examined at 2 shown in FIG. 1, and it had a carbonyl sulfide content of less than 0.1ppm, a mercaptan sulfide content of 400ppm, and a dissolved oxygen content of 5 ppm.
② the catalytic liquefied petroleum gas after the carbonyl sulfide hydrolysis treatment is subjected to hydrogen sulfide removal treatment, i.e. the catalytic liquefied petroleum gas passes through the bed layer of the desulfurizer arranged in the second fixed bed reactor (tower) to catalyze the sulfuration in the liquefied petroleum gasThe product of the reaction between hydrogen (hydrogen sulfide generated by the hydrolysis of carbonyl sulfide and hydrogen sulfide remaining in the catalytic liquefied petroleum gas after the removal of hydrogen sulfide by the alcohol ammonium method) and the chemical adsorption type desulfurizing agent is attached to the desulfurizing agent. The desulfurizing agent used therein was desulfurizing agent E11 obtained in production example 37. The active component of the desulfurizer E11 is FeOOH, namely iron oxyhydroxide, and the support body is CaSO4·2H2O, and iron oxyhydroxide with CaSO4·2H2The molar ratio of O is 1: 1. The diameter of the desulfurizer B1 is 5mm, the length is 15-25 mm, and the specific surface area is 110m2Per g, pore volume of 0.35ml/g, bulk density of 0.85g/cm3The breakthrough sulfur capacity is greater than or equal to (greater than or equal to) 17 weight percent, and the lateral pressure strength is 125N/cm.
1-2 layers of stainless steel wire meshes with diameter less than 2 millimeters (mm) are arranged in the second fixed bed reactor (tower), the stainless steel wire meshes are arranged on a baffle fixed in the tower, and the upper surface of the net is pavedCeramic balls with the thickness of 200-300 mm and the particle size of phi 5-20mm are arranged, a desulfurizer E11 is filled above the ceramic ball layer, 1-2 upper-layer ceramic balls with the thickness of 200-300 mm and the particle size of phi 5-20mm are laid above the desulfurizer E11, and a stainless steel wire mesh is arranged on the upper-layer ceramic balls to form a desulfurizer bed layer. The filling height of the desulfurizer E11 is 7 meters, and the height-diameter ratio is 5: 1. The catalytic liquefied petroleum gas after hydrolyzing carbonyl sulfide flows through a desulfurizer bed layer from bottom to top at the temperature of 20 ℃, the pressure of 1.1MPa and the volume space velocity of 2.5h-1。
The catalytic liquefied petroleum gas was sampled and tested at 3 points shown in FIG. 1, and the hydrogen sulfide content thereof was tested by a WDL-94 microcomputer-based multifunctional sulfur analyzer (manufactured by chemical institute of chemical industry, southwest, chemical division, the lowest test line of the analyzer is 0.02ppm) with a test result of less than 0.1ppm, a mercaptan sulfur content of 400ppm, and a dissolved oxygen of 5 ppm.
In practice, if the catalytic liquefied petroleum gas containing 400ppm of mercaptan sulfur is directly passed through the bed of the double-effect catalyst A11 without adding the oxygen supplementing agent F in the process of converting mercaptan in ③, the result of sampling the catalytic liquefied petroleum gas at 4 shown in FIG. 1 shows that the mercaptan sulfur content in the catalytic liquefied petroleum gas at the outlet rapidly rises to 350ppm, which results in unqualified product quality, the mercaptan sulfur content does not immediately rise to350ppm, because the bed of the double-effect catalyst A11 is newly installed, and air still remains in the catalyst.
③ the catalytic liquefied petroleum gas after hydrogen sulfide removal treatment in the second fixed bed reactor (tower) is converted into mercaptan, that is, a plunger metering pump is used to add a liquid oxygen supplement agent F with effective component of tert-butyl hydroperoxide into the catalytic liquefied petroleum gas in the conveying pipeline between the second fixed bed reactor (tower) and the third fixed bed reactor (tower), the tert-butyl hydroperoxide in the oxygen supplement agent F is dissolved in the catalytic liquefied petroleum gas in flow, when the catalytic liquefied petroleum gas dissolved with tert-butyl hydroperoxide passes through a double-effect catalyst bed layer which is arranged in the third fixed bed reactor (tower) and has both the catalytic performance of decomposing tert-butyl hydroperoxide and the catalytic performance of converting mercaptan, under the effect of the double-effect catalyst, the tert-butyl hydroperoxide in the catalytic liquefied petroleum gas is decomposed to release nascent active oxygen, and the released oxygen oxidizes the mercaptan in the catalytic liquefied petroleum gas into disulfide.
1-2 layers of stainless steel wire meshes with hole diameter less than 2mm (mm) are arranged in the third fixed bed reactor (tower)The silk screen is placed on a baffle fixed in the tower, porcelain balls with the thickness of 200-300 mm and the particle size of phi 5-20mm are laid on the screen, a double-effect catalyst A11 is filled above the porcelain ball layer, then upper layer porcelain balls with the thickness of 200-300 mm and the particle size of phi 5-20mm are laid 1-2 layers above the double-effect catalyst, and then a stainless steel wire mesh is arranged on the upper layer porcelain balls to form a double-effect catalyst bed layer. The filling height of the double-effect catalyst is 7 meters, and the height-diameter ratio is 5: 1. The catalytic liquefied petroleum gas after hydrogen sulfide removal flows through a double-effect catalyst bed layer from bottom to top at the temperature of 20 ℃, the pressure of 1.1MPa and the volume space velocity of 2.5h-1。
The two-way catalyst used therein was the two-way catalyst a11 obtained in production example 1. The double-effect catalyst E1 is cylindrical, and has a diameter of 6.5mm and a height of 6.2-6.5 mm. The specific surface area is 50m2Per g, pore volume of 0.25ml/g, bulk density of 0.85g/cm3The lateral pressure strength was 175N/cm.
The liquid oxygen supplement agent added into the catalytic liquefied petroleum gas is the F to be used, and the speed of adding the oxygen supplement agent F into the catalytic liquefied petroleum gas is 16.7kg/h, so that the molar ratio of the effective oxygen contained in the oxygen supplement agent added into the catalytic liquefied petroleum gas to the mercaptan sulfur contained in the catalytic liquefied petroleum gas is 0.71: 1.
The catalytic liquefied petroleum gas was sampled and measured at 4 shown in FIG. 1, and it had a mercaptan content of less than 0.1ppm, an oxygen content of 10ppm, and a carbonyl sulfide content of less than 0.1 ppm. The relevant data in this example are shown in Table 6. Ppm is referred to herein as mass ratio.
(examples 2 to 6)
Examples 2-6 were performed substantially the same as example 1, with the relevant data shown in Table 6.
(examples 7 to 12)
Examples 7-12 were performed substantially the same as example 1, with the relevant data shown in Table 7.
(examples 13 to 18)
Examples 13-18 were performed substantially the same as example 1, with the relevant data shown in Table 8.
(examples 19 to 24)
Examples 19-24 were performed substantially the same as example 1, with the relevant data shown in Table 9.
(examples 24 to 27)
Examples 24-27 were prepared in substantially the same manner as example 1, with the relevant data shown in Table 10.
(example 28)
The other points are the same as the example 1, except that the method also comprises the step of ④ sequentially carrying out gas fractionation and rectification treatment on the catalytic liquefied petroleum gas after mercaptan conversion treatment, namely obtaining C contained in the catalytic liquefied petroleum gas through gas fractionation3～C4And a catalytic liquefied petroleum gas enriched in disulfide heavy components; then rectifying the catalytic liquefied petroleum gas enriched with the heavy components of the disulfide, and separating the disulfide from the catalytic liquefied petroleum gas enriched with the heavy components of the disulfide through rectification treatment to obtain the ultralow-sulfur or sulfur-free catalytic liquefied petroleum gas and the disulfide.
TABLE 6
| Example number | 1 | 2 | 3 | 4 | 5 | 6 | ||
| Step ①: for catalytic liquid Fossil oil gas Carrying out hydrolysis At carbonyl sulfide In order to solve the problems that, | in sample 1 Related data | Carbonyl sulfide content ppm | 20 | 20 | 20 | 20 | 20 | 20 |
| Mercaptan content ppm | 400 | 400 | 400 | 400 | 400 | 400 | ||
| Dissolved oxygen content ppm | 5 | 5 | 5 | 5 | 5 | 5 | ||
| Hydrolysis of carbonyl sulfide Catalyst and process for preparing same | Code number | D11 | D12 | D13 | D21 | D22 | D23 | |
| Operation process Condition | Temperature of | 20 | 0 | 50 | 20 | 0 | 60 | |
| Pressure MPa | 1.1 | 0.8 | 1.4 | 1.1 | 0.8 | 1.4 | ||
| Volume space velocity h-1 | 2.5 | 1 | 4 | 2.5 | 1 | 4 | ||
| Aspect ratio of filling | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | 6∶1 | ||
| In sample 2 Related data | Carbonyl sulfide content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Step ②: for catalytic liquid Fossil oil gas To carry out desulfurization Treatment of hydrogen | Desulfurizing agent | Code number | E11 | E12 | E13 | E21 | E21 | E21 |
| Operation process Condition | Temperature of | 20 | 0 | 45 | 20 | 0 | 45 | |
| Pressure MPa | 1.1 | 0.8 | 1.4 | 1.1 | 0.8 | 1.4 | ||
| Volume space velocity h-1 | 2.5 | 1 | 4 | 2.5 | 1 | 4 | ||
| Aspect ratio of filling | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | 6∶1 | ||
| In sample 3 Related data | Hydrogen sulfide content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Mercaptan content ppm | 400 | 400 | 400 | 400 | 400 | 400 | ||
| Dissolved oxygen content ppm | 5 | 5 | 5 | 5 | 5 | 5 | ||
| Step ③: for catalytic liquid Fossil oil gas Carrying out the transformation Of thiols Theory of things | Oxygen-supplementing agent | Code number | F | F | F | F | F | F |
| Concentration wt% | 71 | 71 | 71 | 71 | 71 | 71 | ||
| The oxygen supplementing agent contains available oxygen Catalytic liquefied petroleum gas station Containing mercaptan sulfur (molar ratio) | 0.71∶1 | 0.50∶1 | 1.9∶1 | 0.5∶1 | 1.5∶1 | 2.0∶1 | ||
| Double effectCatalyst and process for preparing same | Code number | A11 | A12 | A13 | A21 | A22 | A23 | |
| Operation process Condition | Temperature of | 20 | 0 | 40 | 20 | 0 | 40 | |
| Pressure MPa | 1.1 | 0.8 | 1.4 | 1.1 | 0.8 | 1.4 | ||
| Volume space velocity h-1 | 2.5 | 1 | 4 | 2.5 | 1 | 4 | ||
| Aspect ratio of filling | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | 6∶1 | ||
| In sample 4 Related data | Mercaptan content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Corrosion test of copper sheet | By passing | By passing | By passing | By passing | By passing | By passing | ||
TABLE 7
| Example number | 7 | 8 | 9 | 10 | 11 | 12 | ||
| Step ①: for catalytic liquid Fossil oil gas Carrying out hydrolysis At carbonyl sulfide In order to solve the problems that, | in sample 1 Related data | Carbonyl sulfide content ppm | 25 | 25 | 25 | 20 | 20 | 20 |
| Mercaptan content ppm | 500 | 500 | 500 | 400 | 400 | 400 | ||
| Dissolved oxygen content ppm | 10 | 10 | 10 | 5 | 5 | 5 | ||
| Hydrolysis of carbonyl sulfide Catalyst and process for preparing same | Code number | D31 | D32 | D33 | D11 | D12 | D13 | |
| Operation process Condition | Temperature of | 15 | 0 | 60 | 20 | 0 | 60 | |
| Pressure MPa | 1.1 | 0.8 | 1.4 | 1.1 | 0.8 | 1.4 | ||
| Volume space velocity h-1 | 2.5 | 1 | 4 | 2.5 | 1 | 4 | ||
| Aspect ratio of filling | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | 6∶1 | ||
| In sample 2 Related data | Carbonyl sulfide content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Step ②: for catalytic liquid Fossil oil gas To carry out desulfurization Treatment of hydrogen | Desulfurizing agent | Code number | E31 | E31 | E31 | E11 | E11 | E11 |
| Operation process Condition | Temperature of | 15 | 0 | 45 | 20 | 0 | 45 | |
| Pressure MPa | 1.1 | 0.8 | 1.4 | 1.1 | 0.8 | 1.4 | ||
| Volume space velocity h-1 | 2.5 | 1 | 4 | 2.5 | 1 | 4 | ||
| Aspect ratio of filling | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | 6∶1 | ||
| In sample 3 Related data | Hydrogen sulfide content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Mercaptan content ppm | 400 | 400 | 400 | 400 | 400 | 400 | ||
| Dissolved oxygen content ppm | 5 | 5 | 5 | 5 | 5 | 5 | ||
| Step ③: for catalytic liquid Fossil oil gas Carrying out the transformation Of thiols Theory of things | Oxygen-supplementing agent | Code number | F | F | F | F | F | F |
| Concentration wt% | 71 | 71 | 71 | 71 | 71 | 71 | ||
| The oxygen supplementing agent contains available oxygen Catalytic liquefied petroleum gas station Containing mercaptan sulfur (molar ratio) | 0.8∶1 | 0.50∶1 | 1.8∶1 | 0.5∶1 | 1.5∶1 | 2.0∶1 | ||
| Double-effect catalyst | Code number | A31 | A32 | A33 | B11 | B12 | B13 | |
| Operation process Condition | Temperature of | 20 | 0 | 40 | 20 | 0 | 40 | |
| Pressure MPa | 1.1 | 0.8 | 1.4 | 1.1 | 0.8 | 1.4 | ||
| Volume space velocity h-1 | 2.5 | 1 | 4 | 2.5 | 1 | 4 | ||
| Aspect ratio of filling | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | 6∶1 | ||
| In sample 4 Related data | Mercaptan content ppm | ＜0.1 | 0.5 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Corrosion test of copper sheet | By passing | By passing | By passing | By passing | By passing | By passing | ||
TABLE 8
| Example number | 13 | 14 | 15 | 16 | 17 | 18 | ||
| Step ①: for catalytic liquid Fossil oil gas Carrying out hydrolysis At carbonyl sulfide In order to solve the problems that, | in sample 1 Related data | Carbonyl sulfide content ppm | 20 | 20 | 20 | 20 | 20 | 20 |
| Mercaptan content ppm | 550 | 550 | 550 | 550 | 550 | 550 | ||
| Dissolved oxygen content ppm | 20 | 20 | 20 | 20 | 20 | 20 | ||
| Hydrolysis of carbonyl sulfide Catalyst and process for preparing same | Code number | D21 | D22 | D23 | D31 | D32 | D33 | |
| Operation process Condition | Temperature of | 60 | 15 | 0 | 60 | 20 | 0 | |
| Pressure MPa | 1.4 | 1.1 | 0.8 | 1.4 | 1.1 | 0.8 | ||
| Volume space velocity h-1 | 4 | 2.5 | 1 | 4 | 2.5 | 1 | ||
| Aspect ratio of filling | 6∶1 | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | ||
| In sample 2 Related data | Carbonyl sulfide content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Step ②: for catalytic liquid Fossil oil gas To carry out desulfurization Treatment of hydrogen | Desulfurizing agent | Code number | E21 | E22 | E23 | E31 | E32 | E33 |
| Operation process Condition | Temperature of | 55 | 15 | 0 | 45 | 20 | 0 | |
| Pressure MPa | 1.4 | 1.1 | 0.8 | 1.4 | 1.1 | 0.8 | ||
| Volume space velocity h-1 | 4 | 2.5 | 1 | 4 | 2.5 | 1 | ||
| Aspect ratio of filling | 6∶1 | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | ||
| In sample 3 Related data | Hydrogen sulfide content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Mercaptan content ppm | 550 | 400 | 400 | 400 | 400 | 400 | ||
| Dissolved oxygen content ppm | 20 | 5 | 5 | 5 | 5 | 5 | ||
| Step ③: for catalytic liquid Fossil oil gas Carrying out the transformation Of thiols Theory of things | Oxygen-supplementing agent | Code number | F | F | F | F | F | F |
| Concentration wt% | 71 | 71 | 71 | 71 | 71 | 71 | ||
| The oxygen supplementing agent contains available oxygen Catalytic liquefied petroleum gas station Containing mercaptan sulfur (molar ratio) | 0.8∶1 | 0.50∶1 | 1.8∶1 | 0.5∶1 | 1.5∶1 | 2.0∶1 | ||
| Double-effect catalyst | Code number | B21 | B22 | B23 | B31 | B32 | B33 | |
| Operation process Condition | Temperature of | 50 | 10 | 0 | 40 | 10 | 0 | |
| Pressure MPa | 1.4 | 0.9 | 1.0 | 1.4 | 0.9 | 1.0 | ||
| Volume space velocity h-1 | 2 | 1 | 4 | 2 | 1 | 4 | ||
| Aspect ratio of filling | 3∶1 | 6∶1 | 5∶1 | 3∶1 | 6∶1 | 5∶1 | ||
| In sample 4 Related data | Mercaptan content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Corrosion test of copper sheet | By passing | By passing | By passing | By passing | By passing | By passing | ||
TABLE 9
| Example number | 19 | 20 | 21 | 22 | 23 | 24 | ||
| Step ①: for catalytic liquid Fossil oil gas Carrying out hydrolysis At carbonyl sulfide In order to solve the problems that, | in sample 1 Related data | Carbonyl sulfide content ppm | 20 | 20 | 20 | 20 | 20 | 20 |
| Mercaptan content ppm | 550 | 550 | 550 | 550 | 550 | 550 | ||
| Dissolved oxygen content ppm | 20 | 20 | 20 | 20 | 20 | 20 | ||
| Hydrolysis of carbonyl sulfide Catalyst and process for preparing same | Code number | D11 | D12 | D13 | D21 | D22 | D23 | |
| Operation process Condition | Temperature of | 20 | 0 | 50 | 20 | 0 | 50 | |
| Pressure MPa | 1.1 | 0.8 | 1.4 | 1.1 | 0.8 | 1.4 | ||
| Volume space velocity h-1 | 2.5 | 1 | 4 | 2.5 | 1 | 4 | ||
| Aspect ratio of filling | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | 6∶1 | ||
| In sample 2 Related data | Carbonyl sulfide content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Step ②: for catalytic liquid Fossil oil gas To carry out desulfurization Treatment of hydrogen | Desulfurizing agent | Code number | E11 | E12 | E13 | E21 | E22 | E23 |
| Operation process Condition | Temperature of | 20 | 0 | 50 | 20 | 0 | 50 | |
| Pressure MPa | 1.1 | 0.8 | 1.4 | 1.1 | 0.8 | 1.4 | ||
| Volume space velocity h-1 | 2.5 | 1 | 4 | 2.5 | 1 | 4 | ||
| Aspect ratio of filling | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | 6∶1 | ||
| In sample 3 Related data | Hydrogen sulfide content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Mercaptan content ppm | 400 | 400 | 400 | 400 | 400 | 400 | ||
| Dissolved oxygen content ppm | 5 | 5 | 5 | 5 | 5 | 5 | ||
| Step ③ For catalytic liquid Fossil oil gas Carrying out the transformation Of thiols Theory of things | Oxygen-supplementing agent | Code number | F | F | F | F | F | F |
| Concentration wt% | 71 | 71 | 71 | 71 | 71 | 71 | ||
| The oxygen supplementing agent contains available oxygen Catalytic liquefied petroleum gas station Containing mercaptan sulfur (molar ratio) | 0.8∶1 | 0.50∶1 | 1.8∶1 | 0.5∶1 | 1.5∶1 | 2.0∶1 | ||
| Double-effect catalyst | Code number | C11 | C12 | C13 | C21 | C22 | C23 | |
| Operation process Condition | Temperature of | 10 | 0 | 35 | 10 | 0 | 35 | |
| Pressure MPa | 0.9 | 1.0 | 1.4 | 0.9 | 1.0 | 1.4 | ||
| Volume space velocity h-1 | 1 | 4 | 2 | 1 | 4 | 2 | ||
| Aspect ratio of filling | 6∶1 | 5∶1 | 3∶1 | 6∶1 | 5∶1 | 3∶1 | ||
| In sample 4 Related data | Mercaptan content ppm | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Corrosion test of copper sheet | By passing | By passing | By passing | By passing | By passing | By passing | ||
Watch 10
| Example number | 25 | 26 | 27 | ||
| Step ①: for catalytic liquid Fossil oil gas Carrying out hydrolysis At carbonyl sulfide In order to solve the problems that, | in sample 1 Related data | Carbonyl sulfide content ppm | 20 | 20 | 20 |
| Mercaptan content ppm | 550 | 550 | 550 | ||
| Dissolved oxygen content ppm | 30 | 30 | 30 | ||
| Hydrolysis of carbonyl sulfide Catalyst and process for preparing same | Code number | D31 | D32 | D33 | |
| Operation process Condition | Temperature of | 20 | 0 | 60 | |
| Pressure MPa | 1.1 | 0.8 | 1.4 | ||
| Volume space velocity h-1 | 2.5 | 1 | 4 | ||
| Aspect ratio of filling | 5∶1 | 3∶1 | 6∶1 | ||
| In sample 2 Related data | Carbonyl sulfide content ppm | ＜0.1 | ＜0.1 | ＜0.1 | |
| Step ②: for catalytic liquid Fossil oil gas To carry out desulfurization Treatment of hydrogen | Desulfurizing agent | Code number | E31 | E32 | E33 |
| Operation process Condition | Temperature of | 20 | 0 | 60 | |
| Pressure MPa | 1.1 | 0.8 | 1.4 | ||
| Volume space velocity h-1 | 2.5 | 1 | 4 | ||
| Aspect ratio of filling | 5∶1 | 3∶1 | 6∶1 | ||
| In sample 3 Related data | Hydrogen sulfide content ppm | ＜0.1 | ＜0.1 | ＜0.1 | |
| Mercaptan content ppm | 400 | 400 | 400 | ||
| Dissolved oxygen content ppm | 5 | 5 | 5 | ||
| Step ③: for catalytic liquid Fossil oil gas Carrying out the transformation Of thiols Theory of things | Oxygen-supplementing agent | Code number | F | F | F |
| Concentration wt% | 71 | 71 | 71 | ||
| The oxygen supplementing agent contains available oxygen Catalytic liquefied petroleum gas station Containing mercaptan sulfur (molar ratio) | 1.0∶1 | 0.50∶1 | 1.8∶1 | ||
| Double-effect catalyst | Code number | C31 | C32 | C33 | |
| Operation process Condition | Temperature of | 10 | 0 | 60 | |
| Pressure MPa | 0.9 | 1.0 | 1.4 | ||
| Volume space velocity h-1 | 1 | 4 | 2 | ||
| Aspect ratio of filling | 6∶1 | 5∶1 | 3∶1 | ||
| In sample 4 Related data | Mercaptan content ppm | ＜0.1 | ＜0.1 | ＜0.1 | |
| Corrosion test of copper sheet | By passing | By passing | By passing | ||
In the above embodiments of the present invention, a mixing device may be connected in series to the delivery pipe between the second fixed bed reactor and the third fixed bed reactor, and the mixing device may be a mixing tank (for example, a mixing tank with a cavity inside or a mixing tank with a baffle plate inside) commonly usedin the oil refining industry, or a mixing device with a stirrer; the access mouth of oxygenating agent can directly set up on mixing arrangement, also can set up on the pipeline that is located before the mixing arrangement to make oxygenating agent and catalysis liquefied petroleum gas reach better mixed effect.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And such obvious variations or modifications which fall within the spirit of the invention are intended to be covered by the scope of the present invention.
Claims (16)
1.① A process for refining catalytic liquefied petroleum gas includes such steps as hydrolyzing carbonyl sulfide in the flowing catalytic liquefied petroleum gas by alcohol amine method, generating hydrogen sulfide and carbon dioxide by the action of carbonyl sulfide hydrolyzing catalyst when the catalytic liquefied petroleum gas passes through the bed of carbonyl sulfide hydrolyzing catalyst in the first fixed-bed reactor, removing hydrogen sulfide in the flowing catalytic liquefied petroleum gas by ②, chemically adsorbing the product generated by the reaction between hydrogen sulfide in the catalytic liquefied petroleum gas and chemical absorbent to desulfurizing agent when the catalytic liquefied petroleum gas passes through the bed of desulfurizing agent in the second fixed-bed reactor, ③ a process for converting the flowing catalytic liquefied petroleum gas to mercaptan, adding the catalyst containing tert-butyl hydroperoxide to the flowing catalytic liquefied petroleum gas in the conveying pipeline between the second and third fixed-bed reactors, and decomposing the catalytic liquefied petroleum gas to obtain the tertiary butyl hydroperoxide.
2. The method for refining catalytic liquefied petroleum gas as claimed in claim 1, wherein the step ① is performedThe active component of the carbonyl sulfide hydrolysis catalyst is sodium hydroxide or potassium hydroxide or sodium hydroxide and potassium hydroxide, and the carrier of the carbonyl sulfide hydrolysis catalyst is gamma-Al2O3When active components of the carbonyl sulfide hydrolysis catalyst are sodium hydroxide and potassium hydroxide, the weight ratio of the sodium hydroxide to the potassium hydroxide is 1: 99 to 99: 1, and when the catalytic liquefied petroleum gas after hydrogen sulfide removal treatment by the alcohol amine method is subjected to carbonyl sulfide hydrolysis treatment in step ①, the temperature of the catalytic liquefied petroleum gas is 0-60 ℃, the pressure is 0.8-1.4 MPa, and the volume space velocity of the catalytic liquefied petroleum gas passing through a carbonyl sulfide hydrolysis catalyst bed layer is 1h-1～4h-1(ii) a The filling height-diameter ratio of the carbonyl sulfide hydrolysis catalyst is 3-6: 1.
3. A method of refining a catalytic liquefied petroleum gas according to claim 2, characterized in that: the carrier of the carbonyl sulfide hydrolysis catalyst is gamma-Al prepared by using a rapid removal method2O3(ii) a The weight percentage of the active component in the carbonyl sulfide hydrolysis catalyst is 1 to 7 percent; the specific surface area of the carbonyl sulfide hydrolysis catalyst is 150m2/g～200m2Per g, the pore volume is 0.3 ml/g-0.4 ml/g, and the bulk density is 0.75g/cm3～0.9g/cm3。
4. The method for refining catalytic liquefied petroleum gas as claimed in claim 1, wherein the desulfurizing agent of the chemisorption type used in step ② is a desulfurizing agent whose active component is dicalcium ferrite, tricalcium ferrite hexahydrate or iron oxyhydroxide.
5. The method for refining catalytic liquefied petroleum gas as claimed in claim 4, wherein when the active component of the desulfurizing agent used in the step ② is iron oxyhydroxide, the desulfurizing agent further has CaSO as a support4·2H2O, and iron oxyhydroxide with CaSO4·2H2The molar ratio of O is 1: 1; the desulfurizing agent is cylindrical or strip-shaped, and has a specific surface area of 80m2/g～150m2Per g, pore volume of 0.3-0.4 ml/g, heapThe bulk density is 0.8g/cm3～0.9g/cm3The lateral pressure intensity is 100N/cm-150N/cm.
6. The method for refining catalytic liquefied petroleum gas as claimed in claim 4, wherein when the active component of the desulfurizing agent used in step ② is dicalcium ferrite or tricalcium ferrite hexahydrate, the desulfurizing agent further comprises calcium oxide as a carrier, the active component is present in the desulfurizing agent in an amount of 85-95 wt%, and the desulfurizing agent has a shape of a bar or a cylinder and a specific surface area of 1.8m2/g～10m2Per g, pore volume of 0.2-0.3 ml/g, and bulk density of 1.0g/cm3～1.1g/cm3The lateral pressure intensity is 80N/cm-150N/cm.
7. The method for refining catalytic liquefied petroleum gas as claimed in claim 1, wherein the catalytic liquefied petroleum gas after the carbonyl sulfide hydrolysis treatment is subjected to hydrogen sulfide removal treatment in step ②, the temperature of the catalytic liquefied petroleum gas is 0-60 ℃, the pressure of the catalytic liquefied petroleum gas is 0.8-1.4 MPa, and the volume space velocity of the catalytic liquefied petroleum gas passing through the desulfurizer bed is 1-4 h-1(ii) a The packing height-diameter ratio of the desulfurizer is 3-6: 1.
8. The method for refining and catalyzing liquefied petroleum gas as claimed in claim 1, wherein the dual-purpose catalyst in step ③ is composed of Mn compound as active component, and the dual-purpose catalyst is made of Mn compound pressed into cylindrical or strip shape, and has a specific surface area of 40m2/g～60m2Per g, the pore volume is 0.2 ml/g-0.3 ml/g, and the bulk density is 0.8g/cm3～1.0g/cm3The lateral pressure intensity is 100N/cm-170N/cm.
9. The method for refining catalytic liquefied petroleum gas as claimed in claim 1, wherein the component of the two-way catalyst in step ③ further has CaSO as a support for active component4·2H2The weight percentage of the O and manganese compounds in the double-effect catalyst is 5 to 90 percent; the double-effect catalyst is in a strip shape or a cylinder shapeHaving a specific surface area of 150m2/g～250m2Per g, the pore volume is 0.2 ml/g-0.35 ml/g, and the bulk density is 0.8g/cm3～0.9g/cm3The lateral pressure intensity is 90N/cm-150N/cm.
10. The method as claimed in claim 9, wherein the component of the two-way catalyst in step ③ further comprises iron oxyhydroxide (FeOOH), iron oxyhydroxide (FeOOH) and CaSO4·2H2The molar ratio of O is 1: 1.
11. A method of refining a catalytic liquefied petroleum gas according to any one of claims 8 to 10, wherein: the manganese compound is manganese dioxide, mangano-manganic oxide or manganese carbonate.
12. A method of refining catalytic liquefied petroleum gas according to claim 11, wherein: the manganese compound is manganese dioxide.
13. The method for refining catalytic liquefied petroleum gas as claimed in claim 1, wherein the catalytic liquefied petroleum gas having tert-butyl hydroperoxide dissolved therein in the step ③ is passed through a two-way catalyst disposed in the third fixed bed reactorThe flow direction of the catalytic liquefied petroleum gas is from bottom to top in the bed layer, the molar ratio of the effective oxygen contained in the oxygen supplement agent added into the catalytic liquefied petroleum gas to the mercaptan sulfur contained in the catalytic liquefied petroleum gas in the step ③ is 0.5-2: 1, when the catalytic liquefied petroleum gas dissolved with the tert-butyl hydroperoxide passes through the catalyst bed layer, the temperature of the catalytic liquefied petroleum gas is 0-60 ℃, the pressure is 0.8-1.4 MPa, and the volume space velocity of the catalytic liquefied petroleum gas passing through the double-effect catalyst bed layer is 1h-1～4h-1(ii) a The filling height-diameter ratio of the double-effect catalyst is 3-6: 1.
14. The method for refining catalytic liquefied petroleum gas as claimed in claim 13, wherein the effective oxygen contained in the oxygen supplying agent for catalyzing liquefied petroleum gas and the mercaptan sulfur contained in the catalytic liquefied petroleum gas are added in step ③The molar ratio is 1-1.5: 1; when the catalytic liquefied petroleum gas dissolved with the tert-butyl hydroperoxide passes through the catalyst bed, the temperature of the catalytic liquefied petroleum gas is 20-40 ℃; the volume space velocity is 1.5h-1～3h-1。
15. The method for refining catalytic liquefied petroleum gas as claimed in claim 1, wherein the concentration of the effective component tert-butyl hydroperoxide in the oxygen supplying agent added to the catalytic liquefied petroleum gas in step ③ is 70% to 99% by weight, and the ineffective component in the oxygen supplying agent is di-tert-butyl peroxide.
16. The method for refining catalytic liquefied petroleum gas as claimed in claim 1, wherein the step ④ is further carried out by subjecting the catalytic liquefied petroleum gas after mercaptan conversion treatment to gas fractionation and rectification treatment in order to obtain C contained in the catalytic liquefied petroleum gas by gas fractionation3～C4And a catalytic liquefied petroleum gas enriched in disulfide heavy components; then rectifying the catalytic liquefied petroleum gas enriched with the heavy components of the disulfide, and separating the disulfide from the catalytic liquefied petroleum gas enriched with the heavy components of the disulfide through rectification treatment to obtain the ultralow-sulfur or sulfur-free catalytic liquefied petroleum gas and the disulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100723533A CN1321169C (en) | 2005-05-02 | 2005-05-30 | Method for refining catalytic liquefied petroleum gas |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510070541 | 2005-05-02 | ||
| CN200510070541.2 | 2005-05-02 | ||
| CNB2005100723533A CN1321169C (en) | 2005-05-02 | 2005-05-30 | Method for refining catalytic liquefied petroleum gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1702157A true CN1702157A (en) | 2005-11-30 |
| CN1321169C CN1321169C (en) | 2007-06-13 |
Family
ID=35632121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100723533A Active CN1321169C (en) | 2005-05-02 | 2005-05-30 | Method for refining catalytic liquefied petroleum gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1321169C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591559A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | Each material high precision, capacity dehydration method in a kind of petrochemical process |
| CN101591215A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | The water-retaining agent that uses in a kind of normal-temperature propylene refining technology and this technology |
| CN104524938A (en) * | 2015-01-16 | 2015-04-22 | 重庆地之净科技有限公司 | Device and method for alkali-free desulfuration and deodorization by virtue of liquefied gas fixed bed |
| CN106782002A (en) * | 2015-11-25 | 2017-05-31 | 中国石油天然气股份有限公司 | Gas production training system |
| CN107955661A (en) * | 2016-10-14 | 2018-04-24 | 北京三聚环保新材料股份有限公司 | A kind of liquefied petroleum gas treatment process |
| CN109420417A (en) * | 2017-08-20 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of hydration method separation sour gas technique and device |
| CN114768837A (en) * | 2022-04-28 | 2022-07-22 | 西安元创化工科技股份有限公司 | FeOOH desulfurization catalyst prepared from titanium dioxide byproduct copperas and preparation method thereof |
| CN114768837B (en) * | 2022-04-28 | 2024-06-07 | 西安元创化工科技股份有限公司 | Iron oxyhydroxide desulfurization catalyst prepared from titanium dioxide byproduct copperas and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077984B (en) * | 2007-07-25 | 2010-08-25 | 中国石油大学(北京) | Deep desulfurization method for liquefied petroleum gas |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4329220A (en) * | 1979-02-05 | 1982-05-11 | Atlantic Richfield Company | Catalytic reforming process with liquid phase sulfur removal |
| US6428761B1 (en) * | 2000-09-29 | 2002-08-06 | Engelhard Corporation | Process for reduction of gaseous sulfur compounds |
| CN1194077C (en) * | 2000-10-10 | 2005-03-23 | 北京三聚环保新材料有限公司 | Alkali-free refining process of liquefied petroleum gas or natural gas |
| CN1245488C (en) * | 2001-11-13 | 2006-03-15 | 北京三聚环保新材料有限公司 | Method for indudstrialized refining liquefied petrolium gas (LPG) |
-
2005
- 2005-05-30 CN CNB2005100723533A patent/CN1321169C/en active Active
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591559A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | Each material high precision, capacity dehydration method in a kind of petrochemical process |
| CN101591215A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | The water-retaining agent that uses in a kind of normal-temperature propylene refining technology and this technology |
| CN101591215B (en) * | 2008-05-29 | 2013-06-12 | 北京三聚环保新材料股份有限公司 | Normal-temperature propylene refining technology and water absorbent used therein |
| CN104524938A (en) * | 2015-01-16 | 2015-04-22 | 重庆地之净科技有限公司 | Device and method for alkali-free desulfuration and deodorization by virtue of liquefied gas fixed bed |
| CN106782002A (en) * | 2015-11-25 | 2017-05-31 | 中国石油天然气股份有限公司 | Gas production training system |
| CN106782002B (en) * | 2015-11-25 | 2019-10-11 | 中国石油天然气股份有限公司 | Gas production training system |
| CN107955661A (en) * | 2016-10-14 | 2018-04-24 | 北京三聚环保新材料股份有限公司 | A kind of liquefied petroleum gas treatment process |
| CN109420417A (en) * | 2017-08-20 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of hydration method separation sour gas technique and device |
| CN109420417B (en) * | 2017-08-20 | 2021-04-06 | 中国石油化工股份有限公司 | Process and device for separating acid gas by hydration method |
| CN114768837A (en) * | 2022-04-28 | 2022-07-22 | 西安元创化工科技股份有限公司 | FeOOH desulfurization catalyst prepared from titanium dioxide byproduct copperas and preparation method thereof |
| CN114768837B (en) * | 2022-04-28 | 2024-06-07 | 西安元创化工科技股份有限公司 | Iron oxyhydroxide desulfurization catalyst prepared from titanium dioxide byproduct copperas and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1321169C (en) | 2007-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1702157A (en) | Method for refining catalytic liquefied petroleum gas | |
| JP5075635B2 (en) | System and method for reducing the sulfur content of a hydrocarbon stream | |
| CN1090536C (en) | Porous lithium aluminate carrier of spinel structure for catalyst | |
| CN101811051A (en) | Carbonyl sulfide hydrolysis catalyst prepared by using cobalt(Co)-nickel(Ni)-aluminum(Al) hydrotalcites as precursor and preparation method thereof | |
| CN1313203C (en) | Use of a TiO2 composition as catalyst for hydrolyzing COS and/or HCN in a gas mixture | |
| CN1245488C (en) | Method for indudstrialized refining liquefied petrolium gas (LPG) | |
| CN101733105A (en) | Carbonyl sulfur hydrolyst prepared by using binary type hydrotalcite as precursor and method for preparing same | |
| CN103525474A (en) | Ultrafine desulfurization agent and preparation method thereof | |
| Jiang et al. | Simultaneous removal of hydrogen sulfide and ammonia in the gas phase: a review | |
| CN1086308C (en) | Direct oxidation method for converting sulphur compounds into sulphur with a copper catalyst | |
| CN1021960C (en) | Process for steam-reforming hydrocarbons | |
| CN114192135A (en) | Carbonyl sulfide hydrolyzing agent and preparation method thereof | |
| CN110201540B (en) | Process for removing methyl mercaptan from carbon dioxide gas | |
| CN101791519A (en) | Application process for treating acid gas containing H2S by active carbocoal method | |
| CN113278995A (en) | Method for preparing oxalic acid from carbon dioxide or bicarbonate or carbonate | |
| CN1234809C (en) | Process for transforming thiols contained in light oil | |
| US9919285B2 (en) | Sorbents | |
| CN104524973A (en) | Liquefied gas desulfurizing agent | |
| CN1485416A (en) | Preparation process of immersion for water-gas sulfur-resistant transformation catalyst | |
| CN1805899A (en) | Purification of a mixture of H*/CO by catalysis of the impurities | |
| CN1320958C (en) | Double-effect catalyst and its production process | |
| CN1194077C (en) | Alkali-free refining process of liquefied petroleum gas or natural gas | |
| CN1295875A (en) | Detergent and washing method for harmful gas | |
| CN113058412A (en) | Waste gas treatment process and treatment device thereof | |
| CN1292053C (en) | Process for transforming thiols contained in liquefied petroleum gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: BEIJING SANJU ENVIRONMENTAL PROTECTION AND NEW MAT Free format text: FORMER NAME OR ADDRESS: SANJU ENVIRONMENT PROTECTION NEW MATERIAL CO., LTD., BEIJING |
|
| CP03 | Change of name, title or address |
Address after: Beijing Haidian District people's Congress Road 33, the big line foundation building 9 floor Patentee after: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. Address before: Beijing Haidian District people's Congress Road 33, the big line foundation building 17 floor Patentee before: Beijing SJ Environmental Protection and New Material Co.,Ltd. |
|
| ASS | Succession or assignment of patent right |
Owner name: BEIJING SANJU CHUANGJIE TECHNOLOGY DEVELOPMENT CO. Free format text: FORMER OWNER: BEIJING SANJU NEW ENVIRONMENTAL PROTECTION MATERIALS CO., LTD. Effective date: 20100122 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20100122 Address after: Beijing Haidian District people's Congress Road 33, the big line foundation building 15 Floor Patentee after: Beijing Sanju Chuangjie Technology Development Co.,Ltd. Address before: Beijing Haidian District people's Congress Road 33, the big line foundation building 9 floor Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 100080, Beijing Haidian District Renmin University North Road No. 1 Building No. 33 building foundation building 906 Patentee after: BEIJING SANJU GREEN ENERGY TECHNOLOGY Co.,Ltd. Address before: 100080, Beijing, Haidian District people's Congress Road 33, the big line foundation building 15 Floor Patentee before: Beijing Sanju Chuangjie Technology Development Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200928 Address after: 100080, Beijing, Haidian District North Road, No. 33, building 1, foundation building, 9 floor Patentee after: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. Address before: 100080 Beijing Haidian District Renmin University North Road No. 1 Building No. 33 building 906 Patentee before: BEIJING SANJU GREEN ENERGY TECHNOLOGY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Address before: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |