CN102886275B - 一种原位晶化制备含双分子筛裂化催化剂的方法 - Google Patents
一种原位晶化制备含双分子筛裂化催化剂的方法 Download PDFInfo
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- 238000002425 crystallisation Methods 0.000 title claims abstract description 76
- 230000008025 crystallization Effects 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000005336 cracking Methods 0.000 title claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000002808 molecular sieve Substances 0.000 claims abstract description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000004005 microsphere Substances 0.000 claims abstract description 52
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 28
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 27
- 238000010009 beating Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 230000018044 dehydration Effects 0.000 claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 230000011218 segmentation Effects 0.000 claims abstract description 7
- -1 rare-earth salts Chemical class 0.000 claims abstract description 5
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- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 14
- 150000002910 rare earth metals Chemical class 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 239000002689 soil Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 210000002966 serum Anatomy 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000000295 fuel oil Substances 0.000 abstract description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 238000001694 spray drying Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011066 ex-situ storage Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 241000190022 Pilea cadierei Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
项目 | SiO2 | Al2O3 | Na2O | K2O | MgO | CaO | Fe2O3 | TiO2 |
重% | 52.8 | 44.3 | 0.07 | 0.42 | 0.07 | 0.26 | 0.7 | 0.66 |
原料油密度,克/升 | 918.5 | 钒含量,微克/克 | 0.8 |
原料油残炭,重% | 0.8 | 镍含量,微克/克 | 0.7 |
硫,重% | 2.5 | 氮,重% | 0.13 |
初馏点,℃ | 300 | 70% | 450 |
30% | 350 | 90% | 520 |
50% | 400 | 终馏点,℃ | 590 |
项目 | 对比例1 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
干气 | 4.2 | 3.9 | 4.2 | 4.1 | 4.0 |
液态烃 | 13.2 | 14.0 | 14.3 | 13.9 | 14.4 |
汽油 | 44.2 | 48.2 | 47.3 | 47.5 | 46.8 |
轻油 | 24.1 | 24.1 | 23.8 | 24.3 | 24.9 |
重油 | 9.4 | 5.7 | 6.1 | 5.8 | 6.0 |
焦炭 | 4.9 | 4.1 | 4.3 | 4.4 | 3.9 |
转化率 | 66.5 | 70.2 | 70.1 | 69.9 | 69.1 |
轻烃液收 | 81.5 | 86.3 | 85.4 | 85.7 | 86.1 |
汽油RON | 91.2 | 92.0 | 92.2 | 91.9 | 92.1 |
Claims (10)
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Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104096590B (zh) * | 2013-04-10 | 2016-09-14 | 上海碧科清洁能源技术有限公司 | 混合分子筛催化剂及其制备方法和应用 |
CN104549408B (zh) * | 2013-10-28 | 2017-07-14 | 中国石油化工股份有限公司 | Mcm‑22/zsm‑5原位共生甲醇芳构化催化剂及其制备方法 |
CN104368322A (zh) * | 2014-11-05 | 2015-02-25 | 吴俊荣 | 催化裂化催化剂的制备方法 |
CN106732746B (zh) * | 2016-12-07 | 2019-10-18 | 四川润和催化新材料股份有限公司 | 一种无氨法制备催化裂化催化剂的方法 |
CN112138709A (zh) * | 2019-06-28 | 2020-12-29 | 浙江恒澜科技有限公司 | 催化剂及其制备方法和在环己酮肟气相贝克曼重排反应中的应用 |
CN110479361A (zh) * | 2019-09-03 | 2019-11-22 | 四川润和催化新材料股份有限公司 | 一种降油浆和多产低碳烯烃的助剂及其制备方法与应用 |
CN115055205A (zh) * | 2022-05-20 | 2022-09-16 | 大连理工大学 | 一种zsm-5/y复合分子筛的合成和重油催化裂化催化剂的制备方法 |
Citations (4)
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EP0224992A1 (en) * | 1985-08-30 | 1987-06-10 | Engelhard Corporation | FCC catalysts of increased effective heat capacity |
CN1951567A (zh) * | 2005-10-18 | 2007-04-25 | 中国石油天然气股份有限公司 | 一种高岭土基复合分子筛及其制备方法 |
CN101239327A (zh) * | 2008-03-25 | 2008-08-13 | 北京惠尔三吉绿色化学科技有限公司 | 一种含高岭土原位晶化zsm-5和y型分子筛的固定床催化剂及其制备方法 |
CN101462740A (zh) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | 一种原位晶化制备zsm-5沸石的方法 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0224992A1 (en) * | 1985-08-30 | 1987-06-10 | Engelhard Corporation | FCC catalysts of increased effective heat capacity |
CN1951567A (zh) * | 2005-10-18 | 2007-04-25 | 中国石油天然气股份有限公司 | 一种高岭土基复合分子筛及其制备方法 |
CN101462740A (zh) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | 一种原位晶化制备zsm-5沸石的方法 |
CN101239327A (zh) * | 2008-03-25 | 2008-08-13 | 北京惠尔三吉绿色化学科技有限公司 | 一种含高岭土原位晶化zsm-5和y型分子筛的固定床催化剂及其制备方法 |
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