CN102050462A - 一种提高水热稳定性的双组元改性分子筛及制备方法 - Google Patents
一种提高水热稳定性的双组元改性分子筛及制备方法 Download PDFInfo
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- CN102050462A CN102050462A CN2009102370074A CN200910237007A CN102050462A CN 102050462 A CN102050462 A CN 102050462A CN 2009102370074 A CN2009102370074 A CN 2009102370074A CN 200910237007 A CN200910237007 A CN 200910237007A CN 102050462 A CN102050462 A CN 102050462A
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- molecular sieve
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- reaction
- aqueous solution
- modified molecular
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- 239000002808 molecular sieve Substances 0.000 claims abstract description 71
- 238000001914 filtration Methods 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- -1 phosphorus modified molecular sieve Chemical class 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 48
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 62
- 239000000203 mixture Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 49
- 238000003756 stirring Methods 0.000 description 46
- 230000032683 aging Effects 0.000 description 18
- 239000005995 Aluminium silicate Substances 0.000 description 17
- 206010013786 Dry skin Diseases 0.000 description 17
- 239000004411 aluminium Substances 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 235000012211 aluminium silicate Nutrition 0.000 description 17
- 238000010009 beating Methods 0.000 description 17
- 238000013467 fragmentation Methods 0.000 description 17
- 238000006062 fragmentation reaction Methods 0.000 description 17
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 17
- 238000011835 investigation Methods 0.000 description 16
- 101710134784 Agnoprotein Proteins 0.000 description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 15
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- 239000010457 zeolite Substances 0.000 description 14
- 238000012986 modification Methods 0.000 description 12
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- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 238000010335 hydrothermal treatment 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
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- JRLPEMVDPFPYPJ-UHFFFAOYSA-N 1-ethyl-4-methylbenzene Chemical compound CCC1=CC=C(C)C=C1 JRLPEMVDPFPYPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 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
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
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Abstract
一种提高水热稳定性的双组元改性分子筛及其制备方法,其特征在于将分子筛加入到含磷水溶液中,在pH值、反应温度以及反应压力一定的条件下反应一段时间,然后经过滤、干燥和焙烧,得到磷改性分子筛。然后将磷改性分子筛加入到含银离子水溶液中,在一定的反应温度条件下反应一段时间,然后经过滤、干燥和焙烧,得到双组元改性分子筛。所得改性分子筛含干基含量88~99重%的硅铝比为15~60的分子筛、以氧化物计0.5~10重%的磷与氧化物计0.01~2重%的银。采用该双组元改性分子筛制备模型催化剂比含未改性以及其它方法改性的分子筛模型催化剂有很高的水热稳定性和微活性能。
Description
技术领域
本发明属于分子筛改性技术领域,特别涉及一种提高水热稳定性的双组元改性分子筛及制备方法。
背景技术
近年来,国内外炼油催化剂的研究人员和生产商长期致力于采用各种类型结构的分子筛来改善FCC催化剂性能的研究,提高FCC装置的低碳烯烃产率。这是由于传统制乙烯和丙烯主要方法即蒸汽裂解是通过自由基反应进行的,温度高、对原料要求苛刻。然而,催化裂解制低碳烯烃成本较低,是目前国内外研究增产低碳烯烃的热点。功能择形分子筛作为该类催化转化催化剂的主要活性组分受到广泛关注。
自从1972年,美国Mobil公司开发了ZSM-5沸石分子筛(USP 3,702,886)后,由于其具有较高的硅铝比、独特的孔道结构和优异的热和水热稳定性,ZSM-5沸石分子筛已在烃类的择形裂化(CN 1872415A)、烷基化、异构化、歧化、催化脱蜡、醚化等石油化工过程中得到了极其广泛的应用。尤其在常规催化裂化催化剂或助剂中添加ZSM-5沸石能大幅度提高低碳烯烃的产率和辛烷值(USP5,997,728)。
然而,ZSM-5沸石分子筛在催化裂化水热条件下容易失活,影响其稳定性和选择性。所以,人们对ZSM-5沸石分子筛的改性进行了大量的研究。
USP 4,399,059中用磷酸氢二铵或磷酸二氢铵与NH4-ZSM-5混合并烘干后,经500℃焙烧制成磷改性ZSM-5。该沸石用于二甲苯异构化反应时可显著改善其对位产物的选择性。
USP 5,171,921中公开了一种用磷化合物浸渍改性ZSM-5分子筛,改性后可用作将烯烃或脂肪烃转化为C2~C5烯烃的催化活性组分。
USP 3,972,382和USP 3,965,208公开了HZSM-5采用亚磷酸三甲酯改性后,反应选择性提高。
CN85102828报道了采用浸渍蒸干法改性ZSM-5分子筛,经磷改性后对甲苯乙烯烷基化制取对甲乙苯择形催化活性大大提高。
CN97120271报道了一种含磷八面沸石烃类裂化催化剂,所述含磷八面沸石是将八面沸石与含磷化合物水溶液混合均匀后,干燥,于450~600℃焙烧0.5小时以上制备的,且有较好的催化活性。
CN98117286报道了一种含有90-99.9重的硅铝酸盐沸石和以P2O5计,0.1~10重%的磷的含磷沸石,该沸石具有较高的烃转化活性、对柴油选择性和较好的抗钒、镍等重金属的性能。
CN 1211469A和CN 1211470A报道了一种多产丙烯和乙烯的分子筛组合物,其特征在于将一种五元环分子筛加入到一种含有磷以及碱土金属离子和/或过渡金属离子的化合物的水溶液中混合均匀并浸渍反应得到,该组合物由85~95重%的五元环分子筛、以氧化物计2~10重%的磷、以氧化物计0.3~5重%的碱土金属、以氧化物计0.3~5重%的过渡金属元素所组成。
CN 1072031C和CN 1072032C也报道了一种多产丙烯和乙烯(特别是乙烯)的五元环分子筛组合物,由88~95重%的五元环分子筛、以氧化物计2~8重%的磷、以氧化物计0.3~3重%的碱土金属、以氧化物计0~3重%的过渡金属元素所组成。此组合物制备方法为一步浸渍法,工艺较简单,稳定性好,乙烯产率有明显的提高。
现在工业应用的催化裂化催化剂的低碳烯烃,尤其是丙烯的产率偏低,还不能满足炼油和化工生产的实际需要,因此大幅度提高丙烯的产率意义重大。目前看来,对功能择形裂化分子筛的改性是催化裂化增产低碳烯烃最有效的途径。
然而,目前常规的磷改性分子筛在通过离子交换引入第二改性组分时,分子筛中的磷元素会大量地流失而不能实现双组元改性分子筛的目的,从而影响分子筛的稳定性以及催化活性。
发明内容
本发明的目的在于针对现有分子筛材料与技术,提供一种大幅提高水热稳定性的双组元改性分子筛及制备方法。
一种提高水热稳定性的双组元改性分子筛的改性方法,将分子筛加入到含磷水溶液,然后经过滤、干燥和焙烧,其特征在于该方法是将分子筛加入到含磷水溶液中,在pH值为1~10(最好是2~7)、反应温度70~200℃(最好是90~160℃)以及0.2~1.2MPa(最好是0.2~0.8MPa)反应压力条件下反应10~200分钟,然后经过滤、干燥和焙烧,得到磷改性分子筛;将磷改性分子筛加入到含银离子水溶液中,反应温度0~100℃(最好是20~60℃)条件下避光反应30~150分钟,然后经过滤、干燥和焙烧,得到双组元改性分子筛。
在本发明所提供的方法中,改性过程中的过滤、干燥和焙烧均是采用现有技术中通常使用的工艺过程和技术参数,本发明并不特别加以限制,推荐的干燥温度为100~120℃,焙烧温度为200~800℃,焙烧时间为0.5~10小时。
本发明区别于常规磷改性方法要求的改性条件,其为高温并且同时带一定的压力,通过高温和带有压力的协同效果可进一步加强改性组分在分子筛孔道中的扩散,使改性组分进入更深的分子筛孔道中与其表面的B酸位发生反应,只是高温或低温带有压力均不能达到令人满意的效果,当然其前提还是需要以水作为介质。
本发明所提供的方法中对含磷水溶液并不特别加以限定,通常磷改性分子筛所用的含磷水溶液均可。含磷水溶液中的磷化合物并不特别限定,只要能溶于水即可。含磷水溶液如可以是磷酸溶液、亚磷酸溶液,可溶性磷酸盐水溶液、亚磷酸盐水溶液等等,可以是其中一种或多种,可溶性磷酸盐水溶液、亚磷酸盐水溶液可以是磷酸铵、磷酸氢二铵、磷酸二氢铵等磷酸盐、亚磷酸盐的水溶液。含磷水溶液与分子筛重量比最好为(2~5)∶1。
本发明所说的含银离子水溶液可以为硝酸银、乙酸银中一种或两种混合物的水溶液。含银离子水溶液与分子筛重量比最好为(2~10)∶1,含银离子水溶液浓度最好为0.01~0.1mol/L。
本发明并不需限定该方法中分子筛种类及其组成、磷的组成、银的组成,根据需要而定。所述的分子筛最好是ZSM型、β型、Y型、MCM型分子筛中的一种,优选ZSM型与β型分子筛,其硅铝比为15~100,优选15~60。
本发明还要求保护应用本发明的改性方法得到的改性分子筛。并提供一种使用本发明的改性方法得到最佳改性分子筛:含有干基含量88~99重%、硅铝比为15~60的分子筛、以氧化物计0.5~10重%的磷与氧化物计0.01~2重%的银,该双组元改性分子筛具有很好的水热稳定性和活性。
发明人通过研究发现,磷的引入抑制了ZSM-5沸石骨架在水热条件下的脱铝作用,显著提高了沸石上的酸保留度,从而提高了其催化活性和选择性;另外,为进一步大幅提高分子筛的水热稳定性同时实现调变沸石的表面酸性,需要引入第二种改性元素对其进行改性。ZSM-5分子筛中引入过渡金属银离子后,其氧化作用有利于正碳离子的生成,使反应更容易引发,从而提高了反应活性;与其它过渡金属相比,银对烯烃的吸附较弱,可以减少氢转移反应的发生,有利于烯烃产率的提高,并且银作为过渡金属,在反应中可以接受或给予电子,转变成自由基,再断裂生成烯烃,其氧化-还原作用能使反应按自由基机理进行,因而可以提高低碳烯烃产率。
本发明的优点是在于该方法能够防止磷改性分子筛在进行过渡金属离子交换改性中磷组分的大量流失,所改性制得的双组元改性分子筛及其模型催化剂有极好的水热稳定性和催化活性。
具体实施方式
本发明各实施例和对比例的分析评价方法为:
1.元素分析采用X射线荧光光谱法(XRF)测定,所用仪器为日本理学ZSXprimus型X射线荧光光谱仪。
2.稳定性评价通过800℃×4小时以及800℃×17小时水热老化前后的相对结晶度(ZSM-5%)变化判断,结晶度在日本Rigaku公司的D/max-3C X射线衍射仪上测定。
3.活性评价通过北京华阳公司出品的微反评定装置上测定,原料油采用大港轻柴油,评定条件:催化剂经800℃、100%水蒸汽条件下处理4小时、17小时,催化剂装量5克,反应温度460℃,反应时间70秒,剂油比为3.2。
实施例1
取9.3克(NH4)2HPO4溶于500克蒸馏水中,搅拌的条件下将ZSM-5分子筛样品100克加入溶液中,pH值调节至4。在反应温度为100℃,反应压力为0.2MPa搅拌反应60分钟后过滤,烘干,然后在500℃下焙烧4小时,所得分子筛样品记为PZ-1。
取0.73克AgNO3溶于350克蒸馏水中,将PZ-1分子筛加入到该含银溶液中,在反应温度为20℃下避光搅拌反应120分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZ-1。然后将高岭土(45%)、铝溶胶(15%)以及APZ-1(40%)按以上比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为C-1,取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
实施例2
取18.6克(NH4)2HPO4溶于400克蒸馏水中,搅拌的条件下将ZSM-5分子筛样品100克加入溶液中,pH值调节至3。在反应温度为120℃,反应压力为0.4MPa搅拌反应120分钟后过滤,烘干,然后在550℃下焙烧4小时,所得分子筛样品记为PZ-2.
取1.46克AgNO3溶于350克蒸馏水中,将PZ-2分子筛加入到该含银溶液中,在反应温度为40℃下避光搅拌反应100分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZ-2。然后将高岭土(45%)、铝溶胶(15%)以及APZ-2(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为C-2。取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
实施例3
取37.2克(NH4)2HPO4溶于500克蒸馏水中,搅拌的条件下将ZSM-5分子筛样品100克加入溶液中,pH值调节至2。在反应温度为140℃,反应压力为1MPa搅拌反应200分钟后过滤,烘干,然后在450℃下焙烧6小时,所得分子筛样品记为PZ-3.
取2.19克AgNO3溶于400克蒸馏水中,将PZ-3分子筛加入到该含银溶液中,在反应温度为60℃下避光搅拌反应60分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZ-3。然后将高岭土(45%)、铝溶胶(15%)以及APZ-3(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为C-3。取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
实施例4
取25.1克(NH4)2HPO4溶于500克蒸馏水中,搅拌的条件下将ZSM-5分子筛样品100克加入溶液中,pH值调节至3。在反应温度为140℃,反应压力为0.4MPa搅拌反应200分钟后过滤,烘干,然后在550℃下焙烧4小时,所得分子筛样品记为PZ-4.
取2.19克AgAc溶于400克蒸馏水中,将PZ-4分子筛加入到该含银溶液中,在反应温度为20℃下避光搅拌反应300分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZ-4。然后将高岭土(45%)、铝溶胶(15%)以及APZ-4(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为C-4。取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
实施例5
取16.2克NH4H2PO4溶于250克蒸馏水中,搅拌的条件下将ZSM-5分子筛样品100克加入溶液中,pH值调节至2。在反应温度为120℃,反应压力为0.4MPa搅拌反应60分钟后过滤,烘干,然后在600℃下焙烧2小时,所得分子筛样品记为PZ-5。
取1.46克AgNO3溶于300克蒸馏水中,将PZ-5分子筛加入到该含银溶液中,在反应温度为20℃下避光搅拌反应200分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZ-5。然后将高岭土(45%)、铝溶胶(15%)以及APZ-5(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为C-5。取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
实施例6
取28.2克NH4H2PO4溶于500克蒸馏水中,搅拌的条件下将ZSM-5分子筛样品100克加入溶液中,pH值调节至2。在反应温度为130℃,反应压力为0.6MPa搅拌反应120分钟后过滤,烘干,然后在600℃下焙烧2小时,所得分子筛样品记为PZ-6。
取2.19克AgAc溶于300克蒸馏水中,将PZ-6分子筛加入到该含银溶液中,在反应温度为60℃下避光搅拌反应300分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZ-6。然后将高岭土(45%)、铝溶胶(15%)以及APZ-6(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为C-6。取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
实施例7
取16.2克H3PO4溶于200克蒸馏水中,搅拌的条件下将ZSM-5分子筛样品100克加入溶液中,调节pH值调节至2。在反应温度为200℃,反应压力为1.0MPa搅拌反应60分钟后过滤,烘干,然后在450℃下焙烧6小时,所得分子筛样品记为PZ-7。
取1.46克AgNO3溶于400克蒸馏水中,将PZ-7分子筛加入到该含银溶液中,在反应温度为40℃下避光搅拌反应240分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZ-7。然后将高岭土(45%)、铝溶胶(15%)以及APZ-7(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为C-7。取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
实施例8
取28.2克H3PO4溶于400克蒸馏水中,搅拌的条件下将ZSM-5分子筛样品100克加入溶液中,pH值调节至2。在反应温度为120℃,反应压力为0.6MPa搅拌反应200分钟后过滤,烘干,然后在600℃下焙烧2小时,所得分子筛样品记为PZ-8。
取1.09克AgAc与1.07克AgNO3溶于400克蒸馏水中,将PZ-8分子筛加入到该含银溶液中,在反应温度为60℃下避光搅拌反应300分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZ-8。然后将高岭土(45%)、铝溶胶(15%)以及APZ-8(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为C-8。取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
实施例9
取9.3克(NH4)2HPO4溶于100克蒸馏水中,搅拌的条件下将β分子筛样品100克加入溶液中,pH值调节至4。在反应温度为110℃,反应压力为0.4MPa搅拌反应120分钟后过滤,烘干,然后在500℃下焙烧6小时,所得分子筛样品记为Pβ-1。
取0.73克AgNO3溶于300克蒸馏水中,将Pβ-1分子筛加入到该含银溶液中,在反应温度为20℃下避光搅拌反应100分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APβ-1。然后将高岭土(45%)、铝溶胶(15%)以及APβ-1(40%)按固定比例加入蒸馏水中打浆、120℃干燥,500℃焙烧1小时后破碎过筛,所得催化剂样品记为C-9,取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
实施例10
取18.6克(NH4)2HPO4溶于250克蒸馏水中,搅拌的条件下将β分子筛样品100克加入溶液中,pH值调节至3。在反应温度为160℃,反应压力为0.8MPa搅拌反应60分钟后过滤,烘干,然后在450℃下焙烧6小时,所得分子筛样品记为Pβ-2。
取1.46克AgNO3溶于300克蒸馏水中,将Pβ-2分子筛加入到该含银溶液中,在反应温度为20℃下避光搅拌反应200分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APβ-2。然后将高岭土(45%)、铝溶胶(15%)以及APβ-2(40%)按固定比例加入蒸馏水中打浆、120℃干燥,500℃焙烧1小时后破碎过筛,所得催化剂样品记为C-10,取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
实施例11
取18.6克(NH4)2HPO4与16.2克NH4H2PO4溶于400克蒸馏水中,搅拌的条件下将β分子筛样品100克加入溶液中,pH值调节至5。在反应温度为100℃,反应压力为0.2MPa搅拌反应180分钟后过滤,烘干,然后在600℃下焙烧2小时,所得分子筛样品记为Pβ-3。
取1.09克AgAc与1.07克AgNO3溶于350克蒸馏水中,将Pβ-3分子筛加入到该含银溶液中,在反应温度为20℃下避光搅拌反应90分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APβ-3。然后将高岭土(45%)、铝溶胶(15%)以及APβ-3(40%)按固定比例加入蒸馏水中打浆、120℃干燥,500℃焙烧1小时后破碎过筛,所得催化剂样品记为C-11,取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
对比例1
取18.6克(NH4)2HPO4溶于400克蒸馏水中,搅拌的条件下将100克ZSM-5分子筛加入该溶液中,pH值调节至3。反应温度为90℃,搅拌反应120分钟后过滤,烘干,然后在550℃下焙烧4小时,所得分子筛样品记为PZD-1。
取1.46克AgNO3溶于350克蒸馏水中,将PZD-1分子筛加入到该含银溶液中,在反应温度为40℃下避光搅拌反应100分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZD-1。然后将高岭土、铝溶胶以及APZD-1(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为CD-1,取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
对比例2
取18.6克(NH4)2HPO4溶于400克蒸馏水中,搅拌的条件下将100克ZSM-5分子筛加入该溶液中,pH值调节至3。在反应温度为20℃,反应压力为0.4MPa搅拌反应120分钟后过滤,烘干,然后在550℃下焙烧4小时,所得分子筛样品记为PZD-2。
取2.19克AgNO3溶于400克蒸馏水中,将PZD-2分子筛加入到该含银溶液中,在反应温度为40℃下避光搅拌反应100分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZD-2。然后将高岭土(45%)、铝溶胶(15%)以及APZD-2(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为CD-2,取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
对比例3
取18.6克(NH4)2HPO4与100克ZSM-5分子筛充分机械混合,然后在550℃下焙烧4小时,所得分子筛样品记为PZD-3。
取2.19克AgNO3溶于400克蒸馏水中,将PZD-3分子筛加入到该含银溶液中,在反应温度为40℃下避光搅拌反应100分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZD-3。然后将高岭土(45%)、铝溶胶(15%)以及APZD-3(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为CD-3,取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
对比例4
取9.3克(NH4)2HPO4溶于110克蒸馏水中,将该溶液加入到100克ZSM-5分子筛样品中,浸渍300分钟后烘干,然后在500℃下焙烧4小时,所得分子筛样品记为PZD-4。
取1.46克AgNO3溶于350克蒸馏水中,将PZD-4分子筛加入到该含银溶液中,在反应温度为40℃下避光搅拌反应200分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APZD-4。然后将高岭土(45%)、铝溶胶(15%)以及APZD-4(40%)按以上比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为CD-4,取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
对比例5
取18.6克NH4H2PO4溶于400克蒸馏水中,搅拌的条件下将β分子筛样品100克加入溶液中,pH值调节至2。在反应温度为50℃下,搅拌反应60分钟后过滤,烘干,然后在600℃下焙烧2小时,所得分子筛样品记为PβD-1。
取2.19克AgNO3溶于350克蒸馏水中,将PβD-1分子筛加入到该含银溶液中,在反应温度为40℃下避光搅拌反应100分钟后过滤,烘干,然后在500℃下焙烧2小时,得到双组元改性分子筛APβD-1。然后将高岭土(45%)、铝溶胶(15%)以及APβD-1(40%)按固定比例加入蒸馏水中打浆、120℃干燥,500℃焙烧1小时后破碎过筛,所得催化剂样品记为CD-5,取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
对比例6
取18.6克(NH4)2HPO4溶于400克蒸馏水中,搅拌的条件下将ZSM-5分子筛样品100克加入溶液中,然后加入含1.46克AgNO3溶液10ml,pH值调节至3。在反应温度为120℃,反应压力为0.4MPa搅拌反应120分钟后过滤,烘干,然后在550℃下焙烧4小时,所得分子筛样品记为APZD-5。
然后将高岭土(45%)、铝溶胶(15%)以及APZD-5(40%)按固定比例加入蒸馏水中打浆、120℃干燥,450℃焙烧1小时后破碎过筛,所得催化剂样品记为CD-6。取20~40目颗粒催化剂进行微活考察。样品的组成、老化前后的结晶度及模型催化剂微反活性见表1~3。
表1磷改性分子筛的水热稳定性
*结晶度保留率=水热处理后相对结晶度/水热处理前相对结晶度×100%
表2双组元改性分子筛的水热稳定性
*结晶度保留率=水热处理后相对结晶度/水热处理前相对结晶度×100%
表3改性分子筛模型催化剂的微活性能
从表1与表2数据可以看出,采用实施例1~11的改性方法进行改性的分子筛通过17小时水热处理后,均比其它方法改性的分子筛有较高的相对结晶度。同时,从表3数据也可以看出,采用实施例1~11的方法改性的分子筛模型催化剂均比其它方法改性的分子筛催化剂有较高的微活性能。
Claims (16)
1.一种提高水热稳定性的双组元改性分子筛的制备方法,将分子筛加入到含磷水溶液,然后经过滤、干燥和焙烧,其特征在于该方法是将分子筛加入到含磷水溶液中,在pH值为1~10、反应温度70~200℃以及0.2~1.2MPa反应压力条件下反应10~200分钟,然后经过滤、干燥和焙烧,得到磷改性分子筛;将磷改性分子筛加入到含银离子水溶液中,反应温度0~100℃条件下避光反应30~150分钟,然后经过滤、干燥和焙烧,得到双组元改性分子筛。
2.根据权利要求1所述的制备方法,其特征在于分子筛是ZSM型、β型、Y型、MCM型分子筛中的一种。
3.根据权利要求2所述的制备方法,其特征在于分子筛是ZSM型或β型的分子筛。
4.根据权利要求3所述的制备方法,其特征在于分子筛硅铝比为15~100。
5.根据权利要求3所述的制备方法,其特征在于分子筛硅铝比为15~60。
6.根据权利要求1所述的制备方法,其特征在于含磷水溶液为磷酸溶液、亚磷酸溶液、可溶性磷酸盐水溶液或/和亚磷酸盐水溶液。
7.根据权利要求6所述的制备方法,其特征在于可溶性磷酸盐选自磷酸铵、磷酸氢二铵、磷酸二氢铵中的一种或几种。
8.根据权利要求1所述的制备方法,其特征在于含银离子水溶液为硝酸银水溶液、乙酸银水溶液中一种或两种。
9.根据权利要求1所述的制备方法,其特征在于分子筛加入到含磷水溶液中,控制pH值2~7。
10.根据权利要求1所述的制备方法,其特征在于分子筛加入到含磷水溶液中,控制反应温度为90~160℃。
11.根据权利要求1所述的制备方法,其特征在于分子筛加入到含磷水溶液中,控制反应压力为0.2~0.8MPa。
12.根据权利要求1所述的制备方法,其特征在于含磷水溶液浓度为0.05~1.0mol/L。
13.根据权利要求1所述的制备方法,其特征在于含银离子水溶液与分子筛重量比为(3~7)∶1。
14.根据权利要求1所述的制备方法,其特征在于含银离子水溶液浓度为0.01~0.1mol/L。
15.一种使用权利要求1所述的制备方法获得的双组元改性分子筛。
16.根据权利要求15所述的双组元改性分子筛,其特征在于双组元改性分子筛含有干基含量88~99重%的硅铝比为15~60的分子筛、以氧化物计0.5~10重%的磷与氧化物计0.01~2重%的银。
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CN112206810B (zh) * | 2019-07-09 | 2022-01-04 | 中国石油化工股份有限公司 | 一种制备方法和一种稀土y型分子筛 |
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CN114715911B (zh) * | 2021-01-05 | 2024-03-12 | 中国石油化工股份有限公司 | 含磷和金属的多级孔zsm-5分子筛及其制备方法 |
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JP5677446B2 (ja) | 2015-02-25 |
US20120275994A1 (en) | 2012-11-01 |
CN102050462B (zh) | 2012-10-17 |
CA2779312C (en) | 2016-09-20 |
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