CN107954434B - 纳米片sapo分子筛聚集体、制备方法及其用途 - Google Patents
纳米片sapo分子筛聚集体、制备方法及其用途 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002135 nanosheet Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 241000269350 Anura Species 0.000 title claims description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 229910052593 corundum Inorganic materials 0.000 claims description 24
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 24
- 150000001336 alkenes Chemical class 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- HHQMYHMTYIPFEG-UHFFFAOYSA-M [O-2].[O-2].[O-2].[OH-].O.[Al+3].[Si+4].P Chemical compound [O-2].[O-2].[O-2].[OH-].O.[Al+3].[Si+4].P HHQMYHMTYIPFEG-UHFFFAOYSA-M 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004523 catalytic cracking Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C4/06—Catalytic processes
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Abstract
本发明涉及一种片状硅磷铝SAPO分子筛聚集体的制备方法,主要解决现有技术难以获得具有纳米片结构SAPO分子筛的问题。本发明通过采用模板剂R1、水、磷源、碱处理的铝源和硅源的混合物在‑20℃~100℃条件下水解得到溶胶,然后将其置于反应釜中进行晶化;晶化结束后对样品进行洗涤、干燥和焙烧得到片状硅磷铝SAPO分子筛聚集体的技术方案,较好地解决了该问题,可用于片状分子筛的工业生产中。
Description
技术领域
本发明涉及一种纳米片SAPO分子筛聚集体、制备方法及其在C4烯烃催化裂解中的应用。
背景技术
SAPO-34分子筛是美国联合碳化物公司(UCC)开发的磷酸硅铝系列的分子筛,其具有适宜的酸性和孔道结构、较大的比表面积、较好的吸附性能以及热稳定性和水热稳定性,目前可以说是促进甲醇制烯烃反应过程的最优催化剂。然而,作为一个典型的气-固非均相反应,SAPO-34分子筛孔道内极易因内外扩散阻力而产生积碳,加上反应本身的强放热特性,从而导致催化剂快速失活。
为解决以上问题,近年来研究者从孔结构和晶体尺寸等不同角度采取一系列手段来改善催化剂的性能,研究结果表明:片状SAPO-34分子筛有利于催化性能的提高,特别是纳米尺度的片状分子筛,它有利于缩短反应物及产物分子的扩散路径,减弱扩散的限制(以提高其在MTO反应中的抗积炭失活能力从而延长催化剂寿命。目前,有关纳米片SAPO-34分子筛的报道较少,主要有微波加热法Guoju Yang,Yingxu Wei,Shutao Xu,Jingrun Chen,Jinzhe Li,Zhongmin Liu,Jihong Yu,and Ruren Xu.J.Phys.Chem.C[J],2013,117,8214)和双模板法(Hong Yang,Xiaohui Liu,Guanzhong Lu,Yanqin Wang.Microporous andMesoporous Materials[J],2016,225,144),相比传统的SAPO-34,片状的SAPO-34分子筛在甲醇转化制低碳烯烃(MTO)反应中表现出更高的催化活性。除此之外,Zhu和Liu等研究了以高岭土和SBA-15为原料水热一步法合成具有层状结构的SAPO-34分子筛(Zhu Jie,Gui Yu,Wang Yao,et al.Chem.Commun.,2009,3282-3284;Liu Yuanlin,Wang Lingzhi,ZhangJinlong,et al.Microporous and Mesoporous Materials 145(2011)150-156)。
尽管纳米片状SAPO分子筛显示出优异的催化性能,但目前SAPO纳米片状分子筛晶粒尺寸仍较大,进一步减小晶粒尺寸,提高扩散性能是该领域中的难点之一。由此可见,开发一种晶粒尺寸较小、性能优异的纳米片SAPO分子筛聚集体的制备方法是实现和扩大其实际应用的关键所在。
发明内容
本发明所要解决的技术问题之一是现有SAPO分子筛用于C4烯烃催化裂解中性能较差的问题。本发明提供了一种新的纳米片SAPO分子筛聚集体,该材料具有较好的扩散性能,在C4烯烃催化裂解中性能良好。
本发明所要解决的技术之二是提供一种新的解决技术问题之一的纳米片SAPO分子筛聚集体的制备方法。
本发明所要解决的技术之三是提供一种新的解决技术问题之一的纳米片SAPO分子筛聚集体的用途。
为解决上述技术问题之一,本发明采用的技术方案如下:一种纳米片SAPO分子筛聚集体,其特征在聚集体是由纳米片晶粒排列组成;纳米片晶粒的长宽高尺寸均小于150nm。
上述技术方案中,优选的技术方案为纳米片SAPO分子筛是由纳米片晶粒排列组成;纳米片晶粒的长宽高尺寸均小于100nm。
上述技术方案中,优选地所述聚集体是由纳米片晶粒排列组成;纳米片晶粒的长和宽分别小于100nm,纳米片晶粒的高小于20nm。
为解决上述技术问题之二,本发明采用的技术方案如下:纳米片SAPO分子筛聚集体的制备方法,包括以下步骤:
a)将铝源在碱溶液中进行处理;
b)将磷源、硅源、模板剂R1和水分别加入到a)所得的混合溶液中,在-20℃~100℃条件下,水解得到硅磷铝氧化物溶胶,其中,磷源按理论生成P2O5量计、铝源按理论生成Al2O3量计、硅源按理论生成SiO2量计,混合物重量比组成为:R1/Al2O3=0.1~20;H2O/Al2O3=2.56~30.79;SiO2/Al2O3=0.03~0.90;P2O5/Al2O3=0.05~5.0;
c)将上述硅磷铝氧化物溶胶置于反应釜中,在90℃~220℃下晶化0.1~4天;反应结束后对样品进行洗涤、干燥和焙烧得到纳米片SAPO分子筛聚集体。
硅源选自硅溶胶,正硅酸四甲酯、正硅酸四乙酯、正硅酸四丙酯、正硅酸四丁酯或硅溶胶中的至少一种;铝源选自异丙醇铝、拟薄水铝石、氧化铝、硝酸铝、氯化铝或硫酸铝中的至少一种;磷源选自磷酸、磷酸铵、磷酸氢二铵、磷酸氢铵、磷酸钾、磷酸氢二钾、磷酸氢钾、磷酸钠、磷酸氢二钠或磷酸氢钠中的至少一种。
上述技术方案中步骤a)中碱溶液选自氢氧化钠、氢氧化钾、氨水、四乙基氢氧化胺、四乙基溴化铵、三乙胺或乙二胺中的至少一种。
上述技术方案中,所述将铝源在碱溶液中进行处理搅拌,具体实现为,在0-100℃搅拌0.5-48h。
上述技术方案中,优选地,混合物重量比组成为:R1/Al2O3=0.2~15;H2O/Al2O3=3.00~13.00;SiO2/Al2O3=0.07~0.80;P2O5/Al2O3=0.06~2.30。
上述技术方案中,所述步骤b)中模板剂R1选自四乙基氢氧化胺、四乙基溴化铵、二正丙胺、吗啉、三乙胺或乙二胺中的至少一种。
上述技术方案中,优选地,步骤c)中晶化温度为130~200℃,晶化时间为0.2~3天。
为解决上述技术问题之二,本发明采用的技术方案如下:一种C4烯烃裂解制乙烯的方法,以C4烯烃为原料,在反应温度为300~850℃,反应表压力为0.01MPa~1MPa,反应重量空速为0.1~6h-1的条件下,原料通过催化剂床层与催化剂接触,反应生成低碳烯烃,所用的催化剂为一种纳米片SAPO分子筛聚集体,聚集体是由纳米片晶粒排列组成;纳米晶粒的长宽高尺寸均小于100nm。上述技术方案中,优选的技术方案为反应温度为350~750℃;反应表压力为0.1MPa~0.8MPa;反应重量空速为0.2~5小时-1。
目前,C4烯烃催化裂解反应中普遍存在催化剂失活速度快的问题。这主要是由于催化剂扩散性能差,导致易积碳引起的。积碳主要从两方面影响催化剂的活性:一方面是积碳覆盖催化剂的活性位导致失活;另一方面是积碳堵塞催化剂的孔道,使得反应物无法扩散到达活性位或者产物无法扩散出催化剂孔道。
由于反应分子在分子筛中的扩散路径取决于分子筛的厚度。对于片状形貌的分子筛,其生长过程中,长度和宽度越小,相应的厚度越小,扩散路径就越短。从而有利于反应物分子与催化剂的活性中心接触,同时也有利于反应产物快速扩散出催化剂的孔道,从而减少积炭的生成,使其催化性能比以往催化剂有了明显改善。本发明通过将铝源事先进行碱处理,同时调控其他反应条件,制得由长宽高均小于150nm的纳米片晶粒排列组成的纳米片SAPO分子筛聚集体,制备方法简单,得到的SAPO分子筛聚集体晶粒厚度小,扩散路径短,催化性能高。本发明纳米片SAPO分子筛聚集体作为C4烯烃催化裂解制丙烯的催化剂,同时通过调节反应条件,使丙烯的选择性和收率明显提高,取得了较好的技术效果。
附图说明
图1为【实施例1】得到的纳米片SAPO分子筛聚集体的SEM图;
图2为【实施例1】得到的纳米片SAPO分子筛聚集体的XRD图。
下面通过实施例对本发明作进一步的阐述。
具体实施方式
【实施例1】
首先将12.3克异丙醇铝在氨水溶液中40℃搅拌24h,得到溶液A;然后将5.5克磷酸(85%重量)、45克去离子水、60克四乙基氢氧化铵(25%重量)、6克硅溶胶(40%重量)依次加入到混合溶液A中,在60℃条件下,搅拌均匀后置于反应釜中,在180℃下晶化1天;反应结束后对样品进行洗涤、干燥和焙烧得到纳米片SAPO分子筛聚集体(长99nm宽78nm高15nm)。
各组分的重量比为:TEAOH/Al2O3=10;H2O/Al2O3=7;SiO2/Al2O3=0.4;P2O5/Al2O3=1.1。
所得产物经洗涤、离心、110℃烘干得固体样品,XRD结果表明,所得产品为SAPO-34分子筛原粉。SEM见图1,XRD见图2。
【实施例2~14】
按照【实施例1】的各个步骤及条件,制得纳米片SAPO分子筛聚集体,只是改变原料(表1)配比、碱的种类等参数,具体列于表1。合成的产物经表征说明其结果具有与【实施例1】、产物相似的晶体结构,其具体的物化参数见表2。
表1
【实施例15】
采用固定床催化反应装置,反应器为不锈钢管,对实施例1制备的催化剂进行C4烯烃催化裂解反应活性评价,考察所用的工艺条件为:催化剂装填量0.5g,反应温度为650℃,反应压力为0.1MPa,重量空速为1h-1。全产物在线分析。考评结果如表2所示。
表2
【实施例16~18】
按照【实施例15】所用的工艺条件对实施例1制备的催化剂进行C4烯烃催化裂解反应活性评价,只是改变反应温度,考评结果如表3所示。
表3
【实施例19~21】
按照【实施例15】所用的工艺条件对实施例3制备的催化剂进行C4烯烃催化裂解反应活性评价,只是改变反应压力,考评结果如表4所示。
表4
【实施例22~24】
按照【实施例15】所用的工艺条件对实施例3制备的催化剂进行C4烯烃催化裂解反应活性评价,只是改变重量空速,考评结果如表5所示。
表5
【比较例1】传统SAPO-34分子筛为催化剂
首先将12.3克异丙醇铝、5.5克磷酸(85%重量)、45克去离子水、60克四乙基氢氧化铵(25%重量)、6克硅溶胶(40%重量)依次加入到45克去离子水中,室温条件下,搅拌均匀后置于反应釜中,在180℃下晶化1天;反应结束后对样品进行洗涤、干燥和焙烧得到传统SAPO分子筛(长1300nm宽1300nm高1300nm)。
各组分的重量比为:TEAOH/Al2O3=10;H2O/Al2O3=7;SiO2/Al2O3=0.4;P2O5/Al2O3=1.1。
按照【实施例15】所用的工艺条件对实施例1制备的催化剂(A)和传统方法制备的催化剂(B)进行C4烯烃催化裂解反应活性评价。考评结果如表6所示。
如表6所示
【比较例2】少步骤(a)制备所得到的材料为催化剂
按照【实施例15】所用的工艺条件对实施例1制备的催化剂(A)和实施例1少步骤(a)制备所得到的材料为催化剂(B)(长500nm宽400nm高200nm)进行C4烯烃催化裂解反应活性评价。考评结果如表7所示。
如表7所示
Claims (7)
1.一种纳米片SAPO分子筛聚集体的制备方法,其特征在于,所述聚集体是由纳米片晶粒排列组成;纳米片晶粒的长宽高尺寸均小于150nm,所述制备方法包括以下步骤:
a)将铝源在碱溶液中进行处理;
b)将磷源、硅源、模板剂R1和水分别加入到a)所得的混合溶液中,在-20℃~100℃条件下,水解得到硅磷铝氧化物溶胶,其中,磷源按理论生成P2O5量计、铝源按理论生成Al2O3量计、硅源按理论生成SiO2量计,混合物重量比组成为:R1/Al2O3=0.1~20;H2O/Al2O3=2.56~30.79;SiO2/Al2O3=0.03~0.90;P2O5/Al2O3=0.05~5.0;
c)将上述硅磷铝氧化物溶胶置于反应釜中,在90℃~220℃下晶化0.1~4天;反应结束后对样品进行洗涤、干燥和焙烧得到纳米片SAPO分子筛聚集体;
硅源选自硅溶胶、正硅酸四甲酯、正硅酸四乙酯、正硅酸四丙酯或正硅酸四丁酯中的至少一种;铝源选自异丙醇铝、拟薄水铝石、氧化铝、硝酸铝、氯化铝或硫酸铝中的至少一种;磷源选自磷酸、磷酸铵、磷酸氢铵、磷酸钾、磷酸氢钾、磷酸钠或磷酸氢钠中的至少一种。
2.根据权利要求1所述纳米片SAPO分子筛聚集体的制备方法,其特征在于步骤a)中碱溶液中的碱选自氢氧化钠、氢氧化钾、氨水、四乙基氢氧化铵、三乙胺或乙二胺中的至少一种。
3.根据权利要求1所述纳米片SAPO分子筛聚集体的制备方法,其特征在于步骤b)中混合物重量比组成为:R1/Al2O3=0.2~15;H2O/Al2O3=3.00~13.00;SiO2/Al2O3=0.07~0.80;P2O5/Al2O3=0.06~2.30。
4.根据权利要求1所述纳米片SAPO分子筛聚集体的制备方法其特征在于步骤b)中模板剂R1选自四乙基氢氧化铵、四乙基溴化铵、二正丙胺、吗啉、三乙胺或乙二胺中的至少一种。
5.根据权利要求1所述纳米片SAPO分子筛聚集体的制备方法,其特征在于步骤c)中晶化温度为130~200℃,晶化时间为0.2~3天。
6.一种C4烯烃裂解制乙烯的方法,其特征在于,先按照权利要求1-5任一项所述制备方法制得纳米片SAPO分子筛聚集体,然后以丁烯为原料,在反应温度为300~850℃,反应表压力为0.01MPa~1MPa,反应重量空速为0.1~6h-1,原料通过催化剂床层与所述纳米片SAPO分子筛聚集体接触,反应生成低碳烯烃。
7.根据权利要求6所述C4烯烃裂解制乙烯的方法,其特征在于反应温度为350~750℃;反应表压力为0.1MPa~0.8MPa;反应重量空速为0.2~6小时-1。
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