CN110981458A - 一种盛装硅铝磷分子筛的装置及其制备方法 - Google Patents
一种盛装硅铝磷分子筛的装置及其制备方法 Download PDFInfo
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- CN110981458A CN110981458A CN201911380187.1A CN201911380187A CN110981458A CN 110981458 A CN110981458 A CN 110981458A CN 201911380187 A CN201911380187 A CN 201911380187A CN 110981458 A CN110981458 A CN 110981458A
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- aluminum
- molecular sieve
- silicon
- mass
- additive
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 71
- 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 71
- -1 silicon-aluminum-phosphorus Chemical compound 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 83
- 239000000654 additive Substances 0.000 claims abstract description 35
- 230000000996 additive effect Effects 0.000 claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001868 water Inorganic materials 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 22
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 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 abstract description 9
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 9
- 229910052934 alunite Inorganic materials 0.000 claims abstract description 9
- 239000010424 alunite Substances 0.000 claims abstract description 9
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 9
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 9
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 9
- 239000010431 corundum Substances 0.000 claims abstract description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 9
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 4
- 239000000020 Nitrocellulose Substances 0.000 claims abstract description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 4
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims abstract description 4
- 229910021538 borax Inorganic materials 0.000 claims abstract description 4
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- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 4
- 229920001220 nitrocellulos Polymers 0.000 claims abstract description 4
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 4
- 244000275012 Sesbania cannabina Species 0.000 claims abstract 2
- 239000002002 slurry Substances 0.000 claims description 37
- 238000000498 ball milling Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 20
- 210000001161 mammalian embryo Anatomy 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
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- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910001570 bauxite Inorganic materials 0.000 claims description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000005070 sampling Methods 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
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- 230000009467 reduction Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
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- 239000013078 crystal Substances 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
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- 239000011268 mixed slurry Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
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Abstract
本发明提供了一种盛装硅铝磷分子筛的装置及其制备方法，所述装置为上端具有开口的容器，所述容器包括底部及侧壁；盛装硅铝磷分子筛的装置的制作材料包括胚体及配体，胚体包括莫来石、铝矾石、刚玉、磷酸铵、硝酸铝以及两种以上的氧化物，配体包括脱盐水及磷酸、硝酸铵、硝酸、聚乙烯醇、硼砂、田菁粉中的一种或多种；所述盛装硅铝磷分子筛的装置的制作材料还包括添加剂，添加剂为羧甲基纤维素、聚丙烯酸酯、醋酸乙烯树脂、硝酸纤维素中的一种或多种。本发明所提供的装置具备耐高温、抗磨损、抗腐蚀等性能，同时能较好地避免破坏硅铝磷分子筛的结构，从而避免造成取样后硅铝磷分子筛性能降低，更加真实反映合成分子筛的性能指标。
Description
技术领域
本发明属于甲醇制烯烃催化剂的技术领域，尤其是涉及一种盛装硅铝磷分子筛的装置及其制备方法。
背景技术
丙烯是目前世界上最重要的大宗化工产品和支撑我国经济发展的基础化工原料之一，可制备多种基本有机原料，如环氧丙烷、丙烯醛、丙烯醇、异丙醇、四氯化碳、丁醇等等。近年来，由于受下游衍生物(尤其是聚丙烯)需求的影响，丙烯的需求量大幅增大。由于国内丙烯资源的短缺，远远不能满足国内市场的需求，国内自给率大幅下降，需要大量进口。随着国际市场激烈竞争的环境，发展丙烯及其衍生物必须采用国际上最先进的环境友好工艺技术，达到低成本生产的大型经济规模，中国丙烯的开发利用前景很是广阔。
针对中国丙烯发展前景，中国天辰工程有限公司研制的甲醇制丙烯催化剂主要是一种硅铝磷分子筛，这种分子筛能够使甲醇转化率达到100％或者接近100％，乙烯和丙烯的选择性在78％以上，几乎没有C5以上的产物，而且硅铝磷分子筛突出的水热稳定性和适宜的孔道结构使其性能更加优越，必将成为日后得到广泛应用。
硅铝磷分子筛的制备方法如下：将硅源、铝源、磷源、有机胺、晶种和水在10-40℃进行搅拌混合，制得硅铝磷分子筛的初始浆液，然后把浆液水热晶化，后处理制得硅铝磷分子筛；优选的，所述合成温度为110～210℃，时间为24～30h，且所述硅源、铝源、磷源、有机胺、晶种和水质量比为(0.1-2)：1：(0.5-2)：(0.5-4)：(100-200)；所述硅源为硅溶胶；所述铝源为拟薄水铝石；所述磷源为磷酸；所述有机胺为二乙胺、三乙胺、四丙基溴化铵、正丁胺、异丁胺、四乙基溴化铵的一种或几种；所述晶种为颗粒状硅铝磷分子筛原粉。而在上述合成过程中，需要经常进行取样测试，确保合成的硅铝磷分子筛能达到最佳转化率，目前取样后的硅铝磷分子筛盛装在不锈钢及玻璃材料的容器中，而硅铝磷分子筛因其独特的性质，在不锈钢及玻璃材料中会引起中毒现象，使内部孔道之间断裂或者对孔道进行堵塞，从而影响其转化率和选择性，使取样的硅铝磷分子筛的样品在评价时的性能指标降低，进而无法真实反映硅铝磷分子筛合成过程中的真实情况。因此，寻求一种能够不使硅铝磷分子筛中毒，不会降低硅铝磷分子筛性能指标的取样装置的材料，成为了目前该领域亟待解决的问题。
发明内容
为了解决现有技术的不足，本发明提供一种盛装硅铝磷分子筛的装置及其制备方法，降低硅铝磷分子筛中毒的情况，进一步真实反映硅铝磷分子筛合成过程中分子筛的性能指标。
为了达到上述目的，本发明的技术方案是这样实现的：
一种盛装硅铝磷分子筛的装置，为上端具有开口的容器，所述容器包括底部及侧壁，优选地，容器开口的直径为20～50mm；所述盛装硅铝磷分子筛的装置的制作材料包括胚体及配体，所述胚体包括莫来石、铝矾石、刚玉、磷酸铵、硝酸铝以及两种以上的金属氧化物，所述配体包括脱盐水以及磷酸、硝酸铵、硝酸、聚乙烯醇、硼砂、田菁粉中的一种或多种，所述配体的质量是胚体质量的7～13％。
进一步的，所述胚体中各组分占胚体总质量的百分比分别为：莫来石71～82％、铝矾石13～21％、刚玉0.3～0.8％、磷酸铵1～3％、硝酸铝0.5～3％、金属氧化物0.5～2％；所述配体中脱盐水质量占配体总质量的81～87％。
进一步的，所述盛装硅铝磷分子筛的装置的制作材料还包括添加剂，所述添加剂为羧甲基纤维素、聚丙烯酸酯、醋酸乙烯树脂、硝酸纤维素中的一种或多种，所述添加剂的质量是胚体质量的0.8～1.4％，所述添加剂若由两种物料组成，则其中一种物料的质量占添加剂总质量的80～82％；优选的，所述添加剂若为三种物料组成，则三种物料的质量分别占添加剂总质量的77～83％、15～21％和2～4％；优选的，所述添加剂若由四种物料组成，则四种物料的质量分别占添加剂总质量的72～78％、10～14％、8～10％和1～4％。
进一步的，所述金属氧化物为氧化镧、氧化镁、氧化锌、氧化铝、氧化铜、氧化铍、氧化钙、氧化钴、氧化锆中的两种或两种以上。
进一步的，所述莫来石中所含的氧化铝质量含量不低于75％、氧化硅质量含量不低于22％、其余杂质质量含量不高于1％；所述铝矾石中所含的氧化铝质量含量不低于85％；所述脱盐水的电导率≤5μS/cm，pH值为6-7；所述硝酸为质量分数30-40％的稀硝酸；所述聚乙烯醇为中聚合度，分子量为12～15万。
进一步的，所述盛装硅铝磷分子筛的装置中铁元素质量分数不高于0.85％，优选地，所述盛装硅铝磷分子筛的装置的制作材料中各物料的铁元素质量含量不能超过该物料质量的1.24％。
一种盛装硅铝磷分子筛的装置的制备方法，包括以下步骤：
(1)将胚体及配体混合，形成浆料A；优选地，浆料A中还混合有添加剂，浆料A的配制是室温20～40℃的环境温度下进行；
(2)向浆料A中添加水，将浆料A进行调节至含水量为15～30％的湿料B；
(3)将湿料B放入球磨机中的球磨罐中，在氩气保护下将湜料B研磨成稠浆C；优选地，湿料B放入球磨罐中后所占体积为球磨罐内部体积的40～72％，球磨机转速为220～360r/min，球磨时间为10～27h，所述氩气纯度不低于99.9％；研磨后各物料的平均粒径不大于10μm；
(4)将稠浆C干燥后过筛，得到粉体D；粉体D的平均粒径不大于10μm；优选地，干燥温度为52～77℃，干燥时间为2～8h；
(5)将粉体D装入模具中，在150～320MPa压力下成型，得到样品E，并对样品E进行高温焙烧，优选地，高温焙烧的工艺为：以6～10℃/min的升温速率从室温升至800℃，再以4～6℃/min的升温速率升至1000～1200℃，在1000～1200℃下保温1～18h，然后自然冷却至室温。
本发明所提供的一种盛装硅铝磷分子筛的装置及其制备方法具有以下优势：通过合理化设计，工艺简单，成本低廉，除了具备耐高温、抗磨损、抗腐蚀性能外还能较好的避免破坏硅铝磷分子筛的结构，从而避免造成取样后硅铝磷分子筛性能降低，从而更加真实反映合成分子筛的性能指标。该材料成本低，效果好，杂质少，使取样效率提高。
具体实施方式
除有定义外，以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂，如无特殊说明，均为常规生化试剂；所述实验方法，如无特殊说明，均为常规方法。
下面结合实施例来详细说明本发明。
实施例一：
一种盛装硅铝磷分子筛的装置为上端具有开口的容器，所述容器包括底部及侧壁，开口的直径为25mm；所述盛装硅铝磷分子筛的装置的制作材料包括胚体、胚体及添加剂，胚体构成物料包括：莫来石、铝矾石、刚玉、磷酸铵、硝酸铝、氧化铝、氧化锆，其中各物料质量分别占胚体总质量的75％、20％、0.6％、1.5％、2.4％、0.3％、0.2％；配体构成物料包括：磷酸、脱盐水、聚乙烯醇，其中各物料质量分别占配体总质量的13％、85％、2％，配体的质量是胚体质量的8％；所述添加剂包括：聚丙烯酸酯、硝酸纤维素，其中各物料质量分别占添加剂总质量的82％、18％，添加剂的质量是胚体质量的0.9％。
上述涉及物质中，莫来石所含氧化铝质量含量为77.5％，氧化硅含量为22.1％；铝矾石所含氧化铝质量含量为88.4％；脱盐水的电导率为5μS/cm，pH为6.5；硝酸质量分数为32％；聚乙烯醇选用中等聚合度，分子量为13.5万。
经检测，在上述涉及物料中，每种物料中的铁元素质量含量均不超过1.01％。
盛装硅铝磷分子筛的装置的制备方法如下：
(1)在容器内，将所述胚体、配体以及添加剂所包含的物料按照对应比例分别混合均匀，再将三者混合均匀，形成浆料A；
(2)向浆料A中添加水，将上述混合好的浆料A调节至含水量为22％的湿料B；
(3)将上述调好的湿料B放入球磨机的球磨罐中并在氩气保护下研磨成稠浆C；
(4)将上述稠浆C干燥后过筛，得到粉体D；经检测，粉体D中的铁元素质量含量为0.66％；
(5)将粉体D装入相应的模具中，在180MPa压力下成型，得到样品E；
(6)将样品E高温焙烧，得到盛装硅铝磷分子筛的装置。
浆料A的配制在室温28℃的环境下进行，湿料B放入球磨罐中后所占体积为球磨罐内部体积的56％，球磨转速为227r/min，球磨时间为18h，研磨后各物质的平均粒径均在9μm以下；样品E所用高温焙烧程序为：从室温按照升温速率8℃/min升至800℃，再按照4.5℃/min升至1050℃，保温5h，之后自然冷却至室温。
实施例二
一种盛装硅铝磷分子筛的装置为上端具有开口的容器，所述容器包括底部及侧壁，开口的直径为30mm。
所述盛装硅铝磷分子筛的装置的制作材料包括胚体、胚体及添加剂，胚体构成物料包括：莫来石、铝矾石、刚玉、磷酸铵、硝酸铝、氧化镁、氧化钙，其中各物料质量分别占胚体总质量的79％、16％、0.4％、2.8％、1.1％、0.3％、0.4％；配体构成物料包括：硝酸铵、脱盐水、硝酸，其中各物料质量分别占配体总质量的10％、87％、3％，配体的质量是胚体质量的11.5％；所述添加剂为羧甲基纤维素，添加剂的质量是胚体质量的1.2％。
上述涉及物质中，莫来石所含氧化铝质量含量为75.2％，氧化硅含量为24％；铝矾石所含氧化铝质量含量为86％；脱盐水的电导率为4.5μS/cm，pH为6.8；硝酸质量分数为30％。
经检测，在上述涉及物料中，每种物料中的铁元素质量含量均不超过0.95％。
盛装硅铝磷分子筛的装置的制备方法如下：
(1)在容器内，将所述胚体、配体以及添加剂所包含的物料按照对应比例分别混合均匀，再将三者混合均匀，形成浆料A；
(2)向浆料A中添加水，将上述混合好的浆料A调节至含水量为16.8％的湿料B；
(3)将上述调好的湿料B放入球磨机的球磨罐中并在氩气保护下研磨成稠浆C；
(4)将上述稠浆C干燥后过筛，得到粉体D；经检测，粉体D中的铁元素质量含量为0.59％；
(5)将粉体D装入相应的模具中，在230MPa压力下成型，得到样品E；
(6)将样品E高温焙烧，得到盛装硅铝磷分子筛的装置。
浆料A的配制在室温额23℃的环境下进行，湿料B放入球磨罐中后所占体积为球磨罐内部体积的64％，球磨转速为265r/min，球磨时间为15h，研磨后各物料的平均粒径均在9.5μm以下；样品E所用高温焙烧程序为：从室温按照升温速率9℃/min升至800℃，再按照5.5℃/min升至1100℃，保温12h，之后自然冷却至室温。
实施例三
一种盛装硅铝磷分子筛的装置为上端具有开口的容器，所述容器包括底部及侧壁，开口的直径为40mm。
所述盛装硅铝磷分子筛的装置的制作材料包括胚体、胚体及添加剂，胚体构成物料包括：莫来石、铝矾石、刚玉、磷酸铵、硝酸铝、氧化铝、氧化钙、氧化锆，其中各物料质量分别占胚体总质量的75％、19％、0.8％、2.2％、1.7％、0.3％、0.7％、0.3％；配体构成物料包括：脱盐水、硝酸、硼砂、田菁粉，其中各物料质量分别占配体总质量的86％、4％、3％、7％，配体的质量是胚体质量的10.3％；所述添加剂包括：聚丙烯酸酯、醋酸乙烯树脂、硝酸纤维素，其质量占比分别为79％、17％、4％，添加剂的质量是胚体质量的1.1％。
上述涉及物料中，莫来石所含氧化铝质量含量为76.3％，氧化硅含量为23.1％；铝矾石所含氧化铝质量含量为86％；脱盐水的电导率为4μS/cm，pH为6.2；硝酸质量分数为31％。
经检测，在上述涉及物料中，每种物料中的铁元素质量含量均不超过0.87％。
盛装硅铝磷分子筛的装置的制备方法如下：
(1)在容器内，将所述胚体、配体以及添加剂所包含的物料按照对应比例分别混合均匀，再将三者混合均匀，形成浆料A；
(2)向浆料A中添加水，将上述混合好的浆料A调节至含水量为25.2％的湿料B；
(3)将上述调好的湿料B放入球磨机的球磨罐中并在氩气保护下研磨成稠浆C；
(4)将上述稠浆C干燥后过筛，得到粉体D；经检测，粉体D中的铁元素质量含量为0.36％；
(5)将粉体D装入相应的模具中，在270MPa压力下成型，得到样品E；
(6)将样品E高温焙烧，得到盛装硅铝磷分子筛的装置。
浆料A的配制在室温31℃的环境下进行，湿料B放入球磨罐中后所占体积为球磨罐内部体积的52％，球磨转速为305r/min，球磨时间为22h，经检测，研磨后各物料的平均粒径均在9.7μm以下。样品E所用高温焙烧程序为：从室温按照升温速率7℃/min升至800℃，再按照4℃/min升至1000℃，保温16h，之后自然冷却至室温。
实施例四：
一种盛装硅铝磷分子筛的装置为上端具有开口的容器，所述容器包括底部及侧壁，开口的直径为30mm；所述盛装硅铝磷分子筛的装置的制作材料包括胚体及胚体，胚体构成物料包括：莫来石、铝矾石、刚玉、磷酸铵、硝酸铝、氧化铝、氧化锆，其中各物料质量分别占胚体总质量的79％、16％、0.7％、1.4％、2.1％、0.5％、0.3％；配体构成物料包括：磷酸、脱盐水、聚乙烯醇，其中各物料质量分别占配体总质量的16％、82％、2％，配体的质量是胚体质量的12％。
上述涉及物质中，莫来石所含氧化铝质量含量为75.6％，氧化硅含量为24.1％；铝矾石所含氧化铝质量含量为87.8％；脱盐水的电导率为3.5μS/cm，pH为6.8；硝酸质量分数为37％；聚乙烯醇选用中等聚合度，分子量为14.7万。
经检测，在上述涉及物料中，每种物料中的铁元素质量含量均不超过0.98％。
盛装硅铝磷分子筛的装置的制备方法如下：
(1)在容器内，将所述胚体及配体的物料按照对应比例分别混合均匀，再将两者混合均匀，形成浆料A；
(2)向浆料A中添加水，将上述混合好的浆料A调节至含水量为26％的湿料B；
(3)将上述调好的湿料B放入球磨机的球磨罐中并在氩气保护下研磨成稠浆C；
(4)将上述稠浆C干燥后过筛，得到粉体D；经检测，粉体D中的铁元素质量含量为0.78％；
(5)将粉体D装入相应的模具中，在260MPa压力下成型，得到样品E；
(6)将样品E高温焙烧，得到盛装硅铝磷分子筛的装置。
浆料A的配制在室温21℃的环境下进行，湿料B放入球磨罐中后所占体积为球磨罐内部体积的51％，球磨转速为292r/min，球磨时间为24h，研磨后各物质的平均粒径均在8μm以下；样品E所用高温焙烧程序为：从室温按照升温速率7℃/min升至800℃，再按照5.5℃/min升至1100℃，保温4h，之后自然冷却至室温。
对比案例一：玻璃制容器。
对比案例二：不锈钢制容器。
使用上述三个实施案例和两个对比案例的装置收集以下方法制备而成的硅铝磷分子筛：
将硅源、铝源、磷源、有机胺、晶种和水在35℃进行搅拌混合，制得硅铝磷分子筛的初始浆液，然后把浆液水热晶化，后处理制得硅铝磷分子筛；优选的，所述水热晶化的温度为140℃，时间为27h，且所述硅源、铝源、磷源、有机胺、晶种和水质量比为0.8：1：1.4：3.2：110；所述硅源为硅溶胶；所述铝源为拟薄水铝石；所述磷源为磷酸；所述有机胺为二乙胺；所述晶种为颗粒状硅铝磷分子筛。
分别对用实施例一、实施例二、实施例三、对比例一、对比例二的装置收集到的硅铝磷分子筛进行催化性能的验证，采用常规的实验方法，得出以下数据：
| 乙烯选择性 | 丙烯选择性 | 转化率 | |
| 实施例一 | 39.8％ | 41.3％ | 99.4％ |
| 实施例二 | 39.4％ | 40.9％ | 99.7％ |
| 实施例三 | 39.7％ | 41.0％ | 99.6％ |
| 实施例四 | 39.2％ | 40.3％ | 98.8％ |
| 对比案例一 | 38.1％ | 39.2％ | 97.5％ |
| 对比案例二 | 37.5％ | 38.2％ | 96.8％ |
| 合成后硅铝磷分子筛 | 39.9％ | 41.4％ | 99.8％ |
通过以上实验数据可看出，使用实施例一、实施例二、实施例三、实施例四的装置盛装硅铝磷分子筛，可以大大降低分子筛中毒的现象，分子筛的转化率得到提高，且与合成后的硅铝磷分子筛转化率更为接近，能够更为真实地反映合成过程中硅铝磷分子筛的性能。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种盛装硅铝磷分子筛的装置，其特征在于：为上端具有开口的容器，所述容器包括底部及侧壁；所述盛装硅铝磷分子筛的装置的制作材料包括胚体及配体，所述胚体包括莫来石、铝矾石、刚玉、磷酸铵、硝酸铝以及两种以上的金属氧化物，所述配体包括脱盐水以及磷酸、硝酸铵、硝酸、聚乙烯醇、硼砂、田菁粉中的一种或多种，所述配体的质量是胚体质量的7～13％。
2.根据权利要求1所述的一种盛装硅铝磷分子筛的装置，其特征在于：所述容器开口的直径为20～50mm。
3.根据权利要求1所述的一种盛装硅铝磷分子筛的装置，其特征在于：所述胚体中各组分占胚体总质量的百分比分别为：莫来石71～82％、铝矾石13～21％、刚玉0.3～0.8％、磷酸铵1～3％、硝酸铝0.5～3％、金属氧化物0.5～2％；所述配体中脱盐水质量占配体总质量的81～87％。
4.根据权利要求1所述的一种盛装硅铝磷分子筛的装置，其特征在于：所述盛装硅铝磷分子筛的装置的制作材料还包括添加剂，所述添加剂为羧甲基纤维素、聚丙烯酸酯、醋酸乙烯树脂、硝酸纤维素中的一种或多种，所述添加剂的质量是胚体质量的0.8～1.4％；优选的，所述添加剂若由两种物料组成，则其中一种物料的质量占添加剂总质量的80～82％；优选的，所述添加剂若为三种物料组成，则三种物料的质量分别占添加剂总质量的77～83％、15～21％和2～4％；优选的，所述添加剂若由四种物料组成，则四种物料的质量分别占添加剂总质量的72～78％、10～14％、8～10％和1～4％。
5.根据权利要求1所述的一种盛装硅铝磷分子筛的装置，其特征在于：所述金属氧化物为氧化镧、氧化镁、氧化锌、氧化铝、氧化铜、氧化铍、氧化钙、氧化钴、氧化锆中的两种或两种以上。
6.根据权利要求1所述的一种盛装硅铝磷分子筛的装置，其特征在于：所述莫来石中所含的氧化铝质量含量不低于75％、氧化硅质量含量不低于22％、其余杂质质量含量不高于1％；所述铝矾石中所含的氧化铝质量含量不低于85％；所述脱盐水的电导率≤5μS/cm，pH值为6-7；所述硝酸为质量分数30～40％的稀硝酸；所述聚乙烯醇为中聚合度，分子量为12～15万。
7.一种制备如权利要求1-6任一项所述的盛装硅铝磷分子筛的装置的方法，其特征在于，包括以下步骤：
(1)将胚体及配体混合，形成浆料A；
(2)向浆料A中添加水，将浆料A调节至含水量为15～30％的湿料B；
(3)将湿料B放入球磨机中的球磨罐中，在氩气保护下将湿料B研磨成稠浆C；
(4)将稠浆C干燥后过筛，得到粉体D；
(5)将粉体D装入模具中，在150～320MPa压力下成型，得到样品E，并对样品E进行高温焙烧。
8.根据权利要求7所述的盛装硅铝磷分子筛的装置的制备方法，其特征在于：步骤(1)中的浆料A还包括添加剂，步骤(1)的配制是在室温20～40℃的环境下进行。
9.根据权利要求8所述的盛装硅铝磷分子筛的装置的制备方法，其特征在于：步骤(3)中湿料B放入球磨罐中后所占体积为球磨罐内部体积的40～72％，球磨机转速为220～360r/min，球磨时间为10～27h，所述氩气纯度不低于99.9％；研磨后各物料的平均粒径不大于10μm。
10.根据权利要求8所述的盛装硅铝磷分子筛的装置的制备方法，其特征在于：步骤(4)中干燥温度为52～77℃，干燥时间为2～8h；步骤(5)中高温焙烧的工艺为：以6～10℃/min的升温速率从室温升至800℃，再以4～6℃/min的升温速率升至1000～1200℃，在1000～1200℃下保温1～18h，然后自然冷却至室温。
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