CN108275693B - 一种制备sapo-11分子筛无定形物质的方法 - Google Patents
一种制备sapo-11分子筛无定形物质的方法 Download PDFInfo
- Publication number
- CN108275693B CN108275693B CN201611256802.4A CN201611256802A CN108275693B CN 108275693 B CN108275693 B CN 108275693B CN 201611256802 A CN201611256802 A CN 201611256802A CN 108275693 B CN108275693 B CN 108275693B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sapo
- preparing
- amorphous substance
- hydrochloric acid
- 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.)
- Active
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 108
- 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 104
- 239000000126 substance Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 57
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 4
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000004876 x-ray fluorescence Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001636 atomic emission spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910017089 AlO(OH) Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/02—Amorphous compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Glass Compositions (AREA)
Abstract
本发明公开了一种制备SAPO‑11分子筛无定形物质的方法,该方法包括如下步骤:步骤一,在SAPO‑11分子筛中加入盐酸进行酸解,破坏分子筛的骨架结构;步骤二,在酸解后的分子筛中加入氨水进行沉淀;步骤三,焙烧步骤二所得沉淀得到所述SAPO‑11分子筛无定形物质。本发明采取逆向思维,以待测SAPO‑11分子筛作为原料,直接破坏分子筛骨架结构,100%生成分子筛无定形物质,在此过程中,无物料损失和杂质引入,所制备的SAPO‑11分子筛的无定形物质可用于SAPO‑11分子筛结晶度分析中。
Description
技术领域
本发明涉及一种分子筛无定形物质的合成方法,具体讲是一种制备SAPO-11分子筛无定形物质的方法。
背景技术
SAPO-11分子筛是美国联碳公司在1984年开发的硅磷铝分子筛,骨架由PO4 +,AlO4 -,SiO4四面体组成,含有可交换的阳离子,同时存在B酸和L酸中心,具有一定的酸性。SAPO-11分子筛组成范围很宽,它的无水状态组成可表示为(0-0.3)R(AlxSiyPz)O2,其中R为模板剂,x,y,z分别为Al,Si,P的摩尔分数,且x+y+z=1。此类分子筛以适中的孔道结构及酸性广泛应用于催化、吸附及离子交换等领域,并在包括裂化、芳烃和烷烃烷基化、烷烃和烯烃异构化、二甲苯异构化以及水合等反应中表现出独特催化性能。
结晶度是合成SAPO-11分子筛的重要质量控制指标,结晶度测定一般是两相体系的相定量,即一相为结晶相,另一相为无定形相。采用稀释外推法或无定形强度卡法测定分子筛的结晶度,需要与被测分子筛组成相同的无定形物质作为稀释剂,添加在待测SAPO-11分子筛中。现有技术中,分子筛无定形物质的制备一般是按分子筛组成进行合理复配,进而获得分子筛无定型物质。该方法需购买无定形二氧化硅、氧化铝等复配试剂或昂贵的模板剂、磷酸等合成试剂,成本较高,存在物料损失、杂质引入的问题而且材料采购、筛选合格样品均需要时间,在实际分析分子筛结晶度前期准备中耗时长,不利于测定的效率和便利性,这对于工业分子筛合成监控来说,是不能满足合成工艺对分析监控技术要求的。
发明内容
本发明的目的在于提供一种制备SAPO-11分子筛无定形物质的方法,该方法可简便、准确的制备出所需组成的SAPO-11分子筛无定形物质。
为了实现上述目的,本发明提供了一种制备SAPO-11分子筛无定形物质的方法,该方法包括如下步骤:
步骤一,在SAPO-11分子筛中加入盐酸进行酸解,破坏分子筛的骨架结构;
步骤二,在酸解后的分子筛中加入氨水进行沉淀;
步骤三,焙烧步骤二所得沉淀得到所述SAPO-11分子筛无定形物质。
本发明所述的制备SAPO-11分子筛无定形物质的方法,其中,所述步骤一具体为:将SAPO-11分子筛置于石英或陶瓷坩埚中,先加水润湿,再加入盐酸,摇匀,移至控温加热板上加热,期间补充蒸馏水,以保证加热板上水分未蒸干。
本发明所述的制备SAPO-11分子筛无定形物质的方法,其中,所述步骤一中盐酸为浓盐酸,所述盐酸与SAPO-11分子筛中Al2O3的质量比大于28:5。
本发明所述的制备SAPO-11分子筛无定形物质的方法,其中,所述在控温加热板上加热的温度优选为110℃~180℃。
本发明所述的制备SAPO-11分子筛无定形物质的方法,其中,所述步骤二具体为:在酸解后的SAPO-11分子筛中滴加氨水并搅拌以生成沉淀。
本发明所述的制备SAPO-11分子筛无定形物质的方法,其中,所述步骤二中氨水的质量浓度为26%~28%,所述氨水与SAPO-11分子筛中Al2O3的质量比优选37:5。
本发明所述的制备SAPO-11分子筛无定形物质的方法,其中优选的是,在酸解后的SAPO-11分子筛冷却后再进行滴加氨水的操作。
本发明所述的制备SAPO-11分子筛无定形物质的方法,其中,所述步骤三焙烧温度优选为500℃~700℃,焙烧时间优选为2h~4h。
本发明所述的制备SAPO-11分子筛无定形物质的方法,其中,所述步骤三焙烧温度进一步优选为550℃~650℃,焙烧时间进一步优选为2h~3h。
本发明的有益效果:
本发明从化学分析角度出发,采取逆向思维直接破坏待测分子筛骨架结构,可以100%合成SAPO-11分子筛无定形物质,在此过程中,无物料损失和杂质引入,所制备的SAPO-11分子筛的无定形物质可用于SAPO-11分子筛结晶度分析中,测试结果准确可靠;
本发明方法可以省去购买无定形二氧化硅、氧化铝等复配试剂或昂贵的模板剂、磷酸等合成试剂,降低成本,而且所用盐酸、氨水都极为便宜并易得,还可节省材料采购所需的时间,极大提高分析测定的效率和便利性。
附图说明
图1为实施例1待测SAPO-11分子筛试样的X射线衍射图;
图2为实施例1处理后SAPO-11分子筛无定形物质的X射线衍射图;
图3为对比例1和对比例2处理后SAPO-11分子筛部分无定形物质的X射线衍射图。
具体实施方式
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述的实施例,下列实施例中未注明具体条件的实验方法,通常按照常规条件。
酸解条件:
在本发明中,对步骤一中所述酸解条件并无特别限定,通常步骤一中所述酸解温度为110℃~180℃。
如果酸解温度小于110℃,由于温度较低,导致加热时间的浪费,酸解反应不完全,反应速度过慢,不能保证完全破坏分子筛骨架结构;而酸解温度超过180℃,由于温度过高,易发生液体飞溅、盐酸挥发,样品酸解产物损失,浪费能源,并无其它有益效果。
步骤三中所述焙烧条件:
在本发明中,对步骤三中所述焙烧条件并无特别限定,通常步骤三中所述焙烧条件:焙烧温度为500℃~700℃,焙烧时间为2h~4h。
如果焙烧温度小于500℃,由于焙烧温度较低,导致焙烧时间浪费,偏氢氧化铝脱水分解不完全,不能保证得到SAPO-11分子筛无定形物质;而焙烧温度超过700℃,由于焙烧温度过大,浪费能源,并无其它有益效果;
如果马弗炉焙烧小于2h,由于焙烧时间较短,造成焙烧不完全;而马弗炉焙烧超过4h,由于焙烧时间过长,造成时间和能源浪费,并无其它有益效果。
本发明在制备SAPO-11分子筛无定形物质之前,需要分析待测SAPO-11分子筛中的硅、铝元素含量,可通过XRF、ICP-AES等仪器进行测定或直接由分子筛产品厂家提供;然后通过硅、铝元素含量来计算所需最少盐酸和氨水量。
所述步骤二中SAPO-11分子筛样品中加入氨水处理的步骤是:
酸解后冷却,缓慢滴加氨水并摇动,生成白色无定形絮状凝胶沉淀,其含水量不定,组成也不均匀,统称为无定型水合氧化铝,无定形水合氧化铝在溶液内静止逐渐变为结晶偏氢氧化铝AlO(OH),温度越高,这种转变越快。
本发明制备的SAPO-11分子筛无定形物质可以采用XRD,XRF或ICP-AES表征,证明制备的SAPO-11分子筛无定形物质与SAPO-11分子筛原料化学组成相同或接近。
为进一步描述采用本发明合成的SAPO-11分子筛无定形物质的试验效果如下实施例:
实施例1
在制备SAPO-11分子筛无定形物质之前,需要分析待测SAPO-11分子筛中的硅、铝元素含量,可通过XRF或ICP-AES等仪器进行测定或直接由分子筛产品厂家提供,得到氧化铝含量;根据式(1)计算所需盐酸量根据式(2)计算所需氨水量 根据盐酸、氨水浓度计算反应中所需最少浓盐酸、氨水质量。
本实施例采用的美国ACS公司生产的SAPO-11分子筛,采用XRF进行测定,其中氧化铝质量含量为40%;所用浓盐酸质量浓度为36%~38%,氨水质量浓度为25%~28%,分子筛样品0.50g,本实施例所用浓盐酸、氨水质量分别为1.2g、1.5g。
反应过程如下:
Al2O3+6HCl=2AlCl3+3H2O (1)
AlCl3+3NH3·H2O=3NH4Cl+AlO(OH)↓+H2O (2)
NH4Cl=NH3+HCl (3)
2AlO(OH)=Al2O3+H2O(高温) (4)
步骤一,在SAPO-11分子筛中加入浓盐酸进行酸解,破坏分子筛的骨架结构:称取待测SAPO-11分子筛样品约0.50g,准确至0.01g,置于石英坩埚中,加入少量水润湿,再加入1.20g浓盐酸轻摇,移至控温加热板上,在150℃加热,期间补充蒸馏水,以保证加热板上水分未蒸干。
步骤二,在酸解后的分子筛中加入氨水进行沉淀:缓慢加入1.50g氨水并搅拌,生成白色无定形凝胶沉淀(其含水量不定,组成也不均匀,统称为水合氧化铝,无定形水合氧化铝在溶液内静止逐渐变为结晶偏氢氧化铝AlO(OH),温度越高,这种转变越快)。
步骤三,焙烧步骤二所得沉淀得到所述SAPO-11分子筛无定形物质:用坩埚钳子将石英坩埚转移至600℃马弗炉中,焙烧3h后取出。待测SAPO-11分子筛试样的X射线衍射图见图1。图2为将待测SAPO-11分子筛试样处理后的SAPO-11分子筛无定形物质的X射线衍射图,为验证试验重复性,按实施例1的方法重复四次,并分别进行X射线衍射测定,得到图2四条衍射图。由图2可知,四次试验处理后的SAPO-11分子筛X射线衍射图相似,试验可重复;曲线光滑没有结晶二氧化硅,骨架被破坏。按本方法即盐酸酸处理后,再用氨水中和两步法所制备的物质均为无定形物质。这些样品的X射线衍射谱图不仅可以重复,而且在整个扫描范围内均为一个衍射峰,完全符合X射线衍射定量分析对所需无定形物质的要求,证明本方法是成功的。
表1为SAPO-11分子筛无定形物质采用XRF表征,表中数据为质量分数%,证明制备的SAPO-11分子筛无定形物质与SAPO-11分子筛原料化学组成相同或接近。
表1XRF表征数据
Al<sub>2</sub>O<sub>3</sub>(%) | SiO<sub>2</sub>(%) | P<sub>2</sub>O<sub>5</sub>(%) | |
SAPO-11分子筛 | 40 | 5 | 55 |
SAPO-11分子筛无定形物质 | 39 | 6 | 55 |
由图1、图2和表1可知,本发明方法制备确系SAPO-11分子筛无定形物质。
对比例1
按照实施例1试验方法对相同SAPO-11分子筛进行处理,由实施例1可知,反应中所需最少浓盐酸、氨水质量为1.12g、1.48g。本对比例加入0.60g浓盐酸、0.80g氨水对SAPO-11分子筛进行处理,并分别重复两次,得到图3衍射曲线①;
对比例2
按照实施例1试验方法对相同SAPO-11分子筛进行处理,由实施例1可知,反应中所需最少浓盐酸、氨水质量为1.12g、1.48g。本对比例加入0.40g浓盐酸、0.50g氨水对SAPO-11分子筛进行处理,并分别重复两次,得到图3衍射曲线②;
由图3可知,当加入少于试验所需的浓盐酸和氨水时,反应不完全,无法全部生成SAPO-11分子筛无定形物质,X射线衍射图曲线不光滑,说明生成的物质中除了无定形物质外,还有结晶性的杂质(图3曲线②毛刺峰所示),这些结晶性的杂质为不同晶型的二氧化硅晶体。所制备的物质完全不符合X射线衍射定量分析对所需无定形物质的要求。
因此本发明在制备SAPO-11分子筛无定形物质之前,需要分析待测SAPO-11分子筛中的硅、铝元素含量,可通过XRF、ICP-AES等仪器进行测定或直接由分子筛产品厂家提供;然后通过硅、铝元素含量来计算所需最少盐酸和氨水量。
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (7)
1.一种制备SAPO-11分子筛无定形物质的方法,其特征在于,该方法包括如下步骤:
步骤一,在SAPO-11分子筛中加入盐酸进行酸解,破坏分子筛的骨架结构;
步骤二,在酸解后的分子筛中加入氨水进行沉淀;以及
步骤三,焙烧步骤二所得沉淀得到SAPO-11分子筛无定形物质;
其中,所述步骤一中盐酸为浓盐酸,所述浓盐酸与SAPO-11分子筛中Al2O3的质量比大于28:5;
所述步骤二中氨水的质量浓度为26%~28%,所述氨水与SAPO-11分子筛中Al2O3的质量比大于37:5。
2.根据权利要求1所述的制备SAPO-11分子筛无定形物质的方法,其特征在于,所述步骤一具体为:将SAPO-11分子筛置于石英或陶瓷坩埚中,先加水润湿,再加入盐酸,摇匀,移至控温加热板上加热,期间补充蒸馏水,以保证加热板上水分未蒸干。
3.根据权利要求2所述的制备SAPO-11分子筛无定形物质的方法,其特征在于,所述在控温加热板上加热的温度为110℃~180℃。
4.根据权利要求1所述的制备SAPO-11分子筛无定形物质的方法,其特征在于,所述步骤二具体为:在酸解后的SAPO-11分子筛中滴加氨水并搅拌以生成沉淀。
5.根据权利要求4所述的制备SAPO-11分子筛无定形物质的方法,其特征在于,在酸解后的SAPO-11分子筛冷却后再进行滴加氨水的操作。
6.根据权利要求1所述的制备SAPO-11分子筛无定形物质的方法,其特征在于,所述步骤三焙烧温度为500℃~700℃,焙烧时间为2h~4h。
7.根据权利要求1所述的制备SAPO-11分子筛无定形物质的方法,其特征在于,所述步骤三焙烧温度为550℃~650℃,焙烧时间为2h~3h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611256802.4A CN108275693B (zh) | 2016-12-30 | 2016-12-30 | 一种制备sapo-11分子筛无定形物质的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611256802.4A CN108275693B (zh) | 2016-12-30 | 2016-12-30 | 一种制备sapo-11分子筛无定形物质的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108275693A CN108275693A (zh) | 2018-07-13 |
CN108275693B true CN108275693B (zh) | 2020-04-10 |
Family
ID=62800217
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611256802.4A Active CN108275693B (zh) | 2016-12-30 | 2016-12-30 | 一种制备sapo-11分子筛无定形物质的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108275693B (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5935417A (en) * | 1996-12-17 | 1999-08-10 | Exxon Research And Engineering Co. | Hydroconversion process for making lubricating oil basestocks |
EP2272939A1 (en) * | 2009-07-03 | 2011-01-12 | BP Corporation North America Inc. | Alkene oligomerization process |
CN105668589A (zh) * | 2016-04-21 | 2016-06-15 | 北京化工大学 | 一种高结晶度sapo-11分子筛的制备方法 |
CN106168584A (zh) * | 2015-05-19 | 2016-11-30 | 中国石油天然气股份有限公司 | 测定sapo-11分子筛相对结晶度的方法 |
-
2016
- 2016-12-30 CN CN201611256802.4A patent/CN108275693B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5935417A (en) * | 1996-12-17 | 1999-08-10 | Exxon Research And Engineering Co. | Hydroconversion process for making lubricating oil basestocks |
EP2272939A1 (en) * | 2009-07-03 | 2011-01-12 | BP Corporation North America Inc. | Alkene oligomerization process |
CN106168584A (zh) * | 2015-05-19 | 2016-11-30 | 中国石油天然气股份有限公司 | 测定sapo-11分子筛相对结晶度的方法 |
CN105668589A (zh) * | 2016-04-21 | 2016-06-15 | 北京化工大学 | 一种高结晶度sapo-11分子筛的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN108275693A (zh) | 2018-07-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Meher et al. | Physicochemical characteristics of alumina gel in hydroxyhydrogel and normal form | |
Barnes et al. | A methodology for quantifying sodalite and cancrinite phase mixtures and the kinetics of the sodalite to cancrinite phase transformation | |
CN106629761A (zh) | 一种ssz‑13分子筛的合成方法 | |
Pan et al. | Effects of precipitation activity of desilication products (DSPs) on stability of sodium aluminate solution | |
Mackinnon et al. | Low temperature synthesis of zeolite N from kaolinites and montmorillonites | |
Prokof’ev et al. | Mechanochemical synthesis of granulated LTA zeolite from metakaolin | |
Li et al. | Concentration variation of aluminate ions during the seeded precipitation process of gibbsite from sodium aluminate solution | |
CN103880037A (zh) | 一种zsm-5分子筛及其制备方法 | |
Gordina et al. | Effect of ultrasound on the thermal behavior of the mixtures for the LTA zeolite synthesis based on metakaolin | |
Christensen et al. | Synthesis and characterization of basic bismuth (III) nitrates | |
Norby et al. | In situ studies of zeolite syntheses using powder diffraction methods. Crystallization of “instant zeolite A” powder and synthesis of CoAPO-5. | |
Cividanes et al. | Effect of urea on the mullite crystallization | |
CN108275693B (zh) | 一种制备sapo-11分子筛无定形物质的方法 | |
CN102564890A (zh) | 一种检测石膏中三氧化硫含量的方法 | |
Qi et al. | Effect of calcium to silica ratio on the synthesis of calcium silicate hydrate in high alkaline desilication solution | |
Ke et al. | Elucidation of the role of potassium fluoride in the chemical and physical nature of ZSM-5 zeolite | |
Marocco et al. | The multifarious aspects of the thermal conversion of Ba-exchanged zeolite A to monoclinic celsian | |
Rair et al. | Synthesis and study by FTIR, 31P NMR and electrochemical impedance spectroscopy of vanadium zinc phosphate glasses prepared by sol–gel route | |
Sathupunya et al. | Microwave preparation of Li-zeolite directly from alumatrane and silatrane | |
Chen et al. | Structure transformation of sodium aluminosilicates as desilication agents in the desilication of highly alkaline sodium aluminate solution containing silica | |
Wang et al. | Synthesis, characterization and structure analysis of UZM-22, a MEI-type zeolite framework structure | |
CN106807351A (zh) | 一种介孔活性材料的制备方法 | |
Jakobsson | Determination of Si/Al ratios in semicrystalline aluminosilicates by FT-IR spectroscopy | |
Fink et al. | Thermal Decomposition of Alunite1 | |
Phiriyawirut et al. | VS-1 zeolite synthesized directly from silatrane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |