CN116514135A - 一种zsm-5分子筛的合成方法 - Google Patents
一种zsm-5分子筛的合成方法 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
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 39
- 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 abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 8
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000005507 spraying Methods 0.000 claims abstract description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 239000003518 caustics Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 4
- 238000010009 beating Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 238000005469 granulation Methods 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 description 22
- 238000011065 in-situ storage Methods 0.000 description 11
- 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 10
- 239000005995 Aluminium silicate Substances 0.000 description 9
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 9
- 235000012211 aluminium silicate Nutrition 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000006012 monoammonium phosphate Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006257 total synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical group [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—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
- B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- 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
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明公开了一种ZSM‑5分子筛的合成方法:硫酸铝溶液按照一定比例分两次加入到水玻璃溶液中,控制过程温度<35℃,每次加完硫酸铝均需静置老化30分钟,浆液记做A;硫酸铝按照一定比例加入到偏铝酸钠溶液中,搅拌均匀后加入一定比例的ZSM‑5分子筛,静置老化30分钟,浆液记做B;A与B混合均匀,加入氨水和α‑氧化铝粉末,过滤洗涤;滤饼打浆后喷雾造粒,焙烧固化,获得的颗粒物记做C;将一定比例的水加入C中,分批加入液碱,升温晶化,晶化后产物加入磷酸二氢铵和氯化镧混合溶液进行交换,过滤洗涤后烘干即可得标题物。所得催化剂具有高的丙烯产率。
Description
技术领域:本发明涉及一种ZSM-5分子筛的合成方法,属于分子筛制备领域
背景技术:
ZSM-5沸石是美国Mobil公司于上个世纪六十年代末合成出来的新型沸石分子筛。由于它在化学组成、晶体结构及物化性质方面具有许多独特性,因此在很多有机催化反应中显示出了优异的催化效能,在工业上得到了越来越广泛的应用,成为石油化工的一种颇有前途的新型催化剂。也被引入到FCC催化剂中,用来提高汽油辛烷值和增产低碳烯烃。
FCC催化剂中活性组分的引入一般有两种方式:半合成和全合成方式;所谓的半合成方式是将活性组分与基质、粘结剂混合制成浆液,喷雾干燥造粒制成微球催化剂;所谓的全合成是先将高岭土喷雾制备成微球,经焙烧后,在适当的条件下通过水热晶化的方法将分子筛活性组分生长在高岭土微球上(即原位晶化)。
利用原位晶化方法制备的含Y型分子筛的全白土催化剂国内外很久前就已经开始应用。
近年来,丙烯需求量的日益增长要求提高FCC催化剂中ZSM-5择型分子筛的含量,但微球催化剂的机械强度是有限制的,不能无限制的增加分子筛含量。因此,近年来原位晶化ZSM-5分子筛技术引起了国内外科研人员的广泛关注。
CN101462740A是使用焙烧的高岭土微球和富硅粘土微球,添加有机模板剂原位晶化合成ZSM-5分子筛,其相对结晶度可达到30-90%。该方法还涉及到了在高岭土微球的制备过程中加入ZSM-5晶种,且在不添加有机模板剂的条件下原位晶化合成ZSM-5的实例。
CN101332995A公开了一种用改性高岭土微球原位晶化ZSM-5分子筛的方法。先将高岭土与改性组元混合、成形,高温焙烧后与外加硅铝源、模板剂、晶种、水混合,水热晶化合成了高岭土基ZSM-5分子筛。其产品相对结晶度为30~80%。
USP6908603公开了一种既不使用有机模板剂,也不使用ZSM-5晶种,但需要引入Y分子筛晶种溶液,在高岭土微球上原位合成ZSM-5分子筛方法。该方法的技术特点是在焙烧后的高岭土微球、碱和硅酸盐等混合物体系中引入含Y型分子筛的晶种溶液。
USP5145659采用粘土基质微球、采用有机胺模板剂法合成了ZSM-5分子筛,结晶度可达35%-38%。
EP0156595技术将粘土、硅铝源和高硅分子筛晶种混合成形后,高温焙烧,然后与碱溶液混合制成满足高硅分子筛生成配比的混合物,再经过先低温老化后高温晶化的方式得到了高硅分子筛含量可达60%的原位晶化产物,其中高温晶化时间长达4天。
目前的技术存在的问题:
(1)高岭土微球中的活性硅铝会溶解到碱性介质中,不能保证全部转化为原位晶化分子筛,会生成一部分在液相中晶化形成的非原位分子筛,这部分颗粒比较小,在后续干燥或进入催化裂化再生器时很容易就跑掉了,
(2)为了获得活性硅或铝物种,需要高温焙烧处理,需要专门的高温焙烧设备,能耗也比较高。
(3)晶化过程多数需要外加有机模板剂,价格昂贵且污水难以处理。
(4)预先制成的微球外观在碱性溶液中容易被破坏,而且有部分晶体是长在微球的内部,可接近性差,仅追求结晶度而未考虑后续使用效果。
发明内容:
为了解决以上技术存在的不足,本发明提供了一种ZSM-5分子筛的合成方法,其具体合成步骤如下:
(1)硫酸铝溶液按照一定比例分两次加入到水玻璃溶液中,控制过程温度<35℃,每次加完硫酸铝均需静置老化30分钟,浆液记做A;
(2)硫酸铝按照一定比例加入到偏铝酸钠溶液中,搅拌均匀后加入一定比例的ZSM-5分子筛,静置老化30分钟,浆液记做B;
(3)A与B混合均匀,加入氨水和α-氧化铝粉末,过滤洗涤;
(4)将上述滤饼打浆后喷雾造粒,焙烧固化,获得的颗粒物记做C;
(5)将一定比例的水加入C中,分批加入液碱,升温晶化,晶化后产物加入磷酸二氢铵和氯化镧混合溶液进行交换,过滤洗涤后烘干即可得标题物。
步骤(1)中硫酸铝溶液第一次加入量以氧化物计与水玻璃的质量比为Al2O3:SiO2=(0.150-0.169):1,第二次加入量以氧化物计与水玻璃的质量比为Al2O3:SiO2=(0.375-0.450):1;
步骤(2)中硫酸铝和偏铝酸钠加入量使得浆液中各物质摩尔比为Na2O:Al2O3:SO4 2-:H2O=(1.25-1.38):1:1.38:57;
步骤(2)中偏铝酸钠溶液的浓度为Al2O3=98-102g/L,苛性比1.45-1.50;
其中使用的硫酸铝溶液浓度为Al2O3=88-92g/L,水玻璃溶液浓度为SiO2=120-130g/L;
过程中ZSM-5分子筛和α-氧化铝粉末加入量占标题物的0.5-3wt%和5-10wt%,ZSM-5分子筛硅铝比28-48,应是使用有机模板剂合成的;
步骤(4)中焙烧温度为300-500℃,焙烧时间应不少于一小时;
步骤(5)中液碱的加入量使得浆液中各物质摩尔比为OH-:SiO2=(0.12-0.20):1,磷酸二氢铵和氯化镧的加入量使得标题物干基中P=3-5wt%,RE2O3=0.3-0.9wt%。
本发明的有益之处:
(1)分别制备两种材料,一种富硅一种富铝,并且混入α-氧化铝,避免一个位置点同时被碱释放硅和铝两种离子,使得释放出来的硅铝只能与微球表面的结合晶化,避免溶液中存在过多硅铝而产生非原位晶化分子筛。
(2)A和B可以调整混合比例,两种硅铝含量和结构不同的材料混合成微球,相当于调整了微球局部硅铝分布,再加上有意添加的非活性α-氧化铝,可以控制原位晶化程度,本发明的材料不单纯追求结晶度高低,而更多的是考虑分子筛的可接近性和实际需求。
(3)步骤2中加入一定比例的ZSM-5分子筛,在起始碱性条件下预活化,产生小的硅铝片段,能够更容易导向生成ZSM-5分子筛。
(4)晶化完成后使用磷酸二氢铵交换,一部分用于对分子筛磷改性,提高其水热稳定性和选择性,另外一部分吸附在微球各颗粒之间,受热后分步分解,可以与颗粒上的铝结合,起到稳定微球的粘结作用。
(5)微球晶化时碱液分批加入,控制体系的碱度,既可以控制活性硅铝的溶解速度,又不过度破坏微球的外观形状。
(6)A和B两种材料本身就有独特的结构,有着独特的孔径分布,而且是可控的,使得最终的微球成品更适合于FCC催化。
附图说明
为了更清楚地说明本申请实施例的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,应当理解,以下附图仅示出了本申请的某些实施例,因此不应被看作是对范围的限定,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他相关的附图也属于本申请的保护范围。
图1为实施例1所制备获得分子筛Z-1的孔径分布照片;
图2为实施例2所制备获得分子筛Z-2的孔径分布照片;
图3为实施例1所制备获得分子筛Z-1的XRD全图照片;
图4为实施例2所制备获得分子筛Z-2的XRD全图照片。
具体实施方式:
下面进一步用实施例说明本发明,但本发明并不仅限于这些例子。
实施例中所用原材料规格如下:
以下材料均取自青岛惠城环保科技集团股份有限公司生产车间。
硫酸铝溶液:以氧化铝计90.2g/L;
水玻璃溶液:以氧化硅计125g/L;
偏铝酸钠溶液:以氧化铝计100.5g/L;
α-氧化铝:D50=1.8微米;
ZSM-5分子筛:硅铝比30,灼减15wt%;
碱液:以OH-计200g/L;
磷酸二氢铵溶液:P=5wt%;
氯化镧溶液:以三氧化二镧计20.3wt%。
实施例1:
(1)量取4L水玻璃溶液放入反应釜中,第一次缓缓加入859mL硫酸铝溶液,搅拌均匀,静置30分钟,第二次加入2217mL硫酸铝溶液,搅拌均匀,静置30分钟,应控制过程温度<35℃,浆液记做A;
(2)2.41L水缓缓加入2.2L偏铝酸钠溶液中,要控制加入速度并剧烈搅拌,再加入4.17L的硫酸铝溶液,完毕后继续加入50g的ZSM-5分子筛,所有物料全部加完搅拌均匀后静置老化30分钟,浆液记做B;
(3)将全部A与B混合均匀,加入氨水控制浆液pH值在7-8,然后加入101.5g的α-氧化铝粉末,过滤洗涤;
(4)将上述滤饼打浆后喷雾造粒,450℃焙烧固化,获得的颗粒物记做C;
(5)将一定比例的水加入C中,分三次加入375mL的液碱,升温晶化,晶化后产物加入1184g磷酸二氢铵和41.7g氯化镧混合溶液进行交换,过滤洗涤后烘干,所得分子筛标记为Z-1。实施例2:
(1)量取4L水玻璃溶液放入反应釜中,第一次缓缓加入915mL硫酸铝溶液,搅拌均匀,静置30分钟,第二次加入2411mL硫酸铝溶液,搅拌均匀,静置30分钟,应控制过程温度<35℃,浆液记做A;
(2)2.54L水缓缓加入2.73L偏铝酸钠溶液中,要控制加入速度并剧烈搅拌,再加入4.72L的硫酸铝溶液,完毕后继续加入40.7g的ZSM-5分子筛,所有物料全部加完搅拌均匀后静置老化30分钟,浆液记做B;
(3)将全部A与B混合均匀,加入氨水控制浆液pH值在7-8,然后加入154g的α-氧化铝粉末,过滤洗涤;
(4)将上述滤饼打浆后喷雾造粒,450℃焙烧固化,获得的颗粒物记做C;
(5)将一定比例的水加入C中,分三次加入500mL的液碱,升温晶化,晶化后产物加入1729g磷酸二氢铵和75.7g氯化镧混合溶液进行交换,过滤洗涤后烘干,所得分子筛标记为Z-2。
分子筛的化学组成如下:
Al2O3,% | SiO2,% | P,% | RE2O3,% | Na2O,% | 结晶度 | 比表面 | |
Z-1 | 64.5 | 30.2 | 3.6 | 0.52 | 0.35 | 29.5 | 187 |
Z-2 | 66.9 | 26.4 | 4.1 | 0.82 | 0.19 | 34.7 | 204 |
使用ACE评价装置进行性能评价,所用原料油性质见表1,本发明催化剂添加比例为10%,对比剂为国内市面上性能最好的催化剂,主催化剂使用惠城环保科技生产的AIC系列催化剂。对比评价结果见表2。
表1原料油性质
表2 ACE对比评价结果
从评价数据可以看出,相同添加比例时,本发明的催化剂丙烯收率和丙烯选择性均明显高于对比剂,具有优异的性能。
Claims (8)
1.一种ZSM-5分子筛的合成方法,其合成步骤如下:
(1)硫酸铝溶液按照一定比例分两次加入到水玻璃溶液中,控制过程温度<35℃,每次加完硫酸铝均需静置老化30分钟,浆液记做A;
(2)硫酸铝按照一定比例加入到偏铝酸钠溶液中,搅拌均匀后加入一定比例的ZSM-5分子筛,静置老化30分钟,浆液记做B;
(3)A与B混合均匀,加入氨水和α-氧化铝粉末,过滤洗涤;
(4)将上述滤饼打浆后喷雾造粒,焙烧固化,获得的颗粒物记做C;
(5)将一定比例的水加入C中,分批加入液碱,升温晶化,晶化后产物加入磷酸二氢铵和氯化镧混合溶液进行交换,过滤洗涤后烘干即可得标题物。
2.根据权利要求1所述的合成方法,其特征在于步骤(1)中硫酸铝溶液第一次加入量以氧化物计与水玻璃的质量比为Al2O3:SiO2=(0.150-0.169):1, 第二次加入量以氧化物计与水玻璃的质量比为Al2O3:SiO2=(0.375-0.450):1。
3.根据权利要求1所述的合成方法,其特征在于步骤(2)中硫酸铝和偏铝酸钠加入量使得浆液中各物质摩尔比为Na2O :Al2O3 :SO4 2- :H2O = (1.25-1.38) :1 :1.38 :57。
4.根据权利要求1所述的合成方法,其特征在于步骤(2)中偏铝酸钠溶液的浓度为Al2O3 =98-102g/L,苛性比1.45-1.50。
5.根据权利要求1所述的合成方法,其特征在于硫酸铝溶液的浓度为Al2O3 =88-92g/L,水玻璃溶液浓度为SiO2=120-130g/L。
6.根据权利要求1所述的合成方法,其特征在于ZSM-5分子筛和α-氧化铝粉末加入量占标题物干基的0.5-3wt%和5-10wt%,ZSM-5分子筛硅铝比28-48,应是使用有机模板剂合成的。
7.根据权利要求1所述的合成方法,其特征在于步骤(4)中焙烧温度为300-500℃,焙烧时间应不少于一小时。
8.根据权利要求1所述的合成方法,其特征在于步骤(5)中液碱的加入量使得浆液中各物质摩尔比为OH-:SiO2=(0.12-0.20):1,磷酸二氢铵和氯化镧的加入量使得标题物干基中P=3-5wt%,RE2O3=0.3-0.9wt%。
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