CN102006934A - 催化剂及其制备方法 - Google Patents
催化剂及其制备方法 Download PDFInfo
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- CN102006934A CN102006934A CN2009801136788A CN200980113678A CN102006934A CN 102006934 A CN102006934 A CN 102006934A CN 2009801136788 A CN2009801136788 A CN 2009801136788A CN 200980113678 A CN200980113678 A CN 200980113678A CN 102006934 A CN102006934 A CN 102006934A
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- China
- Prior art keywords
- catalyst
- slurry
- preparation
- metal silicate
- catalysts method
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000002002 slurry Substances 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 57
- 238000001694 spray drying Methods 0.000 claims abstract description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000004615 ingredient Substances 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 239000011651 chromium Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005469 granulation Methods 0.000 claims description 79
- 230000003179 granulation Effects 0.000 claims description 79
- 229910052914 metal silicate Inorganic materials 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 2
- 238000010298 pulverizing process Methods 0.000 abstract description 9
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- 238000007906 compression Methods 0.000 description 22
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000009434 installation Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
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- 239000012798 spherical particle Substances 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
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- 230000002950 deficient Effects 0.000 description 3
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- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000326 densiometry Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
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Images
Classifications
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- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B3/00—Drying solid materials or objects by processes involving the application of heat
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- F26B3/12—Drying solid materials or objects by processes involving the application of heat by convection, i.e. heat being conveyed from a heat source to the materials or objects to be dried by a gas or vapour, e.g. air the gas or vapour carrying the materials or objects to be dried with it in the form of a spray, i.e. sprayed or dispersed emulsions or suspensions
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Abstract
本发明提供催化剂,其使催化剂的结晶表面部分的有效面积增大,同时在不使用粘结剂下使催化剂的造粒体的抗压强度提高。对包含将含有金属硅酸盐的原料利用珠磨机进行微细化而得到的催化剂粉的浆料利用喷雾干燥法进行干燥,得到催化剂的造粒体。上述原料基本上包含具有4.5~6.5埃直径的细孔的金属硅酸盐。可以将上述原料进行微细化以使上述金属硅酸盐的粒径在50%累积频数下为1.0μm以下。可以在上述金属硅酸盐中负载作为金属成分的选自铼、钒、钼、钨、铬及它们化合物中的至少一种以上。可以将上述浆料在进行熟化后供给于上述干燥过程即可。可以在上述浆料中添加聚乙烯醇。
Description
技术领域
本发明涉及以甲烷为主要成分的天然气、生物气体、甲烷水合物的高度利用。天然气、生物气体、甲烷水合物被认为是作为地球变暖对策最有效的能源,在利用技术方面逐渐被关注。对于甲烷资源,发挥其清洁性,作为下一世纪的新有机资源、燃料电池用的氢源备受瞩目。本发明涉及催化剂化学转变技术及催化剂制备方法,所述催化剂化学转变技术用于由甲烷高效地制备作为塑料类等化学制品原料的以苯及萘类为主要成分的芳香族化合物和高纯度的氢气。
背景技术
作为由甲烷制备苯等芳香族化合物和氢的方法,已知有在催化剂的存在下使甲烷反应的方法。作为此时的催化剂,认为ZSM-5系的沸石所负载的钼有效(非专利文献1、专利文献1、专利文献2)。但是,即使在使用有这些催化剂的情况下,也具有如下问题:碳的析出多,由于碳的析出,催化剂性能在短时间劣化,或甲烷的转化率低。
为了改善该问题,正在研究使催化剂的形状为可以用于固定床式的反应设备的丸粒型,进一步提高丸粒中所含的催化剂成分的比例,高效地与甲烷反应。但是,固定床反应式的情况下,从机械强度的关系来看,10%以上的无机及有机粘结剂为必不可少,另外,尺寸也限制为毫米单位以上,因此具有问题。
也设计有可以适用于专利文献3所示流动床式的反应设备的粒子形状的催化剂,但从耐磨损性或耐冲击性的观点考虑,存在于粒子中的催化剂成分的比例为50%以下,与机械强度的调整的固定床式的丸粒型相比较差。另外,由于在短时间内催化剂失活,因此,催化剂的再生必不可少。
现有技术文献
非专利文献
非专利文献1:JOURNAL OF CATALYSIS,1997,pp.165,pp.150-161
专利文献
专利文献1:特开平10-272366号公报
专利文献2:特开平11-60514号公报
专利文献3:特开昭61-266306号公报
发明内容
为了使甲烷的转化率提高,反应气体和催化剂的接触效率的提高必不可少,催化剂的形状也对反应工艺产生大的影响。关于形状,大体上分类为固定床用的丸粒型的成形体和流动床及移动床用的造粒体。对于丸粒型的成形体,使在成型时必需的催化剂以外的材料例如有机粘结材料、无机粘结材料、玻璃纤维、造孔材料等成为必要,也需要考虑这些添加物对催化剂产生的影响。
造粒体的情况下,具有粒径小至数十~数百微米、与反应气体的接触效率升高的优点,另一方面,在反应工艺中需要使造粒体本身流动,因此,耐磨损性或耐热冲击性优异成为绝对条件。为了满足这些,除催化剂材料之外,必须在造粒体中混合或涂布许多粘结材料。特别是根据专利文献3,仅使原料沸石粉末浆料进行喷雾干燥的情况,可得到呈现有大致球状的催化剂的造粒体,但其由于运输等操作及振动而容易破坏,因此,除原料沸石粉末之外,必须配合适当的粘结剂。
因此,用于解决上述课题的催化剂的制备方法为用于由低级烃生成芳香族化合物和氢的催化剂的制备方法,其中,对包含将含有金属硅酸盐的原料利用珠磨机进行微细化而得到的催化剂粉的浆料利用喷雾干燥法进行干燥,得到上述催化剂的造粒体。
另外,用于解决上述课题的催化剂为利用上述制备方法而形成的催化剂。
作为上述含有金属硅酸盐的原料,有包含具有基本上为4.5~6.5埃直径的细孔的金属硅酸盐的原料。可以用珠磨机将上述金属硅酸盐原料微细化使上述金属硅酸盐的粒径在50%累积频数下为1.0μm以下。在上述金属硅酸盐中可以负载选自铼、钒、钼、钨、铬及其化合物中的至少一种以上的金属成分。上述钼的负载量相对于上述催化剂粉的总量可以为2~12重量%。可以将上述浆料在熟化后利用喷雾干燥法进行干燥。作为上述熟化,可举出在常温常压的空气氛围下的静置。可以通过在上述浆料中添加上述金属成分,对上述金属硅酸盐负载上述金属成分。而且,可以在上述浆料中添加聚乙烯醇(以下称为PVA)。
发明效果
根据以上的发明涉及的催化剂的制备方法,可提供催化剂,其催化剂的结晶表面部分的有效面积增大,同时在不使用粘结剂下使催化剂的造粒体的抗压强度提高。
附图说明
图1是实施例1的造粒体的SEM照片(加速电压15.0kV,倍率为1000倍)。
图2是实施例1的造粒体的SEM照片(加速电压15.0kV,倍率为20000倍)。
图3是实施例2的造粒体的SEM照片(加速电压15.0kV,倍率为1000倍)。
图4是实施例2的造粒体的SEM照片(加速电压15.0kV,倍率为20000倍)。
图5是实施例4的造粒体的SEM照片(加速电压15.0kV,倍率为1000倍)。
图6是实施例4的造粒体的SEM照片(加速电压15.0kV,倍率为5000倍)。
图7是表示实施例4的造粒体表面中元素(O、Al、Si、Mo)分布的SEM照片(倍率为1000倍)。
图8是表示实施例4的造粒体表面中元素(O、Al、Si、Mo)分布的SEM照片(倍率为10000倍)。
图9是实施例5的造粒体的SEM照片(加速电压15.0kV,倍率为1000倍)。
图10是实施例5的造粒体的SEM照片(加速电压15.0kV,倍率为5500倍)。
图11是表示实施例5的造粒体表面中元素(O、Al、Si、Mo)分布的SEM照片(倍率为10000倍)。
具体实施方式
发明涉及的催化剂的制备方法在将含有金属硅酸盐的原料利用珠磨机进行微细化且高分散化而形成的含催化剂浆料中,在浆料刚制备之后或熟化一定时间后,利用喷雾干燥将其转变为造粒体。上述熟化可以在常温常压的空气氛围下使浆料静置。
(1)催化剂载体
含有金属硅酸盐的原料包含选自铼、钒、钼、钨、铬及它们的化合物中的至少一种以上的金属成分作为催化剂材料,且包含具有直径基本上为4.5~6.5埃的细孔的金属硅酸盐作为负载该催化剂材料的载体。在日本特开2004-97891号公报中例示了上述金属硅酸盐。具体地,作为金属硅酸盐(多孔金属硅酸盐),例如硅铝酸盐的情况,可举出由二氧化硅及氧化铝形成且作为多孔体的分子筛5A、八面沸石(NaY及NaX)、ZSM-5、MCM-22。另外,可举出沸石载体或含有二氧化硅为主要成分和部分含有氧化铝作为成分并带有中细孔(10~1000埃)的筒状细孔(通道)特征的FSM-16或MCM-41等中细孔多孔载体等,所述沸石载体的特征在于,是以磷酸为主要成分的多孔体,如ALPO-5、VPI-5等并且包含6~13埃的微细孔或通道。而且,除上述氧化铝硅酸盐之外,由二氧化硅及二氧化钛构成的金属硅酸盐等也可以用作催化剂。
(2)金属在催化剂载体的负载
优选在作为载体的金属硅酸盐中含浸负载规定浓度的钼的方法。对于上述钼,其负载量相对于烧成后的催化剂总量优选为2~12重量%。
另外,可以在上述浆料中添加PVA。将利用喷雾干燥法干燥含有已用珠磨机微细化的催化剂粉的浆料而得到的造粒体进行烧成的情形下,在烧成时在造粒体内产生气体,球状的粒子破裂,从而发生在球状的粒子中产生缺陷的现象。因此,添加PVA时,通过在烧成时将PVA气化除去,可以在造粒体中出现许多细孔。通过上述气体从该气孔逃逸到外部,能防止上述破裂并能使缺陷不会产生。上述PVA的添加量相对于浆料中的金属硅酸盐优选0.1~1重量%。
(3)催化剂粉的微细化
对制备其中已将金属硅酸盐原料或负载有上述金属成分的金属硅酸盐利用珠磨机微细化为1微米以下的浆料的方法进行叙述。相对于形成浆料溶液的水,以例如催化剂粉∶水=1∶4来称量金属硅酸盐原料或负载有上述金属成分的金属硅酸盐(以下称为催化剂粉)。混合比率并不限定于此,优选根据使用的金属硅酸盐的物性适当调整。此时的浆料粘度优选100cps以下。在混合催化剂粉和水时,预先在混合器内全量投入水,在搅拌的状态下调整为0.4~1kg/分钟左右以投入催化剂粉。比其快时,催化剂粉凝集,在混合器内沉淀,因此不优选。此时使用叶片形状及旋转数可任意设定的混合器。
叶片形状及旋转数没有特别限定。
用于珠磨机的粉碎用珠优选氧化锆。
使用上述规格的珠磨机,将浆料循环用的软管泵启动,进行催化剂粉的微细化。可以将微细化与珠直径及时间一起调整。可以将上述金属硅酸盐原料利用珠磨机进行微细化以使上述金属硅酸盐的粒径在50%累积频数下为1.0μm以下。例如平均粒径为42μm的ZSM-5原料的情况下,用1小时的粉碎时间可能微细化到0.3μm。催化剂粉已微细化的浆料通过从关闭系统向开放系统转换供给线来回收。
(4)关于造粒
对用喷雾干燥装置将浆料中的催化剂粉进行干燥及造粒的方法进行说明。优选在(3)中制备的浆料利用喷雾干燥装置直接干燥及造粒或熟化一定时间(例如6天)后来使用。喷雾干燥器的型号没有特别限定,优选下方喷雾平行流方式。喷嘴优选2流体喷嘴方式,孔径优选根据浆料的粘度或催化剂粉的粒子形状适当变更。喷雾干燥器的操作条件根据浆料粘度或浆料中的催化剂粉的粒度适当调整。其操作条件没有特别限定。
根据本发明涉及的催化剂的制备方法,可提供催化剂,其中,通过纳米尺寸的催化剂粉的微细化,催化剂的结晶表面部分的有效面积增大,同时即使不添加粘结剂,也使催化剂造粒体的抗压强度提高。因此,可容易地制备旋转造粒方法困难的球状粒子。另外,使无机粘结材料不需要或大幅度地减少,容易进行金属在包含于造粒体中的催化剂粉的负载。
而且,可提供催化剂,其中,通过在含有微细化催化剂粉的浆料中添加上述金属成分并使上述催化剂粉含浸上述金属成分,容易进行在催化剂粉中均匀的金属负载,同时,造粒体的流动性优异且使抗压强度提高。而且,通过在上述浆料中添加PVA,造粒体的抗压强度进一步升高。
以下举出发明涉及的实施例及比较例。
(比较例1)
比较例1涉及的催化剂粉使用了作为具有平均粒径31μm、结晶直径0.08μm的一种金属硅酸盐的质子型ZSM-5。粒径及结晶直径通过算出从电子显微镜照片任意选择的粒子的平均值来测量。在溶剂中使用蒸馏水,按照催化剂粉原料的固形分浓度为20重量%来制备浆料。
然后,在将该浆料搅拌1小时后,利用喷雾干燥装置(ヤマト科学株式会社制造、型号DL-41)进行造粒。操作条件在设定入口温度230~240℃、出口温度90℃后,以干燥空气量0.8m3/min、喷嘴喷雾空气压力0.1MPa、浆料送液量20g/min进行干燥及造粒。得到的造粒体在空气中、在120℃下干燥20小时。关于造粒体的强度,根据JIS Z8841,测量每个粒子的抗压强度。测定得到的15个造粒体的抗压强度。如表3所示,对任一个造粒体,都小于测定机的测定极限值0.06gf/mm2。
(实施例1)
实施例1所述的催化剂粉使用了具有平均粒径42μm、结晶直径5μm的1种金属硅酸盐ZSM-5。催化剂粉原料为氨型,在规定的温度下进行烧成处理而转变为质子型。不对本实施例中使用的ZSM-5进行金属负载。
首先,对催化剂粉利用珠磨机的微细化方法进行说明。相对于催化剂粉1kg,称量纯化水4kg,将纯化水全量投入到搅拌容器。一边旋转搅拌机的叶片,一边以400g/分钟全量投入催化剂粉,使浆料循环泵启动,开始浆料的循环及粉碎。从开始后每经过15分钟抽取一部分浆料,测定浆料粘度及催化剂粉的粒度分布。表1中示出催化剂粉的粒度分布随时间的变化。在从粉碎开始1小时停止循环泵,取体系内的浆料。相对于投入的浆料重量5kg,回收的浆料为3.76kg。
接着对利用催化剂粉的喷雾干燥装置的造粒方法进行说明。将先前制备的浆料熟化5天。上述熟化在常温常压的空气氛围下使浆料静置。其后,用搅拌容器搅拌。设定入口温度230~240℃、出口温度90℃后,在干燥空气风量0.8m3/min、喷嘴喷雾空气压力0.1MPa、浆料送液量20g/min的条件下利用喷雾干燥装置(ヤマト科学株式会社制造,型号DL-41)开始干燥及造粒。将得到的造粒体在空气中、在120℃下干燥了20小时。将干燥后的SEM(扫描型电子显微镜)照片示于图1(倍率为1000倍)、图2(倍率为20000倍)。另外,表3中示出造粒体的抗压强度结果(10点平均值)。
(实施例2)
实施例2涉及的催化剂粉使用了具有平均粒径39μm、结晶直径4.2μm的1种金属硅酸盐ZSM-5。以后的制备条件与实施例1同样。另外,表2中示出利用珠磨机微细化的催化剂粉的粒度分布变化,将利用喷雾干燥装置(ヤマト科学株式会社制造、型号DL-41)的造粒体的SEM照片示于图3(倍率为1000倍)、图4(倍率为20000倍)。另外确认到,表3中没有公开但实施例2涉及的造粒体的抗压强度和实施例1涉及的造粒体的抗压强度大致相同。
由表1及表2的结果可知,可以在短时间进行纳米水平催化剂粉的均匀微细化。而且,通过将微细化的催化剂粉进行喷雾干燥,可得到如图1及图2所示的球状致密造粒体。另外,由表3的结果可知,与仅将浆料进行喷雾干燥而得到的纳米尺寸(结晶直径80nm)的比较例1的催化剂粉相比,在将利用珠磨机微细化的含有催化剂粉的浆料进行熟化后喷雾干燥的实施例1的造粒体可得到更高的抗压强度。而且显示:含有实施例1的造粒体由于将催化剂粉进行微细化,使结晶表面的面积增大,因此,与反应气体的接触效率增加,即使对如流动床工艺的高流速条件下的反应,也可作为高效的催化剂造粒体而起作用。另外确认到:如果将上述金属硅酸盐原料利用珠磨机进行微细化以使金属硅酸盐的粒径按累积频数50%计为1.0μm以下、特别为0.5μm以下,则可得到上述抗压强度。
(实施例3)
实施例3所述的催化剂粉使用了具有平均粒径42μm、结晶直径5μm的1种金属硅酸盐ZSM-5。催化剂粉原料为氨型,在规定的温度下进行烧成处理而转变为质子型。不对本实施例中使用的ZSM-5进行金属负载。
首先,对利用催化剂粉的珠磨机的微细化方法进行说明。相对于催化剂粉5kg,称量纯化水20kg,将纯化水全量投入到搅拌容器。一边旋转搅拌机的叶片,一边以400g/分钟全量投入催化剂粉,使浆料循环泵启动,开始浆料的循环及粉碎。从粉碎开始用1小时进行微粉碎至结晶直径0.2μm并停止循环泵后,取体系内的浆料。相对于投入的浆料重量25kg,回收的浆料为18.9kg。
其次,对利用催化剂粉的喷雾干燥装置的造粒方法进行说明。将先前制备的浆料熟化5天。上述熟化在常温常压的空气氛围下使浆料静置。其后,用搅拌容器进行搅拌。设定入口温度230~240℃、出口温度90℃后,在干燥空气风量0.8m3/min、喷嘴喷雾空气压力0.1MPa、浆料送液量20g/min的条件下利用喷雾干燥装置(ヤマト科学株式会社制造,型号DL-41)开始干燥及造粒。得到的造粒体在空气中、在120℃下干燥20小时。其后,在550℃下烧成5小时。
对上述得到的造粒体的强度,利用根据JIS Z8841的测定法测定15个造粒体的抗压强度。表4示出测定结果。造粒体的平均抗压强度为60.8gf/mm2以下。
关于造粒体的流动性,以通过进行根据JIS Z2504、JIS R6126的体积密度测定法(通过进行拍实,由体积减少的方法得到流动性指数)为基础。根据川上式拍实密度测定法进行测定。表5示出测定结果。川上式流动性指数的数值越小,表示流动性越良好。造粒体的流动性指数为0.38。
(实施例4)
实施例4涉及的催化剂粉使偏硅酸盐负载作为金属成分的钼。另外,本实施例的催化剂的制备方法具有使利用珠磨机微细化的催化剂粉含浸、负载金属成分的步骤,除此之外,与实施例3涉及的催化剂的制备方法相同。
首先,对将催化剂粉利用珠磨机微细化后的含浸负载金属的方法进行说明。将在与实施例3相同的条件下制备的浆料2kg熟化5天,其后,用搅拌容器进行搅拌。而且,在该浆料中投入在200g的水中溶解有七钼酸铵42g的水溶液并搅拌3小时。
以下对利用催化剂粉的喷雾干燥装置的造粒方法进行说明。将上述制备成的浆料设定入口温度230~240℃、出口温度90℃后,在干燥空气风量0.8m3/min、喷嘴喷雾空气压力0.1MPa、浆料送液量20g/min的条件下利用喷雾干燥装置(ヤマト科学株式会社制造,型号DL-41)开始干燥及造粒。得到的造粒体在空气中、在120℃下干燥20小时。其后,在550℃下烧成5小时。
表4中示出造粒体的抗压强度结果(10点平均值),表5中示出流动性指数的结果。抗压强度及流动性指数的测定用与实施例3相同的方法进行。另外,将烧成后的造粒体的SEM照片示于图5(倍率为1000倍)、图6(倍率为5000倍)。而且,将表示造粒体表面中的元素(O、Al、Si、Mo)分布的SEM照片示于图7(倍率为1000倍)、图8(倍率为10000倍)。
(实施例5)
本实施例的催化剂的制备方法具有对投入有七钼酸铵水溶液的浆料进一步添加PVA水溶液的步骤,除此之外,与实施例4所述的催化剂的制备方法相同。
即,将在与实施例3相同的条件下制备的浆料2kg熟化5天,其后,用搅拌容器进行搅拌。而且,在该浆料中投入在200g的水中溶解有七钼酸铵42g的水溶液。进一步添加10%PVA水溶液8g并搅拌3小时。以后的造粒方法与实施例4涉及的催化剂的造粒步骤相同。
表4中示出造粒体的抗压强度结果(10点平均值),表5中示出流动性指数的结果。抗压强度及流动性指数的测定用与实施例3相同的方法进行。另外,将烧成后的造粒体的SEM照片示于图9(倍率为1000倍)、图10(倍率为5500倍)。而且,将表示造粒体表面中的元素(O、Al、Si、Mo)分布的SEM照片(倍率为10000倍)示于图11。
由表4的结果可知,与将实施例3那样的纳米尺寸的原料浆料进行喷雾干燥并烧成相比,在其浆料中含浸负载钼并进行喷雾干燥、烧成而得到的实施例4的造粒体具有高的抗压强度。可知进一步添加PVA并进行喷雾干燥、烧成而得到的实施例5的造粒体具有更高的抗压强度。
根据表5的结果可知:实施例4、5的催化剂与实施例3的催化剂相比,其流动性指数都小,因此,为流动性优异的造粒体。
对于实施例4的造粒体,如图5~图8所示,可得到致密且为球状的造粒体。确认到,根据进一步添加有PVA的实施例5涉及的催化剂的制备方法,如图9~图11所示,得到了缺陷(凹陷)少的造粒体。造粒体中的催化剂粉通过微细化,使结晶表面的面积增大,因此,与反应气体的接触效率增加,即使对流动床工艺那样的高流速条件下的反应,也可作为有效的催化剂造粒体起作用。
另外,在图7、图8、图11的元素分布照片中,“O Ka1”的照片表示氧的分布。“Al Ka1”的照片表示铝的分布。“Si Ka1”的照片表示硅的分布。“Mo La1”的照片表示钼的分布。照片的白色部分表示元素的分布。根据以上的照片可确认,对于造粒体的表面,在均匀地分布的状态下负载有金属元素成分(Al、Mo)。另外可以确认,用于实施例的沸石的主要成分为AlO3和SiO2,主原料的SiO2/Al2O3比为40,因此,在一面浓密地分布有Si。
由以上实施例的结果可知,根据本发明的催化剂的制备方法,通过利用珠磨机的纳米尺寸催化剂粉的微细化,催化剂的结晶表面部分的有效面积增大。另外,可容易制备旋转造粒方法困难的球状粒子。而且,可不需要或大幅度减少无机粘结材料。而且,在含有微细化催化剂粉的浆料中添加例示为钼的金属成分,使对上述催化剂粉含浸上述金属成分,由此对造粒体中所含的催化剂粉的均匀负载金属变得容易。而且,可以使造粒体的流动性良好。而且,造粒体的抗压强度升高。特别是通过添加PVA,可进一步提高抗压强度。
[表1]
用珠磨机粉碎的催化剂(实施例1)粒度分布
[表2]
用珠磨机粉碎的催化剂(实施例2)粒度分布
[表3]
抗压强度(gf/mm2) | |
比较例1 | 小于0.06 |
实施例1 | 60.8 |
[表4]
造粒体的抗压强度(gf/mm2)
造粒体直径 | 40~125μm | 125~250μm |
实施例3 | 66.2 | |
实施例4 | 607.7 | 349.2 |
实施例5 | 848.8 |
[表5]
造粒体的流动性指数
造粒体直径 | 40~125μm |
实施例3 | 0.38 |
实施例4 | 0.28 |
实施例5 | 0.29 |
Claims (10)
1.催化剂的制备方法,所述催化剂用于由低级烃生成芳香族化合物和氢,该制备方法特征在于,
利用喷雾干燥法将包含催化剂粉的浆料干燥以得到所述催化剂的造粒体,其中所述催化剂粉为利用珠磨机将含有金属硅酸盐的原料进行微细化而得到。
2.如权利要求1所述的催化剂的制备方法,其特征在于,所述含有金属硅酸盐的原料包含具有直径基本上为4.5~6.5埃细孔的金属硅酸盐。
3.如权利要求1或2所述的催化剂的制备方法,其特征在于,以金属硅酸盐的粒径在50%累积频数下为1.0μm以下的方式将所述金属硅酸盐原料利用珠磨机进行微细化。
4.如权利要求1~3任一项所述的催化剂的制备方法,其特征在于,所述金属硅酸盐负载有选自铼、钒、钼、钨、铬及它们的化合物中的至少一种以上作为金属成分。
5.如权利要求4所述的催化剂的制备方法,其特征在于,所述钼的负载量相对于所述催化剂粉总量为2~12重量%。
6.如权利要求1~5任一项所述的催化剂的制备方法,其特征在于,将所述浆料进行熟化后利用喷雾干燥法干燥。
7.如权利要求6所述的催化剂的制备方法,其特征在于,所述熟化为在常温常压的空气气氛下使所述浆料静置。
8.如权利要求4~7任一项所述的催化剂的制备方法,其特征在于,通过在所述浆料中添加所述金属成分,对于所述金属硅酸盐负载所述金属成分。
9.如权利要求1~8任一项所述的催化剂的制备方法,其特征在于,在所述浆料中添加聚乙烯醇。
10.催化剂,其用于由低级烃生成芳香族化合物和氢,特征在于其是利用权利要求1~9任一项所述制备方法而形成。
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Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4196102A (en) * | 1975-12-09 | 1980-04-01 | Chiyoda Chemical Engineering & Construction Co., Ltd. | Catalysts for demetallization treatment of _hydrocarbons supported on sepiolite |
JPS61266306A (ja) * | 1985-05-18 | 1986-11-26 | Agency Of Ind Science & Technol | 結晶性アルミノケイ酸塩の微小球状粒子及びその製造方法 |
JPH01236947A (ja) * | 1988-03-18 | 1989-09-21 | Satoyuki Inui | 複合金属メタロシリケート触媒およびこれを使用する低級パラフィン系炭化水素からの芳香族炭化水素の製法 |
US5011667A (en) * | 1988-09-08 | 1991-04-30 | Engelhard Corporation | Self-bound sodium chabazite aggregates and methods for preparation thereof |
US4975180A (en) * | 1989-06-05 | 1990-12-04 | Exxon Research And Engineering Company | Cracking process |
US5552361A (en) * | 1993-11-04 | 1996-09-03 | W. R. Grace & Co.-Conn. | Aluminum phosphate composition with high pore volume and large pore diameter, process for its production and use thereof |
US5369071A (en) * | 1992-12-11 | 1994-11-29 | Mobil Oil Corporation | Manufacture of improved catalyst |
US5403799A (en) * | 1992-12-21 | 1995-04-04 | W. R. Grace & Co.-Conn. | Process upset-resistant inorganic supports for bioremediation |
JP3755955B2 (ja) * | 1997-03-19 | 2006-03-15 | 市川 勝 | 低級炭化水素の芳香族化触媒及び該触媒を用いた芳香族化合物の製造方法 |
JP3745885B2 (ja) * | 1997-08-21 | 2006-02-15 | 市川 勝 | メタンを原料とする芳香族化合物の製造方法 |
EP0909582B1 (en) * | 1997-10-15 | 2005-12-28 | China Petro-Chemical Corporation | Cracking catalytic for the production of light olefins and its preparation |
US6313061B1 (en) * | 1998-12-22 | 2001-11-06 | W. R. Grace & Co.-Conn. | Method of making frangible spray dried agglomerated supports and olefin polymerization catalysts supported thereon |
US20020049133A1 (en) * | 1999-03-02 | 2002-04-25 | Michael S. Ziebarth | High zeolite content and attrition resistant catalyst, methods for preparing the same and catalyzed processes therewith |
US6552243B2 (en) | 2000-07-27 | 2003-04-22 | Conoco Phillips Company | Catalyst and process for aromatic hydrocarbons production from methane |
ES2282488T3 (es) * | 2001-07-02 | 2007-10-16 | Exxonmobil Chemical Patents Inc. | Inhibicion de la formacion de coque en un catalizador en la fabricacion de una olefina. |
JP3985038B2 (ja) * | 2001-07-12 | 2007-10-03 | 独立行政法人産業技術総合研究所 | 低級炭化水素から芳香族炭化水素と水素を製造する方法 |
US6964934B2 (en) * | 2002-08-28 | 2005-11-15 | Albemarle Netherlands B.V. | Process for the preparation of doped pentasil-type zeolite using doped seeds |
US6864202B2 (en) * | 2002-09-16 | 2005-03-08 | Indian Oil Corporation Limited | Process for preparing sodium silicate alkali solution depleted of sodium salt and enriched in silica |
US7179766B2 (en) * | 2002-12-19 | 2007-02-20 | Sud-Chemie Inc. | Method and apparatus for production of enrobed catalyst pastilles or flakes |
US20050146066A1 (en) * | 2003-04-28 | 2005-07-07 | Masafumi Koide | Porous ceramic and method for production thereof |
TWI259106B (en) * | 2003-06-30 | 2006-08-01 | China Petrochemical Technology | Catalyst conversion process for increasing yield of light olefins |
JPWO2005028105A1 (ja) * | 2003-09-17 | 2006-11-30 | 株式会社明電舎 | 低級炭化水素の芳香族化触媒とその製造方法並びに芳香族化合物と水素の製造方法 |
US7241713B2 (en) * | 2003-10-02 | 2007-07-10 | Exxonmobil Chemical Patents Inc. | Molecular sieve catalyst composition, its making and use in conversion processes |
EP3225678B1 (en) | 2004-03-08 | 2022-04-27 | China Petroleum & Chemical Corporation | Am fcc process with two reaction zones |
JP4677194B2 (ja) * | 2004-03-11 | 2011-04-27 | 勝 市川 | 触媒を用いた低級炭化水素の転化方法 |
JP4335061B2 (ja) * | 2004-04-19 | 2009-09-30 | ジェイエフイーホールディングス株式会社 | スラリー床反応用触媒の製造方法 |
US20060183626A1 (en) * | 2005-02-11 | 2006-08-17 | Cavalcanti Fernando Antonio Pe | Process for preparing catalysts and catalysts produced therefrom |
JP4790356B2 (ja) * | 2005-09-16 | 2011-10-12 | 勝 市川 | 低級炭化水素改質触媒 |
US7981834B2 (en) * | 2006-03-16 | 2011-07-19 | Ict Co., Ltd. | Adsorbent for hydrocarbons, catalyst for exhaust gas purification and method for exhaust gas purification |
AU2007241001B2 (en) * | 2006-04-21 | 2010-12-02 | Exxonmobil Chemical Patents Inc. | Process for methane conversion |
-
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