CN112718013A - 一种氧化铝载体及其制备和应用 - Google Patents
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 9
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
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- 150000001299 aldehydes Chemical class 0.000 claims description 4
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
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- 102000054766 genetic haplotypes Human genes 0.000 claims 2
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
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- 238000005984 hydrogenation reaction Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
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- 239000000376 reactant Substances 0.000 description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
本发明公开一种氧化铝载体及其制备方法和应用,所述方法包括如下内容:(1)将酵母溶解于含水溶液中,并与多羟基化合物混合后备用;(2)将步骤(1)的物料与拟薄水铝石粉体混合,经混捏、成型、干燥、焙烧,得到最终氧化铝载体。采用所述的氧化铝载体制备的加氢处理催化剂的活性稳定性显著提高。
Description
技术领域
本发明涉及一种氧化铝载体及其制备方法和应用,具体地说涉及一种用于制备加氢处理催化剂的氧化铝载体及其制备方法和应用。所制备的催化剂特别适合于重质和劣质油品加氢改质过程。
背景技术
随着世界范围内原料深加工要求的提高,主要能源结构逐渐向大分子和高碳方向发展,对于原油普遍重质化的我国更是如此。为有效解决重油组分在催化剂孔道内扩散阻力过大、重金属杂质沉积和结焦而导致的催化剂活性下降或失活等问题,迫切要求在石油化工等行业广泛使用的氧化铝载体具备大孔容和大孔径的特性。以提高大分子化合物向催化剂颗粒内部扩散,大孔容积则有利于提高容金属或焦炭能力。
传统的加氢处理催化剂大多使用Al2O3作为载体,但活性Al2O3( 如γ-Al2O3) 有较多的Lewis 酸中心,易导致催化剂结焦,且γ-Al2O3载体与金属组分之间有较强的相互作用,使得金属组分不易转化为高活性的活性相。活性炭载体的缺点是机械强度差、成本高。氧化铝经表面覆炭得到的载体机械强度高,可作为活性炭载体的替代品使用。在本技术领域已知的是,使用特殊载体如活性炭可减弱金属与载体的强相互作用,因此可以有效提高催化剂的加氢反应活性。
催化剂表面酸性质对加氢催化剂的活性有较大影响,如何减弱金属与载体的强相互作用,如何使催化剂具有合适的酸性,成为高活性加氢催化剂制备的关键。研究表明,可以通过添加助剂对载体进行改性。含硅氧化铝载体中硅和铝可以形成酸性位,具有表面积大,孔容高,孔径分布集中和热稳定性好等特点,将其用作负载型催化剂载体,可提高金属的分散度,增加金属中心的利用率。
CN1302848A公开了一种加氢催化剂及其制备方法,该催化剂是由共沉淀法制备的,具体包括在铝盐溶液加入氟,再分别加入可溶性镍盐水溶液和可溶性钨盐水溶液,采用氨水进行沉淀。该方法虽然可以在孔结构或酸性方面有一定的调节作用,但载体的综合性能不但要求孔结构适宜,酸性适宜,而且还要使孔结构和酸性分布两者有机地相互配合,这样才能提高催化剂的整体性能。
CN201811056468 .7公开一种氧化铝载体及制备方法,在有机聚合物的酸液中加入硅源混合均匀,得到硅源-有机聚合物混合物,氧化铝前驱体中单位含量的有机聚合物比硅源-有机聚合物混合物中有机聚合物的含量高1 .5倍以上,然后将硅源-有机聚合物混合物与氧化铝前驱体混合,经挤条、成型、干燥、焙烧,得到氧化铝载体。
CN200710178804.0 采用重油残渣乳液模板法合成大孔载体及重油加氢催化剂,合成的大孔重油加氢催化剂催化反应的传质阻力低,表观活性高。
CN 1184078A采用并流成胶生成的氢氧化铝作为晶种,利用pH值的摆动控制氧化铝晶粒生长及尺寸,使晶粒间形成较大的孔道。但该方法的总体造孔作用较为有限,所得孔径尺寸一般小于100nm,大孔的分布较为弥散,贯通性较弱。
US4 ,448 ,896介绍以一种拟薄水铝石为原料,并加入炭黑粉作为扩孔剂,经混捏、挤条、干燥和焙烧得到氧化铝载体。其缺点是:加入少量炭黑粉,则易形成“墨水瓶”型孔;加入过多的炭黑粉,则造成载体强度明显降低。虽然上述方法制备的氧化铝载体可以用于生产加氢处理催化剂,但是所生产的加氢处理催化剂活性仍需要进一步提高。
发明内容
针对现有技术中存在的不足,本发明提供了一种氧化铝载体及其制备方法和应用。采用本发明所述的氧化铝载体制备的加氢处理催化剂的活性稳定性显著提高。
一种氧化铝载体的制备方法,包括如下内容:
(1)将酵母溶解于含水溶液中,并与多羟基化合物物混合后备用;
(2)将步骤(1)的物料与拟薄水铝石粉体混合,经混捏、成型、干燥、焙烧,得到最终氧化铝载体。
上述方法中,步骤(1)中所述酵母可以为单倍体型,双倍体型,单双倍体型中的一种或其混合物,溶解于含水溶液中控制pH值为3.0-7.5,优选pH至4-6。
上述方法中,步骤(1)中所述酵母的加入量以最终催化剂重量计为0.02wt%-15wt%,优选0.05wt%-5wt%。
上述方法中,步骤(1)中所述混合物的多羟基化合物可以是多羟基醛、多羟基酮以及能水解生成多羟基醛、多羟基酮的有机化合物及其聚合物。其含量以最终催化剂重量计为0.2%-50%,优选1%-20%。
上述方法中,步骤(1)中所述物料在与步骤(2)拟薄水铝石粉体混合前经历预处理阶段,所述预处理阶段处理温度为10℃-40℃,优选20℃-30℃,时间为0.5-8小时,优选1.5-5小时。
上述方法中,步骤(1)中所述的含水溶液中不仅仅限于水,还可以含有一种或多种酸的混合溶液,所述酸可以是无机酸或者有机酸,优选醋酸、甲酸、苹果酸、乳酸中的一种或几种。
上述方法中,步骤(1)物料采用超声波震荡处理或者磁力搅拌处理。物料经超声波震荡或者磁力搅拌,各组分分散性好,氧化铝载体更容易产生大孔,而且孔径分布更加集中。
上述方法中,步骤(2)中所述的拟薄水铝石粉体可以不含助剂组分,也可以含助剂组分,其中助剂组分可以为磷、氟、硅、锆、硼等中的一种或几种,助剂组分在氧化铝基载体中的含量在30wt%以下,优选20wt%以下,进一步优选为10wt%以下。
上述方法中,步骤(2)中所述的干燥温度为100-140℃,干燥时间为2-8h,本发明中所用的氧化铝基载体是氢氧化铝(比如拟薄水铝石)经过高温焙烧后得到的,高温焙烧的条件如下:在450℃~1000℃焙烧1 .0h~20 .0h,优选为3 .0 h~8 .0 h助剂组分在最终氧化铝载体中的含量为5wt% 以下。
上述方法中,步骤(2)中所述的最终氧化铝载体的形状可以根据需要制成球形、条形(比如三叶草、四叶草或圆柱条)等适宜的形状,成型过程中可以加入常用成型助剂,比如助挤剂、胶溶酸、粘合剂等。
上述方法中,步骤(2)中所述的氧化铝载体可以在氧化铝载体成型的过程中引入或者在氧化铝载体成型之后多次引入助剂。
一种采用上述方法制备的氧化铝载体,所述氧化铝载体的性质如下:比表面积240-340m2/g,孔容0.7-1.0mL/g,平均孔径10-15nm,强度100-150N/cm。
一种以上述方法氧化铝载体制备的加氢处理催化剂,所述加氢处理催化剂的组成如下:活性金属钨和/或钼以氧化物计质量含量为26%-30%,钴和/或镍以氧化物计的质量含量为3%-9%,余量为氧化铝载体。
与现有技术相比,本发明提供的氧化铝载体及其制备方法具有以下有益效果:通过将酵母与扩孔前驱物进行混合并在适宜条件下预处理,可以使氧化铝载体在热处理过程中形成有利于反应物分子扩散的大孔通道,提高的平均孔径有利于提高加氢反应的扩散效率;同时,控制氧化铝载体的干燥和焙烧条件可以形成一定的机械孔,明显减少由于重金属沉积和反应物分子积碳造成的催化剂活性中心中毒及孔口堵塞,从而减少催化剂活性下降,提高催化剂加氢反应的活性稳定性,延长催化剂寿命。
具体实施方式
下面通过实施例及比较例进一步说明本发明方法的作用和效果,但以下实施例不构成对本发明方法的限制。以下实施例及比较例中如果无特殊说明%均为质量百分含量。
实施例1
取1g酵母加入40mL水中溶解,然后向溶液中加入3g葡萄糖,搅拌至完全溶解后在20℃条件下恒温2小时,为混合物A1。取氧化铝干胶粉200g,加入田菁粉和柠檬酸各4g以及A1,混合均匀;称取浓度为68%的稀硝酸9.5g并加去离子水稀释为200mL。将物料混捏15min,然后将酸液加入粉料,根据粉料的干湿程度适度补水,用直径1.7mm的三叶草孔板挤条。经120℃干燥4h后600℃焙烧6h,焙烧后的载体记为Z1。
实施例2
取4g酵母加入40mL水中溶解,然后向溶液中加入15g淀粉,搅拌至完全溶解后在30℃条件下恒温3小时,为混合物A2。取氧化铝干胶粉200g,加入田菁粉和柠檬酸各4g以及A2,混合均匀;称取浓度为68%的稀硝酸9.5g并加去离子水稀释为200mL。将物料混捏15min,然后将酸液加入粉料,根据粉料的干湿程度适度补水,用直径1.7mm的三叶草孔板挤条。经120℃干燥4h后600℃焙烧6h,焙烧后的载体记为Z2。
实施例3
取9g酵母加入50mL醋酸溶液中溶解,然后向溶液中加入35g淀粉,搅拌至完全溶解后在30℃条件下恒温4小时,为混合物A3。取氧化铝干胶粉200g,加入田菁粉和柠檬酸各4g以及A2,混合均匀;称取浓度为68%的稀硝酸9.5g并加去离子水稀释为200mL。将物料混捏15min,然后将酸液加入粉料,根据粉料的干湿程度适度补水,用直径1.7mm的三叶草孔板挤条。经120℃干燥4h后600℃焙烧6h,焙烧后的载体记为Z3。
对比例1
取氧化铝干胶粉200g,加入田菁粉、柠檬酸和木质素各4g,混合均匀;称取浓度为68%的稀硝酸9.5g并加去离子水稀释为200mL。将物料混捏15min,然后将酸液加入粉料,根据粉料的干湿程度适度补水,用直径1.7mm的三叶草孔板挤条。经120℃干燥4h后600℃焙烧6h,焙烧后的载体记为Z4。
对比例2
取氧化铝干胶粉200g,加入田菁粉和柠檬酸4g,混合均匀;称取浓度为68%的稀硝酸9.5g、二氧化硅含量为30%的硅溶胶20g,加去离子水稀释为200mL。将物料混捏15min,然后将酸液加入粉料,根据粉料的干湿程度适度补水,用直径1.7mm的三叶草孔板挤条。经120℃干燥4h后600℃焙烧6h,焙烧后的载体记为Z5。
实施例4
本实施例以上述实施例和对比例所得氧化铝为载体,制备加氢处理催化剂。
取实施例和对比例所制备的氧化铝载体条Z1-Z5,用Mo、Ni、P溶液分别等体积浸渍2h后,120℃烘干,再在450℃下焙烧5h,对应得到加氢处理催化剂C1-C5。催化剂MoO3质量百分含量为25.1%,NiO质量百分含量为3.7wt%
对上述实例及比较例制备的催化剂进行活性评价,比较上述各催化剂活性及稳定性。原料油为伊朗VGO,反应氢压为14.7MPa,氢油体积比为1000:1,体积空速为1.2 h-1,反应温度为350℃。原料油性质见表1 ,运转200h 的活性评价结果见表2,随着运转时间的增加,催化剂的活性降低,为了保持催化剂的活性以满足生产要求,需要对催化剂床层提温,运转5000 小时后催化剂床层温升见表3。
表 1
表2
表 3
从表2可以看出,与对比例催化剂相比,本发明载体制备的加氢处理催化剂均具有较高的加氢脱硫脱氮活性。由表3 数据可以看出,反应5000 小时后,采用本发明提供的催化剂具有较高的活性稳定性。
本发明还可以有其它多种实施例,在不背离发明精神和实质的情况下,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,但这些均属于本发明权利要求的保护范围。
Claims (13)
1.一种氧化铝载体的制备方法,其特征在于:包括如下内容:
(1)将酵母溶解于含水溶液中,并与多羟基化合物物混合后备用;
(2)将步骤(1)的物料与拟薄水铝石粉体混合,经混捏、成型、干燥、焙烧,得到最终氧化铝载体。
2.根据权利要求1所述的方法,其特征在于:步骤(1)中所述酵母为单倍体型、双倍体型、单双倍体型中的一种或其混合物,溶解于含水溶液中控制pH值为3.0-7.5。
3.根据权利要求1所述的方法,其特征在于:步骤(1)中所述酵母的加入量以重量计为最终催化剂的0.02%-15%。
4.根据权利要求1所述的方法,其特征在于:步骤(1)中所述多羟基化合物为多羟基醛、多羟基酮以及能水解生成多羟基醛、多羟基酮的有机化合物及其聚合物,其含量以重量计为最终催化剂的0.2%-50%。
5.根据权利要求1所述的方法,其特征在于:步骤(1)中所述物料在与步骤(2)拟薄水铝石粉体混合前进行预处理,所述预处理阶段处理温度为10℃-40℃,时间为0.5-8小时。
6.根据权利要求5所述的方法,其特征在于:步骤(1)中所述物料在与步骤(2)拟薄水铝石粉体混合前进行预处理,所述预处理阶段处理温度为20℃-30℃,时间为1.5-5小时。
7.根据权利要求1所述的方法,其特征在于:步骤(1)中所述的含水溶液中含有一种或多种酸,所述酸为醋酸、甲酸、苹果酸、乳酸中的一种或几种。
8.根据权利要求1所述的方法,其特征在于:步骤(1)物料采用超声波震荡处理或者磁力搅拌处理。
9.根据权利要求1所述的方法,其特征在于:步骤(2)中所述的拟薄水铝石粉体含助剂组分,助剂组分为磷、氟、硅、锆、硼等中的一种或几种,助剂组分在氧化铝基载体中的含量在30wt%以下。
10.根据权利要求1所述的方法,其特征在于:步骤(2)中所述的干燥温度为100-140℃,干燥时间为2-8h。
11.根据权利要求1所述的方法,其特征在于:步骤(2)中所述的最终氧化铝载体的形状为球形或条形。
12.一种采用权利要求1至11任一方法制备的氧化铝载体,其特征在于:所述氧化铝载体的性质如下:比表面积240-340m2/g,孔容0.7-1.0mL/g,平均孔径10-15nm,强度100-150N/cm。
13.一种加氢处理催化剂,其特征在于:所述催化剂含有权利要求12所述的氧化铝,催化剂的组成如下:活性金属钨和/或钼以氧化物计质量含量为26%-30%,钴和/或镍以氧化物计的质量含量为3%-9%。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101940954A (zh) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种氧化铝载体的制备方法 |
CN102441368A (zh) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | 重油加氢脱金属催化剂的制备方法 |
CN102441436A (zh) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | 一种氧化铝载体的制备方法 |
US20150209766A1 (en) * | 2012-08-29 | 2015-07-30 | Indian Oil Corporation Ltd. | Hydrotreating catalyst and process for preparing the same |
CN105709711A (zh) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | 一种氧化铝载体的制备方法 |
CN107304062A (zh) * | 2016-04-21 | 2017-10-31 | 中国石油化工股份有限公司 | 一种氧化铝载体的制备方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101940954A (zh) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种氧化铝载体的制备方法 |
CN102441368A (zh) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | 重油加氢脱金属催化剂的制备方法 |
CN102441436A (zh) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | 一种氧化铝载体的制备方法 |
US20150209766A1 (en) * | 2012-08-29 | 2015-07-30 | Indian Oil Corporation Ltd. | Hydrotreating catalyst and process for preparing the same |
CN105709711A (zh) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | 一种氧化铝载体的制备方法 |
CN107304062A (zh) * | 2016-04-21 | 2017-10-31 | 中国石油化工股份有限公司 | 一种氧化铝载体的制备方法 |
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