CN107029732B - 一种抽余油加氢催化剂及制备方法 - Google Patents
一种抽余油加氢催化剂及制备方法 Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 claims abstract description 35
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 24
- 229910052718 tin Inorganic materials 0.000 claims abstract description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 13
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- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- 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
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Abstract
本发明公开了一种抽余油加氢催化剂及制备方法，催化剂的组成以氧化物质量计，包括如下组分：具具有大孔结构的氧化铝载体80.0‑92wt％，载体使用壳聚糖作为扩孔剂，活性组分氧化镍8‑20wt％，含有助剂组分锡、镧和镁。本发明提供的催化剂在抽余油芳烃加氢中活性高，抗杂质能力强，具有更长的运转周期。
Description
技术领域
本发明属于加氢催化剂技术领域，尤其涉及一种抽余油加氢催化剂及制备方法，更具体地是一种以具有大孔结构氧化铝为载体的抽余油加氢的催化剂及制备方法。
背景技术
采用炼厂抽余油加氢可以生产多种牌号的溶剂油，溶剂油可泛指利用石油炼制和石化生产的多种产品和副产品加工生产的以其溶解性和挥发性为主要应用性能的一大类产品。脂肪族烃类的溶解性能不如芳烃,但芳烃的毒性严重,生产低芳、无芳的溶剂油成为溶剂油产业的发展方向。国内目前较多采用的方法有磺化-氧化法脱芳、脱烯,分子筛脱芳、脱硫,溶剂萃取脱芳等。而国外溶剂精制的主导方法是深度加氢精制脱芳、脱硫、脱烯。精制技术的差距是我国烃类溶剂不饱和烃及有害杂质含量高、气味大、对操作环境污染重的主要原因。因此采用先进的精制方法,以有竞争力的投资规模建设能够生产绿色环保型溶剂产品的加工装置,已成为我国溶剂油产业发展的当务之急，其中的关键技术就是高活性的抗杂质加氢精制催化剂的研制。
加氢精制催化剂一般是以含氧化铝为载体，以VIII族和VIB族金属元素为活性组分，也有为了提高催化剂的活性和稳定性，对载体进行改进。例如以氧化铝—氧化硅为载体的，或者是加入其他助剂，一般P、F、B、Si、Ti、Zr等。而且前使用W-Mo-Ni-P/Al2O3催化剂以提高活性广泛用于馏分油加氢精制的工业催化剂。
中国专利：ZL03126138.8公开了一种煤油型溶剂油所用的催化剂。在该方法中所用加氢催化剂为W-Ni/TiO2-Al2O3或W-Mo-Ni/TiO2-Al2O3。中国专利：ZL200310112781.5在120℃-280℃的反应温度和氢分压0.2-0.4MPa(表压)的条件下，采用钴钼和镍铝催化剂，对天然气加工的轻油产品和炼油厂生产轻油进行加氢精制，以生产高标准溶剂油。
目前，研究开发的催化剂用于抽余油加氢生产芳烃溶剂油时，催化剂的活性稳定性良好好，工业应用周期较长。
发明内容
本发明提供一种抽余油加氢催化剂及制备方法，该催化剂具有更好的抽余油加氢活性和稳定性。催化剂的载体是具有大孔结构的氧化铝载体，活性组分为镍。该载体比表面积高，孔径大，催化剂芳烃加氢活性高，且催化剂抗杂质能力强，生产运转周期长。
本发明所述的一种抽余油加氢催化剂，由以下组分组成：
具有大孔结构的氧化铝载体80.0-92wt％，活性组分氧化镍8-20wt％；
优选的，具有大孔结构的氧化铝载体80.0-90.0wt％，活性组分氧化镍10-20.0wt％；
本发明所述的一种抽余油加氢催化剂的制备方法，包括如下步骤：
将含镍的可溶性盐配成浸渍液，浸渍具有大孔结构的氧化铝载体，120℃干燥处理6小时，400℃-500℃下焙烧处理5-8小时，得到抽余油加氢催化剂。
本发明所述具有大孔结构的氧化铝载体，采用壳聚糖作为扩孔剂，合成出具有大孔结构的氧化铝载体。
所述的具有大孔结构的氧化铝载体，加入锡、镧和镁作为助剂组分，助剂组分锡、镧和镁的含量占载体质量的百分含量分别为SnO2 0.2-1.5wt％、La2O3 0.5-2.0wt％和MgO1.0-3.0wt％。孔径分布60-180nm，优选65-150nm，大孔比例2-75％，优选5-65％，孔容0.8-2.0ml/g，优选0.8-1.3ml/g或优选1.6-2.0ml/g，比表面积250-300m2/g，载体使用壳聚糖作为扩孔剂。
本发明所述具有大孔结构的氧化铝载体，孔径可以通过变化扩孔剂的加入量以及扩孔剂的分子量大小进行调整。孔径分布可以在60-180nm之间变化，比如60-90nm，100-160nm，120-180nm等范围。大孔比例为2-75％，可以调变为5-30％，35-50％，55-75％等范围。
本发明所述具有大孔结构的氧化铝载体的制备方法，包括如下步骤：首先，用酸溶液酸化壳聚糖，然后将拟薄水铝石和田菁粉加入到捏合机中混合均匀，再加入硝酸锡、硝酸镧和硝酸镁的混合溶液，最后将含壳聚糖的酸溶液加入到拟薄水铝石粉末中捏合均匀，含扩孔剂的酸溶液的加入量为拟薄水铝石的0.1-8wt％，优选0.2-5.0wt％，经过挤条-成型-干燥-焙烧，得到具有大孔结构的氧化铝载体。
所述酸溶液酸化壳聚糖的过程如下：首先将壳聚糖扩孔剂加入到30-95℃的去离子水中，之后滴加酸，直至壳聚糖溶解完全，得到含扩孔剂的酸溶液。所述酸可以是无机酸或者有机酸，优选醋酸、甲酸、苹果酸、乳酸中的一种或多种。酸的加入量以能完全溶解壳聚糖为宜。也可以选用水溶性壳聚糖，比如羧化壳聚糖、壳聚糖盐类、壳聚糖硫酸酯等。壳聚糖酸溶液最好用超声波震荡或者磁力搅拌。超声波震荡10min以上，磁力搅拌0.5-2h。对扩孔剂进行超声波震荡或者磁力搅拌，扩孔剂分散性好，氧化铝载体更容易产生大孔，而且孔径分布更加集中，孔径分布在70-180nm。
所述田菁粉的加入量为拟薄水铝石的0.1-7wt％。
捏合或挤条工艺为，将配置好的含扩孔剂的酸溶液加入到田菁粉和拟薄水铝石中混合均匀，之后挤条、成型，经过100-160℃烘干3-9小时，650-800℃焙烧4-8小时，得到具有大孔结构的氧化铝载体。
本发明所述氧化铝载体采用壳聚糖为扩孔剂，制备的氧化铝载体含有大孔结构，同时还含有介孔结构，介孔范围在2-50nm，介孔比例15-75％，优选15-50％，是一种含介-大孔的氧化铝载体，而且孔径并非均一的孔径结构。
采用上述制备方法得到的具有大孔结构的氧化铝载体，还可以利用锡和镁对载体表面进行改性，锡和镁的浓度不宜过高，最好是配置浓度低于制备载体时的硝酸锡和硝酸镁水溶液喷淋载体表面，优选通过如下步骤进行载体表面改性：配置含硝酸锡和硝酸镁的水溶液喷淋具有大孔结构的氧化铝载体，经干燥、焙烧得到用助剂锡和镁表面改性的氧化铝载体，控制具有大孔结构的氧化铝载体中SnO2和MgO的含量在0.2-1.5wt％和1.0-3.0wt％范围内，并使载体表面SnO2和MgO含量是内部SnO2和MgO含量的1.1-1.3倍。
与现有技术相比，本发明具有以下优点：
1、本发明氧化铝载体采用壳聚糖作为扩孔剂，扩孔剂壳聚糖价格低廉，而且环保无毒，适合工业化生产。得到的具有大孔结构的氧化铝载体，孔径大小可调节，大孔比例可以有效控制。而且载体还含有介孔，是一种介-大孔氧化铝载体。该结构的氧化铝载体在反应中具有更好的活性中心分散性能，抗杂质性能和长周期稳定性。
2、本发明还可以在氧化铝载体中引入锡、镧和镁，得到的具有大孔结构的氧化铝载体，该载体制备成烯烃齐聚催化剂，具有更好的齐聚活性、选择性和稳定性。
3、本发明得到的具有大孔结构的氧化铝载体，利用锡和镁对具有大孔结构的氧化铝载体表面进行改性，并使载体表面SnO2和MgO含量是内部SnO2和MgO含量的1.1-1.3倍。采用喷淋的方式对载体表面进行改性，能够有效胶溶载体表面的部分微孔，这样有利于减少载体表面的微孔比例，提高载体表面介-大孔比例，促进载体表面产生出更多的活性位负载中心，有效提高催化剂活性。
4、本发明提供的抽余油加氢催化剂载体是具有介-大孔结构的氧化铝载体，催化剂加氢反应活性高，活性稳定性好，运转周期长。
附图说明
图1为实施例3制备的具有大孔结构的氧化铝载体的孔径分布图。
具体实施方式
以下通过实施例对本发明一种抽余油加氢催化剂及制备方法进一步的详细说明。但这些实施例不应认为是对本发明的限制。
制备催化剂所用主要原料来源：本发明试剂均为市售产品。
原料油为重整抽余油，芳烃含量2.0％，以溴价表示烯烃含量12.4gBr2/100gOil，碘值6.4gI2/100gOil。
实施例1
首先将8.0g水溶性壳聚糖扩孔剂加入到50℃的去离子水中，之后滴加醋酸，直至壳聚糖溶解完全，得到含扩孔剂的酸溶液。分别称取一定量硝酸锡、硝酸镧和硝酸镁，将硝酸锡、硝酸镧和硝酸镁完全溶解于70g蒸馏水中配成含锡、镧和镁的水溶液。称量350g拟薄水铝石粉和20.0g田菁粉加入到捏合机中，并混合均匀，再加入硝酸锡、硝酸镧和硝酸镁的混合溶液，最后将含壳聚糖的酸溶液加入到拟薄水铝石粉末中捏合均匀，经过捏合-挤条成型为三叶草形状。在120℃干燥8小时，700℃焙烧4小时，得到含锡、镧和镁的氧化铝载体1。载体1中SnO2 1.0wt％、La2O3 1.2wt％和MgO 1.5wt％。具有大孔结构的氧化铝载体比表面积与孔径分布见表1。
取19.68g甲酸镍加入到30ml蒸馏水中，再用去离子水稀释，配成浸渍液浸渍球形具有大孔结构的氧化铝载体100g，得到的催化剂前躯体在120℃烘干6h后在400℃焙烧6h，得到抽余油加氢催化剂1。催化剂1主要组成：氧化镍10wt％，具有大孔结构的氧化铝载体90wt％。
实施例2
将8.0g水溶性壳聚糖扩孔剂加入到50℃的去离子水中，之后滴加醋酸，直至壳聚糖溶解完全，得到含扩孔剂的酸溶液。分别称取一定量硝酸锡、硝酸镧和硝酸镁，将硝酸锡、硝酸镧和硝酸镁完全溶解于70g蒸馏水中配成含锡、镧和镁的水溶液。称量350g拟薄水铝石粉子和20.0g田菁粉加入到捏合机中，并混合均匀，再加入硝酸锡、硝酸镧和硝酸镁的混合溶液，最后将含壳聚糖的酸溶液加入到拟薄水铝石粉末中捏合均匀，经过捏合-挤条成型为三叶草形状。在120℃干燥8小时，700℃焙烧4小时，得到含锡、镧和镁的氧化铝载体2。载体2中SnO2 0.5wt％、La2O31.5wt％和MgO 1.4wt％
再利用锡和镁对载体表面进行改性，配置含硝酸锡和硝酸镁的水溶液喷淋具有大孔结构的氧化铝载体，经120℃干燥8小时，700℃焙烧4小时得到用助剂锡和镁进行表面改性的氧化铝载体2，载体表面表面SnO2和MgO含量是内部SnO2和MgO含量的1.1倍。具有大孔结构的氧化铝载体比表面积与孔径分布见表1。
取29.53g甲酸镍加入到30ml蒸馏水中，再用去离子水稀释，配成浸渍液浸渍球形具有大孔结构的氧化铝载体100g，得到的催化剂前躯体在120℃烘干6h后在450℃焙烧6h，得到催化剂2。催化剂2主要组成：氧化镍14wt％，具有大孔结构的氧化铝载体86wt％。
实施例3
载体的制备方法按照实施例1进行。不同之处在于将水溶性壳聚糖扩孔剂更换为非水溶性壳聚糖扩孔剂，壳聚糖甲酸液用磁力搅拌器搅拌30分钟，得到具有大孔结构的氧化铝载体3。载体中助剂组分锡、镧和镁的含量占载体质量的百分含量分别为SnO21.5wt％、La2O3 0.8wt％和MgO 2.8wt％。其比表面积与孔径分布见表1。
取一定量甲酸镍加入到30ml蒸馏水中，再用去离子水稀释，配成浸渍液浸渍球形具有大孔结构的氧化铝载体100g，得到的催化剂前躯体在120℃烘干6h后在500℃焙烧7h，得到催化剂3。催化剂3主要组成：氧化镍17wt％，具有大孔结构的氧化铝载体83wt％。
实施例4
载体的制备方法按照实施例1进行。不同之处在于将水溶性壳聚糖扩孔剂更换为非水溶性壳聚糖扩孔剂，壳聚糖乙酸液用超声波震荡15分钟。得到具有大孔结构的氧化铝载体。载体中助剂组分锡、镧和镁的含量占载体质量的百分含量分别为SnO2 0.5wt％、La2O31.8wt％和MgO 1.0wt％。。再利用锡和镁对载体表面进行改性，得到载体4，载体4表面SnO2和MgO含量是内部SnO2和MgO含量的1.3倍。具有大孔结构的氧化铝载体4比表面积与孔径分布见表1。
取一定量甲酸镍加入到30ml蒸馏水中，再用去离子水稀释，配成浸渍液浸渍球形具有大孔结构的氧化铝载体100g，得到的催化剂前躯体在120℃烘干6h后在550℃焙烧4h，得到催化剂4。催化剂4主要组成：氧化镍19wt％，具有大孔结构的氧化铝载体81wt％。
将催化剂1-4分别装入100ml固定床反应器中，进行催化剂反应性能评价。用H2对其进行活化，活化条件压力2.0MPa，温度280℃，氢气流量400mL/min的条件下恒温12h。活化结束后开始进重整抽余油，调整到反应工艺条件。反应工艺条件为：反应温度178℃，反应压力1.7MPa，体积空速2.5h-1，氢油体积比500。反应稳定48h后取样分析，催化剂及对比剂反应产品性质分析见表2。
对催化剂1、2、3和4进行稳定性考察，反应条件同上，反应运行2000h，催化剂1、2、3和4芳烃脱除率分别为96.8％、98.9％、97.2％和99.5％，烯烃脱除率100％，100％，100％，100％。
由表2和催化剂稳定性评价数据可以看出，该方法制备的催化剂抽余油加氢活性高、经过表面修饰的催化剂在长周期运转中表现出更加的优异活性稳定性。
表1具有大孔结构的氧化铝载体比表面积与孔径分布
表2反应产品性质
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的保护范围。
Claims (3)
1.一种抽余油加氢催化剂，其特征在于：由以下组分组成：
具有大孔结构的氧化铝载体80.0-90.0wt％，载体使用壳聚糖作为扩孔剂，活性组分氧化镍10-20.0wt％；
所述具有大孔氧化铝载体中含有助剂组分锡、镧和镁，助剂组分锡、镧和镁的含量占载体质量的百分含量分别为SnO2 0.2-1.5wt％、La2O30.5-2.0wt％和MgO 1.0-3.0wt％，所述载体孔径分布在65-150nm，大孔比例5-65％，孔容0.8-1.3ml/g，比表面积250-300m2/g；
所述氧化铝载体同时还含有介孔结构，介孔范围在2-50nm，介孔比例15-75％；
所述氧化铝载体的制备方法包括如下步骤：首先，用酸溶液酸化壳聚糖，然后将拟薄水铝石和田菁粉加入到捏合机中混合均匀，再加入硝酸锡、硝酸镧和硝酸镁的混合溶液，最后将含壳聚糖的酸溶液加入到拟薄水铝石粉末中捏合均匀，含扩孔剂的酸溶液的加入量为拟薄水铝石的0.1-8wt％，经过挤条-成型-干燥-焙烧，得到具有大孔结构的氧化铝载体；
对得到的具有大孔结构的氧化铝载体，利用锡和镁对载体表面进行改性：配置含硝酸锡和硝酸镁的水溶液喷淋具有大孔结构的氧化铝载体，经干燥、焙烧得到用助剂锡和镁进行表面改性的氧化铝载体，控制具有大孔结构的氧化铝载体中SnO2和MgO的含量在0.2-1.5wt％和1.0-3.0wt％范围内，并使载体表面SnO2和MgO含量是内部SnO2和MgO含量的1.1-1.3倍。
2.权利要求1所述的一种抽余油加氢催化剂的制备方法，其特征在于：包括如下步骤：将甲酸镍可溶性盐配成浸渍液，浸渍具有大孔结构的氧化铝载体，120℃干燥处理6小时，400℃-500℃下焙烧处理5-8小时，得到抽余油加氢催化剂；
所述氧化铝载体的制备方法包括如下步骤：首先，用酸溶液酸化壳聚糖，然后将拟薄水铝石和田菁粉加入到捏合机中混合均匀，再加入硝酸锡、硝酸镧和硝酸镁的混合溶液，最后将含壳聚糖的酸溶液加入到拟薄水铝石粉末中捏合均匀，含扩孔剂的酸溶液的加入量为拟薄水铝石的0.1-8wt％，经过挤条-成型-干燥-焙烧，得到具有大孔结构的氧化铝载体；
对得到的具有大孔结构的氧化铝载体，利用锡和镁对载体表面进行改性：配置含硝酸锡和硝酸镁的水溶液喷淋具有大孔结构的氧化铝载体，经干燥、焙烧得到用助剂锡和镁进行表面改性的氧化铝载体，控制具有大孔结构的氧化铝载体中SnO2和MgO的含量在0.2-1.5wt％和1.0-3.0wt％范围内，并使载体表面SnO2和MgO含量是内部SnO2和MgO含量的1.1-1.3倍。
3.根据权利要求2所述的一种抽余油加氢催化剂的制备方法，其特征在于：所述用酸溶液酸化壳聚糖是：首先将壳聚糖扩孔剂加入到30-95℃的去离子水中，之后滴加酸，直至壳聚糖溶解完全，得到含扩孔剂的酸溶液；所述酸为醋酸、甲酸、苹果酸或乳酸中的一种或几种，壳聚糖酸溶液用超声波震荡或者磁力搅拌。
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