CN114011415A - 一种用于油脂加氢脱氧制备绿色柴油的高负载量层状钴催化剂的制备方法 - Google Patents
一种用于油脂加氢脱氧制备绿色柴油的高负载量层状钴催化剂的制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 10
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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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- B01J23/75—Cobalt
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
本发明公开了一种用于油脂加氢脱氧催化剂的制备方法,包括以下步骤:首先将Al2(NO3)3和Co(NO3)2的混合溶液与NaOH/Na2CO3混合溶液混合,通过水热合成法制备出Co‑Al层状双金属氢氧化物(LDH);经过焙烧、还原制备出高负载量片层钴催化剂;在该过程中,硝酸钴作为钴源,Al2O3作为载体;将制得的催化剂和油脂、正十二烷加入到高压反应釜中,在一定反应温度和压力下,反应2~6 h;高负载量层状钴催化剂(CoAl7:1‑200)催化油脂加氢的转化率高于98 wt.%,总烷烃得率高于64 wt.%,远高于常规浸渍法制得的氧化铝负载的钴催化剂(Co/Al2O3)。
Description
技术领域
本发明属于催化剂应用技术领域,具体涉及一种用于油脂加氢脱氧制备绿色柴油的高负载量层状钴催化剂的制备方法。
背景技术
当前,煤炭、石油和天然气等传统化石能源的过度开采和大量使用已经造成了严重的能源危机和环境污染,使用可再生的能源替代化石燃料已经迫在眉睫。柴油是一种重要的能源产品,我国每年的消耗量高达1.4亿吨。目前,柴油主要来源于石油资源。废弃油脂经过催化加氢制得的绿色柴油,即第二代生物柴油,具有和传统的化石柴油相似的化学组分,可以与其以任意比例混合使用。因此,当前国内外对绿色柴油的研究颇受关注。
迄今为止,用于油脂加氢制备绿色柴油的催化剂主要有贵金属催化剂和硫化钼催化剂。然而,贵金属催化剂成本较高,不利于大规模的工业化应用;硫化钼催化剂在硫化过程中直接或间接使用H2S,对环境造成污染,且催化剂在使用过程中硫元素容易流失,导致催化活性降低。钴催化剂价格低廉,而且在其他加氢反应中表现出一定的催化活性。然而,由于钴催化剂的活性位容易团聚,导致活性位分散度低、数量少,从而影响其催化活性。
本发明使用水热合成法首先制备Co-Al层状双金属氢氧化物,然后经过煅烧和还原进一步制得高负载量层状钴催化剂,将油脂高效催化转化为绿色柴油。
发明内容
为解决上述问题,本发明公开了一种高负载量层状钴催化剂在油脂加氢脱氧制备绿色柴油中的应用,及高负载量层状钴催化剂的制备方法,该催化剂具有超高钴负载量、丰富的比表面积、活性位分散性高、活性位数量多等特点,可以将油脂高效转化为绿色柴油。
为达到上述目的,本发明的技术方案如下:
本发明的目的是提供一种高负载量层状钴催化剂在油脂加氢脱氧制备绿色柴油中的应用,包括以下步骤:将高负载量层状钴催化剂、油脂和正十二烷加入高压反应釜,使用氢气冲压至1~3MPa,设定搅拌速率为500 rpm,于200~240℃反应温度下反应2~6 h,得到绿色柴油,反应产物采用气相色谱-质谱联用(GC-MS)进行定性分析,使用气相色谱(GC)进行定量分析。
进一步地,所述高负载量层状钴催化剂、油脂与正十二烷的质量比为0.1~0.4:1~4:20。
进一步地,所述油脂为油酸、菜籽油、微藻油中的一种或多种。
进一步地,所述高负载量层状钴催化剂的制备方法,包括以下步骤:
(1)将硝酸钴、硝酸铝溶于水中,得到溶液A;
(2)将氢氧化钠、碳酸钠溶于水中,得到溶液B;
(3)搅拌下,将溶液A与溶液B混合,继续搅拌30min,得到混合液;
(4)将混合液置于水热反应釜中进行反应,反应完成后,进行抽滤、去离子水洗涤至中性,烘箱中干燥12h,然后置于马弗炉中以10℃/min的升温速率升至400~600℃,保持2~4h,得到催化剂前驱体;
(5)将催化剂前驱体置于管式炉中,通入10%氢气/90%氮气,以10℃/min的升温速率从室温20~30℃至300~500℃,保持2~4h,降至室温20~30℃,在1%O2/99%N2中钝化2~6h,得到高负载量层状钴催化剂。
进一步地,步骤(1)中,所述硝酸钴与硝酸铝的摩尔比为6:1~8:1,所述硝酸盐与水的质量比为11~12:25。
进一步地,步骤(2)中,所述溶液B中NaOH浓度为1.0~1.5 mol/L,Na2CO3浓度为0.5~1.0 mol/L 。
进一步地,步骤(3)中,通过溶液B调节pH,所述混合液的pH为8~10。
进一步地,步骤(4)中,所述反应的温度为50~200℃,反应的时间为12~18 h。
本发明的有益效果为:
本发明制备的高负载量层状钴催化剂具有超高钴负载量、丰富的比表面积、活性位分散性高、活性位数量多等特点,高负载量层状钴催化剂具有非常优异的催化活性,可以将油脂高效转化为绿色柴油,化率达98.00%,烷烃得率达64.26%,远高于浸渍法制备的氧化铝负载的钴催化剂(转化率83.71%,烷烃选择性18.73%)。
附图说明
图1为CoAl 7:1-200和 Co/Al2O3焙烧前的XRD谱图;
图2为 CoAl 7:1-200(左)和 Co/Al2O3(右)焙烧前的SEM图。
具体实施方式
下面结合附图和具体实施方式,进一步阐明本发明,应理解下述具体实施方式仅用于说明本发明而不用于限制本发明的范围。
实施例1
该实施例为优选实施例。称取4.50g NaOH和3.98g Na2CO3,配制75ml的混合碱溶液,记为溶液B,其中NaOH浓度为1.5mol/L,Na2CO3浓度为0.5mol/L。称取9.55g硝酸钴1.75 g硝酸铝(钴与铝的摩尔比为7:1),溶于25 ml的去离子水中,所得硝酸盐的总浓度为1.5mol/L,记为溶液A;将溶液A与溶液B在搅拌条件下缓慢混合,保持混合液pH为10。混合完成后,继续搅拌30min。将混合溶液转移至水热反应釜中晶化,设置晶化温度为200℃反应12 h后,待降至室温,抽滤,并使用去离子水洗涤至中性,将固体置于105℃的烘箱中干燥12 h。然后将所得的固体置于马弗炉中焙烧,以10℃/min的升温速率升至550℃,保持3 h,得到催化剂前驱体。将催化剂前驱体置于管式炉中,在10%氢气/90%氮气气氛下还原。以10℃/min的速率从室温升至400℃,保持3 h后降至室温,在1%O2/99% N2气氛中钝化1h,所得的催化剂记为CoAl7:1-200。
CoAl7:1-200催化油酸加氢反应条件如下:将0.25g催化剂、2.0 g油酸和20.0 g正十二烷放入高压反应釜。使用氢气冲压至2.0 MPa。设定搅拌速率为500 rpm,于220℃反应3h。反应结束后,将反应釜降至室温,放空压力,打开反应釜,取出反应产物。使用气相色谱(GC)对液体产物中的化学组分进行定量分析。
CoAl 7:1-200催化油酸加氢脱氧反应的转化率为98.00%,烷烃得率为64.26%,此条件下制备的催化剂具有最佳的反应效果。
实施例2
催化剂的制备方法和催化油酸加氢反应同实施例1, Co和Al的比例不变,改变晶化温度为150℃,制得的催化剂记为CoAl 7:1-150。
CoAl 7:1-150催化油酸加氢反应的转化率为96.43%,烷烃得率为50.44%。
实施例3
催化剂的制备方法和催化油酸加氢反应同实施例1,Co和Al的比例不变,改变化温度为100℃,制得的催化剂记为CoAl 7:1-100。
CoAl 7:1-100催化油酸加氢反应的转化率为94.23%,烷烃得率为48.33%。
实施例4
催化剂的制备方法和催化油酸加氢反应同实施例1,但是Co和Al的比例不同,硝酸钴的量为9.70g,硝酸铝的量为1.55g,所得到催化剂记为CoAl 8:1-200。
CoAl 8:1-200催化油酸加氢脱氧的转化率为92.14%,烷烃得率为54.55%。
实施例5
催化剂的制备方法和催化油酸加氢反应同实施例1,但是Co和Al的比例不同,硝酸钴的量为9.35g,硝酸铝的量为2.00g,所得到催化剂记为CoAl 6:1-200。
CoAl 6:1-200催化油酸加氢脱氧的转化率为92.63%,烷烃得率为52.41%。
实施例6
催化剂的制备方法和催化油酸加氢反应同实施例1,但是改变加氢反应压力为1MPa,其他条件不变,催化剂记为CoAl 7:1-200。
CoAl 7:1-200在该反应条件下催化油酸加氢脱氧的转化率为93.63%,烷烃得率为45.36。
实施例7
验证催化剂CoAl 7:1-200对菜籽油的加氢脱氧反应效果。加氢脱氧反应的原料由油酸换成菜籽油,其他条件同实施例1。
CoAl 7:1-200催化菜籽油加氢脱氧反应的转化率为96.18%,烷烃得率为58.46%。
实施例8
验证催化剂CoAl 7:1-200对微藻油的加氢脱氧反应效果。加氢脱氧反应的原料由油酸换成微藻油,其他条件同实施例1。
CoAl 7:1-200催化微藻油加氢脱氧反应的转化率为95.27%,烷烃得率为59.86%。
对比例1
以传统浸渍法制备的氧化铝负载的钴催化剂(Co/Al2O3)为对照。称取2.47g硝酸钴,2 g 氧化铝粉末,12g去离子水,置于圆底烧瓶中,室温下搅拌3 h,然后经过旋蒸、干燥12h,去除水分。将得到的固体在马弗炉里焙烧,焙烧条件为:10℃/min的升温速率,升至550℃,保持3 h。然后置于管式炉中在10%氢气/90%氮气气氛下还原。以10℃/min的速率从室温升至400℃,保持3 h后降至室温,在1%O2/99%N2气氛中钝化1 h。
油酸加氢催化反应过程同案例1,油酸加氢脱氧反应在此条件下的转化率为83.71%,烷烃得率为18.73%。
由XRD图像计算的Co化合物的颗粒尺寸和CO化学吸附的结果如表1所示。
表1 CoAl 7:1-200和Co/Al2O3的物化性质
注:催化剂颗粒尺寸通过透射电镜图像计算;分散度通过CO化学吸附计算得到。
CoAl 7:1-200和 Co/Al2O3焙烧前的XRD图谱如图1所示,基于XRD计算得到催化剂的颗粒尺寸。Co/Al2O3的颗粒尺寸为39.02nm,远高于CoAl 7:1-200(21.62nm),说明采用此方法制备的催化剂具有较小的颗粒尺寸,说明具有较好的分散性和更多的活性位。
CoAl 7:1-200(左)和 Co/Al2O3(右)焙烧前的SEM图如图2所示,催可以明显发现CoAl 7:1-200具有非常明显的片层状结构,也证明了其较大的比表面积和较好的稳定性。CoAl 7:1-200的CO脉冲吸附量高达35.80umol/g,远高于Co/Al2O3(5.24umol/g),分散度也远高于Co/Al2O3。
需要说明的是,以上内容仅仅说明了本发明的技术思想,不能以此限定本发明的保护范围,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰均落入本发明权利要求书的保护范围之内。
Claims (8)
1.一种高负载量层状钴催化剂在油脂加氢脱氧制备绿色柴油中的应用,其特征在于,包括以下步骤:将高负载量层状钴催化剂、油脂和正十二烷加入高压反应釜,使用氢气冲压至1~5MPa,设定搅拌速率为500 rpm,于200~260℃反应温度下反应2~6 h,得到绿色柴油。
2.根据权利要求1所述的一种高负载量层状钴催化剂在油脂加氢脱氧制备绿色柴油中的应用,其特征在于,所述高负载量层状钴催化剂、油脂与正十二烷的质量比为0.1~0.4:1~4:20。
3.根据权利要求1所述的一种高负载量层状钴催化剂在油脂加氢脱氧制备绿色柴油中的应用,其特征在于,所述油脂为油酸、菜籽油、微藻油中的一种或多种。
4.根据权利要求1所述的一种高负载量层状钴催化剂在油脂加氢脱氧制备绿色柴油中的应用,其特征在于,所述高负载量层状钴催化剂的制备方法,包括以下步骤:
(1)将硝酸钴、硝酸铝溶于水中,得到溶液A;
(2)将氢氧化钠、碳酸钠溶于水中,得到溶液B;
(3)搅拌下,将溶液A与溶液B混合,继续搅拌30min,得到混合液;
(4)将混合液置于水热反应釜中进行反应,反应完成后,进行抽滤、去离子水洗涤至中性,烘干后置于马弗炉中以10℃/min的升温速率升至400~600℃,保持2~4h,得到催化剂前驱体;
(5)将催化剂前驱体置于管式炉中,通入10%氢气/90%氮气,以10℃/min的升温速率从室温20~30℃至300~500℃,保持2~4h,降至室温20~30℃,在1%O2/99%N2中钝化2~6h,得到高负载量层状钴催化剂。
5.根据权利要求4所述的一种高负载量层状钴催化剂的制备方法,其特征在于,步骤(1)中,所述硝酸钴与硝酸铝的摩尔比为6:1~8:1,所述硝酸盐与水的质量比为11~12:25。
6.根据权利要求4所述的一种高负载量层状钴催化剂的制备方法,其特征在于,步骤(2)中,所述溶液B中NaOH浓度为1.0~1.5 mol/L,Na2CO3浓度为0.5~1.0 mol/L。
7.根据权利要求4所述的一种高负载量层状钴催化剂的制备方法,其特征在于,步骤(3)中,所述混合液的pH为8~10。
8.根据权利要求4所述的一种高负载量层状钴催化剂的制备方法,其特征在于,步骤(4)中,所述反应的温度为50~200 ℃,反应的时间为12~18 h。
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