CN108126734B - 低温甲醇制备芳烃的催化剂及其制备方法 - Google Patents
低温甲醇制备芳烃的催化剂及其制备方法 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000010955 niobium Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 1
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005470 impregnation Methods 0.000 abstract description 11
- 239000000047 product Substances 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 3
- 101100129406 Neurospora africana MTA-1 gene Proteins 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
- B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明涉及一种由甲醇于低温制备芳烃的催化剂及其制备方法。所述催化剂为负载型催化剂。即在分子筛HZSM‑5(载体)上,通过浸渍法负载1wt%~3wt%的金属钴或/和其氧化物、和1wt%~3wt%的金属铌或/和其氧化物(以所述负载型催化剂总重量为100%计)得到。本发明提供的催化剂具有:不仅可实现在较低温度(低于350℃)条件下,由甲醇制得芳烃;而且在所得芳烃产物中均四甲苯的含量较高的特点。因此,本发明为实现由甲醇低温制备芳烃、且联产均四甲苯奠定了基础。
Description
技术领域
本发明涉及一种制备芳烃的催化剂及其制备方法,具体地说,涉及一种由甲醇于低温(温度低于350℃)制备芳烃的催化剂及其制备方法。
背景技术
芳烃是化学工业一种重要的有机原料。目前,芳烃生产主要来源于石油路线的催化重整和蒸汽裂解副产的裂解汽油抽提过程,全球采用石油路线生产的芳烃约占芳烃生产总量的85%以上。但同时在我国石油资源较为匮乏,而煤炭资源较丰富,因此发展煤基甲醇制芳烃技术具有重要的意义。
目前,由甲醇制芳烃的催化剂主要为负载型催化剂,其载体主要选择ZSM-5型等分子筛,且通过负载不同金属组分来改善产物的选择性(如中国专利文献CN 104549479A和CN105435839A等)。现有用于甲醇制芳烃的催化剂的工作条件通常为高温(450℃以上)低压(0.5Mpa左右),而催化剂长期处于高温(450℃以上)状态下,会加剧其结焦失活,因此通过对催化剂的合理改性,降低催化剂的活性温度(工作温度)具有重要的意义。
发明内容
本发明的发明人经研究发现:采用金属钴(Co)和金属铌(Nb)改性分子筛HZSM-5所得到的催化剂(即在分子筛HZSM-5上负载了Co和Nb或/和它们的氧化物),不仅可实现在较低温度(低于350℃)条件下,由甲醇制得芳烃;而且意外发现:在该反应条件下(主要是催化剂及反应温度),所得芳烃产物中均四甲苯(均四甲苯是一种高附加值的精细化工品)的含量较高(换而言之,本发明提供的催化剂对均四甲苯有较好的选择性)。
本发明的一个目的在于,提供一种由Co和Nb改性分子筛HZSM-5所得到的催化剂。
本发明所述的催化剂为一种负载型催化剂,其载体为分子筛HZSM-5,负载物为Co或/和其氧化物、和Nb或/和其氧化物,以所述负载型催化剂总重量为100%计,Co或/和其氧化物占1wt%~3wt%、Nb或/和其氧化物占1wt%~3wt%,余量为载体;
所述负载型催化剂的比表面积(Bet)为120m2/g~300m2/g、平均孔径为2nm~9nm、孔容为0.06mL/g~0.5mL/g。
本发明另一个目的在于,提供一种制备上述负载型催化剂的方法。所述方法包括如下步骤:
(1)纯化载体的步骤;
(2)在经步骤(1)纯化的载体上,按权利要求1中所述的比例负载金属钴或/和其氧化物、或金属铌或/和其氧化物,得到中间体的步骤;
(3)在由步骤(2)所得中间体上,按步骤(2)及权利要求1中所述的比例负载金属铌或/和其氧化物、或金属钴或/和其氧化物,得到目标物的步骤。
具体实施方式
在本发明一个优选技术方案中,所述催化剂的载体为硅铝摩尔比(值)为10-100的HZSM-5分子筛;
所述纯化载体的方法,其主要步骤是:将载体(如HZSM-5分子筛)于400℃~550℃煅烧2小时~6小时,即可。
综上,本发明提供的制备所述催化剂的方法,具体包括如下步骤:
(1)将硅铝摩尔比为10-100的HZSM-5分子筛于400℃~550℃煅烧2小时~6小时,冷却备用;
(2)将金属钴的前驱体或金属铌的前驱体负载在经步骤(1)处理的HZSM-5分子筛上,先室温干燥,然后再在100℃~120℃干燥至少12小时,最后于300℃~600℃煅烧至少4小时,得到中间体;
(3)将金属铌的前驱体或金属钴的前驱体负载在由步骤(2)所得的中间体上,同样,先室温干燥,然后再在100℃~120℃干燥至少12小时,最后于300℃~600℃煅烧至少4小时,得到目标物;
其中,所述金属钴的前驱体是金属钴的水溶性盐,所述金属铌的前驱体是金属铌的水溶性草酸盐。
与现有用于甲醇制芳烃的催化剂比较,本发明提供的催化剂具有:不仅可实现在较低温度(低于350℃)条件下,由甲醇制得芳烃;而且在所得芳烃产物中均四甲苯的含量较高的特点。因此,本发明为实现由甲醇低温制备芳烃、且联产均四甲苯奠定了基础。
下面通过实施例对本发明做进一步阐述,其目的仅在于更好理解本发明的内容。因此,所举之例不限制本发明的保护范围。
实施例1
(1)将Co(NO3)2加入到50℃蒸馏水中,配制0.2mol/L的Co(NO3)2溶液,取出5mL,采用等体积浸渍法,逐滴滴加到5g的HZSM-5载体上,保证Co的质量负载量为1wt%,自然风干12h,烘箱100℃维持12h,在马弗炉500℃焙烧4h,得到中间体-1;
(2)将(NH4)3[Nb(O2)4]加入到50℃的2mol/L的草酸溶液中,配制0.08mol/L的(NH4)3[Nb(O2)2(C2O4)2]溶液,采用等体积浸渍法,逐滴滴加到5g中间体-1上,保证Nb的质量负载量为1wt%,自然风干12h,烘箱110℃维持12h,在马弗炉中500℃焙烧4h,并粉碎至200目以下,得到目标物(简记为“MTA-1”),MTA-1的表征参数见表1。
实施例2
(1)将Co(NO3)2加入到50℃蒸馏水中,配制0.2mol/L的Co(NO3)2溶液,取出5mL,采用等体积浸渍法,逐滴滴加到5g的HZSM-5载体上,保证Co的质量负载量为1wt%,自然风干12h,烘箱100℃维持12h,在马弗炉600℃焙烧4h,得到中间体-2;
(2)将(NH4)3[Nb(O2)4]加入到50℃的2mol/L的草酸溶液中,配制0.08mol/L的(NH4)3[Nb(O2)2(C2O4)2]溶液,采用等体积浸渍法,逐滴滴加到5g的中间体-2上,保证Nb的质量负载量为1wt%,自然风干12h,烘箱110℃维持12h,在马弗炉中600℃焙烧4h,并粉碎至200目以下,得到目标物(简记为“MTA-2”),MTA-2的表征参数见表1。
实施例3
(1)将Co(NO3)2加入到50℃蒸馏水中,配制0.2mol/L的Co(NO3)2溶液,取出5mL,采用等体积浸渍法,逐滴滴加到5g的HZSM-5载体上,保证Co的质量负载量为2wt%,自然风干12h,烘箱100℃维持12h,在马弗炉500℃焙烧4h,得到中间体-3;
(2)将(NH4)3[Nb(O2)4]加入到50℃的2mol/L的草酸溶液中,配制0.08mol/L的(NH4)3[Nb(O2)2(C2O4)2]溶液,采用等体积浸渍法,逐滴滴加到5g的中间体-3上,保证Nb的质量负载量为2wt%,自然风干12h,烘箱110℃维持12h,在马弗炉中500℃焙烧4h,并粉碎至200目以下,得到目标物(简记为“MTA-3”),MTA-3的表征参数见表1。
实施例4
(1)将Co(NO3)2加入到50℃蒸馏水中,配制0.2mol/L的Co(NO3)2溶液,取出5mL,采用等体积浸渍法,逐滴滴加到5g的HZSM-5载体上,保证Co的质量负载量为2wt%,自然风干12h,烘箱100℃维持12h,在马弗炉600℃焙烧4h,得到中间体-4;
(2)将(NH4)3[Nb(O2)4]加入到50℃的2mol/L的草酸溶液中,配制0.08mol/L的(NH4)3[Nb(O2)2(C2O4)2]溶液,采用等体积浸渍法,逐滴滴加到5g的得到中间体-4上,保证Nb的质量负载量为2wt%,自然风干12h,烘箱110℃维持12h,在马弗炉中600℃焙烧4h,并粉碎至200目以下,得到目标物(简记为“MTA-4”),MTA-4的表征参数见表1。
实施例5
(1)将Co(NO3)2加入到50℃蒸馏水中,配制0.2mol/L的Co(NO3)2溶液,取出5mL,采用等体积浸渍法,逐滴滴加到5g的HZSM-5载体上,保证Co的质量负载量为3wt%,自然风干12h,烘箱100℃维持12h,在马弗炉500℃焙烧4h,得到中间体-5;
(2)将(NH4)3[Nb(O2)4]加入到50℃的2mol/L的草酸溶液中,配制0.08mol/L的(NH4)3[Nb(O2)2(C2O4)2]溶液,采用等体积浸渍法,逐滴滴加到5g中间体-5上,保证Nb的质量负载量为3wt%,自然风干12h,烘箱110℃维持12h,在马弗炉中500℃焙烧4h,并粉碎至200目以下,得到目标物(简记为“MTA-5”),MTA-5的表征参数见表1。
实施例6
(1)将Co(NO3)2加入到50℃蒸馏水中,配制0.2mol/L的Co(NO3)2溶液,取出5mL,采用等体积浸渍法,逐滴滴加到5g的HZSM-5载体上,保证Co的质量负载量为3wt%,自然风干12h,烘箱100℃维持12h,在马弗炉600℃焙烧4h,得到中间体-6;
(2)将(NH4)3[Nb(O2)4]加入到50℃的2mol/L的草酸溶液中,配制0.08mol/L的(NH4)3[Nb(O2)2(C2O4)2]溶液,采用等体积浸渍法,逐滴滴加到5g中间体-6上,保证Nb的质量负载量为3wt%,自然风干12h,烘箱110℃维持12h,在马弗炉中600℃焙烧4h,并粉碎至200目以下,得到目标物(简记为“MTA-6”),MTA-6的表征参数见表1.。
表1.催化剂的表征参数
利用上述实施例1-6所得催化剂(即MTA-1~6)及现有催化剂HZSM-5和“ZnNiZSM-5”(现有金属改性分子筛催化剂)在相同条件下,进行甲醇催化制芳烃实验,具体步骤如下:
采用管式固定床反应器,内径12mm,高450mm。原料甲醇由精密流量泵调控到质量空速4h-1,经预热箱加热到150℃送至催化剂床层。催化剂装填在反应器的恒温区,其余由石英砂装填。催化剂床层控温精度维持在2‰以内。在反应温度为320℃,反应压力为4MPa的条件下进行甲醇制芳烃实验,并对生成的液相产物中芳烃的选择性进行测定。甲醇的转化率和芳烃选择性的计算方法如下:
结果见表2。
表2.
*对照物1为HZSM-5
*对照物2为ZnNiZSM-5(Zn和Ni的质量负载量都为3%)
Claims (5)
1.一种用于低温甲醇制备芳烃的催化剂,其特征在于,所述催化剂为负载型催化剂,载体为分子筛HZSM-5,负载物为金属钴或/和其氧化物、和金属铌或/和其氧化物,以所述负载型催化剂总重量为100%计,金属钴或/和其氧化物占1wt%~3wt%、金属铌或/和其氧化物占1wt%~3wt%,余量为载体;
所述负载型催化剂的比表面积为120m2/g~300m2/g、平均孔径为2nm~9nm、孔容为0.06mL/g~0.50mL/g。
2.如权利要求1所述催化剂,其特征在于,其中所用载体为硅铝摩尔比为10-100的HZSM-5分子筛。
3.一种制备权利要求1或2所述催化剂的方法,其特征在于,所述方法包括如下步骤:
(1)纯化载体的步骤;
(2)在经步骤(1)纯化的载体上,按权利要求1所述的比例负载金属钴或/和其氧化物、或金属铌或/和其氧化物,得到中间体的步骤;
(3)在由步骤(2)所得中间体上,按步骤(2)及权利要求1中所述的比例负载金属铌或/和其氧化物、或金属钴或/和其氧化物,得到目标物的步骤。
4.如权利要求3所述的方法,其特征在于,其中,纯化载体的步骤是:将载体于400℃~550℃煅烧2小时~6小时。
5.如权利要求3所述的方法,其特征在于,所述方法包括如下步骤:
(1)将硅铝摩尔比为10-100的HZSM-5分子筛于400℃~550℃煅烧2小时~6小时,冷却备用;
(2)将金属钴的前驱体或金属铌的前驱体负载在经步骤(1)处理的HZSM-5分子筛上,先室温干燥,然后再在100℃~120℃干燥至少12小时,最后于300℃~600℃煅烧至少4小时,得到中间体;
(3)将金属铌的前驱体或金属钴的前驱体负载在由步骤(2)所得的中间体上,同样,先室温干燥,然后再在100℃~120℃干燥至少12小时,最后于300℃~600℃煅烧至少4小时,得到目标物;
其中,所述金属钴的前驱体是金属钴的水溶性盐,所述金属铌的前驱体是金属铌的水溶性草酸盐。
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