CN106311264A - 一种二氧化硅负载镍钨催化剂及其制备方法与应用 - Google Patents
一种二氧化硅负载镍钨催化剂及其制备方法与应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 56
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 title claims abstract description 33
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 238000004090 dissolution Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 5
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Abstract
一种二氧化硅负载镍钨催化剂及其制备方法与应用，涉及甲烷部分氧化催化剂。所述二氧化硅负载镍钨催化剂的组份为镍、钨和二氧化硅，通式为NiWx/SiO2，其中x＝0.01，0.03，0.05，0.07，0.10；钨镍的摩尔比为0.01～0.10；所述二氧化硅为载体，所述二氧化硅负载镍钨催化剂的比表面积为276.2～327.6m2/g。制备方法：将硝酸镍和钨酸铵混合溶解在水中，再加入尿素，水热合成，待混合物冷却至室温后，离心，洗涤，再超声分散在二氧化硅上，浸渍后干燥，焙烧，压片，过筛，即得二氧化硅负载镍钨催化剂。所述二氧化硅负载镍钨催化剂可在甲烷部分氧化反应中应用。
Description
技术领域
本发明涉及甲烷部分氧化催化剂，特别是涉及过渡金属氧化物添加修饰的一种二氧化硅负载镍钨催化剂及其制备方法与应用。
背景技术
我国天然气资源储量丰富，天然气是清洁的能源和优质的化工原料。天然气的主要成分是甲烷，甲烷间接转化制合成气是甲烷化工利用的主要途径，其中，甲烷部分氧化是温和的放热反应，产物中H2和CO的比值为2，适合做甲醇及F-T合成的原料气，因此备受研究者的关注。传统负载型催化剂反应稳定性差，极易失活。因而制备高反应稳定性的催化剂是甲烷部分氧化反应的关键。
目前优异的甲烷部分氧化催化剂主要集中在贵金属催化剂和非贵金属催化剂，贵金属催化剂反应活性高，稳定性好，但其活性组分Rh、Ru、Pt、Ir等由于价格昂贵储量有限，应用范围受到极大的限制；非贵金属催化剂中，镍基催化剂反应活性高，但反应稳定性差，极易失活。
二氧化硅耐酸耐碱，热稳定性高，是一种常见的载体，镍基催化剂具有优异的甲烷部分氧化反应性能，且价格低廉，被广泛应用。传统负载型镍基催化剂，反应稳定性差，当添加少量过渡金属氧化物时，其催化剂反应稳定性明显提高。Zhang(Zhang,CatalysisCommunications,2015,69:123-128)等制备了W掺杂的Ni/SiO2催化剂，该催化剂上双金属以Ni17W3合金的形式存在，在二氧化碳重整反应中形成了α-WC，并参与了CO2的活化，有效的提高了催化剂的稳定性和抗积炭性能。Ouaguenouni(Ouaguenouni,Comptes RendusChimie,2009,12(6-7):740-747)等采用溶胶凝胶法、共沉淀法制备了NiMn混合氧化物催化剂，并用于甲烷部分氧化制合成气，实验结果表明，催化剂在900℃焙烧后形成NiMn2O4尖晶石结构，该结构的存在提高了Ni在催化剂上的稳定性，抑制了活性组分的团聚，表现出优异的POM反应稳定性。
发明内容
本发明的目的旨在提供用于甲烷部分氧化反应时，能实现甲烷部分氧化反应的高稳定性，制备简单易操作，原料廉价易得，钨添加修饰的一种二氧化硅负载镍钨催化剂及其制备方法与应用。
所述二氧化硅负载镍钨催化剂的组份为镍、钨和二氧化硅，通式为NiWx/SiO2，其中x＝0.01，0.03，0.05，0.07，0.10；钨镍的摩尔比为0.01～0.10；所述二氧化硅为载体，所述二氧化硅负载镍钨催化剂的比表面积为276.2～327.6m2/g。
所述二氧化硅负载镍钨催化剂的制备方法，包括以下步骤：
1)将硝酸镍和钨酸铵混合溶解在水中，再加入尿素，水热合成，待混合物冷却至室温后，离心，洗涤；
在步骤1)中，所述硝酸镍可采用Ni(NO3)2·6H2O；所述钨酸铵可采用(NH4)10W12O41；所述水热合成是在聚四氟乙烯反应釜中于恒温干燥箱中水热合成；所述水热合成的温度可为120℃，所述水热合成的时间可为3h；所述离心的速率可为10000r/min，离心的时间可为10min；所述洗涤可采用去离子水洗涤至少2次。
2)将步骤1)中所得产物超声分散在二氧化硅上，浸渍后干燥，焙烧，压片，过筛，即得二氧化硅负载镍钨催化剂，记为NiWx/SiO2(x＝0.01，0.03，0.05，0.07，0.10)。
在步骤2)中，所述超声分散的时间可为10min；所述浸渍的时间可为12h；所述干燥的温度可为60℃，干燥的时间可为12h，所述焙烧的温度可为700℃，焙烧的时间可为2h，焙烧的升温速率为1℃/min；所述过筛可过40～60目筛。
在步骤1)和2)中，所述硝酸镍、钨酸铵、尿素、二氧化硅的质量比可为(0.2908～0.2935)︰(0.0027～0.0270)︰0.1800︰0.5935；
所述二氧化硅负载镍钨催化剂可在甲烷部分氧化反应中应用。
所述二氧化硅负载镍钨催化剂可采用固定床连续流动反应器—气相色谱组合操作系统进行活性评价。反应温度为700℃，反应气为混合气，比例为CH4/O2＝2/1，气体总空速为60000mL/g/h，二氧化硅负载镍钨催化剂用量为30mg。本发明所述二氧化硅负载镍钨催化剂具有优异的甲烷部分氧化反应稳定性，如所制得的催化剂NiW0.07/SiO2在反应10h内，甲烷转化率始终维持在78％，且反应后粒径没有明显的增大，积炭含量为0％。
本发明的优点：
(1)所述二氧化硅负载镍钨催化剂在甲烷部分氧化反应中，催化剂的反应稳定性高，反应后粒子没有发生明显的团聚，且没有检测到积炭的生成。
(2)所述二氧化硅负载镍钨催化剂的组份为镍、钨和二氧化硅，镍的含量较低(9％)，W/Ni摩尔比较低(≤0.10)，原料廉价易得，成本较低。
(3)制备步骤较简单，制备条件温和，有一定的工业价值。
附图说明
图1为PDF#04-0850-Ni标准卡片，PDF#04-0806-W标准卡片，实施例1～5以及对比例1中700℃H2还原1h合成催化剂XRD衍射谱图。
图2为PDF#04-0850-Ni标准卡片，实施例1～4以及对比例1中反应后催化剂的XRD衍射谱图。
图3为实施例1～5以及对比例1的反应性能评价结果。
反应条件：反应温度为700℃，催化剂用量为30mg，原料气为CH4/O2＝2/1，空速GHSV＝60000mL/g。
图中标记对应的催化剂如下：
a：对比例1；b：实施例1；c：实施例2；d：实施例3；e：实施例4；f：实施例5。
具体实施方式
以下实施例结合附图进一步说明本发明。
实施例1
1)将0.2935gNi(NO3)2·6H2O和0.0027g钨酸铵溶解在10mL去离子水中，再加入0.1800g尿素，待完全溶解后转移至聚四氟乙烯反应釜中，放入恒温干燥箱，120℃恒温反应3h，待混合物冷却至室温，离心，用去离子水将沉淀洗涤2次。
2)将步骤1)中所得产物超声分散在0.5935g商品二氧化硅上，常规浸渍12h，60℃干燥12h，然后700℃空气气氛下焙烧2h，所述硝酸镍为Ni(NO3)2·6H2O，钨酸铵为(NH4)10W12O41；将焙烧好的催化剂进行压片，过筛后取40～60目备用，制得催化剂简记为NiW0.01/SiO2。
催化剂的活性评价结果见图3。
实施例2
1)将钨酸铵质量改成0.0081g，其余步骤同实施例1。
2)与实施例1中步骤2)相同，催化剂标记为NiW0.03/SiO2。
实施例3
1)将钨酸铵质量改成0.0135g，其余步骤同实施例1。
2)与实施例1中步骤2)相同，催化剂标记为NiW0.05/SiO2。
实施例4
1)将钨酸铵质量改成0.0189g，其余步骤同实施例1。
2)与实施例1中步骤2)相同，催化剂标记为NiW0.07/SiO2。
实施例5
1)将钨酸铵质量改成0.0270g，其余步骤同实施例1。
2)与实施例1中步骤2)相同，催化剂标记为NiW0.10/SiO2。
对比例1
1)将钨酸铵质量改为0.0000g，其余步骤同实施例1。
2)与实施例1中步骤2)相同，催化剂标记为Ni/SiO2
催化剂的XRD表征是在荷兰PANalytical公司生产的多晶粉末X-射线衍射仪Panalytical X’pert PRO上进行。辐射源为Cu Kα(λ＝0.15406nm)，管压为40kV，管流为30mA，采用石墨单色器滤光，扫描范围为10～90°，连续扫描步长为0.0167°·步-1，结果见图1和图2。
催化剂的BET表征(氮气吸脱附实验)在Micromeritics仪器公司生产的TristarⅡ3000型物理吸附仪上进行。催化剂用量约为100mg，实验前，先将样品于120℃抽空净化1h，然后升温至300℃抽真空处理2h。以高纯氮气作为吸附质，在液氮温度(77K)下测定样品的吸脱附等温曲线。催化剂的比表面积利用BET方程进行计算，孔结构数据通过BJH单点法得到。
实施例1～5和对比例1中催化剂的物理性质比较参见表1。
表1
注：还原后：700℃，H2还原1h；
反应后：反应条件下反应10h(反应条件：反应温度为700℃，催化剂用量为30mg，原料气为CH4/O2＝2/1，空速GHSV＝60000mL/g)。
Claims (10)
1.一种二氧化硅负载镍钨催化剂，其特征在于其组份为镍、钨和二氧化硅，通式为NiWx/SiO2，其中x＝0.01，0.03，0.05，0.07，0.10；钨镍的摩尔比为0.01～0.10；所述二氧化硅为载体，所述二氧化硅负载镍钨催化剂的比表面积为276.2～327.6m2/g。
2.如权利要求1所述一种二氧化硅负载镍钨催化剂的制备方法，其特征在于包括以下步骤：
1)将硝酸镍和钨酸铵混合溶解在水中，再加入尿素，水热合成，待混合物冷却至室温后，离心，洗涤；
2)将步骤1)中所得产物超声分散在二氧化硅上，浸渍后干燥，焙烧，压片，过筛，即得二氧化硅负载镍钨催化剂。
3.如权利要求1所述一种二氧化硅负载镍钨催化剂的制备方法，其特征在于在步骤1)中，所述硝酸镍采用Ni(NO3)2·6H2O；所述钨酸铵采用(NH4)10W12O41。
4.如权利要求1所述一种二氧化硅负载镍钨催化剂的制备方法，其特征在于在步骤1)中，所述水热合成是在聚四氟乙烯反应釜中于恒温干燥箱中水热合成；所述水热合成的温度为120℃，所述水热合成的时间为3h。
5.如权利要求1所述一种二氧化硅负载镍钨催化剂的制备方法，其特征在于在步骤1)中，所述离心的速率为10000r/min，离心的时间为10min。
6.如权利要求1所述一种二氧化硅负载镍钨催化剂的制备方法，其特征在于在步骤1)中，所述洗涤是采用去离子水洗涤至少2次。
7.如权利要求1所述一种二氧化硅负载镍钨催化剂的制备方法，其特征在于在步骤2)中，所述超声分散的时间为10min；所述浸渍的时间可为12h。
8.如权利要求1所述一种二氧化硅负载镍钨催化剂的制备方法，其特征在于在步骤2)中，所述干燥的温度为60℃，干燥的时间为12h；所述焙烧的温度可为700℃，焙烧的时间可为2h，焙烧的升温速率为1℃/min；所述过筛可过40～60目筛。
9.如权利要求1所述一种二氧化硅负载镍钨催化剂的制备方法，其特征在于在步骤1)和2)中，所述硝酸镍、钨酸铵、尿素、二氧化硅的质量比为(0.2908～0.2935)︰(0.0027～0.0270)︰0.1800︰0.5935。
10.如权利要求1所述二氧化硅负载镍钨催化剂在甲烷部分氧化反应中应用。
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