CN112473678A - 用于湿法熄焦蒸气混合重整甲烷的催化剂及其制备方法 - Google Patents
用于湿法熄焦蒸气混合重整甲烷的催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种用于熄焦蒸气混合重整甲烷制合成气的钙钛矿型催化剂及其制备方法，属冶金资源综合利用和催化剂制造技术领域。其特征在于，采用溶胶‑凝胶法制备Pr0.6Sr0.4M1‑ xNixO3‑δ催化剂前驱体，样品经压片、破碎、过筛，去20‑40目即为所得催化剂。本发明所述方法制备的催化剂在一定镍含量下保持钙钛矿结构，具有很好催化活性。Pr0.6Sr0.4Fe1‑xNixO3‑δ催化剂中x＝0.3时表现出最高的催化活性，当温度从725℃升高到850℃时，Pr0.6Sr0.4Fe0.7Ni0.3O3‑δ催化剂的CO2的转化率从53.78％升高到79.48％，CH4的转化率从62.48％升高到87.44％；在800℃下50h的试验周期内，CO2的转化率从71.96％下降到65.36％，CH4的转化率从80.66％下降到73.86％。
Description
技术领域
本发明涉及一种用于熄焦蒸气混合重整甲烷制合成气的钙钛矿型催化剂及其制备方法，属冶金资源综合利用和催化剂制造技术领域。
背景技术
随着钢铁行业的飞速发展，冶金钢铁需要的焦炭量增加，炼焦行业的发展速度也得到提高，炼焦行业不断发展。目前,在焦化行业中湿法熄焦技术因其工艺相对较为简单在我国应用广泛。常规湿法熄焦设施由熄焦车、熄焦塔和凉焦台组成，焦炉产生的焦炭经拦焦车导入熄焦车后，在电机车的牵引下进入熄焦塔下部，通过熄焦塔内喷淋机构喷下的水逆流接触，熄灭红焦，焦炭被冷却熄灭后倒放至晾焦台上晾放。
湿法熄焦过程是在熄焦塔中把1000℃的红焦炭与熄焦水接触，熄焦水吸收红焦的显热汽化，生成的水蒸气经熄焦塔排放到大气中。熄焦时，水的消耗量为0.4-0.5t水/t焦。其中0.3-0.4t水被蒸发掉，0.1t左右的水被焦炭带走，其余循环使用。同时，熄焦过程中水与红焦发生部分水煤气反应，蒸气成分含有CO和H2S等气体。湿法熄焦产生的夹带有大量水蒸气和CO2等气体的熄焦蒸汽，一方面含有CO2、CO、H2S等气体严重污染大气及周围环境，另一方面熄焦蒸汽中的高温水蒸气直接排除，不仅造成水资源的浪费，而且造成能量的损失，如何高效利用熄焦蒸汽，是焦化产业技术升级，实现可持续发展的重中之重。
甲烷水蒸气重整的氧化剂是水，是目前最常用的合成气制备技术，该反应是一个强吸热反应，通常反应条件控制在温度750-900℃，压力2-3MPa，水碳比2.5-3的条件下进行，并制得H2/CO比约为3的合成气。
CH4+H2O→CO+3H2ΔH298K＝206kJ mol-1(1)
甲烷二氧化碳重整是将CO2和CH4转化为CO和H2的强吸热反应，其所需热量比水蒸气所需热量高近15％。
CO2+CH4→2CO+2H2ΔH298K＝247kJ mol-1(2)
水蒸气和二氧化碳重整甲烷产生的合成气中H2/CO＝2，能够直接用于后续含氧化合物合成以及Fischer-Tropsch合成，并且不需要额外调整H2/CO比例。
3CH4+CO2+2H2O→4CO+8H2ΔH298K＝220kJ mol-1(3)
通过熄焦蒸汽混合重整甲烷制合成气，是非常有应用前景的利用途径。因此，发展熄焦蒸汽混合重整甲烷技术的关键在于制备出高活性、高稳定性和优良抗积碳性能的催化剂。
稀土复合钙钛矿氧化物因其独特的物理化学特性，在催化领域受到了越来越多的关注，研究发现一定条件下对其进行掺杂改性，部分取代A位或B位离子后，其晶体结构稳定不发生变化，并且具有强氧化还原性质，被认为是最理想的催化剂。研究已经证明，ABO3钙钛矿型复合氧化物在小分子催化转化中具有良好的活性。而镍基催化剂的催化活性与贵金属催化剂相媲美，并且在储量和成本上有着更大的优势。将镍元素均匀分散在钙钛矿结构的晶格中及对B位离子的部分取代是提高其催化活性和热稳定性的一种重要方法。
发明内容
一种湿法熄焦蒸汽混合重整甲烷气用钙钛矿型催化剂，其特征在于具有以下的组成：
Pr0.6Sr0.4M1-xNixO3-δ
所述M为过渡金属Co、Fe；0≤x≤0.5。
一种熄焦蒸汽混合重整甲烷用钙钛矿型催化剂的制备方法，其特征在于具有以下的工艺过程和步骤：
(d)根据Pr0.6Sr0.4M1-xNixO3-δ的化学计量比将一定量的镨盐、锶盐、镍盐和M盐加入到去离子水中，加热并搅拌直至完全溶解；按金属离子：乙二胺四乙酸：柠檬酸的物质的比为1:1:1.5的比例精确称量乙二胺四乙酸和柠檬酸的质量，将其加入去离子水中，加热并搅拌，直至混合均匀；
(e)将上述两种溶液混合，通过滴加氨水，使溶液的pH值在9-10之间，并在
(f)80-100℃加热搅拌，直至溶液变为溶胶；将所得溶胶物质在100-120℃干燥，直至其完全干燥，膨胀为海绵状多孔固体后取出，在空气气氛中850℃焙烧6小时，得到最后催化剂前驱体；
(g)将所得Pr0.6Sr0.4M1-xNixO3-δ粉体中滴加适当PVA粘结剂，并在研钵中研磨1-2小时，使其造粒及混合均匀，加入适当油酸并在100-200MPa压力下成型，所得片状坯体在400-800℃焙烧3-8小时，经过破碎、过筛，得粒径20-40目的粉体，即为所需的催化剂。
附图说明
图1为本发明所述方法制备的Pr0.6Sr0.4Fe1-xNixO3-δ催化剂的X射线衍射(XRD)图。
图2为本发明所述方法制备的Pr0.6Sr0.4Fe1-xWxO3-δ催化剂的CO2转化率与反应温度的变化关系图。
图3为本发明所述方法制备的Pr0.6Sr0.4Fe1-xWxO3-δ催化剂的CH4转化率与反应温度的变化关系图。
图4为本发明所述方法制备的Pr0.6Sr0.4Fe0.7W0.3O3-δ催化剂的CO2与CH4在800℃转化率与反应时间的变化关系图。
具体实施方式
下面结合附图，对本发明的具体实施例作具体说明。
实施例1
将23.36g Pr(NO3)3·6H2O、7.58g Sr(NO3)2、36.16g Fe(NO3)3·9H2O溶解在去离子水中；取52.36g乙二胺四乙酸和56.43g柠檬酸溶解在另一个装有去离子水的烧杯中，将上述两溶液混合，并加热搅拌，通过滴加氨水调节溶液的pH值为9-10，继续加热至80℃并搅拌直至获得溶胶。将所得溶胶在100℃干燥，直至其膨胀为海绵状多孔固体后取出，在850℃焙烧6小时，得到最后催化剂前驱体。
向所得Pr0.6Sr0.4FeO3-δ粉体中加入5滴粘结剂，在研钵中研磨1小时，使其完全混合且造粒均匀，向所得粉体中加入适当油酸并在180MPa压力下压制成
型，所得片状坯体在600℃焙烧4小时，经过破碎、过筛，得粒径20-40目的分体，即为所需的Pr0.6Sr0.4FeO3-δ催化剂。
实施例2
将23.33g Pr(NO3)3·6H2O、7.57g Sr(NO3)2、32.50g Fe(NO3)3·9H2O、2.60gNi(NO3)2溶解在去离子水中；取52.25g乙二胺四乙酸和56.36g柠檬酸溶解在另一个装有去离子水的烧杯中，将上述两溶液混合，并加热搅拌，通过滴加氨水调节溶液的pH值为9-10，继续加热至80℃并搅拌直至获得溶胶。将所得溶胶在100℃干燥，直至其膨胀为海绵状多孔固体后取出，在850℃焙烧6小时，得到最后催化剂前驱体。
向所得Pr0.6Sr0.4Fe0.9Ni0.1O3-δ粉体中加入5滴粘结剂，在研钵中研磨1小时，使其完全混合且造粒均匀，向所得粉体中加入适当油酸并在180MPa压力下压制成型，所得片状坯体在600℃焙烧4小时，经过破碎、过筛，得粒径20-40目的分体，即为所需的Pr0.6Sr0.4Fe0.9Ni0.1O3-δ催化剂。
实施例3
将23.27g Pr(NO3)3·6H2O、7.55g Sr(NO3)2、25.22g Fe(NO3)3·9H2O、7.78gNi(NO3)2溶解在去离子水中；取52.12g乙二胺四乙酸和56.21g柠檬酸溶解在另一个装有去离子水的烧杯中，将上述两溶液混合，并加热搅拌，通过滴加氨水调节溶液的pH值为9-10，继续加热至80℃并搅拌直至获得溶胶。将所得溶胶在100℃干燥，直至其膨胀为海绵状多孔固体后取出，在850℃焙烧6小时，得到最后催化剂前驱体。
向所得Pr0.6Sr0.4Fe0.7Ni0.3O3-δ粉体中加入5滴粘结剂，在研钵中研磨1小时，使其完全混合且造粒均匀，向所得粉体中加入适当油酸并在180MPa压力下压制成型，所得片状坯体在600℃焙烧4小时，经过破碎、过筛，得粒径20-40目的分体，即为所需的Pr0.6Sr0.4Fe0.7Ni0.3O3-δ催化剂。
实施例4
将23.05g Pr(NO3)3·6H2O、7.48g Sr(NO3)2、15.42g Co(NO3)3·6H2O、10.27gNi(NO3)2溶解在去离子水中；取51.63g乙二胺四乙酸和55.68g柠檬酸溶解在
另一个装有去离子水的烧杯中，将上述两溶液混合，并加热搅拌，通过滴加氨水调节溶液的pH值为9-10，继续加热至80℃并搅拌直至获得溶胶。将所得溶胶在100℃干燥，直至其膨胀为海绵状多孔固体后取出，在850℃焙烧6小时，得到最后催化剂前驱体。
向所得Pr0.6Sr0.4Co0.6Ni0.4O3-δ粉体中加入5滴粘结剂，在研钵中研磨1小时，使其完全混合且造粒均匀，向所得粉体中加入适当油酸并在180MPa压力下压制成型，所得片状坯体在600℃焙烧4小时，经过破碎、过筛，得粒径20-40目的分体，即为所需的Pr0.6Sr0.4Co0.6Ni0.4O3-δ催化剂。
测试实验结果评价分析
取本发明实施例1，例2，例3所制备的Pr0.6Sr0.4Fe1-xNixO3-δ催化剂在微型反应装置上进行。在进行催化性能测试之前，所有样品都在60ml/min的25vol.％H2/N2气氛下600℃原位还原2h。反应温度为725-850℃,催化剂的用量为0.5g，控制进气比例为CH4/CO2/H2O＝1/0.4/0.8,进气速率为100ml/min。
如图1所示，将根据本发明实施例1，例2，例3所制备的Pr0.6Sr0.4Fe1-xNixO3-δ催化剂进行X射线衍射分析，从图中可以看出，用溶胶凝胶法制备的La0.6Sr0.4Fe1-xNixO3-δ催化剂，当Ni掺杂量x≤0.3时，保持着钙钛矿的晶体结构，没有任何杂质生成，但当x≥0.4时，出现杂相，说明Ni的固溶限度为0.3。
如图2，图3所示，本发明实施例1，例2，例3所制备Pr0.6Sr0.4Fe1-xNixO3-δ催化剂CH4和CO2的转化率随着反应温度的升高而增大。Pr0.6Sr0.4Fe0.7Ni0.3O3-δ催化剂表现出最高的催化活性。当温度从725℃升高到850℃时，Pr0.6Sr0.4Fe0.7Ni0.3O3-δ催化剂的CO2的转化率从53.78％升高到79.48％，CH4的转化率从62.48％升高到87.44％。
如图4所示，将根据本发明实施例3所制备的Pr0.6Sr0.4Fe0.7Ni0.3O3-δ催化剂在800℃下，CO2与CH4在转化率随时间变化图，50h的试验周期内，CO2的转化率从71.96％下降到65.36％，CH4的转化率从80.66％下降到73.86％。
Claims (2)
1.一种湿法熄焦蒸汽混合重整甲烷气用钙钛矿型催化剂，其特征在于具有以下的组成：
Pr0.6Sr0.4M1-xNixO3-δ
所述M为过渡金属Co、Fe；0≤x≤0.5。
2.一种熄焦蒸汽混合重整甲烷用钙钛矿型催化剂的制备方法，其特征在于具有以下的工艺过程和步骤：
(a)根据Pr0.6Sr0.4M1-xNixO3-δ的化学计量比将一定量的镨盐、锶盐、镍盐和M盐加入到去离子水中，加热并搅拌直至完全溶解；按金属离子：乙二胺四乙酸：柠檬酸的物质的比为1:1:1.5的比例精确称量乙二胺四乙酸和柠檬酸的质量，将其加入去离子水中，加热并搅拌，直至混合均匀；
(b)将上述两种溶液混合，通过滴加氨水，使溶液的pH值在9-10之间，并在80-100℃加热搅拌，直至溶液变为溶胶；将所得溶胶物质在100-120℃干燥，直至其完全干燥，膨胀为海绵状多孔固体后取出，在空气气氛中850℃焙烧6小时，得到最后催化剂前驱体；
(c)将所得Pr0.6Sr0.4M1-xNixO3-δ粉体中滴加适当PVA粘结剂，并在研钵中研磨1-2小时，使其造粒及混合均匀，加入适当油酸并在100-200MPa压力下成型，所得片状坯体在400-800℃焙烧3-8小时，经过破碎、过筛，得粒径20-40目的粉体，即为所需的催化剂。
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