CN1151908A - 用于对烃流中乙炔选择催化加氢的载体钯催化剂 - Google Patents
用于对烃流中乙炔选择催化加氢的载体钯催化剂 Download PDFInfo
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 19
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims description 4
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
适用于对烃流中乙炔选择性加氢的以二氧化硅为载体的催化剂，以载体催化剂为基础计，它含有0.001至1重量％的钯以及0.005-5重量％的至少一种的元素周期表中第1和第2族的助催化剂金属，通过用一种含至少一种助催化剂金属的溶液浸渍二氧化硅载体，干燥浸渍的载体，再用一种含钯溶液浸渍，干燥和煅烧来制得。
Description
本发明涉及一种新型的、适用对烃流中的乙炔进行选择性催化加氢的、以二氧化硅为载体的催化剂。
本发明进一步涉及一种制备该催化剂的方法，以及使用本发明的催化剂对烃流中的乙炔选择性加氢的方法。
对于各种工业反应，乙炔是一种不受欢迎的原料组分，因为它容易聚合且使过渡金属催化剂失活。更重要的是，在从蒸汽裂化炉中出来的C2流中，乙炔在技术上是不利的。这些气流主要是乙烯和乙烷，还有少量的乙炔。为用于生产聚乙烯，在这些气流中乙炔的含量必须降至低于1ppm。就其选择性和活性来说，对用于乙炔加氢的催化剂的要求是很高的，因为氢化必须在没有乙烯损失的情况下进行。
用于这一目的催化剂主要是以氧化铝为载体的钯催化剂。现有技术的建议包括含有以具有0.1-2m2/gBET表面积的大孔Al2O3为载体的钯的催化剂(JP-B80/047 015；Chem.Abstr.，Vol.82，169991)，含有承载在具有小于5m2/g表面积载体上的钯和任选地铬的催化剂(US-A 45 770 47)，或含有银(EP-A64301)，金(EP-A89252)、锂(US-A3325556)、铬(DE-A1284403)或钾作为助催化剂的钯的催化剂(Park等，J.Chem.Soc.，Chem.Commun.1991，1188；1nd.Eng.Chem Res.31(1992)469)。
US-A4839329描述了TiO2作为载体材料用于对乙炔进行选择性加氢的催化剂，US-A4906800提出了承载于CaCO3上的钯—铅催化剂。DE-A2156544描述了在二氧化硅载体上的钯—锌催化剂。
德国专利申请P19500366.7描述了用钯溶液浸渍载体而制备的一种载体钯催化剂。
在使用所提到的催化剂对在烃流中的少量乙炔进行加氢时需要向待加氢化气流中加入一氧化碳以提高各催化剂的选择性。这有一缺点，即一氧化碳提高选择性的效应对温度有强烈的依赖性。在催化剂床中大的温度梯度对选择性有负效应。另外，向相当大量的气流中计量加入较小量的一氧化碳需要大量的计算和控制。
此外，所提及催化剂的一部分含有大量昂费的贵金属，这从经济角度抑止了它们在工业上的大规模应用。
本发明的目的是提供一种不具有上述缺点的催化剂。尤其是，无需加入一氧化碳，它们就能对烃流中甚至很小量的乙炔高选择性地进行加氢化。
我们发现这一目的可通过这样一种以二氧化硅为载体的催化剂达到，以载体催化剂为基础计，它包含0.001-1重量％的钯以及0.005-5重量％的至少一种元素周期表第1和第2族的助催化剂金属，它是通过用一种至少含一种助催化剂金属的溶液浸渍二氧化硅载体，干燥所浸渍的载体，再用一种含钯溶液浸渍，干燥且煅烧。
本发明还提供了一种制备本发明催化剂的方法，以及一种用所述催化剂对乙炔加氢化的方法。
本发明的载体催化剂是通过对二氧化硅载体逐步浸渍制备的。可以任何所需的形式使用这些载体，如粒状、丸状、片状，但优选挤出物。使用BET表面积不低于50m2/g的二氧化硅是有利的，但优选具有100-300m2/g表面积的载体。所用二氧化硅的化学经历对本发明催化剂的性质没有什么影响；例如可使用沉淀的或火成的二氧化硅。
第一步浸渍将助催化剂涂敷于载体上。用载体所能吸收的最大量的溶液对载体进行掺和是有利的。这一溶液含有的助催化剂金属的量应使最后经煅烧的催化剂将含有0.005-5重量％的助催化剂金属。通过一些预先试验本专业人员很容易确定适当的混合比。
合适的助催化剂金属包括碱金属和碱土金属，如锂、钠、钾、铷、铯、钙、锶和钡。当然，优选铷、锶和钡，特别优选钾。可以使用不仅仅一种而是多种所提及的助催化剂金属。助催化剂金属一般以其盐的形式溶于溶剂，优选水中。合适的盐尤其包括那些易于煅烧成相应氧化物的盐，如所述助催化剂金属的氢氧化物、碳酸盐、硝酸盐、乙酸盐以及甲酸盐。优选氢氧化物。
在用助催化剂金属浸渍之后，干燥载体。干燥一般在低于300℃的温度下进行，这是由于高温的延滞作用会更加有利于硅酸盐的形成。干燥一般进行5-20小时。当溶剂蒸发停止时则干燥完成。
在第二步浸渍中以常用的方式将钯涂敷于预处理的载体上。象涂敷助催化剂金属时一样，这一步骤优选地通过用一载体能完全吸收的溶剂量进行浸渍。用钯盐溶液掺和载体。对钯盐，水是优选的溶剂。仅使用真正的溶液，就是说，不使用含钯溶胶溶液。合适的钯盐例如包括硝酸钯、乙酸钯、乙酰丙酮钯和氯化钯。这些钯盐溶液的一些可因所用的阴离子而显酸性。
在优选的实施例中，在浸渍之前例如用无机酸将中性溶液调至酸性。
在用钯盐溶液浸渍载体之后，将其干燥。干燥温度一般在100-200℃，时间为5-20小时。干燥过程中，优选搅动载体以使干燥均匀进行。
随后，干燥的载体进行煅烧，一般在300-700℃，优选在320-450℃进行0.5-8小时。
在将本发明的催化剂用于对乙炔加氢工艺之前，优选通过用氢或含氢气体在100-550℃温度下还原而进行活化，其中氢气的分压在1-300巴之间是有利的，进行还原直至停止生成水。
本发明的催化剂在助催化剂金属氧化物上有一薄层钯。这一催化剂结构导致高的选择性。
本发明的催化剂例如可用于对烃流中的乙炔选择性加氢化。对于含有乙烯和乙烷作为主成份以及0.01-5体积％的乙炔的蒸汽裂化炉气流，这一应用特别有益。
含乙炔的烃流的加氢是在气相中在10-30巴的氢气压力下进行的。赖于待加氢化乙炔的量，加氢可在一个或多阶段以及有或没有中间冷却的情况下进行，并且氢气以通常的方式输入各单个反应器中。绝热工艺是优选的并且对于低于1体积％的乙炔含量来说是容易达到的。输入第一反应器的含乙炔的烃流的进口温度一般为15-120℃，优选在25-95℃。当仅使用一个反应器时，氢气和乙炔的摩尔比一般为1.1∶1至2∶1，优选1.2∶1至1.6∶1。在使用多个连续的反应器以及将氢气输入各反应器的情况下，相反，则可在0.6∶1至1.2∶1的范围内。
在对乙炔加氢时本发明的催化剂活性很高并且可在较低温度下使用。甚至在低乙炔含量的情况下它们的选择性仍很高，而无需向加氢阶段中计量加入一氧化碳。可能获得约1ppm的残余乙炔含量，并且与现有的催化剂相比，可使用低过化学计量的氢气。
实施例实施例1制备掺杂了钾的催化剂
用92升330克氢氧化钾在水中的溶液浸渍111kg具有270m2/gBET表面积的硅胶载体(直径4mm)。载体于搅拌下在120℃干燥16小时。用95升具有33g钯含量的硝酸钯水溶液进行第二次浸渍。在120℃干燥16小时之后，挤出物于400℃煅烧4小时。实施例2使用本发明催化剂对乙炔进行选择性加氢化
用50升实施例1的催化剂对一具有305mm直径的管式反应器进行填充，用氮气冲洗反应器。接着用20巴氢气在150℃对催化剂还原3小时。
随后向反应器进给150m3/h含有0.71体积％的乙炔以及69.6体积％乙烯和29.6体积乙烷的气流以及具有35℃进口温度的氢气。逐步降低氢气和乙炔的摩尔比。表1显示反应细节。
表1
| 氢气与乙炔的摩尔比 | 加氢后乙炔的含量(ppm) | 转化率(％) | 选择性(％) |
| 1.81 | ＜0.1 | ＞99.999 | 19 |
| 1.54 | ＜0.1 | ＞99.999 | 46 |
| 1.43 | ＜0.1 | ＞99.999 | 56 |
Claims (9)
1.适用于对烃流中乙炔选择性加氢的以二氧化硅为载体的催化剂，以载体催化剂为基础计，它含有0.001至1重量％的钯以及0.005-5重量％至少一种的元素周期表中第1和第2族的助催化剂金属，通过用一种含至少一种助催化剂金属的溶液浸渍二氧化硅载体，干燥浸渍的载体，再用一种含钯溶液浸渍、干燥和煅烧来制得。
2.权利要求1的载体催化剂，包括将钾、铷、锶或钡作为助催化剂金属。
3.根据权利要求1或2的催化剂，通过用氢氧化钾水溶液浸渍二氧化硅载体，干燥并接着用含硝酸钯的溶液进行浸渍。
4.根据权利要求1-3中任一项的载体催化剂，通过浸渍具有100-300m2/gBET表面积的二氧化硅载体制得。
5.一种制备载体催化剂的方法，以载体催化剂为基础计，该催化剂包含0.001至1重量％的钯和0.005至5重量％的至少一种元素周期表第1和第2族的助催化剂金属，其中包括用一种含至少一种助催化剂金属的溶液浸渍二氧化硅载体，干燥浸渍的载体，用一种含钯的溶液浸渍，干燥且煅烧。
6.根据权利要求1-4的任一项的催化剂用于对烃流中的乙炔催化加氢。
7.根据权利要求6的应用，其中在乙烯的存在下对乙炔加氢。
8.一种在烃流中用氢气对乙炔选择性催化加氢的方法，其中包括在气相中在根据权利要求1-4之任一项的催化剂上进行加氢化。
9.根据权利要求8的方法，其中在主要含乙烯和乙烷的、含0.01-5体积％乙炔的气流中对乙炔进行选择性加氢。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19535402A DE19535402A1 (de) | 1995-09-23 | 1995-09-23 | Palladium-haltiger Trägerkatalysator zur selektiven katalytischen Hydrierung von Acetylen in Kohlenwasserstoffströmen |
| DE19535402.8 | 1995-09-23 |
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| Publication Number | Publication Date |
|---|---|
| CN1151908A true CN1151908A (zh) | 1997-06-18 |
| CN1081487C CN1081487C (zh) | 2002-03-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN96112648A Expired - Fee Related CN1081487C (zh) | 1995-09-23 | 1996-09-23 | 用于对烃流中乙炔选择催化加氢的载体钯催化剂 |
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| Country | Link |
|---|---|
| US (2) | US5856262A (zh) |
| EP (1) | EP0764463B1 (zh) |
| JP (1) | JP3939787B2 (zh) |
| KR (1) | KR100418161B1 (zh) |
| CN (1) | CN1081487C (zh) |
| CA (1) | CA2185721C (zh) |
| DE (2) | DE19535402A1 (zh) |
| ES (1) | ES2197222T3 (zh) |
| MX (1) | MX9604031A (zh) |
| TW (1) | TW388722B (zh) |
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| CN107362798A (zh) * | 2017-07-21 | 2017-11-21 | 北京华福工程有限公司 | 用于高纯乙炔加氢制乙烯的Pd‑M基金属催化剂的制备方法和制备乙烯的方法 |
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-
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- 1995-09-23 DE DE19535402A patent/DE19535402A1/de not_active Withdrawn
-
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- 1996-09-11 MX MX9604031A patent/MX9604031A/es not_active IP Right Cessation
- 1996-09-12 US US08/711,904 patent/US5856262A/en not_active Expired - Fee Related
- 1996-09-16 CA CA002185721A patent/CA2185721C/en not_active Expired - Fee Related
- 1996-09-16 ES ES96114801T patent/ES2197222T3/es not_active Expired - Lifetime
- 1996-09-16 DE DE59610365T patent/DE59610365D1/de not_active Expired - Lifetime
- 1996-09-16 TW TW085111311A patent/TW388722B/zh not_active IP Right Cessation
- 1996-09-16 EP EP96114801A patent/EP0764463B1/de not_active Expired - Lifetime
- 1996-09-20 JP JP25035796A patent/JP3939787B2/ja not_active Expired - Fee Related
- 1996-09-21 KR KR1019960041445A patent/KR100418161B1/ko not_active IP Right Cessation
- 1996-09-23 CN CN96112648A patent/CN1081487C/zh not_active Expired - Fee Related
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097480C (zh) * | 1999-06-25 | 2003-01-01 | 中国石油化工集团公司 | 炔烃选择加氢催化剂 |
| US6822127B2 (en) | 2000-09-29 | 2004-11-23 | China Petroleum & Chemical Corporation | Selective hydrogenation catalyst for selectively hydrogenating of unsaturated olefin, process for preparing the same and its use |
| CN102180443A (zh) * | 2003-11-24 | 2011-09-14 | 迈克尔·莱芬费尔德 | 包含碱金属和碱金属合金的硅胶组合物 |
| CN107362798A (zh) * | 2017-07-21 | 2017-11-21 | 北京华福工程有限公司 | 用于高纯乙炔加氢制乙烯的Pd‑M基金属催化剂的制备方法和制备乙烯的方法 |
| CN107362798B (zh) * | 2017-07-21 | 2020-06-16 | 北京华福工程有限公司 | 用于高纯乙炔加氢制乙烯的Pd-M基金属催化剂的制备方法和制备乙烯的方法 |
| CN113477249A (zh) * | 2021-06-21 | 2021-10-08 | 润和科华催化剂(上海)有限公司 | 一种乙炔选择性加氢制乙烯的催化剂、制备方法及应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09141097A (ja) | 1997-06-03 |
| TW388722B (en) | 2000-05-01 |
| US5856262A (en) | 1999-01-05 |
| CA2185721C (en) | 2007-07-31 |
| DE59610365D1 (de) | 2003-05-28 |
| EP0764463A3 (de) | 1998-09-02 |
| ES2197222T3 (es) | 2004-01-01 |
| US5847250A (en) | 1998-12-08 |
| CA2185721A1 (en) | 1997-03-24 |
| EP0764463B1 (de) | 2003-04-23 |
| MX9604031A (es) | 1997-03-29 |
| JP3939787B2 (ja) | 2007-07-04 |
| DE19535402A1 (de) | 1997-03-27 |
| KR970014834A (ko) | 1997-04-28 |
| EP0764463A2 (de) | 1997-03-26 |
| KR100418161B1 (ko) | 2004-04-13 |
| CN1081487C (zh) | 2002-03-27 |
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