WO2018068172A1 - 基于甲酰胺及其衍生物和水的产氢体系及制氢方法 - Google Patents

基于甲酰胺及其衍生物和水的产氢体系及制氢方法 Download PDF

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WO2018068172A1
WO2018068172A1 PCT/CN2016/101619 CN2016101619W WO2018068172A1 WO 2018068172 A1 WO2018068172 A1 WO 2018068172A1 CN 2016101619 W CN2016101619 W CN 2016101619W WO 2018068172 A1 WO2018068172 A1 WO 2018068172A1
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hydrogen
formamide
water
catalyst
hydrogen production
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瞿永泉
张赛
马媛媛
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Xian Jiaotong University
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen

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  • the present disclosure relates to a hydrogen production system and a method for producing hydrogen using the same, and more particularly to a hydrogen production system for formamide and its derivatives and water, and a method for producing hydrogen using the hydrogen production system.
  • Hydrogen is considered to be the green energy with the most advantages and hopes in the future.
  • Water is an ideal source of hydrogen, and a large number of hydrogen production systems based on electrocatalysis and photocatalysis have been studied and invented.
  • this catalytic system has problems such as high energy consumption and low efficiency.
  • other liquid hydrogen storage materials methanol, ethanol, isopropanol, formaldehyde and formic acid
  • there are hidden dangers such as flammable, explosive, and toxic substances for these liquid hydrogen storage materials. Therefore, these hidden dangers also limit the practical application of these systems.
  • Formamide and its derivatives are monoamides in aliphatic amides and are commonly used in industrial applications such as pharmaceutical synthesis, dye synthesis, and solvents, and have not been reported for hydrogen storage and hydrogen production.
  • the technical problem to be solved by the present disclosure is to provide a catalytic hydrogen production system based on a hydrogen storage material of formamide and its derivatives and water to achieve efficient, stable and safe hydrogen production.
  • the catalytic hydrogen production system has high hydrogen production efficiency and high stability of the system, and can stably produce hydrogen for at least 17 days at 120 ° C, and the average hydrogen production rate can reach 3.85.
  • Mol Cu -1 d -1 the highest hydrogen production can reach 0.38 Mol Cu -1 h -1 , the system components are cheap and easy to obtain.
  • the catalytic hydrogen production system of the present disclosure includes:
  • the formamide and its derivative are selected from any one of N, N-diethylformamide, N-ethylformamide, N-methylformamide and formamide or any combination thereof;
  • the catalyst is selected from a copper-based or zinc-based catalytic material
  • the catalyst is selected from any one of a copper salt, a copper oxide, a zinc salt, and a zinc oxide or any Combination of meanings;
  • the copper salt is selected from one of CuCl, CuCl 2 , Cu(NO 3 ) 2 , Cu(CH 3 COO) 2 and CuI or any combination thereof
  • the zinc salt is selected from the group consisting of ZnSO 4 , ZnCl, Zn (CH) One of 3 COO) or Zn(NO 3 ) 2 or any combination thereof.
  • Industrial grade products can be used for the formamide of the present disclosure and its derivatives and catalysts, and distilled water can be used for the water.
  • the amount of each component is:
  • the amount of water is 0-20% by volume, and the amount of the catalyst is 0-1 mmol/mL.
  • the amount of each component is: based on formamide, the amount of water is 0-10% by volume, and the amount of the catalyst is 0-0.15 mmol/mL.
  • the amount of each component is: based on formamide and its derivative, the amount of water is 7.5 % by volume, and the amount of the catalyst is 0.075 mmol / mL.
  • the present disclosure also provides a method for producing hydrogen based on a catalytic hydrogen production system of a hydrogen storage material of formamide and its derivatives and water, comprising the following steps:
  • the hydrogen production can be measured by collecting the gas in the autoclave every 30 minutes.
  • the autoclave is heated to 100-140 ° C
  • the autoclave is heated to 120 °C.
  • the formamide and its derivative are selected from any one of N,N-diethylformamide, N-ethylformamide, N-methylformamide and formamide or any combination thereof.
  • the catalyst is selected from any one of a copper salt, a copper oxide, a zinc salt, and a zinc oxide, or any combination thereof.
  • the remaining liquid which produces hydrogen is separated to obtain dimethylcarbamic acid.
  • the hydrogen production reaction of the hydrogen production system of the present disclosure is as shown in the formula (1):
  • Catalytic hydrogen production system has high hydrogen production efficiency and high stability of the system
  • the remaining liquid product for hydrogen production is dimethyl carbamic acid, which is a commonly used ionic solvent and chemical industrial intermediate with high added value.
  • FIG. 1 Schematic diagram of the apparatus for producing hydrogen in the present disclosure
  • the apparatus of the present disclosure may be as follows: a high pressure reactor 1 is connected to the top of the reactor through a flange fixing bolt 3 , and a pressure sensor 4 and a temperature sensor 5 are disposed on the reaction kettle cover.
  • the hydrogen production pipe 12, the water supply pipe 10, the DMF pipe 11 are added, and the motor 9 is arranged at the bottom of the reactor, and the stirring paddle 8 inside the reaction vessel is connected, and an electric heater is also arranged inside the reactor. Since DMF and water are both stable solvents without corrosion, and the reaction temperature is moderate. Therefore, the required high pressure reactor is made of stainless steel.
  • the first two hours of reaction time is the in situ generation of Cu/Cu 2 O nanocatalyst induced formation process, including the formation of two components.
  • the reaction equation is as shown in the formulas (2) to (5).
  • Example 1 The experiment of Example 1 was repeated, and the reaction temperature was changed for comparison. The result is shown in FIG.
  • the temperature not only affects the time of Cu/Cu 2 O formation, but also affects the rate of hydrogen generation.
  • the temperature was increased from 100 ° C to 140 ° C, the formation time of the Cu/Cu 2 O nanocatalyst was shortened from 6 h to 2 h, and finally only 0.5 h was required.
  • the rate of hydrogen production increases with increasing temperature.
  • Hydrogen production rate is 0.033 Mol Cu -1 h -1 , 0.38 Mol Cu -1 h -1 and 0.51 Mol Cu -1 h -1 corresponds to a reaction temperature of 100 ° C, 120 ° C and 140 ° C, respectively.
  • Example 1 The experiment of Example 1 was repeated to change the amount of water in the reaction system, and the results are shown in Fig. 7.
  • Example 1 The experiment of Example 1 was repeated to change the kind of the copper-based catalyst, and the results are shown in Fig. 8.
  • Example 1 The experiment of Example 1 was repeated to change the kind of the zinc-based catalyst, and the results are shown in Fig. 9.
  • different zinc-based catalysts can also function similarly to hydrogen production. Similar to copper-based catalysts, after a certain period of activation, they can also successfully catalyze the production of hydrogen.
  • Example 1 The experiment of Example 1 was repeated, and the catalytic stability was evaluated. The results are shown in Fig. 10.
  • the catalytic hydrogen production system of the CuCl precursor has good catalytic stability.
  • This catalytic system can be catalyzed for at least 17 days under the reaction conditions of 120 °C. And the average hydrogen production rate of this is 3.85.
  • the TON value based on each exposed Cu catalytic center can reach 87,725.

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Abstract

一种基于甲酰胺及其衍生物和水的储氢材料的催化产氢体系以及使用该产氢体系产氢的方法。催化产氢体系包括甲酰胺及其衍生物，水和催化剂。该催化产氢体系产氢效率高，体系的稳定性高，在120℃可以至少稳定的产氢17天，平均产氢速率可达到3.85molH2 molCu -1d-1，最高产氢可达到0.38molH2 molCu -1h-1，且体系组成成分廉价易得。

Description

基于甲酰胺及其衍生物和水的产氢体系及制氢方法 技术领域
本公开涉及一种产氢体系及利用该体系制备氢气的方法，尤其是涉及一种甲酰胺及其衍生物和水的产氢体系，以及利用该产氢体系制备氢气的方法。
背景技术
氢气被认为是未来最有优势和希望的绿色能源。水作为氢气的理想来源，大量基于电催化和光催化的产氢体系已经被人们研究并发明出来。但是，这种催化体系存在耗能大，效率低等问题。随着研究的深入，其他的液体储氢材料(甲醇，乙醇，异丙醇，甲醛和甲酸)被人们关注。但是，对于这些液体储氢材料存在易燃、易爆、有毒等隐患。因此，这些隐患同样限制着这些体系的实际应用。另外，现在高压液化运输氢气的方式，同样存在着大量的安全隐患。
甲酰胺及其衍生物属于脂肪族酰胺中的单酰胺类，通常用于工业用途，如医药合成、染料合成、用于溶剂等，目前尚未有报道将其用于储氢、制氢的用途。
发明内容
本公开要解决的技术问题是提供一种基于甲酰胺及其衍生物和水的储氢材料的催化产氢体系，实现高效、稳定和安全的产氢。该催化产氢体系产氢效率高，体系的稳定性高，在120℃可以至少稳定的产氢17天，平均产氢速率可达到3.85
Figure PCTCN2016101619-appb-000001
molCu -1d-1，最高产氢可达到0.38
Figure PCTCN2016101619-appb-000002
molCu -1h-1，体系组成成分廉价易得。
为解决上述技术问题，本公开的催化产氢体系，包括：
甲酰胺及其衍生物，水，催化剂。
优选的，甲酰胺及其衍生物选自N，N-二乙基甲酰胺，N-乙基甲酰胺、N-甲基甲酰胺和甲酰胺中的任一种或其任意组合；
优选的，催化剂选自铜基或者锌基的催化材料；
进一步优选的，催化剂选自铜盐、氧化铜、锌盐、氧化锌中的任一种或其任 意组合；
更优选的，铜盐选自CuCl、CuCl2、Cu(NO3)2，Cu(CH3COO)2和CuI中的一种或其任意组合，锌盐选自ZnSO4、ZnCl、Zn(CH3COO)或Zn(NO3)2中的一种或其任意组合。
本公开的甲酰胺及其衍生物和催化剂均可以使用工业级产品，水可以使用蒸馏水。
本公开的催化产氢体系中，各组分的用量为：
以甲酰胺及其衍生物为基础，水的用量为0-20(体积)％，催化剂用量为0-1mmol/mL。
优选的，各组分用量为：以甲酰胺为基础，水的用量为0-10(体积)％，催化剂用量为0-0.15mmol/mL。
进一步优选的，各组分用量为：以甲酰胺及其衍生物为基础，水的用量为7.5(体积)％，催化剂用量为0.075mmol/mL。
本公开还提供一种基于甲酰胺及其衍生物和水的储氢材料的催化产氢体系产氢的方法，包括如下步骤：
在高压反应釜中加入甲酰胺及其衍生物，将适量催化剂加入甲酰胺及其衍生物中，然后再加入适量的水，密闭通入氩气保护，搅拌均匀，将高压反应釜加热至80-180℃，即可产生氢气。
氢气的产量可通过每30min采集高压反应釜内气体，测试氢气的含量。
优选的，将高压反应釜加热至100-140℃
更优选的，将高压反应釜加热到120℃。
优选的，甲酰胺及其衍生物选自N，N-二乙基甲酰胺，N-乙基甲酰胺、N-甲基甲酰胺和甲酰胺中的任一种或其任意组合。
进一步优选的，催化剂选自铜盐、氧化铜、锌盐、氧化锌中的任一种或其任意组合。
更进一步优选的，对产氢剩余的液体进行分离，得到二甲氨基甲酸。
本公开的产氢体系的产氢反应如式(1)所示：
Figure PCTCN2016101619-appb-000003
本公开的有益效果为：
(1)催化产氢体系产氢效率高，体系的稳定性高；
(2)高纯氢气可以直接用于燃料电池、加氢反应和燃烧。因此，这一产氢体系在将来可以用于工业园直接供应氢气，避免了现在高压运输氢气的危险；
(3)产氢剩余的液体产品为二甲氨基甲酸，这是一种常用的离子溶剂和化工的工业中间体，附加值高。
附图说明
图1、本公开的产氢体系装置示意图；
图2、CuCl催化的产氢速率随时间变化曲线；
图3、Cu/Cu2O催化剂形成过程表征；
图4、Cu/Cu2O催化剂高分辨透射电镜照片；
图5、产生氢气的高分辨质谱分析结果；
图6、不同温度下的产生氢气量随时间的变化曲线；
图7、不同水的浓度下的产生氢气量随时间的变化曲线；
图8、不同的铜盐催化产生氢气量随时间的变化曲线；
图9、不同的锌盐催化产生氢气量随时间的变化曲线
图10、产氢系统的催化稳定性测试结果。
具体实施方式
本公开的产氢体系最主要的工业应用优势就是设备简单。如图1所示，本公开的设备可以是如下简单实现方式：包括高压反应釜1，反应釜顶部通过法兰固定螺栓3连接反应釜盖，反应釜盖上设有压力传感器4、温度传感器5、氢气采出管道12、加水管道10、加DMF管道11，反应釜底部设有电机9，连接反应釜内部的搅拌桨8，反应釜内部还设有电加热器。由于DMF和水都是无腐蚀的稳定的溶剂，并且反应温度也适中。因此，所要求的高压反应釜的材质为不锈钢材质即可。
实施例1
0.3mmol的CuCl催化剂加入4mL DMF中，然后再加入300μL的水，密闭通入氩气保护，搅拌均匀。将高压反应釜加热至120℃，每30min采集高压反应釜内气体测试氢气的含量。
如图2所示，在120℃的反应温度下，催化体系前1.5h几乎没有氢气产生。之后的0.5h反应，氢气的产生速率可以达到0.013molH2 molCu -1h-1。当反应2小时后，氢气的产生速率可以稳定在0.38molH2 molCu -1h-1。与此同时，不加水、CuCl催化剂或者DMF，产氢的速率几乎不会发生。
前两小时的反应时间是原位产生Cu/Cu2O纳米催化剂诱导形成过程，包括两个组分的形成。反应方程式如式(2)至式(5)所示。
1.形成Cu2O粒子：
4CuCl+4H2O+O2→2Cu2Cl(OH)3+2HCl   式(2)
Figure PCTCN2016101619-appb-000004
2CuCl+H2O→Cu2O+2HCl   式(3)
2.形成Cu纳米粒子
Figure PCTCN2016101619-appb-000005
Figure PCTCN2016101619-appb-000006
商业化的CuCl粉末是平均粒径大于500nm的无规则颗粒。当反应0.5h后，所得到的催化剂的平均粒径明显减小。最后，经过两个小时的反应过程形成了均匀的平均粒径为61.9±10.7nm的Cu/Cu2O纳米催化剂。如图3所示，XRD谱图可以明显的反应这一变化过程。同时，不断明显而且变窄的UV-Vis吸收光谱也能够反应均匀的Cu2O纳米粒子的形成。
从图4的高分辨TEM照片上，可以看到Cu纳米粒子均匀的分布在Cu2O颗粒表面。这一结论可以从它们清晰的晶格条纹得出。0.178nm的晶格条纹间距对 应于Cu纳米粒子的(200)晶面，而0.238nm的晶格条纹间距对应于Cu2O的(111)晶面。
对产生的氢气进行高分辨质谱分析，参见图5所示。
基于前面的分析，发明人得出本公开的催化产氢的可能的反应机理如下式(6)所示：
Figure PCTCN2016101619-appb-000007
实施例2
重复实施例1的实验，改变反应温度进行比较，结果如图6所示
如图6所示，温度不但影响Cu/Cu2O形成的时间，同时还影响氢气的产生速度。随着温度从100℃增加到140℃，Cu/Cu2O纳米催化剂形成的时间从6h缩短至2h，最后只需要0.5h。同时，氢气的产生速率随着温度的升高而不断加快。氢气的产生速率为0.033
Figure PCTCN2016101619-appb-000008
molCu -1h-1，0.38
Figure PCTCN2016101619-appb-000009
molCu -1h-1和0.51
Figure PCTCN2016101619-appb-000010
molCu -1h-1分别对应于100℃，120℃和140℃的反应温度。
实施例3
重复实施例1的实验，改变反应体系中水的用量，结果如图7所示。
其中，水在这个反应体系中起到重要的作用；
一，它是形成Cu/Cu2O催化剂的重要反应物。从上述的反应方程式可以看出，CuCl必须在水存在的条件进行；
二，水会影响催化产氢的速率。如图7所示，当水的浓度从0.025mL/mL增加到0.075mL/mL时，产氢的速率从0.17
Figure PCTCN2016101619-appb-000011
molCu -1h-1增加到0.38
Figure PCTCN2016101619-appb-000012
molCu -1h-1。继续增加水的浓度至0.10mL/mL，产氢的速率降低至0.14
Figure PCTCN2016101619-appb-000013
molCu -1h-1。很明显，最佳的水的浓度为0.075mL/mL。但是实验表明，水的浓度 在0-10mL/mL的范围内都可以产生氢气；
三，水为产生的氢气提高一个氢源。这一结果可以从高分辨质朴分析结果表明。如图七所示，对于普通的水产生的氢气，它们的分子量可以看出是2g/mol。但是当用重水替换普通的水源后，产生氢气的分子量为3g/mol。这就说明，产生的氢气中的一个氢原子为来源于氘水中的氘氢。因此，很明显水参与到产生反应中，并且提供一个氢原子。而另一个氢原子则来源于DMF分子。
实施例4
重复实施例1的实验，改变铜基催化剂的种类，结果如图8所示。
由图8可看出，不同的铜基催化剂(CuCl、CuCl2、Cu(NO3)2，Cu(CH3COO)2、CuI和CuO)都可以催化这一产氢反应。尽管不同的铜盐催化产氢的速率不同，但它们在经历一段诱导反应后，都可以成功的催化产生氢气。
实施例5
重复实施例1的实验，改变锌基催化剂的种类，结果如图9所示。
由图9可看出，不同的锌基催化剂(ZnO、ZnSO4、ZnCl、Zn(CH3COO)和Zn(NO3)2)同样也可以起到类似的催化产氢的作用。与铜基催化剂类似经过一定时间的活化过程后，它们同样可以成功的催化产生氢气。
实施例6
重复实施例1的实验，对催化稳定性进行评价，结果如图10所示。
由图10可看出，CuCl前驱体的催化产氢体系具有很好的催化稳定性。这一催化体系可以在120℃的反应条件下，至少稳定的催化17天。而这其中的平均产氢速率为3.85
Figure PCTCN2016101619-appb-000014
molCu -1d-1。而基于每一个暴露的Cu催化中心的TON值可以达到87725。
以上显示和描述了本公开的基本原理、主要特征和本公开的优点。本行业的技术人员应该了解，本公开不受上述实施例的限制，上述实施例和说明书中描述的只是说明本公开的原理，在不脱离本公开精神和范围的前提下本公开还会有各种变化和改进，这些变化和改进都落入要求保护的本公开范围内。

Claims (12)

  1. 一种催化产氢体系，包括：
    甲酰胺及其衍生物，水，催化剂。
  2. 根据权利要求1所述的产氢体系，其特征在于，优选的，所述的甲酰胺及其衍生物选自N，N-二乙基甲酰胺，N-乙基甲酰胺、N-甲基甲酰胺和甲酰胺中的任一种或其任意组合。
  3. 根据权利要求1或2所述的产氢体系，其特征在于，所述的催化剂选自铜基或者锌基的催化材料或其组合。
  4. 根据权利要求1或2所述的产氢体系，其特征在于，所述的催化剂选自铜盐、氧化铜、锌盐、氧化锌中的任一种或其任意组合。
  5. 根据权利要求4所述的产氢体系，其特征在于，所述的铜盐选自CuCl、CuCl2、Cu(NO3)2，Cu(CH3COO)2和CuI中的一种或几种，所述的锌盐选自ZnSO4、ZnCl、Zn(CH3COO)或Zn(NO3)2中的一种或几种。
  6. 根据权利要求1所述的产氢体系，其特征在于，各组分的用量为：以甲酰胺及其衍生物为基础，水的用量为0-20(体积)％，催化剂用量为0-1mmol/mL。
  7. 根据权利要求6所述的产氢体系，其特征在于，各组分用量为：以甲酰胺为基础，水的用量为0-10(体积)％，催化剂用量为0-0.15mmol/mL。
  8. 一种基于甲酰胺及其衍生物和水的储氢材料的催化产氢体系产氢的方法，包括如下步骤：
    在高压反应釜中加入甲酰胺及其衍生物；
    将适量催化剂加入甲酰胺及其衍生物中；
    然后再加入适量的水，密闭通入氩气保护，搅拌均匀；
    将高压反应釜加热至80-180℃，即可产生氢气。
  9. 根据权利要求8所述的方法，其特征在于，将高压反应釜加热至100-140℃。
  10. 根据权利要求8所述的方法，其特征在于，所述的甲酰胺及其衍生物选自N，N-二乙基甲酰胺，N-乙基甲酰胺、N-甲基甲酰胺和甲酰胺中的任一种或其任意组合。
  11. 根据权利要求8所述的方法，其特征在于，所述的催化剂选自铜盐、氧化铜、锌盐、氧化锌中的任一种或其任意组合。
  12. 根据权利要求8所述的方法，其特征在于，对产氢剩余的液体进行分离，得到二甲氨基甲酸。
PCT/CN2016/101619 2016-10-10 2016-10-10 基于甲酰胺及其衍生物和水的产氢体系及制氢方法 Ceased WO2018068172A1 (zh)

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Publication number Priority date Publication date Assignee Title
CN101074120A (zh) * 2007-05-23 2007-11-21 浙江工业大学 一种新的有机废水处理和资源化技术

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Publication number Priority date Publication date Assignee Title
CN101074120A (zh) * 2007-05-23 2007-11-21 浙江工业大学 一种新的有机废水处理和资源化技术

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