CN114653343A - Anion pillared ultramicropore adsorbent for hydrogen isotope gas separation and preparation method thereof - Google Patents

Anion pillared ultramicropore adsorbent for hydrogen isotope gas separation and preparation method thereof Download PDF

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CN114653343A
CN114653343A CN202210206807.5A CN202210206807A CN114653343A CN 114653343 A CN114653343 A CN 114653343A CN 202210206807 A CN202210206807 A CN 202210206807A CN 114653343 A CN114653343 A CN 114653343A
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褚效中
王心悦
翟海荣
朱立文
宣霆锋
王飞
吴飞跃
程志鹏
朱凤霞
赵宜江
徐继明
景钰晨
贝中军
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Huaiyin Normal University
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Abstract

The invention discloses an anion pillared ultramicropore adsorbent for hydrogen isotope gas separation and a preparation method thereof, wherein an organic ligand bipyridyl alkane or bipyridyl alkene or bipyridyl alkyne, pillared anion ligand hydrocarbyl disulfonate and nitrate are used as raw materials to prepare a novel ultramicropore adsorbent; the specific synthetic process is as follows: dissolving an organic ligand, a pillared anion ligand and nitrate in methanol or N, N' -dimethylformamide according to a certain molar ratio, stirring for reaction, precipitating, filtering, and drying in vacuum to obtain the ultra-microporous adsorbent. The invention uses cheap organic ligand and anion ligand to react with nitrate to prepare novel anion pillared ultramicropore adsorbent, which has easily adjustable pore diameter, higher adsorption selectivity, better separation effect on hydrogen isotope gas and potential application prospect.

Description

用于氢同位素气体分离的阴离子柱撑的超微孔吸附剂及制备 方法Anion-pillared ultra-microporous adsorbent for hydrogen isotope gas separation and preparation method

技术领域technical field

本发明涉及吸附剂及制备方法，具体涉及一种用于氢同位素气体分离的阴离子柱撑的超微孔吸附剂及制备方法。The invention relates to an adsorbent and a preparation method, in particular to an anion-pillared ultra-microporous adsorbent for hydrogen isotope gas separation and a preparation method.

背景技术Background technique

氢同位素气体广泛应用于核工业、能源、材料、医疗、检测等领域，且氘气纯度决定着可控核聚变反应效率和氘代材料性能。然而电解重水制备氘气的过程中产生D2、HD及H2混合气，必须进行分离方可获得高纯D2；此外，D2与T2作为核聚变反应堆的原料，转化率不到10％，而且氚具有放射性，从聚变堆的经济、安全及环保角度考虑，从等离子室排出的未反应D2和T2需分离回用，这是聚变反应堆核燃料循环过程中必须解决的问题。但氢同位素气体分子具有极其相似的尺寸、形状和热力学性质，如何高效分离氢同位素气体已成为分离技术研究中最富有挑战性的课题之一。氢同位素气体分离方法主要有低温精馏法、热扩散法、色谱法、金属氢化物法与吸附法等。在诸多方法中，吸附法因具有选择性高、能耗低、吸附剂易再生的优点而被广泛研究。由于阴离子柱撑的超微孔材料孔径易调，可与氢同位素形成氢键或金属氢键而强化分离过程，所以发明新型阴离子柱撑的超微孔吸附剂用于氢同位素气体高效分离具有重要的科学意义和市场应用前景。Hydrogen isotope gas is widely used in nuclear industry, energy, materials, medical treatment, testing and other fields, and the purity of deuterium gas determines the efficiency of controllable nuclear fusion reaction and the performance of deuterated materials. However, in the process of electrolyzing heavy water to prepare deuterium gas, a mixture of D 2 , HD and H 2 is generated, which must be separated to obtain high-purity D 2 ; in addition, D 2 and T 2 are used as raw materials for nuclear fusion reactors, and the conversion rate is less than 10 %, and tritium is radioactive. From the perspective of economy, safety and environmental protection of fusion reactors, the unreacted D2 and T2 discharged from the plasma chamber need to be separated and reused , which is a problem that must be solved in the nuclear fuel cycle of fusion reactors. However, hydrogen isotope gas molecules have very similar size, shape and thermodynamic properties. How to efficiently separate hydrogen isotope gas has become one of the most challenging topics in separation technology research. Hydrogen isotope gas separation methods mainly include cryogenic distillation, thermal diffusion, chromatography, metal hydride method and adsorption method. Among many methods, adsorption method has been widely studied due to its advantages of high selectivity, low energy consumption, and easy regeneration of the adsorbent. Since the pore size of anion-pillared ultra-microporous materials is easy to adjust and can form hydrogen bonds or metal hydrogen bonds with hydrogen isotopes to enhance the separation process, it is important to invent a new type of anion-pillared ultra-microporous adsorbent for efficient separation of hydrogen isotope gases. Scientific significance and market application prospects.

发明内容SUMMARY OF THE INVENTION

本发明的目的是：提供一种氢同位素气体分离的阴离子柱撑的超微孔吸附剂及制备方法，以有机配体、柱撑阴离子配体和硝酸盐为原料制备超微孔吸附剂，既充分利用廉价的有机配体和阴离子配体，且反应条件温和，该类吸附剂孔径易调，具有较高的吸附选择性，对氢同位素气体具有较好的分离效果，具有潜在的应用前景。The purpose of the present invention is to provide an anion-pillared ultra-microporous adsorbent for hydrogen isotope gas separation and a preparation method, and the ultra-microporous adsorbent is prepared by using organic ligands, pillared anion ligands and nitrates as raw materials, and both The cheap organic ligands and anionic ligands are fully utilized, and the reaction conditions are mild. The pore size of this type of adsorbent is easily adjustable, and it has high adsorption selectivity and good separation effect on hydrogen isotope gases, and has potential application prospects.

本发明的技术解决方案是：用于氢同位素气体分离的阴离子柱撑的超微孔吸附剂，以有机配体、柱撑阴离子配体和硝酸盐为原料制备超微孔吸附剂；其特征是：有机配体为双吡啶基烷烃或双吡啶基烯烃或双吡啶基炔烃，通式为

Figure BDA0003531354170000011
R为不同的烷烃、烯烃或炔烃；柱撑阴离子配体为烃基二磺酸盐，通式为
Figure BDA0003531354170000012
R1为不同的烃基；超微孔吸附剂孔径介于
Figure BDA0003531354170000013
The technical solution of the present invention is: an anion-pillared ultra-microporous adsorbent for hydrogen isotope gas separation, and the ultra-microporous adsorbent is prepared by using organic ligands, pillared anion ligands and nitrates as raw materials; it is characterized by: : The organic ligand is bipyridyl alkane or bipyridyl alkene or bipyridyl alkyne, the general formula is
Figure BDA0003531354170000011
R is a different alkane, alkene or alkyne; the pillared anion ligand is a hydrocarbyl disulfonate, the general formula is
Figure BDA0003531354170000012
R 1 is a different hydrocarbon group; the pore size of the ultra-microporous adsorbent is between
Figure BDA0003531354170000013

其中，有机配体

Figure BDA0003531354170000014
中烷烃R是亚甲基、乙基、丙基或者是相应的烯烃基或炔烃基，柱撑阴离子配体
Figure BDA0003531354170000015
中烃基为亚甲基、乙基、丙基、苯基、乙烯基、乙炔基。Among them, organic ligands
Figure BDA0003531354170000014
In the alkane R is methylene, ethyl, propyl or the corresponding alkene or alkyne group, pillared anionic ligand
Figure BDA0003531354170000015
The middle hydrocarbon group is methylene, ethyl, propyl, phenyl, vinyl and ethynyl.

其中，所述用于氢同位素气体分离的阴离子柱撑的超微孔吸附剂的制备方法，将有机配体、柱撑阴离子配体和硝酸盐以一定的摩尔比溶解在甲醇或者N,N′-二甲基甲酰胺中，搅拌反应，沉化，过滤，真空干燥，得超微孔吸附剂；其特征是：首先，将有机配体

Figure BDA0003531354170000021
和柱撑阴离子配体
Figure BDA0003531354170000022
按照一定摩尔比溶解在甲醇或者N,N′-二甲基甲酰胺溶剂中，得到溶液A；其次，将硝酸盐按照一定摩尔比溶解在甲醇或者N,N′-二甲基甲酰胺溶剂中，得到溶液B；第三，将溶液B在搅拌条件下缓慢滴加到溶液A中，加热反应一定的时间；第四，停止搅拌，沉化，过滤，并将过滤后的产品真空干燥，得超微孔吸附剂。Wherein, in the preparation method of the anion-pillared ultra-microporous adsorbent for hydrogen isotope gas separation, organic ligands, pillared anion ligands and nitrates are dissolved in methanol or N,N' in a certain molar ratio - in dimethylformamide, stirring reaction, precipitation, filtration, and vacuum drying to obtain ultra-microporous adsorbent; it is characterized in that: first, organic ligands are
Figure BDA0003531354170000021
and pillared anionic ligands
Figure BDA0003531354170000022
Dissolve in methanol or N,N'-dimethylformamide solvent according to a certain molar ratio to obtain solution A; secondly, dissolve nitrate in methanol or N,N'-dimethylformamide solvent according to a certain molar ratio , to obtain solution B; thirdly, slowly drop solution B into solution A under stirring conditions, and heat the reaction for a certain period of time; fourthly, stop stirring, settle, filter, and vacuum dry the filtered product to obtain Ultra-microporous adsorbent.

其中，两种配体的摩尔比为0.5-2：1，有机配体

Figure BDA0003531354170000023
与硝酸盐的摩尔比为0.5-3：1，反应温度为20-160℃，反应时间为0.5-48h，搅拌速率为50-200r/min，真空干燥温度为80℃。Among them, the molar ratio of the two ligands is 0.5-2:1, the organic ligand
Figure BDA0003531354170000023
The molar ratio to nitrate is 0.5-3:1, the reaction temperature is 20-160°C, the reaction time is 0.5-48h, the stirring rate is 50-200r/min, and the vacuum drying temperature is 80°C.

更进一步的是，两种配体的最佳摩尔比为1：1，有机配体

Figure BDA0003531354170000024
与硝酸盐的最佳摩尔比为1.5：1，最佳反应温度为80℃，最佳反应时间为8h。Further, the optimal molar ratio of the two ligands is 1:1, the organic ligand
Figure BDA0003531354170000024
The optimum molar ratio with nitrate is 1.5:1, the optimum reaction temperature is 80℃, and the optimum reaction time is 8h.

本发明具有以下优点：The present invention has the following advantages:

1、本方法制备的阴离子柱撑的超微孔吸附剂所用的有机配体和阴离子配体较为廉价，且反应条件温和。1. The organic ligands and anionic ligands used in the anion-pillared ultra-microporous adsorbent prepared by this method are relatively cheap, and the reaction conditions are mild.

2、该类吸附剂孔径易调，可实现

Figure BDA0003531354170000025
步长的精准调节。2. The pore size of this type of adsorbent is easy to adjust and can be realized
Figure BDA0003531354170000025
Precise adjustment of step size.

3、制备的吸附剂孔径可调节到

Figure BDA0003531354170000026
左右，适用于小分子气体混合物的分离。3. The pore size of the prepared adsorbent can be adjusted to
Figure BDA0003531354170000026
It is suitable for the separation of small molecular gas mixtures.

4、该吸附剂对于氢同位素气体具有较高的吸附选择性，对于77K时摩尔比为1:1H2/D2混合气其穿透法分离因子可达4.5，应用前景良好。4. The adsorbent has high adsorption selectivity for hydrogen isotope gas, and the separation factor of the breakthrough method can reach 4.5 for the mixture gas with a molar ratio of 1:1H 2 /D 2 at 77K, and the application prospect is good.

5、该类吸附剂孔径介于

Figure BDA0003531354170000027
用于氢同位素气体吸附分离时，具有较好的分离效果。5. The pore size of this type of adsorbent is between
Figure BDA0003531354170000027
When used for hydrogen isotope gas adsorption separation, it has better separation effect.

附图说明Description of drawings

图1为容积法测定77K下H2和D2的吸附等温线；Fig. 1 is the adsorption isotherm of H 2 and D 2 at 77K determined by volumetric method;

图2为固定床穿透法测定H2/D2混合气穿透曲线；Fig. 2 is the breakthrough curve of H 2 /D 2 mixture gas measured by fixed bed breakthrough method;

具体实施方式Detailed ways

下面通过实施例对本发明进行具体的描述，有必要在此指出的是实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的技术人员可以根据上述内容作出一些非本质的改进和调整。并且实施例中，运用容积法测定77K下H2和D2的吸附等温线，采用穿透法测定H2/D2混合气在固定床中的穿透曲线。The present invention will be specifically described below through the examples. It is necessary to point out that the examples are only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Those skilled in the art can make some based on the above-mentioned contents. Non-essential improvements and adjustments. And in the embodiment, the volumetric method is used to measure the adsorption isotherms of H 2 and D 2 at 77K, and the breakthrough method is used to measure the breakthrough curve of the H 2 /D 2 mixture in the fixed bed.

实施例1：首先，将有机配体双吡啶基甲烷和阴离子配体亚甲基二磺酸钠按照摩尔比为0.5溶解在甲醇中，得到溶液A；其次，将硝酸镍(有机配体与硝酸盐的摩尔比为0.5)溶解在甲醇中，得到溶液B；第三，在搅拌速率为50r/min条件下，将溶液B缓慢滴加到溶液A中，然后将反应体系加热到20℃，反应0.5h；第四，停止搅拌，沉化，洗涤过滤，并将过滤后的产品真空干燥，得到的吸附剂孔径为

Figure BDA0003531354170000028
最后，采用穿透法测定77K时H2/D2混合气(摩尔比为1:1)在固定床中的穿透曲线，其分离因子为4.0。Embodiment 1: First, the organic ligand bispyridylmethane and the anionic ligand sodium methylene disulfonate are dissolved in methanol according to the molar ratio of 0.5 to obtain solution A; secondly, nickel nitrate (organic ligand and nitric acid) The molar ratio of the salt is 0.5) dissolved in methanol to obtain solution B; thirdly, under the condition that the stirring speed is 50r/min, solution B is slowly added dropwise to solution A, and then the reaction system is heated to 20 ℃, the reaction 0.5h; Fourth, stop stirring, settle, wash and filter, and vacuum dry the filtered product, and the obtained adsorbent has a pore size of
Figure BDA0003531354170000028
Finally, the breakthrough curve of the H 2 /D 2 mixture (molar ratio of 1:1) in the fixed bed at 77K was determined by the breakthrough method, and the separation factor was 4.0.

实施例2：首先，将有机配体双吡啶基乙烷和阴离子配体乙基二磺酸钠按照摩尔比为1溶解在N,N′-二甲基甲酰胺中，得到溶液A；其次，将硝酸锌(有机配体与硝酸盐的摩尔比为1.5)溶解在N,N′-二甲基甲酰胺中，得到溶液B；第三，在搅拌速率为100r/min条件下，将溶液B缓慢滴加到溶液A中，然后将反应体系加热到80℃，反应8h；第四，停止搅拌，沉化，洗涤过滤，并将过滤后的产品真空干燥，得到的吸附剂孔径为

Figure BDA0003531354170000031
最后，采用穿透法测定77K时H2/D2混合气(摩尔比为1:1)在固定床中的穿透曲线，其分离因子为4.5。Example 2: First, the organic ligand bispyridyl ethane and the anionic ligand sodium ethyl disulfonate were dissolved in N,N'-dimethylformamide according to a molar ratio of 1 to obtain solution A; secondly, Dissolve zinc nitrate (the molar ratio of organic ligand to nitrate is 1.5) in N,N'-dimethylformamide to obtain solution B; thirdly, under the condition of stirring speed of 100r/min, dissolve solution B Slowly add it dropwise to solution A, then heat the reaction system to 80°C for 8 hours; fourth, stop stirring, settle, wash and filter, and vacuum dry the filtered product, and the obtained adsorbent has a pore size of
Figure BDA0003531354170000031
Finally, the breakthrough curve of the H 2 /D 2 mixture (molar ratio of 1:1) in the fixed bed at 77K was determined by the breakthrough method, and the separation factor was 4.5.

实施例3：首先，将有机配体双吡啶基乙烯和阴离子配体丙基二磺酸钠按照摩尔比为1.3溶解在甲醇中，得到溶液A；其次，将硝酸盐(有机配体与硝酸盐的摩尔比为1.0)溶解在甲醇中，得到溶液B；第三，在搅拌速率为150r/min条件下，将溶液B缓慢滴加到溶液A中，然后将反应体系加热到100℃，反应12h；第四，停止搅拌，沉化，洗涤过滤，并将过滤后的产品真空干燥，得到的吸附剂孔径为

Figure BDA0003531354170000032
最后，采用穿透法测定77K时H2/D2混合气(摩尔比为1:1)在固定床中的穿透曲线，其分离因子为3.2。Example 3: First, the organic ligand bispyridyl ethylene and the anionic ligand sodium propyl disulfonate were dissolved in methanol according to a molar ratio of 1.3 to obtain solution A; The molar ratio of 1.0) was dissolved in methanol to obtain solution B; thirdly, under the condition that the stirring speed was 150r/min, solution B was slowly added dropwise to solution A, and then the reaction system was heated to 100 ° C and reacted for 12 h Fourth, stop stirring, settle, wash and filter, and vacuum-dry the filtered product, and the obtained adsorbent aperture is
Figure BDA0003531354170000032
Finally, the breakthrough curve of the H 2 /D 2 mixture (molar ratio of 1:1) in the fixed bed at 77K was determined by the breakthrough method, and the separation factor was 3.2.

实施例4：首先，将有机配体双吡啶基丙烯和阴离子配体苯基二磺酸钠按照摩尔比为1.8溶解在N,N′-二甲基甲酰胺中，得到溶液A；其次，将硝酸钴(有机配体与硝酸盐的摩尔比为2.2)溶解在N,N′-二甲基甲酰胺中，得到溶液B；第三，在搅拌速率为180r/min条件下，将溶液B缓慢滴加到溶液A中，然后将反应体系加热到120℃，反应24h；第四，停止搅拌，沉化，洗涤过滤，并将过滤后的产品真空干燥，得到的吸附剂孔径为

Figure BDA0003531354170000033
最后，采用穿透法测定77K时H2/D2混合气(摩尔比为1:1)在固定床中的穿透曲线，其分离因子为3.4。Example 4: First, the organic ligand bispyridylpropene and the anionic ligand sodium phenyldisulfonate were dissolved in N,N'-dimethylformamide according to a molar ratio of 1.8 to obtain solution A; secondly, the Cobalt nitrate (molar ratio of organic ligand to nitrate is 2.2) is dissolved in N,N'-dimethylformamide to obtain solution B; Add dropwise to solution A, then heat the reaction system to 120°C for 24 hours; fourth, stop stirring, settle, wash and filter, and vacuum dry the filtered product, and the obtained adsorbent has a pore size of
Figure BDA0003531354170000033
Finally, the breakthrough curve of the H 2 /D 2 mixture (molar ratio of 1:1) in the fixed bed at 77K was determined by the breakthrough method, and the separation factor was 3.4.

实施例5：首先，将有机配体双吡啶基乙炔和阴离子配体乙烯二磺酸钠按照摩尔比为1溶解在甲醇中，得到溶液A；其次，将硝酸铝(有机配体与硝酸盐的摩尔比为2.6)溶解在甲醇中，得到溶液B；第三，在搅拌速率为200r/min条件下，将溶液B缓慢滴加到溶液A中，然后将反应体系加热到140℃，反应36h；第四，停止搅拌，沉化，洗涤过滤，并将过滤后的产品真空干燥，得到的吸附剂孔径为

Figure BDA0003531354170000034
最后，采用穿透法测定77K时H2/D2混合气(摩尔比为1:1)在固定床中的穿透曲线，其分离因子为3.2。Example 5: First, the organic ligand bispyridyl acetylene and the anionic ligand sodium ethylene disulfonate were dissolved in methanol according to the molar ratio of 1 to obtain solution A; The molar ratio of 2.6) was dissolved in methanol to obtain solution B; thirdly, under the condition of stirring speed of 200r/min, solution B was slowly added dropwise to solution A, and then the reaction system was heated to 140 ℃ and reacted for 36h; Fourth, stop stirring, settle, wash and filter, and vacuum-dry the filtered product, and the obtained adsorbent has a pore size of
Figure BDA0003531354170000034
Finally, the breakthrough curve of the H 2 /D 2 mixture (molar ratio of 1:1) in the fixed bed at 77K was determined by the breakthrough method, and the separation factor was 3.2.

实施例6：首先，将有机配体双吡啶基丁烷和阴离子配体乙炔二磺酸钠按照摩尔比为1.5溶解在N,N′-二甲基甲酰胺中，得到溶液A；其次，将硝酸亚铁(有机配体与硝酸盐的摩尔比为3)溶解在N,N′-二甲基甲酰胺中，得到溶液B；第三，在搅拌速率为100r/min条件下，将溶液B缓慢滴加到溶液A中，然后将反应体系加热到160℃，反应48h；第四，停止搅拌，沉化，洗涤过滤，并将过滤后的产品真空干燥，得到的吸附剂孔径为

Figure BDA0003531354170000035
最后，采用穿透法测定77K时H2/D2混合气(摩尔比为1:1)在固定床中的穿透曲线，其分离因子为2.8。Example 6: First, the organic ligand bispyridyl butane and the anionic ligand sodium acetylene disulfonate were dissolved in N,N'-dimethylformamide according to a molar ratio of 1.5 to obtain solution A; secondly, the Ferrous nitrate (the molar ratio of organic ligand to nitrate is 3) is dissolved in N,N'-dimethylformamide to obtain solution B; thirdly, under the condition of stirring speed of 100r/min, solution B is Slowly add it dropwise to solution A, then heat the reaction system to 160°C and react for 48 hours; fourth, stop stirring, settle, wash and filter, and vacuum dry the filtered product. The obtained adsorbent has a pore size of
Figure BDA0003531354170000035
Finally, the breakthrough curve of the H 2 /D 2 mixture (molar ratio of 1:1) in the fixed bed at 77K was determined by the breakthrough method, and the separation factor was 2.8.

Claims (5)

1. An anion pillared ultramicropore adsorbent for hydrogen isotope gas separation is prepared by taking an organic ligand, a pillared anion ligand and nitrate as raw materials; the method is characterized in that: the organic ligand is dipyridyl alkane, dipyridyl alkene or dipyridyl alkyne with the general formula
Figure FDA0003531354160000011
R is different alkane, alkene or alkyne; the pillared anionic ligand is alkyl disulfonate with the general formula
Figure FDA0003531354160000012
R1Are different hydrocarbyl groups; ultra-microporous adsorbent having pore size between
Figure FDA0003531354160000013
2. The anion-pillared ultramicropore adsorbent for hydrogen isotope gas separation according to claim 1, wherein: organic ligands
Figure FDA0003531354160000014
The alkane R is methylene, ethyl, propyl or corresponding alkenyl or alkynyl, and the anion ligand
Figure FDA0003531354160000015
The hydrocarbyl is methylene, ethyl, propyl, phenyl, ethenyl, or ethynyl.
3. Dissolving an organic ligand, a pillared anion ligand and nitrate in methanol or N, N' -dimethylformamide according to a certain molar ratio, stirring for reaction, precipitating, filtering, and drying in vacuum to obtain the ultramicropore adsorbent; the method is characterized in that: first, an organic ligand is added
Figure FDA0003531354160000016
And pillared anionic ligands
Figure FDA0003531354160000017
Dissolving the mixture in a methanol or N, N' -dimethylformamide solvent according to a certain molar ratio to obtain a solution A; secondly, dissolving nitrate in methanol or N, N' -dimethylformamide solvent according to a certain molar ratio to obtain solution B; thirdly, slowly dripping the solution B into the solution A under the condition of stirring, and heating for reacting for a certain time; fourthly, stopping stirring, precipitating, filtering, and drying the filtered product in vacuum to obtain the ultramicropore adsorbent.
4. Isotope of hydrogen for use according to claim 3The preparation method of the anion pillared ultramicropore adsorbent for gas separation is characterized by comprising the following steps: the molar ratio of the two ligands is 0.5-2: 1, organic ligands
Figure FDA0003531354160000018
The molar ratio of the nitrate to the nitrate is 0.5-3: 1, the reaction temperature is 20-160 ℃, the reaction time is 0.5-48h, the stirring speed is 50-200r/min, and the vacuum drying temperature is 80 ℃.
5. The method for producing an anion-pillared ultramicropore adsorbent for hydrogen isotope gas separation according to claim 4, comprising: the optimal molar ratio of the two ligands is 1:1, organic ligands
Figure FDA0003531354160000019
The optimum molar ratio to nitrate was 1.5: 1, the optimal reaction temperature is 80 ℃, and the optimal reaction time is 8 h.
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