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# Synthesis of Hydroxylamine, Nitroxyl and Methanol in Water Plasma

Roman M Balabin

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## To cite this version:

Roman M Balabin. Synthesis of Hydroxylamine, Nitroxyl and Methanol in Water Plasma. Engineering school. Syngas Nitrogen Russia and CIS, Research Potential in Gas Chemistry: Challenges and Opportunities, Baltschug Kempinski Hotel, Moscow, Russia. 2025, pp.19. [hal-05083637](https://hal.science/hal-05083637v1)

HAL Id: hal-05083637

https://hal.science/hal-05083637v1

Submitted on 25 May 2025

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# Synthesis of Hydroxylamine, Nitroxyl and Methanol in Water Plasma

Prof. Dr. Roman M. Balabin

School of Pharmacy, Jiangxi University of Chinese Medicine, Nanchang, P. R. China
East China University of Technology (ECUT), Nanchang, P. R. China
# Contents

**Part 1. Birkeland-Eyde**
electric arc process

**Part 2. Nitrogen fixation**
in aqueous plasma

**Part 3. Methanol synthesis**
in aqueous plasma

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# Birkeland-Eyde Process: History

* The **very first** industrial process of fixation of atmospheric nitrogen (1903)

* Oxidation of nitrogen in discharge:

$$N_2 + O_2 \rightleftharpoons 2NO$$

* **Advantages:**

* Available raw material – **air**

* **Disadvantages:**

* Complexity of industrial design (electric arc furnace, 3000 °C)

* Low energy efficiency

* Low conversion: **below 5%**

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# Birkeland-Eyde Process: History

* Used until 1940

* Lost in competition (competitive struggle) with Haber-Bosch process

* Main reason:

* Availability of cheap hydrogen source for nitrogen reduction

* Methane from natural gas

* To illustrate energy costs according to Eyde:

* 600 tons of nitric acid ($HNO_3$) = 312,000 USD

* 10 GWh of electricity required = 400,000 USD

* Based on current US prices

HOW THE NITROGEN PROBLEM HAS BEEN
SOLVED.* †

BY

HENRY JERMAIN MAUDE CREIGHTON,
Department of Chemistry, Swarthmore College.
Member of the Institute.

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# Birkeland-Eyde Process: Nowadays

* Numerous attempts by scientists and engineers to “revive” the process in the 21st century

* Many complicated designs of plasma reactors have been proposed

* Various types of plasma have been tested

* Attempts to add a **catalyst** to the system

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* Research results:

* It is chemically (thermodynamically) impossible to overcome the low conversion, <5%

* Catalysts accelerate both the reaction of formation of nitrogen oxide (NO) and its decomposition into the initial nitrogen and oxygen

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# WDRAC: Water Dimer Radical Cation, $(H_2O)_2^{+·}$

* Complex and unusual geometry of the molecule

* Coexistence of multiple structures of WDRAC

* High chemical activity

* **Selective** production of WDRAC in a water discharge is possible on an industrial scale

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* WDRAC react with organic substances in three different ways:

* as electron acceptors

* as proton donors

* as reagents for the exchange of $OH^-$ fragments

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# Catalyst-free Nitrogen Fixation

* Disproportionation of nitrogen:

* simultaneous oxidation and reduction of atmospheric nitrogen

* The process takes place in aqueous plasma without the use of catalysts

* Main reaction:

$$N_2 + (H_2O)_2^{+\bullet} \rightleftharpoons NH_2OH^{+\bullet} + HNO$$

* The reaction occurs at atmospheric pressure and room temperature

* Two valuable products at once:

* Hydroxylamine, $NH_2OH$

* Nitroxyl, $HNO$

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## Efficient catalyst-free $N_2$ fixation by water radical cations under ambient conditions

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# Sophisticated Chemical Mechanism

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* An unusual reaction mechanism involving electronic excitation (activation) of dinitrogen to its triplet state $N_2^+$:

$$N_2^+ + (H_2O)_2^{+\bullet} \Rightarrow \text{HONH-HNOH}^{+\bullet\bullet}$$

$$\text{HONH-HNOH}^{+\bullet\bullet} \Rightarrow \text{NH}_2\text{OH}^{+\bullet} + \text{HNO}$$
Straightforward Hardware Design

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# Pros and Cons

## Advantages of the method:

* Simplicity of a catalyst-free setup

* Availability of raw materials: **water** and **electricity**

* Does not require methane or hydrogen

* Low sensitivity to impurities

* Able to operate in air

* Valuable products

## Disadvantages:

* Novelty of the approach

* Small scale of the operating reactor

* High voltage: from 3-4 kV

* A need to use nitroxyl *in situ*

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# Approximate Project Economics

* Current 30 W „reactor“:

* At 0.1 MWh consumption = 4 USD

* Hydroxylamine for 150 USD

* Nitroxyl (Angeli salt) for 91,000 USD

* 1 kW laboratory reactor:

* Implementation date: Q4 2025

* Expected **increase in conversion**

* Product: caprolactam ($C_6H_{11}NO$)

* Projected 1 MW installation

* Implementation date: Q3 2027

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Stanford
University

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ETH zürich

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Karolinska
Institutet

PURDUE
UNIVERSITY

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Thermo
SCIENTIFIC

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Behind the Paper

# Vitalizing nitrogen: N2 fixation by water radical cations

Published in Chemistry

Feb 21, 2024

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Konstantin Chingin, Roman M. Balabin & Huanwen Chen

3 contributors

Новости

/ Общество

Образование

Культура

Здравоохранение

Мода

Туризм

Мир домашних животных

# Жигулёвец стал соавтором нового метода связывания азота

22 февраля 2024 09:40

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Открыт новый плазменный метод связывания атмосферного азота водой. Среди авторов – два россиянина, один из которых родился в Жигулёвске.

ПРОБЛЕМЫ И МЕТОДЫ НАУКИ

Как вода связала азот

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Эе | ЛІ | Ее | Мм | Ее | НІ | ТІ | Ы,

НОВОСТИ НАУКИ

# Биодоступный азот можно получить связыванием в водной плазме

18.03.2024 • РОМАН БАЛАБИН • ХИМИЯ • 68 КОММЕНТАРИЕВ

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N+1

15:42 | 27.02.24 | * 5:1

Химия

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Ссылка

# Молекулярный азот прореагировал с водяной плазмой

При этом образовались гидроксиламин и нитроксил

Михаил Бойм
# Methanol Synthesis using WDRAC

* Oxidation of methane with water

* The process takes place in water plasma without the use of catalysts

* The main reaction:

$$CH_4 + (H_2O)_2^{+\bullet} \rightleftharpoons CH_3OH + H_2O + H_2 - \bar{e}$$

* The reaction occurs at atmospheric pressure and room temperature

* Classic products of steam reforming:

* Methanol, $CH_3OH$

* Hydrogen, $H_2$

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Thank You for Your Attention!

感谢您的关注!
References (1)

1. Zhang, X.; Su, R.; Li, J.; Huang, L.; Yang, W.; Chingin, K.; Balabin, R.; Wang, J.; Zhang, X.; Zhu, W.; et al. Efficient Catalyst-Free N₂ Fixation by Water Radical Cations under Ambient Conditions. Nature Communications, 2024, 15, 1535. https://doi.org/10.1038/s41467-024-45832-9

2. Zhang, X.; Hu, P.; Duan, M.; Chingin, K.; Balabin, R.; Zhang, X.; Chen, H. Ambient Catalyst-Free Oxidation Reactions of Aromatic Amines Using Water Radical Cations. Chemical Science, 2024, 15, 16125-16132. https://doi.org/10.1039/d4sc04519j

3. Barylyuk, K. V.; Chingin, K.; Balabin, R. M.; Zenobi, R. Fragmentation of Benzylpyridinium "Thermometer" Ions and Its Effect on the Accuracy of Internal Energy Calibration. Journal of the American Society for Mass Spectrometry, 2010, 21, 172-177. https://doi.org/10.1016/j.jasms.2009.09.023

4. Zhu, L.; Hu, Z.; Gamez, G.; Law, W. S.; Chen, H.; Yang, S.; Chingin, K.; Balabin, R. M.; Wang, R.; Zhang, T.; et al. Simultaneous Sampling of Volatile and Non-Volatile Analytes in Beer for Fast Fingerprinting by Extractive Electrospray Ionization Mass Spectrometry. Analytical and Bioanalytical Chemistry, 2010, 398, 405-413. https://doi.org/10.1007/s00216-010-3945-8

5. Chingin, K.; Frankevich, V.; Balabin, R. M.; Barylyuk, K.; Chen, H.; Wang, R.; Zenobi, R. Direct Access to Isolated Biomolecules under Ambient Conditions. Angewandte Chemie International Edition, 2010, 49, 2358-2361. https://doi.org/10.1002/anie.200906213

6. Chingin, K.; Balabin, R. M.; Frankevich, V.; Barylyuk, K.; Nieckarz, R.; Sagulenko, P.; Zenobi, R. Absorption of the Green Fluorescent Protein Chromophore Anion in the Gas Phase Studied by a Combination of FTICR Mass Spectrometry with Laser-Induced Photodissociation Spectroscopy. International Journal of Mass Spectrometry, 2011, 306, 241-245. https://doi.org/10.1016/j.ijms.2011.01.014

7. Chingin, K.; Balabin, R. M.; Frankevich, V.; Chen, H.; Barylyuk, K.; Nieckarz, R.; Fedorov, A.; Zenobi, R. Optical Properties of Protonated Rhodamine 19 Isomers in Solution and in the Gas Phase. Physical Chemistry Chemical Physics, 2010, 12, 14121. https://doi.org/10.1039/c0cp00482k

8. Chingin, K.; Balabin, R. M.; Barylyuk, K.; Chen, H.; Frankevich, V.; Zenobi, R. Rhodamines in the Gas Phase: Cations, Neutrals, Anions, and Adducts with Metal Cations. Physical Chemistry Chemical Physics, 2010, 12, 11710. https://doi.org/10.1039/c000807a

9. Balabin, R. M.; Smirnov, S. V. Interpolation and Extrapolation Problems of Multivariate Regression in Analytical Chemistry: Benchmarking the Robustness on near-Infrared (NIR) Spectroscopy Data. The Analyst, 2012, 137, 1604. https://doi.org/10.1039/c2an15972d

10. Balabin, R. M. Communications: Is Quantum Chemical Treatment of Biopolymers Accurate? Intramolecular Basis Set Superposition Error (BSSE). The Journal of Chemical Physics, 2010, 132, 231101. https://doi.org/10.1063/1.3442466

11. Balabin, R. M. Intermolecular Dispersion Interactions of Normal Alkanes with Rare Gas Atoms: Van Der Waals Complexes of n-Pentane with Helium, Neon, and Argon. Chemical Physics, 2008, 352, 267-275. https://doi.org/10.1016/j.chemphys.2008.06.015

12. Balabin, R. M. Experimental Thermodynamics of Free Glycine Conformations: The First Raman Experiment after Twenty Years of Calculations. Physical Chemistry Chemical Physics, 2012, 14, 99-103. https://doi.org/10.1039/c1cp20805e

13. Syunyaev, R. Z.; Balabin, R. M. Frequency Dependence of Oil Conductivity at High Pressure. Journal of Dispersion Science and Technology, 2007, 28, 419-424. https://doi.org/10.1080/01932690601107773
References (2)

14. Lu, H.; Zhang, H.; Chingin, K.; Xiong, J.; Fang, X.; Chen, H. Ambient Mass Spectrometry for Food Science and Industry. TrAC Trends in Analytical Chemistry, 2018, 107, 99–115. https://doi.org/10.1016/j.trac.2018.07.017.

15. Zhang, X.; Ren, X.; Chingin, K. Applications of Direct Analysis in Real Time Mass Spectrometry in Food Analysis: A Review. Rapid Communications in Mass Spectrometry, 2021, 35, e9013. https://doi.org/10.1002/rcm.9013.

16. Wei, Y.; Chen, L.; Zhou, W.; Chingin, K.; Ouyang, Y.; Zhu, T.; Wen, H.; Ding, J.; Xu, J.; Chen, H. Tissue Spray Ionization Mass Spectrometry for Rapid Recognition of Human Lung Squamous Cell Carcinoma. Scientific Reports, 2015, 5, 10077. https://doi.org/10.1038/srep10077.

17. Balabin, R. M. Conformational Equilibrium in Alanine: Focal-Point Analysis and Ab Initio Limit. Computational and Theoretical Chemistry, 2011, 965, 15–21. https://doi.org/10.1016/j.comptc.2011.01.008.

18. Syunyaev, R. Z.; Balabin, R. M. Polarization of Fluorescence of Asphaltene Containing Systems. Journal of Dispersion Science and Technology, 2008, 29, 1505–1514. https://doi.org/10.1080/01932690802316868.

19. Balabin, R. M. Enthalpy Difference between Conformations of Normal Alkanes: Effects of Basis Set and Chain Length on Intramolecular Basis Set Superposition Error. Molecular Physics, 2011, 109, 943–953. https://doi.org/10.1080/00268976.2011.558858.

20. Balabin, R. M. Boryl Substitution of Acetaldehyde Makes It an Enol: Inconsistency between Gn/CBS and Ab Initio/DFT Data. The Journal of Physical Chemistry A, 2010, 114, 3698–3702. https://doi.org/10.1021/jp911802v.

21. Schmid, T.; Sebesta, A.; Stadler, J.; Opilik, L.; Balabin, R. M.; Zenobi, R. Tip-Enhanced Raman Spectroscopy and Related Techniques in Studies of Biological Materials. SPIE Proceedings, 2010, 7586, 758603. https://doi.org/10.1117/12.845471.

22. Balabin, R. M.; Safieva, R. Z.; Lomakina, E. I. Universal Technique for Optimization of Neural Network Training Parameters: Gasoline near Infrared Data Example. Neural Computing and Applications, 2008, 18, 557–565. https://doi.org/10.1007/s00521-008-0213-3.

23. Balabin, R. V.; Volkomirskaya, L. B.; Gulevich, O. A.; et al. Georadar Sensing from Terrestrial Surface and Shafts: Approaches to Evaluation of Rock Fracturing. Physics of Wave Phenomena, 2015, 23, 143–153. https://doi.org/10.3103/s1541308x15020107.

24. Likhatsky, V. V.; Balabin, R. M.; Syunyaev, R. Z. Calculation of Dipole Moment of Fractal Asphaltene Cluster. Journal of Dispersion Science and Technology, 2011, 32, 1502–1508. https://doi.org/10.1080/01932691.2010.516129.

25. Balabin, R. M. Dispersed Structure of Ethanol-Gasoline Fuel According to Dynamic Light Scattering Method. Journal of Dispersion Science and Technology, 2008, 29, 457–463. https://doi.org/10.1080/01932690701718925.

26. Barylyuk, K.; Fritsche, L.; Balabin, R. M.; Nieckarz, R.; Zenobi, R. Gas-Phase Basicity of Several Common MALDI Matrices Measured by a Simple Experimental Approach. RSC Advances, 2012, 2, 1962. https://doi.org/10.1039/c1ra01117k.

27. Balabin, R. M. The Keto-Enol Equilibrium in Substituted Acetaldehydes: Focal-Point Analysis and Ab Initio Limit. Molecular Physics, 2011, 109, 2341–2351. https://doi.org/10.1080/00268976.2011.587457.
# Roman Balabin: CV

* Formal: **Roman M. Balabin** (Роман Балабин)

## Education and work:

* IT Lyceum #1533 (UNESCO ASPnet, Moscow)

* Faculty of Chemical Engineering, **Gubkin University**

* Bruker Optics (Bremen, Germany)

* Max Planck Institute for Polymer Research (Germany)

* University of Göttingen (Germany)

* University of Heidelberg (Germany)

* University of Basel (Switzerland)

* ITMO University (Saint Petersburg, Russia)

* **ETH Zurich** (Switzerland)

* **BrainWare Analytics** (BWAN, Switzerland)

* Bond Street Holdings (BSH, Nevis)

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GUBKIN
UNIVERSITY

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BRUKER

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UNIVERSITÄT
GÖTTINGEN

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Universität
Basel

ETH zürich

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# Brief Summary of the Presentation

Among the many alternatives to the classical Haber-Bosch method for fixing atmospheric nitrogen, plasma methods are often singled out as the most promising. This study demonstrates for the first time the possibility of fixing nitrogen with aqueous plasma at room temperature and atmospheric pressure – as well as without a catalyst and toxic chemicals – and obtaining two valuable products: nitroxyl (HNO) and hydroxylamine (NH₂OH).

Calculations show that this unusual reaction is caused by the interaction of electronically excited N₂ with the cation-radical of the water dimer (H₂O)₂⁺. The proposed method provides low cost and high energy efficiency of N₂ fixation. The reaction products are collected in a 76-needle discharge reactor with a product yield of 0.37 µg cm⁻² h⁻¹ for HNO and 1.14 µg cm⁻² h⁻¹ for NH₂OH. The first product, HNO, is an expensive drug in biomedical applications – in particular for the treatment of heart diseases. The estimated cost of HNO produced per a single kWh of electric energy is about 700 thousand Russian rubles. The second product, NH₂OH, is widely used to synthesize polymers – in particular nylon. It can also be used to produce drugs, such as paracetamol.

A similar catalyst-free approach based on a reaction with a water dimer cation radical in aqueous plasma has also been demonstrated for the selective and controlled transformation of methane into methanol without overoxidation at room temperature and atmospheric pressure. At this stage of the project, the product yield is already 3–60 times higher than the yields in atmospheric catalytic methods. At the moment, work is underway in the laboratory of Jiangxi TCM University to create larger reactors designed to bind nitrogen and methane with water on an industrial scale. Scaling up the process looks like a promising project, since the installation has no moving parts at all, and the entire process is carried out at atmospheric pressure. Thus, the installation does not need either special vacuum equipment or metal-intensive high-pressure reactors.