CN103796751A - Electronegative-ion-aided method and apparatus for synthesis of ethanol and organic compounds - Google Patents

Abstract

This invention discloses a method and apparatus for reducing carbon dioxide gas to useful products using electronegative ions. In one embodiment, different discharge methods are used to generate non-equilibrium electronegative ions from an electronegative gas, causing carbon dioxide to undergo a reduction reaction to generate organic compounds. When carbon dioxide enters a container containing at least one electronegative gas, such as water, ammonia, bromine, and iodine, a reaction occurs to form organic compounds, for example, ethanol, methanol, and oxalic acid in the case of water, urea in the case of ammonia, and tetraiodomethane in the case of iodine.

Description

Method and equipment for electronegative ion-assisted synthesis of ethanol and organic compounds

Cross References to Related Applications

This application claims priority to US Provisional Application No. 61/575,264 filed on August 19, 2011 and Chinese Patent Application No. 201110268283.4 filed on September 28, 2011, the entire contents of which are incorporated herein by reference.

technical field

The invention discloses a method and equipment for synthesizing ethanol and organic compounds. Under electron discharge conditions such as negative corona, electronegative gases, such as water vapor and carbon dioxide, are used to form ethanol and other organic compounds. In a specific example, electron negative corona discharge forms negatively charged gas ions, such as water vapor anion, carbon dioxide and other anions or active groups, which come from various initial gases, such as OH ^- under high energy conditions. Electronegative gas ions react with electrically neutral gas molecules to form ethanol or other organic compounds. The device of the present invention comprises a reaction container, at least has an electrode and a high voltage power supply for generating negative corona on the top of the electrode. Electronegative gas ions generated in the negative corona region of the container react with nonpolar molecules (eg, electrically neutral molecules) or gas molecules with no electrons attached to form ethanol and other organic compounds.

Background technique

The efficient capture and utilization of carbon dioxide (CO ₂ ) is one of the biggest challenges in the field of energy generation and storage. In order to effectively utilize or reduce _CO2 emissions, it is crucial to find feasible _CO2 utilization technologies from production sources (such as exhaust gases), and therefore many research efforts have been carried out. The exhaust gas is generally a moderate temperature gas having a pressure around atmospheric pressure. Therefore, in order to reduce _CO2 emissions on a large scale, it is particularly important to effectively utilize and reduce _CO2 in waste gas and some large-scale production sources. The main component of greenhouse gases, carbon dioxide, is mainly a product formed after the combustion of fossil fuels and organic compounds, accounting for about two-thirds of greenhouse gases. [1-3]

At present, the international community tends to regard carbon dioxide as a cheap resource material, and use chemical methods to convert it into bulk chemical raw materials, so as to realize the goal of turning waste into treasure. However, carbon dioxide is an extremely stable gas, which is very difficult to handle under normal temperature and pressure conditions. However, the previous method for converting carbon dioxide generally needs to be realized under relatively high temperature and pressure, which increases the processing cost and also has potential safety hazards. Currently, research mainly on the decomposition and recombination of carbon dioxide plasma is in the process of development in order to synthesize useful compounds. [4-6]

At present, electronegative gases have received extensive attention, and the focus of attention is mainly on surface treatment, atmospheric science, environmental research on exhaust gas purification and other related applications. Therefore, in contemporary plasma physics, negative ions play a very important role in many cases, and a lot of research has been done on the basic properties of negative ions. [7-9]

The present invention utilizes a plasma source to obtain electrons to produce electronegative gas ions for converting carbon dioxide into useful chemical substances such as ethanol. In a specific example, a negative corona is formed around the electrodes, generating the desired electrons. Electrodes with high negative potential generate current in one or more electronegative gases (such as water vapor) through the negative corona reaction process, and then form electronegative gases around the electrodes by attaching the gas. The shape of the electrode is needle-shaped or linear, with a pointed point at the top. When the potential gradient at the top of the electrodes develops sufficiently large to emit electrons to the gas, the gas there becomes attached by additional electrons, or negatively ionized, forming electronegative ions. If the charged body has a cusp, the gradient of the gas around that cusp will be much higher than elsewhere. Finally, the generated electronegative ions transfer charge to neighboring regions of lower potential, or recombine to form gas molecules.

For the metals most likely to be used in corona discharge devices, the energy required to remove electrons from the corona electrode surface is approximately 4eV-5eV. Electrodes may consist of nickel, copper, silver, iron, steel, tungsten, carbon, or platinum. The present invention has no specific limitation on the type of electrode material, and any material capable of forming a negative corona to generate electrons with an energy of about 4eV-5eV can be used. Therefore, the discharge electrons with an energy of 4eV-5eV can attach to low-speed electronegative gas molecules with low kinetic energy (about 3/2kT or 0.038eV at 25°C) to transfer energy, thereby forming high-speed negative ions with high kinetic energy. In addition, the potential energy of negative ions may be higher due to the additional charge on the electronegative gas ions. The total internal energy of negative ions may be higher than that of the original molecule, resulting in a strong collision between H ₂ O negative ions and CO ₂ , generating enough energy for the reaction between H ₂ O ^- and CO ₂ to form organic molecules , such as ethanol.

The present invention makes no specific limitation on the type of device. Nonetheless, we believe that gas phase reaction systems use electronegative gases to generate electronegative gas ions by attaching electrons to a negative corona. When additional electrons are attached to gas molecules to form negatively charged groups, due to the generation of corona discharge, charged anions and charged groups with energy of 4eV-5eV are formed on the attached electrons. These higher energy, electronegative gas ions react with lower energy, electrically neutral gas molecules such as CO ₂ to form organic compounds such as ethanol, thereby minimizing their energy.

If electronegative ions cannot be formed by using gas, faster electrons can only collide with molecules with larger masses, thereby transferring the energy of the electrons (such as 4eV to 5eV) to the gas molecules. For the formation of positive ions and electrons, these energies may be much less than the ionization energies of such non-polar molecules (eg 12.6eV (CH ₄ )), lacking sufficient energy to activate the atmospheric environment (atmospheric temperature and pressure ) under the desired reforming reaction (reaction with _CO2 ). Therefore, since non-polar molecules are not charged with negative gas ions, negative ions cannot be formed and energy cannot be efficiently transferred to all molecules, reducing the possibility of activating reactants, resulting in Unable to complete target response.

Therefore, the method of using electronegative gas ions has the following advantages: the energy absorbed by electronegative gas ions comes from negative corona electrons, and the whole process is in a lower temperature and pressure environment, so that high temperature and high pressure conditions can be avoided The following method saves the resulting costs and reduces the difficulty at the same time. In addition, other advantages of the electronegative gas ion method and device adopted in the present invention are also apparent from the description of the related technical field below.

Contents of the invention

One aspect of the invention provides methods for the synthesis of ethanol or the extraction of other organic compounds from _CO ; exposing one or more electronegative gases (such as water vapor, ammonia, bromine, iodine, and carbon dioxide) to a source of electrons to form Electronegative gas ions. The electron source can be a typical plasma source, which produces positive and negative ions. In one specific example, a negative corona is used to create an electronegative gaseous ion source. In this case, one or more electronegative gases are exposed to a negative corona discharge, and electrons attach to the gas molecules to form electronegative gas ions. Electronegative gas ions attached to electrons absorb energy from the electrons and thus have higher energy. Generally, the energy absorbed by an electronegative gas ion from an electron is between 4eV and 5eV. The higher energy, electronegative gas ions react with CO ₂ to form organic compounds such as ethanol, methanol, urea, oxalic acid, and tetraiodomethane. Synthesized organic compounds can be used as fuels or as industrial feedstocks for the preparation of other chemicals.

In another aspect, the methods described herein are practiced using a reaction vessel. The reaction vessel includes a housing containing a plurality of electrodes attached to the sides of the vessel. A high voltage power supply provides a negative charge to the electrodes. Each electrode generates a negative corona, providing additional electrons that can attach to the electronegative gas. Multiple gas inlets are used to charge _CO2 and electronegative gases into the vessel, and exhaust ports are used to move evolved gases out of the reaction vessel. The container may contain one or more magnets as desired to attract the electronegative gas ions and create a region of high concentration of the electronegative gas ions.

The method and device use electronegative gas ions and _CO2 to induce a reaction, reduce _CO2 , and finally synthesize organic compounds. Under normal pressure, without using any catalyst, electronegative gas ions such as water vapor, iodine, bromine or ammonia react with _CO2 to synthesize ethanol, methanol, oxalic acid, tetraiodomethane, urea or other compounds .

Other objects and advantages of the present invention will be described in detail in the following specific embodiments.

Description of drawings

Figure 1 is a schematic diagram of an embodiment of a reaction vessel for generating electronegative gas ions and synthesizing organic compounds from _CO .

Figure 2 shows a flow diagram of an embodiment of a facility for producing ethanol from _CO2 and _H2O .

specific implementation plan

The term "electronegative gas" as used in the description and claims herein refers to a gas whose atoms and molecules can form negative ions through the attachment of additional electrons. All other technical and scientific terms used herein have the same meanings as commonly understood by those of ordinary skill in the art.

In an embodiment of the method of the present invention, the reaction vessel employed comprises at least one electrode capable of forming a plasma or a negative corona. The plasma or negative corona must be of high enough energy to provide electrons that convert _CO2 to the desired organic products. One embodiment of the invention using electrodes to provide a negative corona is described below. It should be noted that the present invention is not limited thereto, and if the electrode can undergo conventional plasma discharge in a sufficiently high energy state and generate electrons, then the electrode can also be used in the present invention.

The electronegative gas and _CO2 are charged into the reaction vessel through one or more gas inlet lines. In the synthesis of organic compounds such as ethanol, water vapor can be used as the electronegative gas. Other organic compounds can be synthesized by filling the reaction vessel with iodine gas, bromine gas, ammonia gas and _CO2 . Batch or continuous modes of operation can be employed, although continuous modes of operation are more suitable for synthesis of larger numbers of products.

Multiple electrodes are placed in the reaction vessel to create a negative corona field around the electrodes. In certain embodiments, the electrodes are linear or needle-shaped elements with a sharp point at the tip of the electrode. The tip may provide a track for a highly negatively charged region immediately adjacent to the tip. Electrodes composed of nickel, copper, silver, iron, steel, tungsten, carbon or platinum or nickel-plated electrodes can be used. The present invention is not limited to a specific type of electrode material, and any material that can form a negative corona to generate electrons with an energy of about 4eV-5eV can be used.

When the electrodes in the container are energized by a high-voltage power supply, a negative corona can be formed at the tip of the electrodes. Electrons with an energy of 4eV to 5eV can be generated in the corona at the tip of the electrode. Electrons attached to electronegative gas molecules (such as water vapor) near the electrodes generate energetic gas ions. The high-energy gas ions collide with other gas molecules in the container and interact to synthesize the various products described below.

The reaction vessel is generally operated at atmospheric pressure or slightly above atmospheric pressure. The reaction vessel should be maintained at a temperature suitable for the reduction of the electronegative gas and product. Generally speaking, the temperature of the container should be between normal temperature and 100°C. For example, when water vapor is used as the electronegative gas, the temperature in the reaction vessel should be as high as 100°C in order to avoid condensation of the water vapor in the vessel on the inner wall of the reaction vessel or other places. Either of the following methods can be used: keep the temperature in the container below 100°C, and prevent the condensation of water vapor by heating the container wall; or inject excess water vapor into the container to maintain sufficient gaseous water vapor. When the generated product is ethanol, the temperature of the container needs to be kept at about 75°C, and for ethanol close to the boiling point, the temperature should be kept at about 78°C.

The reaction vessel should include a magnet mounted within the vessel to attract the electronegative gas ions and create a more dense region of gas ions. This increases the chances that the gas ions will collide with other gas molecules to initiate a reaction. When electronegative gas ions with higher energy and stronger reducing power are generated, these gas ions can undergo a reduction reaction with carbon dioxide to generate desired organic products such as ethanol.

Although the present invention is not limited to a particular reaction mechanism, the inventors believe that electrons and gas ions attach to each other in the corona to generate energy to react the electronegative gas ions with carbon dioxide. As long as the total energy of gas ions obtained from negative corona electron attachment is greater than the Gibbs free energy difference for a given gas reaction, the reduction process can be further promoted to obtain the desired organic product. For example, three moles of water vapor ions are required in the production of ethanol by the following reaction (4). Each water vapor ion gains about 5eV or 482.5 kJ/mole of energy from the attached electrons to drive the reaction process. During the reaction to form ethanol, three moles of water vapor ions can provide 1447.35 kJ/mole of energy, which is higher than the 1306.1 kJ that can be provided by the Gibbs free energy required for the reaction.

The following descriptions illustrate the various ions formed from electrons under corona discharge conditions and the interaction of gas ions with neutral gas molecules in a reaction vessel. Two types of interactions between carbon dioxide and electrons are possible under corona discharge conditions.

co ₂ +e ^- →CO+1/2O ₂ +e ^- (1)

$\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 2</span>}<span\; class="notranslate">\; )</span>$

_CO2 negative ions can react with the neutral gas molecules described below to form organic compounds.

Although water vapor molecules do not have electron affinity due to their closed electron shells, under corona discharge conditions, water vapor has a strong attractive polarization for additional electrons, which can bind additional electrons and release energy. It can be predicted that under negative corona discharge conditions, water vapor can gain extra electrons to form H ₂ O ^- .

According to the process of the present invention, at normal pressure, at 50°C to 150°C, water vapor and _CO2 gas are used to generate ethanol. The ethanol formed contains small amounts of methanol and perhaps traces of oxalic acid as by-products. Carbon dioxide ions may be formed as described above. The formation process of water vapor ions under corona discharge conditions is as follows:

H _z O+e ^- → H ₂ O ^- (3)

Water vapor ions and carbon dioxide ions can react with neutral gas molecules in the reactor to form ethanol. The reaction mechanism for the conversion of _CO2 to ethanol is believed to be as follows:

3H ₂ O ^- +2CO→C ₂ H ₅ OH+20 ₂ +3e ^- (4)

3H ₂ O ^- +2CO ₂ →C ₂ H ₅ OH+3O ₂ +3e ^- (5)

$\mathrm{<span\; class="notranslate">\; 3</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}\mathrm{<span\; class="notranslate">\; o</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; 2</span>}\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; \&Right\; Arrow;</span>{\mathrm{<span\; class="notranslate">\; C</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 5</span>}}\mathrm{<span\; class="notranslate">\; Oh</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; 3</span>}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 6</span>}<span\; class="notranslate">\; )</span>$

Methanol is formed in the reactor as follows:

4H ₂ O ^- +ZCO ₂ →2CH ₃ OH+3O ₂ +4e ^- (7)

2H ₂ O ^- +CO→CH ₃ OH+O ₂ +2e ^- (8)

The formation process of oxalic acid in the reactor is as follows:

$\mathrm{<span\; class="notranslate">\; 6</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}{\mathrm{<span\; class="notranslate">\; o</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; 2</span>}\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; 2</span>}{\mathrm{<span\; class="notranslate">\; C</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 4</span>}}<span\; class="notranslate">\; +</span>\frac{\mathrm{<span\; class="notranslate">\; 1</span>}}{\mathrm{<span\; class="notranslate">\; 2</span>}}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; 6</span>}{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 9</span>}<span\; class="notranslate">\; )</span>$

Ammonia is an electronegative gas that absorbs attached electrons under corona discharge conditions through the following reactions:

$\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 3</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 3</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 10</span>}<span\; class="notranslate">\; )</span>$

${\mathrm{<span\; class="notranslate">\; NH</span>}}_{\mathrm{<span\; class="notranslate">\; 3</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; h</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 11</span>}<span\; class="notranslate">\; )</span>$

Ammonium ions can react with carbon dioxide or carbon monoxide in the reactor to form urea as follows:

$\mathrm{<span\; class="notranslate">\; 2</span>}\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 3</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}\mathrm{<span\; class="notranslate">\; COON</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 4</span>}}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; 2</span>}{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 12</span>}<span\; class="notranslate">\; )</span>$

$\mathrm{<span\; class="notranslate">\; 2</span>}\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 3</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}\mathrm{<span\; class="notranslate">\; COON</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 4</span>}}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; 2</span>}{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 13</span>}<span\; class="notranslate">\; )</span>$

$\mathrm{<span\; class="notranslate">\; 2</span>}\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; CO</span>}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; CO</span>}{<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; )</span>}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; 2</span>}{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 14</span>}<span\; class="notranslate">\; )</span>$

$\mathrm{<span\; class="notranslate">\; 2</span>}\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; CO</span>}{<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; )</span>}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>\frac{\mathrm{<span\; class="notranslate">\; 1</span>}}{\mathrm{<span\; class="notranslate">\; 2</span>}}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; 2</span>}{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 15</span>}<span\; class="notranslate">\; )</span>$

$\mathrm{<span\; class="notranslate">\; 2</span>}\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; CO</span>}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; CO</span>}{<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; N</span>}{\mathrm{<span\; class="notranslate">\; h</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; )</span>}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; 2</span>}{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 16</span>}<span\; class="notranslate">\; )</span>$

Iodine is also an electronegative gas, which can form negative ions under corona discharge conditions. When the temperature is 70°C, tetraiodomethane can be successfully synthesized in carbon dioxide, and the conversion rate is as high as 88%. The steps are as follows:

$\mathrm{<span\; class="notranslate">\; 2</span>}{\mathrm{<span\; class="notranslate">\; I</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; I</span>}}_{\mathrm{<span\; class="notranslate">\; 4</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; 2</span>}{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 17</span>}<span\; class="notranslate">\; )</span>$

$\mathrm{<span\; class="notranslate">\; 2</span>}{\mathrm{<span\; class="notranslate">\; I</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; I</span>}}_{\mathrm{<span\; class="notranslate">\; 4</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 18</span>}<span\; class="notranslate">\; )</span>$

$\mathrm{<span\; class="notranslate">\; 2</span>}{\mathrm{<span\; class="notranslate">\; I</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; CO</span>}<span\; class="notranslate">\; \&Right\; Arrow;</span>\mathrm{<span\; class="notranslate">\; C</span>}{\mathrm{<span\; class="notranslate">\; I</span>}}_{\mathrm{<span\; class="notranslate">\; 4</span>}}<span\; class="notranslate">\; +</span>\frac{\mathrm{<span\; class="notranslate">\; 1</span>}}{\mathrm{<span\; class="notranslate">\; 2</span>}}{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; e</span>}}^{<span\; class="notranslate">\; -</span>}<span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; -</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 19</span>}<span\; class="notranslate">\; )</span>$

Depending on the desired reaction product, other electronegative gases, such as chlorine or bromine, can also be used in carrying out the method provided by the present invention.

Other sources of electrons with sufficient energy to convert _CO2 to organic products can also be used in the method of the invention. Electronegative gas ions can also be generated by other nonthermal or thermal plasma techniques or ion sources of negative ions, including high frequency methods such as radio frequency plasma (RF), microwave plasma, inductively coupled plasma (ICP), and high voltage Methods such as Dielectric Barrier Discharge (DBD) and Electron Beam (EB). Any method that can generate electronegative gas ions with sufficient energy to react with _CO2 can be used in the method of the present invention.

A schematic diagram of an embodiment of a reactor for synthesizing ethanol or other organic molecules is shown in FIG. 1 . The reactor 100 includes a shell 111 which can be made of steel, stainless steel or any other suitable material. Since the reaction is carried out at or very near atmospheric pressure, the shell thickness can be as low as 1/4 inch.

A liner 117 may be built into the shell to reduce the possibility of electric shock to the reactor shell. Liner 117 can be nickel, or other suitable materials. If necessary, insulating material can be added between the inner and outer shells, or an appropriate device can be used to heat the inner shell to reduce the condensation of water vapor or reaction products. The heating device can be a steam jacket electric heating element.

A plurality of electrodes 116 are attached to the inner wall of the reactor. The electrodes can be needle or wire electrodes with pointed ends; the electrode material can be nickel, copper, silver, iron, steel, tungsten, carbon or platinum, or any electrode that can be used to generate a negative corona near the electrode to generate a Other suitable materials for electrons with 4eV-5eV energy; the electrodes can be coated with metal catalysts, and the available noble metal catalysts are: nickel, rhodium, cobalt, phosphorus, cesium and platinum. Any noble metal catalyst capable of generating electrons with energies of about 4 eV to 5 eV can be used.

A negative high voltage power supply (not shown) is connected to the plurality of electrodes 116 . In an embodiment, the negative high voltage power supply provides a voltage of at least 1 kilovolt. The voltage (strength) should be selected such that the electronegative gas delivered to the reactor is highly ionized within the reaction chamber 118 .

During operation, when the electrode 116 is energized by a negative high voltage power supply, a negative corona is formed at the tip of the electrode, which in turn forms a negative corona field. An electronegative gas, such as water vapor, is delivered to the reactor through gas inlet 113 . Water vapor enters the reaction chamber and is exposed to the negative corona field generated by the electrode tips. Charged electrons in the corona attach to water molecules, forming electronegative water ions.

Carbon dioxide is delivered to the reactor through the gas inlet 113, and some carbon dioxide molecules can absorb charged electrons in the corona field, thereby forming negatively charged carbon dioxide molecules. The charged water vapor/carbon dioxide ions react with neutral water vapor/carbon dioxide molecules to form ethanol. When the temperature of the vessel is kept above 78°C, the ethanol vapor, together with the reaction by-products, part of the water vapor and CO ₂ , is exhausted through the exhaust port 110 . If the reaction product is in liquid form, an exhaust pipe can be added at the bottom of the reactor to collect the reaction product.

In an embodiment, cartridge 112 is used in a reactor containing magnetic rods or beads. The barrel 112 can be made of metal mesh, such as nickel mesh, nickel sponge, platinum mesh or graphene, so as to absorb the magnetic rods or beads inside. The magnetic rods or beads generate a magnetic field around the cylinder 112, attracting negatively charged water vapor ions and carbon dioxide ions to form a dense ion body. The cylinder 112 can be supported by the support tube 115 in the container. A flow diagram of an exemplary ethanol production facility is shown in FIG. 2 . A steam generator 210 delivers steam to a reactor 212 through a first gas inlet 214 . A carbon dioxide source 216 delivers carbon dioxide to the reactor 212 through a second gas inlet 218 . When a liquid or solid carbon dioxide gas source is used as the gas source, a control switching device shall be used.

The water vapor is ionized in the reactor and simultaneously reacts with the _CO2 to form ethanol as described above. The ethanol product, together with water vapor, methanol, oxalic acid and other by-products, is discharged from the reactor through the exhaust port 220, and then transported to the condenser 222, condensed into a liquid, and then transported from the condenser 222 to the distillation unit 224 for the separation of ethanol with purification. The ethanol content of the reaction product from the distillation unit can be as high as 95%.

If desired, the reaction product from the distillation unit may be sent to ultrafiltration unit 226 to form the final ethanol product.

Given that the methods described herein are understood by those of ordinary skill in the art, the above-described and other embodiments of the present invention are subject to alteration and modification without exceeding the scope of the appended claims. Therefore, the detailed description of the preferred embodiments should be considered illustrative, not restrictive.

references

All publications and patents mentioned herein, including items listed below, are herein incorporated by reference in their entirety as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference herein. In case of conflict, the present patent application, including all definitions herein, will control.

[1] O'Neill BC., Dalton M., Fuchs R., et al. (2010) Proceedings of the National Academy of Sciences [C]. 107 (41): 17521-17526

[2] Halmann M.M., Steinberg M.(1999) Greenhouse Gas Carbon Dioxide Mitigation[J]. CRC, Press: Boca Raton.

[3]Barzagli F.,Mani F.,Peruzzini M.,(2011)From greenhouse gas to feedstock:formation of ammonium carbamate from CO2and NH3in organic solvents and its catalytic conversion into urea under mild conditions[J].Green Chem.,13 (5):1267-1274.

[4] Pietruszka B., Heintze M., (2004) Methane conversion at low temperature: the combined application of catalysis and non-equilibrium plasma [J]. Catalysis Today, 90 (1-2): 151-158.

Spencer L.F., Gallimore A.D., (2010) Efficiency of CO2Dissociation in a Radio-Frequency Discharge[J].Plasma Chem.Plasma Process,31(1):79-89

[5] Liu C.J., Mallinson R., Lobban L., (1999) Comparative investigations on plasmacatalytic methane conversion to higher hydrocarbons over zeolites[J].Applied Catalysis A:General.178(1):17-27.

[6] Christophorou L.G., (1984) Electron-Molecule Interactions and their Applications [J]. New York: Academic

[7] Stoffels, E, Stoffels, W W and Kroesen, G M W, et al. (2001) Plasma chemistry and surface processes of negative ions [J]. Plasma Sources Sci. Technol. 11 (4): 311-317.

[8]Zhukhovitskii D.I., Schmidt W.F, Illenberger E.,(2003)Stability of negativeions near the surface of a solid[J].Journal of Experimental and Theoretical Physics,97(3):606-614

[9] Chen J., Davidson J.H., (2003) Model of the Negative DC Corona Plasma: Comparison to the Positive DC Corona Plasma[J]. Plasma Chemistry and Plasma Processing, 23(1):83-102.

[10]Rienstra-Kiracofe J.C., Tschumper G.S., Schaefer III H.F., et al. (2002) Atomic and molecular electron affinities: photoelectron experiments and theoreticalcomputations[J], Chem.Rev.102:231-282.

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Claims (18)

1. a method that is organic compound by carbon dioxide conversion, said method comprising the steps of:

In the container with at least one electrode, mix at least one electronegative gas and carbon dioxide;

Described at least one electrode is applied to negative voltage, thereby produce negative corona discharge with the tip at described electrode, thereby generate electronegativity ion, it is organic compound that the energy of described electronegativity ion is enough to described carbon dioxide conversion.

2. method according to claim 1, wherein, the group that described electronegative gas selects free steam, ammonia, iodine gas, bromine gas, chlorine and constitutes.

3. method according to claim 1, wherein, described electronegative gas is steam, and described organic compound is ethanol.

4. method according to claim 1, wherein, described electronegative gas is ammonia, and described organic compound is urea.

5. method according to claim 1, wherein, described electronegative gas is iodine gas, described organic compound is tetraiodo methane.

6. an equipment that is organic compound by carbon dioxide conversion, described equipment comprises:

Inner casing, described inner casing is defined as reaction vessel in shell;

At least one electrode, described electrode is fixedly connected on described shell, and the tip of described electrode is stretched in described reaction vessel;

At least one air supply pipe, described air supply pipe provides unstripped gas to described reaction vessel; And

Efferent duct, product is shifted out described reaction vessel by described efferent duct.

7. equipment according to claim 6, described equipment also comprises multiple electrodes, described electrode is fixedly connected on described shell, and stretches in described reaction vessel.

8. equipment according to claim 7, wherein, described electrode is the shape of pin or line.

9. equipment according to claim 8, wherein, described electrode is made up of metal, and described metal selects the group of free nickel, copper, silver, iron, steel, tungsten or platinum composition.

10. equipment according to claim 8, wherein, described electrode is made up of carbon.

11. equipment according to claim 9, wherein, described electrode is coated with atopic catalysis material.

12. equipment according to claim 11, wherein, described electrode is coated with catalyst, the group that described catalyst selects free nickel, rhodium, cobalt, phosphorus, caesium and platinum to form.

13. equipment according to claim 9, described equipment is also included in the unit that brings out magnetic field in described reaction vessel.

14. equipment according to claim 9, described equipment also comprises the metal column being fixed in described reaction vessel, and wherein, described metal cylinder comprises multiple bar magnets or magnetic bead.

15. equipment according to claim 14, wherein, described metal cylinder is wire netting.

16. equipment according to claim 15, the group that described wire netting selects free nickel screen, is coated with the copper mesh of catalyst, the nickel screen of the nickel screen of sponge nickel parcel and graphite parcel forms.

17. 1 kinds of methods that are organic compound by carbon dioxide conversion, said method comprising the steps of:

In the container with at least one electron source, mix at least one electronegative gas and carbon dioxide, described electron source is used to form anion; And

In described container, produce electron discharge by described electron source, thereby generate electronegativity ion, it is organic compound that the energy of described electronegativity ion is enough to described carbon dioxide conversion.

18. methods according to claim 17, wherein, described electron source selects the group that free radio frequency plasma (RF), microwave plasma, inductively coupled plasma (ICP), dielectric obstacle electric discharge (DBD) and electron beam (EB) form.

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