CN111484618A - Method and device for synthesizing organic silicon compound under assistance of low-temperature plasma electric field - Google Patents
Method and device for synthesizing organic silicon compound under assistance of low-temperature plasma electric field Download PDFInfo
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- CN111484618A CN111484618A CN201910082501.1A CN201910082501A CN111484618A CN 111484618 A CN111484618 A CN 111484618A CN 201910082501 A CN201910082501 A CN 201910082501A CN 111484618 A CN111484618 A CN 111484618A
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Abstract
The invention provides a method and a device for synthesizing an organic silicon compound under the assistance of a low-temperature plasma negative corona discharge electric field, in particular to a method and a device for synthesizing an organic silicon compound by processing carbon-containing gas, hydrogen-containing gas and a silicon-containing compound under the assistance of a low-temperature plasma negative corona discharge electric field; the method of the invention uses the electric energy generated by the low-temperature negative corona discharge electric field to convert the carbon-containing gas and the hydrogen-containing gas into gas molecules, atoms, ions and/or free radicals, and organic hydrocarbon molecules, ions and/or free radicals are obtained by reforming and then are contacted with the silicon-containing compound to form the organic silicon compound.
Description
Technical Field
The invention belongs to the technical field of plasma-assisted chemical reaction, and particularly relates to a method and a device for synthesizing an organic silicon compound under the assistance of a low-temperature plasma electric field; the method is realized by utilizing the reduction and reforming reaction of carbon-containing and hydrogen-containing gas and silicon-containing compound under the low-temperature plasma negative corona discharge electric field.
Background
With the development of industries relying on conventional energy, the generation of carbon dioxide by the combustion of fossil fuels has increased day by day, and carbon dioxide has become a major source of risk driving global warming and greenhouse effect. The influence of carbon dioxide generated by the combustion of fossil fuels on global warming has become a topic of great concern internationally. The control and utilization of carbon dioxide emitted by industry are the main means for dealing with greenhouse effect. The efficient and economical utilization of carbon dioxide to reduce the emission of carbon dioxide has become one of the main contents of sustainable development in the future.
Plasmas can be classified into high temperature, thermal and low temperature plasmas. In low temperature plasma, electrons may have kinetic energy above 5eV, and molecules, radicals, atoms, etc. may be in the range from room temperature to several hundred degrees celsius. Electrons with sufficient energy can generate inelastic collision with gas molecules to convert the gas molecules into excited particles, free radicals (or atoms), ions and other active particles, so that reactants are activated, and catalytic reactions which are difficult to perform in mechanics can be performed at a lower temperature.
At present, low-temperature plasma technology has become a leading-edge hot topic in the fields of environmental governance, energy development and the like, and researches on purifying air and converting carbon dioxide gas by using plasma reaction and the like have been widely carried out. The low-temperature plasma treatment technology can enhance the decomposition and conversion of the carbon dioxide, promote the carbon dioxide to be reformed with other gases and converted into a plurality of valuable products, and has obvious economic advantages and good development prospects.
Disclosure of Invention
The invention aims to provide a method and a device for synthesizing an organic silicon compound by low-temperature plasma electric field assistance, in particular to a method and a device for synthesizing an organic silicon compound by low-temperature plasma negative corona discharge electric field assistance treatment of carbon-containing gas, hydrogen-containing gas and a silicon-containing compound; the method of the invention uses the electric energy generated by low-temperature plasma to convert carbon-containing gas and hydrogen-containing gas into gas molecules, atoms, ions and/or free radicals, organic hydrocarbon molecules, ions and/or free radicals are obtained by reforming, and then the organic hydrocarbon molecules, ions and/or free radicals are contacted with silicon-containing compounds to form organic silicon compounds.
Organosilicon compounds are those which contain Si-C bonds and at least one organic radical which is bonded directly to the silicon atom, and those which are bonded to the silicon atom via an organic radical of oxygen, sulfur, nitrogen or the like are also conventionally referred to as organosilicon compounds. Wherein, the polysiloxane (containing-Si-O-Si-) which takes silicon-oxygen bond (-Si-O-) as a framework is a compound with the most number, the deepest research and the most extensive application in the organosilicon compounds, and accounts for more than 90 percent of the total dosage.
At present, organic silicon products are various, the variety brands are more than ten thousand, more than 4000 varieties are commonly used, and the organic silicon products can be roughly divided into three categories of raw materials, intermediates and products. The silicone intermediate generally used means a linear or cyclic siloxane oligomer such as hexamethyldisiloxane (MM), octamethylcyclotetrasiloxane (D4), Dimethylcyclosiloxane Mixture (DMC), etc.
The silicone has excellent properties, and thus the application range is very wide. It is not only used as special material of aviation, top-end technology and military technology departments, but also used in various departments of national economy, and its application range has been expanded to: building, electronics and electrics, textile, automotive, machinery, leather and paper, chemical light industry, metal and paint, medical treatment, and the like. However, the synthetic route of the organic silicon compound in industry is long, the process control of the monomer synthesis section is strict, the organic silicon monomer is generally synthesized by the catalytic reaction of raw materials such as methanol, hydrogen chloride, silicon powder and the like, and the monomer is hydrolyzed to obtain the ring body. The preparation process is complex, the process requirement is high, the production cost is high, and the environment-friendly effect cannot be achieved.
In order to solve the defects in the prior art, the invention provides a method for synthesizing an organic silicon compound under the assistance of a low-temperature plasma negative corona discharge electric field, which comprises the following steps: introducing a carbon-containing gas and a hydrogen-containing gas into a reactor, wherein the reactor is provided with a negative corona discharge electric field and a solution bed for placing a silicon-containing compound, and the negative corona discharge electric field is a direct current negative corona discharge electric field or other electric field sources capable of providing enough energy to oxidize and decompose reaction gas molecules into atoms, ions, free radicals and the like.
The negative corona discharge electric field of the present invention is not particularly limited and any plasma source known in the art may be used in the present invention. Preferably, the direct current negative corona discharge electric field is a high-frequency high-voltage direct current negative corona discharge electric field.
The invention adopts non-thermodynamic equilibrium plasma technology, and gas molecules (carbon-containing gas and hydrogen-containing gas) are excited by receiving electric field energy to form an aggregate consisting of electrons, ions, atoms, free radicals, molecules and the like. In the low-temperature plasma, electrons can have kinetic energy of about 4-6eV, and electrons with enough energy can generate inelastic collision with gas molecules to be converted into active particles such as excited particles, free radicals (or atoms) and ions, so that reactants are activated. Corona discharge can generate plasma under normal pressure discharge by using an asymmetric electrode, dielectric barrier discharge can generate repeated electron collision with a medium in a crack of an insulating medium under normal pressure or even higher than atmospheric pressure, current density is increased, electric field intensity is strengthened, and therefore rapid and effective chemical reaction is caused. The electrons in the plasma generated in the mode are fast in speed, the thermodynamic temperature is high (for example, 11000K), and the gas temperature is close to room temperature, so that a non-equilibrium thermodynamic system is formed, the reaction system is not limited by the law of thermodynamic equilibrium composition, and all reactants are converted into products to the maximum extent. On one hand, electrons emitted by the electrode have high enough energy to excite, dissociate and reform reactant molecules, so that the reactant molecules and ions are fully reacted in a short time and converted into products; on the other hand, the gas of the reaction is kept at low temperature or close to room temperature, so that the low-temperature gas molecules can effectively obtain the thermodynamic energy required by chemical decomposition or synthesis for rapid reaction, thereby reducing the unnecessary energy consumption of high-temperature and high-pressure processing. It should be noted that such an energized reaction system may eliminate or reduce the use of catalyst, as well as make it possible to avoid the use of high temperature, high pressure process equipment.
According to the invention, the carbon-containing gas and the hydrogen-containing gas react in the negative corona discharge electric field to generate hydrocarbon molecules, ions and/or radicals, and the generated hydrocarbon molecules, ions and/or radicals are contacted with the silicon-containing compound to react, so that silicon dioxide in the silicon-containing compound is reformed to prepare the organic silicon compound. Preferably, the organosilicon compound is preferably an organosiloxane compound, especially organosiloxane oligomer C2nH6nOnSinN is an integer, for exampleSuch as n is 4-20,4-18 or 4-16. It will be appreciated by those skilled in the art that the oligomers synthesized in the present invention are mixtures of various polysiloxanes satisfying the above structural formula.
According to the invention, various carbon-containing gases, such as CH, can be used in the negative corona discharge field4、CO2CO and other carbon-containing gases, various hydrogen-containing gases, such as CH, may be used in the negative corona discharge field4、H2O、H2And other hydrogen-containing gases, which are decomposed by a negative corona discharge electric field to produce various active components, such as H, CO2 -、CO-、CH3And CO; molecules, atoms, ions and/or free radicals of the gas generated by the decomposition tend to entrain electron movement in the densely-erupted large population of electrons and rapidly aggregate and collide with the silicon-containing compound to generate relatively stable molecules of the organosilicon compound.
Preferably, CH may be used in a negative corona discharge electric field4、CO2CO and other carbon-containing gases with H2O、H2And other hydrogen-containing gases.
According to the present invention, the source of the carbon-containing gas is not particularly limited, and may be, for example, a gas generated from a combustion device, a carbon source gas containing methane, or a gas generated from a gas generation device, such as natural gas, shale gas, coal bed gas, biogas, water gas, coke oven gas, flue gas, or the like.
According to the invention, the solution of the silicon-containing compound may be a solution of sodium silicate, lithium silicate, silicic acid, silicon chloride or other silicon-containing compounds, such as water glass, which is commonly known as an aqueous solution of a water-soluble silicate, of the formula R2O·mSiO2In the formula, R2O is alkali metal oxide, m is the ratio of the mole number of silicon dioxide and alkali metal oxide; the concentration of silicon in the solution of the silicon-containing compound is not particularly limited, and may be, for example, 0.5 to 30 wt%, for example, 5 to 25 wt%, such as 22 wt%.
In one embodiment of the invention, a carbon-containing gas and a hydrogen-containing gas are passed into the negative corona-containing dischargeIn an electric field reactor, electrons are ejected by a negative corona discharge electric field to provide energy to gas molecules. Electrons are provided in the region of the negative corona discharge field to bombard the gas molecules, thereby decomposing the gas molecules. In particular with CO2As a carbon source, H2Or H2O is used as hydrogen source, corona discharge is carried out on the electrode of the negative corona discharge electric field in the negative corona discharge electric field area, and a large number of negative electrons are released to be adhered to CO2And H2Or H2The gas molecules trap these high energy electrons to form high energy electronegative gas ions, such as H2 -，CO2 -，CO-Or H-Plasma anion, and CH3And H, and the like, the negative ions are forced to be reduced or reformed into short-chain hydrocarbons or radicals, and the generated short-chain hydrocarbons or radicals can further generate CH under the action of an electric field3And H.and the like. The generated radicals may be contacted with a bed of a solution of a silicon-containing compound to react with the silicon-containing compound (e.g., sodium silicate or silica) to produce an organosilicon compound.
As an example, when the temperature in the reaction system is 100-:
(1)CO2+e-＝＝＝＝>CO+1/2O2 -
(2)CO+H2O+e-＝＝＝＝>CO2+H2 -
(3)CO2 -+H2O-＝＝＝＝>CO+H2 -+O2+e-
(4)H2+2e-＝＝＝＝>2H-<＝＝＝＝>H2 -+e-
(5)CO+2H2 -<＝-＝>CH4+1/2O2+2e-
(6)CH4+e-＝＝>CH3·+H·+e-
(7)(n+1)H2 -+nCO＝＝＝＝>CnH(2n+2)+n/2O2+(n+1)e-
when n is 1 in the reaction formula (7), methane is substantially produced, which is the same as in the reaction formula (5). However, in a negative corona field, higher boiling, more stable organics always tend to form and remain as end products. And methane can easily capture electrons and further decompose into CH3And H, or back to CO and H by the reverse reaction of equation (5)2 -Thus, in most cases, methane is only present as an intermediate. In the present invention, the reactor contains a silicon-containing compound, and methane is decomposed to obtain CH3And H, the reaction is easier to generate gas-liquid interface reaction with the liquid-phase silicon-containing compound, and the gas-liquid interface reaction is captured by silicon dioxide in the silicon-containing compound to generate more stable organic siloxane:
(8)Na2O·SiO2+H2O＝＝＝＝>Na2O+SiO2+H2O
(9)nSiO2+2nCH3·+H·＝＝＝＝>C2nH6nOnSin+nH2O
in the above examples, the carbon-containing gas is not limited to carbon dioxide gas, but may be CO-containing gas produced from a combustion apparatus2CO gas or gas generated by a gas generating device, such as flue gas, automobile exhaust gas, biogas, internal combustion engine exhaust gas, refinery exhaust gas, etc.
According to the invention, the carbon-containing gas, the hydrogen-containing gas and the silicon-containing compound are reformed by the negative corona discharge electric field to obtain the mixed gas, the content of each component in the obtained mixed gas is slightly different according to the difference of the used raw material gas, but under the conventional operation condition, the reformed mixed gas can be separated into gas-liquid two phases after being condensed by the condenser. Wherein the gas phase comprises unreacted carbon oxides and hydrocarbons; the liquid phase includes water and silicone molecules.
The invention also provides a device for low-temperature plasma-assisted synthesis of organosilicon compounds, which comprises a reaction chamber having a plasma region with a negative corona discharge electric field, and a solution bed for placing silicon-containing compounds is arranged below the plasma region.
The invention also provides a device for low-temperature plasma-assisted synthesis of organosilicon compounds, which comprises a reaction chamber having a plasma region with a negative corona discharge electric field, and a solution bed for placing silicon-containing compounds is arranged below the plasma region.
According to the invention, the device has a housing, a reaction chamber is arranged in the housing, a negative corona discharge electric field is arranged in the reaction chamber, and a solution bed for placing a silicon-containing compound is arranged at the lower part of the reaction chamber; an electrode or a metal rod is arranged in the center of the negative corona discharge electric field, and a negative direct-current high-voltage power supply supplies power to the electrode or the metal rod; the electrodes or metal rods provide energetic electrons.
Preferably, the housing of the device is grounded.
Preferably, the device further comprises a temperature control system for maintaining the temperature inside the device at 100-; for example, the temperature inside the reaction chamber is 100-110 deg.C (e.g., 100-105 deg.C, such as 100-102 deg.C).
Preferably, the device is provided with an air inlet, an air outlet, a liquid inlet and a liquid outlet, wherein the air inlet is arranged at the top of the device; the gas outlet is arranged at the bottom of the device, and a gas outlet pipe connected with the gas outlet extends to a gas area above the solution bed, or the gas outlet is arranged on the side wall of the device and is positioned in the gas area above the solution bed; the liquid inlet is arranged on the side wall of the device and is positioned above the solution bed; the liquid outlet is arranged at the bottom of the solution bed; the gas inlet is used for charging carbon-containing gas and hydrogen-containing gas into a negative corona discharge field of the reaction chamber, decomposition products generated in the corona discharge field contact and react with a silicon-containing compound solution interface of the solution bed to generate a gas-phase organic silicon compound, the gas outlet and the connected gas outlet pipe are used for removing a gas-phase product containing the gas-phase organic silicon compound, the liquid inlet is used for injecting the silicon-containing compound solution into the solution bed, and the liquid outlet is used for discharging solution residues of the silicon-containing compound.
Preferably, the carbon-containing gas and the hydrogen-containing gas are introduced into the inlet of the reaction chamber from the gas inlet, and a baffle plate is arranged between the housing and the inlet of the reaction chamber in the cross-sectional direction of the device in order to introduce the gases into the inlet of the reaction chamber.
Preferably, a condensation separator is arranged outside the device and communicated with the air outlet, and the condensation separator is provided with a liquid outlet and a gas outlet.
Preferably, the electrode or metal rod is connected to a source of negative corona discharge electric field.
Preferably, the reaction chamber is a metal cylinder type reaction chamber or a metal tube type reaction chamber.
Preferably, a baffle is provided in the cross-sectional direction of the apparatus between the housing and the reaction chamber at a position near the outlet of the reaction chamber for urging the gas reformed by the negative corona discharge electric field into contact with the silicon-containing compound so that the gas-phase product no longer diffuses to the top of the apparatus and is easily removed from the gas outlet pipe and the gas outlet.
Preferably, an insulating medium thin-layer cylinder can be further placed between the electrode or the metal rod and the outer wall of the metal cylindrical reaction chamber or the metal tubular reaction chamber, the insulating medium thin-layer cylinder can be made of materials with different dielectric constants, such as glass, ceramic, silica gel and the like, the insulating medium thin-layer cylinder and the side wall of the reaction chamber form a gas crack channel, namely a Dielectric Barrier (DBD) discharge structure is formed, and the electric field intensity of the metal cylindrical reaction chamber and the metal tubular reaction chamber is enhanced, so that the reaction process is enhanced.
Preferably, the diameters and the number of the metal cylindrical reaction chambers and the metal tubular reaction chambers are not particularly limited, and may be conventionally selected by those skilled in the art, for example, as shown in fig. 1, 1 metal cylindrical reaction chamber may be used, or more than 2 metal cylinders or metal tubes may be used to form a reaction tube array; when a plurality of metal cylinders or metal pipes are selected, the metal cylinders or the metal pipes have no influence on each other, so that the arrangement mode is not particularly limited, and the metal cylinders or the metal pipes can be reasonably selected according to the size of the device.
Preferably, the number of the metal cylindrical reaction chambers or the metal tubular reaction chambers is one or more, and a plurality of the metal cylindrical reaction chambers or the metal tubular reaction chambers are arranged together to form a cylinder or tubular array tube group.
Preferably, the diameter of the metal cylinder reaction chamber or the metal tube reaction chamber is not particularly limited, and for example, a metal cylinder or a metal tube having a large diameter (for example, 70mm or more) may be used, or a metal cylinder or a metal tube having a large number and a small diameter (for example, 30 to 70mm) may be used; the specific selection also needs to be reasonably selected according to the electric field intensity and the gas quantity to be processed; it is also well known to those skilled in the art that the relative size of the diameter of the metal cylinder or tube also affects the electric field strength within the reaction chamber. For example, when an electrode or a metal rod is disposed at the center of a metal cylindrical reaction chamber or a metal tubular reaction chamber, if a metal cylinder or a metal tube with a larger size is selected, the internal electric field intensity is lower than the electric field intensity formed inside the metal cylinder or the metal tube with a smaller size; likewise, the electric field strength can also be adjusted by the introduction of a medium; the insulating medium layer is added into the electric field with weaker electric field intensity originally, so that the electric field intensity of the electric field can be greatly enhanced; therefore, the electric field intensity is reasonably designed by the technicians in the field according to the factors such as the diameter of the metal cylindrical reaction chamber or the metal tubular reaction chamber, the dielectric constant of the insulating medium substance, the voltage of the external power supply and the like, and then the reforming of the reaction gas is realized.
Preferably, the number of said electrodes is one or more, said electrodes may for example be serrated tip electrodes to generate a negative corona discharge field around the electrodes.
In some embodiments, the electrode is a wire or needle shaped element having a sharp point at the tip of the electrode. The cusp provides a very high charge region around it. The electrodes in the reaction chamber generate electrons by creating a negative corona discharge field at the electrode tip. The electrons are generated in a negative corona at the electrode tip. These electrons are adsorbed on the chemical gas molecules around the electrode tip. In the device of the present invention, the energy required to transport electrons from the surface of the corona electrode is approximately 4-6eV for the metallic material suitable as an electrode in a device with a negative corona discharge field. The electrodes may be of the following materials: cobalt, gold, nickel, copper, silver, iron, tungsten, or platinum. The electrode material is not particularly limited in the present invention, and any material capable of forming corona to generate electrons may be used. The electrodes may also be coated with metals, among which are: cobalt, gold, nickel, rhodium, cesium and platinum. Any metal capable of generating electrons may be used.
Preferably, the shape of the electrodes may be needle-shaped or linear. If the electrode has a sharp point, the potential difference of the gas adjacent to the sharp point will be much higher than other locations around the electrode. Eventually, the resulting high potential electronegative ions will transfer charge to adjacent low potential regions, which will recombine to form gas molecules.
The principle and arrangement of the metal rod are preferably the same as for the electrode. Preferably the metal rod is selected from a fine metal rod.
Other sources that can provide sufficient energy for electrons to be transferred to a gas can also be used in the present invention. Electronegative gas ions may also be generated by other non-thermal or thermal plasma techniques or ion sources, including high frequency methods such as radio frequency plasma, microwave plasma inductively coupled plasma, and the like, such as Electron Beam (EB). Any method that produces electronegative gas ions of sufficient energy and reactivity with the gas can be used in the present invention.
The invention also provides a method for synthesizing the organic silicon compound under the assistance of the low-temperature plasma negative corona discharge electric field, which is based on the device and also comprises the method for synthesizing the organic silicon compound under the assistance of the low-temperature plasma.
The operating conditions of the process and apparatus for plasma-assisted gas phase reactions of the present invention are as follows: the device can be operated under different temperatures and pressures, including normal temperature and normal pressure, carbon-containing gas and hydrogen-containing gas are fed into the device in gaseous form, the treatment gas amount can be arbitrarily selected, the power input is increased along with the increase of the number of a plurality of discharge metal cylinders or metal pipes in the device and the treatment gas amount, the voltage can be 3000-300000 volts, preferably 10000-200000 volts, such as 15000 volts, and the frequency is 15-35 kHz, preferably 20kHz, 25kHz or 35 kHz. It will be appreciated that these conditions are a range of possible preferred operating conditions for the present invention, but that the key to achieving the method and objects of the present invention is the use of the plasma corona discharge itself, which can be determined by routine experimentation and is not limited to the specific description set out above.
Preferably, the apparatus can convert a carbon-containing gas and a hydrogen-containing gas into an organosilicon compound, such as a siloxane.
In addition, other advantages brought by the method and the device of the invention are obvious to those skilled in the art based on the disclosure of the invention. Other aspects and advantages of the invention are described in detail in the following detailed description of the invention.
Drawings
FIG. 1 is a schematic view showing a specific configuration of an apparatus for plasma-assisted gas phase reaction according to the present invention.
Detailed Description
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it is to be understood that various changes or modifications may be made to the invention after reading the contents of the present invention, and equivalents may fall within the scope of the invention defined by the present invention.
"gas" as described in the present specification and claims refers to those gases in which atoms or molecules are capable of capturing additional electrons to form electronegative ions. Other technical and scientific terms used herein have the same general meaning as is known in the art.
The following describes an example of the present invention using electrodes to provide a negative corona discharge electric field. It is to be understood that the invention is not so limited and that electrodes capable of generating a plasma discharge in a sufficiently high energy state to generate electrons may also be used in the present invention.
Fig. 1 shows a schematic view of a specific configuration of the apparatus for plasma-assisted gas phase reaction according to the present invention. In corona discharge, the reaction gas is passed through a high-frequency, high-voltage, negative dc corona discharge field, in which reduction takes place and conversion to products takes place.
In one embodiment of the invention, the negative corona discharge electric field is a high frequency high voltage direct current negative corona discharge electric field. The high voltage is for example 15000 volts. The high frequency is a high frequency voltage, for example 25 kHz. The provision of electrodes or metal rods in the region of the high-frequency high-voltage direct current negative corona discharge field can provide a sufficiently high energy, for example 5eV, to convert the gas molecules. The device 117 has an outer shell that may be made of carbon steel, stainless steel, or other suitable material.
A cylindrical or tubular reaction chamber 111, the material of which can be made of stainless steel, carbon steel or copper and other metals, is arranged in the device 117 formed by the housing. The center of the cylindrical or tubular reaction chamber 111 is provided with an electrode 112 which is a needle-shaped or sawtooth rod electrode with a pointed end. A high frequency high voltage direct current negative voltage is applied to the electrode 112 in the electric field through the electrode distribution plate 123 to form a high frequency high voltage direct current negative corona discharge electric field. The voltage (intensity) should be chosen to satisfy the following conditions: the gas delivered into the apparatus 117 through the gas inlet 110 at the top of the apparatus 117 can be highly ionized in the metal cylinder or metal tube type reaction chamber 111.
An insulating dielectric cylinder 122 is arranged between the electrode 112 and the outer wall of the cylinder or tubular reaction chamber 111, which can form Dielectric Barrier Discharge (DBD) in the electric field, provide a narrow collision reaction zone to strengthen the decomposition of all molecules into free radicals or ions, thereby forming product molecules and enhancing the electric field strength of the plasma auxiliary reaction process. The insulating medium cylinder 122 is made of glass, ceramic, teflon sheet, or the like.
The electrode material of the electrode 112 may be nickel, cobalt, iron, steel, tungsten, nickel, copper, silver, iron, carbon, or platinum, or any other material that can be used in an electrode and that generates a corona around the electrode to generate electrons. The electrodes may also be coated with metals, among which are: cobalt, nickel, rhodium, cesium and platinum. Any metal capable of generating electrons may be used.
In operation, when the electrode 112 is connected to an electric field source through the electrode distribution plate 123, a discharge is formed at the tip of the electrode 112, which in turn forms a corona field discharge, and energetic electrons hit gas molecules, which can initiate reduction and reforming reactions.
The high voltage is sent to the electrode 112 through the electrode distribution plate 123 to discharge. A partition plate 121 is arranged on one side close to the outlet of the cylindrical or tubular reaction chamber 111, and the partition plate 121 divides the device into an upper space and a lower space, and the shell of the device is connected with the ground.
The carbonaceous gas and the hydrogen-containing gas are fed into the negative corona discharge electric field inside the apparatus 117 through a gas inlet 110 at the top of the apparatus 117. Some gas molecules may receive discharged electrons in a negative corona discharge electric field for oxidation and reformation. In a negative corona discharge electric field, gas molecules and ions may be reduced and converted. The gas molecules and ions leave the negative corona discharge electric field and then contact a solution bed of a silicon-containing compound to react to generate organic silicon molecules; when removed through outlet 113 at the bottom of the apparatus and passed through condenser 133 to effect gas-liquid separation, the liquid containing organosilicon compounds can be removed through port 125 and the unreacted oxyhydrogen-containing gas can be removed through port 124.
A silicon compound solution is stored in a silicon compound-containing solution bed 115 at the bottom of the device 117 and may be added through a liquid inlet 118 disposed in the sidewall of the device. After the reaction is completed, the remaining or waste silicon compound solution is discharged through a liquid outlet 120 at the bottom of the apparatus.
The invention takes carbon dioxide and water vapor as raw material gases, the temperature in a reaction chamber is 100-:
from the results of the measurements shown in the above table, it can be seen that the organosilicon compound can be prepared using the apparatus and method of the present application.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing an organic silicon compound by assistance of a low-temperature plasma negative corona discharge electric field, wherein the method comprises the following steps: introducing a carbon-containing gas and a hydrogen-containing gas into a reactor, wherein the reactor is provided with a negative corona discharge electric field and a solution bed for placing a silicon-containing compound, and the negative corona discharge electric field is a direct current negative corona discharge electric field or other electric field sources capable of providing enough energy to oxidize and decompose reaction gas molecules into atoms, ions, free radicals and the like.
2. The method of claim 1, wherein the direct current negative corona discharge electric field is a high frequency, high voltage direct current negative corona discharge electric field.
3. The method according to claim 1 or 2, wherein the carbon-containing gas and the hydrogen-containing gas react in the negative corona discharge electric field to generate hydrocarbon molecules, ions and/or radicals, the generated hydrocarbon molecules, ions and/or radicals contact with the silicon-containing compound to react, and the silicon dioxide in the silicon-containing compound is reformed to prepare the organosilicon compound.
Preferably, the organosilicon compound is preferably an organosiloxane compound, such as organosiloxane oligomer C2nH6nOnSinWherein n is an integer.
4. A method according to any of claims 1-3, wherein various carbon-containing gases, such as CH, can be used in the negative corona discharge field4、CO2CO and other carbon-containing gases, various hydrogen-containing gases, such as CH, may be used in the negative corona discharge field4、H2O、H2And other hydrogen-containing gases which are decomposed by a negative corona discharge electric field to produce various active components, such as O3、H-、H、CH3And CO.
Preferably, CH may be used in a negative corona discharge electric field4、CO2CO and other carbon-containing gases with H2O、H2And a mixed gas of gaseous hydrogen-containing gas.
Preferably, the carbonaceous gas is derived from a gas produced by a combustion device, a carbon source gas containing methane, or a gas produced by a gas generation device, such as natural gas, shale gas, coal bed gas, biogas, water gas, coke oven gas, flue gas, and the like.
Preferably, the solution of the silicon-containing compound may be a solution of sodium silicate, lithium silicate, silicic acid, silicon chloride or other silicon-containing compounds.
5. The method according to any one of claims 1 to 4, wherein CO is used2As a carbon source, H2Or H2O is used as hydrogen source, corona discharge is carried out on the electrode of the negative corona discharge electric field in the negative corona discharge electric field area, and a large number of negative electrons are released to be adhered to CO2And H2Or H2The gas molecules trap these high energy electrons to form high energy electronegative gas ions, such as H2 -，CO2 -，CO-Or H-Plasma anion, and CH3And H, etc., the negative ions are forced to be reduced or reformed into short-chain hydrocarbons or radicals, and the generated short-chain hydrocarbons or radicals can be subjected to the action of an electric fieldFurther generation of e.g. CH3And H.and the like. The generated radicals may be contacted with a bed of a solution of a silicon-containing compound to react with the silicon-containing compound (e.g., sodium silicate or silica) to produce an organosilicon compound.
6. The method according to any one of claims 1 to 5, wherein the carbon-containing gas, the hydrogen-containing gas and the silicon-containing compound are reformed by a negative corona discharge electric field to obtain a mixed gas, and the reformed mixed gas can be separated into a gas phase and a liquid phase after being condensed by a condenser; wherein the gas phase comprises unreacted carbon oxides and hydrocarbons; the liquid phase includes water and silicone molecules.
7. An apparatus for low temperature plasma-assisted synthesis of organosilicon compounds, wherein the apparatus comprises a reaction chamber having a plasma region with a negative corona discharge electric field, below which is disposed a solution bed in which a silicon-containing compound is disposed.
8. The apparatus of claim 7, wherein the apparatus has a housing, a reaction chamber is disposed within the housing, a negative corona discharge electric field is disposed within the reaction chamber, and a solution bed in which the silicon-containing compound is disposed below the reaction chamber; an electrode or a metal rod is arranged in the center of the negative corona discharge electric field, and a negative direct-current high-voltage power supply supplies power to the electrode or the metal rod; the electrodes or metal rods provide energetic electrons.
Preferably, the electrode or metal rod is connected to a source of negative corona discharge electric field.
Preferably, the reaction chamber is a metal cylinder type reaction chamber or a metal tube type reaction chamber.
Preferably, a baffle is provided between the housing and the reaction chamber in the cross-sectional direction of the device, at a position near the outlet of the reaction chamber.
Preferably, a baffle is provided between the housing and the inlet of the reaction chamber in the cross-sectional direction of the device.
Preferably, an insulating dielectric thin-layer cylinder can be further placed between the electrode or the metal rod and the outer wall of the metal cylindrical reaction chamber or the metal tubular reaction chamber, the insulating dielectric thin-layer cylinder can be made of materials with different dielectric constants, such as glass, ceramics, silica gel and the like, and the insulating dielectric thin-layer cylinder and the side wall of the reaction chamber form a gas crack channel, namely a dielectric barrier discharge structure.
Preferably, the number of the metal cylindrical reaction chambers or the metal tubular reaction chambers is one or more, and a plurality of the metal cylindrical reaction chambers or the metal tubular reaction chambers are arranged together to form a cylinder or tubular array tube group.
9. The apparatus of claim 7 or 8, wherein the apparatus has a gas inlet, a gas outlet, a liquid inlet and a liquid outlet, wherein the gas inlet is disposed at a top of the apparatus; the gas outlet is arranged at the bottom of the device, and a gas outlet pipe connected with the gas outlet extends to a gas area above the solution bed, or the gas outlet is arranged on the side wall of the device and is positioned in the gas area above the solution bed; the liquid inlet is arranged on the side wall of the device and is positioned above the solution bed; the liquid outlet is arranged at the bottom of the solution bed.
Preferably, a condensation separator is arranged outside the device and communicated with the air outlet, and the condensation separator is provided with a liquid outlet and a gas outlet.
10. A method for synthesizing an organic silicon compound by low-temperature plasma negative corona discharge electric field assistance, which is based on the apparatus of any one of claims 7 to 9, and which further comprises the method for synthesizing an organic silicon compound by low-temperature plasma negative corona discharge electric field assistance of any one of claims 1 to 6.
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