WO2013060080A1 - Method for converting methanol - Google Patents

Method for converting methanol Download PDF

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Publication number
WO2013060080A1
WO2013060080A1 PCT/CN2011/084954 CN2011084954W WO2013060080A1 WO 2013060080 A1 WO2013060080 A1 WO 2013060080A1 CN 2011084954 W CN2011084954 W CN 2011084954W WO 2013060080 A1 WO2013060080 A1 WO 2013060080A1
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Prior art keywords
reactor
methanol
selectivity
plate
discharge
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PCT/CN2011/084954
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French (fr)
Chinese (zh)
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郭洪臣
张婧
袁启超
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大连理工大学
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Priority claimed from CN201110332201.8A external-priority patent/CN102500303B/en
Priority claimed from CN201110332485.0A external-priority patent/CN102500304B/en
Priority claimed from CN2011103319797A external-priority patent/CN102424646A/en
Priority claimed from CN2011103320898A external-priority patent/CN102417438B/en
Application filed by 大连理工大学 filed Critical 大连理工大学
Priority to US14/354,911 priority Critical patent/US20140284206A1/en
Publication of WO2013060080A1 publication Critical patent/WO2013060080A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0845—Details relating to the type of discharge
    • B01J2219/0847—Glow discharge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0845—Details relating to the type of discharge
    • B01J2219/0849—Corona pulse discharge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0877—Liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894—Processes carried out in the presence of a plasma
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention belongs to the field of plasma synthesis chemistry and relates to a method for directly preparing ethylene glycol from methanol.
  • Methanol is an important basic organic chemical raw material with a wide range of uses. The most striking is the synthesis of dimethyl ether, olefins; in addition to hydrogen, gasoline, carbonates, aromatics, ethanol, ethylene glycol, carbonylation of acetic acid and fuel. Due to the abundant coal resources, the coal-to-methanol industry has developed rapidly and has a large production capacity. Therefore, starting from methanol, it has broad prospects for the production of various high value-added chemical products.
  • the technical feature is: in the presence of a catalyst composed of cobalt, ruthenium, iodine, organic phosphorus, etc., methanol and carbon monoxide, H 2 react at a reaction temperature of 150-250 ° C, and a reaction pressure of 20-60 MPa to form ethanol and n-propanol.
  • Patent US 4,337,371, A Application No. US Pat.
  • the technical feature is that the content of ethylene glycol in the obtained product is obtained by using an organic peroxide such as di-tert-butyl peroxide (DTBP) or dicumyl peroxide (DCP) as an initiator. The highest is 7.71%.
  • DTBP di-tert-butyl peroxide
  • DCP dicumyl peroxide
  • a method of producing ethylene glycol from methanol is disclosed in the patent JP63027445A (Application No. 19860168874, filing date 1986-07-17).
  • the technical feature is that methanol is first dehydrated to form dimethyl ether, and dimethyl ether is oxidatively coupled with oxygen to form dimethoxyethane in the presence of a catalyst, and finally, dimethoxyethane is hydrolyzed. Glycol is produced.
  • a method for producing ethylene glycol is disclosed in the patent US005214182 (Application No. 726715, filed on Jun.
  • the technical feature is: in the presence of heterogeneous polymerization catalyst phosphorus hydride, methanol and ethylene carbonate react to form ethylene glycol, and simultaneously produce dimethyl carbonate, ethylene glycol and dimethyl carbonate have a selectivity of up to 98 %.
  • a method for producing hydrogen by methanol decomposition in corona discharge plasma is reported. Its characteristics are: using DC and AC corona discharge to investigate the effect of methanol decomposition, the sine wave and triangular sine wave of alternating current are very effective for the conversion of methanol, the conversion rate can reach more than 70%, and the hydrogen production rate can reach 50ml.min. -1 , also mentioned that there are trace amounts of ethylene glycol in the reaction product.
  • a method for decomposing methanol by cold plasma is reported. It is characterized by the use of DBD to generate a cold plasma stream, which decomposes methanol under an air atmosphere, and proposes that OH is an important free radical for decomposing methanol, but there is no mention of ethylene glycol formation in the product.
  • the current main method of producing ethylene glycol is ethylene oxide non-catalytic hydration, which is also the only industrial process.
  • the method is mature in technology and large in output, but the production process is long, the equipment is high, the energy consumption is high, and the environmental pollution is serious, so that the cost of ethylene glycol is high.
  • Other new methods for synthesizing ethylene glycol are facing many problems, and industrialization is difficult.
  • Plasma technology is different from conventional thermal catalysis and photocatalysis technology. It is characterized by the use of high-energy electrons generated by discharge to activate reactants to generate corresponding free radicals. The radicals are transported through chains and react to obtain products without using catalysts. .
  • Plasma is the fourth state in which a substance exists.
  • an electrically neutral substance When a high temperature or a high voltage is applied to a substance, an electrically neutral substance generates an atom, an excited substance, an electron, and a positive reaction through excitation, dissociation, ionization, and the like. Ions, anions, free radicals, ultraviolet light, and visible light.
  • These systems consisting of charged particles (ions, electrons) and neutral particles (atoms, molecules, free radicals, etc.) are macroscopically positive and negatively charged, so they are called For the plasma.
  • Electrons in the plasma accumulate kinetic energy under the acceleration of an applied electric field, and electrons with high energy collide with the reactant molecules in an inelastic manner to cause electron excitation or dissociation of the molecules.
  • the ions, excited atoms or molecules and radical species contained in the plasma have high chemical reactivity and can initiate chemical reactions by colliding with each other.
  • the plasma can be classified into a high temperature plasma, a thermal plasma, and a cold plasma depending on the difference in energy state of the plasma, gas temperature, and particle density. Since the cold plasma is in thermodynamic imbalance, electron temperature (T e ) >> ion temperature ( T i ), neutral particle temperature (T n ), it has high electron energy and low ion and gas temperature.
  • non-equilibrium property makes it the most widely used plasma in industrial production: On the one hand, electrons have high enough energy to excite, dissociate and ionize reactant molecules; on the other hand, the reaction system is kept low temperature, so that the reaction system can The consumption is reduced and the reaction is easy to control.
  • Cold plasma that is, non-equilibrium plasma is mainly produced by corona discharge, glow discharge, spark discharge, dielectric barrier discharge, sliding arc discharge, microwave plasma, radio frequency plasma, and the like.
  • the presence of molecules, atoms, molecular ions, atomic ions, and electrons may vary greatly depending on conditions such as gas pressure, electric field strength, discharge current, and discharge frequency, and may also be due to discharge reaction devices.
  • the structure is very different. Since different plasma states contain different numbers of molecules, atoms, excited states, excited states, electrons, positive ions, negative ions, and free radicals, the appropriate reactor structure, discharge pattern, and discharge conditions are selected. It is capable of modulating the energy of electrons in the plasma and the number of active species involved.
  • the particular reactant activation state corresponds to a particular chemical reaction and reaction product. In the technology of plasma conversion of methanol, most of the products are H2, and some technologies have obtained alkanes such as formaldehyde, methane, ethane, and propane, as well as CO, CO 2 and water.
  • the invention mainly obtains an alcohol product such as ethylene glycol, ethanol or propanol from methanol, because the electron energy in the plasma generated by the discharge is different, and the active species are different.
  • the plasma reaction of methanol has the following specific characteristics: when a high voltage is applied to the CH 3 OH molecules entering the discharge reactor, electrons obtain high kinetic energy under the action of an applied electric field, and high-energy electrons and surrounding CH 3 OH molecules occur. Collision, ionization of CH 3 OH molecules, resulting in more electrons, causing electron avalanches, which further inelastically collide with CH 3 OH molecules, transferring energy to CH 3 OH molecules, causing them to become excited CH 3 OH molecule.
  • active species further collide and react with each other to form corresponding reactants HOCH 2 CH 2 OH , C 2 H 6 , CH 3 OCH 3 , H 2 , etc.; these active species collide with high-energy electrons for energy transfer, Further cleavage of chemical bonds can occur, generating free radicals such as CH 2 ⁇ , CH ⁇ , C ⁇ , HCO ⁇ , CO, which can form deep reaction products such as CH 3 CH 2 OH , CH 3 CH 2 CH 2 OH , CH 3 CH 2 CH 3 , C 2 H 2 , C 2 H 4 , C 3 H 6 , even H 2 and coke (C).
  • the specific chemical bonds in the methanol molecules can be selectively activated by modulating the electron energy of the plasma discharge region, thereby achieving the purpose of selectively initiating a specific chemical reaction.
  • CH 3 OH molecule, CH, CO, OH bond energy is 94.57kcal.mol -1, 81.51kcal.mol -1, 104.9kcal.mol -1, respectively, when the plasma in the region of the free electrons e
  • the electric field accelerates to obtain high kinetic energy, it will inelastically collide with the CH 3 OH molecule.
  • the invention provides a method for preparing ethylene glycol by one-step conversion of methanol in a non-equilibrium plasma, which utilizes high-energy electrons in a plasma generated by a discharge to collide with methanol gas molecules, thereby generating a methylol radical ( ⁇ CH 2 OH).
  • the two CH 2 OH are coupled to form ethylene glycol.
  • the present invention achieves the purpose of selectively producing an ethylene glycol product by adjusting the energy of high energy electrons in the plasma region by the following method.
  • the specific technical solutions are as follows:
  • the selectable discharge form is: corona discharge, glow discharge, dielectric barrier discharge;
  • the optional reactor structure is: wire barrel reactor, needle plate reactor, plate plate reactor, tube plate reactor;
  • the parameters to be considered are: discharge zone length, pole spacing, dielectric material, high voltage pole, grounding pole material;
  • the discharge conditions to be optimized are: discharge voltage, discharge frequency, discharge atmosphere, methanol/carrier gas molar ratio, discharge gas pressure, discharge temperature;
  • a plate plate reactor a tube plate reactor, a needle plate reactor and a wire barrel reactor may be used, and the barrier medium is a single layer medium or a double layer medium, which is attached to the surface of the electrode or placed between the two electrodes;
  • the high-voltage pole and the grounding pole of the wire-tube reactor are respectively a wire in the reactor casing and a metal piece, a metal mesh or a wire wound around the outer cylinder wall;
  • the distance between the two poles refers to the distance between the outer wall of the central metal wire electrode located on the axis and the inner wall of the cylindrical ground electrode, and the electrode spacing may be 0.3-20 mm, preferably 1-5 mm.
  • the electrodes of the needle plate reactor are respectively a metal plate with a metal needle array and a metal plate; the two metal plates are horizontally fixed in the reactor casing, and the pole spacing is a vertical distance between the lower end of the metal needle and the metal plate; A barrier medium plate is disposed between the two poles, and the distance between the barrier dielectric plate and the two poles is arbitrarily adjusted; the inlet and outlet of the reactants and products are opened on the reactor wall;
  • the electrodes of the tube plate reactor are a metal tube and a metal plate, respectively.
  • the metal plate is horizontally fixed in the reactor casing, the metal pipe is vertically aligned with the center of the horizontal metal plate, and the vertical distance between the lower end of the metal pipe and the metal plate is a pole spacing; a barrier medium plate is disposed between the two poles, and the dielectric plate is blocked The distance between the two poles can be adjusted arbitrarily.
  • Methanol and carrier gas can enter either from the discharge metal tube or from the upper inlet of the reactor at the fixed electrode, and the reaction product outlet at the lower end.
  • the high voltage and ground electrodes of the plate and plate reactor are respectively two metal plates.
  • the two metal plates are fixed in parallel in the casing of the reactor, the vertical distance between the two plates is the pole spacing, and the blocking dielectric plate is disposed between the high voltage pole and the grounding pole, and the distance between the blocking dielectric plate and the two poles can be arbitrarily adjusted.
  • the barrier medium may be provided as a single layer or multiple layers; the inlet and outlet of reactants and products are opened on the reactor wall.
  • the pole spacing of the above three reactors with plate electrodes may be 0.2-40 mm, preferably 2-10 mm;
  • the casings of the above four reactors are made of insulating materials such as hard glass, alumina ceramics, polytetrafluoroethylene or metal and non-metal composite materials conforming to high-voltage electrical insulation design.
  • the shape and size of the reactor housing can be determined as needed, and the amplification of the reactor can be achieved by a single reactor amplification and the number of parallel reactors.
  • the above-mentioned barrier medium is made of an insulating material which has a smooth surface, heat resistance, high mechanical strength, and does not chemically react with plasma of methanol and carrier gas and methanol alcoholation product, and is preferably quartz glass, hard glass, mica and alumina ceramics.
  • the total thickness of the barrier medium is desirable 0.3-10 mm, preferably 0.5-3.0 mm.
  • the high-voltage electrode and the grounding electrode of the above reactor are made of a metal material with smooth surface, high mechanical strength and high temperature resistance, and the material may be copper, iron, tungsten, aluminum, stainless steel or nickel.
  • the metals of the extranuclear gold, platinum, and palladium, and the stainless steel containing titanium or nickel are preferably copper, iron, tungsten, and stainless steel;
  • the diameter of the metal tube electrode of the above reactor ranges from 0.5 to 12 mm, preferably 2 to 8 mm.
  • the ratio of the diameter of the metal plate to the metal tube is 1-20; the dielectric barrier discharge is a high-voltage AC power source, and the power supply frequency is 1 kHz to 50 kHz, preferably 5 kHz to 20 kHz.
  • the reactor adopts a needle plate structure, one electrode of the reactor is a wire with a tip, and the other electrode is a metal plate.
  • the high voltage electrode and the ground electrode can be exchanged between the needle and the plate, and the power source is high voltage DC. power supply.
  • the two pole spacing of the reactor is desirable 0.5 to 18 mm, preferably 2 to 10 mm, and the two-pole pitch is the distance between the tip end of the pointer electrode and the ground plate electrode.
  • the electrode may be made of a metal material having a smooth surface, high mechanical strength and high temperature resistance, and the material may be copper, iron, tungsten, aluminum, stainless steel, nickel, etc., preferably aluminum, iron, tungsten, nickel;
  • Pulse corona discharge is used: the reactor adopts a wire barrel structure, the central halo electrode of the reactor is a metal wire, and the other electrode is a metal cylinder.
  • the distance between the two poles of the reactor is 5 ⁇ 40mm, preferably 15 ⁇ 30mm
  • the two-pole spacing refers to the distance between the outer wall of the central halo line of the axis and the wall of the metal cylinder.
  • the power supply adopts a pulsed DC high-voltage power supply, and uses a storage capacitor to generate a pulse voltage by means of a spark gap to the load discharge.
  • the peak value of the pulse power supply and the pulse repetition frequency are adjustable.
  • the peak voltage of the above power supply is 20 ⁇ 60kV , preferably 38 ⁇ 46 kV ; the pulse repetition frequency of the power supply is 10 ⁇ 150 Hz , preferably 50 ⁇ 100 Hz ;
  • the electrode may be made of a metal material having a smooth surface, high mechanical strength and high temperature resistance, and may be made of copper, iron, tungsten, aluminum, stainless steel, nickel, platinum, palladium or the like, and among them, iron, stainless steel, nickel, and platinum are preferable.
  • the reactor adopts a wire-tube structure or a plate-and-plate structure.
  • the power supply can be a pulsed DC high voltage power supply or a pulsed AC high voltage power supply.
  • a pulsed DC high-voltage power supply When a pulsed DC high-voltage power supply is used, a pulse voltage is generated by means of a storage capacitor through a spark gap to the load, and the peak voltage of the power source can be taken.
  • the pulse repetition frequency of the power supply can be 10 ⁇ 150Hz, preferably 50 ⁇ 100Hz
  • the peak voltage of the power supply can be 0 ⁇ 30kV, preferably 0 ⁇ 10 kV
  • the pulse repetition frequency of the power supply can be 7 ⁇ 50Hz, preferably 7 ⁇ 30Hz
  • the discharge reactor electrode is made of a metal material having a smooth surface, high mechanical strength and high temperature resistance, and the material may be copper, iron, tungsten, aluminum, stainless steel, nickel, platinum, palladium, etc., among which iron, stainless steel, nickel, platinum are preferred.
  • reactor pole spacing 1 ⁇ 40mm, preferably 5 ⁇ 25mm .
  • the distance between the two poles refers to the distance between the central metal wire electrode located at the axis and the wall of the barrel; when a plate type reactor is used, the distance between the two poles refers to two parallel metals. The vertical distance between the boards.
  • the reaction temperature of the reaction mixture is from 25 to 600 ° C, preferably from 100 to 400 ° C;
  • the discharge reaction pressure is from -0.06 MPa to 0.5 MPa, preferably -0.22 MPa ⁇ 0 2 MPa ;
  • the molar ratio of carrier gas to methanol is 0-20, preferably 0-6;
  • the carrier gas may be N 2 , H 2 , H 2 O, He, Ar, O 2 , CO, CO 2 , CH 4 , One or a mixture of two or more hydrocarbons such as C 2 H 6 , of which H 2 , H 2 O , He , Ar , CH 4 are preferred.
  • the invention has the beneficial effects that the preparation of the ethylene glycol is methanol, and the methanol can be obtained by the synthesis gas of coal, and even the methanol can be obtained by vaporization of the biomass, and has reproducibility.
  • the preparation of ethylene glycol by plasma is a one-step direct synthesis process, which does not require the use of a catalyst, has no pollution to the environment, and has high selectivity.
  • the present invention can also produce a useful product such as ethanol or n-propanol by optimizing the conditions while obtaining ethylene glycol.
  • Figure 1a is a schematic diagram of a dielectric barrier discharge --- single dielectric bobbin reactor.
  • Figure 1b is a schematic diagram of a dielectric barrier discharge --- dual dielectric bobbin reactor.
  • Figure 2 is a schematic diagram of a dielectric barrier discharge --- needle plate electrode structure reactor.
  • Figure 3 is a schematic diagram of a dielectric barrier discharge--tube-plate electrode structure reactor.
  • Figure 4 is a schematic diagram of a dielectric barrier discharge--plate-plate electrode structure reactor.
  • Figure 5 is a schematic of a glow discharge reactor.
  • the reactor adopts a wire barrel electrode structure, and is made of a rigid glass tube with an outer diameter of 15 mm and an inner diameter of 13 mm to form a cylindrical reactor (also serving as a barrier medium).
  • the center electrode is a copper wire having a diameter of 1 mm, and the grounding wall thickness is 1 mm.
  • Cylindrical iron foil (close to the outer wall of the glass tube) with a pole spacing of 7 mm and an effective discharge length of 150 mm for the reactor.
  • the discharge parameters of the reactor are: voltage 5.6kV, current 0.25A, frequency 5kHz; discharge temperature 150 °C
  • the reaction results were: methanol conversion rate of 13%, ethylene glycol selectivity of 3%, ethanol selectivity of 1%, methane selectivity of 60%, carbon monoxide selectivity of 29%, and other hydrocarbon selectivity of 7%. H2 yield 20%.
  • the distance between the two poles is large, the electron (e) energy in the plasma discharge region is too small, the degree of activation of methanol is low, and the conversion rate of methanol is low, mainly in the methanol molecule.
  • the C-O bond produces a product mainly methane.
  • the methanol flow rate is 6 ml/min.
  • the gas is passed into the discharge reactor. After the gas flow is stabilized, the plasma power source is turned on to perform dielectric barrier discharge. With outer diameter of 6mm, inner diameter of 4mm
  • the hard glass tube is made into a tubular reactor (also used as a blocking medium), the center electrode is a tungsten wire with a diameter of 3 mm, and the grounding is a cylindrical aluminum foil tube with a wall thickness of 1 mm (close to the outer wall of the glass tube) with a pole spacing of 1.5mm, the effective discharge length of the reactor is 130mm.
  • the discharge parameters of the reactor are: voltage 20.0kV, current 0.35A, frequency 8kHz; reaction temperature is 170 °C, the reaction results are: methanol conversion rate 73%, ethylene glycol selectivity 5%, ethanol selectivity 2%, n-propanol Selectivity 1%, methane selectivity 30%, carbon monoxide selectivity 60%, other hydrocarbon selectivity 2%, H2 yield 56%.
  • the distance between the two poles is small, the electron (e) energy in the plasma discharge region is too large, and the methanol conversion rate is high, but the OH bond is mainly broken to generate CO and H 2 due to high energy electrons in the plasma region.
  • the number is large, and the probability of colliding with methanol molecules is large, so the reaction mainly produces small molecular products such as methane and CO.
  • a molar ratio of gaseous methanol to Ar of 2:1 at a pressure of 0.08 MPa (where Ar flow rate is 36 ml/min)
  • the methanol flow rate is 18 ml/min.
  • the gas is introduced into the discharge reactor. After the gas flow is stabilized, the high-voltage power source is turned on to perform corona discharge.
  • the reactor uses a needle plate electrode structure with an inner diameter of 6 mm
  • the quartz tube is used as a reactor, and the discharge electrode is fixed at both ends.
  • One electrode is a stainless steel needle with a diameter of 2 mm (high voltage electrode), and the other electrode is a stainless steel circular plate (ground electrode) with a diameter of 6 mm.
  • the electrode spacing is 6 mm. .
  • DC positive corona discharge, positive corona self-sustained discharge voltage is 0.6kV; discharge temperature is 400 °C, the reaction results are: methanol conversion rate of 45%, ethylene glycol selectivity of 0.5%, ethanol selectivity of 3%, methane selectivity of 30 %, carbon monoxide selectivity 60.5%, other hydrocarbon selectivity 6%, H 2 yield 54%.
  • the discharge gas pressure is small, the number of reactant molecules per unit volume is small, and the electrons (e) in the plasma discharge region can fully collide with the reactant molecules and carry out energy transfer, resulting in energy obtained by the reactants.
  • H 2 and gaseous methanol were introduced into the bobbin reactor at a molar ratio of 2.5:1 (where H 2 flow rate was 25 ml/min and methanol flow rate was 10 ml/min) at a pressure of 0.10 MPa.
  • the power supply is subjected to dielectric barrier discharge.
  • a cylindrical reactor (also used as a barrier medium) is made of a hard glass tube with an outer diameter of 11 mm and an inner diameter of 9 mm.
  • the center electrode is a stainless steel wire with a diameter of 2 mm, and the grounding wall has a wall thickness of 0.4 mm.
  • the outer wall of the glass tube has a pole spacing of 4.5 mm and an effective discharge length of the reactor of 160 mm.
  • the discharge parameters of the reactor are: voltage 18.0kV, current 0.28A, frequency 10kHz; discharge temperature 100 °C
  • the discharge frequency and discharge power are kept constant at 10 kHz and 25 W, respectively, when the reactor shell material is modulated, the reaction result is:
  • Hard glass, methanol conversion rate is 26.90%, ethylene glycol selectivity is 31.25%, and ethanol selectivity is 7.15%.
  • the selectivity of n-propanol is 1.17%;
  • Alumina ceramics the conversion of methanol is 33.26%, the selectivity of ethylene glycol is 29.61%, and the selectivity of ethanol is 5.28%.
  • the selectivity of n-propanol is 0.98%;
  • the reactor adopts a double dielectric barrier discharge reactor, and the shell and the inner sleeve are made of hard glass, wherein the inner barrier medium tube has a thickness of 0.8 mm.
  • the reaction result is: methanol conversion rate 18.09%
  • the selectivity of ethylene glycol is 44.39%
  • the selectivity of ethanol is 7.46%
  • the selectivity of n-propanol is 1.44%.
  • the thickness of the medium is 1.5 mm, the conversion of methanol is 23.25%, and the selectivity of ethylene glycol is 17.36%.
  • the selectivity of ethanol is 4.35% and the selectivity of n-propanol is 0.64%;
  • the thickness of the medium is 2.0 mm, the conversion of methanol is 16.34%, and the selectivity of ethylene glycol is 27.54%.
  • the selectivity of ethanol is 5.36% and the selectivity of n - propanol is 0.83% ;
  • the thickness of the medium is 2.5 mm, the conversion of methanol is 12.56%, and the selectivity of ethylene glycol is 32.18%.
  • the selectivity of ethanol is 6.65% and the selectivity of n-propanol is 1.05%;
  • the medium thickness is 3.0 mm, the conversion of methanol is 6.36%, the selectivity of ethylene glycol is 47.34%, and the selectivity of ethanol is 7.15%, the selectivity of n-propanol is 1.77%;
  • the conversion rate of copper mesh and methanol is 18.93%, the selectivity of ethylene glycol is 39.54%, and the selectivity of ethanol is 3.14%.
  • the selectivity of n-propanol is 0.98%;
  • the conversion rate of copper wire and methanol is 13.65%, the selectivity of ethylene glycol is 42.38%, and the selectivity of ethanol is 3.68%.
  • the selectivity of n-propanol is 1.03%;
  • the conversion rate of methanol to methanol is 9.83%, the selectivity of ethylene glycol is 52.53%, and the selectivity of ethanol is 6.34%.
  • the selectivity of n-propanol is 1.56%;
  • the conversion rate of iron wire and methanol is 12.39%, the selectivity of ethylene glycol is 47.45%, and the selectivity of ethanol is 4.39%.
  • the selectivity of n-propanol is 1.16%;
  • the conversion of methanol is 19.53%
  • the selectivity of ethylene glycol is 39.43%
  • the selectivity of ethanol is 5.34%
  • the selectivity of n-propanol is 1.01%
  • the conversion of methanol is 25.36%
  • the selectivity of ethylene glycol is 32.26%
  • the selectivity of ethanol is 4.17%
  • the selectivity of n - propanol was 0.93% ;
  • the housing of the needle plate reactor is made of hard glass with an outer diameter of 12.0 mm
  • the wall thickness is 1.0 mm.
  • the grounded metal plate electrode and the metal rod electrode connected to the high voltage end are made of stainless steel.
  • the diameter of the metal plate is 10 mm, the thickness is 0.2 mm, and the diameter of the metal bar is 1.2.
  • Mm with mica sheet as the blocking medium, placed on the grounding plate; the vertical distance from the lower end of the high voltage pole to the grounding plate (the distance between the two poles) is 6.0 mm.
  • the discharge parameters of the reactor are: voltage 17.0kV, current 0.32A, frequency 7kHz; discharge temperature 80 °C,
  • the reaction results are: medium thickness 0.5 mm, methanol conversion rate 26.38%
  • the selectivity of ethylene glycol is 37.26 %, the selectivity of ethanol is 6.45%, the selectivity of n-propanol is 1.67%, the thickness of medium is 1.0 mm, the conversion of methanol is 18.12%.
  • the selectivity of ethylene glycol is 41.37 %, the selectivity of ethanol is 5.21%, the selectivity of n-propanol is 1.34%, the thickness of medium is 1.5 mm, the conversion of methanol is 11.35%.
  • the selectivity of ethylene glycol is 49.65 %, the selectivity of ethanol is 4.37%, the selectivity of n-propanol is 1.16%, the thickness of medium is 2.0 mm, and the conversion of methanol is 7.73%.
  • the selectivity of ethylene glycol is 53.84%, the selectivity of ethanol is 3.25%, the selectivity of n-propanol is 0.94%, the thickness of medium is 3.0 mm, and the conversion of methanol is 3.62%.
  • the selectivity of ethylene glycol is 61.27 % , the selectivity of ethanol is 1.12% , and the selectivity of n - propanol is 0.72 % ;
  • Example 6 was repeated, but the thickness of the barrier medium was maintained at 1.0 mm, and when the material of the barrier medium was changed, the reaction result was:
  • the conversion of methanol is 21.56%
  • the selectivity of ethylene glycol is 38.24%
  • the selectivity of ethanol is 3.46%
  • the selectivity of n-propanol is 1.17%.
  • Alumina ceramics Alumina ceramics, methanol conversion rate of 15.27%, ethylene glycol selectivity of 49.86%, ethanol selectivity of 5.37%, n-propanol selectivity of 1.52%;
  • the conversion of methanol is 9.35%
  • the selectivity of ethylene glycol is 58.35%
  • the selectivity of ethanol is 6.26%
  • the selectivity of n-propanol is 2.66%.
  • Example 6 was repeated, but the thickness of the barrier medium was maintained at 1.0 mm, and when the electrode pitch was changed, the reaction result was:
  • the pole spacing is 2.0 mm, the conversion of methanol is 42.27%, and the selectivity of ethylene glycol is 23. 35%.
  • the selectivity of ethanol is 9.35%, the selectivity of n-propanol is 1.74%, the polar spacing is 3.0 mm, the conversion of methanol is 31.58%, and the selectivity of ethylene glycol is 3.92%.
  • the selectivity of ethanol is 7.25%, the selectivity of n-propanol is 1.26%, the polar spacing is 4.0 mm, the conversion of methanol is 21.75%, and the selectivity of ethylene glycol is 41.64%.
  • the selectivity of ethanol is 5.42%, the selectivity of n-propanol is 1.04%, the polar spacing is 5.0 mm, the conversion of methanol is 13.52%, and the selectivity of ethylene glycol is 55.56%.
  • the selectivity of ethanol is 4.36% and the selectivity of n - propanol is 0.88% ;
  • Example 6 was repeated, but the thickness of the barrier medium was kept at 1.0 mm, and when the material of the discharge electrode was changed, the reaction result was:
  • the conversion of methanol is 17.35%, the selectivity of ethylene glycol is 37.82%, and the selectivity of ethanol is 6.25%.
  • the selectivity of n-propanol is 1.98%; the conversion rate of aluminum electrode and methanol is 12.25%, the selectivity of ethylene glycol is 42.37%, the selectivity of ethanol is 5.16%, and the selectivity of n-propanol is 2.15% ; cast copper electrode , methanol conversion rate 12.38% , ethylene glycol selectivity 52.78% , ethanol selectivity 6.28% , n - propanol selectivity 0.95% ;
  • the conversion of methanol was 21.85%, the selectivity of ethylene glycol was 39.75%, the selectivity of ethanol was 6.42%, and the selectivity of n-propanol was 0.82%.
  • Example 6 was repeated, but the thickness of the barrier medium was maintained at 1.0 mm, and when the discharge power was changed, the reaction result was:
  • the discharge power is 7.35W, the conversion of methanol is 5.78%, the selectivity of ethylene glycol is 56.25%, and the selectivity of ethanol is 7.32%, the selectivity of n-propanol is 2.24%; the discharge power is 12.38W, the conversion of methanol is 15.27%, the selectivity of ethylene glycol is 49.78%, and the selectivity of ethanol is 6.24%, the selectivity of n-propanol is 1.65%; the discharge power is 25.76W, the conversion rate of methanol is 21.36%, the selectivity of ethylene glycol is 38.45%, and the selectivity of ethanol is 5.24%, the selectivity of n-propanol is 1.05%; the discharge power is 39.83W, the conversion rate of methanol is 39.79%, the selectivity of ethylene glycol is 29.75%, and the selectivity of ethanol is 4.13%, the selectivity of n-propanol is 0.94%; the discharge power is 51.28W
  • Example 6 was repeated, but the thickness of the barrier medium was maintained at 1.0 mm, and when the discharge frequency was changed, the reaction result was:
  • the discharge frequency is 6.0 kHz, the conversion rate of methanol is 29.35%, and the selectivity of ethylene glycol is 26.28%.
  • the selectivity of ethanol is 3.59%, the selectivity of n-propanol is 1.01%, the discharge frequency is 12.0 kHz, the conversion of methanol is 18.72%, and the selectivity of ethylene glycol is 38.27%.
  • the selectivity of ethanol is 5.28%, the selectivity of n-propanol is 1.82%, the discharge frequency is 18.0kHz, the conversion of methanol is 13.27%, and the selectivity of ethylene glycol is 46.37%.
  • the selectivity of ethanol is 6.24%, the selectivity of n-propanol is 2.15%, the discharge frequency is 24.0kHz, the conversion of methanol is 24.27%, and the selectivity of ethylene glycol is 33.28%.
  • the selectivity of ethanol is 4.37%, the selectivity of n-propanol is 1.34%, the discharge frequency is 30.0kHz, the conversion of methanol is 8.76%, and the selectivity of ethylene glycol is 59.79%.
  • the selectivity to ethanol is 7.35% and the selectivity to n-propanol is 2.53%.
  • Example 6 was repeated, but the thickness of the barrier medium was maintained at 1.0 mm, and when the type of the carrier gas was changed, the reaction result was:
  • the selectivity of n-propanol is 1.28%; the conversion of nitrogen:methanol is 17.28%, the selectivity of ethylene glycol is 31.85%, the selectivity of ethanol is 4.93%, and the selectivity of n-propanol is 1.62% ; methane: methanol conversion rate 8.35%, ethylene glycol selectivity 56.75%, ethanol selectivity 7.25%, n-propanol selectivity 2.73%; Hydrogen: methanol conversion rate 16.27%, ethylene glycol selectivity 38.75%, ethanol selectivity 5.27%, n-propanol selectivity 1.72%; helium: methanol conversion rate 10.52%, the selectivity of ethylene glycol was 46.25%, the selectivity of ethanol was 6.31%, and the selectivity of n-propanol was 2.14%.
  • Example 6 was repeated, but the barrier medium thickness was maintained at 1.0 mm, then the carrier gas Ar When the molar ratio of feed to methanol changes, the reaction results are:
  • the molar ratio is 0, the conversion of methanol is 29.52%, the selectivity of ethylene glycol is 15.34%, and the selectivity of ethanol is 3.12%, the selectivity of n-propanol is 0.86%; the molar ratio is 2, the conversion rate of methanol is 25.37%, the selectivity of ethylene glycol is 25.86%, and the selectivity of ethanol is 4.28%.
  • the selectivity of n-propanol is 1.35%; the molar ratio is 6, the conversion of methanol is 18.75%, the selectivity of ethylene glycol is 34.27%, and the selectivity of ethanol is 5.82%.
  • the selectivity of n-propanol is 2.15%; the molar ratio is 12, the conversion of methanol is 13.24%, the selectivity of ethylene glycol is 48.75%, and the selectivity of ethanol is 6.34%.
  • the selectivity of n-propanol is 3.82%; the molar ratio is 18, the conversion of methanol is 8.28%, the selectivity of ethylene glycol is 59.36, and the selectivity of ethanol is 7.52%.
  • the selectivity of n-propanol was 4.22%.
  • Example 6 was repeated, but the thickness of the barrier medium was maintained at 2.0 mm, and when the reaction temperature was changed, the reaction result was:
  • the conversion of methanol was 12.37%, the selectivity of ethylene glycol was 57.62%, and the selectivity of ethanol was 8.34%.
  • the selectivity of n-propanol is 2.18%; the conversion of methanol is 18.25.% at 150 °C, the selectivity of ethylene glycol is 45.37%, and the selectivity of ethanol is 7.52%.
  • the selectivity of n-propanol is 1.97%; the conversion of methanol is 29.37% at 250 °C, the selectivity of ethylene glycol is 35.24%, and the selectivity of ethanol is 6.29%.
  • the selectivity of n-propanol is 1.42%; the conversion of methanol is 34.56% at 350 °C, the selectivity of ethylene glycol is 26.27%, and the selectivity of ethanol is 5.95%.
  • the selectivity of n-propanol is 1.05%; the conversion of methanol is 44.31% at 450 °C, the selectivity of ethylene glycol is 15.48%, and the selectivity of ethanol is 3.84%.
  • the selectivity of n-propanol is 0.82%;
  • Example 6 was repeated, but the thickness of the barrier medium was maintained at 2.0 mm and the reaction temperature was maintained at 220 °C. If the reaction pressure does not change, the result is:
  • the conversion rate of methanol is 28.52%, the selectivity of ethylene glycol is 29.38%, and the selectivity of ethanol is 6.17%, the selectivity of n-propanol is 0.76%; 0.06MPa, the conversion of methanol is 21.37%, the selectivity of ethylene glycol is 37.22%, and the selectivity of ethanol is 7.23%.
  • the selectivity of n-propanol is 0.98%; the conversion of methanol is 0.10MPa, the conversion of methanol is 13.28%, the selectivity of ethylene glycol is 45.76%, and the selectivity of ethanol is 8.32%.
  • the selectivity of n-propanol is 1.37%; the conversion of methanol is 0.16MPa, the conversion of methanol is 10.52%, the selectivity of ethylene glycol is 58.34%, and the selectivity of ethanol is 8.94%.
  • the selectivity of n-propanol is 1.56%;
  • a molar ratio of He to gaseous methanol of 3:1 (where He flow rate is 30ml/min, methanol flow rate of 10ml/min) is passed into the tube-and-plate reactor. After the gas flow is stabilized, the power is turned on for dielectric barrier discharge. .
  • the tube-and-plate reactor housing is made of quartz glass with an outer diameter of 13.0 mm and a wall thickness of 1.5 mm.
  • the metal plate electrode and the metal tube electrode are made of stainless steel; the metal plate electrode has a diameter of 10 Mm, thickness 0.3 mm, electrode spacing 5.0 mm; blocking medium is a single layer of quartz glass with a thickness of 1.0 mm.
  • the discharge parameters of the reactor are: voltage 20.0kV, current 0.42A, frequency 10.0kHz; discharge temperature 150 °C, when the discharge frequency and discharge power are kept constant at 10.0 kHz and 21.5 W, respectively, and the diameter of the metal tube electrode is changed, the reaction result is:
  • the diameter of the metal tube is 2 mm, the conversion of methanol is 38.56%, and the selectivity of ethylene glycol is 29.38%.
  • the selectivity of ethanol is 3.58%, the selectivity of n-propanol is 0.67%, the diameter of metal tube is 3 mm, the conversion of methanol is 27.38%, and the selectivity of ethylene glycol is 34.27%.
  • the selectivity of ethanol is 7.39%, the selectivity of n-propanol is 0.95%, the diameter of metal tube is 5 mm, the conversion of methanol is 18.82%, and the selectivity of ethylene glycol is 41.35%.
  • the selectivity of ethanol is 10.58%, the selectivity of n-propanol is 1.25%, the diameter of metal tube is 6 mm, the conversion of methanol is 11.35%, and the selectivity of ethylene glycol is 59.27%.
  • the selectivity of ethanol is 12.37% and the selectivity of n-propanol is 1.56%;
  • Example 17 Dielectric Barrier Discharge --- Plate and Plate Reactor
  • N 2 and gaseous methanol were fed into the plate-plate reactor at a molar ratio of 4:1 (where N 2 flow rate was 24 ml/min and methanol flow rate was 6 ml/min) under a pressure of 0.12 MPa, and the gas was turned on after the gas flow was stabilized. Perform dielectric barrier discharge.
  • the plate-and-plate reactor has a wall thickness of 3.0 mm and is made of stainless steel with a diameter of 80 mm and an electrode spacing of 12 mm.
  • the blocking medium is quartz glass with a thickness of 0.3 mm.
  • the discharge parameters of the reactor are: voltage 21.0kV, current 0.48A, frequency 13.0kHz; discharge temperature 180 °C, when the discharge frequency and discharge power are kept unchanged at 13.0 kHz and 32 W, respectively, and the number of barrier dielectric layers is modulated, the reaction result is:
  • the conversion of methanol is 36.68%, the selectivity of ethylene glycol is 18.76%, and the selectivity of ethanol is 4.58%, the selectivity of n-propanol is 0.95%; the conversion rate of methanol is 28.18%, the selectivity of ethylene glycol is 25.37%, and the selectivity of ethanol is 5.37%.
  • the selectivity of n-propanol is 1.34%; the conversion rate of methanol is 16.82%, the selectivity of ethylene glycol is 37.25%, and the selectivity of ethanol is 6.47%.
  • n-propanol The selectivity of n-propanol is 1.87%; the conversion rate of methanol is 8.31%, the selectivity of ethylene glycol is 46.73%, and the selectivity of ethanol is 7.21%.
  • the selectivity of n-propanol is 2.19%;
  • H 2 and gaseous methanol were introduced into the discharge reactor at a molar ratio of 5:1 (where H 2 flow rate was 40 ml/min, methanol flow rate was 8 ml/min), and after the gas flow was stabilized, the pulsed high-voltage power source was turned on. Perform a corona discharge.
  • the reactor was constructed with a wire barrel electrode structure with a central halo of 2 mm Pt-plated copper electrodes.
  • the cartridge collecting electrode is a stainless steel cylinder having a length of 250 mm and an inner diameter of 20 mm.
  • the effective discharge length of the reactor was 80 mm.
  • the pulsed DC high voltage power supply uses a storage capacitor to generate a pulse voltage by discharging the spark gap to the load.
  • the discharge parameters of the reactor are: peak value of pulse voltage 30kV, pulse repetition frequency 78Hz; discharge temperature
  • the reaction results at 180 °C were: methanol conversion rate of 33.50%, ethylene glycol selectivity of 17.38%, ethanol selectivity of 6.78%, and n-propanol selectivity of 1.56%.
  • O 2 and gaseous methanol were fed into the discharge reactor at a molar ratio of 1:1 (where O 2 vapor flow rate was 20 ml/min and methanol flow rate was 20 ml/min) under a pressure of 0.12 MPa.
  • the power was turned on. Glow discharge.
  • the rotating spiral electrode in the reactor is connected to the magnetic fluid sealing device via an insulating joint and then connected to the rotating mechanism.
  • the reaction gas chemically reacts in the plasma region formed between the two electrodes, and the reactants all pass vertically through the plasma region during the rotating discharge reaction.
  • the reactor adopts a wire barrel structure, a metal nickel electrode (diameter: 3 mm) is used for the center electrode, and a stainless steel tube (outer diameter: 27 mm, inner diameter: 25 mm) is used for the outer electrode, the pole pitch is 11 mm, and the discharge zone length is 100 mm.
  • the discharge parameters of the reactor are: bipolar high voltage pulse power supply operating frequency is 14.0 kHz, pulse power supply duty cycle is 9%
  • the input electric field peak voltage is 1.6kV; when the discharge temperature is 350 °C, the reaction results are: methanol conversion rate 21.36%, ethylene glycol selectivity 12.57%, ethanol selectivity 6.24% , n-propanol selectivity 2.15%.

Abstract

A method for converting methanol, belonging to the field of plasma synthesis chemistry. In the method, methanol molecules are selectively activated by selecting a discharging method such as dielectric barrier discharge, corona discharge, pulse corona discharge, glow discharge, etc., and then the selectively activated methanol is converted into a target product by setting the residue time of the reaction mixture in the reaction zone, the temperature and the pressure of the discharge reaction, and the molar ratio of the carrier gas to methanol. In the method, methanol is used as a raw material to produce ethylene glycol, with the sources of methanol being various and renewable. The method belongs to a one-step synthesis process without a catalyst, causes no pollution to the environment and is highly selective. While ethylene glycol is obtained in the present method, ethanol and n-propanol can also be produced jointly by optimizing the conditions, and the method therefore has good prospects for industrial applications.

Description

一种转化甲醇的方法 Method for converting methanol
技术领域 Technical field
本发明属于等离子体合成化学领域，涉及一种甲醇直接制备乙二醇的方法。 The invention belongs to the field of plasma synthesis chemistry and relates to a method for directly preparing ethylene glycol from methanol.
背景技术 Background technique
甲醇是一种重要的基本有机化工原料，用途广泛。最引人注目的是用于合成二甲醚，烯烃；另外还有氢气、汽油、碳酸酯、芳烃、乙醇、乙二醇，羰基化制醋酸和燃料等。由于煤炭资源丰富，煤制甲醇工业发展迅速，产能大。因此，从甲醇出发，制取各种高附加值的化工产品具有广阔的前景。 很多公开文献和专利涉及了甲醇转化反应，以下专利涉及了甲醇转化制烯烃反应，如： CN101250080A ； CN101279280A ； CN101270020A ； CN101327446A ； CN101328101A ； US20030621788 ； US20050075286 ； US20050211880 ； US20060503913 ； US20060540802 ； CA20072664404 ； US2009005624A1 ； US20080260751 ； 还有一些专利涉及甲醇转化制二甲醚的方法，这也是甲醇研究领域的热点之一。如： CN1125216A ； CN1301686A ； CN1368493A ； CN1180064A ； CN101119952A ； CN101104575A ； CN101659600A ； US20020188882 ； US20050241321 ； WO2006CN01965 ； US20070310529 ； WO2008090268A1 ； US20080594006 ； US20080663058 ； US20080188882 ； WO2009126765A2; 另外还有一些专利涉及到甲醇转化制氢气、汽油、芳烃、碳酸酯、燃料，等等。如： CN101104813A ； CN201024087 ； CN201068444 ； CN101343574A ； CN101381287A ； JP20030346324 ； US20040476510 ； EP20040746362 ； WO2005JP20699 ； EP20050805952 ； US20060988799 ； US2007207361A1 ； US20070955610。还有很多公开文献涉及甲醇转化制烯烃、芳烃、汽油、二甲醚等。此外也有一些专利涉及到甲醇转化制乙醇、丙醇和乙二醇。如： 专利 US3248432A( 申请号 US19610158870 申请日 1961-12-12 ）披露了一种甲醇制乙醇的方法。其技术特征是：在水溶性钴催化剂，碘促进剂和磷化物的甲醇溶液存在下，甲醇，一氧化碳和 H2 在高压加热下反应生成乙醇。反应温度为 150-250℃，反应压力为20.7-103.5MPa 。 专利 US4424383A （申请号 US19810320008 申请日:1981-11-10 ）披露了一种甲醇制乙醇和正丙醇的方法。其技术特征是：在由钴、钌、碘、有机磷等组成的催化剂存在下，甲醇和一氧化碳、 H2 在反应温度 150~250 ℃，反应压力 20~60MPa 下反应生成乙醇和正丙醇。 专利 US4337371A （申请号 US19800183537 申请日 1980-09-02 ） 披露了一种以甲醇和甲醛为原料，缩合生产乙二醇的方法。其技术特征是：使用 wt%<6% 的有机过氧化物如二叔丁基过氧化物（ DTBP ）、过氧化二异丙苯（ DCP ）作为引发剂，得到的产物中乙二醇的含量最高为 7.71% 。 专利 JP63027445A( 申请号 19860168874 申请日 1986-07-17 ) 披露了一种甲醇制乙二醇的方法。其技术特征是：甲醇首先经脱水反应生成二甲醚，二甲醚再在催化剂的存在下与氧气经氧化偶联反应生成二甲氧基乙烷，最后，二甲氧基乙烷经水解反应生成乙二醇。 专利 US005214182( 申请号 726715 申请日 1991-06-01 ) 披露了一种生产乙二醇的方法。其技术特征是：在非均相聚合催化剂三氢化磷存在下，甲醇和碳酸亚乙酯反应生成乙二醇，并同时联产碳酸二甲酯，乙二醇和碳酸二甲酯共选择性高达 98% 。 另外，以下专利也涉及了甲醇转化制乙醇，丙醇和乙二醇： US4277634A ； US4239924 ； US4235801A ； US4355192A ； JP57122028A ； US19810224199 ； US4472522A ； US4472526A ； US19810223514 ； JP19810206294 ； US20080228572 ； EP2244993 ； EP20080800368 ； WO2008CA01676 ； US4013700 ；Methanol is an important basic organic chemical raw material with a wide range of uses. The most striking is the synthesis of dimethyl ether, olefins; in addition to hydrogen, gasoline, carbonates, aromatics, ethanol, ethylene glycol, carbonylation of acetic acid and fuel. Due to the abundant coal resources, the coal-to-methanol industry has developed rapidly and has a large production capacity. Therefore, starting from methanol, it has broad prospects for the production of various high value-added chemical products. A number of published documents and patents relate to methanol conversion reactions, and the following patents relate to methanol conversion to olefins, such as: CN101250080A; CN101279280A; CN101270020A; CN101327446A; CN101328101A; US20030621788; US20050075286; US20050211880; US20060503913; US20060540802; CA20072664404; US2009005624A1; US20080260751; There are some patents related to the conversion of methanol to dimethyl ether, which is one of the hot spots in the field of methanol research. For example: CN1125216A; CN1301686A; CN1368493A; CN1180064A; CN101119952A; CN101104575A; CN101659600A; US20020188882; US20050241321; WO2006CN01965; US20070310529; WO2008090268A1; US20080594006; US20080663058; US20080188882; WO2009126765A2; Carbonates, fuels, etc. For example: CN101104813A; CN201024087; CN201068444; CN101343574A; CN101381287A; JP20030346324; US20040476510; EP20040746362; WO2005JP20699; EP20050805952; US20060988799; US2007207361A1; US20070955610. There are also many publications relating to the conversion of methanol to olefins, aromatic hydrocarbons, gasoline, dimethyl ether and the like. In addition, some patents involve the conversion of methanol to ethanol, propanol and ethylene glycol. For example, a method for producing ethanol from methanol is disclosed in the patent US Pat. No. 3,248,432, filed on Jan. 1, s. The technical feature is that methanol, carbon monoxide and H2 are reacted under high pressure to form ethanol in the presence of a water-soluble cobalt catalyst, an iodine promoter and a phosphide solution in methanol. The reaction temperature is 150-250 ° C and the reaction pressure is 20.7 - 103.5 MPa. A method for producing ethanol and n-propanol from methanol is disclosed in U.S. Patent No. 4,424,383, issued to A.S. Pat. The technical feature is: in the presence of a catalyst composed of cobalt, ruthenium, iodine, organic phosphorus, etc., methanol and carbon monoxide, H 2 react at a reaction temperature of 150-250 ° C, and a reaction pressure of 20-60 MPa to form ethanol and n-propanol. Patent US 4,337,371, A (Application No. US Pat. The technical feature is that the content of ethylene glycol in the obtained product is obtained by using an organic peroxide such as di-tert-butyl peroxide (DTBP) or dicumyl peroxide (DCP) as an initiator. The highest is 7.71%. A method of producing ethylene glycol from methanol is disclosed in the patent JP63027445A (Application No. 19860168874, filing date 1986-07-17). The technical feature is that methanol is first dehydrated to form dimethyl ether, and dimethyl ether is oxidatively coupled with oxygen to form dimethoxyethane in the presence of a catalyst, and finally, dimethoxyethane is hydrolyzed. Glycol is produced. A method for producing ethylene glycol is disclosed in the patent US005214182 (Application No. 726715, filed on Jun. The technical feature is: in the presence of heterogeneous polymerization catalyst phosphorus hydride, methanol and ethylene carbonate react to form ethylene glycol, and simultaneously produce dimethyl carbonate, ethylene glycol and dimethyl carbonate have a selectivity of up to 98 %. In addition, the following patents also relate to methanol conversion to ethanol, propanol and ethylene glycol: US4277634A; US4239924; US4235801A; US4355192A; JP57122028A; US19810224199; US4472522A; US4472526A; US19810223514; JP19810206294; US20080228572; EP2244993; EP20080800368; WO2008CA01676; US4013700;
另外还有一些公开文献也涉及甲醇制乙二醇方法： 公开文献《催化学报》 . VOL.19 ， No. 6 ， 1998 ， 601-604. 报道了一种由甲醇制备乙二醇的方法。其特点是： 采用主客体结构的纳米 ZnS 为催化剂，在汞灯照射下催化甲醇溶液合成乙二醇， 乙二醇的选择性受光源、催化剂的温度处理、反应时间、溶液 pH 值等的影响，选择性最高可达 90 % 以上。 公开文献《物理化学学报》 .VOL.16 ， No.7 ， 2000 ， 601-607. 报道了一种甲醇氧化偶联制乙二醇的方法。其特点是：用沉淀法制备了 Li3PO4 、 BiPO4 、 Li3PO4·BiPO4 三种固体表面材料，并用频率为 1077cm -1 的激光光子激发固体表面 P=O 键，使其端氧活化，活化的氧与吸附态的甲醇分子作用使其脱氢，进而氧化偶联生成乙二醇。在常压和 120 ℃ 的反应条件下，用 1077cm -1 激光激发 Li3PO4·BiPO4 表面 1000 次，甲醇转化率达 16% ，乙二醇的选择性达 97.7% 。 公开文献 J.Photochem.Photobiol.A:Chem ， 74 ， 1993 ， 85-89. 报道了一种甲醇溶液有效产氢和乙二醇的方法。其特点是：在 ZnS 胶体存在的条件下，甲醇溶液经紫外光照射后直接生成乙二醇和 H2 ，其 H2 和乙二醇的收率及乙二醇的选择性与初始 pH 值及反应温度密切相关，乙二醇的选择性最高达到 95% ，反应 6h 乙二醇的产量在 6.5~44.8mmol 之间 。实验证实：在碱性反应体系 中· CH2OH 是主要的自由基中间体， · CH2OH 的耦合是乙二醇的主要形成途径。 In addition, there are some published documents related to the methanol glycol process: The open literature, Journal of Catalysis. VOL.19, No. 6, 1998, 601-604. A method for preparing ethylene glycol from methanol is reported. Its characteristics are: using nano-ZnS as the catalyst of host-guest structure, the methanol solution is used to synthesize ethylene glycol under the irradiation of mercury lamp. The selectivity of ethylene glycol is affected by the temperature of the light source, the temperature of the catalyst, the reaction time and the pH value of the solution. The selectivity is up to 90% or more. The open literature, Journal of Physical Chemistry, VOL.16, No.7, 2000, 601-607. A method for the oxidative coupling of methanol to ethylene glycol is reported. It is characterized by three solid surface materials of Li 3 PO 4 , BiPO 4 , Li 3 PO 4 ·BiPO 4 prepared by precipitation method, and the laser photon with a frequency of 1077 cm -1 is used to excite the solid surface P=O bond to make its end. Oxygen activation, activated oxygen and desorption of methanol molecules in the adsorption state, and then oxidative coupling to form ethylene glycol. Under normal pressure and 120 °C reaction conditions, the surface of Li 3 PO 4 ·BiPO 4 was excited 1000 times with a 1077 cm -1 laser, the methanol conversion rate was 16%, and the selectivity of ethylene glycol was 97.7%. Publication J. Photochem. Photobiol. A: Chem, 74, 1993, 85-89. A method for efficiently producing hydrogen and ethylene glycol in a methanol solution is reported. Its characteristics are: in the presence of ZnS colloid, methanol solution directly generates ethylene glycol and H 2 after irradiation with ultraviolet light, the yield of H 2 and ethylene glycol and the selectivity and initial pH value of ethylene glycol and reaction The temperature is closely related, the selectivity of ethylene glycol is up to 95%, and the yield of ethylene glycol in reaction is between 6.5 and 44.8 mmol. Experiments have confirmed that in the alkaline reaction system, CH 2 OH is the main free radical intermediate, and the coupling of CH 2 OH is the main formation pathway of ethylene glycol.
以下一些专利、公开文献报道了等离子体放电甲醇转化的研究 : 公开文献《第二届国际氢能论坛青年氢能论坛》， 2003 ， 77-81. 报道了一种冷等离子体放电甲醇制氢的方法。其特点是：在常温常压下利用电晕放电等离子体反应器分解甲醇，产氢量达到 50ml/min ，能效达到 1.5mmol/kJ ，甲醇的最高转化率达 80% ，产物中还有少量的一氧化碳和痕量的乙醇、丙醇、乙二醇生成。 公开文献 《化工学报》， VOL.55 ， No.12 ， 2004 ， 1989-1993. 报道了 一种电晕放电等离子体甲醇分解制氢的方法。其特点是：分别使用直流及交流电晕放电考察了甲醇分解的效果，在交流电的正弦波和三角正弦波对甲醇的转化非常有效，转化率可达 70% 以上，制氢速度可达 50ml.min-1 ，同时提到反应产物中有痕量乙二醇。 公开文献 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS ， VOL.39 ， NO.2 ， MARCH/APRIL 2003 ， 340-345. 报道了一种冷等离子体转化甲醇制氢的方法。其特点是：使用两种不同的反应器：铁电填充床反应器及无声放电等离子体反应器，在不同的反应条件下实现了甲醇的转化，后者的产氢效率低于前者，反应产物中没有提及乙二醇的生成。 公开文献 Chinese Chemical Letters.VOL.14 ， No.6 ， 2003 ， 631-633. 报道了一种电晕放电甲醇分解制氢的方法。其特点是：在室温下使用电晕放电转化液体甲醇产生 H2 ，甲醇溶液中水的含量对反应有显著的影响，当水含量从 1.0% 增加到 16.7% 时，甲醇的转化率从 0.196 提高到 0.284mol/h ，同时，文献中提到随着含水量的增加，乙二醇副产物的收率从 0.0045 增加到 0.0075mol/h ，但总量很少 。 公开文献 Chemistry Letters.VOL.33 ， No.6 ， 2004 ， 744-745. 报道了一种电晕放电等离子体分解甲醇制氢的方法。其特点是：分别使用直流及交流电晕放电进行甲醇等离子体分解制取 H2 ，其中交流电晕放电能获得较高的产氢速率，其制氢能耗低于 0.02Wh/Ncm3H2 ，文献中未提及乙二醇的生成 。 公开文献 JSME International Journal ， Series B ， VOL.48 ， No.3 ， 2005 ， 432-439. 报道了一种冷等离子体分解甲醇的方法。其特点是：使用 DBD 产生冷等离子体流，在空气气氛下分解甲醇，提出 OH 是分解甲醇的重要自由基，但未提及产物中有乙二醇生成。 公开文献 INTERNATIONAL JOURNAL OF HYDROGEN ENERGY ， 34(2009) ， 48-55. 报道了一种辉光放电等离子体电解甲醇溶液的方法。其特点是：分别使用阴极辉光放电、阳极辉光放电电解甲醇溶液，电解主要产物是 H2 和 HCHO ，并且随着甲醇溶液浓度的增加 H2 的收率增加，未提及产物中有乙二醇生成。 公开文献 J.Phys.Chem.A ， VOL.114 ， No.11 ， 2010 ， 4009-4016. 报道了一种等离子体分解甲醇的方法。其特点是：在大气压介质阻挡放电条件下分解甲醇，对比了两种不同等离子体反应器结构，考察了电极表面粗糙度、及不同的填充电解质（ Al2O3 或 BaTiO3 ）对甲醇转化率的影响。其放电主要产物为 H2 和一氧化碳，没有长碳链的碳氢化合物及焦炭产生。The following patents and open literature report on the study of plasma-discharge methanol conversion: The open literature, "The 2nd International Hydrogen Energy Forum Youth Hydrogen Forum", 2003, 77-81. Reported a cold plasma discharge methanol hydrogen production method. Its characteristics are: decomposing methanol by corona discharge plasma reactor under normal temperature and normal pressure, the hydrogen production amount reaches 50ml/min, the energy efficiency reaches 1.5mmol/kJ, the highest conversion rate of methanol reaches 80%, and there is a small amount in the product. Carbon monoxide and trace amounts of ethanol, propanol, and ethylene glycol are formed. The open literature "Journal of Chemical Industry", VOL.55, No.12, 2004, 1989-1993. A method for producing hydrogen by methanol decomposition in corona discharge plasma is reported. Its characteristics are: using DC and AC corona discharge to investigate the effect of methanol decomposition, the sine wave and triangular sine wave of alternating current are very effective for the conversion of methanol, the conversion rate can reach more than 70%, and the hydrogen production rate can reach 50ml.min. -1 , also mentioned that there are trace amounts of ethylene glycol in the reaction product. The publication IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL.39, NO.2, MARCH/APRIL 2003, 340-345. A method for converting methanol to hydrogen by cold plasma is reported. Its characteristics are: using two different reactors: ferroelectric packed bed reactor and silent discharge plasma reactor, the conversion of methanol is realized under different reaction conditions, the latter has lower hydrogen production efficiency than the former, and the reaction product There is no mention of the formation of ethylene glycol. The publication Chinese Chemical Letters. VOL. 14 , No. 6, 2003, 631-633. A method for producing hydrogen by methanol decomposition by corona discharge is reported. It is characterized by the use of corona discharge to convert liquid methanol to H 2 at room temperature. The water content in the methanol solution has a significant effect on the reaction. When the water content increases from 1.0% to 16.7%, the methanol conversion rate increases from 0.196. At 0.284 mol/h, the literature mentions that the yield of ethylene glycol by-product increases from 0.0045 to 0.0075 mol/h with increasing water content, but the total amount is small. Publication Letters. VOL. 33, No. 6, 2004, 744-745. A method for decomposing methanol to produce hydrogen by corona discharge plasma is reported. The characteristics are: using DC and AC corona discharge for methanol plasma decomposition to obtain H 2 , wherein AC corona discharge can obtain higher hydrogen production rate, and its hydrogen production energy consumption is lower than 0.02Wh/Ncm 3 H 2 , literature There is no mention of the formation of ethylene glycol. The open literature JSME International Journal, Series B, VOL. 48, No. 3, 2005, 432-439. A method for decomposing methanol by cold plasma is reported. It is characterized by the use of DBD to generate a cold plasma stream, which decomposes methanol under an air atmosphere, and proposes that OH is an important free radical for decomposing methanol, but there is no mention of ethylene glycol formation in the product. Publications INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, 34 (2009), 48-55. A method of glow-discharge plasma electrolysis of a methanol solution is reported. Its characteristics are: using cathode glow discharge, anode glow discharge electrolysis methanol solution, the main products of electrolysis are H 2 and HCHO, and the yield of H 2 increases with the increase of methanol solution concentration, there is no mention of B in the product. Glycol formation. Publication J. Phys. Chem. A, VOL. 114, No. 11, 2010, 4009-4016. A method for plasma decomposition of methanol is reported. It is characterized by decomposition of methanol under atmospheric pressure dielectric barrier discharge, comparing the structure of two different plasma reactors, and examining the surface roughness of the electrode and the conversion of methanol to different filling electrolytes (Al 2 O 3 or BaTiO 3 ). Impact. The main products of the discharge are H 2 and carbon monoxide, and hydrocarbons and coke without long carbon chains are produced.
在有关等离子体放电的公开文献和专利中，甲醇转化都是以制氢为目的；二甲醚、乙醇、乙二醇只是其中的微量副产品，产量和选择性都很低。到目前为止，还没有专利和公开文献涉及到甲醇经等离子体转化直接制备乙二醇产物的报道。 In the publications and patents relating to plasma discharge, methanol conversion is for the purpose of hydrogen production; dimethyl ether, ethanol, and ethylene glycol are only a minor by-product thereof, and the yield and selectivity are low. To date, no patents or publications have been reported on the direct preparation of ethylene glycol products by plasma conversion of methanol.
目前生产乙二醇的主要方法是环氧乙烷非催化水合法，这也是唯一的工业化方法。该方法技术成熟、产量大，但是生产工艺流程长、设备多、能耗高、对环境污染严重，使乙二醇成本高。其他合成乙二醇的新方法都面临着很多问题，工业化难度大。等离子体技术有别于常规热催化和光催化技术，其特征在于利用放电产生的高能电子活化反应物，产生相应的自由基，自由基经过链传递、反应得到产物，不必使用催化剂，对环境无污染。 The current main method of producing ethylene glycol is ethylene oxide non-catalytic hydration, which is also the only industrial process. The method is mature in technology and large in output, but the production process is long, the equipment is high, the energy consumption is high, and the environmental pollution is serious, so that the cost of ethylene glycol is high. Other new methods for synthesizing ethylene glycol are facing many problems, and industrialization is difficult. Plasma technology is different from conventional thermal catalysis and photocatalysis technology. It is characterized by the use of high-energy electrons generated by discharge to activate reactants to generate corresponding free radicals. The radicals are transported through chains and react to obtain products without using catalysts. .
等离子体是物质存在的第四种状态，当对物质施加高温或外加高电压时，电中性的物质会通过激发、解离、离子化等反应而产生原子、受激态物质、电子、正离子、负离子、自由基、紫外光和可见光等物质，这些由带电粒子（离子、电子）和中性粒子（原子、分子、自由基等）组成的***，在宏观上正负电荷相等，因而称为等离子体。 等离子体中的电子在外加电场的加速作用下累积动能，具有高能量的电子通过非弹性碰撞反应物分子，使分子发生电子激发或离解。等离子体中含有的离子、激发态的原子或分子及自由基物种，具有较高的化学反应活性，能够通过相互碰撞引发化学反应。根据等离子体的能量状态、气体温度和粒子密度的差异，等离子体可分为高温等离子体、热等离子体和冷等离子体。 由于冷等离子体处于热力学不平衡状态，电子温度（ Te ）＞＞离子温度（ Ti ），中性粒子温度（ Tn ），它拥有的高电子能量及较低的离子及气体温度这一非平衡特性使之成为工业生产中应用最广泛的等离子体 : 一方面，电子具有足够高的能量使反应物分子激发、离解和电离；另一方面，反应体系又得以保持低温，使反应体系能耗减少，反应容易控制。冷等离子体即非平衡等离子体的产生方式主要有：电晕放电、辉光放电、火花放电、介质阻挡放电、滑动电弧放电、微波等离子体、射频等离子体等。 各种等离子体产生方法中，分子、原子、分子离子、原子离子及电子的存在情况会因气体压力、电场强度、放电电流、放电频率等条件不同有很大不同，也会因放电反应装置的结构不同有很大差异。 由于不同的等离子体状态所含的分子、原子、激发态分子、激发态原子、电子、正离子、负离子、自由基的数目及能量不同，所以选择适当的反应器结构、放电形式和放电条件就能够调变等离子中电子的能量及所包含的活性物种的数目。特定的反应物活化状态对应于特定的化学反应和反应产物。已有等离子体转化甲醇的技术中，大多数技术的产物是 H2 、也有部分技术得到甲醛、甲烷、乙烷、丙烷等烷烃及 CO 、 CO2 和水等。本发明主要由甲醇得到乙二醇、乙醇、丙醇等醇类产物，其原因就在于放电产生等离子中的电子能量不同，进而产生的活性物种不同。Plasma is the fourth state in which a substance exists. When a high temperature or a high voltage is applied to a substance, an electrically neutral substance generates an atom, an excited substance, an electron, and a positive reaction through excitation, dissociation, ionization, and the like. Ions, anions, free radicals, ultraviolet light, and visible light. These systems consisting of charged particles (ions, electrons) and neutral particles (atoms, molecules, free radicals, etc.) are macroscopically positive and negatively charged, so they are called For the plasma. Electrons in the plasma accumulate kinetic energy under the acceleration of an applied electric field, and electrons with high energy collide with the reactant molecules in an inelastic manner to cause electron excitation or dissociation of the molecules. The ions, excited atoms or molecules and radical species contained in the plasma have high chemical reactivity and can initiate chemical reactions by colliding with each other. The plasma can be classified into a high temperature plasma, a thermal plasma, and a cold plasma depending on the difference in energy state of the plasma, gas temperature, and particle density. Since the cold plasma is in thermodynamic imbalance, electron temperature (T e ) >> ion temperature ( T i ), neutral particle temperature (T n ), it has high electron energy and low ion and gas temperature. The non-equilibrium property makes it the most widely used plasma in industrial production: On the one hand, electrons have high enough energy to excite, dissociate and ionize reactant molecules; on the other hand, the reaction system is kept low temperature, so that the reaction system can The consumption is reduced and the reaction is easy to control. Cold plasma, that is, non-equilibrium plasma is mainly produced by corona discharge, glow discharge, spark discharge, dielectric barrier discharge, sliding arc discharge, microwave plasma, radio frequency plasma, and the like. In various plasma generation methods, the presence of molecules, atoms, molecular ions, atomic ions, and electrons may vary greatly depending on conditions such as gas pressure, electric field strength, discharge current, and discharge frequency, and may also be due to discharge reaction devices. The structure is very different. Since different plasma states contain different numbers of molecules, atoms, excited states, excited states, electrons, positive ions, negative ions, and free radicals, the appropriate reactor structure, discharge pattern, and discharge conditions are selected. It is capable of modulating the energy of electrons in the plasma and the number of active species involved. The particular reactant activation state corresponds to a particular chemical reaction and reaction product. In the technology of plasma conversion of methanol, most of the products are H2, and some technologies have obtained alkanes such as formaldehyde, methane, ethane, and propane, as well as CO, CO 2 and water. The invention mainly obtains an alcohol product such as ethylene glycol, ethanol or propanol from methanol, because the electron energy in the plasma generated by the discharge is different, and the active species are different.
甲醇的等离子体反应具有如下具体特点：当对进入放电反应器中的 CH3OH 分子施加高电压时，电子在外加电场的作用下获得很高的动能，高能电子与周围的 CH3OH 分子发生碰撞，使 CH3OH 分子激发电离，从而生成更多的电子，引起电子雪崩，这些电子进一步与 CH3OH 分子进行非弹性碰撞，将能量传递给 CH3OH 分子，使其变成激发态 CH3OH 分子。当高能电子传递给 CH3OH 分子的能量达到或超过 CH3OH 分子中特定化学键键能时，就会发生化学键的重排或断裂，进而生成 ·CH2OH 、 ·CH3 、 CH3O· 、 H· 、 OH· 、 1 CH2 等自由基及 H2O 、 trans-HCOH 、 cri-HCOH 、 CH2O 等物种。这些活性物种进一步彼此碰撞、反应，便生成相应的反应物 HOCH2CH2OH 、 C2H6 、 CH3OCH3 、 H2 等；这些活性物种如进一步跟高能电子发生碰撞、进行能量传递，可发生化学键的进一步断裂，生成 CH2· 、 CH· 、 C· 、 HCO· 、 CO 等自由基，这些自由基可生成深度反应产物如 CH3CH2OH 、 CH3CH2CH2OH 、 CH3CH2CH3 、 C2H2 、 C2H4 、 C3H6 ，甚至 H2 和焦炭（ C ）。 很显然可以通过调变等离子体放电区的电子能量，选择性地活化甲醇分子中特定的化学键，从而达到选择性引发特定化学反应的目的。例如： CH3OH 分子中 C-H 、 C-O 、 O-H 键的键能分别为 94.57kcal.mol-1 、 81.51kcal.mol-1 、 104.9kcal.mol-1 ，当处于等离子体区中的自由电子 e 被电场加速获得高动能时，它将与 CH3OH 分子发生非弹性碰撞。当高能 e 传递给 CH3OH 分子的能量恰好等于 94.57kcal.mol-1 时，则 CH3OH 分子发生解离生成 ·CH2OH ，两个 ·CH2OH 键合便生成 HOCH2CH2OH ；同理， CH3OH 分子获得的能量恰好等于 81.51kcal.mol-1 时，则 CH3OH 分子发生解离生成 ·CH3 和 OH· ；而 CH3OH 分子获得的能量恰好等于 104.9kcal.mol-1 时，则 CH3OH 分子发生解离生成 CH3O· 、 H· ，后二者都导致副反应。因此通过控制甲醇等离子体中的电子能量，或者说平均电子能量，使之恰好适合于甲醇分子中 C-H 活化的需要。The plasma reaction of methanol has the following specific characteristics: when a high voltage is applied to the CH 3 OH molecules entering the discharge reactor, electrons obtain high kinetic energy under the action of an applied electric field, and high-energy electrons and surrounding CH 3 OH molecules occur. Collision, ionization of CH 3 OH molecules, resulting in more electrons, causing electron avalanches, which further inelastically collide with CH 3 OH molecules, transferring energy to CH 3 OH molecules, causing them to become excited CH 3 OH molecule. When the energy transmitted by the high-energy electrons to the CH 3 OH molecule reaches or exceeds the specific chemical bond energy of the CH 3 OH molecule, rearrangement or cleavage of the chemical bond occurs, thereby generating ·CH 2 OH , ·CH 3 , CH 3 O· Free radicals such as H, OH, and 1 CH 2 and species such as H 2 O, trans-HCOH, cri-HCOH, and CH 2 O. These active species further collide and react with each other to form corresponding reactants HOCH 2 CH 2 OH , C 2 H 6 , CH 3 OCH 3 , H 2 , etc.; these active species collide with high-energy electrons for energy transfer, Further cleavage of chemical bonds can occur, generating free radicals such as CH 2 · , CH· , C· , HCO· , CO, which can form deep reaction products such as CH 3 CH 2 OH , CH 3 CH 2 CH 2 OH , CH 3 CH 2 CH 3 , C 2 H 2 , C 2 H 4 , C 3 H 6 , even H 2 and coke (C). It is obvious that the specific chemical bonds in the methanol molecules can be selectively activated by modulating the electron energy of the plasma discharge region, thereby achieving the purpose of selectively initiating a specific chemical reaction. For example: CH 3 OH molecule, CH, CO, OH bond energy is 94.57kcal.mol -1, 81.51kcal.mol -1, 104.9kcal.mol -1, respectively, when the plasma in the region of the free electrons e When the electric field accelerates to obtain high kinetic energy, it will inelastically collide with the CH 3 OH molecule. When the energy of the high energy e to the CH 3 OH molecule is exactly equal to 94.57kcal.mol -1 , the CH 3 OH molecule dissociates to form CH 2 OH , and the two CH 2 OH bonds form HOCH 2 CH 2 OH. Similarly, when the energy obtained by the CH 3 OH molecule is exactly equal to 81.51 kcal.mol -1 , the CH 3 OH molecule is dissociated to form · CH 3 and OH · ; and the energy obtained by the CH 3 OH molecule is exactly equal to 104.9 kcal. When mol -1 , the CH 3 OH molecule dissociates to form CH 3 O· and H· , both of which cause side reactions. Therefore, by controlling the electron energy in the methanol plasma, or the average electron energy, it is just right for the need for CH activation in methanol molecules.
发明内容 Summary of the invention
本发明提供了一种非平衡等离子体一步转化甲醇制备乙二醇的方法，其利用放电产生的等离子体中的高能电子碰撞甲醇气体分子，进而产生羟甲基自由基 (·CH2OH) ，两个 ·CH2OH 偶联生成乙二醇。The invention provides a method for preparing ethylene glycol by one-step conversion of methanol in a non-equilibrium plasma, which utilizes high-energy electrons in a plasma generated by a discharge to collide with methanol gas molecules, thereby generating a methylol radical (·CH 2 OH). The two CH 2 OH are coupled to form ethylene glycol.
本发明通过以下方法调节等离子体区高能电子的能量，从而达到选择性生成乙二醇产物的目的。具体技术方案如下： The present invention achieves the purpose of selectively producing an ethylene glycol product by adjusting the energy of high energy electrons in the plasma region by the following method. The specific technical solutions are as follows:
a 、通过放电形式选择，可选择的放电形式是：电晕放电、辉光放电、介质阻挡放电； b 、通过反应器结构优化，可选择的反应器结构形式为：线筒式反应器、针板式反应器、板板式反应器、管板式反应器； c 、通过反应器参数优化，应考虑的参数为：放电区长度、极间距、电介质材质、高压极、接地极材质； d 、通过放电条件优化，应优化的放电条件为：放电电压、放电频率、放电气氛、甲醇 / 载气摩尔比、放电气压、放电温度； a, through the discharge form selection, the selectable discharge form is: corona discharge, glow discharge, dielectric barrier discharge; b Through the optimization of the reactor structure, the optional reactor structure is: wire barrel reactor, needle plate reactor, plate plate reactor, tube plate reactor; c Through the optimization of reactor parameters, the parameters to be considered are: discharge zone length, pole spacing, dielectric material, high voltage pole, grounding pole material; d By optimizing the discharge conditions, the discharge conditions to be optimized are: discharge voltage, discharge frequency, discharge atmosphere, methanol/carrier gas molar ratio, discharge gas pressure, discharge temperature;
本发明的技术方案包括如下步骤： The technical solution of the present invention includes the following steps:
（ 1 ）选择下述放电方法之一使甲醇分子得到选择性活化 (1) Select one of the following discharge methods to selectively activate methanol molecules
① 采用介质阻挡放电：可以采用板板式反应器、管板式反应器、针板式反应器和线筒式反应器，阻挡介质是单层介质或双层介质，贴在电极表面或置于两极之间； 1 Dielectric barrier discharge: a plate plate reactor, a tube plate reactor, a needle plate reactor and a wire barrel reactor may be used, and the barrier medium is a single layer medium or a double layer medium, which is attached to the surface of the electrode or placed between the two electrodes;
其中线筒式反应器的高压极和接地极分别为处于反应器壳体内的金属丝和环绕在外筒壁上的金属片、金属网或金属丝； 两极间距是指位于轴线的中心金属线状电极外壁与筒状接地电极内壁之间的距离， 电极间距可取 0.3-20mm ，优选 1-5mm 。线筒式反应器包括两种：一种是反应器壁做阻挡介质的单介质阻挡线筒式反应器；另一种是反应器壁做第一阻挡介质并在两极间***第二阻挡介质的双介质阻挡线筒式反应器；反应器外筒上端设甲醇和载气进口。 Wherein the high-voltage pole and the grounding pole of the wire-tube reactor are respectively a wire in the reactor casing and a metal piece, a metal mesh or a wire wound around the outer cylinder wall; The distance between the two poles refers to the distance between the outer wall of the central metal wire electrode located on the axis and the inner wall of the cylindrical ground electrode, and the electrode spacing may be 0.3-20 mm, preferably 1-5 mm. . There are two types of wire-cylinder reactors: one is a single-medium-barrier reactor with a reactor wall as a barrier medium; the other is a reactor wall as a first barrier medium and a second barrier medium interposed between the two poles. Double medium barrier wire barrel reactor; methanol and carrier gas inlet are arranged at the upper end of the reactor outer cylinder.
针板式反应器的电极分别是一个带有金属针阵列的金属板和一个金属平板；两金属板水平地固定在反应器壳体内，极间距为金属针下端点到金属平板之间的垂直距离；两极之间设阻挡介质板，阻挡介质板与两极的距离任意调节；在反应器壁上开设反应物和产物的进出口； The electrodes of the needle plate reactor are respectively a metal plate with a metal needle array and a metal plate; the two metal plates are horizontally fixed in the reactor casing, and the pole spacing is a vertical distance between the lower end of the metal needle and the metal plate; A barrier medium plate is disposed between the two poles, and the distance between the barrier dielectric plate and the two poles is arbitrarily adjusted; the inlet and outlet of the reactants and products are opened on the reactor wall;
管板式反应器的电极分别是一个金属管和一个金属板。金属板水平地固定在反应器壳体内，金属管垂直对准水平金属板的中心，金属管下端点到金属板之间的垂直距离为极间距；两极之间设阻挡介质板，阻挡介质板与两极的距离可以任意调节。甲醇和载气既可以从放电金属管进入，也可从固定电极的反应器上端进料口进入，下端设反应产物出口。 The electrodes of the tube plate reactor are a metal tube and a metal plate, respectively. The metal plate is horizontally fixed in the reactor casing, the metal pipe is vertically aligned with the center of the horizontal metal plate, and the vertical distance between the lower end of the metal pipe and the metal plate is a pole spacing; a barrier medium plate is disposed between the two poles, and the dielectric plate is blocked The distance between the two poles can be adjusted arbitrarily. Methanol and carrier gas can enter either from the discharge metal tube or from the upper inlet of the reactor at the fixed electrode, and the reaction product outlet at the lower end.
板板式反应器的高压极和接地电极分别为两个金属板。将两个金属板平行地固定在反应器的壳体内，两板间的垂直距离为极间距，高压极和接地极之间设阻挡介质板，阻挡介质板与两极的距离可以任意调节。阻挡介质可设单层或多层；在反应器壁上开设反应物和产物的进出口。 The high voltage and ground electrodes of the plate and plate reactor are respectively two metal plates. The two metal plates are fixed in parallel in the casing of the reactor, the vertical distance between the two plates is the pole spacing, and the blocking dielectric plate is disposed between the high voltage pole and the grounding pole, and the distance between the blocking dielectric plate and the two poles can be arbitrarily adjusted. The barrier medium may be provided as a single layer or multiple layers; the inlet and outlet of reactants and products are opened on the reactor wall.
以上三种带有板式电极的反应器的极间距可取 0.2-40mm ，优选 2-10mm ； The pole spacing of the above three reactors with plate electrodes may be 0.2-40 mm, preferably 2-10 mm;
上述四种反应器的壳体采用硬质玻璃、氧化铝陶瓷、聚四氟乙烯等绝缘材料或符合高压电绝缘设计的金属和非金属复合材料制成。反应器壳体的形状和尺寸可依实际需要确定，反应器的放大可通过单个反应器放大以及反应器的并联个数实现。 上述阻挡介质用表面光洁、耐热、机械强度高且不与甲醇和载气的等离子体以及甲醇醇化产物发生化学反应的绝缘材料制成，优选石英玻璃、硬质玻璃、云母和氧化铝陶瓷。阻挡介质的总厚度可取 0.3-10mm ，优选 0.5-3.0mm 。 上述反应器高压极及接地极使用表面光洁、机械强度高、耐高温的金属材料制成，材质可以是铜、铁、钨、铝、不锈钢、镍 外渡金、铂、钯的金属以及含钛或镍的不锈钢等 ，优选铜、铁、钨、不锈钢； 上述反应器的金属管电极的直径范围为 0.5-12mm ，优选 2-8mm ；金属板与金属管的直径比值为 1-20 ； 介质阻挡放电采用高压交流电源，电源频率取 1 kHz~ 50kHz ，优选 5kHz ~ 20kHz 。 The casings of the above four reactors are made of insulating materials such as hard glass, alumina ceramics, polytetrafluoroethylene or metal and non-metal composite materials conforming to high-voltage electrical insulation design. The shape and size of the reactor housing can be determined as needed, and the amplification of the reactor can be achieved by a single reactor amplification and the number of parallel reactors. The above-mentioned barrier medium is made of an insulating material which has a smooth surface, heat resistance, high mechanical strength, and does not chemically react with plasma of methanol and carrier gas and methanol alcoholation product, and is preferably quartz glass, hard glass, mica and alumina ceramics. The total thickness of the barrier medium is desirable 0.3-10 mm, preferably 0.5-3.0 mm. The high-voltage electrode and the grounding electrode of the above reactor are made of a metal material with smooth surface, high mechanical strength and high temperature resistance, and the material may be copper, iron, tungsten, aluminum, stainless steel or nickel. The metals of the extranuclear gold, platinum, and palladium, and the stainless steel containing titanium or nickel are preferably copper, iron, tungsten, and stainless steel; the diameter of the metal tube electrode of the above reactor ranges from 0.5 to 12 mm, preferably 2 to 8 mm. The ratio of the diameter of the metal plate to the metal tube is 1-20; the dielectric barrier discharge is a high-voltage AC power source, and the power supply frequency is 1 kHz to 50 kHz, preferably 5 kHz to 20 kHz.
② 采用电晕放电：反应器采用针板式结构，反应器的一个电极是带有尖端的金属丝，另一个电极是金属平板，高压电极和接地电极可在针、板间互换，电源用高压直流电源。反应器的两极间距可取 0.5 ~ 18mm ，优选 2 ~ 10mm ，所说的两极间距是指针状电极的尖端与接地平板电极之间的距离。 上述电极可以使用表面光洁、机械强度高、耐高温的金属材料制成，材质可以是铜、铁、钨、铝、不锈钢、镍等，优选铝、铁、钨、镍； 2 Corona discharge is adopted: the reactor adopts a needle plate structure, one electrode of the reactor is a wire with a tip, and the other electrode is a metal plate. The high voltage electrode and the ground electrode can be exchanged between the needle and the plate, and the power source is high voltage DC. power supply. The two pole spacing of the reactor is desirable 0.5 to 18 mm, preferably 2 to 10 mm, and the two-pole pitch is the distance between the tip end of the pointer electrode and the ground plate electrode. The electrode may be made of a metal material having a smooth surface, high mechanical strength and high temperature resistance, and the material may be copper, iron, tungsten, aluminum, stainless steel, nickel, etc., preferably aluminum, iron, tungsten, nickel;
③ 采用脉冲电晕放电：反应器采用线筒式结构，反应器的中心晕线电极是金属丝，另一个电极是金属圆筒。反应器两极间距 5 ~ 40mm ，优选 15 ~ 30mm ，所说的两极间距是指位于轴线的中心晕线外壁与金属筒壁之间的距离。 电源采用脉冲直流高压电源，使用储能电容通过火花间隙向负载泄放的方式产生脉冲电压，脉冲电源的峰值、脉冲重复频率均可调。上述电源的峰值电压取 20 ~ 60kV ，优选 38 ~ 46 kV ；电源的脉冲重复频率取 10 ~ 150Hz ，优选 50 ~ 100Hz ； 上述电极可以使用表面光洁、机械强度高、耐高温的金属材料制成，材质可以是铜、铁、钨、铝、不锈钢、镍、铂、钯等，其中优选铁、不锈钢、镍、铂。 3 Pulse corona discharge is used: the reactor adopts a wire barrel structure, the central halo electrode of the reactor is a metal wire, and the other electrode is a metal cylinder. The distance between the two poles of the reactor is 5 ~ 40mm, preferably 15 ~ 30mm The two-pole spacing refers to the distance between the outer wall of the central halo line of the axis and the wall of the metal cylinder. The power supply adopts a pulsed DC high-voltage power supply, and uses a storage capacitor to generate a pulse voltage by means of a spark gap to the load discharge. The peak value of the pulse power supply and the pulse repetition frequency are adjustable. The peak voltage of the above power supply is 20 ~ 60kV , preferably 38 ~ 46 kV ; the pulse repetition frequency of the power supply is 10 ~ 150 Hz , preferably 50 ~ 100 Hz ; The electrode may be made of a metal material having a smooth surface, high mechanical strength and high temperature resistance, and may be made of copper, iron, tungsten, aluminum, stainless steel, nickel, platinum, palladium or the like, and among them, iron, stainless steel, nickel, and platinum are preferable.
④ 采用辉光放电：反应器采用线筒式结构或板板式结构。 4 Glow discharge: The reactor adopts a wire-tube structure or a plate-and-plate structure.
电源可以采用脉冲直流高压电源，也可以采用脉冲交流高压电源。当采用脉冲直流高压电源时要用储能电容通过火花间隙向负载泄放的方式产生脉冲电压，电源的峰值电压可取 10 ~ 60kV ，优选 30 ~ 50 kV ；电源的脉冲重复频率可取 10 ~ 150Hz ，优选 50 ~ 100Hz ；当采用脉冲交流高压电源时，电源的峰值电压可取 0 ~ 30kV ，优选 0 ~ 10 kV ；电源的脉冲重复频率可取 7 ~ 50Hz ，优选 7 ~ 30Hz ； 上述放电反应器电极使用表面光洁、机械强度高、耐高温的金属材料制成，材质可以是铜、铁、钨、铝、不锈钢、镍、铂、钯等，其中优选铁、不锈钢、镍、铂；反应器两极间距 1~ 40mm ，优选 5 ~ 25mm 。当采用线筒式反应器时，所说的两极间距是指位于轴线的中心金属线状电极与筒壁之间的距离；当采用板板式反应器时，所说的两极间距指两个平行金属板之间的垂直距离。 The power supply can be a pulsed DC high voltage power supply or a pulsed AC high voltage power supply. When a pulsed DC high-voltage power supply is used, a pulse voltage is generated by means of a storage capacitor through a spark gap to the load, and the peak voltage of the power source can be taken. 10 ~ 60kV, preferably 30 ~ 50 kV; the pulse repetition frequency of the power supply can be 10 ~ 150Hz, preferably 50 ~ 100Hz When using pulse AC high voltage power supply, the peak voltage of the power supply can be 0 ~ 30kV, preferably 0 ~ 10 kV; the pulse repetition frequency of the power supply can be 7 ~ 50Hz, preferably 7 ~ 30Hz; The discharge reactor electrode is made of a metal material having a smooth surface, high mechanical strength and high temperature resistance, and the material may be copper, iron, tungsten, aluminum, stainless steel, nickel, platinum, palladium, etc., among which iron, stainless steel, nickel, platinum are preferred. ; reactor pole spacing 1~ 40mm, preferably 5 ~ 25mm . When a bobbin type reactor is used, the distance between the two poles refers to the distance between the central metal wire electrode located at the axis and the wall of the barrel; when a plate type reactor is used, the distance between the two poles refers to two parallel metals. The vertical distance between the boards.
（ 2 ）将选择性活化的甲醇转化为目的产物： 上述反应混合物放电反应温度取 25 ~ 600℃ ，优选 100 ~ 400℃ ； 放电反应压力取 -0.06MPa ~ 0.5MPa ，优选 -0. 02MPa ~ 0. 2 MPa ； 载气与甲醇的摩尔比为 0 ~ 20 ，优选 0 ~ 6 ； 载气可以是 N2 、 H2 、 H2O 、 He 、 Ar 、 O2 、 CO 、 CO2 、 CH4 、 C2H6 等烃类中的一种或二种以上混合物，其中优选 H2 、 H2O 、 He 、 Ar 、 CH4 。(2) The selective reaction of the methanol is converted to the desired product: the reaction temperature of the reaction mixture is from 25 to 600 ° C, preferably from 100 to 400 ° C; the discharge reaction pressure is from -0.06 MPa to 0.5 MPa, preferably -0.22 MPa ~ 0 2 MPa ; the molar ratio of carrier gas to methanol is 0-20, preferably 0-6; the carrier gas may be N 2 , H 2 , H 2 O, He, Ar, O 2 , CO, CO 2 , CH 4 , One or a mixture of two or more hydrocarbons such as C 2 H 6 , of which H 2 , H 2 O , He , Ar , CH 4 are preferred.
本发明的有益效果是乙二醇的制取是以甲醇为原料，而甲醇可通过煤经合成气制得，甚至甲醇还可以通过生物质的汽化得到，具有可再生性。同时，用等离子体制备乙二醇属于一步法直接合成工艺，不必使用催化剂，对环境无污染，而且选择性高。另外，本发明在得到乙二醇的同时，还可以通过条件优化，联产乙醇，正丙醇等有用产品。 The invention has the beneficial effects that the preparation of the ethylene glycol is methanol, and the methanol can be obtained by the synthesis gas of coal, and even the methanol can be obtained by vaporization of the biomass, and has reproducibility. At the same time, the preparation of ethylene glycol by plasma is a one-step direct synthesis process, which does not require the use of a catalyst, has no pollution to the environment, and has high selectivity. In addition, the present invention can also produce a useful product such as ethanol or n-propanol by optimizing the conditions while obtaining ethylene glycol.
附图说明 DRAWINGS
图 1a 是介质 阻挡放电 --- 单介质线筒式反应器示意图。 Figure 1a is a schematic diagram of a dielectric barrier discharge --- single dielectric bobbin reactor.
图 1b 是 介质阻挡放电 --- 双介质线筒式反应器示意图。 Figure 1b is a schematic diagram of a dielectric barrier discharge --- dual dielectric bobbin reactor.
图 2 是 介质阻挡放电 --- 针板式电极结构反应器示意图。 Figure 2 is a schematic diagram of a dielectric barrier discharge --- needle plate electrode structure reactor.
图 3 是 介质阻挡放电 --- 管板式电极结构反应器示意图。 Figure 3 is a schematic diagram of a dielectric barrier discharge--tube-plate electrode structure reactor.
图 4 是 介质阻挡放电 --- 板板式电极结构反应器示意图。 Figure 4 is a schematic diagram of a dielectric barrier discharge--plate-plate electrode structure reactor.
图 5 是 辉光放电反应器示意图。 Figure 5 is a schematic of a glow discharge reactor.
图中： 1高压电极； 2 接地电极； 3 接地线； 4 出气口； 5反应器壳体； 6进气口； 7高压电源； 8 阻挡介质； 9绝缘密封材料； 10保温层； 11搅拌器转轴； 12磁流体密封压盖； 13固定圆筒电极； 14旋转螺旋电极。In the figure: 1 high voltage electrode; 2 grounding electrode; 3 grounding wire; 4 air outlet; 5 reactor housing; 6 air inlet; 7 high voltage power supply; 8 blocking medium; 9 insulating sealing material; 10 insulation layer; 11 agitator shaft; 12 magnetic fluid sealing gland; 13 fixed cylinder electrode; 14 rotating spiral electrode.
具体实施方式detailed description
对比实施例 1 ：单介质阻挡放电 --- 线筒式反应器 Comparative Example 1 : Single dielectric barrier discharge --- Wire-cylinder reactor
在 0.1MPa 压力下，将 H2 与气态甲醇以摩尔比 4:1 （其中 H2 流速为 20ml/min ，甲醇流速为 5ml/min ）通入放电反应器，气流稳定后，接通等离子体电源进行介质阻挡放电。反应器采用线筒式电极结构，用外径 15mm 、内径 13mm 的硬质玻璃管制成筒状反应器（同时也作为阻挡介质），中心电极为直径 1 mm 的铜线，接地极为壁厚为 1mm 圆柱形铁箔（紧贴在玻璃管外壁），极间距为 7mm ，反应器的有效放电长度为 150mm 。Under a pressure of 0.1 MPa, H 2 and gaseous methanol were introduced into the discharge reactor at a molar ratio of 4:1 (where H 2 flow rate was 20 ml/min, methanol flow rate was 5 ml/min), and after the gas flow was stabilized, the plasma power was turned on. Perform dielectric barrier discharge. The reactor adopts a wire barrel electrode structure, and is made of a rigid glass tube with an outer diameter of 15 mm and an inner diameter of 13 mm to form a cylindrical reactor (also serving as a barrier medium). The center electrode is a copper wire having a diameter of 1 mm, and the grounding wall thickness is 1 mm. Cylindrical iron foil (close to the outer wall of the glass tube) with a pole spacing of 7 mm and an effective discharge length of 150 mm for the reactor.
反应器的放电参数为：电压 5.6kV ，电流 0.25A ，频率 5kHz ；放电温度 150 ℃ 时反应结果为：甲醇转化率 13% ，乙二醇选择性 3% ，乙醇选择性 1% ，甲烷选择性 60% 、一氧化碳选择性 29% 、其他碳氢化合物选择性 7% ， H2 产率 20% 。在本实施例中，由于两极间距很大，所以等离子体放电区的电子（ e ）能量过小，甲醇的活化程度低，甲醇的转化率低，主要断裂甲醇分子中的 C-O 键，生成的产物主要是甲烷。 The discharge parameters of the reactor are: voltage 5.6kV, current 0.25A, frequency 5kHz; discharge temperature 150 °C The reaction results were: methanol conversion rate of 13%, ethylene glycol selectivity of 3%, ethanol selectivity of 1%, methane selectivity of 60%, carbon monoxide selectivity of 29%, and other hydrocarbon selectivity of 7%. H2 yield 20%. In this embodiment, since the distance between the two poles is large, the electron (e) energy in the plasma discharge region is too small, the degree of activation of methanol is low, and the conversion rate of methanol is low, mainly in the methanol molecule. The C-O bond produces a product mainly methane.
对比实施例 2 ：单介质阻挡放电 --- 线筒式反应器 Comparative Example 2: Single dielectric barrier discharge --- Wire tube reactor
在 0.1MPa 压力下，将 He 与气态甲醇以摩尔比 5:1 （其中 He 流速为 30ml/min ，甲醇流速为 6ml/min ）通入放电反应器，气流稳定后，接通等离子体电源进行介质阻挡放电。用外径 6mm 、内径 4mm 的硬质玻璃管制成筒状反应器（同时也作为阻挡介质），中心电极为直径 3 mm 的钨线，接地极为壁厚为 1mm 圆柱形铝箔筒（紧贴在玻璃管外壁），极间距为 1.5mm ，反应器的有效放电长度为 130mm 。 A molar ratio of He to gaseous methanol of 5:1 at a pressure of 0.1 MPa (where He flow rate is 30 ml/min) The methanol flow rate is 6 ml/min. The gas is passed into the discharge reactor. After the gas flow is stabilized, the plasma power source is turned on to perform dielectric barrier discharge. With outer diameter of 6mm, inner diameter of 4mm The hard glass tube is made into a tubular reactor (also used as a blocking medium), the center electrode is a tungsten wire with a diameter of 3 mm, and the grounding is a cylindrical aluminum foil tube with a wall thickness of 1 mm (close to the outer wall of the glass tube) with a pole spacing of 1.5mm, the effective discharge length of the reactor is 130mm.
反应器的放电参数为：电压 20.0kV ，电流 0.35A ，频率 8kHz ；放电温度 170 ℃ 时反应结果为：甲醇转化率 73% ，乙二醇选择性 5% ，乙醇选择性 2% ，正丙醇选择性 1% 、甲烷选择性 30% 、一氧化碳选择性 60% 、其他碳氢化合物选择性 2% ， H2 产率 56% 。在本实施例中，由于采用的两极间距很小，所以等离子放电区的电子（ e ）能量过大，甲醇转化率高，但主要发生 O-H 键断裂生成 CO 和 H2 ，由于等离子体区高能电子（ e ）数目较多，碰撞甲醇分子的几率较大，故反应主要生成甲烷、 CO 等小分子产物。The discharge parameters of the reactor are: voltage 20.0kV, current 0.35A, frequency 8kHz; reaction temperature is 170 °C, the reaction results are: methanol conversion rate 73%, ethylene glycol selectivity 5%, ethanol selectivity 2%, n-propanol Selectivity 1%, methane selectivity 30%, carbon monoxide selectivity 60%, other hydrocarbon selectivity 2%, H2 yield 56%. In this embodiment, since the distance between the two poles is small, the electron (e) energy in the plasma discharge region is too large, and the methanol conversion rate is high, but the OH bond is mainly broken to generate CO and H 2 due to high energy electrons in the plasma region. (e) The number is large, and the probability of colliding with methanol molecules is large, so the reaction mainly produces small molecular products such as methane and CO.
对比实施例 3 ：电晕放电 Comparative Example 3: Corona discharge
在 0.08MPa 压力下，将气态甲醇与 Ar 以摩尔比 2:1 （其中 Ar 流速为 36ml/min ，甲醇流速为 18ml/min ）通入放电反应器，气流稳定后，接通高压电源进行电晕放电。反应器采用针板式电极结构，用内径 6mm 的石英管做反应器，两端固定着放电电极，一电极为直径 2mm 不锈钢钢针（高压电极），另一电极为直径 6 mm 的不锈钢圆形平板（接地电极），电极间距为 6mm 。 A molar ratio of gaseous methanol to Ar of 2:1 at a pressure of 0.08 MPa (where Ar flow rate is 36 ml/min) The methanol flow rate is 18 ml/min. The gas is introduced into the discharge reactor. After the gas flow is stabilized, the high-voltage power source is turned on to perform corona discharge. The reactor uses a needle plate electrode structure with an inner diameter of 6 mm The quartz tube is used as a reactor, and the discharge electrode is fixed at both ends. One electrode is a stainless steel needle with a diameter of 2 mm (high voltage electrode), and the other electrode is a stainless steel circular plate (ground electrode) with a diameter of 6 mm. The electrode spacing is 6 mm. .
采用直流正电晕放电，正电晕自持放电电压为 0.6kV ；放电温度 400 ℃ 时反应结果为：甲醇转化率 45% ，乙二醇选择性 0.5% ，乙醇选择性 3% ，甲烷选择性 30% 、一氧化碳选择性 60.5% 、其他碳氢化合物选择性 6% ， H2 产率 54% 。在本实施例中，由于放电气压很小，所以单位体积内的反应物分子较少，等离子放电区的电子（ e ）能与反应物分子充分碰撞并进行能量传递，导致反应物获得的能量过大，甲醇转化率高，但主要发生 O-H 键断裂生成 CO 和 H2 ，由于等离子体区高能电子（ e ）数目较多，碰撞甲醇分子的几率较大，故反应主要生成甲烷、 CO 等小分子产物。DC positive corona discharge, positive corona self-sustained discharge voltage is 0.6kV; discharge temperature is 400 °C, the reaction results are: methanol conversion rate of 45%, ethylene glycol selectivity of 0.5%, ethanol selectivity of 3%, methane selectivity of 30 %, carbon monoxide selectivity 60.5%, other hydrocarbon selectivity 6%, H 2 yield 54%. In this embodiment, since the discharge gas pressure is small, the number of reactant molecules per unit volume is small, and the electrons (e) in the plasma discharge region can fully collide with the reactant molecules and carry out energy transfer, resulting in energy obtained by the reactants. Large, methanol conversion rate is high, but mainly OH bond cleavage to produce CO and H 2 , due to the high number of high-energy electrons (e) in the plasma region, the probability of colliding with methanol molecules is large, so the reaction mainly produces small molecules such as methane and CO. product.
实施例 1 ：介质阻挡放电 --- 线筒式反应器 Example 1: Dielectric Barrier Discharge --- Wire Reactor
在 0.10MPa 压力下，将 H2 与气态甲醇以摩尔比 2.5:1 （其中 H2 流速为 25ml/min ，甲醇流速为 10ml/min ）通入 线筒式反应器，待 气流稳定后，接通电源进行介质阻挡放电 。 用外径 11mm 、内径 9mm 的硬质玻璃管制成筒状反应器（同时也作为阻挡介质），中心电极为直径 2 mm 的不锈钢丝，接地极为壁厚为 0.4mm 圆柱形铝箔筒（紧贴在玻璃管外壁），极间距为 4.5mm ，反应器的有效放电长度为 160mm 。H 2 and gaseous methanol were introduced into the bobbin reactor at a molar ratio of 2.5:1 (where H 2 flow rate was 25 ml/min and methanol flow rate was 10 ml/min) at a pressure of 0.10 MPa. The power supply is subjected to dielectric barrier discharge. A cylindrical reactor (also used as a barrier medium) is made of a hard glass tube with an outer diameter of 11 mm and an inner diameter of 9 mm. The center electrode is a stainless steel wire with a diameter of 2 mm, and the grounding wall has a wall thickness of 0.4 mm. The outer wall of the glass tube) has a pole spacing of 4.5 mm and an effective discharge length of the reactor of 160 mm.
反应器的放电参数为：电压 18.0kV ，电流 0.28A ，频率 10kHz ；放电温度 100 ℃ ， 当放电频率和放电功率分别保持 10kHz 和 25W 不变，反应器壳体材质调变时 ， 反应结果为： The discharge parameters of the reactor are: voltage 18.0kV, current 0.28A, frequency 10kHz; discharge temperature 100 °C When the discharge frequency and discharge power are kept constant at 10 kHz and 25 W, respectively, when the reactor shell material is modulated, the reaction result is:
石英玻璃 ， 甲醇的转化率 20.49% ，乙二醇的选择性为 38.41% ，乙醇的选择性为 8.45% ，正丙醇的选择性为 1.68% Quartz glass, the conversion rate of methanol is 20.49%, the selectivity of ethylene glycol is 38.41%, and the selectivity of ethanol is 8.45%. , the selectivity of n-propanol is 1.68%
硬质玻璃，甲醇的转化率 26.90% ，乙二醇的选择性为 31.25% ，乙醇的选择性为 7.15% ，正丙醇的选择性为 1.17% ； Hard glass, methanol conversion rate is 26.90%, ethylene glycol selectivity is 31.25%, and ethanol selectivity is 7.15%. The selectivity of n-propanol is 1.17%;
聚四氟乙烯，甲醇的转化率 10.64% ，乙二醇的选择性为 45.70% ，乙醇的选择性为 6.72% ，正丙醇的选择性为 1.24% ； Polytetrafluoroethylene, methanol conversion rate of 10.64%, ethylene glycol selectivity of 45.70%, ethanol selectivity of 6.72% , the selectivity of n - propanol is 1.24% ;
氧化铝陶瓷，甲醇的转化率 33.26% ，乙二醇的选择性为 29.61% ，乙醇的选择性为 5.28% ，正丙醇的选择性为 0.98% ； Alumina ceramics, the conversion of methanol is 33.26%, the selectivity of ethylene glycol is 29.61%, and the selectivity of ethanol is 5.28%. The selectivity of n-propanol is 0.98%;
实施例 2 ：介质阻挡放电 --- 线筒式反应器 Example 2: Dielectric Barrier Discharge --- Wire Reactor
重复实施例 1 ，但反应器采用双介质阻挡放电反应器，其壳体和内套管材质均采用硬质玻璃，其中内阻挡介质管的厚度为 0.8 mm 。则反应结果为：甲醇的转化率 18.09% ，乙二醇的选择性为 44.39% ，乙醇的选择性为 7.46% ，正丙醇的选择性为 1.44% 。 Repeating example 1 However, the reactor adopts a double dielectric barrier discharge reactor, and the shell and the inner sleeve are made of hard glass, wherein the inner barrier medium tube has a thickness of 0.8 mm. The reaction result is: methanol conversion rate 18.09% The selectivity of ethylene glycol is 44.39%, the selectivity of ethanol is 7.46%, and the selectivity of n-propanol is 1.44%.
实施例 3 ：介质阻挡放电 --- 线筒式反应器 Example 3: Dielectric Barrier Discharge --- Wire Reactor
重复实施例 2 ，但总阻挡介质厚度（内外阻挡介质厚度之和）发生变化时，则反应结果为： Repeat Example 2, but when the total barrier medium thickness (the sum of the thickness of the inner and outer barrier media) changes, the reaction result is:
介质厚度 1.5 mm ， 甲醇的转化率 23.25% ，乙二醇的选择性为 17.36% ，乙醇的选择性为 4.35% ，正丙醇的选择性为 0.64% ； The thickness of the medium is 1.5 mm, the conversion of methanol is 23.25%, and the selectivity of ethylene glycol is 17.36%. The selectivity of ethanol is 4.35% and the selectivity of n-propanol is 0.64%;
介质厚度 2.0 mm ， 甲醇的转化率 16.34% ，乙二醇的选择性为 27.54% ，乙醇的选择性为 5.36% ，正丙醇的选择性为 0.83% ； The thickness of the medium is 2.0 mm, the conversion of methanol is 16.34%, and the selectivity of ethylene glycol is 27.54%. The selectivity of ethanol is 5.36% and the selectivity of n - propanol is 0.83% ;
介质厚度 2.5 mm ， 甲醇的转化率 12.56% ，乙二醇的选择性为 32.18% ，乙醇的选择性为 6.65% ，正丙醇的选择性为 1.05% ； The thickness of the medium is 2.5 mm, the conversion of methanol is 12.56%, and the selectivity of ethylene glycol is 32.18%. The selectivity of ethanol is 6.65% and the selectivity of n-propanol is 1.05%;
介质厚度 3.0 mm ， 甲醇的转化率 6.36% ，乙二醇的选择性为 47.34% ，乙醇的选择性为 7.15% ，正丙醇的选择性为 1.77% ； The medium thickness is 3.0 mm, the conversion of methanol is 6.36%, the selectivity of ethylene glycol is 47.34%, and the selectivity of ethanol is 7.15%, the selectivity of n-propanol is 1.77%;
实施例 4 ：介质阻挡放电 --- 线筒式反应器 Example 4: Dielectric Barrier Discharge --- Wire Reactor
重复实施例 2 ，但接地极电极材质发生变化时，则反应结果为： Repeat Example 2, but when the grounding electrode material changes, the reaction result is:
铜网 ， 甲醇的转化率 18.93% ，乙二醇的选择性为 39.54% ，乙醇的选择性为 3.14% ，正丙醇的选择性为 0.98% ； The conversion rate of copper mesh and methanol is 18.93%, the selectivity of ethylene glycol is 39.54%, and the selectivity of ethanol is 3.14%. The selectivity of n-propanol is 0.98%;
铜丝 ， 甲醇的转化率 13.65% ，乙二醇的选择性为 42.38% ，乙醇的选择行为 3.68% ，正丙醇的选择性为 1.03% ； The conversion rate of copper wire and methanol is 13.65%, the selectivity of ethylene glycol is 42.38%, and the selectivity of ethanol is 3.68%. The selectivity of n-propanol is 1.03%;
钢网 ， 甲醇的转化率 9.83% ，乙二醇的选择性为 52.53% ，乙醇的选择性为 6.34% ，正丙醇的选择性为 1.56% ； The conversion rate of methanol to methanol is 9.83%, the selectivity of ethylene glycol is 52.53%, and the selectivity of ethanol is 6.34%. The selectivity of n-propanol is 1.56%;
铁丝 ， 甲醇的转化率 12.39% ，乙二醇的选择性为 47.45% ，乙醇的选择性为 4.39% ，正丙醇的选择性为 1.16% ； The conversion rate of iron wire and methanol is 12.39%, the selectivity of ethylene glycol is 47.45%, and the selectivity of ethanol is 4.39%. The selectivity of n-propanol is 1.16%;
实施例 5 ：介质阻挡放电 --- 线筒式反应器 Example 5: Dielectric Barrier Discharge --- Wire Reactor
重复实施例 2 ，但接地电极材质保持不变，则放电区间长度发生变化时，反应结果为： Repeat Example 2, but the grounding electrode material remains unchanged, and when the length of the discharge interval changes, the reaction result is:
5 mm ， 甲醇的转化率 3.28% ，乙二醇的选择性为 57.42% ，乙醇的选择性为 8.45% ，正丙醇的选择性为 1.98% ； 5 mm, the conversion of methanol is 3.28%, the selectivity of ethylene glycol is 57.42%, and the selectivity of ethanol is 8.45%. The selectivity of n - propanol is 1.98% ;
30 mm ， 甲醇的转化率 7.36% ，乙二醇的选择性为 51.45% ，乙醇的选择性为 7.24% ，正丙醇的选择性为 1.54% ； 30 mm, the conversion of methanol is 7.36%, the selectivity of ethylene glycol is 51.45%, and the selectivity of ethanol is 7.24%. The selectivity of n-propanol is 1.54%;
100 mm ， 甲醇的转化率 11.49% ，乙二醇的选择性为 46.25% ，乙醇的选择性为 6.13% ，正丙醇的选择性为 1.26% ； At 100 mm, the conversion of methanol is 11.49%, the selectivity of ethylene glycol is 46.25%, and the selectivity of ethanol is 6.13%, the selectivity of n-propanol is 1.26%;
300 mm ， 甲醇的转化率 19.53% ，乙二醇的选择性为 39.43% ，乙醇的选择性为 5.34% ，正丙醇的选择性为 1.01% ； At 300 mm, the conversion of methanol is 19.53%, the selectivity of ethylene glycol is 39.43%, and the selectivity of ethanol is 5.34%, the selectivity of n-propanol is 1.01%;
400 mm ，甲醇的转化率 25.36% ，乙二醇的选择性为 32.26% ，乙醇的选择性为 4.17% ，正丙醇的选择性为 0.93% ； At 400 mm, the conversion of methanol is 25.36%, the selectivity of ethylene glycol is 32.26%, and the selectivity of ethanol is 4.17% , the selectivity of n - propanol was 0.93% ;
实施例 6 ：介质阻挡放电 --- 针板式反应器 Example 6: Dielectric Barrier Discharge --- Needle Plate Reactor
在 0.12MPa 压力下，将 Ar 与气态甲醇以摩尔比 5:1 （其中 Ar 流速为 35ml/min ，甲醇流速为 7ml/min ）通入到针板式反应器，待气流稳定后，接通电源进行介质阻挡放电。 针板式反应器的壳体采用硬质玻璃制成，外径为 12.0 mm ，壁厚为 1.0 mm ，接地的金属板电极和连接高压端的金属棒电极的材质皆为不锈钢，金属板直径为 10 mm ，厚度为 0.2 mm ，金属棒直径为 1.2 mm ，以云母片为阻挡介质，置于接地极板上；高压极的下端到接地极板地垂直距离（两极间距）为 6.0 mm 。 A molar ratio of Ar to gaseous methanol of 5:1 at a pressure of 0.12 MPa (where Ar flow rate is 35 ml/min) , methanol flow rate of 7ml / min) into the needle plate reactor, after the gas flow is stabilized, the power is turned on for dielectric barrier discharge. The housing of the needle plate reactor is made of hard glass with an outer diameter of 12.0 mm The wall thickness is 1.0 mm. The grounded metal plate electrode and the metal rod electrode connected to the high voltage end are made of stainless steel. The diameter of the metal plate is 10 mm, the thickness is 0.2 mm, and the diameter of the metal bar is 1.2. Mm , with mica sheet as the blocking medium, placed on the grounding plate; the vertical distance from the lower end of the high voltage pole to the grounding plate (the distance between the two poles) is 6.0 mm.
反应器的放电参数为：电压 17.0kV ，电流 0.32A ，频率 7kHz ；放电温度 80 ℃ ， 当放电频率和放电功率分别保持 7kHz 和 18W 不变，阻挡介质厚度调变时 ， 反应结果为： 介质厚度 0.5 mm ， 甲醇的转化率 26.38% ，乙二醇的选择性为 37.26 % ，乙醇的选择性为 6.45% ，正丙醇的选择性为 1.67% ； 介质厚度 1.0 mm ， 甲醇的转化率 18.12% ，乙二醇的选择性为 41.37 % ，乙醇的选择性为 5.21% 正丙醇的选择性为 1.34% ； 介质厚度 1.5 mm ， 甲醇的转化率 11.35% ，乙二醇的选择性为 49.65 % ，乙醇的选择性为 4.37% ，正丙醇的选择性为 1.16% ； 介质厚度 2.0 mm ， 甲醇的转化率 7.73% ，乙二醇的选择性为 53.84 % ， 乙醇的选择性为 3.25% ，正丙醇的选择性为 0.94% ； 介质厚度 3.0 mm ， 甲醇的转化率 3.62% ，乙二醇的选择性为 61.27 % ，乙醇的选择性为 1.12% ，正丙醇的选择性为 0.72% ； The discharge parameters of the reactor are: voltage 17.0kV, current 0.32A, frequency 7kHz; discharge temperature 80 °C, When the discharge frequency and discharge power are kept at 7 kHz and 18 W, respectively, and the thickness of the barrier medium is modulated, the reaction results are: medium thickness 0.5 mm, methanol conversion rate 26.38% The selectivity of ethylene glycol is 37.26 %, the selectivity of ethanol is 6.45%, the selectivity of n-propanol is 1.67%, the thickness of medium is 1.0 mm, the conversion of methanol is 18.12%. The selectivity of ethylene glycol is 41.37 %, the selectivity of ethanol is 5.21%, the selectivity of n-propanol is 1.34%, the thickness of medium is 1.5 mm, the conversion of methanol is 11.35%. The selectivity of ethylene glycol is 49.65 %, the selectivity of ethanol is 4.37%, the selectivity of n-propanol is 1.16%, the thickness of medium is 2.0 mm, and the conversion of methanol is 7.73%. The selectivity of ethylene glycol is 53.84%, the selectivity of ethanol is 3.25%, the selectivity of n-propanol is 0.94%, the thickness of medium is 3.0 mm, and the conversion of methanol is 3.62%. The selectivity of ethylene glycol is 61.27 % , the selectivity of ethanol is 1.12% , and the selectivity of n - propanol is 0.72 % ;
实施例 7 ：介质阻挡放电 --- 针板式反应器 Example 7: Dielectric Barrier Discharge --- Needle Plate Reactor
重复实施例 6 ，但阻挡介质厚度保持为 1.0 mm ，则阻挡介质的材质发生变化时，反应结果为： 石英玻璃，甲醇的转化率 21.56% ，乙二醇的选择性为 38.24% ，乙醇的选择性为 3.46% ，正丙醇的选择性为 1.17% ； 氧化铝陶瓷，甲醇的转化率 15.27% ，乙二醇的选择性为 49.86% ，乙醇的选择性为 5.37% ，正丙醇的选择性为 1.52% ； 硬质玻璃，甲醇的转化率 9.35% ，乙二醇的选择性为 58.35% ，乙醇的选择性为 6.26% ，正丙醇的选择性为 2.66% ； Example 6 was repeated, but the thickness of the barrier medium was maintained at 1.0 mm, and when the material of the barrier medium was changed, the reaction result was: For quartz glass, the conversion of methanol is 21.56%, the selectivity of ethylene glycol is 38.24%, the selectivity of ethanol is 3.46%, and the selectivity of n-propanol is 1.17%. Alumina ceramics, methanol conversion rate of 15.27%, ethylene glycol selectivity of 49.86%, ethanol selectivity of 5.37%, n-propanol selectivity of 1.52%; For hard glass, the conversion of methanol is 9.35%, the selectivity of ethylene glycol is 58.35%, the selectivity of ethanol is 6.26%, and the selectivity of n-propanol is 2.66%.
实施例 8 ：介质阻挡放电 --- 针板式反应器 Example 8: Dielectric Barrier Discharge --- Needle Plate Reactor
重复实施例 6 ，但阻挡介质厚度保持为 1.0 mm ，则电极极间距发生变化时，反应结果为： Example 6 was repeated, but the thickness of the barrier medium was maintained at 1.0 mm, and when the electrode pitch was changed, the reaction result was:
极间距 2.0 mm ， 甲醇的转化率 42.27% ，乙二醇的选择性为 23. 35% ，乙醇的选择性为 9.35% ，正丙醇的选择性为 1.74% ； 极间距 3.0 mm ， 甲醇的转化率 31.58% ，乙二醇的选择性为 3 9.52% ，乙醇的选择性为 7.25% ，正丙醇的选择性为 1.26% ； 极间距 4.0 mm ， 甲醇的转化率 21.75% ，乙二醇的选择性为 41.64% ，乙醇的选择性为 5.42% ，正丙醇的选择性为 1.04% ； 极间距 5.0 mm ， 甲醇的转化率 13.52% ，乙二醇的选择性为 55.56% ，乙醇的选择性为 4.36% ，正丙醇的选择性为 0.88% ； The pole spacing is 2.0 mm, the conversion of methanol is 42.27%, and the selectivity of ethylene glycol is 23. 35%. The selectivity of ethanol is 9.35%, the selectivity of n-propanol is 1.74%, the polar spacing is 3.0 mm, the conversion of methanol is 31.58%, and the selectivity of ethylene glycol is 3.92%. The selectivity of ethanol is 7.25%, the selectivity of n-propanol is 1.26%, the polar spacing is 4.0 mm, the conversion of methanol is 21.75%, and the selectivity of ethylene glycol is 41.64%. The selectivity of ethanol is 5.42%, the selectivity of n-propanol is 1.04%, the polar spacing is 5.0 mm, the conversion of methanol is 13.52%, and the selectivity of ethylene glycol is 55.56%. The selectivity of ethanol is 4.36% and the selectivity of n - propanol is 0.88% ;
实施例 9 ：介质阻挡放电 --- 针板式反应器 Example 9: Dielectric Barrier Discharge --- Needle Plate Reactor
重复实施例 6 ，但阻挡介质厚度保持为 1.0 mm ，则放电电极材质发生变化时，反应结果为： Example 6 was repeated, but the thickness of the barrier medium was kept at 1.0 mm, and when the material of the discharge electrode was changed, the reaction result was:
黄铜电极 ， 甲醇的转化率 17.35% ，乙二醇的选择性为 37.82% ，乙醇的选择性为 6.25% ，正丙醇的选择性为 1.98% ； 铝电极 ， 甲醇的转化率 12.25% ，乙二醇的选择性为 42.37% ，乙醇的选择性为 5.16% ，正丙醇的选择性为 2.15% ； 铸铜电极 ， 甲醇的转化率 12.38% ，乙二醇的选择性为 52.78% ，乙醇的选择性为 6.28% ，正丙醇的选择性为 0.95% ； 钨电极 ， 甲醇的转化率 21.85% ，乙二醇的选择性为 39.75% ，乙醇的选择性为 6.42% ，正丙醇的选择性为 0.82% 。 For brass electrodes, the conversion of methanol is 17.35%, the selectivity of ethylene glycol is 37.82%, and the selectivity of ethanol is 6.25%. The selectivity of n-propanol is 1.98%; the conversion rate of aluminum electrode and methanol is 12.25%, the selectivity of ethylene glycol is 42.37%, the selectivity of ethanol is 5.16%, and the selectivity of n-propanol is 2.15% ; cast copper electrode , methanol conversion rate 12.38% , ethylene glycol selectivity 52.78% , ethanol selectivity 6.28% , n - propanol selectivity 0.95% ; For the tungsten electrode, the conversion of methanol was 21.85%, the selectivity of ethylene glycol was 39.75%, the selectivity of ethanol was 6.42%, and the selectivity of n-propanol was 0.82%.
实施例 10 ：介质阻挡放电 --- 针板式反应器 Example 10: Dielectric Barrier Discharge --- Needle Plate Reactor
重复实施例 6 ，但阻挡介质厚度保持为 1.0 mm ，则放电功率发生变化时，反应结果为： Example 6 was repeated, but the thickness of the barrier medium was maintained at 1.0 mm, and when the discharge power was changed, the reaction result was:
放电功率 7.35W ， 甲醇的转化率 5.78% ，乙二醇的选择性为 56.25% ，乙醇的选择性为 7.32% ，正丙醇的选择性为 2.24% ； 放电功率 12.38W ， 甲醇的转化率 15.27% ，乙二醇的选择性为 49.78% ，乙醇的选择性为 6.24% ，正丙醇的选择性为 1.65% ； 放电功率 25.76W ， 甲醇的转化率 21.36% ，乙二醇的选择性为 38.45% ，乙醇的选择性为 5.24% ，正丙醇的选择性为 1.05% ； 放电功率 39.83W ， 甲醇的转化率 39.79% ，乙二醇的选择性为 29.75% ，乙醇的选择性为 4.13% ，正丙醇的选择性为 0.94% ； 放电功率 51.28W ， 甲醇的转化率 62.74% ，乙二醇的选择性为 17.28% ，乙醇的选择性为 3.58% ，正丙醇的选择性为 0.76% 。 The discharge power is 7.35W, the conversion of methanol is 5.78%, the selectivity of ethylene glycol is 56.25%, and the selectivity of ethanol is 7.32%, the selectivity of n-propanol is 2.24%; the discharge power is 12.38W, the conversion of methanol is 15.27%, the selectivity of ethylene glycol is 49.78%, and the selectivity of ethanol is 6.24%, the selectivity of n-propanol is 1.65%; the discharge power is 25.76W, the conversion rate of methanol is 21.36%, the selectivity of ethylene glycol is 38.45%, and the selectivity of ethanol is 5.24%, the selectivity of n-propanol is 1.05%; the discharge power is 39.83W, the conversion rate of methanol is 39.79%, the selectivity of ethylene glycol is 29.75%, and the selectivity of ethanol is 4.13%, the selectivity of n-propanol is 0.94%; the discharge power is 51.28W, the conversion rate of methanol is 62.74%, the selectivity of ethylene glycol is 17.28%, and the selectivity of ethanol is 3.58%, the selectivity of n-propanol was 0.76%.
实施例 11 ：介质阻挡放电 --- 针板式反应器 Example 11: Dielectric Barrier Discharge --- Needle Plate Reactor
重复实施例 6 ，但阻挡介质厚度保持为 1.0 mm ，则放电频率发生变化时，反应结果为： Example 6 was repeated, but the thickness of the barrier medium was maintained at 1.0 mm, and when the discharge frequency was changed, the reaction result was:
放电频率 6.0kHz ， 甲醇的转化率 29.35% ，乙二醇的选择性为 26.28% ，乙醇的选择性为 3.59% ，正丙醇的选择性为 1.01% ； 放电频率 12.0kHz ， 甲醇的转化率 18.72% ，乙二醇的选择性为 38.27% ，乙醇的选择性为 5.28% ，正丙醇的选择性为 1.82% ； 放电频率 18.0kHz ， 甲醇的转化率 13.27% ，乙二醇的选择性为 46.37% ，乙醇的选择性为 6.24% ，正丙醇的选择性为 2.15% ； 放电频率 24.0kHz ， 甲醇的转化率 24.27% ，乙二醇的选择性为 33.28% ，乙醇的选择性为 4.37% ，正丙醇的选择性为 1.34% ； 放电频率 30.0kHz ， 甲醇的转化率 8.76% ，乙二醇的选择性为 59.79% ，乙醇的选择性为 7.35% ，正丙醇的选择性为 2.53% 。 The discharge frequency is 6.0 kHz, the conversion rate of methanol is 29.35%, and the selectivity of ethylene glycol is 26.28%. The selectivity of ethanol is 3.59%, the selectivity of n-propanol is 1.01%, the discharge frequency is 12.0 kHz, the conversion of methanol is 18.72%, and the selectivity of ethylene glycol is 38.27%. The selectivity of ethanol is 5.28%, the selectivity of n-propanol is 1.82%, the discharge frequency is 18.0kHz, the conversion of methanol is 13.27%, and the selectivity of ethylene glycol is 46.37%. The selectivity of ethanol is 6.24%, the selectivity of n-propanol is 2.15%, the discharge frequency is 24.0kHz, the conversion of methanol is 24.27%, and the selectivity of ethylene glycol is 33.28%. The selectivity of ethanol is 4.37%, the selectivity of n-propanol is 1.34%, the discharge frequency is 30.0kHz, the conversion of methanol is 8.76%, and the selectivity of ethylene glycol is 59.79%. The selectivity to ethanol is 7.35% and the selectivity to n-propanol is 2.53%.
实施例 12 ：介质阻挡放电 --- 针板式反应器 Example 12: Dielectric Barrier Discharge --- Needle Plate Reactor
重复实施例 6 ，但阻挡介质厚度保持为 1.0 mm ，则载气的种类发生变化时，反应结果为： Example 6 was repeated, but the thickness of the barrier medium was maintained at 1.0 mm, and when the type of the carrier gas was changed, the reaction result was:
氧气：甲醇的转化率 23.15% ，乙二醇的选择性为 24.76% ，乙醇的选择性为 4.82% ，正丙醇的选择性为 1.28% ； 氮气：甲醇的转化率 17.28% ，乙二醇的选择性为 31.85% ，乙醇的选择性为 4.93% ，正丙醇的选择性为 1.62% ； 甲烷：甲醇的转化率 8.35% ，乙二醇的选择性为 56.75% ，乙醇的选择性为 7.25% ，正丙醇的选择性为 2.73% ； 氢气：甲醇的转化率 16.27% ，乙二醇的选择性为 38.75% ，乙醇的选择性为 5.27% ，正丙醇的选择性为 1.72% ； 氦气：甲醇的转化率 10.52% ，乙二醇的选择性为 46.25% ，乙醇的选择性为 6.31% ，正丙醇的选择性为 2.14% 。 Oxygen: methanol conversion rate is 23.15%, ethylene glycol selectivity is 24.76%, and ethanol selectivity is 4.82%. The selectivity of n-propanol is 1.28%; the conversion of nitrogen:methanol is 17.28%, the selectivity of ethylene glycol is 31.85%, the selectivity of ethanol is 4.93%, and the selectivity of n-propanol is 1.62% ; methane: methanol conversion rate 8.35%, ethylene glycol selectivity 56.75%, ethanol selectivity 7.25%, n-propanol selectivity 2.73%; Hydrogen: methanol conversion rate 16.27%, ethylene glycol selectivity 38.75%, ethanol selectivity 5.27%, n-propanol selectivity 1.72%; helium: methanol conversion rate 10.52%, the selectivity of ethylene glycol was 46.25%, the selectivity of ethanol was 6.31%, and the selectivity of n-propanol was 2.14%.
实施例 13 ：介质阻挡放电 --- 针板式反应器 Example 13: Dielectric Barrier Discharge --- Needle Plate Reactor
重复实施例 6 ，但阻挡介质厚度保持为 1.0 mm ，则载气 Ar 和甲醇的进料摩尔比发生变化时，则反应结果为： Example 6 was repeated, but the barrier medium thickness was maintained at 1.0 mm, then the carrier gas Ar When the molar ratio of feed to methanol changes, the reaction results are:
摩尔比为 0 ， 甲醇的转化率 29.52% ，乙二醇的选择性为 15.34% ，乙醇的选择性为 3.12% ，正丙醇的选择性为 0.86% ； 摩尔比为 2 ， 甲醇的转化率 25.37% ，乙二醇的选择性为 2 5.86% ，乙醇的选择性为 4.28% ，正丙醇的选择性为 1.35% ； 摩尔比为 6 ， 甲醇的转化率 18.75% ，乙二醇的选择性为 34.27% ，乙醇的选择性为 5.82% ，正丙醇的选择性为 2.15% ； 摩尔比为 12 ， 甲醇的转化率 13.24% ，乙二醇的选择性为 48.75% ，乙醇的选择性为 6.34% ，正丙醇的选择性为 3.82% ； 摩尔比为 18 ， 甲醇的转化率 8.28% ，乙二醇的选择性为 59.36 ，乙醇的选择性为 7.52% ，正丙醇的选择性为 4.22% 。 The molar ratio is 0, the conversion of methanol is 29.52%, the selectivity of ethylene glycol is 15.34%, and the selectivity of ethanol is 3.12%, the selectivity of n-propanol is 0.86%; the molar ratio is 2, the conversion rate of methanol is 25.37%, the selectivity of ethylene glycol is 25.86%, and the selectivity of ethanol is 4.28%. The selectivity of n-propanol is 1.35%; the molar ratio is 6, the conversion of methanol is 18.75%, the selectivity of ethylene glycol is 34.27%, and the selectivity of ethanol is 5.82%. The selectivity of n-propanol is 2.15%; the molar ratio is 12, the conversion of methanol is 13.24%, the selectivity of ethylene glycol is 48.75%, and the selectivity of ethanol is 6.34%. The selectivity of n-propanol is 3.82%; the molar ratio is 18, the conversion of methanol is 8.28%, the selectivity of ethylene glycol is 59.36, and the selectivity of ethanol is 7.52%. The selectivity of n-propanol was 4.22%.
实施例 14 ：介质阻挡放电 --- 针板式反应器 Example 14: Dielectric Barrier Discharge --- Needle Plate Reactor
重复实施例 6 ，但阻挡介质厚度保持为 2.0 mm ，则反应温度发生变化时，反应结果为： Example 6 was repeated, but the thickness of the barrier medium was maintained at 2.0 mm, and when the reaction temperature was changed, the reaction result was:
50 ℃ ，甲醇的转化率 12.37% ，乙二醇的选择性为 57.62% ，乙醇的选择性为 8.34% ，正丙醇的选择性为 2.18% ； 150 ℃ ，甲醇的转化率 18.25.% ，乙二醇的选择性为 45.37% ，乙醇的选择性为 7.52% ，正丙醇的选择性为 1.97% ； 250 ℃ ，甲醇的转化率 29.37% ，乙二醇的选择性为 35.24% ，乙醇的选择性为 6.29% ，正丙醇的选择性为 1.42% ； 350 ℃ ，甲醇的转化率 34.56% ，乙二醇的选择性为 26.27% ，乙醇的选择性为 5.95% ，正丙醇的选择性为 1.05% ； 450 ℃ ，甲醇的转化率 44.31% ，乙二醇的选择性为 15.48% ，乙醇的选择性为 3.84% ，正丙醇的选择性为 0.82% ； At 50 °C, the conversion of methanol was 12.37%, the selectivity of ethylene glycol was 57.62%, and the selectivity of ethanol was 8.34%. The selectivity of n-propanol is 2.18%; the conversion of methanol is 18.25.% at 150 °C, the selectivity of ethylene glycol is 45.37%, and the selectivity of ethanol is 7.52%. The selectivity of n-propanol is 1.97%; the conversion of methanol is 29.37% at 250 °C, the selectivity of ethylene glycol is 35.24%, and the selectivity of ethanol is 6.29%. The selectivity of n-propanol is 1.42%; the conversion of methanol is 34.56% at 350 °C, the selectivity of ethylene glycol is 26.27%, and the selectivity of ethanol is 5.95%. The selectivity of n-propanol is 1.05%; the conversion of methanol is 44.31% at 450 °C, the selectivity of ethylene glycol is 15.48%, and the selectivity of ethanol is 3.84%. The selectivity of n-propanol is 0.82%;
实施例 15 ：介质阻挡放电 --- 针板式反应器 Example 15: Dielectric Barrier Discharge --- Needle Plate Reactor
重复实施例 6 ，但阻挡介质厚度保持为 2.0 mm ，反应温度保持 220 ℃ 不变，而反应压力发生变化时，则结果为： Example 6 was repeated, but the thickness of the barrier medium was maintained at 2.0 mm and the reaction temperature was maintained at 220 °C. If the reaction pressure does not change, the result is:
0.02MPa ，甲醇的转化率 28.52% ，乙二醇的选择性为 29.38% ，乙醇的选择性为 6.17% ，正丙醇的选择性为 0.76% ； 0.06MPa ，甲醇的转化率 21.37% ，乙二醇的选择性为 37.22% ，乙醇的选择性为 7.23% ，正丙醇的选择性为 0.98% ； 0.10MPa ，甲醇的转化率 13.28% ，乙二醇的选择性为 45.76% ，乙醇的选择性为 8.32% ，正丙醇的选择性为 1.37% ； 0.16MPa ，甲醇的转化率 10.52% ，乙二醇的选择性为 58.34% ，乙醇的选择性为 8.94% ，正丙醇的选择性为 1.56% ； 0.02 MPa, the conversion rate of methanol is 28.52%, the selectivity of ethylene glycol is 29.38%, and the selectivity of ethanol is 6.17%, the selectivity of n-propanol is 0.76%; 0.06MPa, the conversion of methanol is 21.37%, the selectivity of ethylene glycol is 37.22%, and the selectivity of ethanol is 7.23%. The selectivity of n-propanol is 0.98%; the conversion of methanol is 0.10MPa, the conversion of methanol is 13.28%, the selectivity of ethylene glycol is 45.76%, and the selectivity of ethanol is 8.32%. The selectivity of n-propanol is 1.37%; the conversion of methanol is 0.16MPa, the conversion of methanol is 10.52%, the selectivity of ethylene glycol is 58.34%, and the selectivity of ethanol is 8.94%. The selectivity of n-propanol is 1.56%;
实施例 16 ：介质阻挡放电 --- 管板式反应器 Example 16: Dielectric Barrier Discharge --- Tube Plate Reactor
在 0.10MPa 压力下，将 He 与气态甲醇以摩尔比 3:1 （其中 He 流速为 30ml/min ，甲醇流速为 10ml/min ）通入 管板式反应器，待 气流稳定后，接通电源进行介质阻挡放电 。管板式反应器的壳体采用石英玻璃制成，其外径为 13.0 mm ，壁厚为 1.5 mm 。金属板电极和金属管电极的材质选用不锈钢；金属板电极的直径为 10 mm ，厚度为 0.3 mm ，电极间距为 5.0 mm ；阻挡介质为单层石英玻璃，其厚度为 1.0 mm 。 At a pressure of 0.10 MPa, a molar ratio of He to gaseous methanol of 3:1 (where He flow rate is 30ml/min, methanol flow rate of 10ml/min) is passed into the tube-and-plate reactor. After the gas flow is stabilized, the power is turned on for dielectric barrier discharge. . The tube-and-plate reactor housing is made of quartz glass with an outer diameter of 13.0 mm and a wall thickness of 1.5 mm. The metal plate electrode and the metal tube electrode are made of stainless steel; the metal plate electrode has a diameter of 10 Mm, thickness 0.3 mm, electrode spacing 5.0 mm; blocking medium is a single layer of quartz glass with a thickness of 1.0 mm.
反应器的放电参数为：电压 20.0kV ，电流 0.42A ，频率 10.0kHz ；放电温度 150 ℃ ， 当放电频率和放电功率分别保持 10.0kHz 和 21.5W 不变，金属管电极直径调变时 ， 反应结果为： The discharge parameters of the reactor are: voltage 20.0kV, current 0.42A, frequency 10.0kHz; discharge temperature 150 °C, when the discharge frequency and discharge power are kept constant at 10.0 kHz and 21.5 W, respectively, and the diameter of the metal tube electrode is changed, the reaction result is:
金属管直径为 2 mm ， 甲醇的转化率 38.56% ，乙二醇的选择性为 29.38% ，乙醇的选择性为 3.58% ，正丙醇的选择性为 0.67% ； 金属管直径为 3 mm ， 甲醇的转化率 27.38% ，乙二醇的选择性为 34.27% ，乙醇的选择性为 7.39% ，正丙醇的选择性为 0.95% ； 金属管直径为 5 mm ， 甲醇的转化率 18.82% ，乙二醇的选择性为 41.35% ，乙醇的选择性为 10.58% ，正丙醇的选择性为 1.25% ； 金属管直径为 6 mm ， 甲醇的转化率 11.35% ，乙二醇的选择性为 59.27% ，乙醇的选择性为 12.37% ，正丙醇的选择性为 1.56% ； The diameter of the metal tube is 2 mm, the conversion of methanol is 38.56%, and the selectivity of ethylene glycol is 29.38%. The selectivity of ethanol is 3.58%, the selectivity of n-propanol is 0.67%, the diameter of metal tube is 3 mm, the conversion of methanol is 27.38%, and the selectivity of ethylene glycol is 34.27%. The selectivity of ethanol is 7.39%, the selectivity of n-propanol is 0.95%, the diameter of metal tube is 5 mm, the conversion of methanol is 18.82%, and the selectivity of ethylene glycol is 41.35%. The selectivity of ethanol is 10.58%, the selectivity of n-propanol is 1.25%, the diameter of metal tube is 6 mm, the conversion of methanol is 11.35%, and the selectivity of ethylene glycol is 59.27%. The selectivity of ethanol is 12.37% and the selectivity of n-propanol is 1.56%;
本反应装置的其他放电参数和针 - 板式反应器的相同。只要采用适当的反应器结构，并以适宜的放电条件和反应条件相配合，都可以完成本发明。 Other discharge parameters and needles of the reaction device - The same is true for the plate reactor. The invention can be carried out as long as a suitable reactor structure is employed and the suitable discharge conditions are combined with the reaction conditions.
实施例 17 ：介质阻挡放电 --- 板板式反应器 Example 17: Dielectric Barrier Discharge --- Plate and Plate Reactor
在 0.12MPa 压力下，将 N2 与气态甲醇以摩尔比 4:1 （其中 N2 流速为 24ml/min ，甲醇流速为 6ml/min ）通入 板板式反应器，待 气流稳定后，接通电源进行介质阻挡放电 。板板式反应器，壁厚为 3.0 mm ，其材质选用不锈钢，其直径为 80 mm ，电极间距为 12 mm ；阻挡介质为石英玻璃，其厚度为 0.3 mm 。N 2 and gaseous methanol were fed into the plate-plate reactor at a molar ratio of 4:1 (where N 2 flow rate was 24 ml/min and methanol flow rate was 6 ml/min) under a pressure of 0.12 MPa, and the gas was turned on after the gas flow was stabilized. Perform dielectric barrier discharge. The plate-and-plate reactor has a wall thickness of 3.0 mm and is made of stainless steel with a diameter of 80 mm and an electrode spacing of 12 mm. The blocking medium is quartz glass with a thickness of 0.3 mm.
反应器的放电参数为：电压 21.0kV ，电流 0.48A ，频率 13.0kHz ；放电温度 180 ℃ ， 当放电频率和放电功率分别保持 13.0kHz 和 32W 不变，阻挡介质层数调变时 ， 反应结果为： The discharge parameters of the reactor are: voltage 21.0kV, current 0.48A, frequency 13.0kHz; discharge temperature 180 °C, when the discharge frequency and discharge power are kept unchanged at 13.0 kHz and 32 W, respectively, and the number of barrier dielectric layers is modulated, the reaction result is:
单层阻挡介质 ， 甲醇的转化率 36.68% ，乙二醇的选择性为 18.76% ，乙醇的选择性为 4.58% ，正丙醇的选择性为 0.95% ； 两层阻挡介质，甲醇的转化率 28.18% ，乙二醇的选择性为 25.37% ，乙醇的选择性为 5.37% ，正丙醇的选择性为 1.34% ； 三层阻挡介质 ， 甲醇的转化率 16.82% ，乙二醇的选择性为 37.25% ，乙醇的选择性为 6.47% ，正丙醇的选择性为 1.87% ； 四层阻挡介质 ， 甲醇的转化率 8.31% ，乙二醇的选择性为 46.73% ，乙醇的选择性为 7.21% ，正丙醇的选择性为 2.19% ； Single layer barrier medium, the conversion of methanol is 36.68%, the selectivity of ethylene glycol is 18.76%, and the selectivity of ethanol is 4.58%, the selectivity of n-propanol is 0.95%; the conversion rate of methanol is 28.18%, the selectivity of ethylene glycol is 25.37%, and the selectivity of ethanol is 5.37%. The selectivity of n-propanol is 1.34%; the conversion rate of methanol is 16.82%, the selectivity of ethylene glycol is 37.25%, and the selectivity of ethanol is 6.47%. The selectivity of n-propanol is 1.87%; the conversion rate of methanol is 8.31%, the selectivity of ethylene glycol is 46.73%, and the selectivity of ethanol is 7.21%. The selectivity of n-propanol is 2.19%;
实施例 18 ：脉冲电晕放电 Example 18: Pulse Corona Discharge
在 0.10MPa 压力下，将 H2 与气态甲醇以摩尔比 5:1 （其中 H2 流速为 40ml/min ，甲醇流速为 8ml/min ）通入放电反应器，气流稳定后，接通脉冲高压电源进行电晕放电。反应器采用线筒式电极结构，中心晕线为 2mm 的镀 Pt 的铜电极。筒式收集电极为长 250mm 、内径为 20mm 的不锈钢圆筒。反应器的有效放电长度为 80mm 。Under a pressure of 0.10 MPa, H 2 and gaseous methanol were introduced into the discharge reactor at a molar ratio of 5:1 (where H 2 flow rate was 40 ml/min, methanol flow rate was 8 ml/min), and after the gas flow was stabilized, the pulsed high-voltage power source was turned on. Perform a corona discharge. The reactor was constructed with a wire barrel electrode structure with a central halo of 2 mm Pt-plated copper electrodes. The cartridge collecting electrode is a stainless steel cylinder having a length of 250 mm and an inner diameter of 20 mm. The effective discharge length of the reactor was 80 mm.
脉冲直流高压电源，采用储能电容通过火花间隙向负载泄放的方式产生脉冲电压。反应器的放电参数为：脉冲电压的峰值 30kV 、脉冲重复频率 78Hz ；放电温度 180 ℃ 时反应结果为：甲醇转化率 33.50% ，乙二醇选择性 17.38% ，乙醇选择性 6.78% ，正丙醇选择性 1.56% 。 The pulsed DC high voltage power supply uses a storage capacitor to generate a pulse voltage by discharging the spark gap to the load. The discharge parameters of the reactor are: peak value of pulse voltage 30kV, pulse repetition frequency 78Hz; discharge temperature The reaction results at 180 °C were: methanol conversion rate of 33.50%, ethylene glycol selectivity of 17.38%, ethanol selectivity of 6.78%, and n-propanol selectivity of 1.56%.
实施例 19 ：辉光放电 Example 19: glow discharge
在 0.12MPa 压力下，将 O2 与气态甲醇以摩尔比 1:1 （其中 O2 蒸汽流速为 20ml/min ，甲醇流速为 20ml/min ）通入放电反应器，气流稳定后，接通电源进行辉光放电。反应器内旋转螺旋状电极经绝缘连接件与磁流体密封装置相连，再连接到转动机构上。当通以交流高压达到气体击穿电压时，反应气体在两电极之间形成的等离子体区发生化学反应，在旋转的放电反应过程中反应物全部垂直通过等离子体区。反应器采用线筒式结构，中心电极使用金属镍电极（直径 3mm ），外电极使用不锈钢筒（外径 27mm 、内径 25mm ），极间距为 11mm ，放电区长度 100mm 。O 2 and gaseous methanol were fed into the discharge reactor at a molar ratio of 1:1 (where O 2 vapor flow rate was 20 ml/min and methanol flow rate was 20 ml/min) under a pressure of 0.12 MPa. After the gas flow was stabilized, the power was turned on. Glow discharge. The rotating spiral electrode in the reactor is connected to the magnetic fluid sealing device via an insulating joint and then connected to the rotating mechanism. When the gas breakdown voltage is reached by the alternating high voltage, the reaction gas chemically reacts in the plasma region formed between the two electrodes, and the reactants all pass vertically through the plasma region during the rotating discharge reaction. The reactor adopts a wire barrel structure, a metal nickel electrode (diameter: 3 mm) is used for the center electrode, and a stainless steel tube (outer diameter: 27 mm, inner diameter: 25 mm) is used for the outer electrode, the pole pitch is 11 mm, and the discharge zone length is 100 mm.
反应器的放电参数为：双极性高压脉冲电源工作频率为 14.0 kHz ，脉冲电源的占空比为 9% ，输入电场峰值电压 1.6kV ；放电温度 350 ℃ 时反应结果为：甲醇转化率 21.36% ，乙二醇选择性 12.57% ，乙醇选择性 6.24% ，正丙醇选择性 2.15% 。 The discharge parameters of the reactor are: bipolar high voltage pulse power supply operating frequency is 14.0 kHz, pulse power supply duty cycle is 9% The input electric field peak voltage is 1.6kV; when the discharge temperature is 350 °C, the reaction results are: methanol conversion rate 21.36%, ethylene glycol selectivity 12.57%, ethanol selectivity 6.24% , n-propanol selectivity 2.15%.

Claims (1)

1 、一种转化甲醇的方法，其特征包括如下步骤：What is claimed is: 1. A method of converting methanol comprising the steps of:
（ 1 ）选择下述放电方法之一使甲醇分子得到选择性活化(1) Select one of the following discharge methods to selectively activate methanol molecules
① 采用介质阻挡放电：采用板板式反应器、管板式反应器、针板式反应器和线筒式反应器，阻挡介质是单层介质或双层介质，贴在电极表面或置于两极之间； 其中线筒式反应器的高压极和接地极分别为处于反应器壳体内的金属丝和环绕在外筒壁上的金属片、金属网或金属丝； 两极间距是指位于轴线的中心金属线状电极外壁与筒状接地电极内壁之间的距离， 电极间距取 0.3-20 mm ；线筒式反应器包括两种：一种是反应器壁做阻挡介质的单介质阻挡线筒式反应器；另一种是反应器壁做第一阻挡介质并在两极间***第二阻挡介质的双介质阻挡线筒式反应器；反应器外筒上端设甲醇和载气进口； 针板式反应器的电极分别是一个带有金属针阵列的金属板和一个金属平板；两金属板水平地固定在反应器壳体内，极间距为金属针下端点到金属平板之间的垂直距离；两极之间设阻挡介质板，阻挡介质板与两极的距离任意调节；在反应器壁上开设反应物和产物的进出口； 管板式反应器的电极分别是一个金属管和一个金属板；金属板水平地固定在反应器壳体内，金属管垂直对准水平金属板的中心，金属管下端点到金属板之间的垂直距离为极间距；两极之间设阻挡介质板，阻挡介质板与两极的距离任意调节；甲醇和载气从放电金属管进入，或从固定电极的反应器上端进料口进入，下端设反应产物出口； 板板式反应器的高压极和接地电极分别为两个金属板；将两个金属板平行地固定在反应器的壳体内，两板间的垂直距离为极间距，高压极和接地极之间设阻挡介质板，阻挡介质板与两极的距离任意调节；阻挡介质设单层或多层；在反应器壁上开设反应物和产物的进出口； 以上三种带有板式电极的反应器的极间距取 0.2-40 mm ；上述阻挡介质的总厚度取 0.3-10 mm ； 上述反应器的金属管电极的直径范围为 0.5-12 mm ， 金属板与金属管的直径比值为 1-20 ； 介质阻挡放电采用高压交流电源，电源频率取 1 kHz~ 50kHz ；1 Dielectric barrier discharge: using a plate plate reactor, a tube plate reactor, a needle plate reactor and a wire barrel reactor, the barrier medium is a single layer medium or a double layer medium, attached to the surface of the electrode or placed between the two poles; Wherein the high-voltage pole and the grounding pole of the wire-tube reactor are respectively a wire in the reactor casing and a metal piece, a metal mesh or a wire wound around the outer cylinder wall; The distance between the two poles refers to the distance between the outer wall of the central metal wire electrode located on the axis and the inner wall of the cylindrical ground electrode, and the electrode spacing is 0.3-20 mm. There are two types of wire-cylinder reactors: one is a single-medium-barrier reactor with a reactor wall as a barrier medium; the other is a reactor wall as a first barrier medium and a second barrier medium between the two poles. Double dielectric barrier wire-tube reactor; methanol and carrier gas inlets are arranged at the upper end of the reactor outer cylinder; The electrodes of the needle plate reactor are respectively a metal plate with a metal needle array and a metal plate; the two metal plates are horizontally fixed in the reactor casing, and the pole spacing is a vertical distance between the lower end of the metal needle and the metal plate; A barrier medium plate is disposed between the two poles, and the distance between the barrier dielectric plate and the two poles is arbitrarily adjusted; the inlet and outlet of the reactants and products are opened on the reactor wall; The electrodes of the tube-and-plate reactor are respectively a metal tube and a metal plate; the metal plate is horizontally fixed in the reactor housing, the metal tube is vertically aligned with the center of the horizontal metal plate, and the vertical distance between the lower end of the metal tube and the metal plate It is a pole spacing; a barrier dielectric plate is arranged between the two poles, and the distance between the blocking dielectric plate and the two poles is arbitrarily adjusted; methanol and carrier gas enter from the discharge metal tube, or enter from the upper inlet of the reactor of the fixed electrode, and the reaction product outlet is set at the lower end. ; The high-voltage pole and the grounding electrode of the plate-plate reactor are respectively two metal plates; the two metal plates are fixed in parallel in the casing of the reactor, the vertical distance between the two plates is the pole spacing, and the high-voltage pole and the grounding pole are disposed between Blocking the dielectric plate, the distance between the blocking dielectric plate and the two poles is arbitrarily adjusted; the blocking medium is provided with a single layer or a plurality of layers; and the inlet and outlet of the reactants and products are opened on the reactor wall; The above three reactors with plate electrodes have a pole pitch of 0.2-40 mm; the total thickness of the above blocking medium is 0.3-10 mm; the diameter of the metal tube electrode of the above reactor ranges from 0.5-12 Mm , the ratio of the diameter of the metal plate to the metal tube is 1-20; the dielectric barrier discharge is a high-voltage AC power source, and the power frequency is 1 kHz to 50 kHz;
② 采用电晕放电：反应器采用针板式结构，反应器的一个电极是带有尖端的金属丝，另一个电极是金属平板，高压电极和接地电极可在针、板间互换，电源用高压直流电源；反应器的两极间距取 0.5 ~ 18mm ，所说的两极间距是指针状电极的尖端与接地平板电极之间的距离；2 Corona discharge is adopted: the reactor adopts a needle plate structure, one electrode of the reactor is a wire with a tip, and the other electrode is a metal plate. The high voltage electrode and the ground electrode can be exchanged between the needle and the plate, and the power source is high voltage DC. Power supply; the two pole spacing of the reactor 0.5 ~ 18mm, the two-pole spacing is the distance between the tip of the pointer electrode and the grounding plate electrode;
③ 采用脉冲电晕放电：反应器采用线筒式结构，反应器的中心晕线电极是金属丝，另一个电极是金属圆筒；反应器两极间距 5 ~ 40mm ，所说的两极间距是指位于轴线的中心晕线外壁与金属筒壁之间的距离； 电源采用脉冲直流高压电源；上述电源的峰值电压取 20 ~ 60kV ；电源的脉冲重复频率取 10 ~ 150Hz ；3 Pulse corona discharge is adopted: the reactor adopts a wire barrel structure, the central halo electrode of the reactor is a metal wire, and the other electrode is a metal cylinder; the distance between the two poles of the reactor is 5 ~ 40mm, the two-pole spacing refers to the distance between the outer wall of the central halo line and the wall of the metal cylinder; the power supply uses a pulsed DC high-voltage power supply; the peak voltage of the above power supply is 20 ~ 60kV The pulse repetition frequency of the power supply is 10 ~ 150Hz;
④ 采用辉光放电：反应器采用线筒式结构或板板式结构；4 Glow discharge: The reactor adopts a wire-tube structure or a plate-and-plate structure;
电源采用脉冲直流高压电源或采用脉冲交流高压电源；当采用脉冲直流高压电源时要用储能电容通过火花间隙向负载泄放的方式产生脉冲电压，电源的峰值电压取 10 ~ 60kV ；电源的脉冲重复频率取 10 ~ 150Hz ；当采用脉冲交流高压电源时，电源的峰值电压取 0 ~ 30kV ；电源的脉冲重复频率取 7 ~ 50Hz ； 反应器两极间距 1~ 40mm ； 当采用线筒式反应器时，所说的两极间距是指位于轴线的中心金属线状电极与筒壁之间的距离；当采用板板式反应器时，所说的两极间距指两个平行金属板之间的垂直距离；The power supply adopts pulsed DC high voltage power supply or pulse AC high voltage power supply; when using pulsed DC high voltage power supply, the storage capacitor is used to generate pulse voltage through the spark gap to the load discharge mode, and the peak voltage of the power supply is taken. 10 ~ 60kV; the pulse repetition frequency of the power supply is 10 ~ 150Hz; when using pulse AC high voltage power supply, the peak voltage of the power supply is 0 ~ 30kV; the pulse repetition frequency of the power supply is taken 7 ~ 50Hz ; the distance between the two poles of the reactor is 1~ 40mm ; When a bobbin type reactor is used, the distance between the two poles refers to the distance between the central metal wire electrode located at the axis and the wall of the barrel; when a plate type reactor is used, the distance between the two poles refers to two parallel metals. The vertical distance between the plates;
（ 2 ）将选择性活化的甲醇转化为目的产物: 上述放电反应温度取 25 ~ 600℃ ；放电反应压力取 -0.06MPa ~ 0.5MPa ；载气与甲醇的摩尔比为 0 ~ 20 ；所说载气是 N2 、 H2 、 H2O 、 He 、 Ar 、 O2 、 CO 、 CO2 、 CH4 、 C2H6 中的一种或二种以上混合物。(2) Converting selectively activated methanol to the target product: the above discharge reaction temperature is 25 ~ 600 ° C; the discharge reaction pressure is -0.06 MPa ~ 0.5 MPa; the molar ratio of carrier gas to methanol is 0 ~ 20; The gas is one or a mixture of two or more of N 2 , H 2 , H 2 O, He, Ar, O 2 , CO, CO 2 , CH 4 , and C 2 H 6 .
2 、根据权利要求 1 所述的一种转化甲醇的方法，其特征在于，放电反应温度取 100~ 400℃ 。2. A method of converting methanol according to claim 1, wherein the discharge reaction temperature is from 100 to 400 ° C .
3 、根据权利要求 1 所述的一种转化甲醇的方法，其特征在于，放电反应压力取 -0. 02MPa ~ 0. 2MPa 。The MPa is 0. 02MPa ~ 0. 2MPa. The pressure of the discharge reaction is -0. 02MPa ~ 0. 2MPa .
4 、根据权利要求 1 所述的一种转化甲醇的方法，其特征在于，载气与甲醇的摩尔比为 0 ~ 6 。4. A method of converting methanol according to claim 1, wherein the molar ratio of carrier gas to methanol is from 0 to 6 .
5 、根据权利要求 1 所述的一种转化甲醇的方法，其特征在于，载气是 H2 、 H2O 、 He 、 Ar 、 CH4 。5. The method of claim 1, the methanol conversion, characterized in that the carrier gas is H 2, H 2 O, He , Ar, CH 4.
PCT/CN2011/084954 2011-10-27 2011-12-29 Method for converting methanol WO2013060080A1 (en)

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