CN104003845B - A kind of method of converting methanol - Google Patents
A kind of method of converting methanol Download PDFInfo
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- CN104003845B CN104003845B CN201410258110.8A CN201410258110A CN104003845B CN 104003845 B CN104003845 B CN 104003845B CN 201410258110 A CN201410258110 A CN 201410258110A CN 104003845 B CN104003845 B CN 104003845B
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Abstract
The invention belongs to plasma synthesis chemical field, relate to a kind of method of converting methanol.By dielectric barrier discharge, corona discharge, corona discharge pulse, glow discharge, radio frequency discharge, slip arc-over and microwave plasma mode, the Selective activation of methanol molecules and the methanol molecules of activation are converted into ethylene glycol; In the Selective activation process of methanol molecules, discharge temp gets 10-650 DEG C; Discharge pressure gets-0.2MPa ~-0.061Mpa.Producing of ethylene glycol is raw material with methyl alcohol, and methyl alcohol obtains through synthetic gas by coal, and even methyl alcohol can also be obtained by the vaporization of biomass, has recyclability.Meanwhile, prepare ethylene glycol with plasma body and belong to single stage method direct synthesis process, need not catalyzer be used, environmentally safe, and selectivity is high.In addition, the present invention, while obtaining ethylene glycol, can also pass through condition optimizing, co-producing ethanol, the useful products such as n-propyl alcohol.
Description
Technical field
The invention belongs to plasma synthesis chemical field, relate to a kind of method of converting methanol.
Background technology
Methyl alcohol is a kind of important basic organic chemical industry raw material, of many uses.The most strikingly for the synthesis of dme, alkene; Also has hydrogen in addition, gasoline, carbonic ether, aromatic hydrocarbons, ethanol, ethylene glycol, carbonylation acetic acid and fuel etc.Due to rich coal resources, ammonia from coal industrial development is rapid, and production capacity is large.Therefore, from methyl alcohol, the Chemicals producing various high added value have broad prospects.
A lot of open source literature relates to preparing olefin by conversion of methanol, aromatic hydrocarbons, gasoline, dme etc.In addition some patents are also had to relate to methanol conversion ethanol, propyl alcohol and ethylene glycol.As:
Patent US3248432A (application number US19610158870 applying date 1961-12-12) discloses a kind of method of Methanol ethanol.Its technical characteristic is: at aqueous cobalt catalyzer, under the methanol solution existence of iodine promotor and phosphide, and methyl alcohol, carbon monoxide and H
2under hyperbaric heating, reaction generates ethanol.Temperature of reaction is 150-250 DEG C, and reaction pressure is 20.7-103.5MPa.But this method tool reaction pressure is too high, and reaction process is complicated, and by-product is more, generates without ethylene glycol.
Patent US4424383A (application number US19810320008 applying date 1981-11-10) discloses a kind of method of Methanol ethanol and n-propyl alcohol.Its technical characteristic is: under the catalyzer be made up of cobalt, ruthenium, iodine, organophosphorus etc. exists, methyl alcohol and carbon monoxide, H
2at temperature of reaction 150-250 DEG C, under reaction pressure 20-60MPa, reaction generates ethanol and n-propyl alcohol.But this method pressure is higher, generates without ethylene glycol.
Patent US4337371A (application number US19800183537 applying date 1980-09-02) disclose a kind of with methyl alcohol and formaldehyde for raw material, the method for ethylene glycol is produced in condensation.Its technical characteristic is: use the organo-peroxide of wt%<6% if ditertiary butyl peroxide (DTBP), dicumyl peroxide (DCP) are as initiator, in the product obtained, the content of ethylene glycol is up to 7.71%.But this method glycol selectivity is lower.
Patent JP63027445A (application number 19860168874 applying date 1986-07-17) discloses a kind of method of Methanol ethylene glycol.Its technical characteristic is: first methyl alcohol generate dme through dehydration reaction, and dme generates glycol dimethyl ether with oxygen through oxidative coupling reaction more in the presence of a catalyst, and finally, glycol dimethyl ether is through hydrolysis reaction generating glycol.But the atom utilization of this method reaction is low, and hydrolysis reaction easily generates a large amount of waste water.
Some open source literatures are also had also to relate to Methanol ethylene glycol method in addition:
Open source literature " catalysis journal " .VOL.19, No.6,1998,601-604. reports a kind of by the method for Methanol for ethylene glycol.Be characterized in: the nanometer ZnS adopting Subjective and Objective structure is catalyzer, catalysis methanol solution synthesizing glycol under Hg lamp irradiation, the selectivity of ethylene glycol is subject to the impact of the Temperature Treatment, reaction times, solution ph etc. of light source, catalyzer, and selectivity reaches as high as more than 90%.
Open source literature " Acta PhySico-Chimica Sinica " .VOL.16, No.7,2000,601-607. reports a kind of method of methanol oxidation coupling preparing ethylene glycol.Be characterized in: prepared Li by the precipitator method
3pO
4, BiPO
4, Li
3pO
4biPO
4three kinds of solid surface materials, and be 1077cm by frequency
-1laser photon excite solid surface P=O key, make its end oxygen activation, the oxygen of activation and the methanol molecules effect of ADSORPTION STATE make its dehydrogenation, and then oxidative coupling generating glycol.Under the reaction conditions of normal pressure and 120 DEG C, use 1077cm
-1laser excitation Li
3pO
4biPO
41000 times, surface, methanol conversion reaches 16%, and the selectivity of ethylene glycol reaches 97.7%.
Open source literature J.Photochem.Photobiol.A:Chem, 74,1993,85-89. report a kind of method that methanol solution effectively produces hydrogen and ethylene glycol.Be characterized in: under ZnS colloid existent condition, methanol solution is direct generating glycol and H after UV-irradiation
2, its H
2with the yield of ethylene glycol and the selectivity of ethylene glycol and initial pH value and temperature of reaction closely related, the selectivity of ethylene glycol is up to 95%, and the output of reaction 6h ethylene glycol is between 6.5-44.8mmol.Experiment confirms: CH in alkali reaction system
2oH is main free radical intermediate, CH
2the coupling of OH is the main forming feature of ethylene glycol.
Applicant directly prepares in ethylene glycol at plasma-converted methyl alcohol and has license:
Patent ZL201110332089.8 (applying date 2011-10-27 authorizes day: 2013-11-06) discloses a kind of method of Methanol ethylene glycol.The technical characteristic of this patent is: under various forms of plasma method, and adjustment reaction pressure, flow rate of carrier gas and reaction tubes parameter, methyl alcohol and carrier gas are by the direct synthesizing glycol of plasma discharge.
Patent CN201110332485.0 (authorizing dispatch sequence number: 2014032500567220 applying date 2011-11-27) discloses a kind of apparatus and method of Methanol ethylene glycol.The technical characteristic of this patent is: under the environment that various different reactor is mated with plasma discharge, and by adjusting the energy of reaction system, methyl alcohol and carrier gas are by the direct synthesizing glycol of plasma discharge.
But in these two patents, the protection domain of pressure is-0.06MPa ~ 0.2MPa, and our exploration discovery by experiment, when pressure decreases beyond-0.06MPa, the transformation efficiency of methyl alcohol and the yield effect of ethylene glycol can be greatly improved.
Summary of the invention
The invention provides a kind of method reducing pressure, nonequilibrium plasma is prepared in the process of ethylene glycol at a step converting methanol and improves ethylene glycol yield.Its essence changes the energy distribution in reaction process, improves the utilization ratio of useful energy, form more CH
2oH free radical, thus the yield improving ethylene glycol.
The present invention regulates the energy of plasma slab high-energy electron by the following method, thus reaches the object of selectivity generating glycol product:
(1) select discharge type, selectable discharge type is: corona discharge, glow discharge or dielectric barrier discharge;
(2) by reaction system condition optimizing, reaction pressure condition etc. is optimized.
Technical scheme of the present invention comprises the steps:
The Selective activation of methanol molecules and the methanol molecules of activation are converted into ethylene glycol:
1. dielectric barrier discharge: dielectric barrier discharge adopts high-voltage ac power, and supply frequency gets 1kHz-60kHz, preferred 7kHz-17kHz.Dielectric barrier discharge can adopt plate plate-type reactor, tube-sheet type reactor, pin-plate reactor or line cartridge reactor, and block media is attached to electrode surface or is placed between the two poles of the earth;
The high pressure of A, pin-plate reactor is very with the metal sheet of metal needle array, and ground connection is metal sheet very; High-pressure stage and earthing pole are horizontally fixed in reactor shell, its spacing be high-pressure stage metal needle lower extreme point to earthing pole metal sheet between vertical range; Block media is established between the two poles of the earth; The wall of pin-plate reactor is offered reaction-ure inlet and product exit.
The high pressure very metal tube of B, tube-sheet type reactor, ground connection is metal sheet very; Metal sheet is horizontally fixed in the housing of tube-sheet type reactor, and metal pipe vertical is in the center of metal sheet; Block media is established between high-pressure stage and earthing pole; Methyl alcohol and carrier gas both can enter from metal tube, and the import also can offered from tube-sheet type reactor upper end enters, and outlet is offered in lower end; The diameter range of the metal tube electrode of above-mentioned reactor is 0.2-15mm, preferred 3-8mm; The diameter ratio of metal sheet and metal tube is 1-30.
High-pressure stage and the ground connection of C, plate plate-type reactor are metal sheet; Establish block media between high-pressure stage and earthing pole, block media can establish single or multiple lift; The wall of plate plate-type reactor is offered import and the outlet of reactant and product.
The desirable 0.1-50mm of above three kinds of interpole gaps with the reactor of plate type electrode, preferred 4-10mm.
The high pressure very wire of D, line cartridge reactor, ground connection is metallic substance very; The desirable 0.2-25mm of interelectrode distance, preferred 2-8mm; Methyl alcohol and carrier gas inlet are established in the upper end of line cartridge reactor.Line cartridge reactor comprises two kinds: a kind of single dielectric impedance line cartridge reactor being reactor wall and doing block media; Another kind is that reactor wall does the first block media and between the two poles of the earth, inserts the bi-medium to block line cartridge reactor of the second block media.
The housing of above-mentioned four kinds of reactors adopts insulating material.The shape and size of reactor shell can be determined according to actual needs, and the amplification of reactor realizes by the number of parallel of single scaling-up and reactor.
Above-mentioned block media selects insulating material, preferred silica glass, hard glass, mica and alumina-ceramic.The desirable 0.1-20mm of total thickness of block media, preferred 1-2.5mm.
2. corona discharge: adopt pin-plate reactor, high pressure very with wire, the ground connection very metal sheet at tip, or high pressure very metal sheet, ground connection very with the wire at tip; Power supply high-voltage DC power supply.The desirable 0.3-20mm of spacing of high-pressure stage and earthing pole, preferred 3-10mm.
3. corona discharge pulse: adopt line cartridge reactor, high pressure is wire very, and ground connection is metal cylinder very.The spacing 4-50mm of high-pressure stage and earthing pole, preferred 20-25mm.
Power acquisition pulse direct current high-voltage power supply, the mode using reservoir capacitance to be released to load by sparking distance produces pulsed voltage, and peak value, the pulse-repetition frequency of the pulse power are all adjustable.The crest voltage of above-mentioned pulse direct current high-voltage power supply gets 15-80kV, preferred 40-50kV; The pulse-repetition frequency of pulse direct current high-voltage power supply gets 5-200Hz, preferred 55-80Hz;
4. glow discharge: adopt line cartridge reactor or plate plate-type reactor; Power supply can adopt pulse direct current high-voltage power supply, also can adopt pulse ac high-voltage power supply.Pulsed voltage is produced by the mode that reservoir capacitance is released to load by sparking distance, the desirable 10-60kV of crest voltage of pulse direct current high-voltage power supply, preferred 30-50kV when adopting pulse direct current high-voltage power supply; The desirable 10-150Hz of pulse-repetition frequency of pulse direct current high-voltage power supply, preferred 50-100Hz; When adopting pulse ac high-voltage power supply, the desirable 0-60kV of crest voltage of pulse ac high-voltage power supply, preferred 2-8kV; The desirable 5-60Hz of pulse-repetition frequency of pulse ac high-voltage power supply, preferred 10-25Hz; The electrode materials adopted is metal; Two interpole gap 1-60mm, preferred 7-20mm.
5. radio frequency discharge: the tubular flow type plasma reactor using external capacitive coupling, two interpole gap 0-30mm, preferred 2-8mm.The radio-frequency power supply adopted, the high frequency of radio-frequency power supply is 1-150MHz, and geseous discharge forms the desirable 5-40MHz of frequency of plasma body, preferred 10-20MHz.Electrode materials is metal.
6. slide arc-over: slip arc plasma generator, and wherein, blade type electrode is metallic substance; The thickness of blade type electrode can get 1-15mm, preferred 3-8mm; The spacing of two blade type electrodes can get 1-15mm, preferred 3-8mm; Nozzle diameter on slip arc plasma generator can get 1-8mm, preferred 2.5-4mm; Blade type electrode starting the arc end can get 3-30mm, preferred 10-15mm apart from nozzle distance.
7. microwave plasma: adopt rectangular waveguide microwave chemical resonant cavity type reactor, this rectangular waveguide microwave chemical resonant cavity type reactor is made up of quartz material, and import is offered in rectangular waveguide microwave chemical resonant cavity type reactor upper end; Microwave source operating frequency is 2.45GHz, and the power input of microwave source is 7-800W, preferred 14-200W.The internal diameter of rectangular waveguide microwave chemical resonant cavity type reactor can get 5-45mm, preferred 10-15mm.
In the Selective activation process of above-mentioned methanol molecules, discharge temp gets 10-650 DEG C, preferred 150-350 DEG C; Discharge pressure gets-0.2MPa ~-0.061MPa, preferably-0.1MPa ~-0.07MPa;
In reaction system, the mol ratio of carrier gas and methyl alcohol is 0-30, preferred 2-8;
Carrier gas can be N
2, H
2, H
2o, He, Ar, O
2, CO, CO
2, CH
4, C
2h
6in one or two or more kinds mixture in hydro carbons, wherein preferred H
2, N
2, He, CH
4.
The invention has the beneficial effects as follows: producing of ethylene glycol is raw material with methyl alcohol, and methyl alcohol obtains through synthetic gas by coal, and even methyl alcohol can also be obtained by the vaporization of biomass, has recyclability.Meanwhile, prepare ethylene glycol with plasma body and belong to single stage method direct synthesis process, need not catalyzer be used, environmentally safe, and selectivity is high.In addition, the present invention, while obtaining ethylene glycol, can also pass through condition optimizing, co-producing ethanol, the useful products such as n-propyl alcohol.
Accompanying drawing explanation
Fig. 1 glow discharge reactor schematic diagram.
Electric pole type radio-frequency plasma discharge tubulose plasma reactor in Fig. 2 a.
Fig. 2 b outer electrode formula radio-frequency plasma discharge tubulose plasma reactor.
Fig. 2 c combination of inner and outside formula radio-frequency plasma discharge tubulose plasma reactor.
Fig. 3 slides arc plasma generator.
Fig. 4 microwave chemical resonant cavity type reactor.
In figure: 1 rotating shaft of stirrer; 2 magnetic current sealing glands; 3AC pulsed high voltage generator; 4 stationary cylinder electrodes; 5 rotating screw electrodes; 6 quartz reactors; 7 reactant entrances; 8 nozzles; 9 blade type electrodes; 10 transformers; 11 AC power; 12 product exit; 13 feed-in microwaves; 14 resonance pistons; 15 resonator cavitys; 16 silica tube microwave reactors; Distance between d high-pressure stage and earthing pole; + high-pressure stage;-earthing pole.
Embodiment
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme and accompanying drawing.
Comparative example 1
Single dielectric barrier discharge---pin-plate reactor
Hydrogen and methanol liquid are transported in interchanger and vaporize, be then transported to the dielectric impedance reactor of pin-plate type electrode structure.The raw materials components mole ratio of hydrogen and methyl alcohol is 2.0, and the residence time of methyl alcohol in electrical discharge zone is 4 × 10
-2s; The housing of pin-plate-type reactor adopts silica glass to make, external diameter is 10.0mm, wall thickness is 1.0mm, the plate electrodes of ground connection is all stainless steel with the material of the metal bar electrode being connected high-pressure side, metal sheet diameter is 8mm, and thickness is 0.3mm, and metal bar diameter is 0.5mm, be block media with sheet mica, be placed on ground connection pole plate; The lower end of high-pressure stage is 5.0mm to ground connection pole plate ground vertical range (two interpole gaps); When discharge frequency and discharge power keep 12kHz and 17W constant respectively; Temperature of reaction is 200 DEG C, and during reaction pressure modulation, reaction result is:
0.19MPa, the transformation efficiency 38% of methyl alcohol, the selectivity of ethylene glycol is 23.8%, and the selectivity of ethanol is 6.7%, and the selectivity of n-propyl alcohol is 3.5%;
0.15MPa, the transformation efficiency 41% of methyl alcohol, the selectivity of ethylene glycol is 25%, and the selectivity of ethanol is 6.58%, and the selectivity of n-propyl alcohol is 1.26%;
0.11MPa, the transformation efficiency 44% of methyl alcohol, the selectivity of ethylene glycol is 26.4%, and the selectivity of ethanol is 7.94%, and the selectivity of n-propyl alcohol is 4.17%;
0.07MPa, the transformation efficiency 45% of methyl alcohol, the selectivity of ethylene glycol is 26.2%, and the selectivity of ethanol is 5.84%, and the selectivity of n-propyl alcohol is 1.93%;
0MPa, the transformation efficiency 46% of methyl alcohol, the selectivity of ethylene glycol is 26.3%, and the selectivity of ethanol is 7.8%, and the selectivity of n-propyl alcohol is 1.82%;
-0.04MPa, the transformation efficiency 47% of methyl alcohol, the selectivity of ethylene glycol is 26.5%, and the selectivity of ethanol is 7.9%, and the selectivity of n-propyl alcohol is 1.78%.
Comparative example 2
Single dielectric barrier discharge---tube-sheet type reactor
Hydrogen and gaseous methanol are passed into discharge reactor with mol ratio 4.0, after steady air current, connects plasma electrical source and carry out dielectric barrier discharge.Reactor uses external diameter 8mm, the horminess glass tube of internal diameter 6mm is made, adopt Tube-Plate Electrodes structure, the iron pipe of high pressure very external diameter 3mm, internal diameter 2mm, ground connection very radius is the circular stainless steel plate of 3mm, dielectric medium is the individual layer mica of thickness 1mm, and interpole gap is 6mm.
The discharge parameter of reactor is: voltage 17.6kV, electric current 0.65A, frequency 8.5kHz; Other reaction conditions of reactor is: reactant at region of discharge residence time 0.28s, discharge temp 550 DEG C.During reaction pressure modulation, reaction result is:
0.19MPa, the transformation efficiency 60% of methyl alcohol, the selectivity of ethylene glycol is 1.7%, and the selectivity of ethanol is 9%, and the selectivity of n-propyl alcohol is 8%;
0.15MPa, the transformation efficiency 65% of methyl alcohol, the selectivity of ethylene glycol is 1.9%, and the selectivity of ethanol is 10%, and the selectivity of n-propyl alcohol is 6%;
0.11MPa, the transformation efficiency 69% of methyl alcohol, the selectivity of ethylene glycol is 2.0%, and the selectivity of ethanol is 11%, and the selectivity of n-propyl alcohol is 9%;
0.07MPa, the transformation efficiency 73% of methyl alcohol, the selectivity of ethylene glycol is 2.3%, and the selectivity of ethanol is 12%, and the selectivity of n-propyl alcohol is 10%;
0MPa, the transformation efficiency 75% of methyl alcohol, the selectivity of ethylene glycol is 2.5%, and the selectivity of ethanol is 10%, and the selectivity of n-propyl alcohol is 5%;
-0.04MPa, the transformation efficiency 79% of methyl alcohol, the selectivity of ethylene glycol is 2.8%, and the selectivity of ethanol is 8%, and the selectivity of n-propyl alcohol is 7%.
Comparative example 3
Corona discharge
Hydrogen and gaseous methanol are passed into discharge reactor with mol ratio 2.0, after steady air current, connects high-voltage power supply and carry out corona discharge.Reactor adopts needle plate type electrode structure, reactor is done with the silica tube of internal diameter 6mm, two ends are fixed wtih discharge electrode, one electrode is diameter 2mm stainless steel draw point (high voltage electrode), another electrode is the stainless steel circular dull and stereotyped (ground-electrode) of diameter 6mm, and interelectrode distance is 6mm.
Adopt direct current positive corona discharge, positive corona self-maintained discharge voltage is 0.6kV; Other reaction conditions of reactor is: reactant at region of discharge residence time 0.19s, discharge temp 400 DEG C.During reaction pressure modulation, reaction result is:
0.19MPa, the transformation efficiency 45% of methyl alcohol, the selectivity of ethylene glycol is 0.5%, and the selectivity of ethanol is 3%, and the selectivity of methane is 30%;
0.15MPa, the transformation efficiency 54% of methyl alcohol, the selectivity of ethylene glycol is 0.6%, and the selectivity of ethanol is 3.3%, and the selectivity of methane is 34%;
0.11MPa, the transformation efficiency 57% of methyl alcohol, the selectivity of ethylene glycol is 0.5%, and the selectivity of ethanol is 3.5%, and the selectivity of n-propyl alcohol is 36%;
0.07MPa, the transformation efficiency 60% of methyl alcohol, the selectivity of ethylene glycol is 0.5%, and the selectivity of ethanol is 3.7%, and the selectivity of n-propyl alcohol is 38%;
0MPa, the transformation efficiency 63% of methyl alcohol, the selectivity of ethylene glycol is 0.4%, and the selectivity of ethanol is 3.2%, and the selectivity of n-propyl alcohol is 39%;
-0.04MPa, the transformation efficiency 67% of methyl alcohol, the selectivity of ethylene glycol is 0.4%, and the selectivity of ethanol is 2.9%, and the selectivity of n-propyl alcohol is 43%.
Embodiment 1
Single dielectric barrier discharge---line cartridge reactor
By H
2pass into discharge reactor with gaseous methanol with mol ratio 9.0, after steady air current, connect plasma electrical source and carry out dielectric barrier discharge.Tubular reactor (simultaneously also as block media) is made with the horminess glass tube of external diameter 9mm, internal diameter 6mm, central electrode is the iron wire of diameter 3mm, ground connection very wall thickness is the cylindrical aluminium foil cylinder of 1mm (being close to Glass tubing outer wall), interpole gap is 3mm, and effective discharge length of reactor is 100mm.
The discharge parameter of reactor is: voltage 8.5kV, electric current 0.38A, frequency 15kHz; Other reaction conditions of reactor is: reactant at region of discharge residence time 4.2s, discharge temp 130 DEG C.During reaction pressure modulation, reaction result is:
-0.07MPa, the transformation efficiency 28.4% of methyl alcohol, the selectivity of ethylene glycol is 40.08%, and the selectivity of ethanol is 6.17%, and the selectivity of n-propyl alcohol is 1.64%;
-0.09MPa, the transformation efficiency 35.3% of methyl alcohol, the selectivity of ethylene glycol is 39.89%, and the selectivity of ethanol is 6.58%, and the selectivity of n-propyl alcohol is 1.26%;
-0.11MPa, the transformation efficiency 39.2% of methyl alcohol, the selectivity of ethylene glycol is 40.15%, and the selectivity of ethanol is 5.94%, and the selectivity of n-propyl alcohol is 2.17%;
-0.15MPa, the transformation efficiency 40.8% of methyl alcohol, the selectivity of ethylene glycol is 40.10%, and the selectivity of ethanol is 5.04%, and the selectivity of n-propyl alcohol is 1.9%;
-0.19MPa, the transformation efficiency 44.3% of methyl alcohol, the selectivity of ethylene glycol is 39.43%, and the selectivity of ethanol is 4.67%, and the selectivity of n-propyl alcohol is 1.93%;
Under identical discharging condition, the yield of ethylene glycol under malleation and condition of negative pressure is as shown in the table:
The present embodiment illustrates, adopts the dielectric barrier discharge reactor of different structure, and suitable discharging condition and reaction conditions, and electron energy can be made to be optimized when adjustment pressure is negative pressure, the yield of ethylene glycol object product is greatly improved.
Embodiment 2
Double-dielectric barrier discharge---line cartridge reactor
By N
2pass into discharge reactor with gaseous methanol with mol ratio 2.0, after steady air current, connect plasma electrical source and carry out dielectric barrier discharge.Tubular reactor (simultaneously also as block media) is made with double-deck polyfluortetraethylene pipe, its middle external tube external diameter 11mm, internal diameter 9mm, interior pipe external diameter 4mm, internal diameter 2mm, central electrode is the copper cash of diameter 2mm, ground connection very wall thickness 1mm is close to the cylindrical stainless (steel) wire (order number is 150) of polyfluortetraethylene pipe outer wall, interpole gap is 4.5mm, and effective discharge length of reactor is 120mm.
The discharge parameter of reactor is: voltage 12.5kV, electric current 0.38A, frequency 13kHz; Other reaction conditions of reactor is: reactant at region of discharge residence time 15.3s, discharge temp 220 DEG C.During reaction pressure modulation, reaction result is:
-0.07MPa, the transformation efficiency 23% of methyl alcohol, the selectivity of ethylene glycol is 42.7%, and the selectivity of ethanol is 8.33%, and the selectivity of n-propyl alcohol is 3.54%;
-0.09MPa, the transformation efficiency 25% of methyl alcohol, the selectivity of ethylene glycol is 44.7%, and the selectivity of ethanol is 9.33%, and the selectivity of n-propyl alcohol is 4.22%;
-0.11MPa, the transformation efficiency 27% of methyl alcohol, the selectivity of ethylene glycol is 44.4%, and the selectivity of ethanol is 7.49%, and the selectivity of n-propyl alcohol is 5.17%;
-0.15MPa, the transformation efficiency 31% of methyl alcohol, the selectivity of ethylene glycol is 45.2%, and the selectivity of ethanol is 6.34%, and the selectivity of n-propyl alcohol is 4.93%;
-0.19MPa, the transformation efficiency 33% of methyl alcohol, the selectivity of ethylene glycol is 46.3%, and the selectivity of ethanol is 7.18%, and the selectivity of n-propyl alcohol is 3.82%;
Under identical discharging condition, the yield of ethylene glycol under malleation and condition of negative pressure is as shown in the table:
The present embodiment illustrates, adopts dissimilar dielectric barrier discharge reactor, and suitable discharging condition and reaction conditions, and electron energy can be made to be optimized when adjustment pressure is negative pressure, the yield of ethylene glycol object product is greatly improved.
Embodiment 3
Corona discharge pulse
Ar and gaseous methanol are passed into discharge reactor with mol ratio 2.0, and after steady air current, make pulse high-voltage power supply carries out corona discharge.Reactor adopts line cartridge type electrode structure, and center hachure is the copper electrode of the plating Pt of 3mm.The stainless steel cylinder that cartridge type collector electrode is long 300mm, internal diameter is 25mm.Effective discharge length of reactor is 100mm.
Pulse direct current high-voltage power supply, the mode adopting reservoir capacitance to be released to load by sparking distance produces pulsed voltage.The discharge parameter of reactor is: the peak value 36kV of pulsed voltage, pulse-repetition frequency 66Hz; Other reaction conditions of reactor is: discharge temp 250 DEG C.During reaction pressure modulation, reaction result is:
-0.07MPa, the transformation efficiency 17% of methyl alcohol, the selectivity of ethylene glycol is 36%, and the selectivity of ethanol is 7%, and the selectivity of n-propyl alcohol is 6%;
-0.09MPa, the transformation efficiency 19.9% of methyl alcohol, the selectivity of ethylene glycol is 36%, and the selectivity of ethanol is 8%, and the selectivity of n-propyl alcohol is 6%;
-0.11MPa, the transformation efficiency 24% of methyl alcohol, the selectivity of ethylene glycol is 38%, and the selectivity of ethanol is 7%, and the selectivity of n-propyl alcohol is 7%;
-0.15MPa, the transformation efficiency 28% of methyl alcohol, the selectivity of ethylene glycol is 37%, and the selectivity of ethanol is 7%, and the selectivity of n-propyl alcohol is 6%;
-0.19MPa, the transformation efficiency 32% of methyl alcohol, the selectivity of ethylene glycol is 38%, and the selectivity of ethanol is 8%, and the selectivity of n-propyl alcohol is 7%;
Under identical discharging condition, the yield of ethylene glycol under malleation and condition of negative pressure is as shown in the table:
The present embodiment illustrates, adopts the plasma body that other electric discharge type produces, by selecting suitable negative pressure, electron energy also can be made to be optimized, thus obtain higher ethylene glycol yield.
Embodiment 4
Glow discharge
By N
2pass into discharge reactor with gaseous methanol with mol ratio 4.0, after steady air current, switch on power and carry out glow discharge.In reactor, rotary relix electrode is connected with device for sealing magnetic fluid through insulated connecting piece, is connected on rotating mechanism.When passing to ac high-voltage and reaching gas breakdown voltage, the plasma slab generation chemical reaction that reactant gases is formed between electrodes, in the exoelectrical reaction process rotated, reactant is all perpendicular through plasma slab.Reactor adopts line core structure, and central electrode uses metallic nickel electrode (diameter 3mm), and outer electrode uses stainless steel cylinder (external diameter 25mm, internal diameter 23mm), and interpole gap is 10mm, region of discharge length 120mm.
The discharge parameter of reactor is: bipolar high-voltage pulse power source operating frequency is 20kHz, and the dutycycle of the pulse power is 9%, input peak electric field voltage 1.8kV; Other reaction conditions of reactor is: reactant at region of discharge residence time 84.0s, discharge temp 440 DEG C.During reaction pressure modulation, reaction result is:
-0.07MPa, the transformation efficiency 39% of methyl alcohol, the selectivity of ethylene glycol is 24%, and the selectivity of ethanol is 7%, and the selectivity of n-propyl alcohol is 3%;
-0.09MPa, the transformation efficiency 41% of methyl alcohol, the selectivity of ethylene glycol is 25%, and the selectivity of ethanol is 8%, and the selectivity of n-propyl alcohol is 3%;
-0.11MPa, the transformation efficiency 43% of methyl alcohol, the selectivity of ethylene glycol is 26%, and the selectivity of ethanol is 7%, and the selectivity of n-propyl alcohol is 3%;
-0.15MPa, the transformation efficiency 46% of methyl alcohol, the selectivity of ethylene glycol is 26%, and the selectivity of ethanol is 7%, and the selectivity of n-propyl alcohol is 3%;
-0.19MPa, the transformation efficiency 49% of methyl alcohol, the selectivity of ethylene glycol is 27%, and the selectivity of ethanol is 7%, and the selectivity of n-propyl alcohol is 4%;
Under identical discharging condition, the yield of ethylene glycol under malleation and condition of negative pressure is as shown in the table:
Embodiment illustrates, adopts the plasma body that other electric discharge type produces, by selecting suitable negative pressure, electron energy also can be made to be optimized, thus obtain higher ethylene glycol yield.
Embodiment 5
Radio frequency discharge
By H
2pass into discharge reactor with gaseous methanol with mol ratio 2.0, after steady air current, connect Radio-frequency plasma torch and carry out radio frequency discharge, supply frequency is 13.56MHz.As shown in Figure 2, adopt outer electrode load mode, inlet mouth is 110mm to the distance of air outlet to reactor; Inner tube diameter is 5mm, and this is also the external diameter value of positive electrode; Outer tube diameter is 10.2mm; Wall thickness is 0.6mm; Inlet mouth is 20mm to the distance of reaction zone; Reaction zone length 25mm, discharging distance is 2mm.
The discharge parameter of reactor is: voltage 1.0kV, electric current 0.13A; Other reaction conditions of reactor is: reactant at region of discharge residence time 1.84s, discharge temp 560 DEG C.During modulation reaction pressure, reaction result is:
-0.07MPa, the transformation efficiency 41% of methyl alcohol, the selectivity of ethylene glycol is 24.2%, and the selectivity of ethanol is 7%, and the selectivity of n-propyl alcohol is 6%;
-0.09MPa, the transformation efficiency 45% of methyl alcohol, the selectivity of ethylene glycol is 25.7%, and the selectivity of ethanol is 8%, and the selectivity of n-propyl alcohol is 5%;
-0.11MPa, the transformation efficiency 46% of methyl alcohol, the selectivity of ethylene glycol is 26.5%, and the selectivity of ethanol is 7%, and the selectivity of n-propyl alcohol is 5%;
-0.15MPa, the transformation efficiency 49% of methyl alcohol, the selectivity of ethylene glycol is 27.3%, and the selectivity of ethanol is 8%, and the selectivity of n-propyl alcohol is 6%;
-0.19MPa, the transformation efficiency 53% of methyl alcohol, the selectivity of ethylene glycol is 29.6%, and the selectivity of ethanol is 8%, and the selectivity of n-propyl alcohol is 6%;
Under identical discharging condition, the yield of ethylene glycol under malleation and condition of negative pressure is as shown in the table:
| Gauge pressure | 0.15 | 0.1 | 0.075 | 0.05 | 0.025 | 0 | -0.07 | -0.09 | -0.11 | -0.15 | -0.19 |
| /MPa | |||||||||||
| Yield | 4.11 | 5.46 | 5.79 | 6.53 | 6.94 | 7.60 | 9.92 | 11.57 | 12.20 | 13.38 | 15.69 |
Embodiment illustrates, adopts the plasma body that other electric discharge type produces, by selecting suitable negative pressure, electron energy also can be made to be optimized, thus obtain higher ethylene glycol yield.
Embodiment 6
Slip arc-over
By CH
4pass into discharge reactor with gaseous methanol with mol ratio 3.0, after steady air current, connect plasma electrical source and discharge, the power acquisition AC power with leakage field structure, supply frequency 50Hz.
As shown in Figure 3, comprise a nozzle and two panels blade type stainless steel electrode in reactor, nozzle diameter is 1.5mm to reactor, thickness of electrode 3mm, and two interpole gaps are 3mm, electrode starting the arc end distance nozzle 15mm.The discharge parameter of reactor is: voltage is 8640V, electric current 0.56A; Other reaction conditions of reactor is: discharge temp 450 DEG C.During modulation reaction pressure, reaction result is:
-0.07MPa, the transformation efficiency 69% of methyl alcohol, the selectivity of ethylene glycol is 29%, and the selectivity of ethanol is 11%, and the selectivity of n-propyl alcohol is 6%;
-0.09MPa, the transformation efficiency 71% of methyl alcohol, the selectivity of ethylene glycol is 29%, and the selectivity of ethanol is 10%, and the selectivity of n-propyl alcohol is 6%;
-0.11MPa, the transformation efficiency 73% of methyl alcohol, the selectivity of ethylene glycol is 30%, and the selectivity of ethanol is 11%, and the selectivity of n-propyl alcohol is 6%;
-0.15MPa, the transformation efficiency 75% of methyl alcohol, the selectivity of ethylene glycol is 30%, and the selectivity of ethanol is 12%, and the selectivity of n-propyl alcohol is 7%;
-0.19MPa, the transformation efficiency 79% of methyl alcohol, the selectivity of ethylene glycol is 31%, and the selectivity of ethanol is 11%, and the selectivity of n-propyl alcohol is 8%;
Under identical discharging condition, the yield of ethylene glycol under malleation and condition of negative pressure is as shown in the table:
| Gauge pressure | 0.15 | 0.1 | 0.075 | 0.05 | 0.025 | 0 | -0.07 | -0.09 | -0.11 | -0.15 | -0.19 |
| /MPa | |||||||||||
| Yield | 7.65 | 9.87 | 12.19 | 13.11 | 15.00 | 16.38 | 20.01 | 20.59 | 21.90 | 22.50 | 24.49 |
Embodiment illustrates, adopts the plasma body that other electric discharge type produces, by selecting suitable negative pressure, electron energy also can be made to be optimized, thus obtain higher ethylene glycol yield.
Embodiment 7
Microwave plasma
As shown in Figure 4, wherein rectangular waveguide model is BJ22 to microwave plasma reactor, is of a size of 109.2mm × 54.6mm.A circular hole is had in upper and lower wide the centerline of rectangular waveguide.The silica tube that outside diameter is 20mm, interior diameter is 16mm passes perpendicularly through the hole of upper and lower wide.
Gaseous methanol is inputted by quartz tube reactor upper end with the flow velocity of 9ml/min, after gas pressure intensity is stable, open microwave source, the microwave power of 2.45GHz is fed into rectangular waveguide, regulate HIGH-POWERED MICROWAVES losser, adjustment short-circuit plunger, makes the resonator cavity comprising quartz reactor reach resonance, produces microwave discharge.As power input 60W, reactant at region of discharge residence time 73.1s, during discharge temp 380 DEG C.During modulation reaction pressure, reaction result is:
-0.07MPa, the transformation efficiency 44% of methyl alcohol, the selectivity of ethylene glycol is 29%, and the selectivity of ethanol is 12%, and the selectivity of n-propyl alcohol is 7%;
-0.09MPa, the transformation efficiency 47% of methyl alcohol, the selectivity of ethylene glycol is 29%, and the selectivity of ethanol is 10%, and the selectivity of n-propyl alcohol is 7%;
-0.11MPa, the transformation efficiency 49% of methyl alcohol, the selectivity of ethylene glycol is 31%, and the selectivity of ethanol is 12%, and the selectivity of n-propyl alcohol is 7%;
-0.15MPa, the transformation efficiency 53% of methyl alcohol, the selectivity of ethylene glycol is 32%, and the selectivity of ethanol is 12%, and the selectivity of n-propyl alcohol is 7%;
-0.19MPa, the transformation efficiency 57% of methyl alcohol, the selectivity of ethylene glycol is 34%, and the selectivity of ethanol is 11%, and the selectivity of n-propyl alcohol is 8%;
Under identical discharging condition, the yield of ethylene glycol under malleation and condition of negative pressure is as shown in the table:
Embodiment illustrates, adopts the plasma body that other electric discharge type produces, by selecting suitable negative pressure, electron energy also can be made to be optimized, thus obtain higher ethylene glycol yield.
Claims (10)
1. a method for converting methanol, is characterized in that, the method is that the Selective activation of methanol molecules and the methanol molecules of activation are converted into ethylene glycol: concrete steps are as follows:
(1) one in following discharge type is selected
1. dielectric barrier discharge: dielectric barrier discharge adopts high-voltage ac power, and supply frequency gets 1kHz ~ 60kHz; Dielectric barrier discharge is plate plate-type reactor, tube-sheet type reactor, pin-plate reactor or line cartridge reactor, and block media is attached to electrode surface or is placed between the two poles of the earth;
The high pressure of A, pin-plate reactor is very with the metal sheet of metal needle array, and ground connection is metal sheet very; High-pressure stage and earthing pole are horizontally fixed in reactor shell, its spacing be high-pressure stage metal needle lower extreme point to earthing pole metal sheet between vertical range; Block media is established between the two poles of the earth; The wall of pin-plate reactor is offered reaction-ure inlet and product exit;
The high pressure very metal tube of B, tube-sheet type reactor, ground connection is metal sheet very; Metal sheet is horizontally fixed in the housing of tube-sheet type reactor, and metal pipe vertical is in the center of metal sheet; Block media is established between high-pressure stage and earthing pole; The reaction-ure inlet that methyl alcohol and carrier gas enter from metal tube or offer from tube-sheet type reactor upper end enters, and product exit is offered in lower end; The diameter of metal tube is 0.2-15mm; The diameter ratio of metal sheet and metal tube is 1-30;
High-pressure stage and the earthing pole of C, plate plate-type reactor are metal sheet; Establish block media between high-pressure stage and earthing pole, block media is single or multiple lift; The wall of plate plate-type reactor offers reaction-ure inlet and product exit;
The spacing of above three kinds of high-pressure stages with the reactor of plate type electrode and earthing pole is 0.1-50mm;
The high pressure very wire of D, line cartridge reactor, ground connection is metallic substance very; Interelectrode distance is 0.2-25mm; Reaction-ure inlet is established in the upper end of line cartridge reactor;
The total thickness of the block media in dielectric barrier discharge is 0.1-20mm;
2. corona discharge: adopt pin-plate reactor, high pressure very with wire, the ground connection very metal sheet at tip, or high pressure very metal sheet, ground connection very with the wire at tip; The spacing of high-pressure stage and earthing pole is 0.3-20mm, power acquisition high-voltage DC power supply;
3. corona discharge pulse: adopt line cartridge reactor, high pressure is wire very, and ground connection is metal cylinder very; The spacing of high-pressure stage and earthing pole is 4-50mm; Power acquisition pulse direct current high-voltage power supply, the mode using reservoir capacitance to be released to load by sparking distance produces pulsed voltage, and the crest voltage of pulse direct current high-voltage power supply is 15-80kV; The pulse-repetition frequency of pulse direct current high-voltage power supply is 5-200Hz;
4. glow discharge: adopt line cartridge reactor or plate plate-type reactor; Power acquisition pulse direct current high-voltage power supply or pulse ac high-voltage power supply; When adopting pulse direct current high-voltage power supply, produce pulsed voltage by the mode that reservoir capacitance is released to load by sparking distance, the crest voltage of pulse direct current high-voltage power supply is 10-60kV; The pulse-repetition frequency of pulse direct current high-voltage power supply is 10-150Hz; When adopting pulse ac high-voltage power supply, the crest voltage of pulse ac high-voltage power supply is 0-60kV; The pulse-repetition frequency of pulse ac high-voltage power supply is 5-60Hz; The electrode materials adopted is metal; Two interpole gap 1-60mm;
5. radio frequency discharge: the tubular flow type plasma reactor using external capacitive coupling, two interpole gap 0-30mm; The radio-frequency power supply adopted, the high frequency of radio-frequency power supply is 1-150MHz, and geseous discharge forms the desirable 5-40MHz of frequency of plasma body; Electrode is metallic substance;
6. slide arc-over: slip arc plasma generator, and wherein, blade type electrode is metallic substance; The thickness of blade type electrode is 1-15mm; The spacing of two blade type electrodes is 1-15mm; Nozzle diameter on slip arc plasma generator is 1-8mm; Blade type electrode starting the arc end is 3-30mm apart from nozzle distance;
7. microwave plasma discharge: adopt rectangular waveguide microwave chemical resonant cavity type reactor, this rectangular waveguide microwave chemical resonant cavity type reactor is made up of quartz material, and reaction-ure inlet is offered in rectangular waveguide microwave chemical resonant cavity type reactor upper end; Microwave source operating frequency is 2.45GHz, and the power input of microwave source is 7-800W; The internal diameter of rectangular waveguide microwave chemical resonant cavity type reactor is 5-45mm;
(2) optimizing reaction system condition
The Selective activation of above-mentioned methanol molecules and the methanol molecules of activation are converted into discharge temp in ethylene glycol process and get 10-650 DEG C; Discharge pressure gets-0.2MPa ~-0.061MPa;
Carrier gas is N
2, H
2, H
2o, He, Ar, O
2, CO, CO
2, CH
4, C
2h
6in one or two or more kinds mixing, the mol ratio of carrier gas and methyl alcohol is 0-30.
2. method according to claim 1, is characterized in that, when adopting dielectric barrier discharge, supply frequency is 7kHz-17kHz; The housing of reactor is that insulating material is made, and single reactor or the parallel connection of multiple reactor realize electric discharge; Described block media selects insulating material, and its total thickness is 1-2.5mm; The diameter of described metal tube is 3-8mm; Wherein, the reactor interpole gap with plate type electrode is 4-10mm, and line cartridge reactor interpole gap is 2-8mm.
3. method according to claim 1, is characterized in that, when adopting corona discharge, and the spacing 3-10mm of high-pressure stage and earthing pole.
4. method according to claim 1, is characterized in that, when adopting corona discharge pulse, the spacing of high-pressure stage and earthing pole is 20-25mm; The crest voltage of pulse direct current high-voltage power supply is 40-50kV; The pulse-repetition frequency of pulse direct current high-voltage power supply is 55-80Hz.
5. method according to claim 1, is characterized in that, when adopting glow discharge, the crest voltage of pulse direct current high-voltage power supply is 30-50kV; The pulse-repetition frequency of pulse direct current high-voltage power supply is 50-100Hz; The crest voltage of pulse ac high-voltage power supply is 2-8kV; The pulse-repetition frequency of pulse ac high-voltage power supply is 10-25Hz; The electrode materials adopted is metal; Two interpole gaps are 7-20mm.
6. method according to claim 1, is characterized in that, when adopting radio frequency discharge, two interpole gaps are 2-8mm; The frequency that geseous discharge forms plasma body is 10-20MHz.
7. method according to claim 1, is characterized in that, when adopting slip arc-over, the thickness of blade type electrode is 3-8mm; The spacing of two blade type electrodes is 3-8mm; Blade type electrode starting the arc end is 10-15mm apart from nozzle distance; Nozzle diameter on slip arc plasma generator is 2.5-4mm.
8. method according to claim 1, is characterized in that, when adopting microwave plasma discharge, the power input of microwave source is 14-200W; The internal diameter of rectangular waveguide microwave chemical resonant cavity type reactor is 10-15mm.
9., according to the arbitrary described method of claim 1-8, it is characterized in that, it is 150-350 DEG C that the Selective activation of methanol molecules and the methanol molecules of activation are converted into discharge temp in ethylene glycol process; Discharge pressure is-0.1MPa ~-0.07MPa.
10., according to the arbitrary described method of claim 1-8, it is characterized in that, described carrier gas is H
2, N
2, He, CH
4in one or more mixing; Described carrier gas and the mol ratio of methyl alcohol are 2-8.
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