CN101033167A - Device for preparing propylene by dehydrogenating propane under hydrogen plasma - Google Patents
Device for preparing propylene by dehydrogenating propane under hydrogen plasma Download PDFInfo
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- CN101033167A CN101033167A CN 200710010843 CN200710010843A CN101033167A CN 101033167 A CN101033167 A CN 101033167A CN 200710010843 CN200710010843 CN 200710010843 CN 200710010843 A CN200710010843 A CN 200710010843A CN 101033167 A CN101033167 A CN 101033167A
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Abstract
This invention relates to a device for preparing propylene by taking off hydrogen from propane under a condition of hydrogen plasma, a structure of coaxial three-layer sleeve of which is made in oxide glass including an inner sleeve, a mid and an outer sleeve, in which, a plasma activation reactor with a dual medium discharge electrode first of all plasmizes the propane and hydrogen, which act with hard electrons formed in the plasma to generate isopropyl free radical and H free radical, and the isopropyl free radical eliminates beta-bit of C-H key acted by H free radical to get propylene.
Description
Technical field
The invention belongs to the device of preparing propylene by dehydrogenating propane under nonthermal plasma chemistry and the basic organic chemicals synthesis technical field, particularly oxygen plasma concrete conditions in the establishment of a specific crime.
Background technology
Propylene is a kind of important colourless flammable hydrocarbon gas, is mainly used in Chemicals such as producing polypropylene, isopropyl benzene, hydroxyl alcohol, acrylon, propylene oxide.Propylene is mainly produced the byproduct of ethene from steam cracking at present, and the byproduct of gasoline, diesel oil is produced in refinery catalytic cracking (FCC).In the face of growing petrochemical industry demand to propylene, only depend on above-mentioned several technology to be difficult to satisfy, demand seeking new production propylene technology urgently, thereby be the hot subject that the feedstock production propylene becomes petrochemical industry rapidly with the propane of aboundresources, less expensive.
Research for preparing propylene by dehydrogenating propane at present mainly concentrates on following three aspects: propane catalytic dehydrogenation, propane is dehydrogenation and oxidative dehydrogenation of propane on membrane reactor.
The propane catalytic dehydrogenating reaction is the reversible reaction that heat absorption, molecule number increase on thermodynamics, and its transformation efficiency depends on thermodynamic(al)equilibrium, carries out to the dehydrogenation direction for making reaction, needs to improve temperature of reaction and reduces pressure.Aspect the catalyst system selection, main platinum group catalyst and chromium-based catalysts two individual system of adopting of investigators.Open source literature (Appl.Catal.A, 2001,221:402; The catalysis journal, 1999,20 (5): 577-580; Petrochemical complex, 2006,35 (3): 217-220) studies show that, on platinum catalyst, obtain higher dehydrogenation selectivity and stability, be unable to do without the effect of auxiliary agent Sn usually.At the effect of Sn auxiliary agent, open source literature has proposed " geometrical effect " (J.Mol.Catal., 1984,25:1-12 again; J.Catal., 1980,63:119-128; J.Mol.Catal., 1984,25:13-29), " electronic effect " (J.Catal., 1981,71:348-359; J.Catal., 1981,71:360-372; Catal.Today., 1991,10:233-249; J.Catal., 1986,99:39-52) and " ' sandwich ' theory of ship structures " (catalysis journal, 1997,18 (2): 97-101; The catalysis journal, 1987,8 (4): 345-351; Chinese science (B collects), 1999,29 (2): viewpoint such as 109-117).Although platinum catalyst is environmentally friendly, activity is also higher, and its stability and selectivity also are not very desirable.Open source literature (J.Catal., 1986,99:149-158; J.Mol.Catal., 1988,46:173-186) studied at Al
2O
3Cr species and active sites that the surface exists with multivalence attitude, multi phase state.Open source literature (Appl.Catal.A, 1999,180:247-260; J.Catal., 1991,127:777-787) point out Cr
3+, Cr
5+And Cr
6+Form multiple compound, and have different reductibilities and catalysis behavior; Cr
5+The initial activity of species and catalyzer is relevant, but main active centre is Cr
2+, and the selectivity of propylene is mainly by Cr
3+The species decision.Because chromium-based catalysts has toxicity, and poor stability, thereby should develop the lower catalyzer of Cr content.
Utilize the big characteristics of the saturating hydrogen amount of membrane reactor, isolate hydrogen at any time, can solve the propene yield problem of molecular balance restriction.Open source literature (Bull.Korean Chem.Soc., 2002,23 (5): 647-678) at p=20kPa, air speed=1800h
-1, T=500 ℃, sweep gas Ar flow velocity be under the reaction conditions of 100mL/min, obtained on membrane reactor, conversion of propane and propylene selectivity are respectively 52% and 93% result.Open source literature (J.Membrane Science, 1997,135:107-115) sweep gas of having studied different components to propane at Pd-Ag/Al
2O
3The influence of dehydrogenation reaction on the membrane reactor.Find that working as sweep gas is air, in the time of 400 ℃, the transformation efficiency of propane is 51%.Though film can alleviate the restriction that propene yield is subjected to thermodynamic equilibrium, the propane catalytic dehydrogenation remains a slow dynamic process.
Because the oxidative dehydrogenation of propane reaction enthalpy diminishes in zero, is thermopositive reaction, need not extraneous heating, and reaction is not subjected to the restriction of thermodynamic(al)equilibrium.Based on this, many investigators have shown great interest to oxidative dehydrogenation of propane.But because the most weak c h bond bond energy of propylene (360.7kJ/mol) is less than propane c h bond bond energy (401.3kJ/mol) in the product, the former is more unstable than the latter, and is oxidized easily, and the propylene selectivity is very low usually.In order to break through the restriction of thermodynamic(al)equilibrium, improve the dehydrogenating propane transformation efficiency, in reaction system, add oxygenant usually (as O
2, CO
2Deng) be used for the H that produces in the oxidizing reaction
2, reaction can be carried out at a lower temperature.Utilize oxygen, adopting the research of catalytic component based on vanadium is the emphasis of this serial reaction.Open source literature (Appl.Catal.A, 1995,127:1-40) think VO with tetrahedral structure
4Be suitable for most alkanes oxidative dehydrogenation reaction, its intrinsic activity depends on contiguous ionic structure, the variation of ionic character and quantity on every side to a great extent.Open source literature (Appl.Catal.A, 1997,157:117-142) summed up the load-type vanadium oxygen compound to low-carbon alkanes (C
2-C
4) catalytic activity of oxidative dehydrogenation, carrier acid-basicity and vanadium charge capacity be to the influence of dispersion, structure, reductibility and the catalyst acid alkalescence matter of oxyvanadium compound on the carrier surface, thinks V
5+Species and on every side element be to influence reactive activity and key factor optionally.Open source literature (catalysis journal, 2000,21,4:333-336; Acta PhySico-Chimica Sinica, 2000,16 (9): 798-803) studied n shape and p shape conductor oxidate, found that P shape semi-conductor has more excellent catalytic performance, adopts Ni to the oxidative dehydrogenation of propane Effect on Performance
3V
2O
8Catalyzer has obtained 18.6% conversion of propane and 49.9% propylene selectivity in the time of 425 ℃.Open source literature (J.Am.Chem.Soc., 1998,120 (380): 9959-9960) reported in the time of 550 ℃, adopted V
2O
5-SiO
2-ZrO
2Catalyzer has obtained conversion of propane and propylene selectivity and has been respectively 8% and 81.5% result.Open source literature (Chem.Lett., 1999, (1): 25-26) on the nickel-base catalyst with the lithium chloride modulation, reaction conditions is 600 ℃ of temperature, reaction gas proportioning n (C
3H
8): n (O
2): n (N
2Under the situation of)=10: 10: 80, reactant flow 60mL/min, obtain 20% conversion of propane and 50% propylene selectivity.Under the reaction conditions of present oxidative dehydrogenation of propane, be easy to make reactant propane and product propylene generation complete oxidation to generate CO and CO
2Therefore, the catalyzer that needs exploitation to have the low-temp reaction performance and have highly selective.
Summary of the invention
The purpose of this invention is to provide a kind ofly under room temperature, normal pressure, propane molecule and hydrogen prepare the device of propylene under plasma-activated condition.
Know-why of the present invention is, utilize a plasma-activated reactor earlier with propane and hydrogen gas plasmaization, propane molecule and hydrogen molecule and the high-energy electron effect that in plasma body, forms, generate sec.-propyl free radical and H free radical respectively, because the H free radical has unique dehydrogenation under condition of plasma, promptly easily capture other molecules or the interior contained hydrogen atom of particle in the plasma body, and with it in conjunction with generating hydrogen, therefore, the sec.-propyl free radical carries out the β position of c h bond under the effect of H free radical eliminates, thereby obtains propylene.
The present invention is achieved through the following technical solutions: the device of preparing propylene by dehydrogenating propane under hydrogen plasma, this device is coaxial three layers of tube-in-tube structure, all adopt oxide glass to make, by inner core 3, middle tube 9 and urceolus 4 constitute, wherein, the upper port and the equal sintering of lower port of middle tube 9 and urceolus 4 seal and are fixed on the insulating material 7, the lower port sintering of inner core 3 seals and is fixed on the insulating material 7, the upper port open-ended of inner core 3, and communicate with outside atmosphere, its barrel apart from the about 8-12 millimeter of upper port place is fixed on the insulating material 7, the fineness ratio of inner core 3 is 300-1, and the annular space distance between inner core 3 and the middle tube 9 is 0.1-100 with the ratio of inner core 3 diameters.Be provided with water electrode 1 in the inner core 3, voltage of alternating current lead-in wire 6 lower ends link to each other with water electrode 1, its upper end is connected with the high voltage end of ac high voltage source, be provided with liquid electrode 10 in the annular space between middle tube 9 and the urceolus 4, be sintered to fix the metal electric current in the bottom of middle tube 9 and urceolus 4 annular spaces and derived line, the one end deeply in tube 9 contact with liquid electrode 10 with the annular space of urceolus 4, the other end stretches out insulating material 7 and is connected with earthing pole 12, liquid electrode 10 is in as ground-electrode, also as the medium of conditioned reaction system temperature.Urceolus 4 side wall lower ends are provided with circulating liquid import 11, the position of urceolus 4 sidewall upper, circulating liquid import 11 offsides is provided with circulating liquid outlet 2, stretch out on the sidewall of urceolus 4 in middle tube 9 upper ends, 2 pairs of side positions of circulating liquid outlet are provided with unstripped gas inlet 5, stretch out on the sidewall of urceolus 4 in middle tube 9 lower ends, the enter the mouth position of 5 offsides of unstripped gas is provided with product gas outlet 8, reactant carries out exoelectrical reaction in inner core 3 and the middle tube 9 tubular annular space spaces that constituted, the barrel of inner core 3 and middle tube 9 is a reactor shell, is again the block media of discharge.When the fineness ratio of inner core 3 is 200-1, when the annular space distance between inner core 3 and the middle tube 9 was 0.1-50 with the ratio of inner core 3 diameters, effect was best.Water in described water electrode 1 and the liquid electrode 10 comprises ordinary tap water, distilled water and the aqueous electrolyte liquid that disposes voluntarily, and the salt in Pei Zhi the aqueous electrolyte liquid preferably selects nitrate, carbonate and the hydrochloride of first main group and second main group voluntarily.The material that described voltage of alternating current lead-in wire 6 and metal electric current are derived line is metal or its alloy or various stainless steels such as platinum, rhodium, palladium, gold, copper, tungsten, iron, nickel, titanium.Described oxide glass contains one or more in silicon oxide, boron oxide, germanium oxide, phosphorus oxide, aluminum oxide, arsenic oxide arsenoxide, Tungsten oxide 99.999, vanadium oxide, bismuth oxide, gallium oxide, titanium oxide, molybdenum oxide and the selenium oxide.
Reactant propane, its purity preferably reach more than 99.99%, make product complicated to avoid the impurity hydrocarbon.Reactant hydrogen gas can adopt the bigger steel cylinder hydrogen of purity.So far, utilize device of the present invention can be under the room temperature normal pressure direct gas phase synthesizing propylene.Implementation result can be weighed with the transformation efficiency of interior alkane and the selectivity of propylene, and propane and propylene and other products carry out joint-detection by a gas-chromatography and a gas-chromatography of being furnished with the oxygen flame detector of being furnished with thermal conductivity cell detector.
Effect of the present invention and benefit are, under the room temperature normal pressure, utilize the direct gas phase synthesizing propylene of hydrogen and propane, consumed power, reaction conditions gentleness, raw material inexpensive clean, operating process is simple, no equipment corrosion and problem of environmental pollution belong to the green synthetic route of low-cost single stage method system propylene, and better industrial application prospects is arranged.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 is a structural representation of the present invention.
Among the figure: 1, water electrode, 2, circulating liquid outlet, 3, inner core, 4, urceolus, 5, the unstripped gas inlet, 6, the voltage of alternating current lead-in wire, 7, insulating material, 8, the outlet of product gas, 9, middle tube, 10, liquid electrode, 11, the circulating liquid import, 12, grounding wire.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
With propane gas, the common cyclinder gas of purity 〉=99.99% and hydrogen, purity 〉=99% is regulated and control by mass-flow gas meter, flow with 10 ml/min and 10 ml/min mixes in mixing tank respectively, propane accounts for 50%, enter reactor from unstripped gas inlet 5 then, after the displaced air 2 minutes, connect ac high voltage source, carry out dielectric barrier discharge, react in the annular space that unstripped gas forms between inner core glass 3 and middle tube glass 9, export detection and the analysis that 8 places carry out product at product gas.The housing of apparatus of the present invention becomes with oxide compound hard glass, and wherein the inner core external diameter is 6.0 millimeters, and the inner core wall thickness is 1.5 millimeters, and distance is 3 millimeters between the annular space between inner core and the middle tube, and region of discharge length is 150 millimeters.Apparatus of the present invention as water electrode 1, feed ordinary tap water as liquid electrode 10 in the annular space that forms with distilled water between inner core glass 3 and middle tube glass 9.At voltage is 22.3kV, and frequency is under the 1.1kHz condition, and the conversion of propane that obtains is 30.9%, and the selectivity of propylene is 11.1%.
Embodiment 2
Repeat embodiment 1, the aqueous solution that feeding contains yellow soda ash 1% (mass ratio) is as liquid electrode 10, and the reaction result that obtains is: conversion of propane is 36.5%, and the selectivity of propylene is 14.8%; When water electrode 1 and liquid electrode 10 all adopted the aqueous solution that contains yellow soda ash 1% (mass ratio), conversion of propane was 43.2%, and the selectivity of propylene is 15.1%.
Embodiment 3
Repeat embodiment 1, when the volume ratio of propane/hydrogen is 60%, at the reaction result that obtains under the different sparking voltages be: when sparking voltage was 16.6kV, conversion of propane was 2.4%, and the selectivity of propylene is 6.8%; When sparking voltage was 19.2kV, conversion of propane was 22.0%, and the selectivity of propylene is 9.3%; When sparking voltage was 25.3kV, conversion of propane was 35.1%, and the selectivity of propylene is 13.5%.
Claims (5)
1, the device of preparing propylene by dehydrogenating propane under hydrogen plasma, it is characterized in that, this device is coaxial three layers of tube-in-tube structure, all adopt oxide glass to make, by inner core (3), middle tube (9) and urceolus (4) constitute, the upper port and the equal sintering of lower port of middle tube (9) and urceolus (4) seal and are fixed on the insulating material (7), the lower port sintering of inner core (3) seals and is fixed on the insulating material (7), the upper port open-ended of inner core (3), and communicate with outside atmosphere, its barrel apart from upper port 8-12 millimeter place is fixed on the insulating material (7), the fineness ratio of inner core (3) is 300-1, annular space distance between inner core (3) and the middle tube (9) is 0.1-100 with the ratio of inner core (3) diameter, be provided with water electrode (1) in the inner core (3), voltage of alternating current lead-in wire (6) lower end links to each other with water electrode (1), its upper end is connected with the high voltage end of ac high voltage source, be provided with liquid electrode (10) in the annular space between middle tube (9) and the urceolus (4), be sintered to fix the metal electric current in the bottom of middle tube (9) and urceolus (4) annular space and derived line, one end deeply middle tube (9) contacts with liquid electrode (10) with the annular space of urceolus (4), the other end stretches out insulating material (7) and is connected with earthing pole (12), liquid electrode (10) is in as ground-electrode, also as the medium of conditioned reaction system temperature, urceolus (4) side wall lower ends is provided with circulating liquid import (11), urceolus (4) sidewall upper, the position of circulating liquid import (11) offside is provided with circulating liquid outlet (2), stretch out on the sidewall of urceolus (4) in middle tube (9) upper end, circulating liquid outlet (2) is provided with unstripped gas inlet (5) to side position, stretch out on the sidewall of urceolus (4) in middle tube (9) lower end, the position of unstripped gas inlet (5) offside is provided with product gas outlet (8), and reactant carries out exoelectrical reaction in the tubular annular space space that inner core (3) and middle (9) are constituted.
2, the device of preparing propylene by dehydrogenating propane under hydrogen plasma according to claim 1, it is characterized in that, the fineness ratio of described inner core (3) is 200-1, and (the annular space distance between 9 is 0.1-50 with the ratio of inner core (3) diameter for inner core (3) and middle tube.
3, the device of preparing propylene by dehydrogenating propane under hydrogen plasma according to claim 1, it is characterized in that, water in described water electrode (1) and the liquid electrode (10) comprises ordinary tap water, distilled water and the aqueous electrolyte liquid that disposes voluntarily, and the salt in Pei Zhi the aqueous electrolyte liquid is nitrate, carbonate and the hydrochloride of first main group and second main group voluntarily.
4, the device of preparing propylene by dehydrogenating propane under hydrogen plasma according to claim 1, it is characterized in that the material that described voltage of alternating current lead-in wire (6) and metal electric current are derived line is platinum, rhodium, palladium, gold, copper, tungsten, iron, nickel, titanium or its alloy or various stainless steel.
5, the device of preparing propylene by dehydrogenating propane under hydrogen plasma according to claim 1, it is characterized in that described oxide glass contains one or more in silicon oxide, boron oxide, germanium oxide, phosphorus oxide, aluminum oxide, arsenic oxide arsenoxide, Tungsten oxide 99.999, vanadium oxide, bismuth oxide, gallium oxide, titanium oxide, molybdenum oxide and the selenium oxide.
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| CN100460371C CN100460371C (en) | 2009-02-11 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109939688A (en) * | 2019-04-03 | 2019-06-28 | 华东理工大学 | Iron gallium base propane dehydrogenation catalyst and preparation method thereof |
| CN110092448A (en) * | 2019-05-06 | 2019-08-06 | 重庆工商大学 | A kind of concentric circles bipolar electrode discharge plasma O/W emulsion breaking device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900042A (en) * | 2006-07-18 | 2007-01-24 | 大连海事大学 | Device for preparing propionic aldehyde by directly oxidizing propylene with molecular oxygen |
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- 2007-04-01 CN CNB200710010843XA patent/CN100460371C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109939688A (en) * | 2019-04-03 | 2019-06-28 | 华东理工大学 | Iron gallium base propane dehydrogenation catalyst and preparation method thereof |
| CN110092448A (en) * | 2019-05-06 | 2019-08-06 | 重庆工商大学 | A kind of concentric circles bipolar electrode discharge plasma O/W emulsion breaking device |
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| CN100460371C (en) | 2009-02-11 |
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