CN102358617A - Methanol hydrogen production apparatus, and method for preparing hydrogen by using the same - Google Patents
Methanol hydrogen production apparatus, and method for preparing hydrogen by using the same Download PDFInfo
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Abstract
The present invention provides a methanol hydrogen production apparatus, and a method for preparing hydrogen by using the methanol hydrogen production apparatus. The method comprises the following steps that: 1) an aqueous solution of methanol is added to a reactor, wherein a volume concentration of the aqueous solution of the methanol is 5-40%; 2) argon gas is introduced to the reactor; 3) a probe of a variable amplitude rod type ultrasonic generator is inserted in the aqueous solution of the methanol in the reactor at a temperature of the aqueous solution of the methanol of 5-20 DEG C to carry out the reaction to obtain the hydrogen, wherein the frequency of the variable amplitude rod type ultrasonic generator is 28-40 kHz, the amplitude is 20-40% of the maximum amplitude (the maximum amplitude is 25 micrometers). With the method of the present invention, the reaction temperature for the hydrogen production by the methanol is reduced to the room temperature from the traditional high temperature, the hydrogen production by the methanol at the room temperature or even at the low temperature is realized. Compared to the prior art, with the method of the present invention, the energy applying manner is direct (the probe is directly inserted into the aqueous solution of the methanol), the ambient temperature is controlled, the argon gas is introduced, the hydrogen production efficiency is substantially improved, and the maximum hydrogen production rate is increased by one or two magnitudes.
Description
[technical field]
The present invention relates to the hydrogen producing technology field, particularly a kind of hydrogen from methyl alcohol device and prepare the method for hydrogen.
[background technology]
Under the dual-pressure of energy scarcity, environmental pollution, the development utilization organic liquid waste is realized cleaning and is handled the new technology that combines with highly effective hydrogen yield and have important practical significance.
Methyl alcohol mainly contains four kinds as the method for hydrogen feedstock at present: pyrolytic decomposition hydrogen manufacturing, partial oxidation hydrogen-preparation, vapour reforming hydrogen producing and partially oxidation and steam reformation associating hydrogen manufacturing, the common feature of these traditional hydrogen production process (except water electrolysis hydrogen production) are all need under hot environment, carry out.
And the hydrogen manufacturing of UW decomposition methanol aqueous solution is a kind of normal temperature hydrogen production process, contains the waste water of methyl alcohol in the industry of both can having degraded, and can obtain hydrogen again.It is a kind of method that is rich in novelty that UW is used for methanol aqueous solution hydrogen manufacturing; This method is compared with other hydrogen production process; Have reaction unit simple in structure, need not external heat power, the required envrionment temperature of reaction is low, unique advantages such as the processing working cost is low, system simple, clean environment firendly.
Although foreign scholar B ü ttner [3]; Rassokhin people such as [4-5] is doing corresponding research aspect high frequency (greater than 200kHz) the ultrasonic degradation methanol aqueous solution; Their work has important directive significance to this hydrogen production process; But their purpose is not hydrogen manufacturing, and research hydrogen is for no other reason than that the output of hydrogen is compared higher with other gases and easily by gas chromatographic detection.In addition, the research of hydrogen manufacturing is still insufficient under the low-frequency ultrasonic waves condition; And the research of influence factor also has very big room for improvement.Domestic scholars Bai Bofeng people such as [1] has proposed UW and has decomposed the methanol aqueous solution hydrogen production process in 2006, because experimental installation at that time is the groove type ultrasonic wave producer, the loss of energy transmission process is bigger, and hydrogen-producing speed is lower.
Reference:
[1] Bai Bofeng, Zuo Zhitao. hydrogen from methyl alcohol method: China, 200610104410.6 [P] .2007.01.24.
[2]R.Sasikala，O.D.Jayakumar.Enhanced?hydrogen?generation?by?particles?during?sonochemical?decomposition?of?water[J].Ultrasonics?Sonochemistry，2007，14：153-156.
[3]J.Büttner，M.Gutierrez，A.Henglein.Sonolysis?of?Water-Methanol?Mixtures[J].J?Phys?Chem，1991，95：1528-1530.
[4]D.N.Rassokhin，G.V.Kovalev，L.T.Bugaenko.Temperature?Effect?on?the?Sonolysis?of?Methanol/water?Mixtures[J].J?Am?Chem?SOC，1995，117：344-347.
[5]D.N.Rassokhin，Lenart.Bugaenko，G.V.Kovalev.The?sonolysis?of?methanol?in?diluted?aqueous?solutions：product?yields[J].Radiat?Phys.Chem，1995，45(2)：251-255.
[6]Y.G.Adewuyi.Sonochemistry：Environmental?Science?and?Engineering?Applications[J].Ind.Eng.Chem.Res，2001，40(22)：4681-4715.
[7]E.A.Neppiras.Acoustic?Cavitation[J].Phys.Rep，1980，61(3)：159-251.
[summary of the invention]
The object of the present invention is to provide the hydrogen from methyl alcohol device under a kind of normal temperature environment and prepare the method for hydrogen.
To achieve these goals, a kind of hydrogen from methyl alcohol device of the present invention adopts following technical scheme:
A kind of hydrogen from methyl alcohol device comprises iron stand, luffing rod-type ultrasonic generator, constant temperature water bath and reactor drum; Constant temperature water bath is arranged on the base of iron stand, and reactor drum is positioned in the water bath with thermostatic control; Luffing rod-type ultrasonic generator is fixed on the iron stand, and luffing rod-type ultrasonic generator comprises transverter, horn and the probe that connects successively; The top of reactor drum is provided with a through hole, and probe passes this through hole and stretches in the reactor drum, and probe seals with O type circle with the reactor drum joint; Reactor drum top is provided with the gas sampling mouth, and uses silicone rubber seal; One aeration tube passes reactor wall and stretches in the reactor drum.
Said reactor drum is the synthetic glass body of wall thickness 8mm.
Said constant temperature water bath comprises a water-bath inlet and a water-bath outlet, and the height of water-bath outlet is higher than the height of water-bath inlet.
To achieve these goals, a kind of hydrogen from methyl alcohol device of the present invention method of preparing hydrogen adopts following technical scheme:
A kind of hydrogen from methyl alcohol device prepares the method for hydrogen, may further comprise the steps:
1) in reactor drum, adding volumetric concentration is the methanol aqueous solution of 5%-40%;
2) take down the Zylox of gas sampling mouth, in the methanol aqueous solution of reactor drum, feed argon gas, drive away oxygen and the air of solution upper space in the methanol aqueous solution through aeration tube; Cut off argon gas then, clog the gas sampling mouth with Zylox;
3) the methanol aqueous solution temperature is under 5-20 ℃ the condition, starts luffing rod-type ultrasonic generator and promptly obtains hydrogen; The frequency of luffing rod-type ultrasonic generator is that 28-40kHz, amplitude are the 20%-40% of peak swing; Peak swing is 25 microns; The probe of luffing rod-type ultrasonic generator inserts in the methanol aqueous solution.
Overall reactor is long-pending to be 90ml, and the amount of methanol aqueous solution is 60ml, and the degree of depth that probe stretches into the methanol aqueous solution of reactor drum is 8-10mm.
Step 2) before experiment, in reaction liquid, feeds 2 hours argon gas, flow velocity 60mlmin in advance in through aeration tube
-1
The volumetric concentration of methanol aqueous solution is 20% in the step 1); The methanol aqueous solution temperature is 10 ℃ in the step 3), and the amplitude of luffing rod-type ultrasonic generator is a peak swing 40%.
Compared with prior art, the present invention has following beneficial effect: hydrogen production process of the present invention makes the temperature of reaction environment of hydrogen from methyl alcohol be reduced to normal temperature environment by the conventional high-temperature environment, has realized the hydrogen manufacturing of methyl alcohol under normal temperature environment even low temperature environment; The present invention compared with prior art because energy applies mode more directly (probe directly inserts in the methanol aqueous solution), the temperature that controls environment simultaneously with expose to the sun into argon gas, so hydrogen generation efficiency has obtained large increase; Maximum hydrogen-producing speed has improved one even two one magnitude.
[description of drawings]
Fig. 1 is an Experimental equipment of the present invention;
Fig. 2 methanol aqueous solution concentration is to the synoptic diagram that influences of hydrogen-producing speed; Frequency 40kHz, amplitude are 20% of peak swing;
Fig. 3 A solution temperature is to the synoptic diagram that influences of methyl alcohol hydrogen-producing speed, and frequency 40kHz, amplitude are 20% of peak swing, methanol concentration 10vol%;
Fig. 3 B solution temperature is to the synoptic diagram that influences of methyl alcohol hydrogen-producing speed, and frequency 28kHz, amplitude are 40% of peak swing, methanol concentration 10vol%;
Fig. 4 amplitude is to the synoptic diagram that influences of methyl alcohol hydrogen-producing speed; Frequency 40kHz, methanol concentration 10vol%, 20 ℃ of temperature;
Fig. 5 the influence synoptic diagram of argon gas that expose to the sun to hydrogen output.
[embodiment]
Below in conjunction with accompanying drawing the present invention is done and to describe in further detail.
See also shown in Figure 1ly, the present invention adopts experimental installation shown in Figure 1 to carry out hydrogen from methyl alcohol; This experimental installation comprises iron stand 1, luffing rod-type ultrasonic generator 2, reactor drum 3 and constant temperature water bath 4.The material of reactor drum 3 is the thick synthetic glass of 8mm.These reactor drum 3 TVs are 90ml, and the amount of reaction soln is 60ml.The base of iron stand 1 is provided with a constant temperature water bath 4, and constant temperature water bath 4 comprises water-bath inlet 41 and water-bath outlet 42, and reactor drum 3 is positioned in the constant temperature water bath 4; Luffing rod-type ultrasonic generator 2 is fixed on the iron stand 1, and luffing rod-type ultrasonic generator 2 comprises transverter 21, the horn 22 that connects successively and pops one's head in 23; Transverter 21 is provided with heat emission fan 24 and louvre 25; The top of reactor drum 3 is provided with a through hole, and probe 23 passes in the reaction soln that this through hole stretches into reactor drum 3, and probe 23 seals with O type circle with reactor drum 3 joints, to prevent gas leakage.Reactor drum 3 tops are provided with gas sampling mouth 31, and use silicone rubber seal; One aeration tube 5 passes reactor wall and stretches in the reaction soln, in reaction liquid, feeds 2 hours argon gas, flow velocity 60mlmin in advance through aeration tube before the experiment
-1, so that the oxygen in the expeling reaction soln and the air of solution upper space.Temperature of reaction is by thermostatic bath control (temperature difference ± 0.1 ℃), and before experiment half a hour open, make the temperature of reaction soln and bath temperature reach balance.Gas sampling adopts microsyringe (500 μ l) to accomplish (each 100 μ l).In order to reduce error, each operating condition of test is got gas 4-6 time, goes three wherein more approaching data to make even all then.Gaseous product is detected by the SP-3420A gas chromatograph.
Luffing rod-type ultrasonic generator of the present invention makes the direct and reaction soln effect of ultrasonic probe, and for control reaction temperature, outside reaction vessel, has made a constant temperature water bath, so that the constant temperature circulation fluid inside flows.The peak swing of luffing rod-type ultrasonic generator is 25 μ m among the present invention, and the amplitude percentage ratio of mentioning among the following embodiment is the percentage ratio of peak swing.
See also shown in Figure 2ly, at the frequency 40kHz of luffing rod-type ultrasonic generator, amplitude is under the condition of peak swing 20% (peak swing is 25 μ m), adopts the methanol aqueous solution of different concns to prepare hydrogen; Concentration of methanol solution presents increase back downward trend earlier to the influence of hydrogen-producing speed, and mainly receive the influence of following two aspects: (1): methyl alcohol is reactant, and the amount that increases reactant under the certain condition helps to improve the output of resultant; (2) methanol concentration raises, and cavitation bubble gas phase zone methanol steam increases, because the specific heat capacity of methyl alcohol is bigger, the temperature when making the cavitation bubble collapse descends, and the temperature of bubble when bursting filling directly determined the power of chemical reaction, so product output descends.
See also shown in Fig. 3 A, at the frequency 40kHz of luffing rod-type ultrasonic generator, amplitude is under the condition of 20% (peak swing is 25 μ m) of peak swing, and adopting concentration is that the methanol aqueous solution of 10vol% prepares hydrogen under differing temps; Solution temperature is to producing the great influence that has of hydrogen rate, produces that two peaks appear in the hydrogen rate and 5 ℃ of minimum value locating.Under the condition of ignoring 5 ℃ of singularity of locating, produce the hydrogen rate and the back downward trend that rises earlier why occurs, mainly receive the influence of following two aspects: (1) temperature raises, and vp Pv rises, and surface tension σ descends.Can know that by formula (3) cavitation threshold descends, therefore increase the formation that temperature helps ultrasonic cavitation.Temperature raises in addition, and the molecular thermalmotion aggravation helps hyperacoustic propagation.Can know by formula (1) and (2) that (2) vp Pv improves, T
MaxAnd P
MaxDescend; Temperature T
0Increase T
MaxRaise.But P
vIncrement be greater than T
0.Take all factors into consideration the influence of two aspects,, produce the hydrogen rate and the back downward trend occurs increasing earlier therefore along with the rising of temperature.
And in Fig. 3 A 5 ℃ locate to produce the hydrogen rate and occur descending significantly, mainly be that the variable density with water has relation.Because the density of water is located maximum at 4 ℃, there is the interaction of hydrogen bond under this temperature between the water molecules, therefore want saboteur's structure to need bigger energy.Therefore 5 ℃ of product hydrogen rates of locating certain decline is arranged.
See also shown in Fig. 3 B, at the frequency 28kHz of luffing rod-type ultrasonic generator, amplitude is under the condition of 40% (peak swing is 25 μ m) of peak swing, and adopting concentration is that the methanol aqueous solution of 10vol% prepares hydrogen under differing temps; Among Fig. 3 B, 5 ℃ are located to produce the hydrogen rate but is the highest, and this is because the amplitude of ultrasonic generator is 40% of a peak swing under the 28kHz; Be that UW output energy has increased; When these energy are broken the hydrogen bond between the water molecules, can produce more cavitation core through the continuity of " tearing " liquid, so cavitation bubble increases; Chemical effect of ultrasound strengthens, so hydrogen-producing speed obviously increases.
See also shown in Figure 4ly, be the influence figure of amplitude hydrogen-producing speed; Can know square being directly proportional of the sound intensity and amplitude by formula (4).Hyperacoustic amplitude directly influences time, the temperature and pressure of bubble collapse.Improve the intensity that amplitude helps to improve the cavitation bubble collapse, strengthen chemical effect of ultrasound.And, increase the increase that amplitude also means ultrasonic power, under the situation, improve the increase that power helps speed of reaction mostly.Therefore, when frequency one timing, within the specific limits, increasing amplitude is favourable to chemical effect of ultrasound.But be not that amplitude is high more good more.
As can beappreciated from fig. 4, amplitude is during less than 30% (peak swing is 25 μ m) of peak swing, and along with the rising of amplitude, hydrogen-producing speed obviously increases; And amplitude is when being 40% (peak swing is 25 μ m) of peak swing, and hydrogen-producing speed slightly descends.Reason is following: on the one hand, increase the speed that amplitude means increases the equilibrium theory of tide particle, promptly increase kinetic energy, therefore help UW and " tear " liquid generation cavatition.Therefore amplitude increases to the process of the amplitude 30% of maximum from 10% of peak swing, and producing the hydrogen rate increases obviously.On the other hand, it is big that amplitude means that greatly particle departs from the distance of equilibrium theory of tide, makes energy be delivered in the surrounding liquid with heat conducting mode, thereby cause power loss.Therefore amplitude is that 40% place's hydrogen-producing speed of peak swing all has decline.If when amplitude (sound intensity) surpasses a certain ultimate value, the cavitation saturated phenomenon can occur, speed of reaction can reduce along with the increase of amplitude (sound intensity).Because when amplitude is increased to certain value, in the breathing space of sound wave, it is excessive that bubble size can become, and in the compression zone, bubble does not have the time enough implosion, thereby limited cavitation processes.In addition, can produce the bubble screen at the vibration surface place when amplitude of superelevation is too high, cause sound wave to be decayed rapidly, make ultransonic energy be not fully utilized.
See also shown in Figure 5ly, be the influence figure of argon gas that expose to the sun hydrogen output; Can know by Fig. 5, feed the output that argon gas can improve hydrogen.Its reason of explained later; Feeding argon gas is equivalent in liquid medium, increase a lot " weak force " on the one hand.The formation that exists for cavitation bubble in these " weak forces " provides the place, thereby has increased the quantity of cavitation bubble; Argon gas has bigger specific heat ratio (γ) and less heat-conduction coefficient on the other hand, and the characteristics of these two parameters are closely related to the intensity that improves the ultrasonic cavitation effect.At first, top temperature and peak pressure when specific heat ratio (γ) influences the cavitation bubble collapse, the γ value is big more, T
MaxAnd P
MaxValue big more.Secondly; Contain argon gas in the cavitation bubble; And the heat-conduction coefficient of argon gas is less, therefore is delivered to the less calories (although the compression process of ultrasonic cavitation is approximately adiabatic process, still having the transmission of heat) of liquid phase region by the bubble gas phase zone; Local temperature that causes during the bubble collapse so and pressure are just big, therefore help improving the intensity of ultrasonic cavitation.To sum up tell, in solution, feed argon gas, not only can increase the quantity of cavitation bubble, and can increase the intensity of ultrasonic cavitation effect.
In addition, say from the angle of chemical reaction that the output of hydrogen is very low under the aerobic environment, the output of carbonic acid gas is but very high; And behind the feeding argon gas, reaction system is under the inert environments, and this moment, combustion reactions can not take place methanol molecules, can only participate in pyrolysis or free radical reaction.Therefore, ar gas environment can improve the output of hydrogen down.
Above result shows: ultrasonic cavitation is the prerequisite of decomposing alcohol solution hydrogen manufacturing, and the concentration of alcohol solution, solution temperature and ultrasonic amplitude have very big influence to hydrogen-producing speed.Reaction mechanism of the present invention mainly is the pyrolysis and the steam reforming reaction of the molecule in the cavitation bubble.
In order to obtain the optimum process condition that the ultrasonic degradation methanol aqueous solution produces hydrogen, need carry out orthogonal experiment research to it.The operating parameters that influences the hydrogen manufacturing of ultrasonic degradation methanol aqueous solution comprises many factors such as strength of solution, temperature, pH, ultrasonic frequency and power; Can know through above experiment of single factor data; Strength of solution, envrionment temperature, three factors of ultrasonic amplitude are relatively responsive to the influence of hydrogen-producing speed; Therefore; In the approximate range that the experiment of single factor result obtains, further select strength of solution, envrionment temperature, three principal elements of ultrasonic amplitude for investigating target, each factor is got 4 levels and is carried out orthogonal experiment (table 1).
Table 2 is the experimental result of orthogonal experiment; Can be known that by table 2 extreme difference of factor A (concentration) is 35.75, the extreme difference of factor B (temperature) is 40.42, and the extreme difference of factor C (amplitude) is 28.22, and temperature that hence one can see that has the greatest impact to hydrogen output, and concentration is taken second place, and what influence was minimum is amplitude.Optimum reaction condition in the experiment parameter scope is A3B2C4, that is, strength of solution 20vol%, 10 ℃ of temperature, amplitude are 40% of peak swing.
Experiment results is seen table 3, obtains 119.4 μ molmin
-1L
-1Hydrogen-producing speed, these data are all higher than the hydrogen output of 16 operating modes of orthogonal experiment.
The factor of table 1 orthogonal experiment and level value thereof
The experimental result of table 2 orthogonal experiment
The checking of table 3 optimum combination A3B2C4
Used formula is following among the present invention:
Can derive the top temperature (T of bubble in collapse moment bubble by the Rayleigh-Plesset equation
Max) and peak pressure (P
Max) expression formula (1) and (2).As follows:
T
max＝T
0P
O(γ-1)/P
v (1)
P
max＝P
v[P
m(γ-1)/P
v]
γ/(γ-1)?(2)
T
0Envrionment temperature, P
vLiquid vapour is pressed, P
mTo the pressure of cavitation bubble, γ is a heat capacity at constant pressure and the ratio of heat capacity at constant volume to the transient cavitation bubble, is called coefficient of heat insulation at the moment liquid medium of caving in.
The expression formula of cavitation threshold is following:
P
cCavitation threshold, P
hHydrostatic pressure, P
vLiquid vapour is pressed, R
0Be the initial radium of cavitation bubble, the surface tension of σ express liquid, P
mPressure in the bubble collapse moment liquid medium.
The expression formula of the sound intensity:
ρ is a density of medium; C is the velocity of sound; A is an amplitude; ω is circular frequency (ω=2 π f).
Claims (7)
1. a hydrogen from methyl alcohol device is characterized in that, comprises iron stand, luffing rod-type ultrasonic generator, constant temperature water bath and reactor drum; Constant temperature water bath is arranged on the base of iron stand, and reactor drum is positioned in the constant temperature water bath; Luffing rod-type ultrasonic generator is fixed on the iron stand, and luffing rod-type ultrasonic generator comprises transverter, horn and the probe that connects successively; The top of reactor drum is provided with a through hole, and probe passes this through hole and stretches in the reactor drum, and probe seals with O type circle with the reactor drum joint; Reactor drum top is provided with the gas sampling mouth, and uses silicone rubber seal; One aeration tube passes reactor wall and stretches in the reactor drum.
2. hydrogen from methyl alcohol device as claimed in claim 1 is characterized in that, said reactor drum is the synthetic glass body of wall thickness 8mm.
3. hydrogen from methyl alcohol device as claimed in claim 1 is characterized in that, said constant temperature water bath comprises a water-bath inlet and a water-bath outlet, and the height of water-bath outlet is higher than the height of water-bath inlet.
4. hydrogen from methyl alcohol device as claimed in claim 1 prepares the method for hydrogen, it is characterized in that, may further comprise the steps:
1) in reactor drum, adding volumetric concentration is the methanol aqueous solution of 5%-40%;
2) in the methanol aqueous solution of reactor drum, feed argon gas through aeration tube, the oxygen in the expeling methanol aqueous solution and the air of solution upper space;
3) the methanol aqueous solution temperature is that the probe of luffing rod-type ultrasonic generator stretches into that reaction promptly obtains hydrogen in the methanol aqueous solution of reactor drum under 5-20 ℃ the condition; The frequency of luffing rod-type ultrasonic generator is that 28-40kHz, amplitude are the 20-40% of peak swing; Peak swing is 25 microns.
5. the method for preparing hydrogen as claimed in claim 4 is characterized in that, overall reactor is long-pending to be 90ml, and the amount of methanol aqueous solution is 60ml, and the degree of depth that probe stretches into the methanol aqueous solution of reactor drum is 8-10mm.
6. the method for preparing hydrogen as claimed in claim 4 is characterized in that step 2) in before experiment, in reaction liquid, feed 2 hours argon gas, flow velocity 60mlmin in advance through aeration tube
-1
7. the method for preparing hydrogen as claimed in claim 4 is characterized in that, the volumetric concentration of methanol aqueous solution is 20% in the step 1); The methanol aqueous solution temperature is 10 ℃ in the step 3), and the amplitude of luffing rod-type ultrasonic generator is 40% of a peak swing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108002347A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of ultrasonic wave added hydrogen production from methanol-steam reforming reactor |
| CN108380154A (en) * | 2018-02-09 | 2018-08-10 | 西北工业大学 | Add the ultrasound polymerization reaction unit and ultrasound polymerization reaction method of aerating system |
| CN109597446A (en) * | 2019-01-07 | 2019-04-09 | 中氢新能技术有限公司 | A kind of high temperature methanol hydrogen manufacturing temperature control constant temperature method |
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| US20050048331A1 (en) * | 2003-08-25 | 2005-03-03 | Stephens Robert D. | System for sono-catalytic production of hydrogen |
| CN1899954A (en) * | 2006-07-27 | 2007-01-24 | 西安交通大学 | Method for preparing hydrogen from methanol |
| CN101735941A (en) * | 2009-12-30 | 2010-06-16 | 重庆大学 | Continuous-flow and ultrasonic-wave light biological hydrogen producing reactor |
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| CN1134912A (en) * | 1996-01-18 | 1996-11-06 | 董银谈 | Cracking process for producing hydrogen and sepecial equipment for producing hydrogen |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108002347A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of ultrasonic wave added hydrogen production from methanol-steam reforming reactor |
| CN108002347B (en) * | 2016-10-28 | 2020-09-22 | 中国石油化工股份有限公司 | Methanol-steam reforming hydrogen production reactor with ultrasonic assistance |
| CN108380154A (en) * | 2018-02-09 | 2018-08-10 | 西北工业大学 | Add the ultrasound polymerization reaction unit and ultrasound polymerization reaction method of aerating system |
| CN109597446A (en) * | 2019-01-07 | 2019-04-09 | 中氢新能技术有限公司 | A kind of high temperature methanol hydrogen manufacturing temperature control constant temperature method |
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