CN106221838A - A kind of method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas - Google Patents
A kind of method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas Download PDFInfo
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Abstract
The invention discloses a kind of method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas.Including: the first step, pretreatment of raw material, under glove box argon gas atmosphere is protected, alkali metal hydride MH is placed in ball grinder and carries out ball-milling treatment, can be prepared by the lightweight high energy hydride that specific surface area is bigger；Second step; static pressure reacts; under argon gas atmosphere is protected; the high energy hydride first step obtained in glove box is put into quiet formula and is added in heat pipe, takes out, be connected with the vacuum-pumping pipeline system equipped with high-precision pressure sensor after closing heating tube valve from glove box; extract argon out; being filled with high-purity carbon dioxide, reaction is carried out at 25～550 DEG C, just creates the mixed gas of methane and hydrogen in adding heat pipe along with the carrying out of reaction；3rd step, product is quantitative, and mixed gas is by the productivity of methane in gas chromatogram and infrared spectrum joint-detection mixed gas.Described method is that the high density storage of methane provides new method while improving prior art deficiency.
Description
Technical field
The present invention relates to a kind of method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas, be specifically related to
A kind of method making alkali metal hydride generate hydrogen and methane mixed gas with carbon dioxide reaction by heating, belongs to clear
Clean energy technology field.
Technical background
Methane (CH4) it is the main component of natural gas, it is a kind of multiduty high-quality clean energy resource, is widely used as sending out
Electricity, traffic, domestic fuel.Meanwhile, methane or the Organic Chemicals of high-quality, be widely used in chemical fertilizer, methanol,
In the production of polyformaldehyde, methylamine etc..Owing to petroleum resources are increasingly exhausted and the appearance of environmental crisis, the need of whole world natural gas
Ask increasing, will be increased to 4.9 tcms to the year two thousand twenty.Although the proved reserves of natural gas are constantly increasing, mesh
The front gap between yield and demand still has the trend widened, the whole nation often to have the situation of large area supply anxiety.Will
Cleaning fuel methane is applied to automobile and has caused the great attention of people.But, compared with gasoline, methane is as combustion
The major defect of material is that volume energy density is low, only the 1/3 of gasoline.The wide variety of main technology of methanol automobile hinders,
Just it is the absence of a kind of fuel memory technology safe and convenient, highdensity.The greenhouse effect brought for carbon dioxide and first
The shortage of alkane and depositing is gone wrong, and researchers are on the one hand at the CO actively seeking economical and efficient2The method of methanation, another
Aspect is striving to find methane safe and convenient, highdensity storage method.
CO2Methanation reaction be by french chemist Paul Sabatier (Rev.Inorg.Chem.1985 volume 7,
Page 315 339) (carbon dioxide reduction technique) that propose, therefore, this reaction is called again Sabatier reaction, and whole world CO2
Cyclic policy solves the CO in the whole world2Emission problem, includes three links, the first step altogether, produces hydrogen with electrolysis；The
Two steps, H2And CO2Reaction generates CH4With other Hydrocarbon a small amount of；3rd step, the CH of generation4As energy resource consumption
Generate again CO2, so move in circles.Core link therein utilizes solar electrical energy generation and CO exactly2Catalytic hydrogenation first
The reaction of alkanisation.Course of reaction is will to mix CO by a certain percentage2And H2Gas passes through the reactor equipped with catalyst,
CO under the conditions of certain temperature and pressure2And H2React generation water and methane.Chemical equation is as follows.
CO2+4H2=CH4+2H2O
This process has much practicality at present, and in the long run, is exploitation with carbon dioxide for Material synthesis natural gas
One of approach of new forms of energy, reclaims carbon dioxide preparation methane from air and then has strategic importance.In recent years, Ren Menfa
Existing, compared with carbon monoxide, the methanation reaction of carbon dioxide has negative free energy change in sizable temperature range
Change, △rG absolute value is relatively big, in terms of thermodynamics, carries out this process without a doubt, and this reaction has relatively low
Activation energy, relatively low reaction temperature and higher selectivity.Therefore, this process has the biggest temptation to chemist
Power.At present, the emphasis point of this respect work essentially consists in and discloses the mechanism of this process and select high performance catalyst to make
Reaction is carried out in acceptable velocity interval.
But this process is heat release, △ H varies with temperature not quite.Too much heat release may make catalyst overheating inactivate also
Temperature is promoted to rise to react the degree being difficult to.In addition, the generation of methane is also relevant with the ratio of unstripped gas.Higher
H2/CO2Than being conducive to improving the productivity of methane.Pressure is little on reaction impact, but has bigger when more than 425 DEG C
Impact.Higher pressure can make reaction at relatively low H2/CO2Carry out under Bi and the carbon distribution of catalyst surface does not occur, but also
May increase because of heat release, too much heat release can cause noble metal catalyst active component to produce sintering and area carbon phenomenon,
Thus cause the poisoning of catalyst.Visible, when carrying out methanation reaction under this system, general control condition is relatively low temperature
Degree, higher H2/CO2Ratio, good radiating condition and suitable pressure limit.Although the source of carbon dioxide is the widest
General storing mode is the most very convenient, but relates to hazardous gas H for this reaction2, and the storage of hydrogen the most more difficulty.
For these reasons, hydrogen reducing CO is utilized so far2Methanation is not the most widely used.Therefore,
Try to explore new thought and technology path to realize CO2Methanation become the focus of current international research.Such as,
Sehoon Park etc. (J.Am.Chem.Soc.2012 volume 134, page 11,404 11407) are at transistion metal compound
Under catalysis, silane is utilized to achieve CO2Methanation；(the J.Chem.Technol.Biot.2012 the 87th such as Jun Chul Lee
Volume, page 844 847) take bioanalysis by CO in fixed bed reactors2It is converted into (the J.Mater. such as methane, H.Park
Chem.2012 volume 22, page 5,304 5307) and Tu, Wenguang etc. (Adv.Funct.Mater.2013 volume 23,
Page 1743 1749) find poroid zinc gallium oxide, TiO2Hydrocarbons is at reduction CO2Prepare methane aspect to show very
High photocatalytic activity.But above-mentioned reaction method has the disadvantage in that
1, utilize silane to pass through transistion metal compound catalysis reduction carbon dioxide to catalyst used in the process of methane more
Expensive (iridium catalyst), and intermediate product generates more and reaction mechanism is the most complex.
2, take bioanalysis by CO2During being converted into methane, the speed of methanation is greatly by hydrogen and titanium dioxide
The constraint of carbon ratio example, needs to insert hydrogen nutrition and produces alkane microorganism in the anaerobism fixed bed reactors needed for methanation, but
Its source is the widest.
3, use photocatalytic method achieve CO2In methanation, the transfer of relatively low carbon dioxide material amount limits dioxy
Changing the rate of reduction of carbon, its reaction rate needs further to improve, and the poroid oxide catalyst preparation process of correspondence
The most relatively complicated.
4, additionally, by after carbon dioxide reduction to methane, still suffer from huge choosing for generating the storage problem of methane
War, at present, methane storage, the technology of traffic density mainly have liquefied methane and compressed methane.But high cost, exist latent
Potential safety hazard and also low-temperature (low temperature) vessel maintenance difficulty is big, there is also the impact of the factors such as evaporation loss.
Summary of the invention
It is an object of the invention to provide a kind of side utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas
Method.Described method can allow under conditions of need not catalyst carbon dioxide is spontaneous under the effect of strong reductant is reduced to first
Alkane.
Realization the technical scheme is that
A kind of method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas, its feature is including following step
Rapid:
The first step, pretreatment of raw material, (H under glove box argon gas atmosphere is protected2O and O2Concentration is less than 1ppm), by alkali
Metal hydride MH is placed in ball grinder and carries out ball-milling treatment, can be prepared by the lightweight high energy hydrogenation that specific surface area is bigger
Thing；
Supplementary notes, under dynamic ball milling condition, can produce the strongest frictional force and touch between ball-milling reaction container and ball milling
Hit power, metal hydride alkaline composition granule can be made to diminish increase reaction contact area.
Second step, static pressure reacts, (H under argon gas atmosphere is protected2O and O2Concentration is less than 1ppm), will in glove box
The high energy hydride that the first step obtains is put into quiet formula and is added in heat pipe, takes out, and join after closing heating tube valve from glove box
The vacuum-pumping pipeline system having high-precision pressure sensor is connected, and extracts argon out, is filled with high-purity carbon dioxide, reaction
Carry out at 25～550 DEG C, in adding heat pipe along with the carrying out of reaction, just create the mixed gas of methane and hydrogen, and along with alkali
The difference of temperature when the difference of metal hydride, reaction, the pressure being filled with carbon dioxide are different, the difference in response time,
Productivity and methane volume fraction in mixed gas that after reaction, methane is final also can change；
3rd step, product is quantitative, and mixed gas is by methane in gas chromatogram and infrared spectrum joint-detection mixed gas
Productivity.
Further, in the first step, alkali metal hydride MH selects LiH or NaH.
In the first step, in ball grinder, ball matter is than for 90:1, and rotating speed is 450 revs/min.
In second step, reaction is carried out at 200～550 DEG C, reacts 1～72h.
In second step, reaction is carried out at 450 DEG C, reacts 48h.
In 3rd step, methane gas calculation of yield method isWherein,For the productivity of methane,For generating the amount of the material of methane,Amount for the material of initial carbon dioxide.MethaneCan be in order to
Obtain by the quantitative test method (standard curve method in external standard method) of gas chromatogram.
The alkali metal oxide M generated in course of reaction2O can be reverted back as alkali again by hydrogenation, electrochemical method
Metal hydride, thus realize recycling of alkali metal hydride.
The reaction mechanism that the present invention relates to is as follows:
(J.Appl.Phys.2009 volume 105, page 023527) alkali metal hydride and NH are pointed out in forefathers' research3Reaction
This kind of reversible hydrogen storage material can release hydrogen the most automatically, is the promising hydrogen storage material of a kind of tool.It is correlated with and puts
Hydrogen reaction is as follows:
MH+NH3→MNH2+H2(M=Li, Na, K)
Research shows that the MH of high energy is except preparing hydrogen with ammonia reaction, moreover it is possible to be used as reducing agent in a mild condition,
Make cinnamic aldehyde height selectivity and high conversion is reduced into cinnamyl alcohol, for containing the molecule of C=C and C=O key simultaneously
(Acta Phys.Chim.Sin.2002 volume 18,55-58 page) selects the meaning being hydrogenated with the most great.In view of CO2
It is weak electronq donor, strong electron acceptor, it is difficult to aoxidize and be prone to reduction, so carbon dioxide activation is commonly used
One of method is exactly reduction activation, and protium is in the period 1, and outermost layer is an electronics, therewith character identical first
In the alkali metal hydride that main group other elements such as Li, Na and protium are formed, protium shows-1 valency, has hydrogen
The common ground of gas, i.e. reproducibility are very strong, so design utilizes alkali metal hydride and CO2Reaction would be even more beneficial to titanium dioxide
The reaction of carbon methanation.
All can carry out according to following reaction with carbon dioxide reaction for alkali metal hydride.
4MH+CO2→2M2O+C+2H2→2M2O+CH4(M=Li, Na) (1)
4MH+3CO2→2M2CO3+C+2H2→2M2CO3+CH4(M=Li, Na) (2)
Research find alkali metal hydride (LiH, NaH) carbon dioxide system not only have negative gibbs free energy change and
Suitably enthalpy change (△ H=210～964KJ/mol), and methanation reaction is exothermic reaction, and these features determine
Alkali metal hydride-carbon dioxide system promises to be high-energy-density and the Gao Rong of the most spontaneous methanation
Amount hydrogen storage material, early-stage Study proves that alkali metal hydride carbon dioxide system is that energy density in a mild condition is
8805.2KJ/L, the energy density of 24.5Mpa methane at room temperature of equal value.This shows alkali metal hydride and CO2Shape
Formula can store the most highdensity methane, and the high density storage for methane provides new method.
Compared with prior art, its remarkable advantage is the present invention:
1, compared with other carbon dioxide methanation systems, MH CO2System has following features；
(1) this system can realize carbon dioxide fixation and be allowed to be converted into useful green energy resource；
(2) there is high volume energy density；With the density of lithium hydride as 820g/L, the density of liquid CO 2 is 706
G/L calculates, 1L LiH CO2The methane amount of storage of system (carrying out according to 4:1) theoretical maximum is that 9.89mol (is equivalent to mark condition
Lower 221.5L), its energy density is 8805.2KJ/L, the energy density of 24.5Mpa methane at room temperature of equal value.This shows
This system is reacted with the form of alkali metal hydride and carbon dioxide can store the most highdensity methane of preparation, for methane
High density storage provide new method；
(3) safety store, used and convenience；Alkali metal hydride is solid powdery material, its storage, fortune
Defeated fool proof, convenient；Carbon dioxide be nontoxic, hold liquescent gas.It is in pressed powder to alkali metal hydride
It is blown into CO2Can conveniently, safely obtain cleaning fuel gas, it is to avoid the dangerous when storage of methane, transport is asked
Topic；
(4) the solid alkali metal oxide M that this reaction generates2O can be reduced again by methods such as hydrogenation, electrochemistry
Returning is alkali metal hydride, thus realizes recycling of alkali metal hydride；
(5) for hydrogen carbon dioxide methanation system, its device preparing methane is complex, and used by urge
Agent is easily poisoned, and the methane prepared need nonetheless remain for being stored by the method for compression, increases its operating cost, and
For alkali metal hydride carbon dioxide system, its reaction preparation facilities is simple, by adding thermokalite gold in enclosed system
Belonging to just can by the methane release that wherein stores out with carbon dioxide gas-solid mixture, and methane just has been stored in seal
In system, but in view of the cost of LiH self compared to for hydrogen the most expensive about 10 times, so body series is applicable to
Regionality on a small scale, produces movably, is suitable for exploitation and the application of vehicular energy.
If alkali metal hydride carbon dioxide is prepared MH and CO in methane system by 22Enter according to certain molal quantity
Row proportioning, is increased to uniform temperature, adds in static pressure reaction and just can generate the flammable of a certain amount of methane and hydrogen in heat pipe and mix
Close gas, and the conversion ratio of mole when carbon dioxide methanation that methane is in mixed gas can be along with the change of reaction condition
And change.Its feature is as follows:
(1) in certain temperature range, the conversion ratio of the methane mole when carbon dioxide methanation in mixed gas
Can raise along with the rising of reaction temperature, wherein LiH CO2System the most just can produce methane,
NaH at a certain temperature with carbon dioxide reaction after methane Volume fraction in gaseous mixture can reach 90%；
(2) same alkali metal hydride under the same conditions can be along with the raising in response time, first with carbon dioxide reaction
The conversion ratio of the alkane mole when carbon dioxide methanation in mixed gas also can improve therewith, and wherein LiH is at a constant temperature
After the lower reaction 1h of degree, the conversion ratio of carbon dioxide methanation just can reach 22%, methane mol ratio in mixed gas
17.6% can be reached；
(3) different alkali metal hydrides under the same conditions with carbon dioxide reaction, methane rubbing in mixed gas
You when carbon dioxide methanation conversion ratio also can difference, after wherein LiH reacts 48h at a certain temperature two
The conversion ratio of carbonoxide methanation can reach 80%.
3, the methane that alkali metal hydride and carbon dioxide system obtain at a certain temperature is very big with the mixed gas of hydrogen
The shortcoming overcoming methane self:
(1) H/C atomic ratio in system is improved owing to being mixed with hydrogen in methane, so can reduce this gaseous mixture
The discharge of GHG carbon dioxide after body burning；
(2) in methane, introduce hydrogen and can improve speed and the stability of flame combustion, when reducing combustion continuation the most at last
Between and improve the thermal efficiency；
(3) in methane, introduce hydrogen can reduce the cancellation interval of methyl hydride combustion, make electromotor just input less energy
Can start easily.
Accompanying drawing explanation
Fig. 1 is MH CO of the present invention2System prepares the pretreatment ball mill device figure of imflammable gas；
Fig. 2 is MH CO of the present invention2System prepares the static pressure reaction unit figure of imflammable gas；
Fig. 3 is alkali metal hydride MH (LiH, NaH) of the present invention and CO2(0.25Mpa) at 450 DEG C, 48h is reacted
The gas chromatogram of rear generation gas；
Fig. 4 is alkali metal hydride MH (LiH, NaH) of the present invention and CO2(0.25Mpa) 200 DEG C, 350 DEG C,
450 DEG C, generate the gas chromatogram of gas after 550 DEG C of heated at constant temperature 48h；
Fig. 5 is alkali metal hydride MH (LiH, NaH) of the present invention and CO2(0.25Mpa) under 450 DEG C of constant temperature respectively
Heating 1h, generates the chromatogram of gas after 24h, 48h, 72h；
Fig. 6 is alkali metal hydride MH (LiH, NaH) of the present invention and CO2(0.25Mpa) 450 DEG C of heated at constant temperature 48
The infrared figure of gas of gas is generated after h；
Fig. 7 is alkali metal hydride MH (LiH, NaH) of the present invention and CO2(0.25Mpa) 200 DEG C, 350 DEG C,
450 DEG C, generate methane molar fraction figure in mixed gas after 550 DEG C of heated at constant temperature 48h, built-in figure is alkali metal
Hydride MH (LiH, NaH) and CO2(0.25Mpa) 200 DEG C, 350 DEG C, 450 DEG C, 550 DEG C of heated at constant temperature
The productivity figure of carbon dioxide methanation after 48h；
Fig. 8 is alkali metal hydride MH (LiH, NaH) of the present invention and CO2(0.25Mpa) add respectively under 450 DEG C of constant temperature
Hot 1h, generates methane molar fraction figure in mixed gas after 24h, 48h, 72h, built-in figure is metal hydride alkaline
Thing MH (LiH, NaH) and CO2(0.25Mpa) under 450 DEG C of constant temperature, 1h, dioxy after 24h, 48h, 72h are heated respectively
Change the productivity figure of carbon methanation.
Detailed description of the invention
In order to be more fully understood that the present invention, illustrated the technology of the present invention below in conjunction with the accompanying drawings by specific embodiment
Scheme.
Embodiment 1
Under glove box argon gas atmosphere is protected, the alkali metal hydride MH (LiH, NaH) of 0.3g is placed in ball grinder (interior
Portion's volume about 70cm3), put into 30 steel balls (diameter 6mm).Then in equipped with the ball grinder of sample, it is filled with 0.1MPaAr
Gas (> 99.999%), ball milling 2h.Ball mill device is planetary ball mill (QM-3SP4), as it is shown in figure 1, ball milling steel ball and
The mass ratio of powder about 90:1, under argon gas atmosphere is protected, at ball matter ratio for 90:1 and condition that rotating speed is 450 revs/min
Lower ball milling 48h, can be prepared by the lightweight high energy hydride that specific surface area is bigger.
Under argon gas atmosphere is protected, in glove box, the alkali metal hydride after ball milling is put into and add in heat pipe, such as Fig. 2 institute
Show, close and take out glove box after adding the reset valve that heat pipe is subsidiary, be filled with high-purity carbon dioxide after being extracted out by argon therein and (divide
Wei 0.25Mpa) so that the molar ratio of alkali metal hydride/carbon dioxide is 4:1, static pressure reaction is added heat pipe as
200 DEG C, 350 DEG C, 450 DEG C, constant temperature 48h in the thermostatic oven of 550 DEG C, then reacted gas is imported
GC detection is carried out so that qualitative and quantitative, wherein with pressure transducer and the vacuum line system that is connected with chromatograph
MH–CO2(NaH–CO2、NaH–CO2) system generates the gas chromatogram of gas such as figure after reacting 48h at 450 DEG C
Shown in 3.
Fig. 4 (a, is b) alkali metal hydride MH (LiH, NaH) with carbon dioxide (0.25Mpa) at 200 DEG C, 350 DEG C,
450 DEG C, generating the chromatogram of gas after 550 DEG C of heated at constant temperature 48h, result shows the alkali gold that static pressure reaction adds in heat pipe
Belong to hydride/carbon dioxide as 200 DEG C, 350 DEG C, 450 DEG C, after 550 DEG C of heated at constant temperature 48h, for LiH CO2
System starts to react from 200 DEG C just has more significantly methane to produce, and NaH CO2Just there is methane raw at about 350 DEG C
Becoming, it should be noted that after NaH reacts at 450 DEG C, methane chromatographic peak area ratio in gaseous mixture is maximum, this
Illustrate that the methane produced shared content in mixed gas is the most most.And for LiH, NaH CO2Both systems enter one
Step is warming up to 550 DEG C, and the peak area of its methane ratio in mixed gas improves the most further, noticeable
It is that two individual system all exist hydrogen at ambient temperature, along with temperature is warming up to 450 DEG C from 200 DEG C, the peak area of hydrogen
Ratio constantly declines, and the peak area of methane is all further up, and this shows alkali metal hydride MH and carbon dioxide
In 200 450 DEG C, the conversion ratio of methane can raise along with the rising of temperature.
Fig. 6 is alkali metal hydride MH (LiH, NaH) with carbon dioxide (0.25Mpa) after 450 DEG C of heated at constant temperature 48h
Generate the infrared spectrogram of gas.As can be seen from Fig., LiH CO2After system reaction, at 3013cm in mixed gas-1
And 1300cm-1There is a more significantly methane infrared absorption peak, and NaH CO2After system reaction, except having in mixed gas
The characteristic absorption peak of methane, have also appeared at 2883cm-1And 1476cm-1Ethane or the characteristic absorption peak of propane, but examine
Consider to the absworption peak of ethane or propane time peak position less relative to the absorption of the secondary main peak of methane, it is believed that by-product second
The growing amount of alkane or propane is less, above description of test LiH CO2System be applicable to react at different temperatures prepare pure
Methane and hydrogen mixed gas, and NaH CO2It is also possible to create the gas of ethane or propane in reaction system, this can
Relation can be had with its complex reaction mechanism.
Fig. 7 is alkali metal hydride MH (LiH, NaH) with carbon dioxide (0.25Mpa) at 200 DEG C, 350 DEG C,
450 DEG C, after 550 DEG C of heated at constant temperature 48h, methane is at the volume fraction figure generated in gas and carbon dioxide methanation productivity
Figure (interior figure).Result shows for LiH CO2For system, just have more significantly methane to produce from about 200 DEG C and
Productivity is 7.2%, and NaH CO2System just has methane to generate at about 350 DEG C, and productivity is relatively low, and only 17%, and
Now LiH CO2System has reached 54.2% at the productivity of 350 DEG C.Two individual system react after 48h them at 200 450 DEG C
The molal volume mark of methane and the productivity of methane all can rise along with the rising of temperature, but when temperature continues to be raised to
After 550 DEG C, the molal volume mark of its methane and the productivity of methane are all without continuing to rise.It should be noted that NaH exists
After reacting 48h at 450 DEG C, methane molal volume mark in gaseous mixture can reach 90%.This illustrates NaH CO2Body
Tie up to react at 450 DEG C and can prepare the purest methane after 48h, and now LiH CO2System is at the product of 450 DEG C
Rate has reached 80%, in sum alkali metal hydride/carbon dioxide reaction yield and molal volume under static pressure reaction condition
Mark reacts optimum at 450 DEG C, and the performance of alkali metal hydride/carbon dioxide methanation is greatly by reaction temperature
Impact.
Embodiment 2
Under glove box argon gas atmosphere is protected, alkali metal hydride alkali metal hydride MH (LiH, NaH) of 0.3g is put
Enter to add (internal volume about 70cm in heat pipe3), put into 30 steel balls (diameter 6mm).Then, equipped with the ball grinder of sample
Inside it is filled with 0.1Mpa Ar gas (> 99.999%), ball milling 2h, balls mill apparatus is planetary ball mill (QM-3SP4),
The mass ratio of ball milling steel ball and powder is about 90:1.Under argon gas atmosphere is protected, it is 450 turns in ball matter than for 90:1 and rotating speed
/ minute under conditions of ball milling 48h, can be prepared by lightweight high energy hydride.
Under argon gas atmosphere is protected, in glove box, high energy alkali metal hydride is put into quiet formula and add in heat pipe, close valve
After take out glove box, then argon therein is extracted out, is filled with high-purity carbon dioxide (respectively 0.25Mpa) so that alkali gold
Belong to hydride carbon dioxide molar ratio be 4:1, static pressure reaction add heat pipe as 450 DEG C at constant temperature heat 1 respectively
H, 24h, 48h, 72h, then import reacted gas with pressure transducer and the vacuum tube that is connected with chromatograph
Road system carries out GC detection.
(c d) is alkali metal hydride MH (LiH, NaH) and CO to Fig. 52(0.25Mpa) under 450 DEG C of constant temperature, heat 1 respectively
Generate the chromatogram of gas after h, 24h, 48h, 72h, result show static pressure react add in heat pipe alkali metal hydride/
Carbon dioxide is as just there being more significantly methane generation after 450 DEG C of heated at constant temperature 1h, it should be noted that except NaH exists
React outside the generation gas after 1h at 450 DEG C, NaH CO under other random times2Methane chromatographic peak in gaseous mixture
Area ratio is relative to LiH CO under equal conditions2System will be big, this explanation produce methane institute in mixed gas
Account for content the most most.For LiH, NaH CO2Both systems extend the time further to 24h, after 48h, and its methane
Chromatographic peak area increase also with the prolongation in response time, and for LiH, NaH CO2Both systems are further
The prolongation time, its methane chromatographic peak area in mixed gas improved the most further to after 72h.At any time
All there is hydrogen in lower two individual system, along with the response time to 72h, hydrogen and the peak area ratio of methane will no longer change,
The molal volume mark of this explanation methane does not rise along with the response time is further up after reaction 48h.To sum up say
The carrying out of response time beneficially alkali metal hydride/carbon dioxide methanation that bright prolongation is certain.
Fig. 8 be alkali metal hydride MH (Li, Na) at 450 DEG C with 0.25Mpa carbon dioxide heated at constant temperature different time
(1h, 24h, 48h, 72h) generates productivity (embedded figure) and the methane molar fraction in mixed gas of methane gas afterwards
Figure, result shows that alkali metal hydride carbon dioxide system adds in heat pipe after 450 DEG C of heated at constant temperature 1h in static pressure reaction
More significantly methane is just had to produce, LiH CO2System productivity of methanation in 1h just reaches 35%.During along with reaction
Between prolongation, the conversion ratio of carbon dioxide methanation and the methane ratio in mixed gas also gradually steps up, and merits attention
Be LiH at 450 DEG C with 0.25Mpa pressure carbon dioxide reaction different time after, methane product in mixed gas
Rate is compared to NaH CO2System is much higher, although NaH CO2In system the gas molar mark of methane after 1h all
Ratio LiH CO2The height of system, but its conversion ratio is relatively low, and this is likely due to its reaction mechanism and LiH CO2System is different
Cause, it should be noted that as NaH CO2System at 450 DEG C with 0.25Mpa pressure carbon dioxide reaction 48h
Rear methane molar fraction in mixed gas reaches maximum 90%, LiH CO described above2The carbon dioxide first of system
Alkanisation conversion ratio is best, and extends certain response time and be conducive to the generation of methane, NaH CO2System is at high temperature
The purest methane gas can be obtained after reaction a period of time.
Above-described detailed description of the invention, has been carried out the purpose of the present invention, technical scheme and beneficial effect the most in detail
Describe in detail bright, be it should be understood that the detailed description of the invention that the foregoing is only the present invention, be not used to limit this
Bright protection domain, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done,
Should be included within the scope of the present invention.
Claims (8)
1. one kind utilizes the method that alkali metal hydride reduction carbon dioxide prepares imflammable gas, it is characterised in that comprise the following steps:
The first step, pretreatment of raw material, under glove box argon gas atmosphere is protected, alkali metal hydride MH is placed in ball grinder and carries out ball-milling treatment, can be prepared by the lightweight high energy hydride that specific surface area is bigger；
Second step; static pressure reacts; under argon gas atmosphere is protected; the high energy hydride first step obtained in glove box is put into quiet formula and is added in heat pipe, takes out, be connected with the vacuum-pumping pipeline system equipped with high-precision pressure sensor after closing heating tube valve from glove box; extract argon out; being filled with high-purity carbon dioxide, reaction is carried out at 25～550 DEG C, just creates the mixed gas of methane and hydrogen in adding heat pipe along with the carrying out of reaction；
3rd step, product is quantitative, and mixed gas is by the productivity of methane in gas chromatogram and infrared spectrum joint-detection mixed gas.
The method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas the most according to claim 1, it is characterised in that in the first step, alkali metal hydride MH selects LiH or NaH.
The most according to claim 1 utilizing the alkali metal hydride reduction carbon dioxide method of preparing imflammable gas, it is characterised in that in the first step, in ball grinder, ball matter ratio is for 90:1, and rotating speed is 450 revs/min.
The method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas the most according to claim 1, it is characterised in that in second step, reaction is carried out at 200～550 DEG C, reacts 1～72h.
The method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas the most according to claim 4, it is characterised in that in second step, reaction is carried out at 450 DEG C, reacts 48h.
The method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas the most according to claim 1, it is characterised in that in second step, alkali metal hydride is 4:1～4:3 with the molar ratio of carbon dioxide.
The method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas the most according to claim 1, it is characterised in that in the 3rd step, methane gas calculation of yield method isWherein,For the productivity of methane,For generating the amount of the material of methane,Amount for the material of initial carbon dioxide.
The method utilizing alkali metal hydride reduction carbon dioxide to prepare imflammable gas the most according to claim 1, it is characterised in that the alkali metal oxide M generated in course of reaction2O can again be reverted back as alkali metal hydride by hydrogenation, electrochemical method, thus be realized recycling of alkali metal hydride.
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