CN109943356A - Using ionic liquid pretreatment coal for being electrolysed liquefied method - Google Patents
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Abstract
It utilizes ionic liquid pretreatment coal for being electrolysed liquefied method the invention discloses a kind of, uses ionic liquid as sweller and coal is pre-processed, to be conducive to coal hydrogenation liquefaction.The step of preprocess method of the present invention includes the treatment process after coal pretreatment process, the preprocessing process of ionic liquid, sample mixed process, swelling process, swelling, the electrolysis liquefaction process after swelling.The present invention selects suitable solvent to be swollen coal, treated, and coal sample particle is more tiny, structure is looser, and macromolecular in coal can be decomposed into the smaller group of molecular weight, has to effectively improve current density and liquefaction yield that coal electrolyzing adds hydrogen.
Description
Technical field
The present invention relates to low-temperature liquefaction treatment process in a kind of coal, at a kind of electrolytic hydrogenation liquefaction of coal
Science and engineering skill is applied to coal liquefaction craft technical field.
Background technique
Coal is the most abundant fossil fuel in the world, is also important global energy.Coal is in China generally as weight
Fuel is wanted, therefore also brings some environmental problems, meanwhile, with being deposited between petroleum supply and demand to the growing of oil demand
In significance difference away from for this status, coal liquefaction technology is the effective means of clean coal utilization.But the tradition of coal liquefaction
Method generally requires high temperature and pressure, the high requirements on the equipment, and causes biggish energy dissipation.
The electrolytic hydrogenation liquefaction of coal refers to that coal carries out cathode in electrolytic cell and adds hydrogen, and it is organic to be converted into soluble low molecule
Product, then it is carried out hydrogen is further added to obtain available fuel and chemical products, DCL/Direct coal liquefaction is usually very high
Under the conditions of temperature and pressure, coal hydrogenation is converted into liquid fuel in the presence of catalyst and hydrogen supply dissolvent and chemical industry produces
The process of product, the electrochemical hydrogenation reduction of coal are the conditions using electric field potential energy instead of high temperature and high pressure.With traditional coal
Charcoal liquifying method is compared, which has reaction condition mild, and equipment is simple, advantage at low cost.Coal sample
State is very big for the liquefaction yield impact of coal, thus by coal carry out effective pretreatment have for coal liquefaction it is important
Effect.
Ionic liquid (ILs) itself has a lot of advantages as a kind of novel solvent, such as low melting point, and low flammability is right
It is environmental-friendly, recuperability and there is unique solubility property etc. to many polarity and non-polar compound.However, in coal
In the liquefied technical field of electrolytic hydrogenation, up to the present, coal is pre-processed and its is electrolysed with ionic liquid is liquefied
For methods and applications still to be common, treatment process is also undesirable, and art is still immature, adds the electric current of hydrogen close to coal electrolyzing is improved
Degree and the effect of liquefaction products yield are limited.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Using ionic liquid pretreatment coal for being electrolysed liquefied method, effective swelling dispersion is carried out to coal using ionic liquid
Pretreatment, and apply it in coal electrolyzing liquefaction.Using the pretreated coal of the method for the present invention, coal can effectively improve
The current density of electrolytic hydrogenation can be good at improving coal electrolyzing hydrogenation liquefaction product suitable for the electrolysis of coal liquefaction
Yield.
In order to achieve the above objectives, the invention uses following inventive concept:
Swelling pretreatment is carried out to coal using the good characteristic of ionic liquid, utilizes 1- butyl -3- methylimidazole villaumite
Cl in ([Bmim] Cl) solution-With biggish cloud density and electronegativity, stronger charge effect can be formed with coal,
Cl can also form hydrogen bond structure with coal, can reinforce the interaction between coal, destroy the network structure in coal,
Be conducive to coal and add hydrogen, operation of the present invention is simple, more environmentally-friendly, can effectively improve coal electrolyzing add hydrogen current density and
Liquefy yield.
Conceived according to foregoing invention, the present invention adopts the following technical scheme:
It is a kind of to utilize ionic liquid pretreatment coal for being electrolysed liquefied method, include the following steps:
A. coal pretreatment process:
By coal in the ball mill to be not less than 80 revs/min progress ball milling at least 10 hours, then at 105~115 DEG C
Under vacuum oven in be dried at least for 24 hours, obtained coal powder is sieved, make sieving collect coal particles
Size is not more than 200 mesh, and the coal particles powder after then taking 10g to be sieved and dry, is 4mol/L's with the concentration of 100ml
HCl solution is filtered again after being cleaned at least 12h, and the solid content being collected by filtration is carried out vacuum at 105~115 DEG C
Dry be at least stored in drier afterwards for 24 hours saves, and obtains coal particles powder, for use；The above-mentioned preferred raw coal of coal；
B. the preprocessing process of ionic liquid:
According to following cleaning process: dish washing liquid-clear water-deionized water-ultrapure water carries out at least 3 cleaning processes,
Clean glass dropper and round-bottomed flask, by after cleaning glass dropper and round-bottomed flask be put into not less than 80 DEG C vacuum ovens
It is dried, then takes ionic liquid to be added in round-bottomed flask with glass dropper, with raw material band and sealed membrane encapsulation water removal dress
It sets, continuous vacuum is carried out to the ionic liquid in round-bottomed flask at 100~120 DEG C and removes water at least 12h, it, will after water removal
Round bottom flask equipped with ionic liquid enters in glove box, using obtained anhydrous ionic liquid as sweller, with to be used；On
It states ionic liquid and preferably uses 1- butyl -3- methylimidazole villaumite ([Bmim] Cl) solution；
C. coal and sweller mixed process:
It takes coal particles powder of the 1g after the step a pre-treatment to be added in another round-bottomed flask, uses simultaneously
Liquid-transfering gun pipettes the sweller that at least 10mL is prepared in the step b, is added in round-bottomed flask, according to above-mentioned coal particles powder
The mixed proportion of body and sweller mixes coal particles powder and sweller, obtains solid-liquid mixing system, then with all
Intellectual circle smears the ground bottle stopper of round-bottomed flask, then bottle stopper is filled in bottleneck to air tight, is finally sealed with sealed membrane, keeps solid-liquid mixed
Zoarium system is isolated with ambient atmosphere；
D. swelling process:
Swelling process carries out in oil bath pan, by the flask oil equipped with the solid-liquid mixing system prepared in the step c
In bath, coal particles powder is set to carry out swelling process at least for 24 hours at 90~150 DEG C, and protect always in swelling process
Magnetic agitation solid-liquid mixing system is held, keeps the swelling of coal particles powder abundant；It is preferred that making coal particles powder at 120~150 DEG C
Body carries out swelling process；
E. the treatment process after being swollen:
After the completion of the swelling process of the step d, deionized water is added and terminates swelling process, then by swollen mixt
Suction filtration separation is carried out, filter cake is washed with deionized 3~5 times, washes away water-soluble substances together, later by filter cake 105
It is dried in vacuo at~115 DEG C at least for 24 hours, the coal sample after being swollen；
F. the electrolysis liquefaction process after being swollen:
Coal sample after being swollen in the step e is subjected to electrolytic hydrogenation liquefaction processing, using potentiostat, electrolysis time
It is that at least for 24 hours, current potential is -2.0~2.1V, working electrode uses Pb electrode, and the surface length and width dimensions of Pb electrode are at least 2 ×
2cm is Pt electrode to electrode, and the surface length and width dimensions of Pt electrode are at least 3 × 3cm, the coal sample after being electrolysed, after making swelling
Electrolysis liquefaction, then will obtain solid-liquid mix products and be filtered, and obtain flammable liquid product.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the method for the present invention uses ionic liquid as sweller and pre-processes to coal, so that being conducive to coal adds hydrogen
Liquefaction, treated, and coal sample particle is more tiny, and structure is looser, macromolecular in coal can be decomposed into molecular weight
Smaller group has to effectively improve current density and liquefaction yield that coal electrolyzing adds hydrogen；
2. the method for the present invention replaces traditional high temperature and high pressure method with the method for ionic liquid pretreatment coal, operation is more
It is convenient, energy conservation and environmental protection, can scale implement, it is easy to accomplish；
3. the coal particles after the ionic liquid swelling of the method for the present invention obviously become more tiny, dispersion is more uniform,
This can increase solubility of the coal sample in alkaline electrolyte, improve hydrogenation liquefaction activity, so as to be suitable for coal well
In the electrolysis liquefaction of charcoal.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention one passes through pre-treatment but do not carry out the raw coal scanning electron microscope (SEM) photograph of swelling treatment.
Fig. 2 is coal scanning electron microscope (SEM) photograph of the embodiment of the present invention three after swelling treatment.
Fig. 3 is that the untreated coal cathode of the embodiment of the present invention two, treated the coal of embodiment three and comparative example adds hydrogen
Polarization curve.
Fig. 4 is one~embodiment of the embodiment of the present invention three and comparative example treated coal liquefaction yield figure.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under:
Embodiment one:
In the present embodiment, a kind of that ionic liquid pretreatment coal is utilized to be used to be electrolysed liquefied method, including walk as follows
It is rapid:
A. coal pretreatment process:
By coal in the ball mill with 80 revs/min progress ball milling 10 hours, then in the vacuum oven at 105 DEG C
It is dried for 24 hours, obtained coal powder is sieved, the coal particles size for collecting sieving is no more than 200 mesh, then
Coal particles powder after taking 10g to be sieved and dry, after carrying out cleaning 12h with the HCl solution of the concentration 4mol/L of 100ml again into
Row filtering, and the solid content being collected by filtration is dried in vacuo to be stored in drier afterwards for 24 hours at 105 DEG C and is saved, obtain coal
Charcoal granular powder, for use；
B. the preprocessing process of ionic liquid:
According to following cleaning process: dish washing liquid-clear water-deionized water-ultrapure water carries out 3 cleaning processes, cleaning
Glass dropper and round-bottomed flask, by after cleaning glass dropper and round-bottomed flask be put into 80 DEG C of vacuum ovens and be dried,
Then ionic liquid 1-butyl-3-methyl imidazolium villaumite ([Bmim] Cl) solution is taken to be added in round-bottomed flask with glass dropper,
De-watering apparatus is encapsulated with raw material band and sealed membrane, continuous vacuum water removal is carried out to the ionic liquid in round-bottomed flask at 110 DEG C
12h after water removal, will enter in glove box equipped with the round bottom flask of ionic liquid, using obtained anhydrous ionic liquid as
Sweller, with to be used；
C. coal and sweller mixed process:
It takes coal particles powder of the 1g after the step a pre-treatment to be added in another round-bottomed flask, uses simultaneously
Liquid-transfering gun pipettes the sweller that 10mL is prepared in the step b, is added in round-bottomed flask, according to above-mentioned coal particles powder and
The mixed proportion of the 1g:10ml of sweller mixes coal particles powder and sweller, obtains solid-liquid mixing system, so
The ground bottle stopper of round-bottomed flask is smeared with vaseline afterwards, then bottle stopper is filled in into bottleneck to air tight, is finally sealed, is made with sealed membrane
Solid-liquid mixing system is isolated with ambient atmosphere；
D. swelling process:
Swelling process carries out in oil bath pan, by the flask oil equipped with the solid-liquid mixing system prepared in the step c
In bath, coal particles powder is set to carry out swelling process for 24 hours at 90 DEG C, and remain magnetic agitation in swelling process
Solid-liquid mixing system keeps the swelling of coal particles powder abundant；
E. the treatment process after being swollen:
After the completion of the swelling process of the step d, deionized water is added and terminates swelling process, then by swollen mixt
Suction filtration separation is carried out, filter cake is washed with deionized 3 times, washes away water-soluble substances together, later by filter cake at 105 DEG C
It is dried in vacuo for 24 hours, the coal sample after being swollen；
F. the electrolysis liquefaction process after being swollen:
Coal sample after being swollen in the step e is subjected to electrolytic hydrogenation liquefaction processing, using potentiostat, electrolysis time
For for 24 hours, current potential is -2.0~2.1V, working electrode uses Pb electrode, and the surface length and width dimensions of Pb electrode are 2 × 2cm, to electrode
Surface length and width dimensions for Pt electrode, Pt electrode are 3 × 3cm, and after being electrolysed, the coal sample electrolysis after making swelling is liquefied, then
It will obtain solid-liquid mix products to be filtered, and obtain flammable liquid product.
Experimental test and analysis:
To flammable liquid product manufactured in the present embodiment, is barked using n-hexane, toluene and tetrahydro and mutter reflux to determine production
Produce rate, referring to fig. 4.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a kind of that ionic liquid pretreatment coal is utilized to be used to be electrolysed liquefied method, including walk as follows
It is rapid:
A. coal pretreatment process:
By coal in the ball mill with 80 revs/min progress ball milling 10 hours, then in the vacuum oven at 105 DEG C
It is dried for 24 hours, obtained coal powder is sieved, the coal particles size for collecting sieving is no more than 200 mesh, then
Coal particles powder after taking 10g to be sieved and dry, after carrying out cleaning 12h with the HCl solution of the concentration 4mol/L of 100ml again into
Row filtering, and the solid content being collected by filtration is dried in vacuo to be stored in drier afterwards for 24 hours at 105 DEG C and is saved, obtain coal
Charcoal granular powder, for use；
B. the preprocessing process of ionic liquid:
According to following cleaning process: dish washing liquid-clear water-deionized water-ultrapure water carries out 3 cleaning processes, cleaning
Glass dropper and round-bottomed flask, by after cleaning glass dropper and round-bottomed flask be put into 80 DEG C of vacuum ovens and be dried,
Then ionic liquid 1-butyl-3-methyl imidazolium villaumite ([Bmim] Cl) solution is taken to be added in round-bottomed flask with glass dropper,
De-watering apparatus is encapsulated with raw material band and sealed membrane, continuous vacuum water removal is carried out to the ionic liquid in round-bottomed flask at 120 DEG C
12h after water removal, will enter in glove box equipped with the round bottom flask of ionic liquid, using obtained anhydrous ionic liquid as
Sweller, with to be used；
C. coal and sweller mixed process:
It takes coal particles powder of the 1g after the step a pre-treatment to be added in another round-bottomed flask, uses simultaneously
Liquid-transfering gun pipettes the sweller that 10mL is prepared in the step b, is added in round-bottomed flask, according to above-mentioned coal particles powder and
The mixed proportion of the 1g:10ml of sweller mixes coal particles powder and sweller, obtains solid-liquid mixing system, so
The ground bottle stopper of round-bottomed flask is smeared with vaseline afterwards, then bottle stopper is filled in into bottleneck to air tight, is finally sealed, is made with sealed membrane
Solid-liquid mixing system is isolated with ambient atmosphere；
D. swelling process:
Swelling process carries out in oil bath pan, by the flask oil equipped with the solid-liquid mixing system prepared in the step c
In bath, coal particles powder is set to carry out swelling process for 24 hours at 120 DEG C, and remain that magnetic force stirs in swelling process
Solid-liquid mixing system is mixed, keeps the swelling of coal particles powder abundant；
E. the treatment process after being swollen:
After the completion of the swelling process of the step d, deionized water is added and terminates swelling process, then by swollen mixt
Suction filtration separation is carried out, filter cake is washed with deionized 3 times, washes away water-soluble substances together, later by filter cake at 105 DEG C
It is dried in vacuo for 24 hours, the coal sample after being swollen；
F. the electrolysis liquefaction process after being swollen:
Coal sample after being swollen in the step e is subjected to electrolytic hydrogenation liquefaction processing, using potentiostat, electrolysis time
For for 24 hours, current potential is -2.0~2.1V, working electrode uses Pb electrode, and the surface length and width dimensions of Pb electrode are 2 × 2cm, to electrode
Surface length and width dimensions for Pt electrode, Pt electrode are 3 × 3cm, and after being electrolysed, the coal sample electrolysis after making swelling is liquefied, then
It will obtain solid-liquid mix products to be filtered, and obtain flammable liquid product.
Experimental test and analysis:
To flammable liquid product manufactured in the present embodiment, is barked using n-hexane, toluene and tetrahydro and mutter reflux to determine production
Produce rate, referring to fig. 4.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of that ionic liquid pretreatment coal is utilized to be used to be electrolysed liquefied method, including walk as follows
It is rapid:
A. coal pretreatment process:
By coal in the ball mill with 80 revs/min progress ball milling 10 hours, then in the vacuum oven at 105 DEG C
It is dried for 24 hours, obtained coal powder is sieved, the coal particles size for collecting sieving is no more than 200 mesh, then
Coal particles powder after taking 10g to be sieved and dry, after carrying out cleaning 12h with the HCl solution of the concentration 4mol/L of 100ml again into
Row filtering, and the solid content being collected by filtration is dried in vacuo to be stored in drier afterwards for 24 hours at 105 DEG C and is saved, obtain coal
Charcoal granular powder, for use；
B. the preprocessing process of ionic liquid:
According to following cleaning process: dish washing liquid-clear water-deionized water-ultrapure water carries out 3 cleaning processes, cleaning
Glass dropper and round-bottomed flask, by after cleaning glass dropper and round-bottomed flask be put into 80 DEG C of vacuum ovens and be dried,
Then ionic liquid 1-butyl-3-methyl imidazolium villaumite ([Bmim] Cl) solution is taken to be added in round-bottomed flask with glass dropper,
De-watering apparatus is encapsulated with raw material band and sealed membrane, continuous vacuum water removal is carried out to the ionic liquid in round-bottomed flask at 120 DEG C
12h after water removal, will enter in glove box equipped with the round bottom flask of ionic liquid, using obtained anhydrous ionic liquid as
Sweller, with to be used；
C. coal and sweller mixed process:
It takes coal particles powder of the 1g after the step a pre-treatment to be added in another round-bottomed flask, uses simultaneously
Liquid-transfering gun pipettes the sweller that 10mL is prepared in the step b, is added in round-bottomed flask, according to above-mentioned coal particles powder and
The mixed proportion of the 1g:10ml of sweller mixes coal particles powder and sweller, obtains solid-liquid mixing system, so
The ground bottle stopper of round-bottomed flask is smeared with vaseline afterwards, then bottle stopper is filled in into bottleneck to air tight, is finally sealed, is made with sealed membrane
Solid-liquid mixing system is isolated with ambient atmosphere；
D. swelling process:
Swelling process carries out in oil bath pan, by the flask oil equipped with the solid-liquid mixing system prepared in the step c
In bath, coal particles powder is set to carry out swelling process for 24 hours at 150 DEG C, and remain that magnetic force stirs in swelling process
Solid-liquid mixing system is mixed, keeps the swelling of coal particles powder abundant；
E. the treatment process after being swollen:
After the completion of the swelling process of the step d, deionized water is added and terminates swelling process, then by swollen mixt
Suction filtration separation is carried out, filter cake is washed with deionized 3 times, washes away water-soluble substances together, later by filter cake at 105 DEG C
It is dried in vacuo for 24 hours, the coal sample after being swollen；
F. the electrolysis liquefaction process after being swollen:
Coal sample after being swollen in the step e is subjected to electrolytic hydrogenation liquefaction processing, using potentiostat, electrolysis time
For for 24 hours, current potential is -2.0~2.1V, working electrode uses Pb electrode, and the surface length and width dimensions of Pb electrode are 2 × 2cm, to electrode
Surface length and width dimensions for Pt electrode, Pt electrode are 3 × 3cm, and after being electrolysed, the coal sample electrolysis after making swelling is liquefied, then
It will obtain solid-liquid mix products to be filtered, and obtain flammable liquid product.
Experimental test and analysis:
To flammable liquid product manufactured in the present embodiment, is barked using n-hexane, toluene and tetrahydro and mutter reflux to determine production
Produce rate, referring to fig. 4.
Comparative example:
A kind of liquefied method of coal electrolyzing, includes the following steps:
(1) coal pretreatment process:
By coal in the ball mill with 80 revs/min progress ball milling 10 hours, then in the vacuum oven at 105 DEG C
It is dried for 24 hours, obtained coal powder is sieved, the coal particles size for collecting sieving is no more than 200 mesh, then
Coal particles powder after taking 10g to be sieved and dry, after carrying out cleaning 12h with the HCl solution of the concentration 4mol/L of 100ml again into
Row filtering, and the solid content being collected by filtration is dried in vacuo to be stored in drier afterwards for 24 hours at 105 DEG C and is saved, obtain coal
Charcoal granular powder, for use；
(2) it is electrolysed liquefaction process:
The coal that pre-treatment is carried out in the step (1) is subjected to electrolytic hydrogenation liquefaction processing, using potentiostat, electricity
Solving the time is that for 24 hours, current potential is -2.0~2.1V, and working electrode uses Pb electrode, and the surface length and width dimensions of Pb electrode are 2 × 2cm,
It is Pt electrode to electrode, the surface length and width dimensions of Pt electrode are 3 × 3cm, the coal sample electrolyte after being electrolysed, after making swelling
Change, then will obtain solid-liquid mix products and be filtered, and obtain flammable liquid product.
Experimental test and analysis:
To flammable liquid product manufactured in the present embodiment, is barked using n-hexane, toluene and tetrahydro and mutter reflux to determine production
Produce rate, referring to fig. 4.
Embodiment three carries out coal and comparative example coal sample elemental analysis before and after swelling treatment, is shown in Table 1.
1. embodiment three of table carries out coal sample and comparative example coal sample element comparative analysis table before and after swelling pretreatment
Table 1 is elemental analysis of the coal before and after swelling, as can be seen from Table 1 after ionic liquid [Bmim] Cl swelling
Carbon content is substantially reduced in coal.This is because small organic molecule during swelling in coal is released, and beat
The structure in coal is broken, therefore the phosphorus content in coal reduces.The content of nitrogen is bright in coal after [Bmim] Cl swelling
Aobvious to increase, this illustrates that sweller is interacted with coal, and can not remove from coal, to increase nitrogen in coal sample
Content.
As seen from Figure 3, the electric current at 150 DEG C after [Bmim] Cl swelling is maximum, this be attributed to coal loose structure and
The release of the low molecular weight substance of reduction is easy on catalysis electrode.The result shows that these are with the pretreated coal of [Bmim] Cl,
Increase coal adds hydrogen electric current, promotes the electroreduction of coal.Above-described embodiment selects suitable solvent to be swollen coal,
Especially under ionic liquid effect, it is used for coal hydrogenation liquefaction, above-described embodiment preprocess method can to effectively improve coal
The current density and liquefaction products yield of charcoal electrolytic hydrogenation.
Fig. 1 is that the embodiment of the present invention one passes through pre-treatment but do not carry out the raw coal scanning electron microscope (SEM) photograph of swelling treatment.Fig. 2 is this
Coal scanning electron microscope (SEM) photograph of the inventive embodiments three after [Bmim] Cl swelling treatment.It is compared by Fig. 1 and Fig. 2, it can be found that from
Coal particles after sub- liquid [Bmim] Cl swelling obviously become more tiny, and dispersion is more uniform, this can increase coal sample and exist
Solubility in alkaline electrolyte improves hydrogenation liquefaction activity.
Fig. 4 is one~embodiment of the embodiment of the present invention three and comparative example treated coal liquefaction yield figure, wherein horizontal
Coordinate type of coal: 1 is raw coal, and 2 be the coal after being swollen at 90 DEG C, and 3 be the coal after being swollen at 120 DEG C, and 4 be at 150 DEG C
As seen from Figure 4, after swelling pretreatment, the electrolysis liquefaction yield of coal obviously increases coal after swelling, and especially 150
Coal at DEG C after [Bmim] Cl swelling pretreatment.
Coal is pre-processed in conclusion above-described embodiment uses ionic liquid as sweller, to be conducive to
Coal hydrogenation liquefaction.The step of preprocess method of the present invention include: coal pretreatment process, ionic liquid preprocessing process,
The electrolysis liquefaction process after treatment process, swelling after sample mixed process, swelling process, swelling, treated coal sample
Particle is more tiny, and structure is looser, and macromolecular in coal can be decomposed into the smaller group of molecular weight, and the present invention is above-mentioned
Coal preprocess method and its electrolytic hydrogenation liquefied application of the embodiment using ionic liquid participation, can be good at being suitable for
In the electrolysis liquefaction of coal, and current density and liquefaction products yield that coal electrolyzing adds hydrogen can be effectively improved, therefore,
The method of the present invention is under ionic liquid pretreatment to the liquefied novel method of the electrolytic hydrogenation of coal.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
Utilize ionic liquid pretreatment coal for being electrolysed the technical principle and inventive concept of liquefied method without departing from the present invention,
Belong to protection scope of the present invention.
Claims (4)
1. a kind of utilize ionic liquid pretreatment coal for being electrolysed liquefied method, which comprises the steps of:
A. coal pretreatment process:
By coal in the ball mill to be not less than 80 revs/min progress ball milling at least 10 hours, then at 105~115 DEG C
It is dried in vacuum oven at least for 24 hours, obtained coal powder is sieved, the coal particles size for collecting sieving
No more than 200 mesh, coal particles powder after then taking 10g to be sieved and dry, the HCl for being 4mol/L with the concentration of 100ml is molten
Liquid is filtered again after being cleaned at least 12h, and the solid content being collected by filtration is dried in vacuo at 105~115 DEG C
It is at least stored in drier and saves afterwards for 24 hours, obtain coal particles powder, for use；
B. the preprocessing process of ionic liquid:
According to following cleaning process: dish washing liquid-clear water-deionized water-ultrapure water carries out at least 3 cleaning processes, cleaning
Glass dropper and round-bottomed flask, by after cleaning glass dropper and round-bottomed flask be put into not less than 80 DEG C vacuum ovens and carry out
It is dry, it then takes ionic liquid to be added in round-bottomed flask with glass dropper, encapsulates de-watering apparatus with raw material band and sealed membrane,
At 100~120 DEG C in round-bottomed flask ionic liquid carry out continuous vacuum remove water at least 12h, after water removal, will equipped with from
The round bottom flask of sub- liquid enters in glove box, using obtained anhydrous ionic liquid as sweller, with to be used；
C. coal and sweller mixed process:
It takes coal particles powder of the 1g after the step a pre-treatment to be added in another round-bottomed flask, while using liquid relief
Rifle pipettes the sweller that at least 10mL prepared in the step b and is added in round-bottomed flask, according to above-mentioned coal particles powder and
The mixed proportion of sweller mixes coal particles powder and sweller, obtains solid-liquid mixing system, then uses vaseline
The ground bottle stopper of round-bottomed flask is smeared, then bottle stopper is filled in into bottleneck to air tight, is finally sealed with sealed membrane, makes solid-liquid mixture
System is isolated with ambient atmosphere；
D. swelling process:
Swelling process carries out in oil bath pan, by the flask oil bath pan equipped with the solid-liquid mixing system prepared in the step c
In, so that coal particles powder is carried out swelling process at least for 24 hours at 90~150 DEG C, and remain magnetic in swelling process
Power stirs solid-liquid mixing system, keeps the swelling of coal particles powder abundant；
E. the treatment process after being swollen:
After the completion of the swelling process of the step d, deionized water is added and terminates swelling process, then carries out swollen mixt
Separation is filtered, filter cake is washed with deionized 3~5 times, washes away water-soluble substances together, later by filter cake 105~115
It is dried in vacuo at DEG C at least for 24 hours, the coal sample after being swollen；
F. the electrolysis liquefaction process after being swollen:
Coal sample after being swollen in the step e is subjected to electrolytic hydrogenation liquefaction processing, using potentiostat, electrolysis time is extremely
Few current potential is -2.0~2.1V for 24 hours, and working electrode uses Pb electrode, and the surface length and width dimensions of Pb electrode are at least 2 × 2cm, right
Electrode is Pt electrode, and the surface length and width dimensions of Pt electrode are at least 3 × 3cm, the coal sample electrolyte after being electrolysed, after making swelling
Change, then will obtain solid-liquid mix products and be filtered, and obtain flammable liquid product.
2. utilizing ionic liquid pretreatment coal for being electrolysed liquefied method according to claim 1, it is characterised in that:
In the step d, coal particles powder is made to carry out swelling process at 120~150 DEG C.
3. utilizing ionic liquid pretreatment coal for being electrolysed liquefied method according to claim 1, it is characterised in that:
In the step b, the ionic liquid is 1- butyl -3- methylimidazole villaumite ([Bmim] Cl) solution.
4. utilizing ionic liquid pretreatment coal for being electrolysed liquefied method according to claim 1, it is characterised in that:
In the step a, the coal is raw coal.
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| CN201910196951.3A CN109943356A (en) | 2019-03-15 | 2019-03-15 | Using ionic liquid pretreatment coal for being electrolysed liquefied method |
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| CN111378986A (en) * | 2020-04-02 | 2020-07-07 | 上海大学 | Preparation method of porous lead composite nickel-iron alloy catalytic electrode and application of porous lead composite nickel-iron alloy catalytic electrode in coal electrolysis liquefaction |
| CN112125848A (en) * | 2020-09-17 | 2020-12-25 | 西安科技大学 | Method for synthesizing imidazole ionic liquid under assistance of ultrasonic waves and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111378986A (en) * | 2020-04-02 | 2020-07-07 | 上海大学 | Preparation method of porous lead composite nickel-iron alloy catalytic electrode and application of porous lead composite nickel-iron alloy catalytic electrode in coal electrolysis liquefaction |
| CN112125848A (en) * | 2020-09-17 | 2020-12-25 | 西安科技大学 | Method for synthesizing imidazole ionic liquid under assistance of ultrasonic waves and application |
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