CN106517189A - Uniform ultra-microporous activated carbon for gas separation and preparation method of uniform ultra-microporous activated carbon - Google Patents

Uniform ultra-microporous activated carbon for gas separation and preparation method of uniform ultra-microporous activated carbon Download PDF

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CN106517189A
CN106517189A CN201611060108.5A CN201611060108A CN106517189A CN 106517189 A CN106517189 A CN 106517189A CN 201611060108 A CN201611060108 A CN 201611060108A CN 106517189 A CN106517189 A CN 106517189A
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activated carbon
uniform
coke
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CN106517189B (en
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童仕唐
张景灿
张春桃
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Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/508Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/16Pore diameter
    • C01P2006/17Pore diameter distribution

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Abstract

The invention relates to uniform ultra-microporous activated carbon for gas separation and a preparation method of the uniform ultra-microporous activated carbon. According to the technical scheme of the preparation method, mixing semi-coke with KOH in a mass ratio being 1: (0.01-0.2), adding water and an activating aid to impregnate the mixture for 1-36 h; increasing the temperature to 800-950 DEG C in a programmed manner under N2 protection, controlling thermal decomposition, and introducing water for activation of part of steam for 0.5h-1.5h; finally, washing the mixture with acid and water until the mixture is neutral to obtain the uniform ultra-microporous activated carbon. The pore size is distributed centrally between 0.45 and 0.55 nm, the pores belong to ultra-micropores and have microporosity of 70% or more, and the adsorption capacity of hydrogen is 77cm<3>/g or higher. The semi-coke is taken as a raw material, low in price and low in energy consumption and needs not to be carbonized; an activation method integrates KOH impregnation pretreatment and activation of part of steam, little KOH is consumed, and the activation method has the characteristics of being low in cost and pollution, helpful for reducing corrosion of equipment and the like. The activated carbon prepared with the method has the characteristics of uniform pore size distribution, extremely rich ultra-microporous structure and the like, and can be used in gas separation fields such as pressure swing adsorption hydrogen making or hydrogen storage and the like.

Description

It is a kind of to be used for detached uniform ultra micro mesoporous activated carbon of gas and preparation method thereof
Technical field
The invention belongs to functional activity charcoal preparing technical field.It is specifically related to a kind of to be used for the detached uniform ultramicropore of gas Activated carbon and preparation method thereof.
Background technology
Many advantages, such as gas absorption isolation technics have efficient, energy-conserving and environment-protective, process is simple, being widely used to The fields such as work, metallurgy, medical and health, environmental conservation and biological engineering.The key of adsorption separation technology application is adsorbent, and is lived Property charcoal be one of common adsorbent, relax as its adsorption strength to gas is relative so that desorption is easier to, therefore It is in gas separation process, often superior than other adsorbents as the activated carbon of adsorbent.It is industrial improve gas separate because Plain it is critical only that adsorbent has abundant uniform ultra-microporous(0.3~0.5nm), so preparing uniform ultra-microporous Activated carbon be solve efficient gas isolation technics key.
At present, the technology of preparing to large-scale production and application in the detached uniform ultra micro mesoporous activated carbon of efficient gas does not also have Break through, cause pore-size distribution unreasonable, it is of low quality, and due to producing in enormous quantities, it is expensive etc., limit activity Application and popularization of the charcoal in gas separation field.Therefore, consider in terms of performance of raw material sources, cost and product etc., It is contemplated that finding a kind of method for preparing uniform ultra micro mesoporous activated carbon, to realize the regulation and control to activated carbon capillary, make made Standby uniform ultra micro mesoporous activated carbon has efficient Molecular Sieving Properties, facilitates implementation large-scale production, and reduces producing and make Use cost.
Semi-coke, also known as semicoke, structure is bulk, is the high-volatile bituminous coal without cohesiveness or weakly caking in middle low temperature bar The solid carbonaceous product of the relatively low volatile that carbonization is obtained under part.In recent years, go deep into people with circular economy concept The heart, the downstream industry chain of semi-coke industry are gradually expanded, and the wherein activated activated carbon for preparing of semi-coke is considered as most having development latent Power.According to statistics, Shenmu County has more than 600,000 tons of 43 family of semi-coke enterprise, 80,000,000 tons of annual Shenmu County's local mine producing coal, wherein 1/3rd by dry distilling into semi-coke, and semi-coke market has tended to saturation.From the point of view of semi-coke nature, it is by low metamorphic grade Low temperature distillation in coal, fixed carbon content more than 75%, content of ashes are less than 10%, in the structure of charcoal containing a large amount of oxygen-containing, sulfur, Dan Deng functional groups, they are that charcoal possesses chemically active material base;In addition, semi-coke has higher mechanical strength, retains Low rank coal possesses the characteristics such as abundant pore structure.
During production activated carbon, it is to increase specific surface area and regulation and control pore structure, according to activation method used not Together, generally using different activators, such as carbon dioxide, water vapour, NaOH, KOH, H3PO4, HNO3, ZnCl2Deng.Wherein using compared with It is KOH activation methods for a kind of extensive activation method, the main hydrophilicity using KOH so as to make with hydrophobic carbon surface Used time, play pore-creating effect(Ru Ling Tseng, Szu Kung Tseng, KOH are activated to activated carbon pore structure and suction The impact of attached performance, colloid and interface science, 2005,287:428-437).As " a kind of fast activating prepares high-specific surface area work The method of property charcoal "(CN103771414A,2014-05-07)High specific surface micro-pore activated carbon is prepared using said method, but Alkali charcoal ratio used is 1 ~ 4:1, alkali consumption is larger.KOH activation methods are had the following disadvantages during production of active carbon: (1)Activation yield is relatively low, and charcoal consumption is larger, and production cost is larger.(2)Under hot conditionss, KOH is rotten to structure of reactor material Corrosion is strong, and equipment construction cost is high, and service life is short;(3) slurry amount is big, also needs sometimes to use Fluohydric acid., causes a large amount of High concentration basic fluoride waste is discharged, and causes Heavy environmental pollution.Another kind of method for preparing activated carbon is gas activation, At present widely used activated gas are vapor, be by raw material carbonization after, contact with vapor and react, in which Portion forms the gap structure of prosperity.Because the tar that raw material is produced in carbonization process and Hydrocarbon plug carbide hole Gap so as to which specific surface area reduces, activity is reduced, and hence with this oxidizing gas activation of vapor, not only can be removed residual The tar stayed in carbide and surface impurity, dredge the hole being blocked, and at the same time it can also corrode carbide surface, are formed New pore structure, makes carbide structure more flourishing.However, during steam activation, only with single activation gas Body so that the generation of hole is that the reactivity by gas with carbon structure is determined, even if different thermal decompositions are controlled in activation process Parameter (activation temperature, soak time etc.), micropore, the generating process of mesopore are similar.Therefore activated using pure gases Specific pore structure should not be generated, it is difficult to significantly regulate and control pore structure characteristic.
In sum, adopt at present for the detached active charcoal preparing process of gas, exist and be difficult to effective trim products Pore-size distribution, production cost height, difficult control of reaction conditions, prouctiveness is low, equipment corrosion is serious and seriously polluted etc. asks Topic.
The content of the invention
It is contemplated that overcoming prior art defect, it is therefore an objective to provide one kind with semi-coke as raw material, soaked using low alkali carbon ratio The uniform ultramicropore method for preparation of active carbon that stain pretreatment is combined with part steam activation.The activated carbon hole of the method production Footpath is evenly distributed, and possesses extremely abundant ultra-microporous, can be used for efficient gas separation, with low production cost, yield it is high, Consumption alkali is low, simple production process, advantages of environment protection.
The technical solution used in the present invention is carried out as follows:
Step one, with semi-coke as raw material, first the KOH for accounting for raw material 1 ~ 20wt% of semi-coke, the activation for accounting for raw material 1 ~ 12wt% of semi-coke are helped Agent and water are mixed, and are configured to impregnation liquid, and the quality of wherein water is 0.8 ~ 1.2 times of raw material semi-coke;Again semi-coke is added and is soaked 1 ~ 36h of normal temperature dipping in stain liquid, is obtained pre-feed;
Step 2, by obtained in step one pre-feed move into tube furnace in, in N2Thermal decomposition is controlled under protective atmosphere, wherein N2The flow of protective atmosphere is 150 ~ 300ml/min;Described control thermal decomposition is first by tube furnace with the intensification of 3 ~ 8 DEG C/min Ramp is incubated 0.5 ~ 1.5 h, then is continuously heating to 800 ~ 950 DEG C with the heating rate of 3 ~ 8 DEG C/min to 350 ~ 400 DEG C Carry out part steam activation;Described part steam activation is introduced into reaction tube under 800 ~ 950 DEG C of temperature conditionss The flow of current, wherein water is 1 ~ 5ml/min, closes current, finally in N after 0.5 ~ 1.5h of activation2It is cooled under protective atmosphere Room temperature, is obtained uniform ultramicropore activated carbon crude product;
Step 3, uniform ultramicropore activated carbon crude product obtained in step 2 is carried out washing, filtered with 5% HCl solution, be used in combination Distilled water cyclic washing is obtained uniform ultra micro mesoporous activated carbon to neutrality then in 110 DEG C of 12 h of freeze-day with constant temperature;
The aperture integrated distribution of the uniform ultra micro mesoporous activated carbon of the preparation between 0.45 ~ 0.55nm belongs to ultramicropore, compares table Area reaches 840m2/ more than g, up to more than 70%, hydrogen sorption capacity reaches 77cm to microporosity3/ more than g.
Described semi-coke raw material is by the dry distilling under middle cryogenic conditions of the high-volatile bituminous coal without cohesiveness or weakly caking The solid carbonaceous product of the relatively low volatile that pyrolysis is obtained.
Described assistant activator is by 1 ~ 30% hydrogen peroxide, KNO3, 1 ~ 5wt% dodecylbenzene sodium sulfonate ethanol solution composition, In mass ratio 4:5:3 proportions.
The condition determination of the maximum adsorption capacity of described hydrogen is 25 DEG C, adsorptive pressure 11.4MPa.
There is following technique effect compared with prior art due to adopting above-mentioned technical proposal, the present invention:
(1) present invention, with semi-coke as raw material, is only (0.01 ~ 0.2) in alkali charcoal ratio:Raw material semi-coke is soaked under conditions of 1 Stain, is controlled thermal decomposition under the vapor atmosphere of part, and uniform ultra micro mesoporous activated carbon is obtained.As semi-coke possesses necessarily in itself Pore structure, surface contains abundant oxygen-containing functional group, the K in dipping process+Can be in OHEasily enter under lubrication Semi-coke pore interior.As temperature rises to 350 ~ 400 DEG C, KOH is in molten condition, and KOH is reacted with carbon, makes aromatic structure In branched carbon atoms and KOH be combined into-C-OK structures, the structure is easily decomposed at higher temperatures and leaves micropore, is conducive to hole The development of structure, increases porosity.In preparation process, KOH consumptions are very little, not only effective reduces cost, it is often more important that can To slow down the corrosion of equipment and materials, simultaneously because alkali charcoal is than little, the increase of carbon source loadings is also increased substantially beneficial to equipment capacity.
(2) present invention is selected using the control rate of heat addition, the method for the control thermal decomposition of temperature and time condition 0.5 ~ 1.5 h is incubated at a temperature of 350 ~ 400 DEG C, it is ensured that KOH can be immersed inside charcoal granule in the molten state, with aromatic structure In branched carbon atoms be combined into-C-OK structures, the structure can with temperature raise gradually decompose and stay micropore, be conducive to Uniform ultra-microporous development.
(3) in the selection of activation method, the present invention is adopted and is impregnated with very small amount KOH, prepared by part vapor activation Uniform ultra micro mesoporous activated carbon.KOH has pore-creating, corrodes and catalytic action to raw material, but KOH consumptions are few, overcomes because adopting The corrosion to equipment and the shortcoming of the pollution to environment that alkali activation is caused, while adopting N2With the mixed atmosphere of vapor, water The consumption of steam is few, reduces reactivity, makes charcoal avoid excessive ablation, caused caving in for microporous wall, and also overcomed Specific pore structure should not be generated using pure gases activation and be difficult significantly to regulate and control a difficult problem for ultramicropore structure.
(4) the aperture integrated distribution of activated carbon prepared by the present invention between 0.45 ~ 0.55nm belongs to ultramicropore, compares table Area reaches 840m2/ more than g, up to more than 70%, the maximum adsorption capacity of hydrogen reaches 77cm to microporosity3/ more than g.
(5) present invention can also prepare uniform ultra micro mesoporous activated carbon for raw material from industrial waste Ramsbottom carbon powder, itself Possess abundant microcellular structure, with fixed carbon content it is high, ratio resistance is high, chemism is high, containing ash it is low, aluminum is low, sulfur is low, phosphorus Low characteristic, belongs to the carbon source with certain degree of graphitization.And Ramsbottom carbon powder is a kind of trade waste, it is raw material system by it Standby ultra micro mesoporous activated carbon, comprehensive utilization are turned waste into wealth, realize the recycling of Ramsbottom carbon powder, solve activated carbon preparation Raw material problem, saved cost.
Therefore the present invention has that low production cost, alkali consumption be few, few to equipment corrosion, production process is controllable and environmental friendliness The features such as, the activated carbon of preparation has uniform ultra-microporous, with large specific surface area and less mean pore sizes, narrow hole The ability of good adsorbent hydrogen is distributed and possesses, and be can be applicable to gas separation, pressure swing adsorption is particularly suitable for use with from coal gas Middle separation hydrogen.
Description of the drawings
Fig. 1 is the graph of pore diameter distribution for the detached uniform ultra micro mesoporous activated carbon of gas prepared by embodiment 1.
Fig. 2 is the N for the detached uniform ultra micro mesoporous activated carbon of gas prepared by embodiment 12Adsorption/desorption curve.
Fig. 3 is that the TEM for the detached uniform ultra micro mesoporous activated carbon of gas prepared by embodiment 1 schemes.
Fig. 4 is absorption of pressure-variable adsorption hydrogen for the detached uniform ultra micro mesoporous activated carbon of gas prepared by embodiment 1 etc. Warm line chart.
Specific embodiment
The present invention is described further with reference to embodiment, not limiting of its scope.
Embodiment 1
It is a kind of to be used for detached uniform ultra micro mesoporous activated carbon of gas and preparation method thereof, comprise the steps:
Step one, raw material semi-coke is ground, cross 150 ~ 200 mesh sieves, be dried, obtain Ramsbottom carbon powder, raw material semi-coke 15wt% will be accounted for KOH, the assistant activator and water that account for raw material semi-coke 5wt% mixed, be configured to impregnation liquid, the quality of wherein water is that raw material is blue 0.8 times of charcoal;Semi-coke is added normal temperature dipping 24h in impregnation liquid again, pre-feed is obtained;
Step 2, by obtained in step one pre-feed move into tube furnace in, in N2Thermal decomposition is controlled under protective atmosphere, wherein N2The flow of protective atmosphere is 200 ~ 250ml/min;Described control thermal decomposition is first by tube furnace with the intensification of 4 ~ 6 DEG C/min Ramp is incubated 1 h, then is continuously heating to 900 DEG C with the heating rate of 4 ~ 6 DEG C/min, be passed through water, wherein water to 370 DEG C Flow be 2ml/min, activation 1h after stop be passed through water, finally in N2Room temperature is cooled under protective atmosphere, uniform ultra micro is obtained Mesoporous activated carbon crude product;
Step 3, uniform ultramicropore activated carbon crude product obtained in step 2 is carried out washing, filtered with 5% HCl solution, be used in combination Distilled water is rinsed repeatedly to neutrality, then in 110 DEG C of 12 h of freeze-day with constant temperature, and uniform ultra micro mesoporous activated carbon is obtained;
As a result:The iodine sorption value of activated carbon obtained by the present embodiment is 888.1mg/g, and specific surface area is 840.5m2/ g, microporosity is 70.4%.Graph of pore diameter distribution and N2As shown in Figure 1, 2, TEM schemes as shown in figure 3, absorption of pressure-variable adsorption hydrogen etc. adsorption/desorption curve Warm line chart is as shown in Figure 4.From Fig. 1,2, the activated carbon prepared by the invention based on ultramicropore, pore-size distribution concentrate, companion There is a small amount of mesopore to provide the passage of transport gas.
Embodiment 2
It is a kind of to be used for detached uniform ultra micro mesoporous activated carbon of gas and preparation method thereof, comprise the steps:
Step one, by industrial waste Ramsbottom carbon powder grind, cross 150 ~ 200 mesh sieves, be dried, obtain Ramsbottom carbon powder, raw material semi-coke will be accounted for The KOH of 10wt%, the assistant activator and water for accounting for raw material semi-coke 10wt% are mixed, and are configured to impregnation liquid, and the quality of wherein water is 1.2 times of raw material semi-coke;Semi-coke is added normal temperature dipping 18h in impregnation liquid again, pre-feed is obtained;
Step 2, by obtained in step one pre-feed move into tube furnace in, in N2Thermal decomposition is controlled under protective atmosphere, wherein N2The flow of protective atmosphere is 200ml/min;Described control thermal decomposition is first by tube furnace with the heating rate of 4 ~ 6 DEG C/min 350 DEG C are warming up to, and are incubated 1h, then 950 DEG C are continuously heating to the heating rate of 4 ~ 6 DEG C/min, are passed through water, the wherein flow of water It is 5ml/min, stops being passed through water after activation 0.5h, finally in N2Room temperature is cooled under protective atmosphere, uniform ultramicropore is obtained and is lived Property charcoal crude product;
Step 3, uniform ultramicropore activated carbon crude product obtained in step 2 is carried out washing, filtered with 5% HCl solution, be used in combination Distilled water is rinsed repeatedly to neutrality, then in 110 DEG C of 12 h of freeze-day with constant temperature, and uniform ultra micro mesoporous activated carbon is obtained;
The iodine sorption value of activated carbon obtained by the present embodiment is 804.1mg/g, and specific surface area is 692.2m2/ g, microporosity is 64.2%。
Embodiment 3
It is a kind of to be used for detached uniform ultra micro mesoporous activated carbon of gas and preparation method thereof, comprise the steps:
Step one, by industrial waste Ramsbottom carbon powder grind, cross 150 ~ 200 mesh sieves, be dried, obtain Ramsbottom carbon powder, raw material semi-coke will be accounted for The KOH of 5wt%, the assistant activator and water for accounting for raw material semi-coke 10wt% are mixed, and are configured to impregnation liquid, and the quality of wherein water is former 1.2 times of semi-coke of material;Semi-coke is added normal temperature dipping 12h in impregnation liquid again, pre-feed is obtained;
Step 2, by obtained in step one pre-feed move into tube furnace in, in N2Thermal decomposition is controlled under protective atmosphere, wherein N2The flow of protective atmosphere is 300ml/min;Described control thermal decomposition is first by tube furnace with the heating rate of 4 ~ 6 DEG C/min 400 DEG C are warming up to, and are incubated 1h, then 800 DEG C are continuously heating to the heating rate of 4 ~ 6 DEG C/min, are passed through water, the wherein flow of water It is 1ml/min, stops being passed through water after activation 1h, finally in N2Room temperature is cooled under protective atmosphere, uniform ultramicropore activity is obtained Charcoal crude product;
Step 3, uniform ultramicropore activated carbon crude product obtained in step 2 is carried out washing, filtered with 5% HCl solution, be used in combination Distilled water is rinsed repeatedly to neutrality, then in 110 DEG C of 12 h of freeze-day with constant temperature, and uniform ultra micro mesoporous activated carbon is obtained;
The iodine sorption value of activated carbon obtained by the present embodiment is 754.1mg/g, and specific surface area is 619.2m2/ g, microporosity is 59.2%。

Claims (5)

1. a kind of preparation method for the detached uniform ultra micro mesoporous activated carbon of gas, it is characterised in that it is concrete according to the following steps Complete:
Step one, with semi-coke as raw material, first the KOH for accounting for raw material 1 ~ 20wt% of semi-coke, the activation for accounting for raw material 1 ~ 12wt% of semi-coke are helped Agent and water are mixed, and are configured to impregnation liquid, and the quality of wherein water is 0.8 ~ 1.2 times of raw material semi-coke;Again semi-coke is added and is soaked 1 ~ 36h of normal temperature dipping in stain liquid, is obtained pre-feed;
Step 2, by obtained in step one pre-feed move into tube furnace in, in N2Thermal decomposition is controlled under protective atmosphere, wherein N2The flow of protective atmosphere is 150 ~ 300ml/min;Described control thermal decomposition is first by tube furnace with the intensification of 3 ~ 8 DEG C/min Ramp is incubated 0.5 ~ 1.5 h, then is continuously heating to 800 ~ 950 DEG C with the heating rate of 3 ~ 8 DEG C/min to 350 ~ 400 DEG C Carry out part steam activation;Described part steam activation is introduced into reaction tube under 800 ~ 950 DEG C of temperature conditionss The flow of current, wherein water is 1 ~ 5ml/min, closes current, finally in N after 0.5 ~ 1.5h of activation2It is cooled under protective atmosphere Room temperature, is obtained uniform ultramicropore activated carbon crude product;
Step 3, uniform ultramicropore activated carbon crude product obtained in step 2 is carried out washing, filtered with 5% HCl solution, be used in combination Distilled water cyclic washing is obtained uniform ultra micro mesoporous activated carbon to neutrality then in 110 DEG C of 12 h of freeze-day with constant temperature;
The aperture integrated distribution of the uniform ultra micro mesoporous activated carbon of the preparation between 0.45 ~ 0.55nm belongs to ultramicropore, compares table Area reaches 840m2/ more than g, up to more than 70%, hydrogen sorption capacity reaches 77cm to microporosity3/ more than g.
2. the preparation method for the detached uniform ultra micro mesoporous activated carbon of gas according to claim 1, it is characterised in that Described semi-coke raw material is that under middle cryogenic conditions, carbonization is obtained by the high-volatile bituminous coal without cohesiveness or weakly caking Relatively low volatile solid carbonaceous product.
3. the preparation method for the detached uniform ultra micro mesoporous activated carbon of gas according to claim 1, it is characterised in that Described assistant activator is by 1 ~ 30% hydrogen peroxide, KNO3, 1 ~ 5wt% dodecylbenzene sodium sulfonate ethanol solution composition, in mass ratio 4:5:3 proportions.
4. the preparation method for the detached uniform ultra micro mesoporous activated carbon of gas according to claim 1, it is characterised in that The condition determination of the maximum adsorption capacity of described hydrogen is 25 DEG C, adsorptive pressure 11.4MPa.
5. it is a kind of to be used for the detached uniform ultra micro mesoporous activated carbon of gas, it is characterised in that the uniform ultra micro mesoporous activated carbon is root According to any one of claim 1 ~ 4 for the detached uniform ultra micro mesoporous activated carbon of gas preparation method prepared by it is uniform super Microporous activated carbon.
CN201611060108.5A 2016-11-28 2016-11-28 A kind of uniform ultra micro mesoporous activated carbon and preparation method thereof for gas separation Expired - Fee Related CN106517189B (en)

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CN115461315A (en) * 2020-04-30 2022-12-09 圣戈班石膏板公司 Gypsum-based materials
CN112169762A (en) * 2020-10-27 2021-01-05 山东津挚环保科技有限公司 Pressure swing adsorption hydrogen extraction adsorbent, preparation method and application
CN115282947A (en) * 2022-03-11 2022-11-04 常州大学 Method for preparing high-specific-surface-area metal/activated carbon composite material by using isosorbide residual tar
CN115282947B (en) * 2022-03-11 2023-08-22 常州大学 Method for preparing high specific surface area metal/activated carbon composite material by utilizing isosorbide residual tar

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