CN106345410A - Carbon adsorbent for separating methane/nitrogen and preparation method of carbon adsorbent - Google Patents
Carbon adsorbent for separating methane/nitrogen and preparation method of carbon adsorbent Download PDFInfo
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- CN106345410A CN106345410A CN201610868719.6A CN201610868719A CN106345410A CN 106345410 A CN106345410 A CN 106345410A CN 201610868719 A CN201610868719 A CN 201610868719A CN 106345410 A CN106345410 A CN 106345410A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/105—Removal of contaminants of nitrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/12—Regeneration of a solvent, catalyst, adsorbent or any other component used to treat or prepare a fuel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
Abstract
The invention discloses a carbon adsorbent for separating methane/nitrogen and a preparation method of the carbon adsorbent. An asphalt carbon source and a starch carbon source are taken as raw materials; the raw materials are heated in a nitrogen atmosphere at a temperature of 800-850 DEG C to obtain carbonized materials, and the carbonized materials are treated in a carbon dioxide atmosphere at a temperature of 780-830 DEG C to obtain the carbon adsorbent, wherein a mass ratio of the asphalt carbon source to the starch carbon source is 2:1-1:2. The carbon adsorbent prepared by the preparation method disclosed by the invention can realize methane-adsorbing capacity of 17mL/g<-1> or more and a methane/nitrogen equilibrium separation ratio of 3.1 or more, exhibits efficient CH4/N2 adsorbing and separating performance, and can realize effective separation of methane and nitrogen in pressure swing adsorption, so that the requirement for separating the CH4/N2 through industrial pressure swing adsorption is met, and industrial operation cost is reduced.
Description
Technical field
The invention belongs to gas separation technique field, it is related to a kind of adsorbent for gas separation, particularly one kind is used for first
Alkane and the adsorbent of nitrogen separation, and the preparation method of this adsorbent.
Background technology
Coal bed gas is a kind of and coal deposits association or the mineral resources coexisting, and its key component is ch4, the also a small amount of heavy hydrocarbon of association
Class gas and n2、h2、co2、so2Deng.Compared with fire coal, coal bed gas is cleaner mineral resources and the energy, but is harm
Safety of coal mines, cause harmful source of atmospheric pollution and greenhouse effect.Therefore, separating-purifying methane from mine coal seam gas, for
The effectively utilizes and the environmental conservation that improve coal bed gas are significant.
Due to ch4With n2Kinetic diameter close and at supercritical conditions property similar so as to become coal bed gas composition
In be most difficult to detached system.Therefore, the key developing coal bed gas is ch4/n2Separation, this is also a difficult problem for separation field.
Ch at present4/n2The separation method of admixture of gas mainly has cryogenic distillation process, membrane separation process and pressure swing adsorption
(psa) etc..Equipment is simple, the low superiority of flexible and convenient operation, operation energy consumption because having for pressure swing adsorption, becomes and enjoys weight
Depending on ch4/n2Isolation technics.Its core is the performance of adsorbent, and high efficiency separation adsorbent requirement adsorption capacity is big, segregative line
Number height, low production cost, mechanical strength are good, operation energy consumption is low.
, due to high-specific surface area, good methane adsorption ability is it is considered to be have promising first for carbonaceous class adsorbing material
Alkane is enriched with adsorbent.Cn 103086354a discloses a kind of preparation method of carbon molecular sieve, the carbon molecular sieve prepared in this way
Can be used for concentrating purification methane from coal bed gas.The method be using micropowder shape phenolic resin be raw material, after carbonization again with
Adjust hole agent to carry out carbon laydown and prepare carbon molecular sieve, wherein adjust hole agent to be the organic compound such as benzene,toluene,xylene, cause technique
The problems such as complexity and environmental pollution.Cn 102363117a discloses a kind of special carbon adsorbent of methane in pressure swing adsorption, and this carbon is inhaled
Attached dose adopts coal dust, coal tar, potassium hydroxide, potassium nitrate, Calcium Carbonate and magnesium chloride to be raw material, and composition is complicated although methane is inhaled
Attached capacity reaches 25.0ml/g, but does not refer to the segregation ratio of methane/nitrogen.
Content of the invention
It is an object of the invention to provide a kind of process is simple, the little methane/nitrogen separation carbon adsorbent of pollution, Yi Jisuo
State the preparation method of carbon adsorbent.The carbon adsorbent prepared in the process of the present invention has methane adsorption capacity height, methane/nitrogen divides
From the big advantage of coefficient, it is capable of efficiently separating of methane in pressure swing adsorption and nitrogen.
Methane of the present invention/nitrogen separation carbon adsorbent is with Colophonium carbon source and starch carbon source as raw material, first exists
Under 800～850 DEG C of nitrogen atmosphere, heating obtains carbonized material, and under 780～830 DEG C of carbon dioxide atmosphere, high-temperature process obtains
The carbon adsorbent arriving.
Wherein, in described raw material, Colophonium carbon source is 2: 1～1: 2 with the mass ratio of starch carbon source.
Further, described starch carbon source is the soluble starch such as corn starch, potato starch.
In the present invention, described Colophonium carbon source preferably uses powdered asphalt.
The preparation method of methane of the present invention/nitrogen separation carbon adsorbent be by Colophonium carbon source and starch carbon source according to
2: 1～1: 2 mass ratio is mixed to get pretreated feedstock, is heated to 800～850 DEG C of constant temperature 2～4h, obtains under nitrogen atmosphere
Carbonized material, then carbonized material is warming up to 780～830 DEG C under carbon dioxide atmosphere, constant temperature 6～24h, to prepare carbon adsorbent.
In the above-mentioned preparation method of the present invention, for making material asphalt carbon source mix homogeneously with starch carbon source, preferably can first by
Described Colophonium carbon source is added to the water with starch carbon source mixs homogeneously, and dries and obtains pretreated feedstock, then pretreated feedstock is heated
Carbonization.
Wherein, carbon source and the mass ratio of water are preferably 20: 9～20.
The aqueous mixtures of described Colophonium carbon source and starch carbon source are preferably dried by the present invention at 150～180 DEG C.
And then, in preparation method of the present invention, the process that in described nitrogen atmosphere, carbonized material is prepared in heating is by described pre- place
Reason raw material first under the nitrogen atmosphere of flow velocity 10～30ml/min with the ramp of 3～5 DEG C/min to 400～450 DEG C of constant temperature 2
～4h, then with the ramp of 3～5 DEG C/min to 800～850 DEG C of constant temperature 2～4h to obtain carbonized material.
In preparation method of the present invention, the preparation process of described carbon adsorbent is in flow velocity 10～30ml/ by described carbonized material
With the ramp of 3～5 DEG C/min to 780～830 DEG C under the carbon dioxide atmosphere of min, constant temperature 6～24h, prepared carbon adsorption
Agent.
Wherein, the flow velocity of described carbon dioxide atmosphere is preferably 20ml/min.
The carbon adsorbent that the present invention prepares is to ch4Adsorption capacity can reach 17ml/g-1More than, ch4/n2Balance
Segregation ratio reaches more than 3.0, embodies its efficient ch4/n2Adsorption separation performance, can obviously reduce pressure-variable adsorption and separates ch4/
n2Industry park plan cost.
The preparation method process is simple of the present invention, raw material is cheap, and adopts carbon dioxide activation, both can reduce into
This, can prevent by alkali corrosion again, has low cost, pollutes little feature.
Specific embodiment
Following embodiments are only the preferred technical solution of the present invention, are not used to carry out any restriction to the present invention.For
For those skilled in the art, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made
Any modification, equivalent substitution and improvement etc., should be included within the scope of the present invention.
Embodiment 1
Take asphalt powder 10g, corn starch 10g, add mix homogeneously in 12ml water, be heated to 180 DEG C of drying 15h, obtain pre- place
Reason raw material.Pretreated feedstock is put in pipe reaction stove, in the presence of flow velocity is for the nitrogen of 20ml/min, with 5 DEG C/min's
Ramp keeps after 2h to 450 DEG C, then with the ramp of 5 DEG C/min to 850 DEG C, isothermal reaction 2h, obtain carbonized material.With
The carbon dioxide replacement for 20ml/min for the flow velocity goes out the nitrogen in tubular type reacting furnace, with the ramp of 5 DEG C/min to 830 DEG C,
Isothermal reaction 24h, prepared methane/nitrogen separation carbon adsorbent.
Take the above-mentioned carbon adsorbent of 0.07g, be placed in the nova1200e adsorption instrument of quantachrome company of the U.S., test
Carbon adsorbent is to pure component ch4And n2Adsorption isotherm.After testing, under the conditions of 25 DEG C, 100kpa, described carbon adsorbent
ch4Adsorbance is 22.4cm3/ g, n2Adsorbance is 6.0cm3/ g, ch4/n2Equilibrium separation compares 3.7.
Under same test conditions, replace above-mentioned carbon adsorbent using conventional ball type activated carbon and commercial cocoanut active charcoal, survey
The ch obtaining4Adsorbance is respectively 10.4cm3/ g and 16.1cm3/ g, n2Adsorbance is 3.9cm3/ g and 6.3cm3/ g, ch4/n2Balance
Segregation ratio is respectively 2.7 and 2.6.
By contrast, carbon adsorbent manufactured in the present embodiment not only has high ch4Adsorbance, and have efficient
ch4/n2Equilibrium separation ratio.
Embodiment 2
Take asphalt powder 10g, soluble starch reagent 10g, add mix homogeneously in 12ml water, dry 15h at 180 DEG C, obtain pre- place
Reason raw material；Then it is warmed up to 450 DEG C with 5 DEG C/min in the presence of nitrogen in tube furnace, constant temperature 2h, is then heated up with 5 DEG C/min
To 850 DEG C, constant temperature 2h, obtain carbonized material；Finally, heated up 830 DEG C with 5 DEG C/min in the presence of carbon dioxide, constant temperature 24h, system
Obtain carbon adsorbent.
Under the conditions of 25 DEG C, 100kpa, the ch of this sample4And n2Adsorbance is respectively 17.0cm3/ g and 4.7cm3/ g, ch4/
n2Equilibrium separation is than for 3.6.
Embodiment 3
Take asphalt powder 10g, potato starch 10g, add mix homogeneously in 12ml water, 15h will be dried at 180 DEG C, and obtain pretreatment
Raw material；Then it is warmed up to 450 DEG C with 5 DEG C/min in the presence of nitrogen in tube furnace, constant temperature 2h, then it is warmed up to 5 DEG C/min
850 DEG C, constant temperature 2h, obtain carbonized material；Finally, heated up 830 DEG C with 5 DEG C/min in the presence of carbon dioxide, constant temperature 24h, it is obtained
Carbon adsorbent.
Under the conditions of 25 DEG C, 100kpa, the ch of this sample4And n2Adsorbance is respectively 25.6cm3/ g and 8.5cm3/ g, ch4/
n2Equilibrium separation is than for 3.0.
Embodiment 4
Take asphalt powder 10g, corn starch 10g, add mix homogeneously in 12ml water, dry 15h at 180 DEG C, obtain pretreated feedstock；
Then it is warmed up to 450 DEG C with 5 DEG C/min in the presence of nitrogen in tube furnace, constant temperature 2h, then it is warmed up to 850 DEG C with 5 DEG C/min,
Constant temperature 2h, obtains carbonized material；Finally, heated up 830 DEG C with 5 DEG C/min in the presence of carbon dioxide, constant temperature 6h, prepared carbon adsorption
Agent.
Under the conditions of 25 DEG C, 100kpa, the ch of this sample4And n2Adsorbance is respectively 18.0cm3/ g and 5.3cm3/ g, ch4/
n2Equilibrium separation is than for 3.4.
Embodiment 5
Take asphalt powder 10g, corn starch 10g, add mix homogeneously in 12ml water, dry 15h at 180 DEG C, obtain pretreated feedstock；
Then it is warmed up to 450 DEG C with 5 DEG C/min in the presence of nitrogen in tube furnace, constant temperature 2h, then it is warmed up to 850 DEG C with 5 DEG C/min,
Constant temperature 2h, obtains carbonized material；Finally, heated up 800 DEG C with 5 DEG C/min in the presence of carbon dioxide, constant temperature 24h, prepared carbon adsorption
Agent.
Under the conditions of 25 DEG C, 100kpa, the ch of this sample4And n2Adsorbance is respectively 25.7cm3/ g and 6.9cm3/ g, ch4/
n2Equilibrium separation is than for 3.7.
Embodiment 6
Take asphalt powder 10g, corn starch 10g, add mix homogeneously in 20ml water, dry 24h at 160 DEG C, obtain pretreated feedstock；
Then it is warmed up to 400 DEG C with 3 DEG C/min in the presence of nitrogen in Muffle furnace, constant temperature 4h, then it is warmed up to 800 DEG C with 3 DEG C/min,
Constant temperature 4h, obtains carbonized material；Finally, heated up 830 DEG C with 3 DEG C/min in the presence of carbon dioxide, constant temperature 12h, prepared carbon adsorption
Agent.
Under the conditions of 25 DEG C, 100kpa, the ch of this sample4And n2Adsorbance is respectively 23.1cm3/ g and 7.4cm3/ g, ch4/
n2Equilibrium separation is than for 3.1.
Embodiment 7
Take asphalt powder 10g, corn starch 10g, add mix homogeneously in 12ml water, dry 15h at 180 DEG C, obtain pretreated feedstock；
Then it is warmed up to 450 DEG C with 5 DEG C/min in the presence of nitrogen in tube furnace, constant temperature 2h, then it is warmed up to 850 DEG C with 5 DEG C/min,
Constant temperature 2h, obtains carbonized material；Finally, heated up 780 DEG C with 5 DEG C/min in the presence of carbon dioxide, constant temperature 24h, prepared carbon adsorption
Agent.
Under the conditions of 25 DEG C, 100kpa, the ch of this sample4And n2Adsorbance is respectively 26.2cm3/ g and 7.9cm3/ g, ch4/
n2Equilibrium separation is than for 3.3.
Embodiment 8
Take asphalt powder 13g, corn starch 7g, add mix homogeneously in 12ml water, dry 15h at 180 DEG C, obtain pretreated feedstock；
Then it is warmed up to 450 DEG C with 5 DEG C/min in the presence of nitrogen in Muffle furnace, constant temperature 2h, then it is warmed up to 850 DEG C with 5 DEG C/min,
Constant temperature 2h, obtains carbonized material；Finally, heated up 800 DEG C with 5 DEG C/min in the presence of carbon dioxide, constant temperature 24h, prepared carbon adsorption
Agent.
Under the conditions of 25 DEG C, 100kpa, the ch of this sample4And n2Adsorbance is respectively 21.7cm3/ g and 5.7cm3/ g, ch4/
n2Equilibrium separation is than for 3.8.
Embodiment 9
Take asphalt powder 7g, corn starch 13g, add mix homogeneously in 12ml water, dry 15h at 180 DEG C, obtain pretreated feedstock；
Then it is warmed up to 450 DEG C with 5 DEG C/min in the presence of nitrogen in Muffle furnace, constant temperature 2h, then it is warmed up to 850 DEG C with 5 DEG C/min,
Constant temperature 2h, obtains carbonized material；Finally, heated up 800 DEG C with 5 DEG C/min in the presence of carbon dioxide, constant temperature 24h, prepared carbon adsorption
Agent.
Under the conditions of 25 DEG C, 100kpa, the ch of this sample4And n2Adsorbance is respectively 26.5cm3/ g and 8.7cm3/ g, ch4/
n2Equilibrium separation is than for 3.3.
Embodiment 10
Take asphalt powder 8g, corn starch 12g, add mix homogeneously in 9ml water, dry 20h at 150 DEG C, obtain pretreated feedstock；So
It is warmed up to 450 DEG C with 3 DEG C/min afterwards in the presence of nitrogen in Muffle furnace, constant temperature 2h, then it is warmed up to 830 DEG C with 3 DEG C/min, permanent
Warm 3h, obtains carbonized material；Finally, heated up 800 DEG C with 3 DEG C/min in the presence of carbon dioxide, constant temperature 18h, prepared carbon adsorbent.
Under the conditions of 25 DEG C, 100kpa, the ch of this sample4And n2Adsorbance is respectively 26.0cm3/ g and 8.4cm3/ g, ch4/
n2Equilibrium separation is than for 3.1.
Embodiment 11
Take asphalt powder 9g, corn starch 11g, add mix homogeneously in 20ml water, dry 24h at 180 DEG C, obtain pretreated feedstock；
Then it is warmed up to 430 DEG C with 3 DEG C/min in the presence of nitrogen in Muffle furnace, constant temperature 3h, then it is warmed up to 850 DEG C with 3 DEG C/min,
Constant temperature 4h, obtains carbonized material；Finally, heated up 830 DEG C with 3 DEG C/min in the presence of carbon dioxide, constant temperature 12h, prepared carbon adsorption
Agent.
Under the conditions of 25 DEG C, 100kpa, the ch of this sample4And n2Adsorbance is respectively 24.6cm3/ g and 7.5cm3/ g, ch4/
n2Equilibrium separation is than for 3.3.
Claims (10)
1. methane/nitrogen separation carbon adsorbent, is with Colophonium carbon source and starch carbon source as raw material, first in 800～850 DEG C of nitrogen
Under gas atmosphere, heating obtains carbonized material, the carbon adsorbent that high-temperature process obtains under 780～830 DEG C of carbon dioxide atmosphere；
Wherein, in described raw material, Colophonium carbon source is 2: 1～1: 2 with the mass ratio of starch carbon source.
2. carbon adsorbent according to claim 1, described starch carbon source is corn starch or potato starch.
3. carbon adsorbent according to claim 1, described Colophonium carbon source uses powdered asphalt.
4. the preparation method of methane described in claim 1/nitrogen separation carbon adsorbent, be by Colophonium carbon source and starch carbon source by
Mass ratio according to 2: 1～1: 2 is mixed to get pretreated feedstock, is heated to 800～850 DEG C of constant temperature 2～4h and obtains under nitrogen atmosphere
To carbonized material, it is warming up to 780～830 DEG C under carbon dioxide atmosphere, constant temperature 6～24h prepares carbon adsorbent.
5. preparation method according to claim 4, is characterized in that being added to the water described Colophonium carbon source and starch carbon source mixed
Close uniformly, dry and obtain pretreated feedstock.
6. preparation method according to claim 5, is characterized in that described carbon source is 20: 9～20 with the mass ratio of water.
7. preparation method according to claim 5, is characterized in that described drying temperature is 150～180 DEG C.
8. preparation method according to claim 4, is characterized in that described pretreated feedstock first in flow velocity 10～30ml/
With the ramp of 3～5 DEG C/min to 400～450 DEG C of constant temperature 2～4h under the nitrogen atmosphere of min, then the speed with 3～5 DEG C/min
Rate is warmed up to 800～850 DEG C of constant temperature 2～4h to obtain carbonized material.
9. preparation method according to claim 4, is characterized in that described carbonized material the two of flow velocity 10～30ml/min
With the ramp of 3～5 DEG C/min to 780～830 DEG C under carbonoxide atmosphere, constant temperature 6～24h is obtained carbon adsorbent.
10. preparation method according to claim 9, is characterized in that the flow velocity of described carbon dioxide atmosphere is 20ml/min.
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Cited By (8)
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| CN108057420A (en) * | 2017-12-21 | 2018-05-22 | 煤炭科学技术研究院有限公司 | High-performance cocoanut active charcoal adsorbent for separation of methane/nitrogen and preparation method thereof |
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| CN111604033B (en) * | 2019-02-25 | 2023-04-28 | 威尔资源有限公司 | Adsorbent material and method for treating contaminants |
| CN110354803A (en) * | 2019-07-10 | 2019-10-22 | 大连理工大学 | A kind of separation of methane and the monoblock type composite porous charcoal adsorbent material of nitrogen and preparation method thereof |
| CN110523374A (en) * | 2019-08-09 | 2019-12-03 | 华南理工大学 | A kind of adsorbing separation CH4/N2、C2H6/CH4Rice base granular carbon material and the preparation method and application thereof |
| CN110898800A (en) * | 2019-12-20 | 2020-03-24 | 中国地质科学院郑州矿产综合利用研究所 | Natural clinoptilolite adsorbent and application thereof |
| CN112919461A (en) * | 2021-03-31 | 2021-06-08 | 国家能源集团宁夏煤业有限责任公司 | Preparation method of coal-based activated carbon for nitrogen/methane separation and prepared activated carbon |
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