CN109351333A - A kind of preparation method of the semi-coke base adsorbent for separation of methane/nitrogen - Google Patents
A kind of preparation method of the semi-coke base adsorbent for separation of methane/nitrogen Download PDFInfo
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- 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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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
Abstract
The invention discloses a kind of preparation methods of semi-coke base adsorbent for separation of methane/nitrogen, this method first aoxidizes semi-coke powder using improved Hummers method to obtain oxidation semi-coke powder, then to oxidation semi-coke powder successively carry out hot soarfing from and activation, obtain semi-coke base adsorbent.The present invention is using semi-coke as raw material, successively carry out Hummers method oxidation and hot soarfing from, oxygen-containing functional group is first generated inside semi-coke, so that rear surface of the semi-coke of the smooth densification in script surface Jing Guo oxidation processes layer structure is occurred, then expands the hole of large volume from oxygen-containing functional group is eliminated by hot soarfing, to reach better pore-creating effect, obtained semi-coke base adsorbent pore structure is flourishing, has higher absorption property, can separate CH with efficient absorption4/N2。
Description
Technical field
The invention belongs to adsorbent preparation technical fields, and in particular to a kind of semi-coke base suction for separation of methane/nitrogen
Attached dose of preparation method.
Background technique
Main component has CH in coal bed gas4、CO2And N2, wherein CO2With CH4Molecular physics nature difference is big, and the two is easy to point
From；Coal seam association methane gas (CH4/N2Gaseous mixture) be an important factor for leading to greenhouse effects, while being also that one kind can be used as work
The high heating value clean energy resource of industry raw material, but N2With CH4Physical property it is close, kinetic diameter is close, is not readily separated, how to have
Effect separation CH4And N2Always restrict the bottleneck of concentrate enriching low-concentration coal bed gas development.
Pressure swing adsorption (PSA) becomes standby because having many advantages, such as that easy to operate, investment cost is few, low energy consumption, the period is short
Valued CH4One of isolation technics, and the key of PSA adsorbing separation is adsorbent.Currently, used CH4/N2Separation
Adsorbent mainly active charcoal, zeolite molecular sieve and carbon molecular sieve (CMS) etc., for separating CH4/N2Coal base adsorbent it is usual
It needs by multiple steps such as gangue mixed-forming, charing, activation, gel ageing, room temperature aging, crystallization, washing, drying,
Flow operations are complicated and time-consuming larger, therefore, exploitation separation CH4/N2High-quality adsorbent be urgently to be resolved in gas utilization
Key link.
Semi-coke is one kind at 500~700 DEG C, the high solid product of the fixation carbon content obtained by distillation process.Mesh
Before, about 53,000,000 tons of domestic semi-coke market capacity.Semi-coke powder accounts for about the 10% of semi-coke gross mass, is often considered cheap material processing
Or thrown aside in river, the edge of a field, large quantities of wastings of resources is not only caused, but also dust pollution can be generated.Semi-coke powder was normal in recent years
It is used for ferroalloy coke, calcium carbide reducing agent, blast furnace injection material etc., not only economic benefit is not so good as people's will, does not also fill
The advantages of semi-coke powder is waved in distribution.
Summary of the invention
It is a kind of for separating technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, providing
The preparation method of methane/nitrogen semi-coke base adsorbent.Hummers of this method using semi-coke as raw material, after successively improving
Method oxidation and hot soarfing from, first oxygen-containing functional group is generated inside semi-coke, make the semi-coke of the smooth densification in script surface through peroxidating at
There is layer structure in the rear surface of reason, then expands the hole of large volume, to reach more from oxygen-containing functional group is eliminated by hot soarfing
Good pore-creating effect, obtained semi-coke base adsorbent pore structure is flourishing, has higher absorption property, can be separated with efficient absorption
Methane/nitrogen.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of semi-coke for separation of methane/nitrogen
The preparation method of base adsorbent, which is characterized in that first aoxidize semi-coke powder using improved Hummers method to obtain oxidation semi-coke
Powder, then to oxidation semi-coke powder successively carry out hot soarfing from and activation, obtain semi-coke base adsorbent.
A kind of preparation method of above-mentioned semi-coke base adsorbent for separation of methane/nitrogen, which is characterized in that this method
The following steps are included:
Step 1: semi-coke being successively crushed, being ground and being crossed 45 mesh~60 meshes, then it is dried, obtains semi-coke powder；
Step 2: by semi-coke powder and KMNO obtained in step 14Mixing, is then slowly added dropwise into mixed acid solution and carries out
Heating stirring, then it is poured slowly into 0 DEG C~5 DEG C of H2O2In ice water liquid, mixed solution is obtained；
Step 3: mixed solution obtained in step 2 is once separated by solid-liquid separation, obtained filtrate is successively passed through once
Secondary separation of solid and liquid is carried out again after centrifugation and washing, and obtained filtrate discards supernatant liquid after secondary centrifuging, then uses ether
Solidified, obtains oxidation semi-coke powder through vacuum drying after suction filtration；
Step 4: will obtained in step 3 oxidation semi-coke powder be placed in porcelain boat in air heating carry out hot soarfing from；
Step 5: deionized water is added after the oxidation semi-coke powder in step 4 through hot soarfing from after is mixed with activator, so
After stir to sticky and be not easy flow regime, place into activation furnace and activated, obtain semi-coke base adsorbent.
Using semi-coke as raw material, the Hummers method after the semi-coke powder obtained first to crushing improves aoxidizes the present invention,
Oxygen-containing functional group is generated inside semi-coke, and rear surface of the semi-coke of the smooth densification in script surface Jing Guo oxidation processes is made stratiform knot occur
Then structure carries out hot soarfing from elimination oxygen-containing functional group expands the hole of large volume, to reach more preferable to the semi-coke powder after oxidation
Pore-creating effect, finally activated, obtained semi-coke base adsorbent pore structure is flourishing, has higher absorption property.
A kind of preparation method of above-mentioned semi-coke base adsorbent for separation of methane/nitrogen, which is characterized in that the orchid
Charcoal is that Jurassic Basins in Northwestern China low-disintegration coal is prepared through low temperature distillation.Semi-coke base adsorbent of the present invention prepares waving for raw material semi-coke
Sending out part is 7%~15%, and ash is 5%~20%, is common kind in industry, and materials are convenient, is conducive to the absorption of semi-coke base
The preparation of agent.
A kind of preparation method of above-mentioned semi-coke base adsorbent for separation of methane/nitrogen, which is characterized in that step 1
Described in dry temperature be 105 DEG C, time 2h.It is dried using above-mentioned technological parameter, as far as possible in removing semi-coke powder
Moisture, be conducive to going on smoothly for subsequent semi-coke powder oxidation.
A kind of preparation method of above-mentioned semi-coke base adsorbent for separation of methane/nitrogen, which is characterized in that step 2
Described in semi-coke powder and KMNO4Mass ratio be 1:(5~7), the mixed acid solution by mass concentration be 95% H2SO4Solution
The H for being 85% with mass concentration3PO4Solution is according to (7~9): 1 volume ratio is prepared and is obtained.Using the semi-coke powder of above-mentioned mass ratio
And the mixed acid solution of oxidant and above-mentioned composition, so that the oxidation of semi-coke powder is more abundant, oxygen-containing functional group increases and semi-coke powder
The layer structure that surface occurs is obvious, and the absorption property for obtaining semi-coke base adsorbent is good, and adsorbance is high.
A kind of preparation method of above-mentioned semi-coke base adsorbent for separation of methane/nitrogen, which is characterized in that step 2
Described in the temperature of heating be 50 DEG C, time of the stirring is 10h~12h, the H2O2Ice water liquid is by H2O2Solution and ice water
Composition, the H2O2H in solution2O2Volumetric concentration be 30%~40%.Above-mentioned heating temperature and mixing time are conducive to semi-coke
Each ingredient is sufficiently mixed the speed for uniformly improving oxidation reaction in powder oxidation system, keeps semi-coke powder fully oxidized, oxygen-containing function
Group is richer, to help the generation of semi-coke base adsorbent porous structure.
A kind of preparation method of above-mentioned semi-coke base adsorbent for separation of methane/nitrogen, which is characterized in that step 3
Described in be once separated by solid-liquid separation and the method for secondary separation of solid and liquid was 40 mesh~50 meshes, the vacuum drying temperature is
30 DEG C~40 DEG C, the time is 10h~12h, and the time being once centrifuged is 12h, and the time of secondary centrifuging is 4h, primary to be centrifuged
Revolving speed with secondary centrifuging is 7000rpm.Using 40 mesh~50 meshes method be separated by solid-liquid separation, using above-mentioned primary
The revolving speed and centrifugation time of centrifugation and secondary centrifuging are conducive to improve the efficiency being separated by solid-liquid separation, and shorten preparation time.
A kind of preparation method of above-mentioned semi-coke base adsorbent for separation of methane/nitrogen, which is characterized in that step 3
Described in wash the detergent used and be followed successively by water, volumetric concentration as 30% hydrochloric acid solution and dehydrated alcohol, and use every kind
40 mesh~50 meshes were both needed to after the detergent washing.Above-mentioned washing and sieving can be mentioned except the impurity in deoxidation semi-coke powder
The high rate of recovery of oxidation semi-coke powder.
A kind of preparation method of above-mentioned semi-coke base adsorbent for separation of methane/nitrogen, which is characterized in that step 4
Described in heating temperature be 280 DEG C~320 DEG C, soaking time be 10min~12min.Above-mentioned heating temperature and soaking time
Facilitate semi-coke hot soarfing and open and remove from oxidation semi-coke powder surface layer structure more completely, is facilitated, generates more holes
Structure.
A kind of preparation method of above-mentioned semi-coke base adsorbent for separation of methane/nitrogen, which is characterized in that step 5
Described in activator be KOH, the mass ratio of the KOH and oxidation semi-coke powder through hot soarfing from after is (3~6): 1, the activation
Temperature be 500 DEG C~800 DEG C, the time be 30min~90min.Above-mentioned activation method by activator KOH through hot soarfing from after
Oxidation semi-coke powder internal structure carry out pore-creating, temperature requirement is low and time-consuming few, has prepared semi-coke base adsorbent
Surface chemistry abundant.
Compared with the prior art, the present invention has the following advantages:
1, the semi-coke of the invention high value added utilization to have not yet been reached at this stage is raw material, in common adsorbents preparation process
On the basis of raw material semi-coke is improved first after Hummers method oxidation and removing, pass through improved Hummers method aoxidize
Oxygen-containing functional group is generated inside semi-coke, and rear surface of the semi-coke of the smooth densification in script surface Jing Guo oxidation processes is made stratiform occur
Structure, then by carrying out hot soarfing from elimination oxygen-containing functional group expands the hole of large volume, to reach more to the semi-coke after oxidation
Good pore-creating effect, obtained semi-coke base adsorbent pore structure is flourishing, has higher absorption property.
2, preparation method process flow of the invention is simple, eliminates the processes such as the charing for preparing conventional adsorbent, crystallization,
Using chemical activation method by chemical reagent pore-creating in semi-coke internal structure, temperature requirement is low and time-consuming few, saves big
Amount cost and time, resulting semi-coke base adsorbent have the advantages that specific surface area height and iodine absorption number are big, can be with efficient absorption
Separate CH4/N2, separation with higher has large-scale separation CH4And N2Potentiality.
3, the present invention using be considered cheap material processing or by throw aside in river, the edge of a field semi-coke powder preparation semi-coke adsorb
Agent avoids the waste of resource and the pollution to environment, has given full play to the value of semi-coke powder, and it is economical to reduce that increased production cost
Benefit realizes the two-win of environmental protection and solid waste recycling.
Below by embodiment, the present invention is described in further detail.
Specific embodiment
The specific surface area and pore structure for the semi-coke base adsorbent being prepared in 1~embodiment of the embodiment of the present invention 3 are tested
The ASAP2020 type physical adsorption appearance for being all made of Micromeritics company is measured, and iodine sorption value is living as qualitative characterization
Property charcoal microcellular structure index, be measured according to the method in GB/T7702.7-2008, equilibrium adsorption capacity use Bei Shide instrument
The 3H-2000PH2 type high-temperature high-pressure adsorption instrument of device scientific & technical corporation is measured.
Embodiment 1
Semi-coke used in the present embodiment originates from northern Shensi, is prepared for Jurassic Basins in Northwestern China low-disintegration coal through low temperature distillation,
The composition analysis result and elemental analysis result of semi-coke are shown in Table down 1 and the following table 2 respectively.
The composition analysis result of 1 semi-coke of table
The elemental analysis result of 2 semi-coke of table
* it indicates to be calculated containing constituent content by minusing.
The present embodiment the following steps are included:
Step 1: semi-coke being successively crushed, being ground and being crossed 60 meshes, then it is dried, obtains semi-coke powder；It is described dry
Dry temperature is 105 DEG C, time 2h；
Step 2: by the KMNO of semi-coke powder and 18g obtained in 3g step 14Mixing, is then slowly added dropwise molten into nitration mixture
Liquid is simultaneously heated to 50 DEG C of magnetic agitation 12h, then is poured slowly into the H that 400mL temperature is 5 DEG C2O2In ice water liquid, mixed solution is obtained；
The H that the mixed acid solution is 95% by 360mL mass concentration2SO4The H that solution and 40mL mass concentration are 85%3PO4Solution is matched
It makes and obtains；The H2O2Ice water liquid by 3mL H2O2Solution and 397mL ice water composition, the H2O2H in solution2O2Volumetric concentration
It is 30%；
It is once separated by solid-liquid separation Step 3: mixed solution obtained in step 2 is crossed 50 meshes, obtained filtrate exists
Revolving speed carries out primary centrifugation 12h under conditions of being 7000rpm, then successively use 50mL water, 50mL volumetric concentration for 30%
Hydrochloric acid solution and 50mL dehydrated alcohol wash 6 times, and using being both needed to 50 meshes after every kind of detergent washing, wash for the 6th time
Secondary separation of solid and liquid is carried out after washing sieving, obtained filtrate discards after secondary centrifuging 4h under conditions of revolving speed is 7000rpm
Then clear liquid is solidified with ether, vacuum drying 11h obtains oxidation semi-coke powder under conditions of temperature is 35 DEG C after suction filtration；
It is heated to 300 DEG C of heat preservations in air Step 4: oxidation semi-coke powder obtained in step 3 is placed in porcelain boat
11min carry out hot soarfing from；
Step 5: after the oxidation semi-coke powder in 2g step 4 through hot soarfing from after is mixed with the KOH of 12g be added 30mL go from
Sub- water, then magnetic agitation 2h is not easy flow regime to sticky, places into activation furnace and is activated, and obtains the absorption of semi-coke base
Agent；The activation carries out under nitrogen protection, and the flow of the nitrogen is 40L/min, the detailed process of the activation are as follows: with 25
DEG C it is initial temperature, is first warming up to 600 DEG C with the rate of 5 DEG C/min and keeps the temperature 60min, then through cooled to room temperature.
Through detecting, the iodine sorption value for the semi-coke base adsorbent that the present invention is prepared is 917.41mg/g, and specific surface area is
1132.60m2/ g, the CH of semi-coke base adsorbent under conditions of temperature is 303K, pressure is 3MPa4Saturated extent of adsorption is
3.584mmol/g CH4And N2Separation be 3.16, have large-scale separation CH4/N2Potentiality.
Embodiment 2
The present embodiment the following steps are included:
Step 1: semi-coke being successively crushed, being ground and being crossed 45 meshes, then it is dried, obtains semi-coke powder；It is described dry
Dry temperature is 105 DEG C, time 2h；The semi-coke is that Jurassic Basins in Northwestern China low-disintegration coal is prepared through low temperature distillation, described
The fugitive constituent of semi-coke is 11.88%, ash 9.89%；
Step 2: by the KMNO of semi-coke powder and 15g obtained in 3g step 14Mixing, is then slowly added dropwise molten into nitration mixture
Liquid is simultaneously heated to 50 DEG C of magnetic agitation 10h, then is poured slowly into the H that 400mL temperature is 0 DEG C2O2In ice water liquid, mixed solution is obtained；
The H that the mixed acid solution is 95% by 356mL mass concentration2SO4The H that solution and 44mL mass concentration are 85%3PO4Solution is matched
It makes and obtains；The H2O2Ice water liquid by 3mL H2O2Solution and 397mL ice water composition, the H2O2H in solution2O2Volumetric concentration
It is 40%；
It is once separated by solid-liquid separation Step 3: mixed solution obtained in step 2 is crossed 40 meshes, obtained filtrate exists
Revolving speed carries out primary centrifugation 10h under conditions of being 8000rpm, then successively use 50mL water, 50mL volumetric concentration for 30%
Hydrochloric acid solution and 50mL dehydrated alcohol wash 6 times, and using being both needed to 40 meshes after every kind of detergent washing, wash for the 6th time
Secondary separation of solid and liquid is carried out after washing sieving, obtained filtrate discards after secondary centrifuging 4h under conditions of revolving speed is 7000rpm
Then clear liquid is solidified with ether, vacuum drying 12h obtains oxidation semi-coke powder under conditions of temperature is 30 DEG C after suction filtration；
It is heated to 320 DEG C of heat preservations in air Step 4: oxidation semi-coke powder obtained in step 3 is placed in porcelain boat
10min carry out hot soarfing from；
Step 5: after the oxidation semi-coke powder in 2g step 4 through hot soarfing from after is mixed with the KOH of 10g be added 30mL go from
Sub- water, then magnetic agitation 2h is not easy flow regime to sticky, places into activation furnace and is activated, and obtains the absorption of semi-coke base
Agent；The activation carries out under nitrogen protection, and the flow of the nitrogen is 40L/min, the detailed process of the activation are as follows: with 25
DEG C it is initial temperature, is first warming up to 800 DEG C with the rate of 5 DEG C/min and keeps the temperature 30min, then through cooled to room temperature.
Through detecting, the iodine sorption value for the semi-coke base adsorbent that the present invention is prepared is 876.53mg/g, and specific surface area is
1039.75m2/ g, the CH of semi-coke base adsorbent under conditions of temperature is 303K, pressure is 3MPa4Saturated extent of adsorption is
2.987mmol/g CH4And N2Separation be 3.09, have large-scale separation CH4/N2Potentiality.
Embodiment 3
Step 1: semi-coke being successively crushed, being ground and being crossed 50 meshes, then it is dried, obtains semi-coke powder；It is described dry
Dry temperature is 105 DEG C, time 2h；The semi-coke is that Jurassic Basins in Northwestern China low-disintegration coal is prepared through low temperature distillation, described
The fugitive constituent of semi-coke is 10.76%, ash 12.34%；
Step 2: by the KMNO of semi-coke powder and 21g obtained in 3g step 14Mixing, is then slowly added dropwise molten into nitration mixture
Liquid is simultaneously heated to 50 DEG C of magnetic agitation 11h, then is poured slowly into the H that 400mL temperature is 2 DEG C2O2In ice water liquid, mixed solution is obtained；
The H that the mixed acid solution is 95% by 315mL mass concentration2SO4The H that solution and 45mL mass concentration are 85%3PO4Solution is matched
It makes and obtains；The H2O2Ice water liquid by 3mL H2O2Solution and 397mL ice water composition, the H2O2H in solution2O2Volumetric concentration
It is 32%；
It is once separated by solid-liquid separation Step 3: mixed solution obtained in step 2 is crossed 48 meshes, obtained filtrate exists
Revolving speed carries out primary centrifugation 10h under conditions of being 8000rpm, then successively use 50mL water, 50mL volumetric concentration for 30%
Hydrochloric acid solution and 50mL dehydrated alcohol wash 6 times, and using being both needed to 48 meshes after every kind of detergent washing, wash for the 6th time
Secondary separation of solid and liquid is carried out after washing sieving, obtained filtrate discards after secondary centrifuging 4h under conditions of revolving speed is 7000rpm
Then clear liquid is solidified with ether, vacuum drying 10h obtains oxidation semi-coke powder under conditions of temperature is 40 DEG C after suction filtration；
It is heated to 280 DEG C of heat preservations in air Step 4: oxidation semi-coke powder obtained in step 3 is placed in porcelain boat
12min carry out hot soarfing from；
Step 5: after the oxidation semi-coke powder in 2g step 4 through hot soarfing from after is mixed with the KOH of 6g be added 30mL go from
Sub- water, then magnetic agitation 2h is not easy flow regime to sticky, places into activation furnace and is activated, and obtains the absorption of semi-coke base
Agent；The activation carries out under nitrogen protection, and the flow of the nitrogen is 40L/min, the detailed process of the activation are as follows: with 25
DEG C it is initial temperature, is first warming up to 500 DEG C with the rate of 5 DEG C/min and keeps the temperature 90min, then through cooled to room temperature.
Through detecting, the iodine sorption value for the semi-coke base adsorbent that the present invention is prepared is 876.53mg/g, and specific surface area is
1142.53m2/ g, the CH of semi-coke base adsorbent under conditions of temperature is 303K, pressure is 3MPa4Saturated extent of adsorption is
3.087mmol/g CH4And N2Separation be 3.12, have large-scale separation CH4/N2Potentiality.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (10)
1. a kind of preparation method of the semi-coke base adsorbent for separation of methane/nitrogen, which is characterized in that first using improved
Semi-coke powder is aoxidized to obtain oxidation semi-coke powder by Hummers method, then to oxidation semi-coke powder successively carry out hot soarfing from and activation, obtain
Semi-coke base adsorbent.
2. a kind of preparation method of semi-coke base adsorbent for separation of methane/nitrogen according to claim 1, feature
It is, method includes the following steps:
Step 1: semi-coke being successively crushed, being ground and being crossed 45 mesh~60 meshes, then it is dried, obtains semi-coke powder；
Step 2: by semi-coke powder and KMNO obtained in step 14Mixing, is then slowly added dropwise into mixed acid solution and is heated
Stirring, then it is poured slowly into 0 DEG C~5 DEG C of H2O2In ice water liquid, mixed solution is obtained；
Step 3: mixed solution obtained in step 2 is once separated by solid-liquid separation, obtained filtrate is successively once centrifuged
With secondary separation of solid and liquid is carried out after washing again, obtained filtrate discards supernatant liquid after secondary centrifuging, is then carried out with ether
Solidify, obtains oxidation semi-coke powder through vacuum drying after suction filtration；
Step 4: will obtained in step 3 oxidation semi-coke powder be placed in porcelain boat in air heating carry out hot soarfing from；
Step 5: deionized water is added after the oxidation semi-coke powder in step 4 through hot soarfing from after is mixed with activator, then stir
It mixes to sticky and is not easy flow regime, place into activation furnace and activated, obtain semi-coke base adsorbent.
3. a kind of preparation method of semi-coke base adsorbent for separation of methane/nitrogen according to claim 1 or 2,
It is characterized in that, the semi-coke is that Jurassic Basins in Northwestern China low-disintegration coal is prepared through low temperature distillation.
4. a kind of preparation method of semi-coke base adsorbent for separation of methane/nitrogen according to claim 2, feature
It is, dry temperature described in step 1 is 105 DEG C, time 2h.
5. a kind of preparation method of semi-coke base adsorbent for separation of methane/nitrogen according to claim 2, feature
It is, semi-coke powder described in step 2 and KMNO4Mass ratio be 1:(5~7), the mixed acid solution by mass concentration be 95%
H2SO4The H that solution and mass concentration are 85%3PO4Solution is according to (7~9): 1 volume ratio is prepared and is obtained.
6. a kind of preparation method of semi-coke base adsorbent for separation of methane/nitrogen according to claim 2, feature
It is, the temperature of heating described in step 2 is 50 DEG C, and the time of the stirring is 10h~12h, the H2O2Ice water liquid by
H2O2Solution and ice water composition, the H2O2H in solution2O2Volumetric concentration be 30%~40%.
7. a kind of preparation method of semi-coke base adsorbent for separation of methane/nitrogen according to claim 2, feature
It is, is once separated by solid-liquid separation described in step 3 and the method for secondary separation of solid and liquid was 40 mesh~50 meshes, the vacuum
Dry temperature is 30 DEG C~40 DEG C, and the time is 10h~12h, and the time being once centrifuged is 12h, the time of secondary centrifuging
For 4h, the revolving speed of primary centrifugation and secondary centrifuging is 7000rpm.
8. a kind of preparation method of semi-coke base adsorbent for separation of methane/nitrogen according to claim 2, feature
It is, the detergent used is washed described in step 3 and is followed successively by water, volumetric concentration as 30% hydrochloric acid solution and dehydrated alcohol,
And 40 mesh~50 meshes were both needed to after washing using every kind of detergent.
9. a kind of preparation method of semi-coke base adsorbent for separation of methane/nitrogen according to claim 2, feature
It is, the temperature of heating described in step 4 is 280 DEG C~320 DEG C, and soaking time is 10min~12min.
10. a kind of preparation method of semi-coke base adsorbent for separation of methane/nitrogen according to claim 2, special
Sign is, activator described in step 5 is KOH, the mass ratio of the KOH and the oxidation semi-coke powder through hot soarfing from after for (3~
6): 1, the temperature of the activation is 500 DEG C~800 DEG C, and the time is 30min~90min.
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