CN105312026B - Normal temperature methane efficient absorption material - Google Patents
Normal temperature methane efficient absorption material Download PDFInfo
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- CN105312026B CN105312026B CN201410324816.XA CN201410324816A CN105312026B CN 105312026 B CN105312026 B CN 105312026B CN 201410324816 A CN201410324816 A CN 201410324816A CN 105312026 B CN105312026 B CN 105312026B
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract
The present invention relates to a kind of normal temperature methane efficient absorption material and preparation method.The material characteristics are that on the active carbon ceramic being made based on activated carbon and molecular sieve growth in situ is prepared containing transition-metal FeIII、ZnII、CuII、NiII、CoIIIMetal organic framework composite.Its preparation method is characterised by Fe3+、Zn2+、Cu2+、Ni2+、Co3+Chlorate, the one or more of sulfate and high-specific surface area cocos active carbon, Y type molecular sieve, attapulgite, kaolin, methylcellulose dry-mixed ball milling in proportion, add after a certain amount of water wet mixing, through kneading, vacuum pugging, ageing, extrusion molding, dry in the shade, microwave irradiation sizing after obtain the active carbon ceramic moulding material containing transition metal, the moulding material is immersed in a certain proportion of organic solvent, deprotonation alkali and organic carboxyl acid part mixed liquor again, with（120~180）6 ~ 24h is reacted at DEG C, micro-wave vacuum after separation of solid and liquid, washing obtains metal organic framework active carbon ceramic composite.The material specific surface area is big, hole is flourishing, compression strength is high, big with methane adsorption capacity, CH4/N2And CH4/CO2The features such as separation is high, is widely used in the fields such as the separation of methane pressure-variable adsorption, low-concentration methane recovery.
Description
Technical field
The present invention relates to a kind of normal temperature methane efficient absorption material and preparation method, material is applied to methane pressure-variable adsorption point
From fields such as, low-concentration methane recovery, methane-rich.
Technical background
Methane is the main component in device in Gas（95%）, it is most common pernicious gas in colliery.Temperature produced by methane
Room effect is 21 times of carbon dioxide, and density ratio air is small, is gathered in above coal mine roadway, it is possible to decrease oxygen content causes in air
Asphyxia, easily sets off an explosion at concentration 5~16%.China's coal bed gas reserves are 36.8 tcms, equivalent to 45,000,000,000 tons marks
Quasi- coal or 35,000,000,000 tons of standard oils, comprehensive development and utilization coal bed gas have very great social effect and economic benefit.Due to coal
Extraction technical finesse, most low concentration gas gas are used mine gas more（Methane content is less than 10%）Often do not have after extraction
There is method effectively to be utilized, typically directly discharge is with air, causing great environmental pollution and energy waste.
Current low concentration gas gas（Coal bed gas）, casing-head gas, biogas, landfill gas or other source it is low-quality
The method of purification of methane gas mainly has the methods such as low-temperature deep separation, UF membrane, adsorbing separation and absorption and separation.Wherein adsorb
Separation concentration purification methane technology is because its economic flexibly, cleaning is friendly, adaptability is good as one of technology paid close attention to the most.Low product
It is methane, nitrogen and carbon dioxide that matter methane gas, which is mainly constituted, and wherein methane nitrogen separation is that current adsorbing separation purification is natural
The difficult point of gas.
The key of low-quality methane gas separating-purifying is the exploitation of adsorbent, various commercialization adsorbent such as molecular sieves
13X, zeolite, activated carbon, carbon molecular sieve and novel molecular sieve ETS-4, DDR etc. attempt to be applied to methane separation purification.Charcoal base
Sorbing material is commonly used non-polar material in current low-quality methane gas adsorption separation technology, cheap extensively with raw material
The features such as being easy to get, with larger methane/nitrogen and methane/oxygen separation, but existing acticarbon is when using
The circulating air scale of construction is big, and the low shortcoming of efficiency is easily influenceed by water content, and pure carbon easily has the hidden danger of blast；Zeolite molecular sieve class
Sorbing material especially clinoptilolite has preferable methane nitrogen separation, but there is the shortcomings of adsorption capacity is low.Except this
Outside, its unique hole size of titanium silicon molecular sieve ETS-4-4, it is believed that be preferable methane purification material, but be highly prone in source of the gas
Impurity effect and inactivate.With abundant and the functional innovation research, metal organic framework material of sorbing material species in recent years
Material（MOFs）Because of its pore structure high-sequential, structure has flexibility, and the controllable advantage of the functional group of hole size and hole surface is inhaled
The extensive concern on attached boundary.But its metal-organic framework materials（MOFs）Synthesize cost higher, it is difficult to be molded, be unfavorable for extensive work
Industry is promoted.
The content of the invention
The present invention is a kind of normal temperature methane efficient absorption material and preparation method, and material is applied to methane pressure-variable adsorption point
From fields such as, low-concentration methane recovery, methane-rich.The material appearance can be cellular, column, it is characterised in that：Coconut husk
The wt% of activated carbon content 45 ~ 65, the wt% of Y molecular sieve content 10 ~ 18, attapulgite 20 ~ 25wt% of content, 5 ~ 8wt% of kaolin, gold
Belong to organic backbone（MOFs）The wt% of material 3 ~ 10, compression strength> 0.8MPa.Preparation method characteristic is：By Fe3+、Zn2+、Cu2 +、Ni2+、Co3+Chlorate, sulfate one or more with high-specific surface area cocos active carbon, Y type molecular sieve, concave convex rod
Soil, kaolin, methylcellulose are dry-mixed in proportion to be milled to 300~400 mesh, a certain amount of water wet mixing is added, through kneading, vacuum
Pugging, ageing, extrusion molding, dry in the shade, obtain the active carbon ceramic moulding material containing transition metal after microwave irradiation sizing, then will
The moulding material is immersed in a certain proportion of organic solvent, deprotonation alkali and organic carboxyl acid part mixed liquor, in 120~180 DEG C
12 ~ 24h of lower reaction, micro-wave vacuum is obtained after separation of solid and liquid, washing.What the material was made based on activated carbon and molecular sieve
Growth in situ is prepared containing transition-metal Fe on active carbon ceramicIII、ZnII、CuII、NiII、CoIIIMetal organic framework answer
Condensation material, specific surface area is big, hole is flourishing, compression strength is high, big with methane adsorption capacity, CH4/N2And CH4/CO2Segregative line
The features such as number is high.
Normal temperature methane efficient absorption material proposed by the present invention and preparation method, mainly including herein below：
A kind of normal temperature methane efficient absorption material, including the wt% of coconut activated carbon content 45 ~ 65, Y molecular sieve content 10 ~ 18
Wt%, attapulgite 20 ~ 25wt% of content, 5 ~ 8wt% of kaolin, metal organic framework（MOFs）The wt% of material 3 ~ 10, compression strength
> 0.8MPa。
Described cocoanut active charcoal particle diameter is 300 ~ 400 mesh, and iodine number is 1400~2600 mg/g, and specific surface area is 1700
~3000 m2/ g, ash content< 2 wt%.
Described metal organic framework（MOFs）Material is loaded in the Fe in active carbon ceramic3+、Zn2+、Cu2+、Ni2+、Co3+'s
Chlorate, sulfate are made corresponding with situ under the conditions of organic solvent, deprotonation alkali and organic carboxyl acid part Hybrid Heating
FeIII、ZnII、CuII、NiII、CoIIIComplexed metal organic framework material.
Described organic solvent is formic acid, acetic acid, methanol, ethanol, ethyl acetate, one or more mixing among DMF.
Described deprotonation alkali is one or more mixing in triethylamine, monoethanolamine, pyridine, imidazoles.
Described organic carboxyl acid part：Bidentate ligand succinic acid, terephthalic acid (TPA), tartaric acid, biphenyl dicarboxylic acid, 3- pyridines
Sulfonic acid and the one or more in tridentate ligand trimesic acid, 2,5- pyridinedicarboxylic acids.
A kind of preparation method of normal temperature methane efficient absorption material：By Fe3+、Zn2+、Cu2+、Ni2+、Co3+Chlorate, sulphur
The one or more of hydrochlorate are pressed with high-specific surface area cocos active carbon, Y type molecular sieve, attapulgite, kaolin, methylcellulose
Ratio is dry-mixed to be milled to 300~400 mesh, a certain amount of water wet mixing is added, through kneading, vacuum pugging, ageing, extrusion molding, the moon
The active carbon ceramic moulding material containing transition metal is obtained after dry, microwave irradiation sizing, then moulding material immersion is necessarily compared
Example organic solvent, deprotonation alkali and organic carboxyl acid part mixed liquor in, at 120~180 DEG C react 6 ~ 24h, separation of solid and liquid,
Micro-wave vacuum is obtained after washing.
Reclaimed suitable for the separation of methane pressure-variable adsorption, low-concentration methane, methane adsorption capacity（25 DEG C, 36 atm）>170
V/V,（25 DEG C, 1 atm）>35 mL/g, CH4/N2Separation>7 and CH4/CO2Separation>12.
Outward appearance can be cellular, column.
The metal organic framework of methane adsorption proposed by the present invention-active carbon ceramic composite, advantage is as follows：1）Material
For moulding material, more conducively compression strength height, industrial applications；3）Effectively compound MOFs materials, significantly lift methane separation
Coefficient；2）Overcome traditional pure charcoal methylmethane sorbing material separation it is low, it is inflammable the shortcomings of； 4）Carried using specific area raw material of wood-charcoal
MOFs material decentralization is risen, traditional MOFs material specific surface areas are overcome lowly, not the shortcomings of easy-formation；5）Composite methane
Adsorption capacity is big, and methane separation coefficient is high, compares pure MOFs material costs lower.
Embodiment
The present invention is further illustrated below by way of example：
Embodiment 1
By the g of cocoanut active charcoal 500（The mg/g of iodine number 1700）, the g of Y molecular sieve 100, the g of attapulgite 200, kaolin 50
G, the g of methylcellulose 10 are milled to 300~400 mesh, add 800 mL water wet methods and mediate 0.5~1h, -0.09MPa vacuum puggings
3~5h, is aged 6~12h, and extrusion molding is made under the thick embryo of Alveolate activated carbon ceramics, thick embryo normal temperature and dried in the air in vertical extruder
24~48h is after sizing under 550 DEG C of vacuum of microwave irradiation（The kw/kg of microwave irradiation density 2.0）It is made and is lived without transition metal
Property charcoal ceramics.
Transition metal active charcoal ceramic material compression strength should be free of>0.9Mpa, methane adsorption capacity（25 DEG C, 36
atm）110 V/V,（25 DEG C, 1 atm）15 mL/g, CH4/N2Separation 4.2 and CH4/CO2Separation 8.3.
Embodiment 2
By the g of cocoanut active charcoal 500（The mg/g of iodine number 1700）, the g of Y molecular sieve 100, the g of attapulgite 200, kaolin 50
G, the g of methylcellulose 10, the g of zinc chloride 40 are milled to 300~400 mesh, add 800 mL water wet methods and mediate 0.5~1h ,-
0.09MPa 3~5h of vacuum pugging, are aged 6~12h, and Alveolate activated carbon ceramics are made slightly in extrusion molding in vertical extruder
24~48h is dried in the air under embryo, thick embryo normal temperature after sizing under 550 DEG C of vacuum of microwave irradiation（The kw/kg of microwave irradiation density 2.0）It is made
Active carbon ceramic containing Zn.
This contains Zn active carbon ceramic compression strength>0.8Mpa, methane adsorption capacity（25 DEG C, 36 atm）130 V/V,（25
DEG C, 1 atm）21mL/g, CH4/N2Separation 4.4 and CH4/CO2Separation 8.7.
Embodiment 3
By the g of cocoanut active charcoal 500（The mg/g of iodine number 1700）, the g of Y molecular sieve 100, the g of attapulgite 200, kaolin 50
G, the g of methylcellulose 10, the g of zinc chloride 25 are milled to 300~400 mesh, add 800 mL water wet methods and mediate 0.5~1h ,-
0.09MPa 3~5h of vacuum pugging, are aged 6~12h, and the thick embryo of column-shaped active carbon ceramics is made in extrusion molding in vertical extruder,
24~48h is dried in the air under thick embryo normal temperature after sizing under 550 DEG C of vacuum of microwave irradiation（The kw/kg of microwave irradiation density 2.0）It is made and contains
Zn active carbon ceramics.
By column active carbon ceramic containing Zn material 800g immerse 400 mL ethanol, 400mL water, 400mLDMF mixed solvents,
Add in 40 g triethylamines and 20 g trimesic acid mixed liquors, it is solid in pocket type plate centrifuge in reacting 12h at 140 DEG C
Liquid is separated, and after being washed with 1000 mL ethanol, microwave vacuum（- 0.09MPa, the kw/kg of microwave irradiation density 0.8））80 DEG C are done
Dry 0.5h is obtained.
This contains Zn active carbon ceramic MOFs composite compression strength>0.8Mpa, methane adsorption capacity（25 DEG C, 36
atm）150 V/V,（25 DEG C, 1 atm）26mL/g, CH4/N2Separation 5.4 and CH4/CO2Separation 7.7.
Embodiment 4
By the g of cocoanut active charcoal 500（The mg/g of iodine number 1700）, the g of Y molecular sieve 100, the g of attapulgite 200, kaolin 50
G, the g of methylcellulose 10, the g of iron chloride 36 are milled to 300~400 mesh, add 800 mL water wet methods and mediate 0.5~1h ,-
0.09MPa 3~5h of vacuum pugging, are aged 6~12h, and the thick embryo of column-shaped active carbon ceramics is made in extrusion molding in vertical extruder,
24~48h is dried in the air under thick embryo normal temperature after sizing under 550 DEG C of vacuum of microwave irradiation（The kw/kg of microwave irradiation density 2.0）It is made and contains
Fe active carbon ceramics.
By column active carbon ceramic containing Fe material 800g immerse 300 mL ethanol, 500mL water, 400mLDMF mixed solvents,
Add in 56 g monoethanolamines and 80 g tartaric acid mixed liquors, in reacting 8 h at 180 DEG C, solid-liquid divides in pocket type plate centrifuge
From, and after being washed with 1000 mL ethanol, microwave vacuum（- 0.09MPa, the kw/kg of microwave irradiation density 0.8））80 DEG C of dryings
0.5h is obtained.
This contains Fe active carbon ceramic MOFs composite compression strength>0.8Mpa, methane adsorption capacity（25 DEG C, 36
atm）163 V/V,（25 DEG C, 1 atm）32 mL/g, CH4/N2Separation 6.4 and CH4/CO2Separation 6.8.
Embodiment 5
By the g of cocoanut active charcoal 500（The mg/g of iodine number 1700）, the g of Y molecular sieve 100, the g of attapulgite 200, kaolin 50
G, the g of methylcellulose 10, the g of ferric sulfate 16, the g of nickel chloride 30 are milled to 300~400 mesh, add 800 mL water wet methods and mediate
0.5~1h, -0.09MPa 3~5h of vacuum pugging, are aged 6~12h, and column-shaped active carbon is made in extrusion molding in vertical extruder
24~48h is dried in the air under ceramic thick embryo, thick embryo normal temperature after sizing under 550 DEG C of vacuum of microwave irradiation（The kw/ of microwave irradiation density 2.0
kg）Active carbon ceramic containing Fe-Ni is made.
Column active carbon ceramic containing Fe-Ni material 800g is immersed into 400 mL ethanol, 300mL water, 500mLDMF mixing is molten
Agent, is added in 30 g imidazoles and 90 g succinic acid mixed liquors, in reacting 8 h at 180 DEG C, the solid-liquid in pocket type plate centrifuge
Separation, and after being washed with 500 mL ethanol+500mL acetic acid, microwave vacuum（- 0.09MPa, the kw/kg of microwave irradiation density 0.8））
80 DEG C of dry 0.5h are obtained.
This contains Fe-Ni active carbon ceramic MOFs composite compression strength>0.8Mpa, methane adsorption capacity（25 DEG C, 36
atm）168 V/V,（25 DEG C, 1 atm）32 mL/g, CH4/N2Separation 6.9 and CH4/CO2Separation 10.8.
Embodiment 6
By the g of cocoanut active charcoal 500（The mg/g of iodine number 1700）, the g of Y molecular sieve 100, the g of attapulgite 200, kaolin 50
G, the g of methylcellulose 10, the g of copper chloride 15, the g of cobalt chloride 25 are milled to 300~400 mesh, add 800 mL water wet methods and mediate
0.5~1h, -0.09MPa 3~5h of vacuum pugging, are aged 6~12h, and cellular activated carbon is made in extrusion molding in vertical extruder
24~48h is dried in the air under ceramic thick embryo, thick embryo normal temperature after sizing under 550 DEG C of vacuum of microwave irradiation（The kw/ of microwave irradiation density 2.0
kg）Active carbon ceramic containing Cu-Co is made.
The cellular material of active carbon ceramic containing Cu-Co 800g is immersed into 400 mL ethanol, 300mL water, 500mLDMF mixing
Solvent, is added in 40 g monoethanolamines, 60 g trimesic acids and 30 g succinic acid mixed liquors, in reacting 8 h at 160 DEG C, in bag
Separation of solid and liquid in formula plate centrifuge, and after being washed with 400 mL ethanol+600mL acetic acid, microwave vacuum（- 0.09MPa, microwave
The kw/kg of irradiation density 0.8））80 DEG C of dry 0.5h are obtained.
This contains Cu-Co active carbon ceramic MOFs composite compression strength>0.8Mpa, methane adsorption capacity（25 DEG C, 36
atm）172V/V,（25 DEG C, 1 atm）36 mL/g, CH4/N2Separation 7.1 and CH4/CO2Separation 12.4.
Claims (9)
1. a kind of normal temperature methane efficient absorption material, it is characterised in that：The work that the material is made based on activated carbon and molecular sieve
Property the upper growth in situ of charcoal ceramics prepare containing transition-metal FeIII、ZnII、CuII、NiII、CoIIIMetal organic framework be combined
Material, the composite includes the coconut activated wt% of carbon content 45 ~ 65, the wt% of Y molecular sieve content 10 ~ 18, attapulgite content
20 ~ 25wt%, 5 ~ 8wt% of kaolin, the wt% of metal-organic framework materials 3 ~ 10, compression strength> 0.8MPa.
2. a kind of normal temperature methane efficient absorption material as claimed in claim 1, it is characterised in that：Described coconut activated carbon granule
Footpath is 300 ~ 400 mesh, and iodine number is 1400~2600 mg/g, and specific surface area is 1700~3000 m2/ g, ash content< 2 wt%.
3. a kind of normal temperature methane efficient absorption material as claimed in claim 1, it is characterised in that：Described metal organic framework
Material is loaded in the Fe in active carbon ceramic3+、Zn2+、Cu2+、Ni2+、Co3+Chlorate, sulfate and organic solvent, deprotonation alkali
And obtained corresponding Fe in situ under the conditions of organic carboxyl acid part Hybrid HeatingIII、ZnII、CuII、NiII、CoIIIComplexed metal is organic
Framework material.
4. a kind of normal temperature methane efficient absorption material as claimed in claim 1, it is characterised in that：Suitable for methane pressure-variable adsorption
Separation, low-concentration methane are reclaimed, the methane adsorption capacity under the conditions of 25 DEG C, 36 atm>170 V/V, CH4/N2Separation>7
And CH4/CO2Separation>12.
5. a kind of normal temperature methane efficient absorption material as claimed in claim 1, it is characterised in that：Outward appearance is cellular or post
Shape.
6. a kind of normal temperature methane efficient absorption material as claimed in claim 3, is characterised by：Described organic solvent be formic acid,
Acetic acid, methanol, ethanol, ethyl acetate, the one or more among DMF.
7. a kind of normal temperature methane efficient absorption material as claimed in claim 3, is characterised by：The deprotonation alkali be triethylamine,
One or more in monoethanolamine, pyridine, imidazoles.
8. a kind of normal temperature methane efficient absorption material as claimed in claim 3, it is characterised in that：Described organic carboxyl acid part is
Bidentate ligand succinic acid, terephthalic acid (TPA), tartaric acid, biphenyl dicarboxylic acid, 3- pyridine-sulfonic acids and tridentate ligand trimesic acid, 2,
One or more in 5- pyridinedicarboxylic acids.
9. a kind of preparation method of claim 1 normal temperature methane efficient absorption material, it is characterised in that：By Fe3+、Zn2+、Cu2+、
Ni2+、Co3+Chlorate, sulfate one or more with high-specific surface area cocos active carbon, Y type molecular sieve, attapulgite,
Kaolin, methylcellulose are dry-mixed in proportion to be milled to 300~400 mesh, adds a certain amount of water wet mixing, practices through kneading, vacuum
Mud, ageing, extrusion molding, dry in the shade, obtain the active carbon ceramic moulding material containing transition metal after microwave irradiation sizing, then should
Moulding material is immersed in a certain proportion of organic solvent, deprotonation alkali and organic carboxyl acid part mixed liquor, at 120~180 DEG C
6 ~ 24h is reacted, micro-wave vacuum is obtained after separation of solid and liquid, washing.
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