CN103933939A - Metal-organic framework MOF material with high methane adsorption and storage density - Google Patents
Metal-organic framework MOF material with high methane adsorption and storage density Download PDFInfo
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Abstract
The invention relates to a metal-organic framework MOF material with the high methane adsorption and storage density. According to the metal-organic framework MOF material, naphthalene binary or ternary carboxylic acid organic ligands and derivatives of naphthalene binary or ternary carboxylic acid organic ligands are used in match with metal cations of ferric iron, lanthanum, bismuth, nickel, aluminum and cerium to form a three-dimensional neat network porous channel structure in the presence of coordinate bonds or ionic bonds; nitrogenous, oxygenic and sulfuric functional groups with the extremely strong polarity are introduced into the organic ligands, so that the methane adsorption and storage amount of the MOF material can be effectively increased; the metal-organic framework material has a suitable porous channel size being 1.0-2.0nm, a specific surface area being greater than 2000m<2>/g, a pore volume performance and the good heat stability, so that the material can be reused; meanwhile, the material is relatively low in synthetic cost and has the methane absorption and storage amount of 190-210V/V under 3.5MPa. By adopting the metal-organic framework MOF material with the high methane adsorption and storage density, the problems of low methane absorption capacity, high operation pressure and dissatisfactory absorption/desorption rate in the prior art are solved. The metal-organic framework material can be used as an efficient methane adsorbent and is wide in application prospects.
Description
Technical field
The invention belongs to the adsorbent technical field of chemical materials, be specifically related to a kind of metal-organic framework MOF material of high methane absorbing and storing density.
Background technology
Natural gas methane is a kind of important energy, and the clean methane natural gas technology of coal system is the important directions of the using energy source of current China, national strategy.Coal preparing natural gas is based on the feature of domestic energy resource structure just, and by efficient utilization and the clean production natural gas that rationally transforms of coal, its energy conversion efficiency is far above coal liquefaction, coal derived DME, coal methyl alcohol processed, generating.But the how extensive effectively transport of coal preparing natural gas is in this industry development, to be badly in need of one of bottleneck problem solving.
The mode of taking adsorbent adsorbed methane accumulating (ANG) is the novel mode in natural gas accumulating.Carry out storage and the transport of natural gas by high-performance adsorbent, with compare in the conventional natural gas accumulating mode of three kinds of pipe natural gas (PNG), liquefied natural gas (LNG), compressed natural gas (CNG), this kind of mode is in operation power consumption, the investment of building a station, safety, have unique advantage for aspects such as medium and small source of the gas and Firsthand Users.Carry out the exploitation of ANG key technology, can the clean natural gas of coal system effectively be stored and be carried on the one hand, can promote on the other hand the innovation of industry peak regulation, there is important economic benefit, social benefit.And this wherein efficiently, the preparation of adsorbent cheaply and microcellular structure, the preparation method etc. of various sorbing materials be one of subject matter of current ANG technology on the impact of absorption property.
From the current both at home and abroad research and development achievement of relevant Adsorption Natural Gas material, desirable Adsorption Natural Gas material should have narrow pore-size distribution about large as far as possible Micropore volume and 1.5nm, larger specific area, applicable hole surface character and good heat and mass efficiency.The test that a large amount of research of people concentrates on Carbon Materials raw material in micropore acticarbon preparation, physics and chemistry activation method, activator, activation condition, processing and forming, post-processing approach etc. is selected upper, has made the larger super micropore active carbon of Adsorption Natural Gas amount.Patent CN101003015 discloses a kind of high molecular derivatives Si-C composite material for absorbing and storing methane and preparation method thereof.The method, in alkaline distilled water, adds surfactant and organo-silicon compound, is hydrolyzed and emulsification, then obtains polymer-silicon hybridization precursor by vinylidene chloride polymerisation.By the washing of this precursor, dry after, under inert atmosphere by its progressively carbonization, its specific area of the composite obtaining 1700m
2more than/g, more than pore volume 0.90ml/g, to the adsorbance 140V/V of methane.Although this adsorbent can be under the temperate condition of 3.5MPa effective adsorbed methane, the adsorbance of methane is also lower than the Technical Economy index of 160 V/V.Patent CN1258638 discloses a kind of preparation method of active carbon of absorbing and storing methane, the method is taking petroleum coke or pitch coke as raw material, KOH is the active carbon that activator makes high-specific surface area powdery, then powdered activated carbon is mixed with the ratio of 1: 0.30-0.60 with binding agent, compressing under 20-130 DEG C, 50-320MPa pressure, in 700-1000 DEG C of charings, recycling steam or carbon dioxide activation processing at 700-1000 DEG C, make moulding active carbon with high specific surface area.The type charcoal that the method makes volume adsorption for methane under 3.5MPa reaches 140-170V/V.This active carbon has advantages such as methane volume adsorption are larger, but raw materials petroleum coke or pitch coke change of properties are large, and preparation process step is longer, and product quality is wayward with repeatability.CN101531365 discloses a kind of preparation method of pressed active carbon for pressure swing adsorption/separation of methane/nitrogen.Although it is simple that this preparation method has technical process, cost is low, pollute little feature, and the active carbon of preparation has advantages of that methane/nitrogen separation is effective, and methane volume adsorption is less, therefore it can not be as the Special adsorbent of absorbing and storing methane.Therefore although active carbon itself has very large specific area and pore-size distribution, larger to methane adsorption capacity, in the kind of active carbon, preparation method, gas, water content etc. is very obvious on methane adsorbance and the impact such as selective.On the other hand, the intrinsic processing and forming inconvenience of absorbent charcoal material, sorption and desorption variations in temperature are large, the wider problem of pore-size distribution is difficult to solve well comprehensively, have affected the performance of its practical effect.The exploitation of high-efficiency adsorbent will be depended on research and the application of novel nano poromerics and duct thereof and finishing technology etc.
Due to visible, the development of high-performance natural gas adsorbent and optimize the main key of absorbed natural gas (ANG) storing technology.Comparatively ideal ANG adsorbent should have larger specific area and suitable microcellular structure, and its specific area is greater than 2000 m2/g, and pore-size distribution is concentrated (aperture 1.0～2.0nm, more than Micropore volume accounts for total pore volume 85 %); And natural gas adsorbent should have good thermal conductivity, the speed of adsorption and desorption is high; The long service life of adsorbent simultaneously, the use of regenerating.
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) is a kind of novel hybride porous material with the fastest developing speed in the world nearly ten years, and MOF material has the characteristic of high adsorption capacity, pore structure high-sequential.With traditional inorganic porous material as compared with zeolite, silica gel, CNT, active carbon etc., its feature is selected or modified and can carry out Effective Regulation change to duct shape and pore size, duct surface nature by organic ligand, to increase absorption affinity and the adsorption capacity to specific adsorbate.So MOF material has obvious advantage at three major parameters of surface area, pore-size distribution, micropore quantity that determine performance of the adsorbent, for the Design & preparation of novel porous adsorbent provides a kind of new way.
CN102962037A has related to a kind of one metalloid-organic framework materials for methane adsorbing separation and preparation method, and this metal organic frame material is to react and prepare with the organic ligand of at least one monodentate that contains nitrogen, oxygen or sulphur atom or multiple tooth organic compound with at least one metallic compound in Li, Mg, Al, Fe, Co, Ni, Cu, Zn, Mn, Zr, La, Sm.The specific area of this metal organic frame porous structure material is greater than 200m2/g, and pore-size distribution is between 0.4nm-2.0nm.Such material preparation process is simple, and material self property is stable, is applicable to the separation of low-quality methane gas and the purification process of high dense methane gas.But because specific area is lower, pore-size distribution is wider, methane adsorbance is less, is not suitable as the material of methane absorption storage.CN103100372A discloses a kind of metal organic frame material for methane absorption and storage and preparation method thereof.The three-dimensional net structure that described metal organic frame material consists of coordinate bond or intermolecular force transition metal ions and organic ligand 5,5 '-(pyridine-2,5-bis-bases)-M-phthalic acid and derivative thereof.The preparation technology of this three-dimensional net structure material is simple, and specific area is greater than 2000 m
2/ g, its pore volume is greater than 1.0 cm
3/ g; Absorption and memory space as methane absorption and storage medium methane under alternating temperature, transformation condition are high, but metal organic frame stability of material is not strong, and organic ligand used is comparatively special, and synthetic cost is high, is difficult to enter application.CN103221126A discloses active carbon-metallic organic framework composite (AC@MOF) of the gas absorption capacity with increase.Adopt and in metallic organic framework (MOF), use " gap filling method "---it is by realizing as the process situ of Cu-BTC adds selection type and appropriate active carbon at synthetic MOF---for the atmosphere storage including methane.But this AC@MOF composite material preparation process complexity, quality is unstable, and gas absorption capacity still can not meet the requirement as methane absorption storage material.
Comparatively ideal ANG adsorbent should have larger specific area and the concentrated microcellular structure of pore-size distribution, good thermal conductivity, and the speed of adsorption and desorption is high; The preparation quality of adsorbent is controlled simultaneously, and cost is suitable, long service life, and the use of regenerating.Due to known, in the adsorption storage natural gas performance of the natural gas adsorbent of development, all exist organic ligand comparatively special at present, synthetic cost is high, or complicated process of preparation, quality is unstable, and methane adsorbance is less, can't better meet the needs of methane absorption storage material.
In numerous organic ligands, people start application organic carboxyl acid more to favor as the synthetic Coordination Polymers of part.This is that the negative charge density of carboxy moiety is larger, stronger with the coordination ability of metal ion because carboxyl has unique electronic structure and can form interesting topology the first; The second, carboxyl has multiple coordination mode, can form metal carboxylate bunch or bridged linkage, has increased stability and the rigidity of agent structure, can prevent the formation of interpenetrating networks.We are in recent years according to naphthalene series aromatics resource abundant in China's coal tar, making naphthalene by alkylation and oxidation reaction is binary or tricarboxylic acid organic ligand and derivative thereof, actively develop the development of novel metal-organic backbone (MOF) material of serial practicality, different Carboxylic acid ligand complexings forms the MOF of different structure, thereby the size and shape in MOF hole is regulated and controled.Research has characterized these organic ligands and metal ion to the when impact of density of MOFs pore structure, aperture, pore volume.More than our result of study shows that the methane absorbing and storing density of the MOF molecular sieve analog material of preparing under 3.5 Mpa low pressure reaches 200V/V, desorption rate >=99 %, desorption gas methane concentration is more than 98%; There is the good prospect of further Application and Development.Intend by combining with mature pressure-variable adsorption separating technology (PSA), be expected to develop into the high-efficiency methane gas storage material that next-generation technology economy is good.
Summary of the invention
In the adsorption storage natural gas performance of natural gas MOF adsorbent for development in the past, all exist organic ligand comparatively special, the problem such as synthetic cost is high, or preparation and complex forming technology, and quality is unstable, and methane adsorbance is less.The present invention proposes that a kind of synthesis material cost is lower, and preparation quality is reliable and stable, and pore structure high-sequential, specific area are large, the metal-organic framework MOF material of the high methane absorbing and storing density of high adsorption capacity.
The metal-organic framework MOF material of a kind of high methane absorbing and storing density of the present invention, comprises following component in parts by weight:
(1) naphthalene is a kind of in binary or tricarboxylic acid organic ligand or 50 ~ 80 parts, wantonly two kinds of mixtures;
(2) 20～50 parts of the metal cations of divalence or trivalent, its gross weight umber is 100 parts.
In the present invention, described binary or tricarboxylic acid organic ligand are selected from 1-nitro, 2,6-naphthalenedicarboxylic acid, 3-amino, 2,6-naphthalenedicarboxylic acid, 5-sulfonic group, 2,7-naphthalenedicarboxylic acid, 4-hydroxyl, 2,7-naphthalenedicarboxylic acid, 2,4,6-naphthalenetricarboxylic acid or 2, in 5,7-naphthalenetricarboxylic acid any.
In the present invention, the metal cation chosen from Fe of described trivalent, lanthanum, bismuth, nickel, aluminium or, in ce metal cation any.
In the metal-organic framework MOF of a kind of high methane absorbing and storing density of the present invention material preparation method, adopt and encircle alcohol or heptaline is auxiliary pore former, consumption is 10 wt%-30 wt% of MOF material synthesis reaction mixture.
The metal-organic framework MOF material of high methane absorbing and storing density of the present invention as the adsorbance of adsorbent methane under low pressure 35bar, room temperature 25 degree at 190-210 V/V.
The novel metal-organic framework MOF poromerics methane adsorbent that the present invention proposes, is that a kind of pore structure high-sequential, aperture are the three-dimensional regular pore canal system micropore molecular sieve analog of 1.2 nm--1.8 nm, and specific area is greater than 2000 m
2/ g, pore volume is 1. 1 m
3more than/g.Thereby show excellent molecular diffusion and absorption--desorption performance, adsorption capacity is large.Meanwhile, the preparation method of methane adsorbent of the present invention is easy, and cost of material is lower, and steady quality is reliable, and complex art economy is good, is the efficient storage material of a kind of methane gas being with a wide range of applications.
Detailed description of the invention
Below by the following example, the present invention is further illustrated.
Embodiment 1:
By 5-sulfonic group, 2,7-naphthalenedicarboxylic acid 0.92 g and iron chloride hexahydrate 0.30 g add in 100mLTeflon stainless steel cauldron, add again and encircle alcohol 15 mL, ethanol 10 mL and deionized water 20 mL, stir after sealing, at 110-120 DEG C, react 20 – 24 hours, product is cooled to room temperature and obtains colourless bulk crystals, after filtering airing, at 110 DEG C, in nitrogen stream, moisture and solvent are removed in volatilization again, make MOF adsorbent I.
Embodiment 2:
By 1-nitro, 2,6-naphthalenedicarboxylic acid 0.78 g and hydration alchlor 0.35 g add in 100mLTeflon stainless steel cauldron, add again and encircle alcohol 10 mL, ethanol 15 mL and deionized water 20 mL, stir after sealing, at 110-120 DEG C, react 20 – 24 hours, product is cooled to room temperature and obtains colourless bulk crystals, after filtering airing, at 110 DEG C, in nitrogen stream, moisture and solvent are removed in volatilization again, make MOF adsorbent II.
Embodiment 3:
By 3-amino, 2,6-naphthalenedicarboxylic acid 0.95 g and nitric hydrate lanthanum 0.62 g add in 100mLTeflon stainless steel cauldron, add again heptaline 5 mL, ethanol 12 mL and deionized water 20 mL, stir after sealing, at 110-120 DEG C, react 20 – 24 hours, product is cooled to room temperature and obtains colourless bulk crystals, after filtering airing, at 110 DEG C, in nitrogen stream, moisture and solvent are removed in volatilization again, make MOF adsorbent III.
Embodiment 4:
By 4-hydroxyl, 2,7-naphthalenedicarboxylic acid, 0.82 g and nitric hydrate cerium 0.75 g add in 100mLTeflon stainless steel cauldron, add again heptaline 16 mL, ethanol 15 mL and deionized water 20 mL, stir after sealing, at 110-120 DEG C, react 20-24 hours, product is cooled to room temperature and obtains colourless bulk crystals, airing after filtering, then in nitrogen stream, volatilize and remove moisture and solvent at 110 DEG C, MOF adsorbent IV made.
Embodiment 5:
By 2,4,6-naphthalenetricarboxylic acid 0.98 g and nitric hydrate bismuth 0.96 g add in 100mLTeflon stainless steel cauldron, add again and encircle alcohol 13 mL, ethanol 15 mL and deionized water 20 mL, stir after sealing, at 110-120 DEG C, react 20 – 24 hours, product is cooled to room temperature and obtains colourless bulk crystals, airing after filtering, then in nitrogen stream, volatilize and remove moisture and solvent at 110 DEG C, MOF adsorbent V made.
Embodiment 6:
By 2,5,7-naphthalenetricarboxylic acid 0.68 g and hydration nickel chloride 0.16 g add in 100mLTeflon stainless steel cauldron, add again and encircle alcohol 8 mL, ethanol 16 mL and deionized water 20 mL, stir after sealing, at 110-120 DEG C, react 20 – 24 hours, product is cooled to room temperature and obtains colourless bulk crystals, airing after filtering, then in nitrogen stream, volatilize and remove moisture and solvent at 110 DEG C, MOF adsorbent VI made.
Comparative example 7:
By 2,6-naphthalenedicarboxylic acid 0.75 g and hydration nickel chloride 0.18g add in 100mLTeflon stainless steel cauldron, add again and encircle alcohol 8 mL, ethanol 16 mL and deionized water 20 mL, stir after sealing, at 110-120 DEG C, react 20 – 24 hours, product is cooled to room temperature and obtains colourless bulk crystals, after filtering airing, at 110 DEG C, in nitrogen stream, moisture and solvent are removed in volatilization again, make reference MOF adsorbent VII.
Comparative example 8:
By 1,4-phthalic acid 0.72 g and hydration nickel chloride 0.17g add in 100mLTeflon stainless steel cauldron, add again and encircle alcohol 8 mL, ethanol 16 mL and deionized water 20 mL, stir after sealing, at 110-120 DEG C, react 20 – 24 hours, product is cooled to room temperature and obtains colourless bulk crystals, after filtering airing, at 110 DEG C, in nitrogen stream, moisture and solvent are removed in volatilization again, make reference MOF adsorbent VIII.
Embodiment 9:
Six kinds of methane MOF adsorbent I, II, III, IV, V, VI and reference MOF adsorbent VII are made in employing, investigate it at methane adsorption capacity and desorption performance in constant temperature, constant voltage on methane adsorbent equipment.Appreciation condition adopts: 25 DEG C of adsorption temps; Pressure 3.5MPa; 50 DEG C of desorption temperatures; Desorption vacuum 400mmHg; Evaluate initial adsorption capacity/desorption rate, 30 average adsorption capacity/desorption rates of absorption/desorption, result is as shown in the table.
As seen from the above table, it is MOF molecular sieve analog material prepared by binary or tricarboxylic acid and derivative organic ligand thereof and trivalent metal ion that the present invention adopts naphthalene, with 2,6-naphthalenedicarboxylic acid, 1, it is better that the MOF adsorbent that 4-phthalic acid is made as organic ligand is compared performance, methane gas adsorption storage effect significantly improves, and its adsorption capacity improves more than 20%.The methane absorbing and storing density of metal-organic framework (MOF) material of development under 3.5 MPa low pressure is up to 210V/V, desorption rate >=99 %.Reach the Technical Economy index request of commercial Application, there is the good prospect of further Application and Development.
Claims (5)
1. a metal-organic framework MOF material for high methane absorbing and storing density, is characterized in that this material comprises following component in parts by weight:
(1) naphthalene is a kind of in binary or tricarboxylic acid organic ligand or 50 ~ 80 parts, wantonly two kinds of mixtures;
(2) 20～50 parts of the metal cations of trivalent, its gross weight umber is 100 parts.
2. the metal-organic framework MOF material of high methane absorbing and storing density according to claim 1, it is characterized in that described naphthalene is that binary or tricarboxylic acid organic ligand are selected from 1-nitro, 2,6-naphthalenedicarboxylic acid, 3-amino, 2,6-naphthalenedicarboxylic acid, 5-sulfonic group, 2,7-naphthalenedicarboxylic acid, 4-hydroxyl, 2,7-naphthalenedicarboxylic acid, 2,4,6-naphthalenetricarboxylic acid or 2, in 5,7-naphthalenetricarboxylic acid any.
3. the metal-organic framework MOF material of high methane absorbing and storing density according to claim 1, is characterized in that in metal cation chosen from Fe, lanthanum, bismuth, nickel, aluminium or the ce metal cation of described trivalent any.
4. the metal-organic framework MOF material of high methane absorbing and storing density according to claim 1, it is characterized in that in metal-organic framework MOF material preparation process, employing encircles alcohol or heptaline is auxiliary pore former, and consumption is 10 wt%-30 wt% of MOF material synthesis reaction mixture.
5. the metal-organic framework MOF material of high methane absorbing and storing density according to claim 1, it is characterized in that described MOF material as the adsorbance of adsorbent methane under low pressure 35bar, room temperature 25 degree at 190-210 V/V.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106622291A (en) * | 2016-12-16 | 2017-05-10 | 南开大学 | Method for preparing zinc oxide/zinc sulfide nano heterojunction photocatalyst |
| CN106866985A (en) * | 2017-01-07 | 2017-06-20 | 青岛科技大学 | A kind of metal-organic framework materials for for acetylene and methane adsorption separate and preparation method thereof |
| CN108290136A (en) * | 2015-11-27 | 2018-07-17 | 巴斯夫欧洲公司 | The method for preparing moulding compound and preparing formed body |
| CN112295545A (en) * | 2019-08-02 | 2021-02-02 | 中国石油化工股份有限公司 | High-capacity methane storage material and preparation method and application thereof |
| CN113209941A (en) * | 2021-04-14 | 2021-08-06 | 山东大学 | Hydrophobic dual-ligand metal organic framework material, preparation method and application in VOCs adsorption |
| CN113490537A (en) * | 2018-12-21 | 2021-10-08 | 梅西大学 | Metal organic framework for gas adsorption |
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| CN113209941A (en) * | 2021-04-14 | 2021-08-06 | 山东大学 | Hydrophobic dual-ligand metal organic framework material, preparation method and application in VOCs adsorption |
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Application publication date: 20140723 |