CN114797778A - Application of coffee-grounds-based molded porous carbon adsorbent in efficient methane/nitrogen separation - Google Patents
Application of coffee-grounds-based molded porous carbon adsorbent in efficient methane/nitrogen separation Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 108
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 238000000926 separation method Methods 0.000 title claims abstract description 51
- 239000003463 adsorbent Substances 0.000 title claims abstract description 50
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 25
- 229910052909 inorganic silicate Inorganic materials 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims description 16
- 238000001994 activation Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 10
- 241000219782 Sesbania Species 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940094522 laponite Drugs 0.000 claims description 2
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 239000003245 coal Substances 0.000 abstract description 3
- 239000002893 slag Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- JVFDADFMKQKAHW-UHFFFAOYSA-N C.[N] Chemical compound C.[N] JVFDADFMKQKAHW-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 102000020897 Formins Human genes 0.000 description 4
- 108091022623 Formins Proteins 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
-
- 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
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/10—Nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
Abstract
The invention provides an application of a coffee-slag-based molded porous carbon adsorbent in high-efficiency methane/nitrogen separation. The raw materials of the invention are cheap and easy to obtain, the preparation process is simple, and the mechanical strength of the coffee grounds-based formed porous carbon adsorbent is higher than 120Ncm ‑1 The wear resistance is more than 99 percent, the loss in the transportation and use process can be reduced, and the method is suitable for industrial application; the adsorbent containing rich mesoporous structure and proper amount of surface oxygen-containing functional groups can be obtained by adding proper inorganic silicate, the selective adsorption of methane is facilitated, and the dynamic adsorption capacity of the adsorbent to methane reaches 0.25mmol g under the conditions of 298K and 1.1bar ‑1 The separation selectivity of methane/nitrogen reaches 10.6(3/7, v/v), which is higher than most reports in the prior literature, and the method has good industrial prospect in the separation and purification of methane-containing gases such as coal bed gas, methane and the like.
Description
Technical Field
The invention belongs to the technical field of gas separation, and particularly relates to an application of a coffee-residue-based molded porous carbon adsorbent in high-efficiency methane/nitrogen separation.
Background
Coal bed gas is an important unconventional natural gas energy source, and the main effective component is methane (CH) 4 ) And impurities (CO) in the feed gas 2 、N 2 ) The calorific value of the gas is significantly reduced and should be removed. At present, the common gas separation and purification technologies include cryogenic technology, membrane separation, pressure swing adsorption and the like, wherein the pressure swing adsorption technology has low energy consumption and high gas purity, and is a potential gas separation and purification technology, and the key point of the pressure swing adsorption technology is to construct an efficient adsorbent. Common porous adsorbents mainly comprise Metal Organic Frameworks (MOFs), zeolite molecular sieves, porous carbon and the like. The porous carbon is widely applied to adsorption separation operation due to high specific surface area, large pore volume, developed pore structure, good hydrophobicity, good mechanical property, high chemical stability and thermal stability, wherein the biomass carbon is low in price, rich in raw materials and wide in distribution, and the biomass is the most promising precursor of the porous carbon in consideration of the industrial application requirements of low cost and sustainability. Coffee is one of three major beverages in the world, consumes about 1000 ten thousand tons every year, generates about 650 thousand tons of coffee grounds waste every year, and is a very abundant and cheap raw material.
The good adsorption selectivity in industry can reduce the energy consumption of separation, and the current report is used for CH 4 /N 2 The selectivity of the porous carbon is not ideal. Chinese patent CN106345410A discloses a porous carbon adsorbent, which uses pitch and starch as carbon sources, and is carbonized and then subjected to CO treatment at 780-830 DEG C 2 The porous carbon is obtained by activation treatment, and the separation ratio is only 3.8; li or the like directly carbonizes the granular rice with CO 2 The PRC particles obtained after activation had a specific surface area of 776m 2 g -1 At 298K and 1.1bar, its CH 4 /N 2 The adsorption selectivity was 5.7(chem.eng.j.2020,384: 123388.); wang et al prepared monolithic ultramicropore carbon particles by carbonizing and KOH activating granular oil-tea shells as carbon sources, and treated CH under the conditions of 1.0bar and 298K 4 /N 2 The selectivity of (A) was 5.8(AIChE journal.2021,67 (9)), and the selectivities were all low. Moreover, the use of direct biomass molding is omittedThe molding step is adopted, but the prepared sample is irregular, and the problem of easy pulverization exists in the steps of transportation, filling, use and the like; the micropores generated in the activation process of the biomass carbon improve the methane adsorption amount and the nitrogen adsorption amount, so that the selectivity is not high, and how to prepare the high-selectivity integral carbon is always the focus of research.
Disclosure of Invention
The invention aims to provide an application of a coffee grounds-based molded porous carbon adsorbent in efficient methane/nitrogen separation, aiming at the problems of low methane/nitrogen separation selectivity, low strength and easy pulverization of the existing carbon adsorbent.
The technical scheme of the invention is as follows:
an application of a coffee-grounds-based molded porous carbon adsorbent in high-efficiency methane/nitrogen separation, which adopts an adsorption separation method to separate methane and nitrogen from a mixed gas of methane and nitrogen or purify methane; the preparation method of the coffee grounds-based molded porous carbon adsorbent comprises the following steps:
(1) mixing the coffee grounds with an extrusion aid, and marking as a sample A;
(2) uniformly mixing an inorganic silicate solution and the sample A, and marking as a sample B, wherein the mass ratio of the inorganic silicate solution to the coffee grounds is 1.4:1-1.6: 1;
(3) extruding and molding the sample B in a strip extruding machine, breaking the strip, and drying at room temperature to obtain a sample C;
(4) putting the sample C into a carbonization furnace, and carbonizing and activating under the protection of inert gas to obtain a porous carbon material;
(5) and (3) placing the porous carbon material in an alkali solution at 50-100 ℃ for 24h, and washing with deionized water to be neutral to obtain the coffee grounds-based formed porous carbon adsorbent.
The coffee grounds-based molded porous carbon adsorbent contains a rich micropore-mesopore series pore structure, micropores are mainly concentrated at 0.4-0.6nm, mesopores are distributed at 22-86 nm, and a proper amount of oxygen-containing functional groups are arranged on the surface of the adsorbent.
The inorganic silicate is one or more of kaolin, sepiolite, laponite, montmorillonite, sodium silicate, calcium silicate and potassium silicate; sodium silicate is preferred.
The mass fraction of the inorganic silicate solution is 8 to 15 percent
The extrusion aid is sesbania powder, and the mass ratio of the sesbania powder to the coffee grounds is 0.05:1-0.1: 1.
The alkaline solution is sodium hydroxide solution, the solvent is a mixture of water and absolute ethyl alcohol, and the volume ratio of the water to the absolute ethyl alcohol is 0-2.
The carbonization temperature is 700-1000 ℃, and the carbonization time is 1-3 h; the activation temperature is 750-;
the activating gas in the activating process is as follows: one or two of water vapor, carbon dioxide and air; preferably the gas is water vapour;
the flow rate of the activating agent is 0.1-2.5ml min -1 ；
The carbonization furnace is a rotary carbonization furnace with the rotating speed of 5-15rmin -1 。
Dynamic separation conditions: methane/nitrogen is 0.1-0.9, the temperature of adsorption separation is 273-198K, and the total pressure of the mixed gas is 1-5 bar.
The adsorption principle of the invention is as follows:
the coffee grounds-based molded porous carbon has a hierarchical pore structure, micropores are favorable for methane adsorption, and mesopores are favorable for gas transmission; meanwhile, a proper amount of oxygen-containing functional groups are beneficial to the adsorption of methane with higher polarizability; for nitrogen with low polarizability, the action force with porous carbon is weak, and the nitrogen hardly adsorbs, so that high selectivity is realized. In a dynamic penetration test, due to the rich mesoporous structure and a proper amount of oxygen-containing functional groups of the porous carbon, the nitrogen is penetrated at the first with extremely low adsorption capacity, so that the efficient separation of methane/nitrogen is realized.
The invention has the following beneficial effects: the coffee grounds are used as raw materials, mixed with the extrusion aid and the inorganic silicate, and subjected to extrusion molding, carbonization and activation, and alkaline washing to prepare the coffee grounds-based molded porous carbon adsorbent, the raw materials are cheap and easy to obtain, the preparation process is simple, the repeatability is strong, the operation and the amplification are easy, and the mechanical strength of the coffee grounds-based molded porous carbon adsorbent is higher than 120N cm -1 The wear resistance is higher than 99 percent, the loss in the transportation and use process can be reduced,the method is suitable for industrial application, and the addition of the inorganic silicate is suitable for obtaining the adsorbent with rich mesoporous structure and a proper amount of oxygen-containing functional groups on the surface, thereby being beneficial to the high-selectivity adsorption of methane. The addition amount of the inorganic silicate is too small, the oxygen-containing functional groups on the surface are too small, the acting force between the inorganic silicate and methane is not strong, the addition amount of the inorganic silicate is too large, the oxygen-containing functional groups on the surface are too much, the acting force between the inorganic silicate and nitrogen is increased, and methane adsorption is not facilitated. Under the conditions of 298K and 1.1bar, the dynamic adsorption capacity to methane reaches 0.25mmol g -1 The separation selectivity of methane/nitrogen reaches 10.6, which is higher than most reports in the prior literature, and the method has good industrial prospect in the separation and purification of methane-containing gases such as coal bed gas, methane and the like.
Drawings
Fig. 1 is a nitrogen adsorption graph of porous carbon adsorbents prepared according to example 1 of the present invention, comparative example 1, and comparative example 2.
Fig. 2 is a mesoporous pore size distribution diagram of the porous carbon adsorbents prepared according to example 1 of the present invention, comparative example 1, and comparative example 2.
FIG. 3 is a pore size distribution diagram of the micropores of the porous carbon adsorbent prepared in inventive example 1.
Fig. 4 is an infrared spectrum of the porous carbon adsorbents prepared in inventive example 1 and comparative example 2.
Fig. 5 is a dynamic permeation diagram of the porous carbon adsorbent prepared in inventive example 1 and comparative example 1 under normal pressure.
Fig. 6 is a graph showing dynamic breakthrough of the porous carbon adsorbent prepared in example 1 of the present invention under high pressure.
Fig. 7 is a graph of adsorption and desorption cycle regeneration of the porous carbon adsorbent prepared in example 1 of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to make the purpose and technical solution of the present invention more clear, the present invention is described in detail with reference to the following examples. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
The dynamic adsorption capacity and the dynamic selectivity related in the embodiment of the invention are obtained by calculating through a dynamic penetration curve, and the calculation formula is as follows:
wherein q is i Is the amount of adsorption of the i component on the adsorbent; f is the total flow of the mixed gas; c i,0 Is the influent concentration of the i component; c i,t The real-time outflow concentration of the component i at the moment t is shown; t is t i Is the adsorption time of the i component; v dead Is the dead volume in the pores and pipelines of the adsorption column; m is the loading mass of the adsorbent.
The separation coefficient in the present invention is calculated from the following formula
Wherein q is i 、q j The adsorption amounts of the i component and the j component on the adsorbent are respectively; y is i 、y j The mole fractions of the i and j components in the mixed gas are respectively.
Example 1
Weighing 50g>Adding 3.5g of sesbania powder serving as an extrusion aid into 100-mesh coffee grounds, and uniformly stirring the coffee grounds and the sesbania powder in a stirrer to obtain a sample A; preparing 75g of 9 wt% sodium silicate aqueous solution, adding the sodium silicate aqueous solution in batches, uniformly stirring to obtain a sample B, adding the sample B into a strip extruding machine for extrusion molding, finishing the strip into 10-20mm, drying to obtain a sample C, placing the sample C into a carbonization furnace for carbonization at 3 ℃ for min -1 Heating to 800 deg.C, holding the temperature for 120min, and heating to 5 deg.C for 5 min -1 Heating to 850 deg.C for water vapor activation for 40min to obtain porous carbon material D, placing porous carbon material D in 50 deg.C alkaline solution for one day, washing with deionized water to neutrality to obtain coffee residue-based porous carbon adsorbent with mechanical strength of 123N cm -1 And the wear resistance is more than 99%. As shown in FIG. 1, the nitrogen adsorption test results showed that the BET surface area was about 527m 2 g -1 The mesoporous pore size distribution is shown in fig. 2, the micropore pore size distribution is shown in fig. 3, and the infrared spectrum is shown in fig. 4.
To testThe separation performance of the columnar porous carbon on methane nitrogen was evaluated on a fixed bed apparatus. Separation conditions are as follows: 298K, 1.1bar, the volume ratio of methane to nitrogen is 3:7, and the total flow of the mixed gas is 3ml min -1 . The dynamic adsorption capacity of the coffee residue-based porous carbon adsorbent to methane is calculated to be 0.25mmol g under 298K and 1.1bar -1 The dynamic adsorption amount of nitrogen was 0.05mmol g -1 The methane/nitrogen separation selectivity reached 10.6, and the dynamic breakthrough curve at atmospheric pressure is shown in fig. 5. Separation conditions are as follows: 298K, 5bar, the volume ratio of methane to nitrogen is 3:7, and the total flow of the mixed gas is 10ml min -1 . The dynamic adsorption capacity of the coffee-grounds-based porous carbon adsorbent to methane is calculated to be 0.49mmol g under 298K and 5bar -1 The dynamic adsorption amount of nitrogen was 0.06mmol g -1 The methane/nitrogen separation selectivity reached 17.9, and the dynamic breakthrough curve at high pressure is shown in FIG. 6. The static adsorption capacity is 0.87mol g under 298K and 1bar -1 The IAST result is 10.3, which is higher than the value reported in the general literature.
The cycle stability test was performed at 298K at 1.1bar and showed good reproducibility over ten adsorption cycles as shown in FIG. 7.
Example 2
The carbon precursor prepared in example 1 (sample C) was placed in a carbonization furnace for carbonization at 3 ℃ for min -1 Heating to 800 deg.C, holding the temperature for 120min, and heating to 5 deg.C for 5 min -1 And (3) heating to 800 ℃ for water vapor activation, wherein the activation time is 20min, obtaining a porous carbon material D, placing the porous carbon material D in an alkali solution at the temperature of 50 ℃ for one day, and washing with deionized water until the solution is neutral, thus obtaining the coffee grounds-based porous carbon adsorbent. The nitrogen adsorption test results show that the BET surface area is about 433m 2 g -1 。
In order to test the separation performance of the above coffee grounds-based porous carbon adsorbent on methane nitrogen, the separation performance was evaluated on a fixed bed apparatus. Separation conditions are as follows: 298K, 1.1bar, the volume ratio of methane to nitrogen is 3:7, and the total flow of the mixed gas is 3ml min -1 . The dynamic adsorption capacity of the coffee residue-based porous carbon adsorbent to methane is calculated to be 0.26mmol g under 298K and 1.1bar -1 The dynamic adsorption amount of nitrogen was 0.085mmol g -1 The separation selectivity of methane/nitrogen reached 7.2.
Example 3
The carbon precursor prepared in example 1 was put into a carbonization furnace to be carbonized at 3 ℃ for min -1 Heating to 850 deg.C, holding the temperature for 120min, and heating to 5 deg.C for 5 min -1 And (3) heating to 900 ℃ for water vapor activation, wherein the activation time is 20min, obtaining a porous carbon material D, placing the porous carbon material D in an alkali solution at the temperature of 50 ℃ for one day, and washing with deionized water until the solution is neutral, thus obtaining the coffee grounds-based porous carbon adsorbent. The nitrogen adsorption test results show that the BET surface area is about 358m 2 g -1 。
In order to test the separation performance of the above coffee grounds-based porous carbon adsorbent on methane nitrogen, the separation performance was evaluated on a fixed bed apparatus. Separation conditions are as follows: 298K, 1.1bar, the volume ratio of methane to nitrogen is 3:7, and the total flow of the mixed gas is 3ml min -1 . The dynamic adsorption capacity of the columnar porous carbon to the methane is calculated to be 0.23mmol g under 298K and 1.1bar -1 The dynamic adsorption amount of nitrogen was 0.096mmol g -1 The separation selectivity of methane/nitrogen reached 6.4.
Comparative example 1
Charring the granular coffee residue in a charring furnace at 3 deg.C for 3 min -1 Heating to 800 deg.C, holding the temperature for 120min, and heating to 5 deg.C for 5 min -1 And (3) heating to 850 ℃ for water vapor activation, wherein the activation time is 40min, and obtaining the porous carbon material. As shown in FIG. 1, the nitrogen adsorption test results showed a BET surface area of about 346m 2 g -1 The mesoporous size distribution is shown in figure 2.
In order to test the separation performance of the above coffee grounds-based porous carbon adsorbent on methane nitrogen, the separation performance was evaluated on a fixed bed apparatus. Separation conditions are as follows: 298K, 1.1bar, the volume ratio of methane to nitrogen is 3:7, and the total flow of the mixed gas is 3ml min -1 . The dynamic adsorption capacity of the columnar porous carbon to the methane is calculated to be 0.34mmol g under 298K and 1.1bar -1 The dynamic adsorption amount of nitrogen was 0.5mmol g -1 The methane/nitrogen separation selectivity was 1.6, and the dynamic breakthrough curve at atmospheric pressure is shown in FIG. 5.
Comparative example 2
Weighing50g>Adding 3.5g of sesbania powder serving as an extrusion aid into 100-mesh coffee grounds, and uniformly stirring the coffee grounds and the sesbania powder in a stirrer to obtain a sample A; preparing 65g of 9 wt% sodium silicate aqueous solution, adding the sodium silicate aqueous solution in batches, stirring uniformly to obtain a sample B, adding the sample B into a strip extruding machine for extrusion molding, finishing the strip into 10-20mm, drying to obtain a sample C, placing the sample C into a carbonization furnace for carbonization at 3 ℃ for min -1 Heating to 800 deg.C, holding the temperature for 120min, and heating to 5 deg.C for 5 min -1 And (3) heating to 850 ℃ for water vapor activation, wherein the activation time is 40min, so as to obtain a porous carbon material D, placing the porous carbon material D in an alkali solution at 50 ℃ for one day, and washing with deionized water until the solution is neutral, so as to obtain the coffee grounds-based porous carbon adsorbent. As shown in FIG. 1, the nitrogen adsorption test results showed that the BET surface area was about 335m 2 g -1 The mesoporous size distribution is shown in fig. 2, and the infrared spectrum is shown in fig. 4, it can be seen that example 1 contains more oxygen-containing functional groups and is richer in mesopores.
In order to test the separation performance of the coffee grounds-based porous carbon adsorbent on methane nitrogen, the separation performance was evaluated on a fixed bed apparatus. Separation conditions are as follows: 298K, 1.1bar, the volume ratio of methane to nitrogen is 3:7, and the total flow of the mixed gas is 3ml min -1 . The dynamic adsorption capacity of the coffee residue-based porous carbon adsorbent to methane is calculated to be 0.29mmol g under 298K and 1.1bar -1 The dynamic adsorption amount of nitrogen was 0.14mmol g -1 The separation selectivity of methane/nitrogen reached 4.7.
Claims (6)
1. The application of the coffee grounds-based molded porous carbon adsorbent in high-efficiency methane/nitrogen separation is characterized in that: the preparation method of the coffee grounds-based molded porous carbon adsorbent comprises the following steps:
(1) mixing the coffee grounds with an extrusion aid, and marking as a sample A;
(2) uniformly mixing an inorganic silicate solution and the sample A, and marking as a sample B, wherein the mass ratio of the inorganic silicate solution to the coffee grounds is 1.4:1-1.6: 1;
(3) extruding and molding the sample B in a strip extruding machine, breaking the strip, and drying at room temperature to obtain a sample C;
(4) putting the sample C into a carbonization furnace, and carbonizing and activating under the protection of inert gas to obtain a porous carbon material;
(5) and (3) placing the porous carbon material in an alkali solution at 50-100 ℃ for 24h, and washing with deionized water to be neutral to obtain the coffee grounds-based formed porous carbon adsorbent.
2. The use of a coffee grounds-based shaped porous carbon adsorbent in high efficiency methane/nitrogen separation as claimed in claim 1, wherein: the inorganic silicate is one or more of kaolin, sepiolite, laponite, montmorillonite, sodium silicate, calcium silicate and potassium silicate.
3. The use of a coffee grounds-based shaped porous carbon adsorbent in high efficiency methane/nitrogen separation as claimed in claim 1, wherein: the mass fraction of the inorganic silicate solution is 8-15 wt%.
4. The use of a coffee grounds-based shaped porous carbon adsorbent in high efficiency methane/nitrogen separation as claimed in claim 1, wherein: the extrusion aid is sesbania powder, and the mass ratio of the sesbania powder to the coffee grounds is 0.05:1-0.1: 1.
5. The use of a coffee grounds-based shaped porous carbon adsorbent in high efficiency methane/nitrogen separation as claimed in claim 1, wherein: the carbonization temperature is 700-1000 ℃, and the carbonization time is 1-3 h; the activation temperature is 750-.
6. The use of a coffee grounds-based shaped porous carbon adsorbent in high efficiency methane/nitrogen separation as claimed in claim 1, wherein: methane/nitrogen is 0.1-0.9, the temperature of adsorption separation is 273-298K, and the total pressure of the mixed gas is 1-5 bar.
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