CN115090265A - Preparation method of refinery dry gas ethylene high-efficiency adsorbent - Google Patents
Preparation method of refinery dry gas ethylene high-efficiency adsorbent Download PDFInfo
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- CN115090265A CN115090265A CN202210776696.1A CN202210776696A CN115090265A CN 115090265 A CN115090265 A CN 115090265A CN 202210776696 A CN202210776696 A CN 202210776696A CN 115090265 A CN115090265 A CN 115090265A
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000005977 Ethylene Substances 0.000 title claims abstract description 37
- 239000003463 adsorbent Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 41
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 39
- 239000001923 methylcellulose Substances 0.000 claims abstract description 39
- 235000010981 methylcellulose Nutrition 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000013335 mesoporous material Substances 0.000 claims abstract description 19
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 54
- 238000001035 drying Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 59
- 239000003795 chemical substances by application Substances 0.000 abstract description 20
- 238000005469 granulation Methods 0.000 abstract description 19
- 230000003179 granulation Effects 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 26
- 239000012621 metal-organic framework Substances 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 238000003795 desorption Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005406 washing Methods 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
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- Organic Chemistry (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a preparation method of a refinery dry gas ethylene high-efficiency adsorbent, wherein the main body of the adsorbent is UTSA-280(Ca (C) 4 O 4 ) UTSA-280 raw powder material and active carbon or ordered mesoporous material are simply and mechanically mixed according to a certain proportion, and after the raw powder material and the active carbon or ordered mesoporous material are uniformly mixed, a forming agent is prepared, the forming agent is environment-friendly methyl cellulose, the MOF-based adsorbent with certain granularity, mechanical strength and excellent adsorption performance and a multistage pore structure can be simply and massively produced by simply mixing again and adopting an extrusion type granulation mode, the MOF-based adsorbent shows excellent trapping effect on low-concentration ethylene in refinery dry gas, and can be used for trapping low-concentration ethylene in refinery dry gasThe ethylene of the low-concentration refinery dry gas is desorbed and purified to more than 80 percent in one step.
Description
Technical Field
The invention relates to a gas separation technology, in particular to a preparation method of a refinery dry gas ethylene high-efficiency adsorbent.
Background
During the secondary processing of crude oil, a large amount of dry gas is generated, such as the production processes of catalytic cracking, thermal cracking and the like of heavy oil, the main components of the dry gas are methane, ethylene, ethane, propylene, hydrogen, nitrogen and the like, and catalytic cracking (FCC) is the most important secondary processing method for increasing the processing depth of crude oil. A large amount of dry gas is generated in the production process, and generally accounts for 4-5% of the crude oil processing amount. The natural gas fuel contains a large amount of light hydrocarbon and hydrogen, has high utilization value, but has overhigh energy consumption for separation and purification, is generally conveyed to a natural gas pipeline network to be used as fuel gas, even some natural gas fuel is directly introduced into a torch to be combusted, and a large amount of energy resources are wasted. The improvement of the utilization rate of the gases and the conversion of the gases into green clean chemical products with economic value are a great challenge to green chemical production.
With the increasing requirements of adsorption separation technology and the continuous emphasis on cleanness and environmental protection, more efficient, green, structure-customizable and surface-property-adjustable adsorbents are increasingly emphasized. In the development of porous adsorption materials for more than twenty years, the application of MOF materials in the adsorption field is receiving wide attention. Compared with the traditional porous solid material, the MOF has the advantages of higher specific surface area and pore volume, functionalizable pore surface, adjustable pore size and the like. The MOF is considered as an advanced porous nano material in the field of adsorption separation and shows a huge application prospect.
However, in the prior art, MOF synthesis and formation have limited large-scale application in the field of gas separation due to harsh preparation conditions and low yield, and different MOF materials have different formation conditions due to different structural characteristics. Although some MOF forming processes exist in the prior art, the forming processes are difficult to be applied to other types of MOFs, and the forming process of one MOF is often only applicable to the forming of the MOF, so that the application of the MOF to other MOF materials is difficult to expand. CN112705168A selects polyvinyl alcohol and methylcellulose to compound ZIF-7 powder for molding, so as to obtain ZIF-7 spherical particles with higher loading rate, and on the premise of ensuring higher mechanical strength, the adsorption amount also maintains 89% of the original powder, and the separation performance is close to that of the original powder, but the molding method is not suitable for UTSA-280 materials, and the adsorption effect of MOF can be greatly influenced.
Accordingly, the present invention has been made keeping in mind the above problems.
Disclosure of Invention
The invention provides a preparation method of an ethylene high-efficiency adsorbent for refinery dry gas, which reduces the molding difficulty of MOF materials and furthest reserves the adsorption performance of UTSA-280 materials.
The technical scheme adopted by the invention is as follows:
a preparation method of a refinery dry gas ethylene high-efficiency adsorbent comprises the following steps:
step 1: uniformly mixing UTSA-280 and activated carbon or an ordered mesoporous material to form a powder mixture;
and 2, step: mixing the aqueous solution of the methyl cellulose with the powder mixture in the step 1, stirring the mixture into blocks, and molding the blocks by using extrusion molding equipment;
further, in the step 1, activated carbon or an ordered mesoporous material is adopted to be pretreated, the influence of impurities is removed, and the activated carbon or the ordered mesoporous material is washed for two to three times by absolute ethyl alcohol and dried; the active carbon is 100-mesh active carbon.
Further, in the step 2, the dosage of the methyl cellulose is 3-5% of the mass of the mixed solid powder;
further, the mass percentage of the methyl cellulose in the methyl cellulose water solution is 3-7%; the mass of the methyl cellulose water solution is 80-90% of that of the powder mixture; the mass ratio of the activated carbon or the ordered mesoporous material to the powder mixture is 5-40: 100.
further, in step 3, during the drying and curing process, the curing time is controlled within 12-36 hours according to the size of the particles to be prepared.
In the forming process, active carbon or ordered mesoporous materials (SBA-15, MCM-41 and the like) are pretreated, absolute ethyl alcohol is used for washing away surface stains, the influence of impurity molecules on adsorption and separation effects is reduced, water-soluble methyl cellulose is used as a forming agent, the using amount is small, rapid granulation can be realized through a simple granulation technology, solidification can be realized after drying, and the forming agent is put into production and use.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1) compared with the traditional MOF forming preparation method, the invention adopts a mixed forming method by adding activated carbon or ordered mesoporous materials, reserves the contact channel of the UTSA-280 material and avoids the blockage of the directly formed pore channel; meanwhile, the 100-mesh active carbon has very low alkane and olefin adsorption amount, plays a role in mass transfer conduction, realizes the effect of strengthening mass transfer, further improves the adsorption performance, and can reach about 80 percent of the adsorption performance of the original powder compared with the adsorption performance of unformed UTSA-280.
2) Compared with the MOF prepared by traditional forming, the MOF prepared by the invention has the advantages that the adsorption performance of the MOF is well reserved, and the MOF has a more excellent trapping effect on the efficient trapping of low-concentration ethylene.
Drawings
FIG. 1 is an XRD pattern of shaped particles after shaping with various shaping agents;
FIG. 2 shows the ethylene adsorption capacity of particles formed by using carboxymethyl cellulose, polymethyl methacrylate, sesbania powder, and polyvinyl alcohol as forming agents;
FIG. 3 shows the ethylene adsorption amount of granules formed by using methylcellulose, polyethylene glycol, hydroxypropyl cellulose and polyvinylpyrrolidone as forming agents;
FIG. 4 shows the ethylene adsorption amount of the formed particles by adding SBA-15 in different proportions to methyl cellulose as a forming agent;
FIG. 5 shows the ethylene adsorption amount of particles formed by adding activated carbon in different proportions to methylcellulose as a forming agent;
FIG. 6 is an ethylene capture penetration curve of shaped particles under a simulated refinery dry gas environment, wherein methylcellulose is used as a shaping agent, 100-mesh 8 wt% activated carbon is added, and the loading capacity of an adsorbent is 1.5kg, and the gas flow is 3L/min;
FIG. 7 shows an ethylene capture desorption curve of shaped particles in a simulated refinery dry gas environment, wherein the ethylene capture desorption curve is formed by adding 100-mesh activated carbon with a mass fraction of 8 wt% into methyl cellulose serving as a shaping agent, and the loading capacity of an adsorbent is 1.5kg, and the desorption gas flow is 2L/min;
FIG. 8 shows the desorption curve of ethylene capture desorption percentage (unit adjustment according to FIG. 7) of the formed particles in the dry gas environment of a simulated refinery by adding 100 mesh 8 wt% activated carbon into methyl cellulose as forming agent
FIG. 9 shows that methyl cellulose is used as a forming agent, 100 meshes of 8 wt% active carbon is added for forming particles, and ethane and ethylene pressure swing adsorption and desorption are carried out under a simulated cycle test, and the loading capacity of the adsorbent is 1.5kg, and the gas flow is 1L/min;
fig. 10 shows the performance of the prepared adsorbent in room temperature air environment, humid air environment, and simulated industrial acid and alkali gas atmosphere.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific examples and experimental data, and it should be understood that the specific examples described herein are only for the purpose of explaining the present invention and are not intended to limit the present invention.
Example 1
Mixing 9.5g of UTSA-280 powder with 0.5g of sesbania powder, adding 8ml of deionized water, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying in an oven at 60 ℃ for 12h, and characterizing the mechanical strength and the adsorption performance.
Example 2
Mixing 9.5g of UTSA-280 powder with 0.5g of polyvinyl alcohol, adding 8ml of deionized water, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying in an oven at 60 ℃ for 12h, and characterizing the mechanical strength and the adsorption performance.
Example 3
Mixing 9.5g of UTSA-280 powder with 0.5g of carboxymethyl cellulose, adding 8ml of deionized water, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying in an oven at 60 ℃ for 12 hours, and characterizing the mechanical strength and the adsorption performance.
Example 4
Mixing 9.5g of UTSA-280 powder with 0.5g of methylcellulose, adding 8ml of deionized water, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying in an oven at 60 ℃ for 12h, and characterizing the mechanical strength and the adsorption performance.
Example 5
Mixing 9.5g of UTSA-280 powder with 0.5g of polymethyl methacrylate, adding 8ml of deionized water, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying in an oven at 60 ℃ for 12 hours, and characterizing the mechanical strength and the adsorption performance of the particles.
Example 6
Mixing 9.5g of UTSA-280 powder with 0.5g of hydroxypropyl cellulose, adding 8ml of deionized water, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying in an oven at 60 ℃ for 12h, and characterizing the mechanical strength and the adsorption performance.
Example 7
Mixing 9.5g of UTSA-280 powder with 0.5g of polyethylene glycol, adding 8ml of deionized water, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying in an oven at 60 ℃ for 12h, and characterizing the mechanical strength and the adsorption performance.
Example 8
Adding 9.5g of UTSA-280 powder and 0.5g of polyvinylpyrrolidone into 8ml of deionized water, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying in an oven at 60 ℃ for 12h, and characterizing the mechanical strength and the adsorption performance.
Example 9
Adding 9.5g of UTSA-280 powder and 0.5g of erythritol into 8ml of deionized water, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying in an oven at 60 ℃ for 12h, and characterizing the mechanical strength and the adsorption performance of the particles.
Example 10
Mixing 9.5g UTSA-280 powder with 20-30ml water, stirring, adding 0.5g sodium alginate, and dripping into CaCl containing 0.1mol/L 2 In the solution, particles with the particle size of 2-3mm are obtained by controlling the flow rate and the opening size of a dropping ball tube, and are dried in a 60 ℃ oven for 12 hours, and the mechanical strength and the adsorption performance of the particles are represented.
Example 11
Adding 9.5g of UTSA-280 powder and 0.5g of kaolin into 8ml of deionized water, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying in an oven at 60 ℃ for 12h, and characterizing the mechanical strength and the adsorption performance of the particles.
The mechanical strength of the above examples is shown in the following table, and the adsorption performance is characterized as shown in fig. 1.
And (3) verifying the mechanical strength of the obtained formed particles, and screening out a part of materials with better mechanical strength and complete XRD signal peaks for carrying out adsorption performance test. As can be seen from examples 1-11, carboxymethylcellulose, methylcellulose, polyethylene glycol have higher mechanical strength, indicating that these components can greatly enhance the mechanical strength and abrasion resistance of MOF. Only products with the mechanical strength of more than 20N can be applied to the industry, and the research on the adsorption performance of the products with the mechanical strength of more than 20N on ethylene shows that the molded products prepared from the methylcellulose have higher adsorption strength, and the adsorption capacity can reach 30-40cm 3 The adsorption capacity of other products is far lower than that of methyl cellulose, because the forming agent can cause certain pore channel blockage in the forming process, which is a main problem existing in most MOF forming processes, and in order to further improve the adsorption performance after MOF forming, the blocking effect of the forming agent on MOF pore channels needs to be reduced.
Example 12
Uniformly mixing 6.65g of UTSA-280 powder and 3.35g of SBA-15, adding 0.5g of methylcellulose into 8ml of deionized water, mixing the powder and the methylcellulose solution, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying for 12 hours in a 60 ℃ oven to obtain a sample classification, namely a control group 1, and characterizing the mechanical strength and the adsorption performance of the sample classification.
Example 13
Uniformly mixing 7.5g of UTSA-280 powder and 2.5g of SBA-15, adding 0.5g of methylcellulose into 8ml of deionized water, mixing the powder and the methylcellulose solution, stirring the mixture into blocks, then granulating the blocks by using granulation equipment to obtain particles with the particle size of 2-3mm, drying the particles in an oven at the temperature of 60 ℃ for 12 hours to obtain a sample classification, namely a control group 2, and characterizing the mechanical strength and the adsorption performance of the sample classification.
Example 14
Uniformly mixing 9g of UTSA-280 powder and 1g of SBA-15, adding 0.5g of methylcellulose into 8ml of deionized water, mixing the powder and the methylcellulose solution, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying for 12 hours in a 60 ℃ oven to obtain a sample classification group, namely a control group 3, and characterizing the mechanical strength and the adsorption performance of the sample classification group.
Example 15
Uniformly mixing 9g of UTSA-280 powder and 1g of activated carbon, adding 0.5g of methylcellulose into 8ml of deionized water, mixing the powder and a methylcellulose solution, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying for 12 hours in a 60 ℃ oven to obtain a sample classification simply called as a control group 4, and characterizing the mechanical strength and the adsorption performance of the sample classification simply called as a control group 4.
Example 16
Uniformly mixing 8g of UTSA-280 powder and 2g of activated carbon, adding 0.5g of methylcellulose into 8ml of deionized water, mixing the powder and a methylcellulose solution, stirring into blocks, granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying for 12 hours in a 60-DEG C oven to obtain a sample classification reference group 5, and characterizing the mechanical strength and the adsorption performance of the sample classification reference group.
Example 17
Uniformly mixing 6.67g of UTSA-280 powder and 3.33g of activated carbon, adding 0.5g of methylcellulose into 8ml of deionized water, mixing the powder and the methylcellulose solution, stirring into blocks, then granulating by using granulation equipment to obtain particles with the particle size of 2-3mm, drying for 12 hours in a 60 ℃ oven to obtain a sample classification, namely a control group 6, and characterizing the mechanical strength and the adsorption performance of the sample classification.
TABLE 2 mechanical Strength results for the products of the examples and comparative examples
The adsorption is characterized by selecting ASAP 2020, the adsorption performance is shown in the attached drawing, the capture performance test of ethylene in refinery dry gas is carried out on the particles which are modified and formed by the activated carbon and take methylcellulose as the forming agent, the test flow is 3L/min, the loading capacity of the adsorbent is 1.5kg, and the adsorption pressure is 3 bar.
TABLE 3 composition of refinery dry gas
From the mechanical strength and the adsorption performance of examples 12 to 17, it can be found that the mechanical strength of the formed UTSA-280 is reduced by the activated carbon or the mesoporous material, but the actual industrial requirements can be met, and the mechanical strength is greater than 20N, so that the UTSA-280 can be industrially applied in a large scale. Although the mesoporous material can reduce the mechanical strength of the formed UTSA-280, the mesoporous material can increase the adsorption performance of the formed UTSA-280, particularly reduce the blockage of the pore channel of the UTSA-280 caused by a forming agent, and play a role in mass transfer during gas adsorption, thereby improving the adsorption performance of the UTSA-280, and the adsorption performance of the mesoporous material can reach about 80 percent at most compared with the adsorption performance of the UTSA-280 formed without the mesoporous material. The control groups 1-3 and 4-6 show the adsorption performance of UTSA-280 after adding activated carbon or ordered mesoporous material, and the rich mesopores of SBA-15 or activated carbon reduce the blockage of the forming agent and efficiently adsorb ethylene at lower concentration.
In order to further verify the adsorption effect of the formed UTSA-280 on the refinery dry gas, an ethylene capture penetration experiment under a refinery dry gas ring simulation is carried out on UTSA-280 formed particles added with an activated carbon mesoporous material and a forming agent of methyl cellulose, wherein the loading capacity of an adsorbent is 1.5kg, the gas flow is 3L/min, the adsorption pressure is 3bar, and other experimental steps are the same as those recorded in the prior art. The results of fig. 6, 7 and 8 show that the UTSA-280 formed particles added with activated carbon and methyl cellulose as the forming agent have good adsorption selectivity to low-concentration ethylene in refinery dry gas, have significant adsorption effect on the low-concentration ethylene, can desorb and purify the low-concentration ethylene to more than 85-95% in one step, and only need to remove CO by simple subsequent treatment 2 And the high-purity ethylene can be obtained by four components of carbon, on the basis, a cyclic PSA adsorption breakthrough test of ethane/ethylene (50/50) is carried out, the purity of the ethylene can be obtained by stages and is more than 85%, and meanwhile, the material prepared as shown in figure 10 can still maintain excellent adsorption service performance under the room-temperature air environment, the humid air environment and the simulated industrial acid and alkali gas atmosphere.
Claims (7)
1. A preparation method of a refinery dry gas ethylene high-efficiency adsorbent is characterized by comprising the following steps:
step 1: uniformly mixing UTSA-280 and activated carbon or an ordered mesoporous material to form a powder mixture;
step 2: mixing the aqueous solution of the methyl cellulose with the powder mixture in the step 1, stirring the mixture into blocks, and molding the blocks by using extrusion molding equipment;
step 3; and drying and curing the formed particles in an oven.
2. The method for preparing the refinery dry gas ethylene high-efficiency adsorbent according to claim 1, wherein in the step 1, the activated carbon or the ordered mesoporous material needs to be pretreated to remove the influence of impurities, washed two to three times by the anhydrous ethanol and dried.
3. The method for preparing the refinery dry gas ethylene high-efficiency adsorbent according to claim 1, wherein in the step 2, the mass of the methylcellulose is 3-5% of the mass of the mixed solid powder; the mass percentage of the methyl cellulose in the methyl cellulose water solution is 3-7%.
4. The method for preparing the refinery dry gas ethylene high-efficiency adsorbent according to claim 1, wherein in the step 2, the mass of the aqueous solution of the methyl cellulose is 80-90% of that of the powder mixture; the ordered mesoporous material is SBA-15.
5. The preparation method of the refinery dry gas ethylene high-efficiency adsorbent as claimed in claim 1, wherein the mass ratio of the activated carbon or the ordered mesoporous material to the powder mixture is 5-40: 100.
6. the method for preparing the refinery dry gas ethylene high-efficiency adsorbent according to claim 1, wherein in the step 3, the solidification time is controlled within 12-36 hours.
7. The method for preparing the refinery dry gas ethylene high-efficiency adsorbent according to claim 1, wherein the activated carbon is 100-mesh activated carbon.
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