CN113117638B - Preparation method of special-shaped adsorbent - Google Patents
Preparation method of special-shaped adsorbent Download PDFInfo
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- CN113117638B CN113117638B CN201911418460.5A CN201911418460A CN113117638B CN 113117638 B CN113117638 B CN 113117638B CN 201911418460 A CN201911418460 A CN 201911418460A CN 113117638 B CN113117638 B CN 113117638B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000008188 pellet Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 22
- 239000002808 molecular sieve Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000004898 kneading Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 10
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 10
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 10
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- 229920002261 Corn starch Polymers 0.000 claims description 9
- 229930006000 Sucrose Natural products 0.000 claims description 9
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000008120 corn starch Substances 0.000 claims description 9
- 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 9
- 239000005720 sucrose Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 239000000546 pharmaceutical excipient Substances 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 6
- 229960000892 attapulgite Drugs 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910052625 palygorskite Inorganic materials 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 241001494479 Pecora Species 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
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- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 3
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000002639 bone cement Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035040 seed growth Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005563 spheronization Methods 0.000 description 1
Classifications
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- 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
- 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
- B01J20/28042—Shaped bodies; Monolithic structures
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of special-shaped adsorbent particles. In the method, firstly, extruding the mixed material, and rounding the obtained strip-shaped particles and hard inert pellets in a rounding machine to obtain a round cake-shaped adsorbent with concave centers on two sides; and carrying out subsequent treatment on the cake-shaped adsorbent particles to obtain the special-shaped adsorbent. The special-shaped adsorbent particles prepared by the method have the advantages of large external specific surface area, high gas mass transfer rate and the like; meanwhile, the production process is simple, the equipment investment is low, the yield is high, and the method is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of catalyst or adsorbent design, in particular to preparation and application of a special-shaped adsorbent.
Background
In the pressure swing adsorption field, spherical and bar adsorbents are commonly used. Although the spherical adsorbent is regularly filled, the utilization rate of the inside of the spherical adsorbent is low, and meanwhile, the void ratio among the adsorbents is low, so that the pressure drop is large. The strip-shaped adsorbent has the defects of simple preparation, easy abrasion, high filling void ratio, easy penetration of gas and the like.
In the aspect of adsorbent design, researchers pay attention to raw powder of the adsorbent, a binder, a preparation method and the like, and the influence on the shape of the adsorbent is rarely reported. In the prior patent, a report on a special-shaped catalyst is mainly provided, and CN 106824254A reports a special-shaped catalyst carrier, a preparation method and application thereof. The invention adopts a seed growth mode, the shape of the surface of the catalyst carrier is controlled by adjusting the concentration of the sprayed acid solution, the obtained special-shaped catalyst is a barbed spherical catalyst carrier particle, the shape is uniform, the surface area is large, the sphericity is reserved at the same time, the pressure drop of the reaction gas passing through a bed layer is more favorable to be reduced, the phenomenon of uneven gas distribution in a reactor is improved, the phenomena of channeling and dead volume are reduced, but the preparation method is too complicated, and the large-scale industrial production is unfavorable.
Disclosure of Invention
Aiming at the defects of the prior art, the invention develops the special-shaped adsorbent which has large external specific surface area and high gas mass transfer rate and is easy for industrial production.
The preparation method of the special-shaped adsorbent comprises the following steps:
(1) Fully kneading the mixed material with a certain amount of water;
(2) Adding the uniformly kneaded dough into a strip extruder for strip extrusion to obtain a strip-shaped adsorbent;
(3) The strip-shaped adsorbent and the inert pellets obtained in the step (2) are put into a rounding machine for rounding, and in the rounding process, the round-cake-shaped adsorbent (or erythrocyte-shaped adsorbent) with concave centers on two sides is formed due to the extrusion of the two sides of the inert pellets;
(4) And (3) screening the material obtained in the step (3), recycling the inert pellets, and carrying out subsequent treatment on the round cake-shaped special-shaped adsorbent.
The mixed material in the step (1) is prepared by uniformly mixing a molecular sieve, a binder and an auxiliary agent according to a certain proportion.
Specifically, the molecular sieve is a 4A molecular sieve. The binder is one or more of kaolin, bentonite, sheep's sweet soil and attapulgite. The auxiliary agent is one or more of sesbania powder, corn starch, tannin extract, citric acid and tartaric acid.
The extrusion operation described in step (2) is familiar to those skilled in the art.
The inert pellets in step (3) have a mohs hardness of 9 or more and a density similar to that of the adsorbent in the form of a bar. The diameter of the inert pellets is 1/2-1/4 of the diameter of the strip-shaped adsorbent in the step (2), and the number of the inert pellets is generally 2-3 times that of the strip-shaped adsorbent. The inert adsorption beads may be selected from one of zirconia beads and inert porcelain beads, preferably zirconia beads.
In order to enhance the shaping effect of the inert pellets on the strip-shaped adsorbent, the inert pellets are preferably subjected to a pre-wetting treatment prior to addition to step (3). The pre-wetting may be achieved by rapid impregnation of the inert pellets with water or sucrose solution.
Further, in step (3), an excipient is added to the spheronization system along with the inert pellets. The excipient is generally selected from at least one of microcrystalline cellulose and bone gelatin, preferably microcrystalline cellulose. The addition amount of the excipient is generally 1 to 5 percent of that of the inert pellets.
The subsequent treatment process described in the step (4) is generally as follows: drying the obtained special-shaped adsorbent at 50-150 ℃, and roasting at 600-750 ℃; after cooling, carrying out crystal transformation in NaOH solution with the concentration of 0.05 mol/L-3 mol/L; then the concentration of CaCl is 0.05mol/L to 3mol/L 2 Exchanging in solution, drying at 50-150deg.C, and calcining at 300-450deg.C to obtain the final product.
Compared with the prior art, the method has the beneficial effects that:
1. the method can prepare the erythrocyte type adsorbent material, and the shape adsorbent has the advantages of both the strip adsorbent and the spherical adsorbent, and has the characteristics of low abrasion rate and high mass transfer rate.
2. The excipient is added in the process of rounding the strip-shaped adsorbent material, so that the method is beneficial to the forming of the erythrocyte-shaped adsorbent in the process of rounding, and further improves the yield of the special-shaped adsorbent.
3. According to the invention, the inert pellets are immersed in water or pre-immersed in a sucrose solution before being added, so that the zirconia pellets are more easily attached to the surface of the adsorbent, and the yield of the special-shaped adsorbent can be improved.
4. The special-shaped particle adsorbent prepared by the method has high mass transfer efficiency and certain strength particles, and the preparation method is simple and is beneficial to large-scale production.
Drawings
FIG. 1 is a schematic diagram of a special-shaped adsorbent obtained by the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Mixing the raw 4A molecular sieve powder with the mass fraction of 85%, kaolin with the mass fraction of 13% and corn starch with the mass fraction of 2%, and fully kneading the uniformly mixed materials with a certain amount of water; adding the uniformly kneaded dough into a single-screw strip extruder for strip extrusion, cutting the obtained strip-shaped adsorbent into cylinders with the length of 3mm, wherein the die is a round hole with the length of 1.5 mm; putting 1000 strip-shaped adsorbents into a rounding machine for rounding, and simultaneously adding 2000 zirconia pellets with the diameter of 0.5mm to obtain a round cake-shaped adsorbent with concave centers on two sides; drying the obtained special-shaped adsorbent at 100deg.C, roasting at 700deg.C, cooling, crystallizing in NaOH solution with concentration of 1mol/L, and crystallizing in CaCl of 0.25mol/L 2 Exchanging in the solution, drying at 100 ℃, and roasting at 350 ℃ to obtain the special-shaped adsorbent finished product.
Example 2
Mixing the raw 4A molecular sieve powder with the mass fraction of 85%, kaolin with the mass fraction of 13% and corn starch with the mass fraction of 2%, and fully kneading the uniformly mixed materials with a certain amount of water; adding the uniformly kneaded dough into a single-screw strip extruder for strip extrusion, cutting the obtained strip-shaped adsorbent into cylinders with the length of 3mm, wherein the die is a round hole with the length of 1.5 mm; putting 1000 strip-shaped adsorbents into a rounding machine for rounding, simultaneously adding 2000 zirconia pellets with the diameter of 0.5mm, and adding microcrystalline cellulose with the mass fraction of 2% of the zirconia pellets to obtain a round cake-shaped adsorbent with concave centers on both sides; adsorbing the obtained special-shaped adsorbentDrying the agent at 100deg.C, roasting at 700deg.C, cooling, crystallizing in NaOH solution with concentration of 1mol/L, and crystallizing in CaCl of 0.25mol/L 2 Exchanging in the solution, drying at 100 ℃, and roasting at 350 ℃ to obtain the special-shaped adsorbent finished product.
Example 3
Mixing the raw 4A molecular sieve powder with the mass fraction of 85%, kaolin with the mass fraction of 13% and corn starch with the mass fraction of 2%, and fully kneading the uniformly mixed materials with a certain amount of water; adding the uniformly kneaded dough into a single-screw strip extruder for strip extrusion, cutting the obtained strip-shaped adsorbent into cylinders with the length of 3mm, wherein the die is a round hole with the length of 1.5 mm; putting 1000 strip-shaped adsorbents into a rounding machine for rounding, simultaneously adding 2000 zirconia pellets soaked by sucrose solution with the diameter of 0.5mm, and adding microcrystalline cellulose with the mass fraction of 2% of the zirconia pellets to obtain a round cake-shaped adsorbent with concave centers on both sides; drying the obtained special-shaped adsorbent at 100deg.C, roasting at 700deg.C, cooling, crystallizing in NaOH solution with concentration of 1mol/L, and crystallizing in CaCl of 0.25mol/L 2 Exchanging in the solution, drying at 100 ℃, and roasting at 350 ℃ to obtain the special-shaped adsorbent finished product.
Example 4
Mixing 80% of 4A molecular sieve raw powder, 18% of kaolin and 2% of corn starch, and fully kneading the uniformly mixed materials with a certain amount of water; adding the uniformly kneaded dough into a single-screw strip extruder for strip extrusion, cutting the obtained strip-shaped adsorbent into cylinders with the length of 3mm, wherein the die is a round hole with the length of 1.5 mm; putting 1000 strip-shaped adsorbents into a rounding machine for rounding, simultaneously adding 2000 zirconia pellets soaked by sucrose solution with the diameter of 0.5mm, and adding microcrystalline cellulose with the mass fraction of 2% of the zirconia pellets to obtain a round cake-shaped adsorbent with concave centers on both sides; drying the obtained special-shaped adsorbent at 100deg.C, roasting at 750deg.C, cooling, and adding into NaOH solution with concentration of 1mol/LTransferring crystal, then adding CaCl of 0.25mol/L 2 Exchanging in the solution, drying at 100 ℃, and roasting at 350 ℃ to obtain the special-shaped adsorbent finished product.
Example 5
Mixing 85% of 4A molecular sieve raw powder, 13% of attapulgite and 2% of sesbania powder, and fully kneading the uniformly mixed materials with a certain amount of water; adding the uniformly kneaded dough into a single-screw strip extruder for strip extrusion, cutting the obtained strip-shaped adsorbent into cylinders with the length of 3mm, wherein the die is a round hole with the length of 1.5 mm; putting 1000 strip-shaped adsorbents into a rounding machine for rounding, simultaneously adding 2000 zirconia pellets soaked by sucrose solution with the diameter of 0.5mm, and adding microcrystalline cellulose with the mass fraction of 2% of the zirconia pellets to obtain a round cake-shaped adsorbent with concave centers on both sides; drying the obtained special-shaped adsorbent at 100deg.C, roasting at 750deg.C, cooling, crystallizing in NaOH solution with concentration of 1mol/L, and crystallizing in CaCl of 0.25mol/L 2 Exchanging in the solution, drying at 100 ℃, and roasting at 350 ℃ to obtain the special-shaped adsorbent finished product.
Example 6
Mixing the raw 4A molecular sieve powder with the mass fraction of 85%, kaolin with the mass fraction of 12%, corn starch with the mass fraction of 2% and citric acid with the mass fraction of 1%, and fully kneading the uniformly mixed materials with a certain amount of water; adding the uniformly kneaded dough into a single-screw strip extruder for strip extrusion, cutting the obtained strip-shaped adsorbent into cylinders with the length of 3mm, wherein the die is a round hole with the length of 1.5 mm; putting 1000 strip-shaped adsorbents into a rounding machine for rounding, simultaneously adding 2000 zirconia pellets soaked by sucrose solution with the diameter of 0.5mm, and adding microcrystalline cellulose with the mass fraction of 3% of the zirconia pellets to obtain a round cake-shaped adsorbent with concave centers on both sides; drying the obtained special-shaped adsorbent at 100deg.C, roasting at 700deg.C, cooling, crystallizing in NaOH solution with concentration of 1mol/L, and crystallizing in CaCl of 0.25mol/L 2 Exchange in solution at 100deg.CDrying and roasting at 350 ℃ to obtain the finished product of the special-shaped adsorbent.
Example 7
Mixing 85% of 4A molecular sieve raw powder, 13% of attapulgite and 2% of sesbania powder, and fully kneading the uniformly mixed materials with a certain amount of water; adding the uniformly kneaded dough into a single-screw strip extruder for strip extrusion, cutting the obtained strip-shaped adsorbent into cylinders with the length of 3mm, wherein the die is a round hole with the length of 1.5 mm; putting 1000 strip-shaped adsorbents into a rounding machine for rounding, simultaneously adding 2000 zirconia pellets soaked by sucrose solution with the diameter of 0.5mm, and adding microcrystalline cellulose with the mass fraction of 2% of the zirconia pellets to obtain a round cake-shaped adsorbent with concave centers on both sides; drying the obtained special-shaped adsorbent at 100deg.C, roasting at 750deg.C, cooling, crystallizing in NaOH solution with concentration of 1mol/L, and crystallizing in CaCl of 0.25mol/L 2 Exchanging in the solution, drying at 100 ℃, and roasting at 350 ℃ to obtain the special-shaped adsorbent finished product.
Example 8
Mixing 85% of 4A molecular sieve raw powder, 13% of attapulgite and 2% of sesbania powder, and fully kneading the uniformly mixed materials with a certain amount of water; adding the uniformly kneaded dough into a single-screw strip extruder for strip extrusion, cutting the obtained strip-shaped adsorbent into cylinders with the length of 3mm, wherein the die is a round hole with the length of 1.5 mm; putting 1000 strip-shaped adsorbents into a rounding machine for rounding, simultaneously adding 2000 zirconia pellets soaked by sucrose solution with the diameter of 0.5mm, and adding microcrystalline cellulose with the mass fraction of 2% of the zirconia pellets to obtain a round cake-shaped adsorbent with concave centers on both sides; drying the obtained special-shaped adsorbent at 120deg.C, roasting at 750deg.C, cooling, crystallizing in 2mol/L NaOH solution, and crystallizing in 0.5mol/L CaCl 2 Exchanging in the solution, drying at 100 ℃, and roasting at 350 ℃ to obtain the special-shaped adsorbent finished product.
Comparative example 1
Mixing raw 4A molecular sieve powder with a mass fraction of 85%, kaolin with a mass fraction of 13% and corn starch with a mass fraction of 2%, fully kneading the uniformly mixed materials with a certain amount of water, adding the uniformly kneaded dough into a single-screw extruding machine for extruding strips, cutting the obtained strip-shaped adsorbent into cylinders with a length of 3mm, drying the obtained strip-shaped adsorbent at 100 ℃, roasting at 750 ℃, cooling, carrying out crystal transformation in a NaOH solution with a concentration of 1mol/L, and then carrying out crystal transformation in CaCl with a concentration of 0.25mol/L 2 Exchanging in the solution, drying at 100 ℃, and roasting at 350 ℃ to obtain the special-shaped adsorbent finished product.
Comparative example 2
Mixing raw 4A molecular sieve powder with the mass fraction of 85%, kaolin with the mass fraction of 13% and corn starch with the mass fraction of 2%, fully kneading the uniformly mixed materials with a certain amount of water, adding the uniformly kneaded dough into a single-screw bar extruder for bar extrusion, cutting the obtained bar-shaped adsorbent into cylinders with the length of 3mm, putting the bar-shaped adsorbent into a rounding machine for rounding, drying the obtained spherical adsorbent at 100 ℃, roasting at 750 ℃, cooling, performing crystal transformation in a NaOH solution with the concentration of 1mol/L, and then performing crystal transformation in CaCl with the concentration of 0.25mol/L 2 Exchanging in the solution, drying at 100 ℃, and roasting at 350 ℃ to obtain the special-shaped adsorbent finished product.
In order to further compare the influence of the special-shaped adsorbent obtained by the preparation method of the invention on the adsorption performance, the finished adsorbent products prepared in examples 1-7 and comparative examples 1-2 are dried at 100 ℃ for 4 hours and baked at 550 ℃ for 4 hours. The adsorption performance is evaluated by adopting an adsorption reactor with an inner diameter of 15mm, a filling height of 230mm and a height-diameter ratio of 15. The laboratory adopts two paths of mass flow meters to perform gas distribution, wherein one path is nitrogen, the flow is 20mL/min, the other path is helium, the flow is 280mL/min, the system pressure is stabilized at 1.5MPa, and the temperature is 30 ℃. By N 2 Penetration time to examine mass transfer rate of adsorbent, N 2 The longer the breakthrough time, the faster the gas mass transfer rate.
TABLE 1
Claims (9)
1. A preparation method of the special-shaped adsorbent comprises the following steps:
(1) Fully kneading the mixed material with a certain amount of water;
(2) Adding the uniformly kneaded dough into a strip extruder for strip extrusion to obtain a strip-shaped adsorbent;
(3) The strip-shaped adsorbent and the inert pellets are put into a rounding machine for rounding, so that a round cake-shaped adsorbent with concave centers on two sides is formed;
(4) Screening the material obtained in the step (3), recycling the inert pellets, and carrying out subsequent treatment on the round cake-shaped special-shaped adsorbent;
the diameter of the inert pellets is 1/2-1/4 times of the diameter of the strip-shaped adsorbent obtained in the step (2), and the number of the inert pellets is 2-3 times of the number of the strip-shaped adsorbent.
2. The method for preparing the special-shaped adsorbent according to claim 1, wherein the mixed material in the step (1) is prepared by uniformly mixing a molecular sieve, a binder and an auxiliary agent according to a certain proportion.
3. The method for preparing a shaped adsorbent according to claim 2, wherein the molecular sieve is a 4A molecular sieve; the binder is one or more of kaolin, bentonite, sheep glycerol and attapulgite; the auxiliary agent is one or more of sesbania powder, corn starch, tannin extract, citric acid and tartaric acid.
4. The method for producing a shaped adsorbent according to claim 1, wherein the inert pellets in step (3) have a mohs hardness of 9 or more and a density similar to that of the adsorbent in the form of a bar.
5. The method for producing a shaped adsorbent according to claim 1, wherein the inert adsorbent pellets are selected from one of zirconia pellets and inert porcelain pellets.
6. The method for preparing a shaped adsorbent according to claim 1, wherein the inert pellets are pre-wetted prior to being fed into the spheronizer, said pre-wetting being achieved by rapid impregnation of the inert pellets with water or sucrose solution.
7. The method for preparing a shaped adsorbent according to claim 1, wherein in the step (3), an excipient selected from at least one of microcrystalline cellulose and bone cement is added to the spheronizer together with the inert pellets.
8. The method for preparing a shaped adsorbent according to claim 7, wherein the excipient is added in an amount of 1 to 5% by mass of the inert pellets.
9. The method for preparing the special-shaped adsorbent according to claim 1, wherein the subsequent treatment process in the step (4) is as follows: drying the obtained special-shaped adsorbent at 50-150 ℃, and roasting at 600-750 ℃; after cooling, carrying out crystal transformation in NaOH solution; and then exchanging in Ca solution, drying and secondarily roasting to obtain the special-shaped adsorbent finished product.
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| WO2017110736A1 (en) * | 2015-12-25 | 2017-06-29 | 高橋金属株式会社 | Absorbent particles |
| CN108404970A (en) * | 2018-03-05 | 2018-08-17 | 中国科学院山西煤炭化学研究所 | A kind of apple shape hollow molecules sieve microballoon and its preparation method and application |
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| CN105668586A (en) * | 2016-03-27 | 2016-06-15 | 山东泓泰恒瑞新材料有限公司 | Nano ZSM-5 molecular sieve and preparation method of phosphorus-modified ZSM-5 molecular sieve thereof |
| CN108404970A (en) * | 2018-03-05 | 2018-08-17 | 中国科学院山西煤炭化学研究所 | A kind of apple shape hollow molecules sieve microballoon and its preparation method and application |
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