CN114433016A - High-efficiency 5A molecular sieve adsorbent and preparation method thereof - Google Patents
High-efficiency 5A molecular sieve adsorbent and preparation method thereof Download PDFInfo
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- CN114433016A CN114433016A CN202011199018.0A CN202011199018A CN114433016A CN 114433016 A CN114433016 A CN 114433016A CN 202011199018 A CN202011199018 A CN 202011199018A CN 114433016 A CN114433016 A CN 114433016A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 100
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003463 adsorbent Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005342 ion exchange Methods 0.000 claims abstract description 36
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011575 calcium Substances 0.000 claims abstract description 26
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 41
- 230000009466 transformation Effects 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 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
- 239000002245 particle Substances 0.000 claims description 9
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 230000001131 transforming effect Effects 0.000 claims 1
- 239000012716 precipitator Substances 0.000 abstract description 16
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 239000011148 porous material Substances 0.000 abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 6
- 238000007598 dipping method Methods 0.000 abstract description 4
- 230000000717 retained effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000004898 kneading Methods 0.000 description 11
- 238000002791 soaking Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 150000002500 ions Chemical group 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- 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
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
-
- 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
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
-
- 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
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of an efficient 5A molecular sieve adsorbent. After the molecular sieve is subjected to ion exchange, the calcium-containing solution is further soaked, and calcium ions are precipitated by a precipitator. In the process of dipping the calcium-containing solution, calcium ions enter the pore canal structure of the molecular sieve, and can be retained in the pore canal of the molecular sieve after calcium precipitation treatment; after subsequent drying and roasting treatment, calcium ions deposited in the pore passages of the molecular sieve can be further exchanged with sodium ions which are not exchanged in the parent body of the molecular sieve. The method can greatly improve the calcium exchange degree of the molecular sieve, thereby improving the adsorption performance of the molecular sieve.
Description
Technical Field
The invention belongs to the technical field of adsorption separation, and particularly relates to a high-efficiency 5A molecular sieve adsorbent and a preparation method thereof.
Background
The pressure swing adsorption technology is widely applied to the separation and purification of gas. The core of pressure swing adsorption technology is the development of high efficiency adsorbents. The molecular sieve is used as a porous material with stable structure, and can be used for separation and purification of various gases. In the development of molecular sieve adsorbents, the adsorption capacity of adsorbate gas is an important index, and the adsorption capacity of 5A molecular sieve is directly related to the exchange degree of calcium ions. In the preparation process of the 5A molecular sieve, the 4A molecular sieve is usually exchanged to the 5A molecular sieve by using a method such as calcium ion solution exchange. However, due to the limitations of exchange conditions, exchange time, exchange method, etc., the ion exchange process not only has the problems of high energy consumption and high pollution, but also has a poor exchange degree for molecular sieve calcium ions.
Chinese patent CN103933932A discloses a 5A molecular sieve adsorbent and a preparation method thereof, which comprises the steps of rolling balls formed by powder containing a 4A molecular sieve and a binder source, drying and roasting the balls to obtain matrix balls; prewetting the substrate pellets, carrying out crystal transformation, and finally carrying out calcium exchange to obtain the 5A molecular sieve pellets. The calcium exchange process of the invention is carried out by calcium chloride solution, and the calcium exchange degree is limited by solution mass transfer, so that the calcium exchange degree of the product adsorbent is not high and the adsorption performance is not good.
Chinese patent CN1962047A discloses a method for preparing a molecular sieve adsorbent with high adsorption capacity, which comprises mixing a 4A molecular sieve with calcium oxide, calcium hydroxide or calcium salt, using kaolin as a binder, extruding and forming, roasting, alkali treatment, calcium chloride solution exchange, and activating to obtain the molecular sieve adsorbent. The solid-phase calcium-containing substance added in the preparation process of the method can not be effectively combined with the sodium ion exchange center of the 4A molecular sieve under the forming condition, so that the calcium exchange degree can not be obviously improved, and the adsorption performance of the product adsorbent is influenced.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention provides a high-efficiency 5A molecular sieve adsorbent and a preparation method thereof.
The invention relates to a high-efficiency 5A molecular sieve adsorbent and a preparation method thereof, wherein the adsorbent comprises the following components:
(1) mixing and molding a 4A molecular sieve raw material and a binder;
(2) carrying out crystal conversion and ion exchange post-treatment on the formed adsorbent obtained in the step (1);
(3) dipping the adsorbent obtained in the step (2) into a calcium-containing solution;
(4) performing calcium precipitation treatment on the adsorbent obtained in the step (3);
(5) and (4) drying and roasting the adsorbent obtained in the step (4).
Further, the average particle size of the 4A molecular sieve in the step (1) is 1-10 μm, and preferably 2-8 μm.
The binder in the step (1) is at least one selected from kaolin, bentonite and attapulgite, and is preferably kaolin. The mesh number of the binder is 50-1000 meshes, preferably 150-800 meshes.
Further, the weight ratio of the molecular sieve to the binder in the step (1) is 1-50: 1, preferably 2-45: 1. The mixing and forming process comprises the steps of mixing, kneading, forming and the like of the molecular sieve raw powder and the binder. The prepared molded adsorbent comprises a strip-shaped, spherical and special-shaped adsorbent. The diameter of the adsorbent is 0.25-6.5 mm, preferably 0.5-5 mm.
The crystal transformation process in the step (2) is as follows: firstly, the formed adsorbent is roasted at a high temperature, wherein the roasting temperature is 850 ℃ at 300-. And then putting the adsorbent intermediate into NaOH solution for crystal transformation. The solubility of the NaOH solution is 0.1-8 mol/L, preferably 0.25-6 mol/L; the crystal transformation temperature is 35-110 ℃, and preferably 40-100 ℃; the crystal transformation time is 2-15 h, preferably 4-11 h.
The ion exchange process in the step (2) is as follows: placing the adsorbent after crystal transformation into CaCl2Ion exchange is carried out in the solution. The CaCl is2The solubility of the solution is 0.2-10 mol/L, preferably 0.5-9 mol/L; the ion exchange temperature is 40-120 ℃, and preferably 45-110 ℃; the ion exchange time is 1.5-15 h, preferably 3-13 h.
And (3) after the ion exchange process in the step (2) is finished, drying and roasting the molecular sieve. The drying temperature is 40-150 ℃, preferably 50-130 ℃, and the drying time is 2-20 hours, preferably 5-15 hours; the roasting temperature is 200-850 ℃, preferably 250-800 ℃, and the roasting time is 0.5-15 h, preferably 1-10 h.
The calcium-containing solution in the step (3) is selected from one of a calcium chloride solution, a calcium nitrate solution and a calcium sulfate solution, and is preferably a calcium chloride solution.
Further, the amount of calcium ions added into the molecular sieve in the step (3) is 0.5-30% of the mass of the molecular sieve, and preferably 1-25%; the impregnation time is from 0.4 to 7h, preferably from 1 to 6 h.
The calcium precipitation in the step (4) is realized by dipping a precipitator. The precipitant is selected from one of sodium carbonate solution, ammonium carbonate solution, potassium carbonate solution, and magnesium carbonate solution, preferably ammonium carbonate solution.
Further, the amount of the precipitator added into the molecular sieve in the step (4) is 80-200 percent, preferably 90-170 percent of the amount of calcium ions in the molecular sieve added in the step (3); the impregnation time is 0.2 to 8h, preferably 0.5 to 6 h.
The drying temperature in the step (5) is 50-140 ℃, preferably 60-120 ℃, and the drying time is 1-15 hours, preferably 2-10 hours; the roasting temperature is 300-900 ℃, preferably 350-800 ℃, and the roasting time is 2.5-20 hours, preferably 3-17 hours. And after roasting, washing the molecular sieve with deionized water, wherein the amount of the washing water is 5-50g of water/g of molecular sieve, and preferably 10-40g of water/g of molecular sieve. After washing, roasting treatment is carried out, wherein the roasting temperature is 200-450 ℃, and preferably 240-400 ℃.
Compared with the traditional molecular sieve, the invention further impregnates the molecular sieve with calcium-containing solution after ion exchange, and precipitates calcium ions through a precipitator. Because calcium ions in the solution can enter the pore structure of the molecular sieve in the process of dipping the calcium-containing solution, the calcium ions can be retained in the pore of the molecular sieve after the precipitator is precipitated. Through subsequent further drying and roasting treatment, calcium ions deposited in the pore passages of the molecular sieve can be further exchanged with sodium ions which are not exchanged in the parent body of the molecular sieve, so that the calcium exchange degree of the molecular sieve is greatly improved, and the adsorption performance of the molecular sieve is improved.
Compared with the prior art, the method has the beneficial effects that:
the calcium ions are retained in the molecular sieve pore passages by immersing a calcium-containing solution in the molecular sieve pore passages and precipitating by a precipitator. After further roasting treatment, sodium ions in the molecular sieve can be exchanged for calcium ions at high temperature. The prepared molecular sieve adsorbent has high calcium exchange degree and good adsorption performance.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the examples described below, and various modifications and implementations are included within the technical scope of the present invention without departing from the content and scope of the present invention.
Example 1
1500g of 4A molecular sieve and 500g of kaolin are mixed uniformly and then added into a kneader, and 500g of deionized water is sprayed gradually for kneading. And extruding the mixture by a strip extruder after kneading to obtain the strip-shaped adsorbent with the particle size of 2 mm. Roasting the adsorbent at 500 ℃ for 3h, and then placing the obtained adsorbent in a 5mol/L NaOH solution for crystal transformation treatment, wherein the crystal transformation temperature is 85 ℃ and the crystal transformation time is 6 h. Placing the adsorbent after crystal transformation into 7mol/L CaCl2Ion exchange is carried out in the solution, the ion exchange temperature is 110 ℃, and the ion exchange time is 10 h. The ion exchanged adsorbent was dried at 80 ℃ for 13h and calcined at 450 ℃ for 9 h. Adding calcium chloride solution accounting for 5% of the mass of the molecular sieve in terms of calcium ions into the obtained molecular sieve adsorbent, soaking for 5 hours, and then adding ammonium carbonate precipitator accounting for 110% of the mass of the calcium ions into the molecular sieve adsorbent, and soaking for 4.5 hours. Drying the molecular sieve adsorbent treated by the precipitator at 90 ℃ for 9h, and roasting at 400 ℃ for 15 h. The molecular sieve was washed with 15g water/g molecular sieve in deionized water and calcined at 250 c to obtain the adsorbent product.
Comparative example 1
1500g of 4A molecular sieve and 500g of kaolin are mixed uniformly and then added into a kneader, and 500g of deionized water is sprayed gradually for kneading. And extruding the mixture by a strip extruder after kneading to obtain the strip-shaped adsorbent with the particle size of 2 mm. Roasting the adsorbent at 500 ℃ for 3h, and then placing the obtained adsorbent in a 5mol/L NaOH solution for crystal transformation treatment, wherein the crystal transformation temperature is 85 ℃ and the crystal transformation time is 6 h. Placing the adsorbent after crystal transformation into 7mol/L CaCl2Ion exchange is carried out in the solution, the ion exchange temperature is 110 ℃, and the ion exchange time is 10 h.Drying the adsorbent at 80 ℃ for 13h after ion exchange, and roasting at 450 ℃ for 9h to obtain an adsorbent product.
Example 2
1600g of 4A molecular sieve and 400g of kaolin are mixed uniformly and then added into a kneader, and 450g of deionized water is sprayed gradually for kneading. And extruding the mixture by a strip extruder after kneading to obtain the strip-shaped adsorbent with the particle size of 2.5 mm. Roasting the adsorbent at 600 ℃ for 2.5h, and then placing the obtained adsorbent in 2.5mol/L NaOH solution for crystal transformation treatment, wherein the crystal transformation temperature is 75 ℃, and the crystal transformation time is 8 h. Placing the adsorbent after crystal transformation into 6.5mol/L CaCl2Ion exchange is carried out in the solution, the ion exchange temperature is 100 ℃, and the ion exchange time is 9.5 h. The ion exchanged adsorbent was dried at 85 ℃ for 9h and calcined at 350 ℃ for 7 h. Adding calcium sulfate solution accounting for 8% of the mass of the molecular sieve in terms of calcium ions into the obtained molecular sieve adsorbent, soaking for 4 hours, and then adding potassium carbonate precipitator accounting for 130% of the mass of the calcium ions into the molecular sieve adsorbent, and soaking for 6 hours. Drying the molecular sieve adsorbent treated by the precipitator at 110 ℃ for 10h, and roasting at 500 ℃ for 13 h. The molecular sieve was washed with 20g water/g molecular sieve in deionized water and calcined at 280 ℃ to obtain the adsorbent product.
Comparative example 2
1600g of 4A molecular sieve and 400g of kaolin are mixed uniformly and then added into a kneader, and 450g of deionized water is sprayed gradually for kneading. And extruding the mixture by a strip extruder after kneading to obtain the strip-shaped adsorbent with the particle size of 2.5 mm. Roasting the adsorbent at 600 ℃ for 2.5h, and then placing the obtained adsorbent in 2.5mol/L NaOH solution for crystal transformation treatment, wherein the crystal transformation temperature is 75 ℃, and the crystal transformation time is 8 h. Placing the adsorbent after crystal transformation into 6.5mol/L CaCl2Ion exchange is carried out in the solution, the ion exchange temperature is 100 ℃, and the ion exchange time is 9.5 h. And drying the ion-exchanged adsorbent at 85 ℃ for 9h, and roasting at 350 ℃ for 7h to obtain an adsorbent product.
Example 3
1750g of 4A molecular sieve and 250g of bentonite are uniformly mixed and then sprayed with 380g of deionized water gradually in a forming machine for granulation, so as to obtain the spherical adsorbent with the particle size of 2.8 mm. Roasting the adsorbent at 450 ℃ for 4hThen, the obtained adsorbent is placed in 2mol/L NaOH solution for crystal transformation treatment, the crystal transformation temperature is 70 ℃, and the crystal transformation time is 7.5 h. Placing the adsorbent after crystal transformation into 5mol/L CaCl2Ion exchange is carried out in the solution, the ion exchange temperature is 105 ℃, and the ion exchange time is 8 h. The ion exchanged adsorbent was dried at 75 ℃ for 10.5h and calcined at 400 ℃ for 7.5 h. Adding calcium nitrate solution accounting for 12% of the mass of the molecular sieve in terms of calcium ions into the obtained molecular sieve adsorbent, soaking for 4.5h, and then adding magnesium carbonate precipitator accounting for 125% of the mass of the calcium ions into the molecular sieve adsorbent, and soaking for 5 h. Drying the molecular sieve adsorbent treated by the precipitator at 95 ℃ for 12h, and roasting at 600 ℃ for 14.5 h. The molecular sieve was washed with 30g water/g molecular sieve in deionized water and calcined at 300 ℃ to obtain the adsorbent product.
Example 4
1400g of 4A molecular sieve and 600g of attapulgite are uniformly mixed and then sprayed into 550g of deionized water in a forming machine step by step for granulation, so as to obtain the spherical adsorbent with the particle size of 2.3 mm. Roasting the adsorbent at 550 ℃ for 3.5h, and then placing the obtained adsorbent in a 3mol/L NaOH solution for crystal transformation treatment, wherein the crystal transformation temperature is 78 ℃ and the crystal transformation time is 6.5 h. Placing the adsorbent after crystal transformation into 7.5mol/L CaCl2Ion exchange is carried out in the solution, the ion exchange temperature is 110 ℃, and the ion exchange time is 7 h. The adsorbent after ion exchange was dried at 90 ℃ for 11h and calcined at 300 ℃ for 8.5 h. Adding calcium chloride solution accounting for 15% of the mass of the molecular sieve in terms of calcium ions into the obtained molecular sieve adsorbent, soaking for 4 hours, and then adding potassium carbonate precipitator accounting for 115% of the mass of the calcium ions into the molecular sieve adsorbent, and soaking for 5.5 hours. The molecular sieve adsorbent treated by the precipitator is dried at 105 ℃ for 11.5h and roasted at 550 ℃ for 12.5 h. The molecular sieve was washed with 25g water/g molecular sieve in deionized water and calcined at 275 deg.C to obtain the adsorbent product.
Example 5
1550g of 4A molecular sieve and 450g of bentonite are uniformly mixed and then added into a kneader, and 470g of deionized water is gradually sprayed in for kneading. And extruding the mixture by a strip extruder after kneading to obtain the strip-shaped adsorbent with the particle size of 1.5 mm. Roasting the adsorbent at 600 ℃ for 5h, and placing the obtained adsorbent in 3.5molCarrying out crystal transformation treatment in a/L NaOH solution, wherein the crystal transformation temperature is 80 ℃, and the crystal transformation time is 8.5 h. Placing the adsorbent after crystal transformation into 5.5mol/L CaCl2Ion exchange is carried out in the solution, the ion exchange temperature is 95 ℃, and the ion exchange time is 7.5 h. The ion exchanged adsorbent was dried at 95 ℃ for 12h and calcined at 400 ℃ for 8 h. Adding calcium nitrate solution accounting for 10 percent of the mass of the molecular sieve in terms of calcium ions into the obtained molecular sieve adsorbent, soaking for 3.5 hours, and then adding ammonium carbonate precipitator accounting for 120 percent of the mass of the calcium ions into the molecular sieve adsorbent, and soaking for 4 hours. The molecular sieve adsorbent treated by the precipitator is dried for 10.5 hours at 100 ℃ and roasted for 14 hours at 450 ℃. The molecular sieve was washed with 40g water/g molecular sieve in deionized water and calcined at 250 c to obtain the adsorbent product.
The properties of the 5A molecular sieve adsorbents obtained in examples and comparative examples are shown in table 1.
The calcium exchange degree is measured by X-ray fluorescence spectrum to determine the contents of calcium ions and sodium ions in the exchanged molecular sieve, and the calcium exchange degree is calculated according to the following formula.
Degree of calcium exchange = (calcium ion content × 2)/{ (calcium ion content × 2) + sodium ion content }
The nitrogen adsorption capacity test is carried out by adopting a high-pressure adsorption instrument, the used nitrogen is high-purity nitrogen, and the test conditions are 1bar and 25 ℃.
TABLE 1
Claims (16)
1. A preparation method of a high-efficiency 5A molecular sieve adsorbent comprises the following steps:
(1) mixing and molding a 4A molecular sieve raw material and a binder;
(2) carrying out crystal conversion and ion exchange post-treatment on the formed adsorbent obtained in the step (1);
(3) impregnating the adsorbent obtained in the step (2) with a calcium-containing solution;
(4) performing calcium precipitation treatment on the adsorbent obtained in the step (3);
(5) and (4) drying and roasting the adsorbent obtained in the step (4).
2. The method according to claim 1, wherein the 4A molecular sieve in the step (1) has an average particle size of 1 to 10 μm, preferably 2 to 8 μm.
3. The method according to claim 1, wherein the binder in the step (1) is at least one selected from kaolin, bentonite and attapulgite, preferably kaolin.
4. The method according to claim 3, wherein the binder has a mesh size of 50 to 1000 mesh.
5. The method according to claim 1, wherein the weight ratio of the molecular sieve to the binder in step (1) is 1 to 50: 1.
6. The method according to claim 1, wherein the molded adsorbent prepared in step (1) comprises a strip-shaped, spherical or shaped adsorbent having a diameter of 0.25 to 6.5 mm.
7. The method according to claim 1, wherein the step (2) of transforming the crystal comprises: firstly, roasting the formed adsorbent at high temperature, and then placing the adsorbent intermediate into NaOH solution for crystal transformation treatment.
8. The preparation method according to claim 7, wherein the solubility of the NaOH solution is 0.1-8 mol/L, the crystal transformation temperature is 35-110 ℃, and the crystal transformation time is 2-15 h.
9. The preparation method as claimed in claim 7, wherein the calcination temperature is 300-850 ℃ and the calcination time is 1-7 h.
10. The method according to claim 1, wherein the ion exchange process in the step (2) is: placing the adsorbent after crystal transformation into CaCl2Ion exchange is carried out in the solution.
11. The method of claim 1, wherein the molecular sieve is dried and calcined after the ion exchange process in step (2) is completed.
12. The method according to claim 1, wherein the calcium-containing solution in step (3) is one selected from the group consisting of a calcium chloride solution, a calcium nitrate solution, and a calcium sulfate solution.
13. The method of claim 1, further comprising the step of adding calcium ions to the molecular sieve in the step (3) in an amount of 0.5 to 30% by mass of the molecular sieve, and wherein the impregnation time is 0.4 to 7 hours.
14. The method according to claim 1, wherein the calcium precipitation treatment in the step (4) is carried out by impregnating a precipitant selected from the group consisting of a sodium carbonate solution, an ammonium carbonate solution, a potassium carbonate solution and a magnesium carbonate solution.
15. The method according to claim 14, wherein the amount of the precipitant added to the molecular sieve in the step (4) is 80 to 200% of the amount of the calcium ion added to the molecular sieve in the step (3), and the impregnation time is 0.2 to 8 hours.
16. 5A molecular sieve adsorbent obtained by the preparation method of any one of claims 1 to 15.
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