WO2024021342A1 - 一种吸附剂及其制备方法与应用 - Google Patents

一种吸附剂及其制备方法与应用 Download PDF

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WO2024021342A1
WO2024021342A1 PCT/CN2022/128567 CN2022128567W WO2024021342A1 WO 2024021342 A1 WO2024021342 A1 WO 2024021342A1 CN 2022128567 W CN2022128567 W CN 2022128567W WO 2024021342 A1 WO2024021342 A1 WO 2024021342A1
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molecular sieve
adsorbent
solution
preparation
flocculant
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PCT/CN2022/128567
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French (fr)
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胡晓倩
王凤
湛洪丽
周君梦
尹冬雪
李丽
王闯
袁龙
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正大能源材料(大连)有限公司
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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
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/08—Xylenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/06—Alkylated phenols
    • C07C39/07—Alkylated phenols containing only methyl groups, e.g. cresols, xylenols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention belongs to the technical field of adsorbents, and specifically relates to a molecular sieve type adsorbent and its preparation method and application.
  • the adsorption separation process is widely used in industrial processes such as separation and purification of organic substances such as xylene, hydrogen production, and oxygen production.
  • the principle is to use the difference in adsorption capacity of each component in the mixture on the solid surface of the adsorbent to separate the adsorbent.
  • the performance has an important influence on the adsorption and separation effect.
  • Adsorbents include activated carbon, silica gel, activated alumina, polymer resin, molecular sieves, etc. Among them, molecular sieve adsorbents have the advantages of large specific surface area, high selectivity, high mechanical strength, and stable chemical properties. Commonly used ones are A type, X type, and Y type. Type, ZSM-5 and mordenite, etc.
  • An ideal adsorbent should have large adsorption capacity, high adsorption selectivity and fast mass transfer rate.
  • the molecular sieve grains aggregate into small balls.
  • the molecular sieve grains inside the small balls are piled up, and mesopores or macropores are formed between the grains.
  • the inside of the molecular sieve grains are micropores, so the adsorbate is in the molecular sieve adsorbent.
  • the mass transfer within the molecular sieve is divided into mass transfer in the adsorbed mesopores or macropores and mass transfer in the micropores within the molecular sieve crystal grains.
  • the mass transfer efficiency in mesopores or macropores is improved by adding pore formers or reducing the size of the adsorbent during the molding process of the adsorbent, and the mass transfer efficiency in micropores is improved by using small particle size or multi-stage pore molecular sieves. Quality efficiency.
  • Invention patent application CN108430924A discloses a method for manufacturing FAU type binder-free adsorbent. This method converts the kaolin binder into a reactive form by activating the adsorbent at a higher temperature.
  • the metakaolin is converted into FAU type zeolite in sodium silicate and caustic alkali solution, and the zeolite content in the adsorbent is higher than 98%.
  • This method increases the adsorption capacity per unit mass of the adsorbent by increasing the content of active components in the adsorbent.
  • the method of converting the binder zeolite alone is no longer sufficient to meet the requirements for the adsorption device.
  • the bulk density of the adsorbent should also be increased at the same time. When the volume of the adsorption tower is constant, the higher the packing density of the adsorbent, the greater the adsorption capacity of the entire adsorption tower.
  • the packing density is the mass of the adsorbent per unit volume.
  • the packing density of the adsorbent is related to the compactness of the molecular sieve grains. Since the volume of the industrial adsorption device is fixed, it is necessary to pack as much mass of adsorbent as possible within the limited volume to increase the overall adsorption capacity and raw material processing capacity of the device and improve production capacity.
  • One of the purposes of the present invention is to provide an adsorbent with excellent adsorption performance
  • a further object of the present invention is to provide an adsorbent with high bulk density and excellent adsorption performance
  • the second object of the present invention is to provide a method for preparing an adsorbent.
  • An adsorbent the adsorbent has metal ions and molecular sieve active components
  • the adsorbent has a bulk density of not less than 600kg/ m3 ;
  • the molecular sieve active component is obtained in the following manner: Raw molecular sieve is contacted and mixed with a flocculant to form a solution, which is then dried and pulverized to obtain a molecular sieve; wherein,
  • the ratio of the added mass of the flocculant to the added mass of the molecular sieve is (0.05 ⁇ 1):1; more preferably, the ratio is (0.1 ⁇ 0.5):1;
  • the particle size D90 of the Raw molecular sieve does not exceed 1.5 ⁇ m; more preferably, the particle size D90 of the Raw molecular sieve is in the range of 0.2 to 1 ⁇ m.
  • the above-mentioned adsorbent uses flocculant to treat Raw-molecular sieves, and the particle size of the selected Raw-molecular sieves determines that the adsorbent provided by the present invention has high bulk density and high mass transfer rate. , high adsorption capacity and high mechanical strength are the key.
  • Raw-molecular sieves are charged due to their high surface energy, and flocculants have polar groups or charged groups, which can neutralize the surface charge of molecular sieve grains, eliminate the repulsive force between grains, and make the grains pack tightly. .
  • the technical solution provided by the present invention uses Raw-molecular sieve as the active component to ensure that the prepared adsorbent has good mass transfer performance.
  • Raw-molecular sieve As the active component to ensure that the prepared adsorbent has good mass transfer performance.
  • flocculant Through the treatment of flocculant, it can neutralize the surface charge of Raw-molecular sieve grains. It eliminates the repulsive force between crystal grains and enables the crystal grains to be packed closely, thus overcoming the shortcomings of low packing density and low compressive strength of adsorbents prepared from Raw molecular sieves.
  • the obtained molecular sieve after the Raw-NaX molecular sieve is treated with a flocculant, the obtained molecular sieve will generally have a bulk density of not less than 600kg/ m3 ; in a more preferred case, the obtained molecular sieve will generally have a Bulk density of 650 ⁇ 10kg/ m3 .
  • the type of metal ion can be selected arbitrarily according to the purpose; as a preferred solution, the metal ion is preferably a Group IIA metal that is at least one of magnesium, strontium, and barium.
  • the Raw molecular sieve is NaX molecular sieve, and the sodium oxide content in the final adsorbent is not higher than 0.6wt%, based on this:
  • the metal ion is barium
  • the adsorbent generally has a bulk density of not less than 800 kg/m 3 , preferably a bulk density in the range of 880 ⁇ 10 kg/m 3 ;
  • the metal ion is strontium
  • the adsorbent generally has a bulk density of not less than 700kg/ m3 , preferably a bulk density in the range of 760 ⁇ 10kg/ m3 ;
  • the metal ion is magnesium
  • the adsorbent generally has a bulk density of not less than 600kg/ m3 , preferably a bulk density in the range of 630 ⁇ 10kg/ m3 ;
  • the metal ion is barium or strontium
  • the adsorbent generally has a bulk density of not less than 770kg/ m3 , preferably a bulk density in the range of 770-880kg/ m3 ;
  • the metal ion is barium or magnesium
  • the adsorbent generally has a bulk density of not less than 650kg/m 3 , and preferably has a bulk density in the range of 650 to 880kg/m 3 .
  • Raw-molecular sieve refers to molecular sieves that have not been treated with flocculants. Different types of Raw molecular sieves can be selected for different specific applications of the adsorbent, such as depending on the target substances adsorbed by the adsorbent:
  • the target substance is p-xylene or p-cresol
  • alkaline earth metal-loaded FAU molecular sieve is preferred.
  • the "FAU molecular sieve” includes X molecular sieve and Y molecular sieve; such as “Synthesis of FAU Zeolite Molecular Sieve and Its Membrane” and Characterization” (Lu Ying, Jilin University, 2014) has a detailed description of FAU-type molecular sieves.
  • Li-X molecular sieve When used to separate O 2 from air, "Li-X molecular sieve” is preferred.
  • Ca-A molecular sieve When used to separate normal isoparaffins, "Ca-A molecular sieve” is preferred.
  • the flocculant can be exemplified by polyacrylamide, polydimethyldiallylammonium chloride, sodium polyacrylate, sodium polystyrene sulfonate and sodium lignosulfonate. One or more than one.
  • the time of the standing treatment is not less than 10 minutes, preferably not less than 30 minutes.
  • the standing treatment can be 10 to 120 minutes; more preferably, the standing time is 30 to 90 minutes.
  • the separation method is centrifugal separation, and the centrifugal speed is not less than 2000r/min.
  • the flocculant is configured into a solution of 1 to 10 wt%, and then contacted with the molecular sieve; the volume ratio of the flocculant solution to the molecular sieve is (2 to 15): 1, and the preferred ratio is (2 to 5). :1.
  • a preparation method of an adsorbent the adsorbent is loaded with metal ions and has a bulk density of not less than 600kg/ m3 ; the preparation steps include the following:
  • the Raw-molecular sieve is contacted and mixed with the flocculant to form a solution, which is then dried and pulverized to obtain the molecular sieve; the particle size D90 of the Raw-molecular sieve does not exceed 1.5 ⁇ m;
  • the mixture containing molecular sieves, binders and pore-forming agents is shaped and then subjected to high temperature treatment;
  • the adsorbent is loaded with metal ions using a solution containing target metal ions.
  • the use of flocculants to treat Raw molecular sieves and the particle size of the Raw molecular sieves selected determine that the adsorbent provided by the present invention has high bulk density and high mass transfer rate.
  • high adsorption capacity and high mechanical strength are the key.
  • Raw-molecular sieves are charged due to their high surface energy, and flocculants have polar groups or charged groups, which can neutralize the surface charge of molecular sieve grains, eliminate the repulsive force between grains, and make the grains pack tightly.
  • the technical solution provided by the present invention uses Raw-molecular sieve as the active component to ensure that the prepared adsorbent has good mass transfer performance.
  • the macroscopic structural form of the "particles" which can be spherical, strip-shaped or flake-shaped; in some embodiments, the macroscopic form of the "particles” is spherical.
  • the "granule” molding method described here can be any currently known molding method, such as the known oil column molding method, extrusion molding method, spray molding method, rolling molding method, etc.
  • the size of the particles which can be determined according to requirements.
  • the particles have a particle size in the range of 0.3 to 3 mm, and further preferably have a particle size in the range of 0.3 to 1 mm;
  • in-situ crystallization treatment is generally performed in an alkaline solution.
  • the conditions for in-situ crystallization treatment are as follows: crystallization temperature 90-120°C, crystallization time 4-12 hours;
  • the alkaline solution generally has a concentration of 1 to 3 mol/L, and the alkali type is generally sodium hydroxide and potassium hydroxide. Based on this, it contains alkali metal ions such as Na + , K + , etc.;
  • the molecular sieve and the flocculant are first stirred to fully contact each other to exert the flocculation effect, and then left to allow the molecular sieve to slowly agglomerate and precipitate. After standing for a period of time, the flocculation The agent can more fully exert its flocculation effect, and then the molecular sieve and the flocculant solution are separated by centrifugation, and the flocculant solution can be reused.
  • the standing treatment time is not less than 10 minutes, preferably not less than 30 minutes.
  • the resting time is 10 to 120 minutes; in some more preferred embodiments, the resting time is 30 to 90 minutes. If the standing time is too short, the flocculant will not fully exert its flocculation effect. When the concentration of the flocculant solution is low, if the standing time is too long, such as 24 hours, the flocculant will be easily degraded or the concentration will be uneven.
  • the separation method is centrifugal separation, and the centrifugal speed is not less than 2000 r/min.
  • the size of the centrifugal speed also needs to be considered, as it is known to affect the degree of separation between the molecular sieve and the flocculant solution, that is, it affects the yield of the molecular sieve.
  • the flocculant remaining in the molecular sieve can act as a binder additive during the molding process due to its certain viscosity. The flocculant solution after centrifugation can be reused.
  • the drying temperature does not exceed 150°C, preferably 90 to 130°C, and more preferably 90 to 110°C.
  • the appropriate drying temperature should be selected, especially the maximum temperature should not exceed 150°C, and try not to exceed 130°C. The reason is that research has found that too high a drying temperature will cause the flocculant to degrade before the molecular sieve is formed. , ultimately affecting the bulk density of the adsorbent.
  • the flocculant is configured into a solution of 1 to 10 wt%, and then contacted with the molecular sieve;
  • the volume ratio of the flocculant solution and molecular sieve is (2-15):1;
  • the flocculation temperature can usually be room temperature.
  • the concentration of the flocculant solution cannot be too low, otherwise it will not produce ideal flocculation; the concentration of the flocculant solution cannot be too high, otherwise the flocculant solution will be relatively viscous; or the volume of the flocculant solution is too small, Theoretically, the volume ratio of the flocculant solution and the molecular sieve should not be less than 2, otherwise the mixed slurry will not be easily stirred evenly after the molecular sieve is added to the flocculant solution, and the flocculant and molecular sieve will not be fully in contact.
  • the volume ratio of the flocculant solution and molecular sieve is (2-5):1.
  • the added amount of molecular sieve is higher than the added amount of binder, but the added amount of binder is not less than 5wt% of the total added amount of molecular sieve and binder; as a preferred solution, the molecular sieve is The added amount is at least four times the added amount of the binder, and the added amount of the binder is not less than 5wt% of the added amount of the molecular sieve; as a further preferred option, the added mass ratio of the molecular sieve to the binder is (80 ⁇ 95 ): (5 ⁇ 20);
  • the added amount of the pore-forming agent is 1 to 5 wt% of the total dry weight of the molecular sieve and the binder; further preferably, it is 1 to 3 wt%;
  • the temperature of the high-temperature treatment is 550-950°C; a further preferred temperature is 550-750°C;
  • the processing time of high temperature treatment is 1 to 8 hours.
  • the flocculant and pore-forming agent can be decomposed into volatile components under the roasting conditions and removed, or only sodium or potassium remains, or the remaining components do not affect the subsequent binder crystallization process. And can be removed by washing with water.
  • the flocculant includes one or more of polyacrylamide, polydimethyldiallylammonium chloride, sodium polyacrylate, sodium polystyrene sulfonate and sodium lignosulfonate;
  • the pore-forming agent includes one or more of starch, lignin, polyethylene glycol, and sodium carbonate;
  • the binder includes one or more types of kaolin, bentonite, perlite, and halloysite.
  • the crystallized product is directly contacted with a solution containing target metal ions to perform cation exchange to achieve loading of target metal ions, thereby obtaining the metal-loaded adsorbent product.
  • the M is a metal ion species carried by the molecular sieve itself, such as sodium ions, in which case M X O is Na 2 O.
  • the S4 specifically includes
  • the saturated water absorption capacity of the product after ammonium ion exchange treatment is determined, and the amount of the solution containing target metal ions does not exceed the saturated water absorption capacity of the product.
  • ammonium ion exchange treatment includes:
  • the added concentration of the ammonium salt is 0.05-0.3 mol/L.
  • alkali metal ions as described here especially include ions introduced in the crystallization treatment step.
  • the crystallization treatment is generally carried out in an alkaline solution.
  • the alkaline solution generally has a concentration of It is 1 to 3 mol/L.
  • the base type is generally sodium hydroxide and potassium hydroxide. Based on this, it contains ions such as Na + and K + waiting to be removed.
  • the ammonium salt is soluble and is generally any one or more of ammonium chloride, ammonium carbonate and ammonium sulfate.
  • the treatment temperature is maintained at 60-80°C. After the treatment is completed, it is washed with deionized water until the pH is neutral, and then dried at a temperature not exceeding 100°C. Dry.
  • the crystallized product is placed in a container, and a solution containing ammonium ions is continuously passed into the container;
  • the container has a liquid inlet and a liquid outlet
  • the volume space velocity through which the ammonium salt solution is introduced is 2 to 8 h -1 . It is further preferred that the space velocity is 3 to 6 h -1 .
  • the solution containing the target metal ions is brought into contact with the product after ammonium ion exchange treatment in the form of small droplets, then left to stand, and finally dried and treated at high temperature.
  • the gravity of the liquid, surface tension and the adsorption of the carrier are used to diffuse the solution containing the target metal ions into the molecular sieve pores, and then the water is evaporated through drying so that the target metal ions are evenly distributed on the inner surface of the molecular sieve. , which not only reduces the dosage of the solution containing the target metal ions, but also improves the utilization rate of the solution containing the target metal ions, and the load distribution of the target metal ions is even and the load amount can be accurately controlled.
  • the product after the ammonium ion exchange treatment is stirred while spraying the solution containing the target metal ions onto the ammonium ions.
  • the product after ion exchange treatment is completely wetted.
  • the standing treatment time is 30 to 120 minutes.
  • the purpose of the "standing treatment” as described here is to fully diffuse the solution containing target metal ions into the pores of the molecular sieve.
  • the standing time will affect the degree of dispersion of the target metal ions on the adsorbent. If the "time for standing treatment” is too short, less than 30 minutes, such as 15 minutes, the metal ions will be distributed unevenly;
  • the metal is a Group IIA metal, such as magnesium, strontium, and barium.
  • the adsorbent prepared by any of the above methods is used to separate the target product from the mixture through adsorption; the target product includes p-xylene, p-cresol, etc.
  • Figure 1 is an electron microscope image of Raw-molecular sieve raw powder used in Example 1;
  • Figure 2 is an electron microscope image of the large particle size molecular sieve raw powder used in Comparative Example 1.
  • the present invention will be further described below with reference to specific examples, but the examples do not limit the present invention in any form.
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.
  • the essential features and significant effects of the present invention can be reflected from the following embodiments.
  • the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Therefore, they do not limit the present invention in any way.
  • Those skilled in the art can make some non-essential improvements and adjustments based on the contents of the present invention, which all fall within the protection scope of the present invention.
  • the Raw molecular sieve used in Examples 1-3 and 5-13 has a particle size (D90) of no more than 1.5 ⁇ m. D90 was detected using a Malvern particle size analyzer (model Malvern MS2000).
  • the detection instruments used include: online mass spectrometer (model Hiden HPR20), gas chromatograph (model Agilent 7890B), inductively coupled plasma emission spectrometer (model ThermoiCAP 7000).
  • the method for in-situ crystallization treatment is as follows: place the adsorbent precursor in a mixed solution of 1.6 mol/L NaOH and 0.4 mol/L KOH, and crystallize at 100°C for 6 hours.
  • the calculation method of the barium exchange degree of the adsorbent is: the molar amount of barium in the sample is W1, the molar amount of aluminum is W2, then the barium exchange degree is [(2*W1)/W2]*100%.
  • the barium content in the sprayed barium solution is such that the barium exchange degree of the NH 4 + type molecular sieve can theoretically reach 99%.
  • the specific method for measuring the saturated water absorption of a sample is as follows: add water dropwise to 1g of NH 4 + powder sample while stirring continuously until the sample surface is completely wetted, that is, the saturated water absorption per unit mass of the sample is obtained.
  • the active component content in the adsorbent reaches more than 98%, so it can be considered that the saturated water absorption rates of NH 4 + type powder and pellets are the same.
  • the specific method for measuring the adsorption capacity of the adsorbent is: load a certain mass of adsorbent into a fixed bed reactor, purge it in nitrogen at 550°C for 1 hour, cool to 40°C, and pass in 500ppm toluene (nitrogen balance) until adsorption Saturation, use an online gas mass spectrometer to quantitatively analyze the gas composition at the end of the adsorbent.
  • the adsorption capacity of the adsorbent is the amount of toluene adsorbed before the breakthrough point.
  • the specific method for measuring the bulk density of the adsorbent is as follows: roast the adsorbent at 550°C for 1 hour, transfer it to a vacuum desiccator and lower it to room temperature, then pour the adsorbent into a measuring cylinder, shake it until the volume no longer changes, and record the value in the measuring cylinder.
  • the volume and mass of the adsorbent are used to calculate the mass of the adsorbent per unit volume.
  • the specific method for measuring the mechanical strength of the adsorbent is: absorb water in the air until it is saturated, then put the adsorbent into a stainless steel cylinder, cover it with a cylindrical thimble that matches the inner diameter of the stainless steel cylinder, and then place it on a particle strength tester and press it at 250N for 5 minutes. , after the pressure is released, pour the adsorbent into a 300 ⁇ m standard sieve for sieving. Calculate the ratio of the mass of the crushed sample to the initial mass, which is the crushing rate.
  • the ratio of molecular sieve to kaolin is 82:18;
  • the pellets were calcined at 600°C for 6 hours to obtain the adsorbent precursor.
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized beads are contacted with a barium chloride solution to perform cation exchange.
  • the ratio of molecular sieve to bentonite is 80:20;
  • the pellets were calcined at 550°C for 8 hours to obtain the adsorbent precursor.
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized pellets are contacted with a barium nitrate solution to perform cation exchange.
  • the molecular sieve and flocculant solution were centrifuged, dried in an oven at 100°C, and then crushed with a pulverizer to obtain a molecular sieve with closely packed crystal grains.
  • the ratio of molecular sieve to perlite is 84:16;
  • the pellets are dried and sieved, and 0.3-1 mm pellets are roasted at 950°C for 1 hour to obtain the adsorbent precursor.
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized beads are contacted with a barium acetate solution to perform cation exchange.
  • the ratio of molecular sieve to halloysite is 95:5;
  • the added amount of sodium carbonate accounts for 4wt% of the total weight of the molecular sieve and halloysite on a dry basis; the amount of the sodium carbonate aqueous solution is the total weight of the molecular sieve and halloysite on a dry basis. 15wt%.
  • the pellets are dried and then sieved.
  • the 0.3-1mm pellets are roasted at 900°C for 1 hour to obtain the adsorbent precursor.
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized beads are contacted with a barium chloride solution to perform cation exchange.
  • the ratio of molecular sieve to kaolin is 90:10;
  • adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized beads are contacted with a barium chloride solution to perform cation exchange.
  • the ratio of molecular sieve to bentonite is 86:14;
  • the pellets were calcined at 700°C for 4 hours to obtain the adsorbent precursor.
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized beads are contacted with a barium acetate solution to perform cation exchange.
  • the ratio of molecular sieve to halloysite is 92:8;
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized beads are contacted with a barium acetate solution to perform cation exchange.
  • the ratio of molecular sieve to kaolin is 88:12;
  • pellets are dried and then sieved, and 0.3-1 mm pellets are roasted at 650°C for 5 hours to obtain the adsorbent precursor.
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized pellets are contacted with a barium nitrate solution to perform cation exchange.
  • Example 1 All relevant parameters involved in the preparation process of the adsorbent in this comparative example are the same as those in Example 1. The only difference is that the NaX molecular sieve selected is a large particle size NaX molecular sieve. Prepare 1wt% polyacrylamide aqueous solution, add large particle size NaX molecular sieve and mix thoroughly. The volume ratio of flocculant solution and molecular sieve is 15:1. After standing for 30 minutes, the molecular sieve and flocculant solution were centrifuged, dried in an oven at 90°C, and then crushed with a pulverizer to obtain a molecular sieve with closely packed crystal grains.
  • the NaX molecular sieve selected is a large particle size NaX molecular sieve. Prepare 1wt% polyacrylamide aqueous solution, add large particle size NaX molecular sieve and mix thoroughly. The volume ratio of flocculant solution and molecular sieve is 15:1. After standing for 30 minutes, the molecular sieve and flocculant
  • the NaKX molecular sieve was not treated with a flocculant solution (10 wt% polydimethyldiallylammonium chloride in water).
  • adsorbents A-B were prepared. All relevant parameters involved in the preparation process are the same as those in Example 1. The only difference is:
  • Adsorbent A After the flocculant solution comes into contact with the molecular sieve, no standing treatment is performed; the rest is the same as in Example 1.
  • Adsorbent B After contact between the flocculant solution and the molecular sieve, the rest time is 24 hours; the rest is the same as in Example 1.
  • adsorbents C-D were prepared. All relevant parameters involved in the preparation process were the same as those in Example 1. The only difference was:
  • Adsorbent C Use 0.5wt% flocculant solution to treat the molecular sieve, and the rest is the same as in Example 1.
  • Adsorbent D Use 15wt% flocculant solution to treat the molecular sieve, and the rest is the same as in Example 1.
  • Comparative Example 1-3-A after the molecular sieve and flocculant solutions were stirred evenly, they were centrifuged without standing still. The flocculant did not fully exert its effect, the flocculation effect was poor, and the bulk density of the prepared adsorbent was low.
  • Comparative Example 1-3-B the standing time after flocculation was too long, the flocculant was partially degraded, the flocculation effect was poor, and the bulk density of the prepared adsorbent was low.
  • Comparative Example 1-4-C the flocculant concentration is too low, resulting in poor flocculation effect.
  • Comparative Example 1-4-D the concentration of the flocculant is too high.
  • the ratio of molecular sieve to kaolin is 85:15;
  • the pellets are dried and then sieved.
  • the 0.3-1mm pellets are roasted at 600°C for 6 hours to obtain the adsorbent precursor.
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized pellets are loaded into a stainless steel tubular container, and 0.1 mol/L ammonium chloride solution is introduced until the sodium content in the outlet solution is less than 0.1 wt%.
  • the exchange temperature is 60°C, and the volume space velocity is 5h -1 .
  • wash with deionized water until the pH is neutral, and dry at 100°C to obtain NH 4 X pellets.
  • the barium exchange degree of the prepared p-xylene adsorbent is 98.6%. Its bulk density, mechanical strength and adsorption capacity are shown in Table 2.
  • the ratio of molecular sieve to bentonite is 88:12;
  • the pellets are dried and then sieved, and 0.3-1 mm pellets are roasted at 700°C for 4 hours to obtain the adsorbent precursor.
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized pellets are loaded into a stainless steel tubular container, and 0.15 mol/L ammonium chloride solution is introduced until the sodium content in the outlet solution is less than 0.1 wt%.
  • the exchange temperature is 80°C, and the volume space velocity is 2h -1 . After exchange, wash with deionized water until the pH is neutral, and dry at 100°C to obtain NH 4 X pellets.
  • the barium exchange degree of the prepared p-xylene adsorbent is 99.1%. Its bulk density, mechanical strength and adsorption capacity are shown in Table 2.
  • the ratio of molecular sieve to halloysite is 92:8;
  • the pellets are dried and then sieved.
  • the 0.3-1mm pellets are roasted at 725°C for 3 hours to obtain the adsorbent precursor.
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized pellets are loaded into a stainless steel tubular container, and 0.3 mol/L ammonium chloride solution is introduced until the sodium content in the outlet solution is less than 0.1 wt%.
  • the exchange temperature is 70°C, and the volume space velocity is 3h -1 . After exchange, wash with deionized water until the pH is neutral, and dry at 100°C to obtain NH 4 X pellets.
  • the barium exchange degree of the prepared p-xylene adsorbent is 98.9%. Its bulk density, mechanical strength and adsorption capacity are shown in Table 2.
  • the pellets After drying the pellets, they are then calcined to obtain an adsorbent precursor; the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets; the crystallized pellets are subjected to ammonium exchange to obtain NH 4 X ball.
  • the barium exchange degree of the obtained adsorbent is 86.2 ⁇ 103.7wt%. Its bulk density, mechanical strength and adsorption capacity are shown in Table 2.
  • the pellets After drying the pellets, they are then calcined to obtain an adsorbent precursor; the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets; the crystallized pellets are subjected to ammonium exchange to obtain NH 4 X ball.
  • the barium exchange degree of the prepared p-xylene adsorbent is 98.5%. Its bulk density, mechanical strength and adsorption capacity are shown in Table 2.
  • a refers to the molar amount of barium salt required to prepare 100g of adsorbent
  • b refers to the molar amount of barium salt in the waste liquid produced when preparing 100g of adsorbent.
  • Comparative Example 2-1 instead of spraying the barium solution, the beads were directly placed in the barium solution.
  • the uneven distribution of the liquid resulted in uneven distribution of barium.
  • Comparative Example 2-2 did not undergo standing treatment, and the barium solution did not fully diffuse into the pores of the molecular sieve, resulting in uneven barium distribution.
  • the barium content on the outer surface of the pellet was high and the internal barium content was low.
  • the ratio of molecular sieve to kaolin is 85:15;
  • the pellets were dried and calcined at 600°C for 4 hours to obtain the adsorbent precursor.
  • the adsorbent precursor is crystallized in an alkali solution to obtain crystallized pellets.
  • the crystallized pellets are loaded into a stainless steel tubular container, and 0.2 mol/L ammonium chloride solution is introduced until the sodium content in the outlet solution is less than 0.1 wt%.
  • the exchange temperature is 70°C, and the volume space velocity is 3h -1 . After exchange, wash with deionized water until the pH is neutral, and dry at 100°C to obtain NH 4 X pellets.

Abstract

本发明公开了一种吸附剂及其制备方法与应用，所述吸附剂具有金属离子、分子筛其中，所述，分子筛粉末经由以下方式处理得到：Raw-分子筛与絮凝剂接触混合形成溶液，进行干燥、粉碎处理，得到分子筛粉末。

Description

一种吸附剂及其制备方法与应用 技术领域
本发明属于吸附剂技术领域，具体涉及一种分子筛型吸附剂及其制备方法及应用。
背景技术
吸附分离工艺广泛应用于如二甲苯之类的有机物质的分离提纯、制氢、制氧等工业过程，其原理是利用混合物中各个组分在吸附剂固体表面吸附能力差异来进行分离，吸附剂的性能对吸附分离效果具有重要影响。吸附剂包括活性炭、硅胶、活性氧化铝、聚合树脂、分子筛等，其中分子筛吸附剂具有比表面积大、选择性高、机械强度高、化学性质稳定等优点，常用的有A型、X型、Y型、ZSM-5和丝光沸石等。
理想的吸附剂应具有较大的吸附容量、较高的吸附选择性和较快的传质速率。通过滚动成球、分子筛晶粒聚集成小球，小球内部的分子筛晶粒呈堆积状，晶粒之间形成介孔或大孔，分子筛晶粒内部是微孔，所以吸附质在分子筛吸附剂内的传质分为在吸附的介孔或大孔中的传质和在分子筛晶粒内微孔中的传质，由于分子筛的孔道尺寸和吸附质分子的动力学直径更为接近，所以晶粒内传质的影响更大。一般通过在吸附剂的成型过程中添加造孔剂或减小吸附剂尺寸来改善介孔或大孔中的传质效率，并通过使用小粒径或多级孔分子筛来提高微孔中的传质效率。
分子筛一般呈粉末状、无法直接应用于固定床吸附装置，因此在使用中需要加入粘结剂成型以提供一定的机械强度。成型吸附剂由于粘结剂的存在，导致有效活性组分含量降低。发明专利申请CN108430924A公开了一种制造FAU型无粘结剂吸附剂的方法，该方法通过将吸附剂在较高温度下活化使高岭土粘结剂转化为具有反应活
性的偏高岭土，然后将偏高岭土在硅酸钠和苛性碱溶液中转化为FAU型沸石，吸附剂中沸石含量高于98％。该方法通过提高吸附剂中活性组分的含量来增加单位质量吸附剂的吸附容量，但随着吸附剂制备工艺不断的更新换代，仅通过粘结剂沸石转化的方法已不足以满足对吸附装置处理量的要求，故还应同时增加吸附剂的堆积密度。吸附塔体积一定的情况下，吸附剂的堆积密度越高，整个吸附塔的吸附容量越大。
减小分子筛晶粒尺寸可有效缩短扩散路径、提高传质效率，但Raw-分子筛的堆积密度较小，由此而来的问题是导致以Raw-分子筛为活性组分的成型吸附剂的堆积密度较小、抗压强度较低。
堆积密度即单位体积吸附剂的质量，在吸附剂颗粒尺寸一定的情况下，吸附剂的堆积密度和分子筛晶粒堆积的紧实程度有关。由于工业吸附装置的体积一定，在有限的体积内需要 装填尽可能多质量的吸附剂以提高装置整体的吸附容量和原料处理量、提高生产能力。
发明内容
1.要解决的问题
基于现有吸附剂无法实现兼具高吸附容量及高传质速率的问题：
本发明的目的之一，是提供一种吸附性能优异的吸附剂；
本发明进一步的目的，是提供一种具有高堆积密度的、吸附性能优异的吸附剂；
本发明的目的之二，提供吸附剂的制备方法。
2.技术方案
为了解决上述问题，本发明所采用的技术方案如下：
一种吸附剂，所述吸附剂具有金属离子，及分子筛活性组分；
所述吸附剂具有不低于600kg/m 3的堆积密度；
其中，所述分子筛活性组分经由以下方式处理得到：Raw-分子筛与絮凝剂接触混合形成溶液，进行干燥、粉碎处理，得到分子筛；其中，
所述絮凝剂的添加质量与分子筛的添加质量比为(0.05～1)：1；更为优选地，所述比例为(0.1～0.5)：1；
所述，Raw-分子筛的粒径尺寸D90不超过1.5μm；更为优选地，所述Raw-分子筛的粒径尺寸D90在0.2～1μm范围内。
在此需要说明的是，上述吸附剂，利用絮凝剂对Raw-分子筛进行处理，以及所选用的Raw-分子筛的粒径尺寸，是决定本发明提供的吸附剂具有高堆积密度、高传质速率、高吸附容量，同时兼具高机械强度的关键。Raw-分子筛由于表面能较高而带有电荷，而絮凝剂具有极性基团或带电荷基团、能够中和分子筛晶粒表面电荷，消除晶粒之间的排斥力，使晶粒紧密堆积。基于此，本发明提供的技术方案，以Raw-分子筛为活性组分，保证了制备得到的吸附剂具有良好的传质性能，通过絮凝剂的处理，能够中和Raw-分子筛晶粒表面电荷，消除晶粒之间的排斥力，使晶粒紧密堆积，克服了Raw-分子筛制备的吸附剂堆积密度小、抗压强度低的缺陷。
在一些实施例中，利用絮凝剂对Raw-NaX型分子筛进行处理完成后，所得到的分子筛一般会具有不低于600kg/m 3的堆积密度；比较优选的情形下所得到的分子筛一般会具有650±10kg/m 3的堆积密度。
基于上述，进一步说明的是；
Ⅰ)如在此所述的，金属离子的种类可根据目的任意选择；作为优选方案的是，所述金属离子优选IIA族金属为镁、锶、钡中至少一种。在一些实施例中，Raw-分子筛为NaX分子 筛，最终吸附剂中氧化钠含量不高于0.6wt％，基于此：
在一些实施例中，所述金属离子为钡，则所述吸附剂一般具有不低于800kg/m 3的堆积密度，优选具有880±10kg/m 3范围内的堆积密度；
在另一些实施例中，所述金属离子为锶，则所述吸附剂一般具有不低于700kg/m 3的堆积密度，优选具有760±10kg/m 3范围内的堆积密度；
在另一些实施例中，所述金属离子为镁，则所述吸附剂一般具有不低于600kg/m 3的堆积密度，优选具有630±10kg/m 3范围内的堆积密度；
在另一些实施例中，所述金属离子为钡、锶，则所述吸附剂一般具有不低于770kg/m 3的堆积密度，优选具有770～880kg/m 3范围内的堆积密度；
在另一些实施例中，所述金属离子为钡、镁，则所述吸附剂一般具有不低于650kg/m 3的堆积密度，优选具有650～880kg/m 3范围内的堆积密度。
Ⅱ)如在此所述的，“Raw-分子筛”是指未经过絮凝剂处理的分子筛。针对吸附剂的具体应用不同可以选择不同类型的Raw-分子筛，比如根据吸附剂所吸附的目标物质的不同：
所述目标物质为对二甲苯或者对甲酚，则优选碱土金属负载的FAU型分子筛，进一步地，所述“FAU型分子筛”包括X分子筛和Y分子筛；比如“FAU沸石分子筛及其膜的合成与表征”(陆莹，吉林大学，2014年)中就有关于FAU型分子筛的详细描述。
当应用于从空气中分离出O 2，则优选“Li-X分子筛”；
当应用于清除H 2中的CO杂质，则优选“Cu-Y分子筛”；
当应用于分离正异构烷烃，则优选“Ca-A分子筛”。
Ⅲ)如在此所述的，所述絮凝剂可以列举如聚丙烯酰胺、聚二甲基二烯丙基氯化铵、聚丙烯酸钠、聚苯乙烯磺酸钠和木质素磺酸钠中的一种或一种以上。
进一步地，所述处理得到分子筛的过程中：Raw-分子筛与絮凝剂接触混合形成溶液后，先进行静置处理，然后分离出沉淀物进行干燥、粉碎处理；
所述静置处理的时间不低于10min，优选不低于30min。比如静置处理可以为10～120分钟；进一步优选静置时间为30～90分钟。
进一步地，所述分离方式为离心分离，所述离心转速不低于2000r/min。
进一步地，将所述絮凝剂配置为1～10wt％的溶液，然后与分子筛进行接触；所述絮凝剂溶液和分子筛的体积比为(2～15)：1，优选比例为(2～5)：1。
一种吸附剂的制备方法，所述吸附剂负载有金属离子，并具有不低于600kg/m 3的堆积密度；制备步骤包括以下内容：
S1.制备分子筛：
Raw-分子筛与絮凝剂接触混合形成溶液，后进行干燥、粉碎处理，得到分子筛；所述，Raw-分子筛的粒径尺寸D90不超过1.5μm；
S2.制备吸附剂前驱体：
对含有分子筛、粘结剂以及造孔剂的混合物，进行成型处理，后进行高温处理；
S3.晶化处理
在碱性体系下对吸附剂前驱体进行晶化处理；
S4.金属离子负载。
利用含目标金属离子的溶液，进行吸附剂的金属离子的负载。
在此需要说明的是，上述方案中，利用絮凝剂对Raw-分子筛进行处理，以及所选用的Raw-分子筛的粒径尺寸，是决定本发明提供的吸附剂具有高堆积密度、高传质速率、高吸附容量，同时兼具高机械强度的关键。Raw-分子筛由于表面能较高而带有电荷，而絮凝剂具有极性基团或带电荷基团、能够中和分子筛晶粒表面电荷，消除晶粒之间的排斥力，使晶粒紧密堆积。基于此，本发明提供的技术方案，以Raw-分子筛为活性组分，保证了制备得到的吸附剂具有良好的传质性能，通过絮凝剂的处理，能够中和Raw-分子筛晶粒表面电荷，消除晶粒之间的排斥力，使晶粒紧密堆积，克服了Raw-分子筛制备的吸附剂堆积密度小、抗压强度低的缺陷。
基于上述，进一步说明的是：
Ⅰ)S2中，对于分子筛、粘结剂、造孔剂的接触顺序没有特别的要求。作为优选方案，通常先将分子筛和粘结剂混合形成混合物，然后使造孔剂以水溶液的形式与混合物接触混合，目的是最终形成包含分子筛、粘结剂和造孔剂的“成型”化处理的制品，目的是最终形成包含分子筛、粘结剂和造孔剂的“颗粒”；
对于所述“颗粒”的宏观结构形态，没有严格的要求，可以是球状、条状或者片状；在一些实施例中，所述“颗粒”的宏观形态为球状。如在此所述的“颗粒”成型方式，可以为现有已知的成型方式，比如已知的油柱成型法、挤条成型法、喷雾成型法、滚动成型法等。对于颗粒的大小没有特别的限制，可根据需求确定，作为优选的方案，颗粒具有0.3～3mm范围的粒径，进一步优选具有0.3～1mm范围的粒径；
Ⅱ)S3中，原位晶化处理一般在碱性溶液中进行。作为优选的方案，原位晶化处理的条件如下：晶化温度90～120℃，晶化时间4～12小时；
所述碱性溶液一般为浓度1～3mol/L，碱类型一般为氢氧化钠、氢氧化钾，基于此含有如Na +、K +等的碱金属离子；
进一步地，S1中，Raw-分子筛与絮凝剂接触混合形成溶液后，先进行静置处理，然后分 离出沉淀物进行干燥、粉碎处理；
在此需要说明的是，Raw-分子筛加入絮凝剂溶液中后，先搅拌使分子筛和絮凝剂充分接触发挥絮凝作用，然后静置让分子筛慢慢团聚、沉淀下来，通过静置一段时间后，絮凝剂可以更加充分发挥其絮凝作用，然后通过离心将分子筛和絮凝剂溶液分离，絮凝剂溶液可重复使用。
作为优选地，所述静置处理的时间不低于10min，优选不低于30min。在一些实施例中，静置处理10～120分钟；在一些更为优选的实施例中，静置时间为30～90分钟。静置时间过短则絮凝剂未充分发挥絮凝作用。当絮凝剂溶液浓度较低时，若静置时间过长，如24小时，则絮凝剂易降解或浓度不均匀。
进一步地，S1中，所述分离方式为离心分离，所述离心转速不低于2000r/min。
在此需要说明的是，离心转速的大小，也需要考量，已知的会影响分子筛和絮凝剂溶液的分离程度，即影响分子筛的收率。此外，分子筛中残留的絮凝剂由于具有一定粘度可在成型过程中起到粘结剂助剂的作用。离心分离后的絮凝剂溶液可重复使用。
进一步地，S1中，所述干燥温度不超过150℃，优选为90～130℃，进一步优选温度为90～110℃。
在此需要说明的是，应选择合适的干燥温度，尤其是其最高温度不能超过150℃，尽量不超过130℃，原因是研究中发现，干燥温度过高会导致絮凝剂在分子筛成型前发生降解，最终影响吸附剂的堆积密度大小。
进一步地，S1中，将所述絮凝剂配置为1～10wt％的溶液，然后与分子筛进行接触；
所述絮凝剂溶液和分子筛的体积比为(2～15)：1；
絮凝温度通常可以选择室温。
在此需要说明的是，絮凝剂溶液浓度不能太低，否则不会产生理想的絮凝作用；絮凝剂溶液浓度也不能太高，否则絮凝剂溶液会比较粘稠；或者絮凝剂溶液体积过少，理论上絮凝剂溶液和分子筛的体积比应不低于2，否则将分子筛加入絮凝剂溶液后混合浆料不易搅拌均匀、使絮凝剂和分子筛不能充分接触。
作为优选方案，所述絮凝剂溶液和分子筛的体积比为(2～5)：1。
进一步地，S2中，分子筛的添加量高于粘结剂的添加量，但粘结剂的添加量占比不低于分子筛和粘结剂总的添加量的5wt％；作为优选方案，分子筛的添加量至少为粘结剂的添加量的四倍，粘结剂的添加量不低于分子筛的添加量5wt％；作为进一步的优选方案，分子筛与粘结剂的添加质量比为(80～95)：(5～20)；
所述造孔剂添加量为分子筛与粘结剂干基总重的1～5wt％；进一步优选为1～3wt％；
进一步地，S2中，高温处理的温度为550～950℃；进一步优选温度为550～750℃；
高温处理的处理时间为1～8小时。
在此需要说明的是，所述絮凝剂和造孔剂在该焙烧条件下可分解为挥发性组分而去除，或只残留钠或钾，或残留组分不影响后续粘结剂晶化过程并可通过水洗除去。
进一步地，所述絮凝剂包括聚丙烯酰胺、聚二甲基二烯丙基氯化铵、聚丙烯酸钠、聚苯乙烯磺酸钠和木质素磺酸钠中的一种或一种以上；
所述造孔剂包括淀粉、木质素、聚乙二醇、碳酸钠中的一种或一种以上；
所述粘结剂包括高岭土、膨润土、珍珠石、埃洛石中的一种或一种以上。
进一步地，S4中，使晶化处理后的产物直接与含有目标金属离子的溶液接触，进行阳离子交换，实现目标金属离子的负载，得到所述负载有金属的吸附剂产物。
交换至吸附剂中M XO含量不高于0.6wt％。所述M为分子筛自身所带有的金属离子种类，如钠离子，此时M XO为Na 2O。
进一步地，所述S4，具体包括
首先，利用铵盐溶液，对晶化处理后的产物进行铵离子交换处理；
然后，与含目标金属离子的溶液接触，实现目标金属离子的负载，得到所述负载有金属的吸附剂产物。
其中，确定经过铵离子交换处理后产物的饱和吸水量，所述含目标金属离子的溶液的量不超过所述产物的饱和吸水量。
进一步地，所述铵离子交换处理包括：
使含有铵离子的溶液与晶化处理后的产物接触，对接触过后的溶液进行碱金属离子的含量检测，使碱金属离子的含量≤0.1wt％，则待除去离子的去除化处理完成；
作为优选方案地，所述铵盐的添加浓度为0.05～0.3mol/L。
在此需要说明的是，Ⅰ)如在此所述的“碱金属离子”尤其包括晶化处理步骤所引入的离子，晶化处理一般在碱性溶液中进行，所述碱性溶液一般为浓度为1～3mol/L，碱类型一般为氢氧化钠、氢氧化钾，基于此含有如Na +、K +等待除去的离子。
Ⅱ)所述铵盐具有可溶性，一般为氯化铵、碳酸铵、硫酸铵中的任意一种或者一种以上。作为优选方案的，所述碱金属离子去除化处理过程中，保持处理温度为60～80℃，处理完成后用去离子水洗涤至pH为中性，然后在不超过100℃的温度下进行烘干。
进一步地，将晶化处理后的产物置于容器中，连续向容器通入含有铵离子的溶液；
其中，所述容器具有进液口、出液口；
所述铵盐溶液通入的体积空速为2～8h -1。进一步优选空速为3～6h -1。
进一步地，使含目标金属离子的溶液以小液滴的形式与铵离子交换处理后的产物实现接触，然后静置处理，最后进行干燥、高温处理。
在此需要说明的是，利用液体的重力、表面张力和载体的吸附性使含目标金属离子的溶液扩散到分子筛孔内，然后通过干燥将水分蒸发从而使目标金属离子均匀分布在分子筛的内表面，由此不但降低了含目标金属离子的溶液的用量，提升了含目标金属离子的溶液的的利用率，且目标金属离子的负载分布均匀、负载量可精确控制。
作为优选方案地，含有目标金属离子的溶液以小液滴的形式与铵离子交换处理后的产物实现接触过程中，对铵离子交换处理后的产物边翻动边喷洒含有目标金属离子的溶液至铵离子交换处理后的产物完全润湿。
进一步地，所述静置处理的时间为30～120min。
在此需要说明的是，Ⅰ)采用雾化器将含目标金属离子的溶液雾化成尽可能细密的微小液滴，液滴越小越有利于溶液喷洒均匀；
II)如在此所述的“静置处理”的目的是使含目标金属离子的溶液充分扩散进分子筛的孔道中，静置时间会影响目标金属离子在吸附剂上的分散程度。若“静置处理的时间”过短低于30min，如为15min，则会使金属离子分布不均匀；
进一步地，所述金属为IIA族金属，如镁、锶、钡。
以上任一所述方法制备得到的吸附剂，将其应用于从混合物中通过吸附分离得到目标产物；所述目标产物包括对二甲苯、对甲酚等。
附图说明
图1为实施例1所使用Raw-分子筛原粉的电镜图；
图2为对比例1所使用大粒径分子筛原粉的电镜图。
具体实施方式
通过参考结合附图和示例的以下描述可以更容易地理解本公开，所有附图和示例构成本公开的一部分。应当理解的是，本公开不限于本文描述和/或示出的特定产品、方法、条件或参数。进一步地，本文使用的术语仅用于通过示例的方式描述特定实施例的目的并且不旨在限制，除非另有说明。
还应当理解的是，为了清楚起见，本公开的某些特征可以在单独实施例的上下文中被描述在本文中，但是也可以在单个实施例中彼此组合地被提供。即，除非明显不兼容或特别地不包括，否则每个单独的实施例被认为可与任何其它实施例可组合，并且该组合被认为代表另一个不同的实施例。相反地，为了简明起见，在单个实施例的上下文中描述的本公开的各种特征也可以单独地或以任何子组合来提供。最后，虽然特定实施例可以被描述为一系列步 骤的部分或更通用的结构的部分，但是每个步骤或子结构本身也可以被认为是独立的实施例。
除非另有说明，否则应当理解的是，列表中的每个单独元素和该列表中的单独元素的每个组合将被解释为不同的实施例。例如，表示为“A、B或C”的实施例的列表应被解释为包括实施例“A”、“B”、“C”、“A或B”、“A或C”、“B或C”或“A、B或C”。
在本公开中，冠词“一”、“一个”和“该”的单数形式还包括相应的复数个提及物，并且对特定数值的提及至少包括该特定值，除非上下文另有明确说明。因此，例如，对“物质”的提及是对这种物质及其等同物中的至少一种的提及。
包括诸如“第一”和“第二”的序数的术语可用于解释各种组件或者流体，但这些组件、流体不受这些术语的限制。因此，在没有背离本公开的教导的情况下，这些术语仅用于将该组件/流体与另一组件/流体区分开来。
当通过使用结合性术语“……和/或……”等来描述项目时，描述应被理解为包括相关联的所列项目中的任何一个以及其中的一个或多个的所有组合。
通常，术语“约”的使用表示可以根据通过所公开的主题所获得的期望特性而变化的近似值，并且将基于功能以依赖于上下文的方式来解释。因此，本领域普通技术人员将能够在个案的基础上解释一定程度的差异。在一些情况下，表达特定值时使用的重要数字的数量可以是用于确定由术语“约”允许的差异的代表性技术。在其它情况下，可以使用一系列值中的渐变来确定由术语“约”允许的差异的范围。进一步地，本公开中的所有范围都是包含性的和可组合的，并且对范围中所述的值的提及包括该范围内的每个值。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同；本文所使用的术语和/或包括一个或多个相关的所列项目的任意的和所有的组合。
以下结合具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。本发明的实质特点和显著效果可以从下述的实施例中得以体现，所描述的实施例是本发明一部分实施例，而不是全部的实施例，因此，它们并不对本发明作任何限制，本领域的技术人员根据本发明的内容做出一些非本质的改进和调整，均属于本发明的保护范围。
以下具体实施例中：
实施例1-3、5-13所使用的Raw-分子筛具有不超过1.5μm内的粒径尺寸(D90)。D90使用马尔文粒度分析仪进行检测(型号Malvern MS2000)。
所使用的检测仪器有：在线质谱仪(型号Hiden HPR20)，气相色谱仪(型号Agilent 7890B)，电感耦合等离子体发射光谱仪(型号ThermoiCAP 7000)。
进行原位晶化处理的方法为：将吸附剂前驱体置于1.6mol/L NaOH和0.4mol/L KOH的混合溶液中，100℃晶化6小时。
吸附剂的钡交换度的计算方法为：样品中钡的摩尔量为W1，铝的摩尔量为W2，则钡交换度为[(2*W1)/W2]*100％。以下实施例中，所喷洒的钡溶液中钡含量为理论上使NH 4 +型分子筛的钡交换度达到99％。
测定样品饱和吸水率的具体方法为：向1gNH 4 +型粉末样品中逐滴加水同时不断搅拌，直至样品表面恰好完全润湿，即得单位质量样品的饱和吸水量。通过使粘结剂沸石化，吸附剂中活性组分含量达到98％以上，故可认为NH 4 +型粉末和小球的饱和吸水率相同。
测定吸附剂的吸附容量的具体方法为：将一定质量吸附剂装填到固定床反应器中，在氮气中于550℃吹扫1小时，降温至40℃，通入500ppm甲苯(氮气平衡)直至吸附饱和，使用在线气体质谱仪对吸附剂尾端气体组成进行定量分析，吸附剂的吸附容量即为穿透点前的甲苯吸附量。
测定吸附剂的堆积密度的具体方法为：将吸附剂在550℃焙烧1小时，转移至真空干燥器中降至室温，然后将吸附剂倒入量筒中、震荡至体积不再变化，记取量筒中吸附剂的体积和质量，计算得到单位体积吸附剂的质量。
测定吸附剂的机械强度的具体方法为：将吸附剂在空气中吸水至饱和后装入不锈钢筒中，盖上和不锈钢筒内径匹配的圆柱顶针，然后置于颗粒强度测定仪上于250N压5分钟，卸压后将吸附剂倒入300μm标准筛进行筛分，计算压碎样品的质量与初始质量的比例即为破碎率。
实施例1
配制1wt％聚丙烯酰胺水溶液，加入Raw-NaX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为15：1。静置30分钟后将分子筛和絮凝剂溶液离心分离，于90℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和高岭土的比例为82:18；
将NaX分子筛和高岭土搅拌均匀，然后加入占分子筛和高岭土干基总重3wt％的淀粉，充分搅拌均匀后滚动成型，烘干后筛取0.3～1mm的小球。
将小球于600℃焙烧6小时得吸附剂前驱体。将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球与氯化钡溶液接触，进行阳离子交换。
Raw-NaX分子筛的电镜结果见图1，其D90为0.9μm。吸附剂的堆积密度、机械强度和吸附容量见表1。
实施例2
配制10wt％聚二甲基二烯丙基氯化铵水溶液，加入Raw-NaKX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为2：1。静置10分钟后将分子筛和絮凝剂溶液离心分离，于130℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和膨润土的比例为80:20；
将分子筛和膨润土搅拌均匀，然后加入占分子筛和膨润土干基总重5wt％的木质素，充分搅拌均匀后滚动成型，烘干后筛取0.3～1mm的小球。
将小球于550℃焙烧8小时得吸附剂前驱体。将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球与硝酸钡溶液接触，进行阳离子交换。
其堆积密度、机械强度和吸附容量见表1。
实施例3
配制3wt％聚丙烯酸钠水溶液，加入Raw-NaX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为10：1。
静置120分钟后将分子筛和絮凝剂溶液离心分离，于100℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和珍珠石的比例为84:16；
将分子筛和珍珠石搅拌均匀，边滚动成型边加入适量聚乙二醇水溶液，聚乙二醇的添加量占分子筛和珍珠石干基总重的1wt％；所述聚乙二醇水溶液的量为分子筛和珍珠石干基总重的20wt％。
将小球烘干后筛分，取0.3～1mm的小球于950℃焙烧1小时得吸附剂前驱体。将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球与醋酸钡溶液接触，进行阳离子交换。
其堆积密度、机械强度和吸附容量见表1。
实施例4
配制5wt％聚苯乙烯磺酸钠水溶液，加入Raw-NaX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为5：1。静置60分钟后将分子筛和絮凝剂溶液离心分离，于120℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和埃洛石的比例为95:5；
将分子筛和埃洛石混合，边滚动成型边加入适量碳酸钠水溶液，碳酸钠的添加量占分子筛和埃洛石干基总重的4wt％；所述碳酸钠水溶液的量为分子筛和埃洛石干基总重的15wt％。
小球烘干后筛分，取0.3～1mm的小球于900℃焙烧1小时得吸附剂前驱体。将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球与氯化钡溶液接触，进行阳离子交换。
其堆积密度、机械强度和吸附容量见表1。
实施例5
配制8wt％木质素磺酸钠水溶液，加入Raw-NaKX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为13：1。静置20分钟后将分子筛和絮凝剂溶液离心分离，于110℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和高岭土的比例为90:10；
将分子筛和高岭土搅拌均匀，边滚动成型边加入适量聚乙二醇水溶液形成小球；所述聚乙二醇的添加量占分子筛和高岭土干基总重的1wt％。所述聚乙二醇水溶液的量为分子筛和高岭土干基总重的20wt％；
小球烘干后，取0.3～1mm的小球于800℃焙烧2小时得吸附剂前驱体。将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球与氯化钡溶液接触，进行阳离子交换。
其堆积密度、机械强度和吸附容量见表1。
实施例6
配制4wt％聚丙烯酰胺水溶液，加入Raw-NaX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为8：1。静置90分钟后将分子筛和絮凝剂溶液离心分离，于100℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和膨润土的比例为86:14；
将分子筛和膨润土搅拌均匀，然后加入占分子筛和膨润土干基总重2wt％的淀粉，充分搅拌均匀后滚动成型，烘干后筛取0.3～1mm的小球；
将小球于700℃焙烧4小时得吸附剂前驱体。将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球与醋酸钡溶液接触，进行阳离子交换。
其堆积密度、机械强度和吸附容量见表1。
实施例7
配制6wt％聚苯乙烯磺酸钠水溶液，加入Raw-NaX分子筛
充分混合均匀，絮凝剂溶液和分子筛的体积比为10：1。静置15分钟后将分子筛和絮凝剂溶液离心分离，于110℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和埃洛石的比例为92:8；
将分子筛和埃洛石搅拌均匀，然后加入占分子筛和埃洛石干基总重3wt％的木质素，充分搅拌均匀后滚动成型，烘干后筛取0.3～1mm的小球，于725℃焙烧3小时得吸附剂前驱体。
将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球与醋酸钡溶液接触，进行阳离子交换。
其堆积密度、机械强度和吸附容量见表1。
实施例8
配制2wt％木质素磺酸钠水溶液，加入Raw-NaX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为4：1。静置50分钟后将分子筛和絮凝剂溶液离心分离，于120℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和高岭土的比例为88:12；
将分子筛和高岭土搅拌均匀，边滚动成型边加入适量碳酸钠水溶液，碳酸钠的添加量占分子筛和高岭土干基总重的5wt％；所述碳酸钠水溶液的量为分子筛和高岭土干基总重的20wt％。
小球烘干后筛分，取0.3～1mm的小球于650℃焙烧5小时得吸附剂前驱体。
将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球与硝酸钡溶液接触，进行阳离子交换。
其堆积密度、机械强度和吸附容量见表1。
对比例1-1
本对比例中吸附剂的制备过程中涉及的各相关参数均同实施例1，区别仅在于选用的NaX分子筛为大粒径NaX分子筛。配制1wt％聚丙烯酰胺水溶液，加入大粒径NaX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为15：1。静置30分钟后将分子筛和絮凝剂溶液离心分离，于90℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
其余同实施例1。
所选用的大粒径NaX分子筛的电镜结果见图2，其D90为2.5μm。
最终所得吸附剂的堆积密度、机械强度和吸附容量见表1。
对比例1-2
本对比例中吸附剂的制备过程中涉及的各相关参数均同实施例2，区别仅在于：
不利用絮凝剂溶液(10wt％聚二甲基二烯丙基氯化铵水溶液)对NaKX分子筛进行处理。
直接将Raw-NaKX分子筛和膨润土混合，然后加入木质素，进而制备得到最终的吸附剂。
最终所得吸附剂的堆积密度、机械强度和吸附容量见表1。
对比例1-3
本对比例中制备得到了吸附剂A-B，制备过程中涉及的各相关参数均同实施例1，区别仅在于：
吸附剂A：絮凝剂溶液和分子筛接触后，不进行静置处理；其余同实施例1。
吸附剂B：絮凝剂溶液和分子筛触后，静置时间为24小时；其余同实施例1。
最终所得吸附剂A-B的堆积密度、机械强度和吸附容量见表1。
对比例1-4
本对比例中制备得到了吸附剂C-D，制备过程中涉及的各相关参数均同实施例1，区别仅在于：
吸附剂C：利用0.5wt％絮凝剂溶液对分子筛进行处理，其余同实施例1。
吸附剂D：利用15wt％絮凝剂溶液对分子筛进行处理，其余同实施例1。
最终所得吸附剂C-D的堆积密度、机械强度和吸附容量见表1。
对比例1-5
本对比例中吸附剂制备过程中涉及的各相关参数均同实施例1，区别仅在于：
将分子筛和絮凝剂溶液混合后，静置，离心分离，然后于200℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛，其余同实施例1。
最终所得吸附剂的堆积密度、机械强度和吸附容量见表1。
实施例9
堆积密度、机械强度和吸附容量测试结果。按照前述，进行吸附剂的堆积密度、机械强度和吸附容量测试，结果如表1所示。
表1各样品的堆积密度、机械强度和吸附容量
Figure PCTCN2022128567-appb-000001
Figure PCTCN2022128567-appb-000002
由表1可以看出，实施例1～8中，Raw-分子筛经絮凝剂溶液处理后消除了晶粒之间的排斥力，使晶粒紧密堆积，所制备的吸附剂具有较高的堆积密度和机械强度。对比例1-1中，大粒径分子筛所制备的吸附剂由于传质限制导致吸附容量较低。对比例1-2中，Raw-分子筛未经絮凝剂处理、晶粒之间空隙大，所制备的吸附剂堆积密度较低、机械强度较差。对比例1-3-A中，分子筛和絮凝剂溶液搅拌均匀后，不静置即离心分离，絮凝剂未充分发挥作用，絮凝效果不佳，所制备吸附剂的堆积密度较低。对比例1-3-B中，絮凝后静置时间过长，絮凝剂部分降解，絮凝效果不佳，所制备吸附剂的堆积密度较低。对比例1-4-C中，絮凝剂浓度过低导致絮凝效果不佳。对比例1-4-D中，絮凝剂浓度过高，絮凝剂和分子筛混合后体系黏度较大，混合不均匀，絮凝效果略差。对比例1-5中，烘干温度过高导致絮凝剂部分降解，絮凝效果不佳。
实施例10
配置1wt％聚丙烯酰胺水溶液，加入Raw-NaX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为5:1；静置30分钟后将分子筛和絮凝剂溶液离心分离，于120℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和高岭土的比例为85:15；
将分子筛和高岭土搅拌均匀，边滚动成型边加入适量聚乙二醇水溶液形成小球；所述聚乙二醇的添加量占分子筛和高岭土干基总重的1wt％；所述聚乙二醇水溶液的量为分子筛和高岭土干基总重的20wt％。
小球烘干后筛分，取0.3～1mm的小球于600℃焙烧6小时得吸附剂前驱体。将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球装填在不锈钢管式容器中，通入0.1mol/L氯化铵溶液至出口溶液中钠含量低于0.1wt％。交换温度60℃，体积空速5h -1。交换后用去离子水洗涤至pH为中性，于100℃烘干得NH 4X小球。
将NH 4X小球边翻动边喷洒浓度为0.1mol/L氯化钡溶液至小球完全润湿(使之以喷雾液滴的形式与小球接触)，静置30分钟，干燥后于500℃焙烧1小时。
所制备的对二甲苯吸附剂钡交换度为98.6％，其堆积密度、机械强度和吸附容量见表2。
实施例11
配置2wt％聚丙烯酸钠水溶液，加入Raw-NaX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为8:1；静置20分钟后将分子筛和絮凝剂溶液离心分离，于120℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和膨润土的比例为88:12；
将分子筛和膨润土搅拌均匀，边滚动成型边加入适量碳酸钠水溶液形成小球；所述碳酸钠的添加量占分子筛和膨润土干基总重的3wt％；所述碳酸钠水溶液的量为分子筛和膨润土干基总重的15wt％。
小球烘干后筛分，取0.3～1mm的小球于700℃焙烧4小时得吸附剂前驱体。将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球装填在不锈钢管式容器中，通入0.15mol/L氯化铵溶液至出口溶液中钠含量低于0.1wt％。交换温度80℃，体积空速2h -1。交换后用去离子水洗涤至pH为中性，于100℃烘干得NH 4X小球。
将NH 4X小球边翻动边喷洒浓度为0.15mol/L氯化钡溶液至小球完全润湿(使之以喷雾液滴的形式与小球接触)，静置60分钟，干燥后于350℃焙烧5小时。
所制备的对二甲苯吸附剂钡交换度为99.1％，其堆积密度、机械强度和吸附容量见表2。
实施例12
配置6wt％聚苯乙烯磺酸钠水溶液，加入Raw-NaX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为6:1；静置60分钟后将分子筛和絮凝剂溶液离心分离，于120℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和埃洛石的比例为92:8；
将分子筛和埃洛石混合，加入占分子筛和埃洛石干基总重3wt％的木质素，充分搅拌均匀后滚动成型。
小球烘干后筛分，取0.3～1mm的小球于725℃焙烧3小时得吸附剂前驱体。将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球装填在不锈钢管式容器中，通入0.3mol/L氯化铵溶液至出口溶液中钠含量低于0.1wt％。交换温度70℃，体积空速3h -1。交换后用去离子水洗涤至pH为中性，于100℃烘干得NH 4X小球。
将NH 4X小球边翻动边喷洒浓度为0.05mol/L硝酸钡溶液至小球完全润湿(使之以喷雾液滴的形式与小球接触)，静置90分钟，干燥后于450℃焙烧2小时。
所制备的对二甲苯吸附剂钡交换度为98.9％，其堆积密度、机械强度和吸附容量见表2。
对比例2-1
本对比例中吸附剂的制备过程中涉及的各相关参数均同实施例10，区别仅在于制备方法不同，具体如下：
将聚丙烯酰胺处理过的、晶粒紧密堆积的Raw-NaX分子筛和高岭土搅拌均匀，边滚动成型边加入适量聚乙二醇水溶液形成小球；
将小球烘干后，再焙烧得吸附剂前驱体；将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球；对晶化后的小球进行铵交换得到NH 4X小球。
将NH 4X小球直接放入氯化钡溶液中，轻柔搅动直至溶液被小球完全吸收，氯化钡溶液的量为NH 4X小球的饱和吸水量。静置、干燥、焙烧后得吸附剂。
由于钡溶液分布不均匀，所得吸附剂的钡交换度为86.2～103.7wt％，其堆积密度、机械强度和吸附容量见表2。
对比例2-2
本对比例中吸附剂的制备过程中涉及的各相关参数均同实施例10，区别仅在于制备方法不同，具体如下：
将聚丙烯酰胺处理过的、晶粒紧密堆积的Raw-NaX分子筛和高岭土搅拌均匀，边滚动成型边加入适量聚乙二醇水溶液形成小球；
将小球烘干后，再焙烧得吸附剂前驱体；将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球；对晶化后的小球进行铵交换得到NH 4X小球。
将NH 4X小球边翻动边喷洒氯化钡溶液至小球完全润湿(使之以喷雾液滴的形式与小球 接触)后，不进行静置处理而直接干燥、焙烧得吸附剂。
所制备的对二甲苯吸附剂钡交换度为98.5％，其堆积密度、机械强度和吸附容量见表2。
表2各样品的堆积密度、机械强度和吸附容量
Figure PCTCN2022128567-appb-000003
备注：a指制备100g吸附剂所需钡盐的摩尔量；b指制备100g吸附剂所产生的废液中钡盐的摩尔量。
对比例2-1不是喷洒钡溶液而是将小球直接置于钡溶液中，液体分布不均匀从而导致钡分布不均匀。
对比例2-2没有进行静置处理，钡溶液未充分扩散进分子筛的孔道中，导致钡分布不均匀，小球外表面钡含量高而内部钡含量低。
实施例13
配置2wt％聚丙烯酰胺水溶液，加入Raw-NaX分子筛充分混合均匀，絮凝剂溶液和分子筛的体积比为7:1；静置30分钟后将分子筛和絮凝剂溶液离心分离，于100℃烘箱中干燥后用粉碎机粉碎得到晶粒紧密堆积的分子筛。
分子筛和高岭土的比例为85:15；
将分子筛和高岭土搅拌均匀，边滚动成型边加入适量聚乙二醇水溶液形成小球；所述聚乙二醇的添加量占分子筛和高岭土干基总重的1wt％；所述聚乙二醇水溶液的量为分子筛和高岭土干基总重的20wt％。
小球烘干后于600℃焙烧4小时得吸附剂前驱体。将该吸附剂前驱体在碱液中进行晶化处理得到晶化后的小球。
将晶化后的小球装填在不锈钢管式容器中，通入0.2mol/L氯化铵溶液至出口溶液中钠含量低于0.1wt％。交换温度70℃，体积空速3h -1。交换后用去离子水洗涤至pH为中性，于100℃烘干得NH 4X小球。
将NH 4X小球边翻动边喷洒浓度为0.05mol/L氯化锂溶液至小球完全润湿(使之以喷雾液滴的形式与小球接触)，静置30分钟，干燥后于500℃焙烧1小时得LiX吸附剂。

Claims (18)

  1. 一种吸附剂，其特征在于，
    所述吸附剂包括金属离子，以及分子筛；
    所述吸附剂具有不低于600kg/m 3的堆积密度；
    其中，
    所述，分子筛经由以下方式进行处理：Raw-分子筛与絮凝剂接触混合形成溶液，后进行干燥、粉碎处理；其中，
    絮凝剂的添加质量与分子筛的添加质量比为(0.05～1)：1；
    所述Raw-分子筛的粒径尺寸D90不超过1.5μm。
  2. 根据权利要求1所述的吸附剂，其特征在于，
    所述絮凝剂包括聚丙烯酰胺、聚二甲基二烯丙基氯化铵、聚丙烯酸钠、聚苯乙烯磺酸钠和木质素磺酸钠中的一种或一种以上；
  3. 一种吸附剂的制备方法，其特征在于，
    所述吸附剂负载有金属离子；
    制备步骤包括以下内容：
    S1.Raw-分子筛处理：
    Raw-分子筛与絮凝剂接触混合形成溶液，后进行干燥、粉碎处理，得到处理过后的分子筛；所述，Raw-分子筛的粒径尺寸D90不超过1.5μm；
    S2.制备吸附剂前驱体：
    对含有分子筛、粘结剂以及造孔剂的混合物，进行成型处理，然后进行高温处理；
    S3.晶化处理
    在碱性体系下对吸附剂前驱体进行晶化处理；
    S4.金属离子负载
    利用含目标金属离子的溶液，进行吸附剂的金属离子的负载。
  4. 根据权利要求3所述的吸附剂的制备方法，其特征在于，
    S1中，Raw-分子筛与絮凝剂接触混合形成溶液后，先进行静置处理，然后分离出沉淀物进行干燥、粉碎处理；
    所述静置处理的时间不低于10min。
  5. 根据权利要求4所述的吸附剂的制备方法，其特征在于，
    所述分离方式为离心分离，所述离心转速不低于2000r/min。
  6. 根据权利要求3所述的吸附剂的制备方法，其特征在于，
    S1中，所述干燥温度不超过150℃。
  7. 根据权利要求3所述的吸附剂的制备方法，其特征在于，
    所述絮凝剂包括聚丙烯酰胺、聚二甲基二烯丙基氯化铵、聚丙烯酸钠、聚苯乙烯磺酸钠和木质素磺酸钠中的一种或一种以上。
  8. 根据权利要求3～7任一所述的吸附剂的制备方法，其特征在于，
    S1中，将所述絮凝剂配置为1～10wt％的水溶液，然后与分子筛进行接触；
    所述絮凝剂溶液和分子筛的体积比为(2～15)：1。
  9. 根据权利要求3所述的吸附剂的制备方法，其特征在于，
    S2中，分子筛的添加量高于粘结剂的添加量；
    造孔剂的添加量为分子筛与粘结剂干基总重的1～5wt％。
  10. 根据权利要求3所述的吸附剂的制备方法，其特征在于，
    S2中，高温处理的温度为550～950℃；高温处理的处理时间为1～8小时。
  11. 根据权利要求3～7任一所述的吸附剂的制备方法，其特征在于，
    S4中，使晶化处理后的产物直接与含有目标金属离子的溶液接触，进行阳离子交换，实现目标金属离子的负载，得到所述负载有金属的吸附剂产物。
  12. 根据权利要求8所述的吸附剂的制备方法，其特征在于，
    所述S4，具体包括
    首先，利用铵盐溶液，对晶化处理后的产物进行铵离子交换处理；
    然后，与含目标金属离子的溶液接触，实现目标金属离子的负载，得到所述负载有金属的吸附剂产物；
    确定经过铵离子交换处理后产物的饱和吸水量，所述含目标金属离子的溶液的量不超过所述产物的饱和吸水量。
  13. 根据权利要求12所述的吸附剂的制备方法，其特征在于，
    所述铵离子交换处理包括：
    使含有铵离子的溶液与晶化处理后的产物接触，对接触过后的溶液进行碱金属离子的含量检测，使碱金属离子的含量≤0.1wt％。
  14. 根据权利要求13所述的吸附剂的制备方法，其特征在于，
    所述铵盐的添加浓度为0.05～0.3mol/L。
  15. 根据权利要求13所述的吸附剂的制备方法，其特征在于，
    将晶化处理后的产物置于容器中，连续向容器通入含有铵离子的溶液；
    其中，所述容器具有进液口、出液口；
    所述铵盐溶液通入的体积空速为2～8h -1。
  16. 根据权利要求12所述的吸附剂的制备方法，其特征在于，
    使含目标金属离子的溶液雾化成小液滴的形式与铵离子交换处理后的产物实现接触，然后静置处理，最后进行干燥、高温处理。
  17. 根据权利要求16所述的吸附剂的制备方法，其特征在于，
    所述静置处理的时间为30～120min；
    高温处理的温度为350～500℃；高温处理的时间为1～5小时。
  18. 根据权利要求1～2任一项所述的吸附剂，或者权利要求3～17中任意一项所制备的吸附剂的应用，其特征在于：
    用于从混合物中通过吸附分离得到目标产物；
    所述目标产物包括对二甲苯、对甲酚中的任意一种或者两种。
PCT/CN2022/128567 2022-07-29 2022-10-31 一种吸附剂及其制备方法与应用 WO2024021342A1 (zh)

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