CN110523380B - Honeycomb ceramic-based aluminum-MOF (Metal organic framework) adsorbent and in-situ synthesis method thereof - Google Patents

Honeycomb ceramic-based aluminum-MOF (Metal organic framework) adsorbent and in-situ synthesis method thereof Download PDF

Info

Publication number
CN110523380B
CN110523380B CN201910641671.9A CN201910641671A CN110523380B CN 110523380 B CN110523380 B CN 110523380B CN 201910641671 A CN201910641671 A CN 201910641671A CN 110523380 B CN110523380 B CN 110523380B
Authority
CN
China
Prior art keywords
honeycomb ceramic
fumaric acid
aluminum
blank
adsorbent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910641671.9A
Other languages
Chinese (zh)
Other versions
CN110523380A (en
Inventor
梁向晖
谭冰琼
方玉堂
汪双凤
高学农
张正国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201910641671.9A priority Critical patent/CN110523380B/en
Publication of CN110523380A publication Critical patent/CN110523380A/en
Application granted granted Critical
Publication of CN110523380B publication Critical patent/CN110523380B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/261—Drying gases or vapours by adsorption
    • 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
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water

Abstract

The invention discloses a honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent and an in-situ synthesis method thereof. The method comprises the following steps: uniformly mixing fumaric acid, an alkaline substance and water, adding a thickening agent, uniformly mixing to obtain a mixed solution, soaking the honeycomb ceramic matrix blank in the mixed solution, and drying to obtain a blank containing deprotonated fumaric acid; and (3) soaking the embryo body containing deprotonated fumaric acid in an aluminum salt solution, heating in a water bath, cooling to room temperature, filtering to obtain a precipitate, washing, drying, heating, and performing sintering activation treatment to obtain the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent. According to the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent provided by the invention, the adsorption active substances are uniformly and compactly distributed on the honeycomb ceramic fiber blank, and the loading amount is high; the adsorbent has low crystallization temperature and high crystallization rate; the product is S-shaped water vapor adsorption isothermal, has the characteristics of high adsorption rate, high equilibrium adsorption capacity, easy desorption and the like, and can be applied to preparation of adsorption type dehumidification rotating wheels or total heat recoverers.

Description

Honeycomb ceramic-based aluminum-MOF (Metal organic framework) adsorbent and in-situ synthesis method thereof
Technical Field
The invention belongs to the field of gas adsorption type drying purification and heat recovery, and particularly relates to an in-situ synthesis method of a honeycomb ceramic-based aluminum-MOF adsorbent.
Background
The honeycomb ceramic-based dehumidifying adsorbent is formed by organically combining ceramic fibers and an adsorbent, and can be applied to an adsorption type dehumidifying runner and a total heat recovery system. Among them, the core of the system is the dehumidification rotary core (bulk adsorbent), and the performance of the dehumidification rotary core determines the energy efficiency of the system. The evaluation of the dehumidification core-rotating performance mainly comprises two aspects: (1) performance of the adsorbent itself: the adsorbent has higher equilibrium adsorption capacity; lower desorption temperature. (2) The composite process of the adsorbent and the base material comprises the following steps: the adsorbent is tightly combined with the honeycomb base material to prevent the adsorbent from falling off; has high loading capacity of the adsorbent so as to improve the adsorption performance of the block adsorbent.
The aluminum-fumaric acid Metal Organic Framework (MOF) adsorbent has the characteristics of high saturated adsorption capacity (more than 0.4 g/g), good thermal stability, isothermal S-shaped water vapor adsorption, low desorption temperature (about 70 ℃) and the like. The dehumidifying rotary wheel (dehumidifying rotary core or block adsorbent) made of the material has large dehumidifying amount, and can be regenerated by using low-grade heat sources such as solar energy and industrial waste heat. The existing honeycomb ceramic-based block adsorbent mainly comprises silica gel, a molecular sieve and the like. The silica gel is mainly used in high humidity environment; has a lower desorption temperature (150 ℃), but has a considerably lower adsorption capacity (less than 5%) at low humidity or at higher temperatures. Silicate molecular sieves such as NaA, 13X and the like show extremely strong moisture absorption capacity, but the dehumidification rotary core made of the silicate molecular sieves is still insufficient: (1) the molecular sieve has low equilibrium adsorption capacity (generally below 0.25 g/g); (2) the regeneration temperature of the molecular sieve is high (above 200 ℃), which is not beneficial to saving energy of the system; (3) in the preparation process, a honeycomb blank made of ceramic or glass fiber paper is usually selected as a base material, an industrial molecular sieve with larger granularity (the particle size is 2-5 mu m) is used as an adsorbent, and the honeycomb blank is bonded by a dipping coating method on the premise of adding inorganic glue or organic/inorganic composite glue without adsorption capacity as an adhesive. For example, US 4886769 "active gas adsorption unit and manufacturing method", chinese patent ZL 200610123763.0 "method for preparing molecular sieve/modified silica gel composite block adsorbent" relates to a process for preparing molecular sieve adsorbent. On one hand, the addition of the adhesive can block the pore passages of the molecular sieve, so that the moisture removal capacity of the adsorbent is reduced; on the other hand, the introduction of the adhesive can reduce the loading (gel hanging amount) of the adsorbent on the substrate (generally below 45%, if the gel hanging amount is increased, the adsorbent can fall off powder), so that the preparation of a novel dehumidification rotary core (block adsorbent) with high dehumidification capacity, high gel hanging amount and lower regeneration temperature is particularly important for improving the system efficiency.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent and an in-situ synthesis method thereof.
The in-situ synthesis method of the honeycomb ceramic-based aluminum-MOF adsorbent is a novel in-situ synthesis method of the honeycomb ceramic-based aluminum-MOF adsorbent, which has the advantages of high adsorbent loading, high equilibrium adsorption amount, high adsorption rate and strong actions between the adsorbents and common fibers.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides an in-situ synthesis method of a honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent, which comprises the following steps:
(1) dipping the honeycomb ceramic matrix blank: mixing fumaric acid, alkaline substances (fumaric acid and alkaline substances are used as basic raw materials) and water (water is used as a solvent) at room temperature, uniformly stirring, then adding a thickening agent (hydrophilic polymer can be preferably used as the thickening agent), uniformly mixing to obtain a mixed solution, soaking the honeycomb ceramic matrix blank in the mixed solution (a clear and transparent solution), taking out and drying to obtain a blank containing deprotonated fumaric acid;
(2) in-situ synthesis of the honeycomb ceramic-based aluminum-MOF adsorbent: and (2) soaking the embryo body containing deprotonated fumaric acid in the step (1) in an aluminum salt solution, heating in a water bath (namely in-situ crystallization reaction at the temperature of 30-80 ℃ for 20-120min), cooling to room temperature, filtering to obtain precipitate, washing, drying, heating, and sintering and activating to obtain the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent.
Further, the alkaline substance in the step (1) is an inorganic alkaline substance or an organic alkaline substance; the alkaline substance is more than one of sodium hydroxide, potassium hydroxide, ammonia water, methylamine, ethylamine, propylamine, butylamine, diethylamine, dipropylamine and dibutylamine; the molar ratio of the alkaline substance to the fumaric acid is 2.5-4.0: 1; the molar ratio of the water to the fumaric acid is 4-120: 1. in the step (1), the alkaline substance is added to protonate the fumaric acid, so as to reduce the crystallization temperature of the aluminum-fumaric acid; the fumaric acid has high protonation degree and large crystallization reaction temperature reduction.
Preferably, the molar ratio of the alkaline substance to the fumaric acid in the step (1) is 3.0-3.8: 1.
preferably, the molar ratio of water to fumaric acid in step (1) is 60-100: 1.
preferably, the alkaline substance in step (1) is one or two of sodium hydroxide and potassium hydroxide. Strong inorganic bases (sodium hydroxide and potassium hydroxide) are preferred because ammonia and organic amines are volatile, toxic, and expensive to some extent.
In the step (1), adding a certain amount of fumaric acid and alkali as basic raw materials in the preparation of the deprotonated fumaric acid honeycomb ceramic-based blank body, and using water as a solvent; the molar ratio of fumaric acid/alkali/water is 1.0/2.5-4.0/40-120. Theoretically, the molar ratio of fumaric acid to base is 1/2, depending on the aluminum-fumaric acid MOF product structure. In order to increase the protonation degree of fumaric acid, an excess of base is added; the excessive alkali can improve the viscosity of the mixed solution A, so that the deprotonated fumaric acid can be conveniently loaded on the honeycomb ceramic fiber blank; similarly, the added solvent has less water, the viscosity of the system is high, and the embryo body is convenient to deprotonate fumaric acid load; however, the added water is too little, and the deprotonated fumaric acid is unevenly loaded on the surface of the ceramic fiber blank; on the contrary, the added water amount is large, the viscosity of the system is small, and the embryo body loading is not facilitated.
Further, the thickening agent in the step (1) is more than one of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), sodium carboxymethyl cellulose (CMC) and the like; the mass of the thickening agent accounts for 0.1 wt% -1 wt% of the mass of the mixed solution.
Preferably, the mass of the thickening agent in the step (1) accounts for 0.3-0.6% of the mass of the mixed solution.
In the step (1), a small amount of hydrophilic polymer is added as a thickening agent in the preparation of the deprotonated fumaric acid honeycomb ceramic-based embryo body, so that the glue hanging amount of the honeycomb ceramic-based embryo body on the deprotonated fumaric acid is increased, and the honeycomb ceramic-based adsorbent containing more target products is synthesized. Hydrophilic polymers include polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), sodium carboxymethyl cellulose (CMC), and the like. The adding amount accounts for 0.1-1% of the mixed solution A by mass; the added thickening agent is less, and the tackifying effect is not obvious; the addition amount is large; the viscosity of the mixed solution A is high, and the amount of deprotonated fumaric acid coated on the embryo body is high but the distribution is not uniform; preferably, it accounts for 0.3-0.6% of the mass of the mixed solution A.
Further, the drying temperature in the step (1) is 30-100 ℃, and the drying time is 3-12 h.
If the drying temperature is low and the drying time is short, the formed deprotonated fumaric acid embryo body has a loose structure, and the acting force of the formed adsorbed active substances and the base material is weak; if the drying temperature is high, the drying time is long, the formed deprotonated fumaric acid blank has a compact structure, aluminum salt is difficult to enter the blank for crystallization reaction, the crystallization time is long, and the product has defects. Therefore, preferably, the drying temperature in the step (1) is 50-80 ℃, and the drying time is 5-10 h.
Further, the preparation of the honeycomb ceramic matrix blank in the step (1) comprises the following steps: respectively carrying out hot rolling on the plain paper and the surface paper of the fiber paper and sizing material on a corrugated roller and a plain roller of a corrugated paper machine, laminating to obtain single-sided corrugated paper, then covering and rolling the single-sided corrugated paper into a honeycomb ceramic-based core body under the action of the sizing material, cutting and polishing the surface of the honeycomb ceramic-based core body, heating for sintering treatment, and removing organic matters to obtain the honeycomb ceramic-based blank body.
The invention selects ceramic fiber paper as a base material, and the ceramic fiber paper is processed by the working procedures of coating, hot press molding, lapping, sintering and the like to form a honeycomb ceramic base blank, and the honeycomb ceramic blank is dried in an oven for standby before test use. Since the ceramic fiber paper is only used as a carrier, other inorganic carriers such as glass fiber paper can also be used as the carrier, and the ceramic fiber paper has no influence on the synthesis and the performance of the block adsorbent.
Further, in the preparation process of the honeycomb ceramic matrix blank, the fiber paper can be one of ceramic fiber paper and glass fiber paper; the glue material is inorganic glue andmore than one of organic glue; the inorganic adhesive is silica Sol (SiO)2) Alumina sol (Al)2O3) Titanium sol (TiO)2) And zirconium sol (ZrO)2) One of the like; the organic glue is one of polyvinyl acetate (VAE), polyvinyl alcohol glue (PVA), acrylate, organic silicon modified acrylate and the like; the sintering treatment temperature is 350-700 ℃, and the sintering treatment time is 10-24 h.
Preferably, in the preparation process of the honeycomb ceramic matrix blank, the sintering treatment temperature is 400-600 ℃, and the sintering treatment time is 12-18 h.
Further preferably, in the preparation process of the honeycomb ceramic matrix blank, the sintering treatment temperature is 500 ℃; the time of the sintering treatment is 16 h.
Furthermore, in the preparation process of the honeycomb ceramic matrix blank, the addition of the sizing material is convenient for forming corrugated paper and rewinding; the organic glue can improve the toughness; the inorganic adhesive can improve the heat resistance and the rigidity of the inorganic adhesive; the honeycomb ceramic matrix blank formed by the single rubber material has loose structure and low strength; preferably, therefore, the size is an organic/inorganic hybrid size (i.e. organic size is used in combination with inorganic size), such as SiO2With VAE, Al2O3With VAE, SiO2With PVA, Al2O3And any one of four combinations of PVA or the compound combination of two or more of the glue stocks.
Further, the aluminum salt solution in the step (2) is a mixture of aluminum salt and water which are uniformly mixed; the aluminum salt is more than one of aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum potassium sulfate and the like; the mass percentage concentration of the aluminum salt solution is 5-20 wt%.
Preferably, the aluminum salt in the step (2) is one or more of aluminum sulfate and aluminum nitrate.
Preferably, the concentration of the aluminum salt solution of step (2) is 8-15%.
In the step (2), in the in-situ synthesis of the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent, a deprotonated fumaric acid-containing blank is soaked in an aluminum salt solution, and the aluminum salt used comprises one or more than one of crystalline salts such as aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum potassium sulfate and the like. The influence of impurity cations on the purity of the adsorbent crystals is eliminated from the corrosiveness of the aluminum salt, the source of the raw material and as far as possible.
In the in-situ crystallization synthesis of the honeycomb ceramic-based aluminum-MOF adsorbent in the step (2), the mass concentration of the added aluminum salt solution is 5-20%. The aluminum salt has high concentration, and the aluminum salt migrates to the blank body at a high speed, so that the aluminum-fumaric acid in-situ crystallization reaction is facilitated, but the crystallization degree of a crystallization reaction product is reduced due to the high concentration, and the crystal is not uniformly dispersed on the blank body; similarly, the aluminum salt concentration is low, the migration speed to the embryo body is slow, and the aluminum salt is not beneficial to the aluminum-fumaric acid in-situ crystallization reaction, and is preferably 8-15%;
further, the temperature of the water bath heating treatment in the step (2) is 30-80 ℃, and the time of the water bath heating treatment is 20-120 min.
Preferably, the temperature of the water bath heating treatment in the step (2) is 40-70 ℃, and the time of the water bath heating treatment is 40-80 min.
In the step (2), during the in-situ crystallization synthesis of the honeycomb ceramic-based aluminum-MOF adsorbent, the reaction is carried out for 20-120min in water bath at the temperature of 30-80 ℃. The temperature is too low, the reaction rate of the aluminum-fumaric acid on the glass fiber is too slow, so that the loading amount of the aluminum-fumaric acid on the glass fiber is too small; when the temperature is too high, the reaction rate of the aluminum-fumaric acid on the glass fiber is too fast, so that the aluminum-fumaric acid is peeled off. The same problem also exists in the crystallization time, and too short crystallization time can cause too little loading of the aluminum-fumaric acid on the glass fiber; the time is too long, so that the aluminum-fumaric acid is peeled off. Preferably, the reaction is carried out for 40-80min in water bath at 40-70 ℃.
Further, the temperature of the sintering activation treatment in the step (2) is 345-355 ℃, and the time of the sintering activation treatment is 6-12 h.
Preferably, the temperature of the sintering activation treatment in the step (2) is 350 ℃.
Preferably, the drying temperature in the step (2) is 150 ℃, and the drying time is 12-24 h.
The invention provides a honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent prepared by the preparation method.
The in-situ synthesis method provided by the invention adopts a honeycomb blank made of ceramic fiber paper as a base material, and a reactant (deprotonated fumaric acid) of self-reaction raw materials fumaric acid and alkali as an adhesive; soaking the honeycomb ceramic fiber blank in a mixed solution containing deprotonated fumaric acid, and forming a deprotonated fumaric acid-containing honeycomb blank under the tackifying of a water-soluble high polymer; placing the blank body in a reaction liquid of aluminum salt for crystallization, and washing and drying to prepare the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent; the prepared honeycomb ceramic-based aluminum-MOF adsorbent is a block adsorbent (dehumidification rotary core) and can be applied to assembling an adsorption type dehumidification rotary wheel or a total heat recoverer.
The working principle of the process according to the invention is illustrated below by way of example with sodium hydroxide as deprotonating agent:
by taking a honeycomb ceramic fiber blank as a base material, firstly, impregnating an alkaline mixture of sodium fumarate on the blank under the auxiliary action of a water-soluble polymer of a tackifier by an impregnation method, wherein the obtained sodium fumarate mixed solution has strong adhesive property with the ceramic fiber blank due to the viscosity of the mixed solution, so that the honeycomb ceramic fiber blank uniformly loaded with the sodium fumarate can be formed; sodium fumarate and aluminium salt can be subjected to crystallization reaction at a lower temperature due to deprotonation; when the sodium fumarate-containing embryo body is immersed in the aluminum salt reaction liquid, sodium ions in the sodium fumarate and aluminum ions in the reaction liquid are subjected to ion exchange, the aluminum ions migrate to the ceramic fiber embryo body, the sodium ions migrate to the aluminum salt solution, and under a certain water bath temperature and reaction time, the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent can be formed.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the in-situ synthesis method provided by the invention, due to the adsorption characteristics of the adopted aluminum-fumaric acid MOF adsorbent, the prepared honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent has higher adsorption performance (measured by equilibrium adsorption quantity), the equilibrium adsorption quantity can reach 30-36%, and the desorption temperature (namely desorption activation energy) can reach 60-80 ℃;
(2) according to the in-situ synthesis method provided by the invention, the aluminum-fumaric acid adsorbent is generated in situ, and no additional inorganic adhesive or inorganic/organic composite adhesive is added (the organic high polymer tackifier added into the mixed solution A is eliminated in the activation process), so that the in-situ generated adsorbent has high load which can reach 65-75 percent and can reach 75.97 percent at most and is far higher than the load of the existing molecular sieve (below 45 percent);
(3) compared with the method for preparing the block adsorbent by using the binder, the in-situ synthesis method provided by the invention has the advantages that the acting force between the crystal grains of the adsorbent synthesized by the in-situ synthesis method and between the crystal grains of the adsorbent and the ceramic fiber is strong, and the phenomenon of powder falling of the adsorbent is not easy to occur.
Drawings
FIG. 1 is an XRD spectrum of a honeycomb ceramic based aluminum-fumaric acid MOF adsorbent provided in example 1 versus a comparative example aluminum-fumaric acid adsorbent powder;
FIG. 2 is an SEM image of a honeycomb ceramic based aluminum-fumaric MOF adsorbent provided in example 1 versus a comparative example aluminum-fumaric acid adsorbent powder;
FIG. 3 is a static water adsorption curve of the honeycomb ceramic based aluminum-fumaric MOF adsorbent provided in example 1 versus the comparative example aluminum-fumaric acid powder;
FIG. 4 is a dynamic isothermal water adsorption curve of the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent provided by the invention.
Detailed Description
The following description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Comparative example
Under room temperature and magnetic stirring, taking a 500mL beaker, adding 23.2g of fumaric acid, 26.0g of sodium hydroxide and 300mL of deionized water into the beaker according to the molar ratio of fumaric acid/alkali/water of 1.0/3.25/83, adding 2.0g of PVA powder (polyvinyl alcohol) after the raw materials are dissolved and uniformly stirred, and continuously stirringObtaining a clear and transparent solution A, wherein the mass of the added PVA powder accounts for 0.5 wt% of the mass of the clear and transparent solution A; another 500ml beaker is filled with 66.6g of Al2(SO4)3·18H2Dissolving O in 300ml of deionized water, and stirring until the O is dissolved to form a solution B (the mass percent concentration of the solution B is 9.33%); uniformly mixing the clear transparent solution A and the clear transparent solution B, and heating in a water bath at 60 ℃ for 60min to obtain a suspension containing white precipitates; and then, carrying out centrifugal filtration on the suspension containing the white precipitate to obtain the white precipitate, washing the white precipitate twice by using deionized water, drying the white precipitate for 16h at 150 ℃, and then activating the white precipitate for 8h at 350 ℃ to obtain aluminum-fumaric acid adsorbent powder.
Example 1
(1) Preparing a honeycomb ceramic blank: 23g/m2Quantitative ceramic fiber paper (the mass ratio of flat paper to surface paper is 1:1) is respectively coated on a corrugated roller and a flat roller of a corrugated paper machine to form single-sided corrugated paper through the action of sizing material and hot rolling (180 ℃) lamination, wherein the sizing material comprises 45 wt% of SiO2Sol with 55 wt% VAE gum; then, under the action of the sizing material, the honeycomb ceramic matrix core is formed by rolling; finally, the surface of the ceramic substrate is cut and polished, and the ceramic substrate is sintered for 16h at 500 ℃ to remove organic matters, so that a honeycomb ceramic substrate blank (the size of which is phi 4cm (D) multiplied by 6cm (H)) is formed.
(2) Under room temperature and magnetic stirring, taking a 500mL beaker, adding 23.2g of fumaric acid, 26.0g of sodium hydroxide and 300mL of deionized water into the beaker according to the molar ratio of fumaric acid to alkali to water of 1.0/3.25/83, stirring uniformly, adding 2.0g of PVA powder, and continuously stirring to obtain a clear and transparent solution A, wherein the mass of the added PVA powder accounts for 0.5 wt% of the mass of the clear and transparent solution A; soaking the honeycomb ceramic blank in the clear transparent solution A, taking out after the honeycomb ceramic blank is completely wetted, and drying the honeycomb ceramic blank at the temperature of 60 ℃ for 8 hours to form a honeycomb ceramic blank containing sodium fumarate; another 500ml beaker is taken, and 66.6gAl is added2(SO4)3·18H2Dissolving O in 300ml of deionized water, and stirring until the O is dissolved to form a solution B (the mass percent concentration of the solution B is 9.33 wt%); immersing the honeycomb ceramic blank containing sodium fumarate into the solution B, and then placing the honeycomb ceramic blank at the water bath temperature to be heated in the water bath at the temperature of 60 ℃ for 60miAnd n, cooling to room temperature, centrifuging to obtain a precipitate, washing with deionized water for three times, drying at 150 ℃ for 16h, and activating at 350 ℃ for 8h to obtain the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent.
Example 2
(1) Preparing a honeycomb ceramic blank: 23g/m2Quantitative ceramic fiber paper (the mass ratio of flat paper to surface paper is 1:1) is respectively subjected to the action of sizing materials on a corrugated roller and a flat roller of a corrugated paper machine, hot rolling is carried out at 180 ℃, and single-side corrugated paper is laminated, wherein the sizing materials comprise 45 wt% of alumina sol and 55 wt% of acrylate glue; then, under the action of the sizing material, the honeycomb ceramic matrix core is formed by rolling; finally, the surface of the ceramic substrate is cut and polished, and the ceramic substrate is sintered for 10 hours at 700 ℃ to remove organic matters, so that a honeycomb ceramic substrate blank (the size of which is phi 4cm (D) multiplied by 6cm (H)) is formed.
(2) Under room temperature and magnetic stirring, taking a 500mL beaker, adding 23.2g of fumaric acid, 36.4g of potassium hydroxide and 300mL of deionized water into the beaker according to the molar ratio of fumaric acid to alkali to water of 1.0/3.25/83, stirring uniformly, adding 2.0g of PVP powder, and continuing stirring to obtain a clear and transparent solution A, wherein the mass of the added PVA powder accounts for 0.5 wt% of the mass of the clear and transparent solution A; soaking the honeycomb ceramic blank in the clear transparent solution A, taking out after the honeycomb ceramic blank is completely wetted, and drying the honeycomb ceramic blank at the temperature of 50 ℃ for 10 hours to form a honeycomb ceramic blank containing potassium fumarate; another 500ml beaker is taken, and 75.0g of Al (NO) is added3)3·9H2Dissolving O in 400ml of deionized water, and stirring until the O is dissolved to form a solution B (the mass percent concentration of the solution B is 8.97 wt%); and (3) soaking the honeycomb ceramic blank containing sodium fumarate in the solution B, placing the honeycomb ceramic blank at the water bath temperature, heating the honeycomb ceramic blank in the water bath at 60 ℃ for 60min, cooling the honeycomb ceramic blank to room temperature, centrifuging the honeycomb ceramic blank to obtain a precipitate, washing the precipitate with deionized water for three times, drying the precipitate at 150 ℃ for 12h, and then activating the precipitate at 350 ℃ for 12h to obtain the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent.
Example 3
(1) Preparing a honeycomb ceramic blank: 23g/m2Quantitative ceramic fiber paper (the mass ratio of flat paper to surface paper is 1:1) is respectively subjected to the action of sizing material on a corrugated roller and a flat roller of a corrugated paper machine, hot rolled (180 ℃) and stuck to form a sheetSurface corrugated paper, wherein the composition of the sizing material is 45 wt% of SiO2Sol with 55 wt% VAE gum; then, under the action of the sizing material, the honeycomb ceramic matrix core is formed by rolling; finally, the surface of the ceramic substrate is cut and polished, and the ceramic substrate is sintered for 24 hours at 350 ℃, organic matters are removed, and a honeycomb ceramic substrate blank (the size of phi is 4cm (D) multiplied by 6cm (H)) is formed.
(2) Under room temperature and magnetic stirring, taking a 500mL beaker, adding 23.2g of fumaric acid, 42.6g of potassium hydroxide and 360mL of deionized water into the beaker according to the molar ratio of fumaric acid to alkali to water of 1.0/3.8/100, after the raw materials are dissolved and uniformly stirred, adding 2.4g of CMC powder (sodium carboxymethylcellulose), and continuously stirring to obtain a clear and transparent solution A, wherein the mass of the added CMC powder accounts for 0.56 wt% of the mass of the clear and transparent solution A; soaking the honeycomb ceramic blank in the clear transparent solution A, taking out after the honeycomb ceramic blank is completely wetted, and drying the honeycomb ceramic blank at the temperature of 70 ℃ for 6 hours to form a honeycomb ceramic blank containing potassium fumarate; another 500ml beaker is filled with 75.0g of Al (NO)3)3·9H2Dissolving O in 300ml of deionized water, and stirring until the O is dissolved to form a solution B (the mass percent concentration of the solution B is 11.3 wt%); and (3) soaking the honeycomb ceramic blank containing sodium fumarate in the solution B, placing the honeycomb ceramic blank at the water bath temperature, heating the honeycomb ceramic blank in the water bath at 60 ℃ for 60min, cooling the honeycomb ceramic blank to room temperature, centrifuging the honeycomb ceramic blank to obtain a precipitate, washing the precipitate with deionized water for three times, drying the precipitate at 150 ℃ for 24h, and sintering and activating the precipitate at 350 ℃ for 6h to obtain the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent.
Example 4
(1) Preparing a honeycomb ceramic blank: 23g/m2Quantitative ceramic fiber paper (the mass ratio of flat paper to surface paper is 1:1) is respectively subjected to the action of sizing materials on a corrugated roller and a flat roller of a corrugated paper machine, hot rolling is carried out at 180 ℃, and single-side corrugated paper is laminated, wherein the sizing materials comprise 30 wt% of titanium sol and 70 wt% of VAE (vinyl acetate) adhesive; then, under the action of the sizing material, the honeycomb ceramic matrix core is formed by rolling; finally, the surface of the ceramic substrate is cut and polished, and the ceramic substrate is sintered for 18h at 400 ℃, organic matters are removed, and a honeycomb ceramic substrate blank (the size of which is phi 4cm (D) multiplied by 6cm (H)) is formed.
(2) Under the condition of room temperature and magnetic stirring, a 500mL beaker is taken, and the molar ratio of fumaric acid/alkali/water is 1.0/3.060, adding 23.2g of fumaric acid, 24.0g of sodium hydroxide and 216ml of deionized water into a beaker, adding 1.5g of PVA powder after the raw materials are dissolved and uniformly stirred, and continuously stirring to obtain a clear and transparent solution A, wherein the mass of the added PVA powder accounts for 0.57 wt% of the mass of the clear and transparent solution A; soaking the honeycomb ceramic blank in the clear transparent solution A, taking out after the honeycomb ceramic blank is completely wetted, and drying the honeycomb ceramic blank at the temperature of 80 ℃ for 5 hours to form a honeycomb ceramic blank containing potassium fumarate; another 500ml beaker is taken, and 66.6g of Al is added2(SO4)3·18H2Dissolving O in 240ml of deionized water, and stirring until the O is dissolved to form a solution B (the mass percent concentration of the solution B is 11.2 wt%); and (3) soaking the honeycomb ceramic blank containing sodium fumarate in the solution B, placing the honeycomb ceramic blank at the water bath temperature, heating the honeycomb ceramic blank in the water bath at 50 ℃ for 70min, cooling the honeycomb ceramic blank to room temperature, centrifuging the honeycomb ceramic blank to obtain a precipitate, washing the precipitate with deionized water for three times, drying the precipitate at 150 ℃ for 18h, and then activating the precipitate at 350 ℃ for 8h to obtain the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent.
Example 5
(1) Preparing a honeycomb ceramic blank: 23g/m2Quantitative ceramic fiber paper (the mass ratio of flat paper to surface paper is 1:1) is respectively subjected to the action of sizing materials on a corrugated roller and a flat roller of a corrugated paper machine, hot rolling is carried out at 180 ℃, and single-side corrugated paper is laminated, wherein the sizing materials consist of 40 wt% of SiO2Sol and 60 wt% VAE gum; then, under the action of the sizing material, the honeycomb ceramic matrix core is formed by rolling; finally, the surface of the ceramic substrate is cut and polished, and the ceramic substrate is sintered for 16h at 500 ℃ to remove organic matters, so that a honeycomb ceramic substrate blank (the size of which is phi 4cm (D) multiplied by 6cm (H)) is formed.
(2) Under room temperature and magnetic stirring, taking a 500mL beaker, adding 23.2g of fumaric acid, 39.2g of potassium hydroxide and 324mL of deionized water into the beaker according to the molar ratio of fumaric acid to alkali to water of 1.0/3.5/90, after the raw materials are dissolved and uniformly stirred, adding 1.5g of CMC powder, and continuously stirring to obtain a clear transparent solution A, wherein the mass of the added CMC powder accounts for 0.39 wt% of the mass of the clear transparent solution A; soaking the honeycomb ceramic blank in the clear transparent solution A, taking out after the honeycomb ceramic blank is completely wetted, and drying the honeycomb ceramic blank at the temperature of 50 ℃ for 10 hours to form a honeycomb ceramic blank containing potassium fumarate; another 500ml beaker66.6g of Al2(SO4)3·18H2O is dissolved in 200ml of deionized water and stirred until the O is dissolved to form a solution B (the mass percent concentration of the solution B is 12.8%). And (3) soaking the honeycomb ceramic blank containing sodium fumarate in the solution B, placing the honeycomb ceramic blank at the water bath temperature, heating the honeycomb ceramic blank in the water bath at 40 ℃ for 80min, cooling the honeycomb ceramic blank to room temperature, centrifuging the honeycomb ceramic blank to obtain a precipitate, washing the precipitate with deionized water for three times, drying the precipitate at 150 ℃ for 12h, and then activating the precipitate at 350 ℃ for 8h to obtain the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent.
Example 6
(1) Preparing a honeycomb ceramic blank: 23g/m2Quantitative ceramic fiber paper (the mass ratio of flat paper to surface paper is 1:1) is respectively subjected to the action of sizing materials on a corrugated roller and a flat roller of a corrugated paper machine, hot rolling is carried out at 180 ℃, and single-side corrugated paper is laminated, wherein the sizing materials consist of 20 wt% of SiO2Mixing the sol and 80 wt% of polyvinyl alcohol glue; then, under the action of the sizing material, the honeycomb ceramic matrix core is formed by rolling; finally, the surface of the ceramic substrate is cut and polished, and the ceramic substrate is sintered for 16h at 500 ℃ to remove organic matters, so that a honeycomb ceramic substrate blank (the size of which is phi 4cm (D) multiplied by 6cm (H)) is formed.
(2) Under room temperature and magnetic stirring, taking a 500mL beaker, adding 23.2g of fumaric acid, 28.8g of sodium hydroxide and 288mL of deionized water into the beaker according to the molar ratio of fumaric acid to alkali to water of 1.0/3.6/80, after the raw materials are dissolved and uniformly stirred, adding 2.0g of PVP powder, and continuously stirring to obtain a clear transparent solution A, wherein the mass of the added PVA powder accounts for 0.59 wt% of the mass of the clear transparent solution A; and soaking the honeycomb ceramic blank in the clear transparent solution A, taking out after the honeycomb ceramic blank is completely wetted, and drying the honeycomb ceramic blank at the temperature of 70 ℃ for 8 hours to form a honeycomb ceramic blank containing sodium fumarate. Another 500ml beaker is filled with 75.0g of Al (NO)3)3·9H2Dissolving O in 240ml of deionized water, and stirring until the O is dissolved to form a solution B (the mass percent concentration of the solution B is 13.5 wt%); soaking the honeycomb ceramic blank containing sodium fumarate in the solution B, placing the honeycomb ceramic blank at a water bath temperature of 70 ℃ for heating in a water bath for 40min, cooling to room temperature, centrifuging to obtain a precipitate, washing with deionized water for three times, drying at 150 ℃ for 20h, and activating at 350 ℃ for 7h to obtain the sodium fumarate-containing honeycomb ceramic blankThe honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent.
Example 7
(1) Preparing a honeycomb ceramic blank: 23g/m2Quantitative ceramic fiber paper (the mass ratio of flat paper to surface paper is 1:1) is respectively subjected to the action of sizing materials on a corrugated roller and a flat roller of a corrugated paper machine, hot rolling is carried out at 180 ℃, and single-side corrugated paper is laminated, wherein the sizing materials consist of 45 wt% of SiO2Sol with 55 wt% VAE gum; then, under the action of the sizing material, the honeycomb ceramic matrix core is formed by rolling; finally, the surface of the ceramic substrate is cut and polished, and the ceramic substrate is sintered for 16h at 500 ℃ to remove organic matters, so that a honeycomb ceramic substrate blank (the size of which is phi 4cm (D) multiplied by 6cm (H)) is formed.
(2) Under room temperature and magnetic stirring, taking a 500mL beaker, adding 23.2g of fumaric acid, 35.8g of potassium hydroxide and 252mL of deionized water into the beaker according to the molar ratio of fumaric acid to alkali to water of 1.0/3.2/70, after the raw materials are dissolved and uniformly stirred, adding 1.8g of PVA powder, and continuously stirring to obtain a clear transparent solution A, wherein the mass of the added PVA powder accounts for 0.58 wt% of the mass of the clear transparent solution A; soaking the honeycomb ceramic blank in the clear transparent solution A, taking out after the honeycomb ceramic blank is completely wetted, and then drying the honeycomb ceramic blank at the temperature of 50 ℃ for 10 hours to form a honeycomb ceramic blank containing potassium fumarate; another 500ml beaker is taken, and 66.6g of Al is added2(SO4)3·18H2Dissolving O in 240ml of deionized water, and stirring until the O is dissolved to form a solution B (the mass percent concentration of the solution B is 11.1 wt%); and (3) soaking the honeycomb ceramic blank containing sodium fumarate in the solution B, placing the honeycomb ceramic blank at the water bath temperature, heating the honeycomb ceramic blank in the water bath at 60 ℃ for 50min, cooling the honeycomb ceramic blank to room temperature, centrifuging the honeycomb ceramic blank to obtain a precipitate, washing the precipitate with deionized water for three times, drying the precipitate at 150 ℃ for 24h, and then activating the precipitate at 350 ℃ for 12h to obtain the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent.
Example 8
(1) Preparing a honeycomb ceramic blank: 23g/m2Quantitative ceramic fiber paper (the mass ratio of flat paper to surface paper is 1:1) is respectively subjected to the action of sizing materials on a corrugated roller and a flat roller of a corrugated paper machine, hot rolling is carried out at 180 ℃, and single-side corrugated paper is laminated, wherein the sizing materials consist of 80 wt% of SiO2Sol and 20 wt% VAE glue(ii) a Then, under the action of the sizing material, the honeycomb ceramic matrix core is formed by rolling; finally, the surface of the ceramic substrate is cut and polished, and the ceramic substrate is sintered for 16h at 500 ℃ to remove organic matters, so that a honeycomb ceramic substrate blank (the size of which is phi 4cm (D) multiplied by 6cm (H)) is formed.
(2) Under room temperature and magnetic stirring, taking a 500mL beaker, adding 23.2g of fumaric acid, 27.2g of sodium hydroxide and 360mL of deionized water into the beaker according to the molar ratio of fumaric acid to alkali to water of 1.0/3.4/100, stirring uniformly, adding 1.5g of PVP powder, and continuously stirring to obtain a clear and transparent solution A, wherein the mass of the added PVA powder accounts for 0.37 wt% of the mass of the clear and transparent solution A; soaking the honeycomb ceramic blank in the clear transparent solution A, taking out after the honeycomb ceramic blank is completely wetted, and drying the honeycomb ceramic blank at the temperature of 80 ℃ for 5 hours to form a honeycomb ceramic blank containing potassium fumarate; another 500ml beaker is taken, and 66.6gAl is added2(SO4)3·18H2Dissolving O in 240ml of deionized water, and stirring until the O is dissolved to form a solution B (the mass percent concentration of the solution B is 11.1 wt%); and (3) soaking the honeycomb ceramic blank containing sodium fumarate in the solution B, placing the honeycomb ceramic blank at the water bath temperature, heating the honeycomb ceramic blank in the water bath at 50 ℃ for 60min, cooling the honeycomb ceramic blank to room temperature, centrifuging the honeycomb ceramic blank to obtain a precipitate, washing the precipitate with deionized water for three times, drying the precipitate at 150 ℃ for 20h, and then activating the precipitate at 350 ℃ for 10h to obtain the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent.
Test conditions and methods
The activation conditions of the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent (example) and the powder aluminum-fumaric acid (comparative example) are activation treatment at 350 ℃ for 3h, and then the test is carried out;
the loading of the honeycomb ceramic based aluminum-fumaric acid MOF adsorbent (example) was calculated:
setting the mass of the honeycomb ceramic matrix blank as m1The total mass of the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent obtained by activation after crystallization reaction is m2Then, the loading a of the honeycomb ceramic based aluminum-fumaric acid MOF adsorbent can be expressed as:
Figure BDA0002132100370000161
x-ray diffraction analysis
Respectively preparing the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent (example) and the powder aluminum-fumaric acid (comparative example) into XRD samples, and then performing phase analysis on the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent sample (example) and the powder aluminum-fumaric acid sample (comparative example) by using a full-automatic X-ray diffractometer (XRD) with the model D8 advanced of Bruker company in Germany; testing parameters: the scanning range is 5-50 degrees, the scanning speed is 0.1 second/step, the scanning step length is 0.02 degrees, and the Cu target is obtained.
Scanning Electron Microscope (SEM)
Preparing SEM samples of the honeycomb ceramic based aluminum-fumaric acid MOF adsorbent (example) and powdered aluminum-fumaric acid (comparative example), respectively; firstly, gold target coating is carried out on a sample, and then scanning is carried out respectively, wherein the scanning voltage is 5 kv.
Crystalline state adsorption kinetics curves of the honeycomb ceramic based aluminum-fumaric acid MOF adsorbent (example)
The honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent (example) was placed in a chamber at a constant temperature and humidity (25 ℃, RH 60%) and weighed in an electronic balance (sartorius S220), and changes in the mass of the sample were recorded at regular intervals (60S) to collect and analyze the data.
The weight of the honeycomb ceramic based aluminum-fumaric MOF adsorbent (example) is recorded as M1Then recording the weight of the adsorbent under the conditions of constant temperature and constant humidity as M2The weight at saturation (mass no longer changes) is M3。
The adsorption rate R and the saturation adsorption rate R of the adsorbentsCan be expressed as
R＝(M2-M1)/M1 (2)；
Rs＝(M3-M1)/M1 (3)。
Dynamic isothermal water vapor adsorption curve:
the test uses AQUADYNE DVS gravity type water adsorption analyzer manufactured by Quantachrome instruments, usa, to measure the water vapor isothermal adsorption line. The precise microbalance is arranged in the instrument, the precision can reach +/-0.0001 mg, the variation of the quality of a sample in the constant temperature control box along with the water vapor content can be directly recorded, the water content of gas is precisely controlled, the Relative Humidity (RH) is controlled, and the measured humidity range is 0-90%. Before the measurements were performed, the honeycomb ceramic based aluminum-fumaric acid MOF adsorbent sample (example) and the powdered aluminum-fumaric acid sample (comparative example) (50.0000 mg each) were activated at 150 ℃ for 10 hours, respectively.
Differential commercial thermogravimetric analysis (DTG) analysis:
the desorption properties of the samples were tested using a TG 209F3 thermogravimetric analyzer (TG) from Netzsch, germany. At room temperature to 150 deg.C, respectively at 4, 6, 8, 10, 12 deg.C/min-1Programmed desorption was carried out at a constant temperature rise rate. Before the measurement, the sample was heated to 150 ℃ to remove impurities, then cooled to 25 ℃ and saturated with water vapor at a relative humidity of 60%. The sample weight was measured to be 15 mg. The peak temperature (T) at each heating rate can be directly read by doing a derivative of the TG curvep) The corresponding desorption activation energy (E) can be calculated according to the Cinge equationd)。
Figure BDA0002132100370000181
Wherein Ed is desorption activation energy and the unit is kJ. mol-1(ii) a R is a gas constant of 8.314J/(mol.K); t isPDenotes the desorption temperature (K); beta is the rate of temperature rise (K.min)-1)。
The XRD spectra of example 1 and comparative example are shown in FIG. 1. From fig. 1, it can be seen that the XRD peak shape and peak position of the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent synthesized by the in-situ method (example 1) are consistent with those of powdered aluminum-fumaric acid (comparative example), which proves that the aluminum-fumaric acid MOF adsorbent can be synthesized on the surface of ceramic fiber by the in-situ method. The effect of the adsorbent prepared in other examples is similar to that of example 1, and all the adsorbents are aluminum-fumaric acid MOF adsorbents synthesized by an in-situ method, which can be seen in figure 1.
The scanning electron micrographs of example 1 and comparative example are shown in FIG. 2. As can be seen from the part a (cross section) of FIG. 2, the coating thickness of the honeycomb ceramic matrix aluminum-fumaric acid MOF adsorbent of example 1 is about 245 μm, and the substance with adsorption effect is tightly combined with the ceramic fiber; as can be seen from part b of fig. 2, in the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent of example 1, the ceramic fibers and the substance having the adsorption effect are tightly combined together, and the front view (part b) is enlarged to obtain part c of fig. 2, and it can be seen that the aluminum-fumaric acid strip crystals growing in situ on the ceramic fibers are connected with each other to form a porous three-dimensional network structure. Due to this structure, water vapor is easily adsorbed on the substrate by the aluminum-fumaric acid adsorbent, and adsorbed in the micropores of the aluminum-fumaric acid by the action of hydrogen bonds, capillary forces and chemical bonds of unsaturated metal sites. Section d of figure 2 shows that the crystalline powders of the directly synthesized powdered aluminum-fumaric acid (comparative) are more tightly bound to each other than the honeycomb ceramic based aluminum-fumaric acid MOF adsorbent of example 1, indicating that the powdered aluminum-fumaric acid (comparative) has a higher heat and mass transfer resistance. Other examples the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent prepared by other examples has similar effect to that of example 1, and is also a porous three-dimensional network structure, and ceramic fibers and substances with adsorption effect are also tightly combined together, and can be seen in figure 2.
The static water adsorption curves of example 1 and comparative example are shown in fig. 3. The results show that the saturated adsorption rates of the honeycomb ceramic based aluminum-fumaric acid MOF adsorbent of example 1 and powdered aluminum-fumaric acid (comparative example) are 27.35% and 34.26%, respectively. Considering the loading of aluminum-fumaric acid on the ceramic fibers (75.97%), the theoretical equilibrium adsorption was 36.00% slightly higher than that of powdered aluminum-fumaric acid (comparative example). In addition, the honeycomb ceramic based aluminum-fumaric acid MOF adsorbent of example 1 has a higher early adsorption rate (saturation reached within 6 minutes) compared to powdered aluminum-fumaric acid (comparative), which means that the honeycomb ceramic based aluminum-fumaric acid MOF adsorbent of example 1 synthesized by in situ method is more suitable for rotary wheel dehumidification. Other embodiments have similar effects to those of embodiment 1, and the prepared honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent is also suitable for rotary wheel dehumidification, and can be referred to fig. 3.
FIG. 4 dynamic isothermal water adsorption curves for adsorption of the synthesized honeycomb ceramic based aluminum-fumaric acid MOF adsorbents of examples 1-5. As is clear from FIG. 4, the water vapor adsorption isotherms of the adsorbents obtained in examples 1 to 5 were S-shaped. Among them, example 1 has higher equilibrium adsorption capacity of water vapor (0.3906g/g), and the theoretical equilibrium adsorption capacity reaches 0.5141g/g, which is much higher than that of the conventional molecular sieve (below 0.25 g/g). The adsorbents obtained in examples 6, 7 and 8 had similar effects to those of example 1, and also had S-shaped water vapor adsorption isotherms and similarly high equilibrium adsorption amounts, as shown in FIG. 4.
The following table 1 shows the loading of the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent synthesized in examples 1 to 5, wherein the loading is 64.42-75.97%, which indicates that the loading of the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent synthesized on the honeycomb ceramic substrate by the in-situ crystallization process is far higher than the loading of the molecular sieve in the conventional coating process (less than 45%), and the highest loading is 75.97% in example 1.
TABLE 1
Figure BDA0002132100370000201
Table 2 below shows desorption temperatures (T.sub.T) at different ramp rates for aluminum-fumaric acid powder (comparative example) and in situ synthesized honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent (example 1)p) And desorption activation energy (E)d). By comparison, the desorption temperature of the honeycomb ceramic based aluminum fumarate MOF adsorbent (example 1) was much lower than the desorption temperature of the powdered aluminum fumarate (comparative) at the same temperature ramp rate. And calculated, a honeycomb ceramic based aluminum-fumaric acid MOF adsorbent (example 1, 55.8 kJmol)-1) The desorption activation energy of (1) was lower than that of powdered aluminum-fumaric acid (comparative example, 66.1 kJmol)-1). Indicating that the former has a lower desorption temperature. Other examples have similar desorption effects to example 1, and also have lower desorption temperatures, which can be referred to in table 2.
TABLE 2
Figure BDA0002132100370000211
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (7)

1. An in-situ synthesis method of a honeycomb ceramic-based aluminum-MOF adsorbent is characterized by comprising the following steps: (1) mixing fumaric acid, an alkaline substance and water, stirring uniformly, then adding a thickening agent, mixing uniformly to obtain a mixed solution, soaking the honeycomb ceramic matrix blank in the mixed solution, taking out and drying to obtain a blank containing deprotonated fumaric acid; (2) soaking the embryo body containing deprotonated fumaric acid in the step (1) in an aluminum salt solution, heating in a water bath, cooling to room temperature, filtering to obtain a precipitate, washing, drying, heating, and performing sintering activation treatment to obtain the honeycomb ceramic-based aluminum-fumaric acid MOF adsorbent; the thickening agent in the step (1) is more than one of polyvinyl alcohol, polyvinylpyrrolidone and sodium carboxymethyl cellulose; the mass of the thickening agent accounts for 0.1 wt% -1 wt% of the mass of the mixed solution;
the drying temperature in the step (1) is 30-100 ℃, and the drying time is 3-12 h;
the temperature of the water bath heating treatment in the step (2) is 30-80 ℃, and the time of the water bath heating treatment is 20-120 min.
2. The in-situ synthesis method according to claim 1, wherein the alkaline substance in step (1) is an inorganic alkaline substance or an organic alkaline substance; the alkaline substance is more than one of sodium hydroxide, potassium hydroxide, ammonia water, methylamine, ethylamine, propylamine, butylamine, diethylamine, dipropylamine and dibutylamine; the molar ratio of the alkaline substance to the fumaric acid is 2.5-4.0: 1; the molar ratio of the water to the fumaric acid is 4-120: 1.
3. the in situ synthesis method according to claim 1, wherein the step (1) of preparing the honeycomb ceramic matrix blank comprises: and hot rolling and attaching the fiber paper into single-sided corrugated paper under the action of sizing material, then rolling the single-sided corrugated paper into a honeycomb ceramic-based core body, and heating and sintering the honeycomb ceramic-based core body to obtain the honeycomb ceramic-based blank.
4. The in situ synthesis method according to claim 3, wherein the fiber paper is one of ceramic fiber paper and glass fiber paper; the sizing material is more than one of silica sol, aluminum sol, titanium sol, zirconium sol, polyvinyl acetate, polyvinyl alcohol glue, acrylate and organic silicon modified acrylate; the sintering treatment temperature is 350-700 ℃, and the sintering treatment time is 10-24 h.
5. The in-situ synthesis method according to claim 1, wherein the aluminum salt solution in step (2) is a mixture of aluminum salt and water; the aluminum salt is more than one of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum potassium sulfate; the mass percentage concentration of the aluminum salt solution is 5-20 wt%.
6. The in-situ synthesis method as claimed in claim 1, wherein the temperature of the sintering activation treatment in step (2) is 345 ℃ and 355 ℃, and the time of the sintering activation treatment is 6-12 h.
7. A honeycomb ceramic-based aluminum-fumarate MOF adsorbent made by the method of making of any of claims 1-6.
CN201910641671.9A 2019-07-16 2019-07-16 Honeycomb ceramic-based aluminum-MOF (Metal organic framework) adsorbent and in-situ synthesis method thereof Active CN110523380B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910641671.9A CN110523380B (en) 2019-07-16 2019-07-16 Honeycomb ceramic-based aluminum-MOF (Metal organic framework) adsorbent and in-situ synthesis method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910641671.9A CN110523380B (en) 2019-07-16 2019-07-16 Honeycomb ceramic-based aluminum-MOF (Metal organic framework) adsorbent and in-situ synthesis method thereof

Publications (2)

Publication Number Publication Date
CN110523380A CN110523380A (en) 2019-12-03
CN110523380B true CN110523380B (en) 2022-04-22

Family

ID=68660324

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910641671.9A Active CN110523380B (en) 2019-07-16 2019-07-16 Honeycomb ceramic-based aluminum-MOF (Metal organic framework) adsorbent and in-situ synthesis method thereof

Country Status (1)

Country Link
CN (1) CN110523380B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114177889B (en) * 2021-11-29 2023-06-09 浙江理工大学 Aluminum fumarate/aerogel composite material and preparation method and application thereof
JP2024005801A (en) * 2022-06-30 2024-01-17 株式会社エフ・シー・シー Sheet material provided with metal-organic structural body
CN115212652A (en) * 2022-07-01 2022-10-21 北京师范大学 Argil water filtration material containing metal organic framework derived carbon and argil water purifier
CN116020423A (en) * 2022-12-13 2023-04-28 华南理工大学 Solar-driven glass fiber-based composite MOF block moisture absorbent and preparation method and application thereof
CN115873264B (en) * 2022-12-30 2023-09-22 佛山市顺德区阿波罗环保器材有限公司 MOFs adsorption material formed in one step and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103446893A (en) * 2013-09-06 2013-12-18 南京工业大学 Method for preparing metal organic framework membrane on inner wall of tube-type ceramic support body
CN107020067A (en) * 2017-04-28 2017-08-08 华南理工大学 A kind of ceramic honey comb base fine grain NaA molecular sieve block adsorbent and in-situ synthetic method and application
CN107297218A (en) * 2017-06-27 2017-10-27 中国第汽车股份有限公司 Molecular sieve cordierite honeycomb carrier method for preparing catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103446893A (en) * 2013-09-06 2013-12-18 南京工业大学 Method for preparing metal organic framework membrane on inner wall of tube-type ceramic support body
CN107020067A (en) * 2017-04-28 2017-08-08 华南理工大学 A kind of ceramic honey comb base fine grain NaA molecular sieve block adsorbent and in-situ synthetic method and application
CN107297218A (en) * 2017-06-27 2017-10-27 中国第汽车股份有限公司 Molecular sieve cordierite honeycomb carrier method for preparing catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Advancement of sorption-based heat transformation by a metal coating of highly-stable, hydrophilic aluminium fumarate MOF;Felix Jeremias等;《RSC Adv.》;20140513;第4卷;第24073-24082页 *

Also Published As

Publication number Publication date
CN110523380A (en) 2019-12-03

Similar Documents

Publication Publication Date Title
CN110523380B (en) Honeycomb ceramic-based aluminum-MOF (Metal organic framework) adsorbent and in-situ synthesis method thereof
CN112755965B (en) Preparation method of composite dehumidification adsorbent paper sheet made of MOF material and lithium chloride
US20180043303A1 (en) Porous Adsorbent Structure for Adsorption of CO2 from a Gas Mixture
JP2579767B2 (en) Ultra-low concentration gas adsorption element and gas adsorption removal device
CN1986046B (en) Preparing process of composite block adsorbent of molecular sieve and modified silica gel
CN108246122B (en) Method for synthesizing NaA molecular sieve membrane
CN110975817B (en) Aluminum foil-based aluminum-fumaric acid MOF adsorbent coating and mixed solvent in-situ synthesis method and application thereof
WO2022183776A1 (en) Composite type-a molecular sieve raw powder containing wave-absorbing material, full-zeolite molecular sieve, preparation method therefor, and application thereof
CN107020067A (en) A kind of ceramic honey comb base fine grain NaA molecular sieve block adsorbent and in-situ synthetic method and application
US20160199778A1 (en) Honeycomb matrix comprising macroporous desiccant, process and use thereof
CN101524637A (en) Preparation method of LSX-molecular-sieve-rich cementing-agent-free absorbent
US5254195A (en) Process for manufacturing moisture exchange element
CN101972627A (en) Rare-earth modified molecular-sieve dehumidification adsorbent paper sheet and preparation method thereof
CN107185487B (en) A-type molecular sieve dehumidification carrier and preparation method thereof
Tan et al. A solar-driven adsorbent based on Al-fumarate metal-organic framework coating with high water cycle efficiency
CN110787768A (en) Composite dehumidifying material and preparation method thereof
JP5754927B2 (en) Hygroscopic material
EP1130161B1 (en) Method for the production of a dehumidifying element
CN106698451B (en) A kind of synthetic method of DD3R molecular screen membranes
CN114920258A (en) Method for synthesizing molecular sieve integral material by using pre-adsorption-drying-in-situ crystallization method
Tan et al. Improved desorption performance of NaA zeolite by rare earth (Re= La, Nd) ion exchange
JP2008168259A (en) Desiccant material and air dehumidification method using the same
TWI364322B (en) Dehumidifying agent and dehumidifying material
JP2002079045A (en) Dehumidifying material and method for manufacturing the same
CN113457641A (en) Active carbon-sodium polyacrylate composite desiccant coating and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant