CN111715189A - Preparation of amino acid modified cellulose composite membrane with efficient formaldehyde adsorption characteristic - Google Patents

Preparation of amino acid modified cellulose composite membrane with efficient formaldehyde adsorption characteristic Download PDF

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Publication number
CN111715189A
CN111715189A CN202010578026.XA CN202010578026A CN111715189A CN 111715189 A CN111715189 A CN 111715189A CN 202010578026 A CN202010578026 A CN 202010578026A CN 111715189 A CN111715189 A CN 111715189A
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cellulose
amino acid
solution
filter paper
composite membrane
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CN202010578026.XA
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Chinese (zh)
Inventor
霍丹
熊瑞芳
韩潇
谷丞
杨秋林
司传领
王冠华
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Tianjin University of Science and Technology
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Tianjin University of Science and Technology
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Priority to CN202010578026.XA priority Critical patent/CN111715189A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/72Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81Solid phase processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid 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
    • B01J20/28033Membrane, sheet, cloth, pad, lamellar or mat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid 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 surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area

Abstract

The invention particularly discloses a preparation method of an amino acid/cellulose composite membrane with a formaldehyde efficient adsorption function. The raw materials are cellulose and common amino acid. The preparation method comprises the following steps: cellulose is prepared into cellulose alkaline solution after being hydrolyzed, and then amino acid with certain mass ratio is added into the cellulose alkaline solution at certain temperature to obtain amino acid/cellulose composite solution; quantitative filter paper is taken as a carrier, and is immersed in an amino acid/cellulose solution to be compounded into an amino acid/cellulose composite membrane. The amino acid/cellulose composite membrane has the advantages of high strength performance, strong formaldehyde adsorption property and the like, and is expected to be well applied to the production of wallpaper with a formaldehyde self-purification function.

Description

Preparation of amino acid modified cellulose composite membrane with efficient formaldehyde adsorption characteristic
Technical Field
The invention relates to the technical field of air filter paper, in particular to a preparation method of composite filter paper with formaldehyde adsorption property, which is prepared from amino modified cellulose.
Background
Formaldehyde is one of the indoor pollutants and one of the major volatile organic compounds emitted in building and coating materials, including paints, wood panels, laminates, and smoke panels. Formaldehyde not only carries peculiar smell, but also has toxicity, and when various organs such as eyes, nose, respiratory mucosa and the like, even skin, are contacted with formaldehyde gas for a long time, the organs are greatly stimulated, thereby causing a series of potential diseases. Therefore, the removal of formaldehyde in the room is critical to human health.
Currently, methods for removing formaldehyde include physical adsorption, chemical neutralization, ozone oxidation, and photocatalytic oxidative decomposition. Among them, the adsorption method is the most common and effective method for treating formaldehyde pollution. The adsorption materials on the market at present comprise activated carbon, silica fume-based materials, composite nano materials, natural extracts, amino acid adsorption materials and the like. Most of the adsorbing materials lack formaldehyde specificity, namely other small molecules in the air can be adsorbed while formaldehyde is adsorbed, so that the adsorbing sites of formaldehyde are occupied, and the adsorbing efficiency is reduced. Meanwhile, part of the physical adsorption materials are greatly influenced by the temperature, and formaldehyde adsorbed by the temperature is desorbed again. Amino in the amino acid compound can perform addition condensation reaction with formaldehyde to generate a stable compound, namely the hydroxymethyl derivative. Therefore, the adsorption to formaldehyde has the advantages of good stability and difficult desorption.
As one of the natural materials with abundant reserves in the nature, the cellulose has low cost, wide sources, no toxicity, no harm, biodegradability and biocompatibility. The cellulose belongs to one of porous materials, and the surface of the cellulose also contains a plurality of active groups such as hydroxyl groups and the like, so that the cellulose can be used for adsorbing volatile organic compounds such as formaldehyde and the like. However, the removal effect of the cellulose on formaldehyde molecules is limited, and the disadvantages of the cellulose in many aspects are very unfavorable for the wide application of the cellulose in the field of volatile organic compound absorption.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of an amino modified cellulose composite film which is simple and easy to implement, has excellent performance and can efficiently remove formaldehyde as a pollutant in indoor air.
The preparation method of the cellulose/amino acid composite film provided by the invention comprises the following steps:
step (1): weighing a certain amount of cellulose raw material, adding the cellulose raw material into a hydrochloric acid/ethanol solution, continuously stirring for 0.5-3h at 50-100 ℃ in a water bath, centrifugally separating the mixture, washing the mixture to be neutral by deionized water, and then freeze-drying to obtain the acid hydrolysis cellulose.
Step (2): dissolving the acidolysis cellulose obtained in the step (1) in an alkaline solution at the temperature of-15 to-12 ℃ to obtain the cellulose alkaline solution with the mass fraction of 1 wt% -10 wt%.
And (3): adding a certain amount of amino acid into the alkaline cellulose solution obtained in the step (2), and fully stirring at 0-60 ℃ to obtain a uniform and transparent amino acid-cellulose solution with a certain mass ratio.
And (4): and (4) dipping neutral quantitative filter paper in situ into the transparent uniform amino acid modified cellulose solution obtained in the step (3), dipping for a certain time at a certain temperature, taking out the filter paper after reaching the reaction time point, and freeze-drying to obtain the composite filter paper.
And (5): and (4) detecting the formaldehyde adsorption characteristic of the composite filter paper prepared in the step (4) by using self-made formaldehyde adsorption measuring equipment.
Preferably, the cellulose raw material in the step (1) is any one of eucalyptus dissolving pulp, nano-cellulose, microcrystalline cellulose, bamboo dissolving pulp and poplar sulfate pulp.
Preferably, the alkaline solution for dissolving cellulose in step (3) is any one of NaOH/urea/water, NaOH/thiourea/water, KOH/urea/water, KOH/thiourea/water.
Preferably, the amino acid in step (3) is one or more of lysine, glycine, proline, glutamic acid and tyrosine.
Preferably, the in-situ impregnation temperature in the step (4) is 0-60 ℃ and the time is 0-12 h.
The invention can form hydrogen bond by using hydroxyl in amino acid and cellulose hydroxyl, thereby forming uniform transparent solution. The amino group in the amino acid can react with formaldehyde to generate a hydroxymethyl compound, so that formaldehyde in the air can be fixed. The preparation condition of the amino acid modified cellulose composite membrane is mild, the process is simple, the operation is safe, the environment is protected, and the obtained cellulose porous filter membrane has excellent mechanical property and high specific surface area. The composite membrane material contains a large number of amino groups, provides abundant active sites for adsorbing formaldehyde, adsorbs the formaldehyde in the air in a chemical reaction mode, does not have the problem of formaldehyde desorption in the later stage, is a high-efficiency and environment-friendly formaldehyde adsorption material, and can realize effective removal of formaldehyde molecules in the air. The prepared composite membrane is expected to be developed and applied in functional wallpaper with formaldehyde adsorption.
Drawings
FIG. 1 is a simplified self-made formaldehyde gas detection apparatus; FIG. 2 is a SEM microstructure of glycine/cellulose composite filter paper; FIG. 3 is an SEM microstructure of a lysine/cellulose composite filter paper.
Detailed Description
Example 1
A preparation method of an amino acid modified cellulose composite membrane with efficient formaldehyde adsorption characteristic comprises the following steps:
step (1) pretreatment of cellulose raw material: adding the eucalyptus dissolving pulp into an ethanol/hydrochloric acid mixed solution, continuously stirring at 70 ℃ for reaction for 2 hours, filtering and washing to be neutral, and then freeze-drying to obtain an acidolyzed cellulose raw material;
step (2) preparation of cellulose solution: the prepared acidified cellulose raw material is dissolved in NaOH/urea/water (mass ratio is 7: 12: 81), and is continuously stirred at the temperature of-12 ℃ by a low-temperature cooling liquid circulating pump until the acidified cellulose raw material is dissolved to obtain a cellulose solution (2 wt%).
Step (3) preparation of cellulose/amino acid composite solution: adding a certain amount of glycine into the cellulose solution obtained in the step (2), fully stirring at 60 ℃ to prepare a uniform and transparent mixed solution with the cellulose/glycine mixing mass ratio of 1: 0.2, and storing at 4 ℃ for later use.
And (4) preparing the amino acid modified cellulose composite filter paper: and (3) selecting the medium-speed quantitative filter paper after drying and constant weight as a carrier, soaking the carrier in the cellulose/amino acid mixed solution prepared in the step (3) for 0.5h at room temperature, taking out the filter paper after reaching the soaking time, and drying the filter paper in a drying oven at low temperature of 35 ℃ to obtain the amino acid/cellulose composite filter paper.
Detecting the formaldehyde adsorption characteristic of the composite filter paper: the formaldehyde adsorption characteristics of the prepared composite filter paper were tested using a self-made simple formaldehyde gas adsorption experimental apparatus as shown in fig. 1. The prepared glycine/cellulose composite filter paper can adsorb 92.92% of formaldehyde in a container within 5h, and the formaldehyde adsorption efficiency is 0.0734 mg/g.h. The physical strength of the glycine/cellulose composite filter paper is as follows: the tensile strength is 47.1Kn/m, the folding endurance is 87.33 times, and the physical strength is greatly improved compared with that of a blank filter paper (the tensile strength is 34.2kN/m, and the folding endurance is 6.67 times). The SEM image of fig. 2 shows that the glycine/cellulose composite solution forms a dense film covering the fiber surface of the filter paper carrier and penetrates into the inside of the fiber.
Example 2
A preparation method of an amino acid modified cellulose composite membrane with efficient formaldehyde adsorption characteristic comprises the following steps:
step (1) pretreatment of cellulose raw material: adding the eucalyptus dissolving pulp into an ethanol/hydrochloric acid mixed solution, continuously stirring at 70 ℃ for reaction for 2 hours, filtering and washing to be neutral, and then freeze-drying to obtain an acidolyzed cellulose raw material;
step (2) preparation of cellulose solution: the prepared acidified cellulose raw material is dissolved in NaOH/urea/water (mass ratio is 7: 12: 81), and is continuously stirred at the temperature of-12 ℃ by a low-temperature cooling liquid circulating pump until the acidified cellulose raw material is dissolved to obtain a cellulose solution (2 wt%).
Step (3) preparation of cellulose/amino acid composite solution: adding a certain amount of lysine into the cellulose solution obtained in the step (2), fully stirring at 60 ℃, preparing a uniform and transparent mixed solution with the mixing mass ratio of the cellulose to the lysine of 1: 0.2, and storing at 4 ℃ for later use.
And (4) preparing the amino acid modified cellulose composite filter paper: and (3) selecting the medium-speed quantitative filter paper after drying and constant weight as a carrier, soaking the carrier in the cellulose/lysine mixed solution prepared in the step (3) for 0.5h, taking out the filter paper after reaching the soaking time, and drying the filter paper in a drying oven at a low temperature of 35 ℃ to obtain the amino acid/cellulose composite filter paper.
Detecting the formaldehyde adsorption characteristic of the composite filter paper: the prepared composite filter paper was tested for its formaldehyde adsorption characteristics using a homemade formaldehyde gas adsorption experimental set-up as shown in fig. 1. The prepared lysine/cellulose composite filter paper can adsorb 90.38% of formaldehyde in a container within 5h, and the formaldehyde adsorption rate is as follows: 0.0711 mg/g.h, realizing the high-efficiency adsorption of formaldehyde in the air. The physical strength of the lysine/cellulose composite filter paper is as follows: the tensile strength is 45.1Kn/m, the folding endurance is 11 times, and the physical strength is improved compared with that of a blank filter paper (the tensile strength is 34.2kN/m, and the folding endurance is 6.67 times). The plan microscopic structure and cross-sectional microscopic structure of the composite filter paper in the SEM of FIG. 3 show that the lysine/cellulose composite solution permeates into the filter paper fibers and forms a layer of dense formaldehyde adsorption film on the fiber surfaces.
Example 3
A preparation method of an amino acid modified cellulose composite membrane with efficient formaldehyde adsorption characteristic comprises the following steps:
step (1) pretreatment of cellulose raw material: adding the eucalyptus dissolving pulp into an ethanol/hydrochloric acid mixed solution, continuously stirring at 70 ℃ for reaction for 2 hours, filtering and washing to be neutral, and then freeze-drying to obtain an acidolyzed cellulose raw material;
step (2) preparation of cellulose solution: the prepared acidified cellulose raw material is dissolved in NaOH/urea/water (mass ratio is 7: 12: 81), and is continuously stirred at the temperature of-12 ℃ by a low-temperature cooling liquid circulating pump until the acidified cellulose raw material is dissolved to obtain a cellulose solution (2 wt%).
Step (3) preparation of cellulose/amino acid composite solution: adding a certain amount of lysine into the cellulose solution obtained in the step (2), fully stirring at 60 ℃, preparing into a uniform and transparent mixed solution with the mixing mass ratio of cellulose to glycine of 1: 1.5, and storing at 4 ℃ for later use.
And (4) preparing the amino acid modified cellulose composite filter paper: and (3) selecting the medium-speed quantitative filter paper after drying and constant weight as a carrier, soaking the carrier in the cellulose/amino acid mixed solution prepared in the step (3) for 12 hours, taking out the filter paper after the soaking time is reached, and drying the filter paper in a drying oven at a low temperature of 35 ℃ to obtain the amino acid/cellulose composite filter paper.
The prepared amino acid/cellulose composite filter paper can adsorb 88.73% of formaldehyde in a container within 5h, and the formaldehyde adsorption rate of the prepared amino acid/cellulose composite filter paper is as follows: 0.0641 mg/g.h, the tensile strength of 37.1kN/m and the folding endurance of 10.33 times are improved compared with the physical strength of blank filter paper (the tensile strength of 34.2kN/m and the folding endurance of 6.67 times), the high-efficiency adsorption of formaldehyde in the air is realized, the strength performance of the composite membrane is ensured, and the composite membrane is expected to be better applied to functional wallpaper with formaldehyde adsorption.

Claims (4)

1. A preparation method of an amino acid modified cellulose composite membrane with efficient formaldehyde adsorption characteristic is characterized by comprising the following steps:
step (1): weighing a certain amount of cellulose raw materials, adding the cellulose raw materials into a hydrochloric acid/ethanol solution, continuously stirring for 0.5-3h in a water bath at 50-100 ℃, centrifugally separating the mixture, washing the mixture to be neutral by deionized water, and finally freezing and drying to obtain the acid hydrolysis cellulose.
Step (2): dissolving the acidolysis cellulose obtained by the treatment of the step (1) in an alkaline solution at the temperature of-15 to-12 ℃ to obtain a cellulose solution with the mass fraction of 1-10 wt%.
And (3): adding amino acid into the cellulose solution obtained in the step (2), and fully stirring and mixing at 0-60 ℃ to obtain a uniform and transparent amino acid-cellulose solution with a certain mass ratio.
And (4): and (3) dipping the neutral quantitative filter paper in the amino acid-cellulose solution obtained in the step (3) in situ for 0-12h at the dipping temperature of 0-60 ℃, and taking out the filter paper after the reaction time point is reached. And (5) freeze-drying to obtain the composite filter paper.
2. The preparation method of the high efficiency formaldehyde adsorption amino modified cellulose composite membrane according to claim 1, wherein the cellulose is one or more of eucalyptus dissolving pulp, bamboo dissolving pulp, microcrystalline cellulose, nano cellulose and poplar sulfate pulp.
3. The preparation method of the high efficiency formaldehyde adsorption amino modified cellulose composite membrane as claimed in claim 1, wherein the amino acid is one or more of lysine, glycine, proline, glutamic acid, and tyrosine.
4. The preparation method of the high efficiency formaldehyde adsorption amino modified cellulose composite membrane according to claim 1, wherein the alkaline solution for dissolving cellulose is any one of NaOH/urea/water, NaOH/thiourea/water, KOH/urea/water, KOH/thiourea/water.
CN202010578026.XA 2020-06-23 2020-06-23 Preparation of amino acid modified cellulose composite membrane with efficient formaldehyde adsorption characteristic Pending CN111715189A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113512425A (en) * 2021-06-16 2021-10-19 广西博世科环保科技股份有限公司 Preparation method of wood fiber-based microorganism-loaded material for repairing organic contaminated soil

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113512425A (en) * 2021-06-16 2021-10-19 广西博世科环保科技股份有限公司 Preparation method of wood fiber-based microorganism-loaded material for repairing organic contaminated soil

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