CN102125819A - Iron-loaded cotton fiber material and preparation method thereof - Google Patents

Abstract

The invention discloses an iron-loaded wool fiber material with absorbent cotton fiber as the basic skeleton and a preparation method thereof, belonging to the technical field of polymer materials. The structure of the fibrous material contains iron hydroxide in an amorphous state. The preparation method is as follows: the absorbent cotton fiber is used as the basic skeleton, and the trivalent iron salt solution is dispersed and hydrolyzed, so that the fiber structure contains iron hydroxide in an amorphous form. The reaction process is simple, the conditions are mild, the reaction reagents used are non-toxic, and the environment is friendly. The fiber material maintains the fibrous shape of absorbent cotton fibers, and has stable performance in the air. When used as an adsorbent in water, it will not cause changes in the pH value of the water body. The adsorbent has a stable form of iron and can effectively adsorb arsenic in water Acid ion.

Description

A kind of iron wool fiber material and preparation method thereof

technical field

The invention relates to a fibrous material, in particular to an iron-loaded wool fiber material and a preparation method thereof, belonging to the technical field of polymer materials.

Background technique

Because certain metal oxides or hydroxides have strong adsorption and removal capabilities for inorganic ions such as arsenic and fluorine, these metal oxides or hydroxides are loaded on some carriers to prepare some supported metal oxides. Or the inorganic anion adsorption material of hydroxide has become a research hotspot in this field. At present, the carrier materials used for iron-loaded adsorbents can basically be divided into: (1) natural minerals and inorganic materials. For example, CN200610078899 "a preparation method of tetragonal sulfate lepidosite adsorbent for arsenic removal", CN200610008135 "preparation, use and regeneration method of an iron-manganese composite oxide/diatomite adsorbent" and reports by Yan Yingtao, etc. A preparation method of iron-loaded silica gel (Journal of Chang'an University, Issue 03, 2004); (2) Activated carbon and activated carbon fiber. Such as CN200510110226 "preparation method of iron-loaded activated carbon arsenic removal adsorbent", HRISTOVSKI etc. (Journal of Environmental Science and Health, Part A (2009) 44, 354–361) and Zhang etc. (Carbon, Volume 48, Issue 1, January 2010, Pages 60-67) The literature involves the preparation of iron-loaded adsorbents such as KIM etc. (Journal of Environmental Science and Health, Part A (2010) 45, 177–182) with activated carbon fibers as the carrier Prepare the sorbent. (3) Natural polymer materials. Such as CN1593745A "iron-loaded spherical cellulose adsorbent and its preparation and application", CN1589959A "preparation method of highly selective iron-loaded ligand exchange cotton fiber adsorbent", Guo etc. (Environ. Sci. Technol., 2005 , 39 (17), pp 6808–6818), studied the preparation of adsorbents based on cotton cellulose, Altundogan etc. (Process Biochemistry.,Volume 40, Issues 3-4, March 2005, Pages 1443-1452 ) will Iron loaded on betaine pulp, preparation of iron-loaded sorbent, Dupont etc. (Environmental Chemistry Letters, Volume 5, Number 3 / August 2007) Preparation of sorbent with lignocellulose as carrier, Katsutoshi etc. (Kagaku Kogaku Ronbunshu , VOL.29;NO.3;PAGE.389-394(2003)) Preparation of adsorbent with cross-linked pectinic acid as carrier. (4) Modified polymer materials. Such as CN200910028414 "iron-loaded bimetallic nanocomposite cation exchange resin and its preparation method and application"; Rau etc. (Journal of Radioanalytical and Nuclear Chemistry, Volume 246, Number 3 / December 2000), Shao etc. (Hydrometallurgy, Volume 91, Issues 1-4, March 2008, Pages 138-143), Pan etc. (Water Research, 44 (2010) 815–824) prepared adsorbents with resin materials as carriers; Lin etc. (Environmental Engineering Science, Volume 26, Number 11, 2009), Vatutsina etc. (Reactive & Functional Polymers 67 (2007) 184–201), prepared adsorbents with functional polymer fiber materials as carriers.

Among the above-mentioned carrier materials, since cotton fiber is a natural and renewable material, the carrier has good hydrophilicity and large porosity, and has been widely used as a bioactive material. Cotton fiber is used as the iron-carrying material to carry iron. In the current research, iron is carried by spherical cellulose as the carrier, such as CN1593745A, CN1589959A, Guo etc. (Environ. Sci. Technol., 2005, 39 ( 17), pp 6808–6818) et al. However, there are relatively few studies on loading iron on cotton fiber materials without changing the fiber state of cotton fiber materials. At present, due to the vigorous development of fibrous materials and obvious unique advantages such as large specific surface area, small flow resistance, and application in various forms, iron-carrying fibrous adsorbent materials will have great potential for application and development.

Contents of the invention

The purpose of the present invention is to provide an iron-loaded fiber adsorbent that does not change the fiber state of the cotton fiber material and has strong hydrophilicity, good mechanical properties and good adsorption effect; another purpose of the present invention is to provide its preparation method.

In order to realize the object of the present invention, a kind of iron-loaded fiber adsorbent with high iron content is prepared to realize the technical scheme of the present invention by using natural polymer material cotton fiber as a carrier through a simple, mild and environment-friendly synthetic route.

The iron-carrying fiber adsorbent of the present invention uses the absorbent cotton fiber as a basic skeleton, contains iron hydroxide existing in an amorphous state, and maintains the fibrous shape of the absorbent cotton fiber.

The synthesis method is as follows: wash the absorbent cotton fiber with water, soak it in the ferric iron aqueous solution with a mass percentage of 2%~10% and a temperature of 10~50°C, stir after 1~3 hours, and add 0.5~2M Alkali solution and ferric salt are dispersed and hydrolyzed, loaded into absorbent cotton, left to stand in the air for 3-8 hours, washed with water until neutral, and dried at 30-80°C. The iron content increases with the increase of iron loading times, and the fiber weight gain is controlled at 10%~40%.

The absorbent cotton fiber used in the present invention is a commercially available commercial grade absorbent cotton, the length of the monofilament is 3-7cm, and the tensile strength is 0.021-0.054N. The ferric iron solution used is ferric chloride, ferric sulfate, ferric nitrate solution and the like. The alkali solution used is sodium hydroxide, ammonia water, etc. The maximum volume ratio of ferric iron solution to alkali solution is 1:3.

The beneficial effects of the present invention are: (1) The raw material absorbent cotton fiber has a wide range of sources and stable performance and quality. (2) The reaction process is simple and easy to control, the reaction conditions are mild, there is no need to increase pressure and too high reaction temperature, and it is convenient for industrial production. (3) No organic cross-linking agent is used to avoid the pollution of toxic reagents; the reagents used are cheap, easy to obtain and non-toxic. (4) The product obtained from the reaction is a fibrous adsorption material loaded with iron. Compared with granular or spherical adsorption materials, fiber adsorption materials have the advantages of large specific surface area, small flow resistance, good mechanical strength, easy elution and regeneration, and can be processed into various forms (fiber bundles, non-woven fabrics, fabrics, etc.) . (5) The material contains more hydroxides of amorphous iron, has more active adsorption sites, and has a strong adsorption capacity for arsenous acid pollutants in water bodies, with a saturation capacity of 13-25 mg/g fiber. (6) The material is stable in the air, no special storage method is required, and the pH change of the water body will not be affected when used.

Description of drawings:

Fig. 1 is the comparison of the XRD spectra of the iron-loaded wool fiber material of the present invention and the raw material absorbent cotton fiber. Among them, curve 1 is the iron-loaded cotton fiber; curve 2 is the original absorbent cotton fiber.

Fig. 2 is a microscope photo (×400) of iron-loaded wool fiber material and raw material absorbent cotton fiber of the present invention. Among them, the picture a is the original absorbent cotton fiber; the picture b is the iron-loaded cotton fiber.

Figure 3 is the adsorption curve of the arsenic (III) concentration in the effluent water and the amount of treated water after being treated with the iron-loaded wool fiber material of the present invention.

Figure 4 is the adsorption curve of the arsenic (III) concentration in the effluent and the amount of treated water after being treated with the iron-loaded wool fiber material of the present invention.

Detailed ways

For better describing the present invention in detail, give examples as follows:

Example 1

Submerge 6g of absorbent cotton fibers in 100mL of 5% ferric chloride solution, raise the temperature to 30°C, and after 2 hours, add 105mL of 1M sodium hydroxide solution dropwise with stirring, and the adding speed is controlled at 1ml/min. When the pH value of the solution rose to 4, the addition of sodium hydroxide was stopped, the solution was poured out, and the fiber was washed with water several times, and the above-mentioned addition process of sodium hydroxide was repeated 6 times. After loading the iron, let it stand for 5 hours, then take it out, wash it with water until it is neutral, and dry it in an oven at 45°C. After weighing, the weight of the fiber increases by 27.8%. Its XRD spectrum and micrograph are shown in accompanying drawing 1 and accompanying drawing 2 respectively. It can be seen from Figure 1 that the iron in the iron-loaded fiber exists in the form of amorphous hydroxide; it can be seen from Figure 2 that after the absorbent cotton is loaded with iron, it still maintains a fibril shape.

Example 2

Submerge 350g of absorbent cotton fibers in 2000mL of 10% ferric sulfate solution, raise the temperature to 25°C, and after 3 hours, add 2050mL of 0.5M sodium hydroxide solution dropwise under stirring, and the adding speed is controlled at 20ml/min. When the pH value of the solution rose to 4, the addition of sodium hydroxide was stopped, the solution was poured out, and the fiber was washed with water several times, and the above-mentioned addition process of sodium hydroxide was repeated 6 times. After loading the iron, let it stand for 5 hours, then take it out, wash it with water until neutral, and dry it in an oven at 60°C. After weighing, the weight of the fiber increases by 16.9%. Its XRD spectrum and micrograph are as embodiment 1.

Application example 1

Weigh 0.1 g of the fiber material prepared in Example 1, put it into 50 ml of water sample with an arsenic concentration of 100 mg/L prepared with sodium arsenite, shake and adsorb at 25° C. for 12 hours, and measure the arsenic concentration in the solution Reduced to 50.6mg/L, the calculated arsenic adsorption of the fiber material is 24.7mg/g fiber.

Application example 2

Weigh 0.1 g of the fiber material prepared in Example 2, put it into 50 ml of water sample with arsenic concentration of 100 mg/L prepared with sodium arsenite, and shake and adsorb for 12 hours at 25 ° C to measure the arsenic concentration in the solution Reduced to 59.3mg/L, the calculated arsenic adsorption of the fiber material is 20.3mg/g fiber.

Application example 3

Take by weighing 2 g of the fiber material prepared in Example 1, fill it into an adsorption column with a height of 10 cm and a diameter of 1 cm, and a water sample with an arsenic (III) concentration of 1 mg/L passes through the adsorption column at a flow rate of 1 mL/min. Influent pH=6.96, monitor the arsenic concentration in the effluent, when the treated water volume is within 40.3L, the arsenic concentration in the effluent is lower than 50mg/L, and the effluent pH=6.93. The adsorption curve is shown in Figure 3. And by detecting the concentration of iron ions in the influent and effluent water, it is shown that the iron-carrying adsorbent is stable in form.

Application example 4

Take by weighing 2 g of the fiber material obtained in Example 2, fill it into an adsorption column with a height of 10 cm and a diameter of 1 cm, and a water sample with arsenic (III) concentration of 1 mg/L passes through the adsorption column at a flow rate of 1 mL/min. Influent pH=6.96, monitor the arsenic concentration in the effluent, when the treated water volume is within 35.8L, the arsenic concentration in the effluent is lower than 50mg/L, and the effluent pH=6.92. The adsorption curve is shown in Figure 4. And by detecting the concentration of iron ions in the influent and effluent water, it is shown that the iron-carrying adsorbent is stable in form.

Claims (5)

1. An iron-loaded cotton fiber material is characterized in that: take the absorbent cotton fiber as the basic skeleton, contain iron hydroxide existing in an amorphous state, and keep the fibrous form of the absorbent cotton fiber. 2. The iron-loaded wool fiber material as claimed in claim 1, characterized in that: the monofilament length of the absorbent cotton used is 3-7 cm, and the tensile strength is 0.021-0.054N. 3. the preparation method of iron-loaded wool fiber material as claimed in claim 1 or 2, is characterized in that: realize by the following steps: the degreasing cotton fiber is washed, soaked in the mass percentage is 2%～10%, temperature is 10～50 After 1~3 hours in the aqueous solution of ferric iron at ℃, stir, and add 0.5~2M alkali solution drop by drop. Wash with water until neutral, and dry at 30~80°C. 4. The preparation method of iron-loaded wool fiber material as claimed in claim 3, characterized in that: the maximum volume ratio of the ferric iron solution to the alkali solution is 1:3. 5. The preparation method of iron-loaded wool fiber material as claimed in claim 3, characterized in that: fiber weight gain is controlled at 10%-40%.

Images