CN102258976A - Preparation method of eucalyptus biomorphic Fe2O3/Fe3O4 composite heavy metal adsorbent - Google Patents

Abstract

The invention discloses a preparation method of a eucalyptus biomorphic Fe2O3/Fe3O4 composite heavy metal adsorbent. According to the invention, dilute ammonia water is adopted as a digestion agent, and a pretreatment of extraction is carried out. Ferric nitrate is adopted as a precursor solution, and the eucalyptus biomorphic Fe2O3/Fe3O4 composite heavy metal adsorbent with a natural plant structural form is produced through a manual controlled preparation technology. Experimental measurements are carried out upon phase, structure, components and appearance characteristics of the absorbent. The adsorbent is applied in a water environment toxic heavy metal absorption treatment experiment. As a result, the material is cheap and environment-friendly. The preparation method provided by the invention provides a novel method and a novel approach of eucalyptus wood material utilization.

Description

A kind of eucalyptus is lost attitude Fe＜sub〉2＜/sub〉O＜sub〉3＜/sub 〉/Fe＜sub〉3＜/sub〉O＜sub〉4＜/sub〉preparation method of compound heavy metal absorbent

Technical field

The invention belongs to changing waste into resources utilization and water-treatment technology field, relate to a kind of eucalyptus and lose attitude Fe ₂O ₃/ Fe ₃O ₄The preparation method of compound heavy metal absorbent utilizes eucalyptus to be the plant template especially, through technology controlling and process, prepares with Fe ₂O ₃/ Fe ₃O ₄Heavy metal composite adsorbent for main material.

Background technology

Heavy metal is a kind of poisonous element that can accumulate in vivo, along with industrial expansion, heavy metal pollution is subjected to extensive attention, heavy metal can be accumulated and enrichment in biological chain after entering environment, and can not be by biodegradation, can hide in environment for a long time, and follow food chain to enter human body serious harm life and health.At present the place to go method of heavy metal mainly contains chemical precipitation method, electroflotation, ion-exchange, membrane separation process and absorption method in the water, and wherein absorption method is because advantage such as it has the secondary pollution of not producing, renewable recovery and enjoy attention.At present, the most frequently used adsorbent has activated carbon and modified cellulose etc., and still most adsorbent is because of the cost height or complex manufacturing limits its application.

Lose the attitude material and be use that nature is multi-level through the biology self in 1 years, the intrinsic structure of multidimensional, many structures, by manual method, change its structural constituent, prepare and both keep the nature biotechnology fine structure, by selectively compound, the people is for giving characteristic and materials with function again.It mainly introduces the mechanism of plant template the preparation of the synthetic and composite of inorganic material, with the natural plants structure is template, prepare variously have that distinct plant structure characteristics, unique microscopic structure, institutional framework are controlled, physics and the controlled ordered porous inorganic fibers of mechanical property, thereby prepare something lost attitude material with high comprehensive performance that string ecological ceramic and metal material had.

At present, domestic and international research person have been that template prepares the something lost attitude porous oxide that possesses different tendency functions attempting with different fibrous material (as cotton, rice husk, jute, paper products etc.).Wood materials can form the raw material of wood-charcoal material with loose structure by charing, and processing can have very strong adsorption activity through special surface to change material, can be applicable to water body purification, improves living environment, fields such as environmental protection such as electromagnetic wave shielding.

Eucalyptus is one of the world's three big quick growing species of trees.The cultivated area of Guangxi eucalyptus in 2010 has reached 2,400 ten thousand mu, is maximum timber source, Guangxi seeds.Utilization to eucalyptus at present mainly concentrates on system paper pulp, makes on fiber and the glued board; and mainly utilize the eucalyptus bodywood; to the eucalyptus root and branch abandons usually with top or as firewood; these parts are as the recyclability waste material; if deal with improperly, not only can cause the wasting of resources, more can form pollution; bring pressure to environmental protection, be unfavorable for the sustainable development of ecological environment.In addition, eucalyptus timber has the ordered porous special anatomical structure of different scale scope, the existence of pit membrane and torus, make that pit is not a kind of natural perforate, can easily soaking of guide hole in the timber be filled out soma by the preliminary treatment of suitable digestion agent and remove, increase considerably the three-dimensional network connectedness of waiting to try the eucalyptus wood internal structure, improve the later stage saturating machine, improve the network connectivty of product simultaneously, be beneficial to preparation plant template porous adsorbing material.

Summary of the invention

The purpose of this invention is to provide a kind of is the digestion agent with the weak aqua ammonia, and ferric nitrate is that precursor solution prepares eucalyptus something lost attitude Fe ₂O ₃/ Fe ₃O ₄The method of compound heavy metal absorbent, by Artificial Control preparation technology, synthetic eucalyptus with natural plants structural form is lost attitude Fe ₂O ₃/ Fe ₃O ₄Compound heavy metal absorbent, to its carry out thing with structure, become to be grouped into and the shape characteristic Experimental Characterization, and be applied to the adsorption treatment experiment of water environment toxic heavy metal element, be a kind of cheapness and environment-friendly material, for the eucalyptus wood utilization provides a kind of new method, new way.

Concrete steps are:

(1) with eucalyptus root or the peeling of limb timber, drying;

(2) the configuration volumetric concentration is that the weak aqua ammonia of 5%-8% is as the digestion agent;

(3) ferric nitrate being dissolved in volume ratio is in ethanol-ultra-pure water mixed solvent of 1: 1, and compound concentration is that the iron nitrate solution of 1.2-2.0mol/L is as precursor solution;

(4) step (1) being obtained product and place step (2) the digestion agent that obtains, is digestion 6 hours under 100 ℃ of conditions with temperature, finishes the extracting preliminary treatment;

(5) step (4) is obtained product and clean, and be 80 ℃ baking oven inner drying 24 hours in temperature with ultra-pure water;

(6) step (5) acquisition product being immersed in step (3) obtains in the precursor solution, and be 60 ℃ of water bath heat preservations under the condition 3 days in temperature, not timing is during this time added precursor solution to guarantee that timber is in submerged state all the time, after from solution, taking out timber, be to dry 24 hours under 60 ℃ of left and right sides conditions in temperature;

(7) repeating step is (6) 3 times;

(8) step (7) is obtained product and placed under 600 ℃ of-800 ℃ of conditions of Muffle furnace roasting 3-6 hour, stove is chilled to room temperature;

(9) step (7) is obtained product and grind, cross the 100-150 mesh sieve, promptly obtain eucalyptus and lose attitude Fe ₂O ₃/ Fe ₃O ₄Compound heavy metal absorbent.

The present invention is simple for process, and the preparation process expense is cheap, owing to utilize eucalyptus timber to be main raw material(s), material is easy to get, and through technology controlling and process, has improved the absorption property of material to heavy metal greatly; The product of gained can be widely used in the heavy metal pollution water treatment.

Description of drawings

Fig. 1 is a product infrared spectrogram of the present invention (FI-IR).

Fig. 2 is a product X-ray diffractogram of the present invention (XRD).

Fig. 3 is product SEM microscopy figure of the present invention (SEM, a: * 100; B: * 3000).

Fig. 4 is under the different pH values of the present invention, and product is to Cr VI eliminating rate of absorption variation diagram.

Fig. 5 is pH value of the present invention=9, and product is to the eliminating rate of absorption variation diagram of variable concentrations arsenic.

The specific embodiment

Embodiment 1:

One, eucalyptus is lost attitude Fe ₂O ₃/ Fe ₃O ₄The preparation of compound heavy metal absorbent:

(1) with eucalyptus root or limb timber 1kg, peeling, dry back cut lengths are about: the blocks of length * wide * height=30mm * 10mm * 3mm;

(2) the configuration volumetric concentration is that 5% weak aqua ammonia is as the digestion agent;

(3) ferric nitrate being dissolved in volume ratio is that compound concentration is that the 1.2mol/L iron nitrate solution is as precursor solution in ethanol-ultra-pure water mixed solvent of 1: 1;

(4) step (1) being obtained product and place step (2) the digestion agent that obtains, is digestion 6 hours under 105 ℃ of conditions with temperature, finishes the extracting preliminary treatment;

(5) step (4) is obtained product and clean, and be 80 ℃ baking oven inner drying 24 hours in temperature with ultra-pure water;

(6) step (5) being obtained product is immersed in the precursor solution that step (3) obtained, and be 60 ℃ of water bath heat preservations under the condition 3 days in temperature, not timing is during this time added precursor solution and is in submerged state to guarantee the water bath heat preservation process, after from solution, taking out timber, be to dry 24 hours under 60 ℃ of conditions in temperature;

(7) repeating step is (6) 3 times;

(8) step (7) is obtained product and placed under 600 ℃ of conditions of Muffle furnace roasting 3 hours, stove is chilled to room temperature;

(9) step (7) is obtained product and grind, cross 100 mesh sieves, promptly obtain eucalyptus and lose attitude Fe ₂O ₃/ Fe ₃O ₄Compound heavy metal absorbent.

Eucalyptus is lost attitude Fe ₂O ₃/ Fe ₃O ₄The thing of compound heavy metal absorbent and structure, become to be grouped into and shape characteristic adopts X-ray diffractometer (XRD, X ' Pert PRO), the thermogravimetric-infrared logotype (STA-449C of system; 470FT-IR), (SEM JSM-6380LV) carries out observation test for elemental analyser (Perkin-Elmer) and SEM.

Two, heavy metal absorbent is to chromic adsorption effect:

(1) uses K ₂Cr ₂O ₇The pending liquid of Cr VI that to dispose 4 bottles of concentration be 10mg/L uses HNO ₃Regulating 4 bottles of pending liquid pH values respectively with NaOH is 1.0,2.0,3.0,4.0;

(2) pipetting the pending liquid numbering of 50ml respectively bottles standby in the 100ml centrifuge tube;

(3) add the above-mentioned eucalyptus something lost of 0.5g attitude Fe respectively in every bottle of pending liquid ₂O ₃/ Fe ₃O ₄Compound heavy metal absorbent carries out 25 ℃ of constant temperature vibration 6h, then with 4000rmin after sealing ^-1Speed is carried out centrifugal 5min operation;

(4) get step (3) product and cross 0.45 μ m miillpore filter, use diphenyl carbazide spectrophotometry (visible spectrophotometer) that solution is carried out hexavalent chromium concentration and measure, obtain the pH value be under 1.0,2.0,3.0,4.0 conditions product to concentration be 10mg/L the pending liquid adsorption effect of Cr VI as shown in Figure 4.

Three, heavy metal absorbent is to the adsorption effect of arsenic:

(1) uses Na ₃AsO ₄Dispose the pending liquid of arsenic that 4 bottles of concentration are respectively 2mg/L, 4mg/L, 6mg/L, 8mg/L, use HNO ₃Regulating pending liquid pH value respectively with NaOH is 9.0;

(2) pipetting the pending liquid numbering of 50ml respectively bottles standby in the 100ml centrifuge tube;

(3) add the above-mentioned eucalyptus something lost of 0.5g attitude Fe respectively in every bottle of pending liquid ₂O ₃/ Fe ₃O ₄Compound heavy metal absorbent carries out 25 ℃ of constant temperature vibration 6h, then with 4000rmin after sealing ^-1Speed is carried out centrifugal 5min operation;

(4) get step (3) product and cross 0.22 μ m miillpore filter, use GFAAS (Atomic Absorption Spectrometer [Perkin-Elmer AAnalyst700]) to carry out arsenic concentration determination in the solution, acquisition concentration be under 2mg/L, 4mg/L, 6mg/L, the 8mg/L condition product to the pH value be 9.0 arsenic solution adsorption effect as shown in Figure 5.

Claims (1)

1. an eucalyptus is lost attitude Fe ₂O ₃/ Fe ₃O ₄The preparation method of compound heavy metal absorbent is characterized in that concrete steps are:

(1) with eucalyptus root or the peeling of limb timber, drying;

(2) the configuration volumetric concentration is that the weak aqua ammonia of 5%-8% is as the digestion agent;

(3) ferric nitrate being dissolved in volume ratio is in ethanol-ultra-pure water mixed solvent of 1: 1, and compound concentration is that the iron nitrate solution of 1.2-2.0mol/L is as precursor solution;

(4) step (1) being obtained product and place step (2) the digestion agent that obtains, is digestion 6 hours under 100 ℃ of conditions with temperature, finishes the extracting preliminary treatment;

(5) step (4) is obtained product and clean, and be 80 ℃ baking oven inner drying 24 hours in temperature with ultra-pure water;

(6) step (5) acquisition product being immersed in step (3) obtains in the precursor solution, and be 60 ℃ of water bath heat preservations under the condition 3 days in temperature, not timing is during this time added precursor solution to guarantee that timber is in submerged state all the time, after from solution, taking out timber, be to dry 24 hours under 60 ℃ of left and right sides conditions in temperature;

(7) repeating step is (6) 3 times;

(8) step (7) is obtained product and placed under 600 ℃ of-800 ℃ of conditions of Muffle furnace roasting 3-6 hour, stove is chilled to room temperature;

(9) step (7) is obtained product and grind, cross the 100-150 mesh sieve, promptly obtain eucalyptus and lose attitude Fe ₂O ₃/ Fe ₃O ₄Compound heavy metal absorbent.

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