CN102949983B

CN102949983B - Preparation method of Na2Ti3O7 absorbing agent

Info

Publication number: CN102949983B
Application number: CN201210539454.7A
Authority: CN
Inventors: 沈建兴; 张加艳; 王泰林; 魏长宝
Original assignee: Shandong Institute of Light Industry
Current assignee: Shandong Institute of Light Industry
Priority date: 2012-12-14
Filing date: 2012-12-14
Publication date: 2015-01-14
Anticipated expiration: 2032-12-14
Also published as: CN102949983A

Abstract

The invention belongs to the technical field of synthesis of inorganic functional materials, and particularly relates to a preparation method of a Na2Ti3O7 absorbing agent. The preparation method is characterized by comprising the following steps of: adopting P23 nano TiO2 as a base material, adopting NaOH as reaction solvent, adopting a hydrothermal method to prepare a meshed Na2Ti3O7 precursor, arranging the meshed Na2Ti3O7 precursor in a muffle furnace for calcining and obtaining the Na2Ti3O7 absorbing agent. The heavy-metal ion absorbing agent (Na2Ti3O7 absorbing agent) prepared by the preparation method is of a meshed structure, not only is beneficial to improving the absorbing capacity of heavy-metal ions, but also is convenient for separation from the absorbed heavy-metal ions, realizes cyclic utilization of the heavy-metal ion absorbing agent and the heavy-metal ions, and is obvious in energy-saving and material-saving effects; and the precursor is calcined, then the strength of the heavy-metal ion absorbing agent is improved, and the dispersion of the heavy-metal ion absorbing agent in a water body and the secondary pollution possibly caused in the use process of the heavy-metal ion absorbing agent are reduced.

Description

A kind of Na 2ti 3o 7the preparation method of adsorbent

(1) technical field

The invention belongs to novel inorganic functional material synthesis technical field, particularly a kind of Na ₂ti ₃o ₇the preparation method of adsorbent.

(2) background technology

Heavy-metal pollution is one of pollution of most refractory reason in water pollution.Some heavy metal element in water body, as chromium, cadmium, lead etc., has larger harm to human body, and therefore, effectively the heavy metal ion removed in sewage has become one of the most urgent current task.And the absorption heavy metal ion reclaimed in sewage is not only the important component part of sewage handling problem, in the recycling of heavy metal ion, also has profound significance simultaneously.

Exploitation and the selection of adsorbent is the most important thing is in absorption method.The adsorbent being applied to Industrial Wastewater Treatment at present mainly contains active carbon, biological adsorption agent and some other adsorbent being still in the laboratory simulation stage, as clay class adsorbent, polymeric sorbent, the adsorbent utilizing discarded object to prepare and compound adsorbent etc.Wherein active carbon can be used for most of heavy metal, the removing of organic molecule and high adsorption capacity as a kind of effective Wastewater processing absorbent, just active carbon resource-constrained, improvement waste water cost in enormous quantities is high, life-span is short, regenerative operation costly, to be more difficultly widely used in the still underdeveloped area of economy.Other adsorbents also exist adsorption efficiency low, easily produce secondary pollution, cannot problems such as recycling be realized.Therefore, how to improve the adsorption efficiency of adsorbent, increase adsorbent to recycle number of times and reduce the secondary pollution problem caused in adsorbent use procedure be one of significant challenge of facing of current adsorbent research field.

(3) summary of the invention

The invention provides a kind of Na ₂ti ₃o ₇the preparation method of adsorbent, this Na ₂ti ₃o ₇adsorbent overcome general absorption method administer adsorption efficiency in sewage process not high, easily cause secondary pollution, be difficult to administer current water and the problems such as sorbing material and heavy metal ion recycle cannot be realized.

The present invention is achieved through the following technical solutions:

A kind of Na ₂ti ₃o ₇the preparation method of adsorbent, its special character is: with P25 nano-TiO ₂for matrix material, take NaOH as reaction dissolvent, adopt hydro-thermal method to prepare netted Na ₂ti ₃o ₇presoma, is placed in Muffle furnace and calcines, and obtains Na ₂ti ₃o ₇adsorbent.

Na of the present invention ₂ti ₃o ₇the preparation method of adsorbent, the concentration of NaOH is 5-15mol/l.

Na of the present invention ₂ti ₃o ₇the preparation method of adsorbent, hydrothermal temperature is 160-220 DEG C, and the reaction time is 24-72h.

Na of the present invention ₂ti ₃o ₇the preparation method of adsorbent, Na ₂ti ₃o ₇presoma calcining heat in Muffle furnace is 550-650 DEG C, and the time is 0.5-4h.

Na of the present invention ₂ti ₃o ₇the preparation method of adsorbent, Na ₂ti ₃o ₇adsorbent is network structure.

The present invention adopts hydro-thermal method to prepare adsorbent for heavy metal-Na ₂ti ₃o ₇adsorbent, adsorbent microstructure is made to be network structure, both be conducive to improve heavy metal ion adsorption capacity (rate of adsorption of heavy metal ion and the more general adsorbent of adsorption capacity higher, can up to 97%) be convenient to again and adsorbed separation of heavy metal ions, realize recycling of adsorbent for heavy metal and heavy metal ion, energy-saving material-saving Be very effective; Presoma is calcined, improves the intensity of adsorbent for heavy metal, reduce the secondary pollution that may cause in its dispersion in water body and use procedure.

(4) accompanying drawing explanation

Accompanying drawing 1 is Na ₂ti ₃o ₇sEM figure under the low multiplication factor of adsorbent;

Accompanying drawing 2 is Na ₂ti ₃o ₇the XRD figure of adsorbent;

Accompanying drawing 3 is Na ₂ti ₃o ₇sEM figure under adsorbent high-amplification-factor;

Accompanying drawing 4 is Na ₂ti ₃o ₇adsorbent is to Cd ²⁺adsorpting rate curve;

Accompanying drawing 5 is Na ₂ti ₃o ₇adsorbent is to Cd ²⁺desorption rate curve;

Accompanying drawing 6 is Na ₂ti ₃o ₇the adsorption efficiency of adsorbent with recycle number of times relation curve;

Accompanying drawing 7 is Na ₂ti ₃o ₇adsorbent is compared with the SEM figure under high-amplification-factor.

(5) detailed description of the invention

Embodiment 1

32g NaOH is placed in the beaker filling 160ml distilled water, magnetic agitation to room temperature, then by 2g P25 nano-TiO ₂pour in beaker, ultrasonic cleaning 15min, solution is mixed, mixed solution is evenly divided into 4 parts, be placed in stainless steel cauldron that 40ml liner is polytetrafluoroethylene (PTFE), close, tighten reactor, four reactors are placed in the Constant Temp. Oven of 180 DEG C, respectively isothermal reaction 40h, after completion of the reaction, naturally cool to room temperature, with glass bar by product Na ₂ti ₃o ₇presoma takes out and puts into beaker, adds distilled water, and cleaning repeatedly, suction filtration to solution are neutral, put it into dry 5h in the drying box of 110 DEG C, obtain netted Na ₂ti ₃o ₇presoma, is placed in the Muffle furnace of 650 DEG C, and calcining 0.5h, with stove cool to room temperature, obtains netted adsorbent for heavy metal-Na ₂ti ₃o ₇adsorbent.

Embodiment 2

96g NaOH is placed in the beaker filling 160ml distilled water, magnetic agitation to room temperature, then by 2g P25 nano-TiO ₂pour in beaker, ultrasonic cleaning 15min, solution is mixed, mixed solution is evenly divided into 4 parts, be placed in stainless steel cauldron that 40ml liner is polytetrafluoroethylene (PTFE), close, tighten reactor, four reactors are placed in the Constant Temp. Oven of 160 DEG C, respectively isothermal reaction 72h, after completion of the reaction, naturally cool to room temperature, with glass bar by product Na ₂ti ₃o ₇presoma takes out and puts into beaker, adds distilled water, and cleaning repeatedly, suction filtration to solution are neutral, put it into dry 4h in the drying box of 120 DEG C, obtain netted Na ₂ti ₃o ₇presoma, is placed in the Muffle furnace of 600 DEG C, and calcining 3h, with stove cool to room temperature, obtains netted adsorbent for heavy metal-Na ₂ti ₃o ₇adsorbent.

Embodiment 7

64g NaOH is placed in the beaker filling 160ml distilled water, magnetic agitation to room temperature, then by 2g P25 nano-TiO ₂pour in beaker, ultrasonic cleaning 15min, solution is mixed, mixed solution is evenly divided into 4 parts, be placed in stainless steel cauldron that 40ml liner is polytetrafluoroethylene (PTFE), close, tighten reactor, four reactors are placed in the Constant Temp. Oven of 220 DEG C, respectively isothermal reaction 24h, after completion of the reaction, naturally cool to room temperature, with glass bar by product Na ₂ti ₃o ₇presoma takes out and puts into beaker, adds distilled water, and cleaning repeatedly, suction filtration to solution are neutral, put it into dry 6h in the drying box of 100 DEG C, obtain netted Na ₂ti ₃o ₇presoma, is placed in the Muffle furnace of 550 DEG C, and calcining 4h, with stove cool to room temperature, obtains netted adsorbent for heavy metal-Na ₂ti ₃o ₇adsorbent.

Embodiment 8

Tested by above-described embodiment products therefrom, acquired results is as follows:

Accompanying drawing 1 is Na ₂ti ₃o ₇the XRD figure of adsorbent, from XRD data, prepared sample is 10 °, 29 ° at 2 θ respectively has a very strong diffraction maximum, respectively with Na ₂ti ₃o ₇(001) peak, (300) peak of (JCPDS card 31-1329) are corresponding, 23 °, 34 °, the 48 ° diffraction maximums that respectively appearance one is more weak, with Na ₂ti ₃o ₇(011), (203), (020) diffraction maximum corresponding, illustrates that the sample synthesized is Na ₂ti ₃o ₇.

Accompanying drawing 2,7,3 is respectively Na ₃ti ₈o ₁₇under the low multiplication factor of adsorbent, compared with the SEM figure under high-amplification-factor, under high-amplification-factor, as seen from the figure, Na ₂ti ₃o ₇two nanobelts that adsorbent contacts with each other tightly be embedded in together, substantially increase the intensity of adsorbent, its nanobelt intersect, overlapping, growth evenly.

By above-described embodiment products therefrom-Na ₂ti ₃o ₇adsorbent carries out adsorption test to various heavy, its process and the data obtained similar, with Na ₂ti ₃o ₇adsorbent is to Cd in water sample ²⁺absorption analyze.

Accompanying drawing 4 is Na ₂ti ₃o ₇adsorbent is to Cd ²⁺adsorpting rate curve, as seen from the figure, along with the prolongation of adsorption time, Cd in water sample ²⁺ion concentration constantly reduces, adsorption rate raises gradually, when adsorption time reaches 150min, almost reach absorption saturation state, ion concentration is only 0.005mg/L, adsorption rate reaches 95.0%, after this, along with adsorption time continues to extend, adsorption rate change is little, this is because in the absorption incipient stage, Cd in water sample ²⁺ion concentration is relatively high, and along with being adsorbed Cd ²⁺the continuous accumulation of ion, Na ₂ti ₃o ₇the limited surface area of adsorbent constantly reduces until adsorb saturation state.

Accompanying drawing 5 is Na ₂ti ₃o ₇adsorbent is to Cd ²⁺desorption rate curve, condition determination be adopt NaOH solution by almost reach absorption saturation state water sample pH be adjusted to 12, as seen from the figure, in the incipient stage, the Cd in water sample ²⁺ion concentration increases fast, and desorption rate is very fast, along with the prolongation of desorption time, and Cd in water sample ²⁺ion concentration continues to increase, and when the parsing time reaches 245min, desorption efficiency is 94%, still has the Cd of 6% ²⁺not from Na ₂ti ₃o ₇desorb in adsorbent, this may be due to part Cd ²⁺enter Na ₂ti ₃o ₇crystal structure in cause.

Accompanying drawing 6 is Na ₂ti ₃o ₇the adsorption efficiency of adsorbent with recycle number of times relation curve, as seen from the figure, Na ₂ti ₃o ₇adsorbent first adsorption rate is higher, is 97%, and when second time uses, adsorption rate declines comparatively large, and be reduced to 95%, this may be due to Cd ²⁺can not completely from Na ₂ti ₃o ₇in desorb, part Cd ²⁺remain in Na ₂ti ₃o ₇crystal structure in cause, but next sorbent circulation stability is better, and after 10 circulations, adsorption rate still can remain on 85%, illustrates and remains in Na ₂ti ₃o ₇cd in crystal structure ²+ there is better stability, little to subsequent adsorbtion tests affect.

Claims

1. a Na ₂ti ₃o ₇the preparation method of adsorbent, is characterized in that: 32g NaOH is placed in the beaker filling 160ml distilled water, magnetic agitation to room temperature, then by 2g P25 nano-TiO ₂pour in beaker, ultrasonic cleaning 15min, solution is mixed, mixed solution is evenly divided into 4 parts, be placed in stainless steel cauldron that 40ml liner is polytetrafluoroethylene (PTFE), close, tighten reactor, four reactors are placed in the Constant Temp. Oven of 180 DEG C, respectively isothermal reaction 40h, after completion of the reaction, naturally cool to room temperature, with glass bar by product Na ₂ti ₃o ₇presoma takes out and puts into beaker, adds distilled water, and cleaning repeatedly, suction filtration to solution are neutral, put it into dry 5h in the drying box of 110 DEG C, obtain netted Na ₂ti ₃o ₇presoma, is placed in the Muffle furnace of 650 DEG C, and calcining 0.5h, with stove cool to room temperature, obtains netted adsorbent for heavy metal-Na ₂ti ₃o ₇adsorbent, Na ₂ti ₃o ₇two nanobelts that adsorbent contacts with each other tightly be embedded in together, its nanobelt intersects, overlapping, growth evenly.

2.Na ₂ti ₃o ₇the preparation method of adsorbent, is characterized in that: 96g NaOH is placed in the beaker filling 160ml distilled water, magnetic agitation to room temperature, then by 2g P25 nano-TiO ₂pour in beaker, ultrasonic cleaning 15min, solution is mixed, mixed solution is evenly divided into 4 parts, be placed in stainless steel cauldron that 40ml liner is polytetrafluoroethylene (PTFE), close, tighten reactor, four reactors are placed in the Constant Temp. Oven of 160 DEG C, respectively isothermal reaction 72h, after completion of the reaction, naturally cool to room temperature, with glass bar by product Na ₂ti ₃o ₇presoma takes out and puts into beaker, adds distilled water, and cleaning repeatedly, suction filtration to solution are neutral, put it into dry 4h in the drying box of 120 DEG C, obtain netted Na ₂ti ₃o ₇presoma, is placed in the Muffle furnace of 600 DEG C, and calcining 3h, with stove cool to room temperature, obtains netted adsorbent for heavy metal-Na ₂ti ₃o ₇adsorbent, Na ₂ti ₃o ₇two nanobelts that adsorbent contacts with each other tightly be embedded in together, its nanobelt intersects, overlapping, growth evenly.

3.Na ₂ti ₃o ₇the preparation method of adsorbent, is characterized in that: 64g NaOH is placed in the beaker filling 160ml distilled water, magnetic agitation to room temperature, then by 2g P25 nano-TiO ₂pour in beaker, ultrasonic cleaning 15min, solution is mixed, mixed solution is evenly divided into 4 parts, be placed in stainless steel cauldron that 40ml liner is polytetrafluoroethylene (PTFE), close, tighten reactor, four reactors are placed in the Constant Temp. Oven of 220 DEG C, respectively isothermal reaction 24h, after completion of the reaction, naturally cool to room temperature, with glass bar by product Na ₂ti ₃o ₇presoma takes out and puts into beaker, adds distilled water, and cleaning repeatedly, suction filtration to solution are neutral, put it into dry 6h in the drying box of 100 DEG C, obtain netted Na ₂ti ₃o ₇presoma, is placed in the Muffle furnace of 550 DEG C, and calcining 4h, with stove cool to room temperature, obtains netted adsorbent for heavy metal-Na ₂ti ₃o ₇adsorbent, Na ₂ti ₃o ₇two nanobelts that adsorbent contacts with each other tightly be embedded in together, its nanobelt intersects, overlapping, growth evenly.