CN115608322B - Preparation and application methods of regenerable adsorbent for cooperatively removing heavy metals and new organic pollutants in water - Google Patents
Preparation and application methods of regenerable adsorbent for cooperatively removing heavy metals and new organic pollutants in water Download PDFInfo
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- CN115608322B CN115608322B CN202211413780.3A CN202211413780A CN115608322B CN 115608322 B CN115608322 B CN 115608322B CN 202211413780 A CN202211413780 A CN 202211413780A CN 115608322 B CN115608322 B CN 115608322B
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- 238000000034 method Methods 0.000 title claims abstract description 54
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 239000002131 composite material Substances 0.000 claims abstract description 62
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 55
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a preparation method and application of a renewable adsorbent for cooperatively removing emerging organic pollutants and heavy metals in water, and belongs to the technical field of water treatment. The composite material is a homogeneous composite of a series of porous carbon materials derived from metal organic framework materials and nano titanate materials, is synthesized by a hydrothermal method, and can be doped with other metals on the basis. The composite material is applied to the synergistic removal of heavy metals and new organic matters in water, and has the advantages of quick adsorption kinetics process, large adsorption quantity and remarkable synergistic adsorption addition effect. The heavy metal can be regenerated and reused through acid and alkali after being saturated; after the adsorption of new organic pollutants is saturated, the organic pollutants can be reused after regeneration by light. The invention has the advantages of low price of the adopted raw materials, simple and easy method, clean and pollution-free application process, and suitability for large-scale treatment of drinking water, domestic sewage, industrial wastewater and landfill leachate, groundwater remediation and natural water pollution emergency treatment.
Description
Technical Field
The invention belongs to the technical field of water treatment, relates to a preparation and application method of a renewable adsorbent for cooperatively removing heavy metals and new organic pollutants in water, and in particular relates to a preparation method of derivative carbon/nano titanate multiphase composite materials (CTCs) capable of realizing multi-metal doping and an application method of the renewable adsorbent for cooperatively removing emerging organic pollutants and heavy metals in water, which are suitable for large-scale drinking water treatment, domestic sewage treatment, industrial wastewater treatment, landfill leachate treatment, groundwater remediation and natural water pollution emergency treatment.
Background
Water is essential in all aspects of human survival, but 97.5% of the water on earth is unavailable in the ocean, with only about 1% of the water available for human use. In recent years, as new substances are produced and applied in agriculture and industry sectors, the types of pollutants discharged as sewage and wastewater are becoming more and more diversified, and water pollution is becoming a major challenge for human survival. Of particular concern are so-called emerging organic pollutants (EOCs), which term is intended to encompass not only known pollutant species, but also newly developed compounds that have a negative impact on the environment and human health. EOCs come from hundreds of pollution sources, covering a variety of different compounds: pharmaceutical and Personal Care Products (PPCPs), pesticides, veterinary drugs (e.g. veterinary hormones), industrially prepared compounds and by-products and food additives. The above-mentioned pollutants are highly toxic, and trace-level pollutants pose a great environmental risk. In addition, excessive emissions of heavy metals also raise concerns. Since the 70 s of the last century, a great number of public sewage treatment plants are newly built in developed countries, and after point source treatment, the quality of human discharged water is improved to a certain extent, but the concentration of pollutants in water body is continuously increased and the water pollution is increased increasingly because emerging organic pollutants and heavy metals are difficult to be purified naturally.
To remove EOCs from contaminated water, a variety of techniques have been developed, including adsorption and redox techniques. In the adsorption technology, the EOCs can be effectively adsorbed by using activated carbon, carbon nano tubes, carbon fibers, a metal-organic framework and ion exchange resin. However, these adsorption methods have serious drawbacks, including: 1) The technology can not degrade EOCs, thus realizing detoxification; 2) Regeneration of the adsorbent is costly and typically requires expensive and toxic organic solvents, producing large amounts of regenerated waste residue, requiring additional expensive disposal and disposal costs. The advanced oxidation technology is used as one of the most mature water treatment technologies, and the high-efficiency removal of EOCs can be realized by utilizing free radical attack organic pollutants generated under the conditions of high temperature, high pressure, light irradiation, electricity, catalysis and the like. However, EOCs in water exist in trace levels (mug/L or ng/L), so that the advanced oxidation technology with high energy consumption and high medicament dosage is not suitable to be directly used, the problem that the mineralization of the EOCs in trace levels is incomplete exists, and degradation products of part of the EOCs possibly have higher toxicity than original pollutants, so that the environmental risk of the polluted water is not reduced and raised.
In addition, heavy metals have high physiological toxicity, easy migration and high biological enrichment, are easily absorbed by microorganisms and plants, and enter human bodies along food chains in an enrichment way, so that skin, nerve and viscera damage is caused, the poisoning is light, and the death is heavy. Currently, common methods include: adsorption, electrolytic, chemical precipitation, solvent extraction, biological treatment and the like, wherein the adsorption method has the advantages of excellent treatment effect, simple and convenient operation, no strict application limit and the like, but the adsorbent can generate a large amount of solid waste after being used and has the risk of secondary pollution.
Therefore, there is a need to find a material and a method for efficiently, safely, environmentally friendly and low-energy-consumption removal of pollutants such as EOCs and heavy metals of pollutants.
Disclosure of Invention
In order to solve the problems and realize the purposes of efficiently, safely, environmentally-friendly and low-energy consumption removal of pollutants such as EOCs and heavy metals of pollutants, the invention provides a preparation and application method of a renewable adsorbent for cooperatively removing heavy metals and emerging organic pollutants in water. Specifically, the technology of the invention is to enrich pollutants in water body in solid phase materials by using derivative carbon/nano titanate composite materials (CTCs) firstly, and then to realize degradation of EOCs and transfer of heavy metals and the like respectively by using a photocatalysis method and an acid-base leaching method, and to realize material regeneration simultaneously. The technical system can be applied to drinking water treatment, domestic sewage treatment, hospital sewage treatment, cultivation sewage treatment, industrial wastewater treatment, landfill leachate treatment, groundwater remediation and natural water pollution emergency treatment.
The invention is as follows: the invention provides a composite material, the main body part of which comprises a derivative carbon carrier and nano titanate conjugated with the derivative carbon carrier. In addition, the invention also comprises a method for cooperatively removing one or more novel organic pollutants and heavy metals from water, and meanwhile, the material can realize the green pollution-free and low-energy-consumption rapid regeneration of the adsorbent through a simple light regeneration method and an acid-base method.
A first object of the present invention is to provide a method for preparing a class of derivatized carbon/nanotitanate composites (CTCs), comprising the steps of:
mixing titanium dioxide, derived carbon and NaOH solution as raw materials, performing hydrothermal reaction for 3-96 hours at the temperature of 110-210 ℃, performing solid-liquid separation, washing precipitate, and drying to obtain the derived carbon/nano titanate composite material; wherein the derived carbon is prepared from one or more of metal organic framework materials such as ZIF-8, ZIF-67, MIL-88A and the like by high-temperature calcination.
In one embodiment of the present invention, the high temperature calcination is performed in an inert atmosphere of nitrogen or argon at 550 to 1000 ℃ for 2 to 4 hours after the predetermined temperature is reached when the derivative carbon is prepared.
In one embodiment of the invention, the titanium dioxide is one or more of pure anatase, pure rutile, and P25 (80% anatase and 20% rutile).
In one embodiment of the invention, the mass ratio of the titanium dioxide to the derived carbon is 1:5 to 10:1.
In one embodiment of the present invention, the concentration of the NaOH solution is 0.5 to 10mol/L.
In one embodiment of the invention, the raw material mixing process is carried out by means of ultrasonic dispersion.
In one embodiment of the present invention, the wash is preferably performed with deionized water to neutrality.
In one embodiment of the invention, the drying is preferably carried out at 60 to 100 ℃.
In one embodiment of the invention, the method further comprises: adding the prepared derivative carbon/nano titanate composite material into an ultra-high dispersion metal salt solution, uniformly mixing, standing, separating solid from liquid, drying, and performing two-stage precise temperature control annealing calcination in an inert atmosphere to obtain the single-metal doped derivative carbon/nano titanate composite material.
In one embodiment of the invention, CTCs are added in an amount of 10 to 200 times the mass of the metal element to be doped.
In one embodiment of the present invention, the doped metal element includes one or more of manganese, cobalt, copper, etc., and when Mn and Co are binary doped, the mass ratio of Mn to Co is 1: 2-1: 4, when Mn and Cu are subjected to binary doping, the mass ratio of Mn to Cu is 1: 2-1: 5, when Co and Cu are subjected to binary doping, the mass ratio of Co to Cu is 1:1 to 1:5.
in one embodiment of the present invention, the metal salt is a chloride salt or nitrate salt of a metal element.
In one embodiment of the present invention, the metal salt solution is water or an aqueous ammonia solution of a metal salt.
In one embodiment of the invention, the ultra-high dispersion mode of the metal salt solution is a dispersing agent-sodium carboxymethyl cellulose with a molecular weight of 3000-15000.
In one embodiment of the invention, the mass ratio of sodium carboxymethylcellulose to the metal to be doped is 5: 1-20: 1.
in one embodiment of the invention, the inert atmosphere is a nitrogen or argon atmosphere.
In one embodiment of the invention, the temperature of the precisely controlled annealing calcination is 200-600 ℃ and the time period is 2-10 hours.
In one embodiment of the invention, the two-stage precise temperature control annealing is performed, wherein the first-stage annealing temperature is 200-300 ℃ and the duration is 1-6 hours; after the first stage annealing, the material is cooled to room temperature, washed to remove impurities, dried and then subjected to the second stage annealing calcination, wherein the temperature is 500-600 ℃ and the duration is 1-6 hours.
In one embodiment of the invention, when binary metal doping is performed, the doping and three-stage precise temperature control annealing process is as follows: doping the first metal, carrying out first annealing, doping the second metal, carrying out second annealing, and carrying out third annealing.
In one embodiment of the invention, when binary metal doping is performed, the temperature of the first and second anneals is 200-300 ℃ for 1-6 hours, the temperature of the third anneals is 500-600 ℃ for 1-6 hours.
In one embodiment of the present invention, when binary metal doping is performed, the metal doping order does not significantly affect the adsorption and photocatalytic properties of the material.
The second object of the invention is to provide the doped metal or undoped metal derived carbon/nano titanate composite material prepared by the preparation method.
It is a third object of the present invention to provide the use of the above metal doped or undoped derived carbon/nanotitanate composite material in water treatment including, but not limited to, potable water treatment, domestic sewage treatment, industrial wastewater treatment, landfill leachate treatment, groundwater remediation and natural water pollution emergency treatment.
A fourth object of the present invention is to provide the use of the above-described metal doped or undoped derivatized carbon/nanotitanate composite for the removal of heavy metals and/or emerging organic contaminants.
In one embodiment of the invention, the emerging organic contaminants include, but are not limited to, perfluoro/polyfluoroalkyl-based compounds (PFAS), active drugs, and the like.
In one embodiment of the invention, the heavy metal ions include, but are not limited to, lead, mercury, cadmium, chromium, uranium.
In one embodiment of the invention, the metal doped or undoped derivatized carbon/nanotitanate composite is used in a dosage range of 0.01 to 200kg/m 3 ；
And/or the concentration of contaminants in the water is greater than 20ng/L;
and/or, the applicable pH range is pH >2.8;
and/or, a suitable temperature is less than 50 ℃.
A fifth object of the present invention is to provide a method for regenerating a metal doped or undoped derivatized carbon/nanotitanate composite material, the regeneration method comprising a photo-regeneration method for organic contaminants and an acid-base regeneration method for inorganic cations.
In one embodiment of the present invention, the light regeneration method is to irradiate under a light source for a certain time to regenerate the composite material;
among them, the photo-regeneration reaction is preferably performed in a photo-reactor including, but not limited to, a fixed bed type photo-reactor, a fluidized bed type photo-reactor, an optical fiber type photo-reactor, and a filter membrane type photo-reactor;
and/or the light source can be an ultraviolet light source, a visible light source, a near infrared light source, an infrared light source, a sunlight light source and a mixed light source of the light sources, and the light intensity is more than 1mW/cm 2 ；
And/or, in the regeneration process, the mass ratio of the water to the composite material after being mixed is greater than 1:10 (water: CTCs);
and/or, in the regeneration process, the reaction temperature is greater than 5 ℃;
and/or, during regeneration, the pH condition is a pH greater than 2.4.
In one embodiment of the invention, the acid-base regeneration method refers to regeneration in an acid or lye for a period of time;
wherein the acid is strong acid such as hydrochloric acid, sulfuric acid, nitric acid, etc., and the concentration of nitric acid is 0.05-0.2 mol/L;
the alkali used is NaOH, and the concentration of the NaOH is 0.05-0.2 mol/L;
the reaction time of the regeneration process of the acid and the alkali is respectively 1-4 hours and 1-6 hours.
The application technology of CTCs material comprises two core steps, namely 1) CTCs are firstly used as an adsorbent, and trace pollutants in water are enriched on a solid phase material through adsorption mechanisms such as hydrophobic effect, ion exchange, electrostatic attraction and the like; 2) Transferring the CTCs material pre-enriched with pollutants into a regeneration unit, realizing high-efficiency degradation of pre-enriched EOCs by using a photocatalysis advanced oxidation technology, simultaneously realizing material regeneration, and transferring and concentrating the pre-enriched heavy metals of the CTCs by using an elution method of acid leaching-alkali regeneration. The application technology is used in different scenes, and the difference is mainly reflected in the adsorption stage of pollutant enrichment:
the method 1 has the application scene of drinking water treatment, domestic sewage treatment, industrial wastewater treatment, landfill leachate treatment and the like, and comprises the following steps:
1) Aiming at partial industrial wastewater and landfill leachate, a wastewater cooling tank and a wastewater pH adjusting tank are preset, and the temperature and the pH of the wastewater are adjusted and homogenized so that the temperature of the wastewater is lower than 50 ℃ and the pH value is higher than 2.8;
2) And filling the adsorption tower with CTCs material, continuously pumping sewage into the adsorption tower by using a water pump, and discharging the water after pollutant adsorption.
3) When the material adsorption reaches saturation or the effluent quality does not reach the standard, the adsorbent is replaced, and the CTCs material with saturated adsorption is collected and transferred to a material regeneration process unit for material regeneration.
The method 2, the application scene is the emergency treatment for restoring natural water pollution by groundwater, and the steps are as follows:
1) The CTCs are put into an SMS composite non-woven cloth bag and are distributed in a water body to be repaired or treated in an emergency way through a water well or other modes;
2) Taking out the material every 48 hours, and replacing the new material or continuously using the regenerated material;
3) And when the material is saturated in adsorption, replacing the adsorbent, collecting the CTCs material saturated in adsorption, and transferring the material to a regeneration process unit for material regeneration.
The beneficial effects are that:
(1) The novel material developed by the invention prepares the derivative carbon and nano titanate composite material by a hydrothermal method, wherein the material has 3-grade derivative carbon with different particle diameters, and comprises the derivative carbon (more than 200 nm) serving as a carrier, nano carbon spheres (20-50 nm) attached to the surface of the nano titanate material and carbon quantum dot materials (less than 2 nm) embedded between the nano titanate layers. The novel material is prepared by compounding 3-grade derived carbon and nano titanate material, the internal pore canal structure of the material is distributed in a large number of stages, the specific surface area is large, the capillary effect is obvious, the ion exchange performance is excellent, the surface functional groups are diversified, and the adsorption sites and the active sites are rich, so that pollutants can be adsorbed, degraded and transferred rapidly.
(2) The material has good sedimentation performance, and can be separated from water in a short time after being used.
(3) The material has good stability, and can be used for carrying out the cycle of pollutant adsorption and material regeneration continuously for many times. In the resolving process, calcium and magnesium ions are easy to elute, the regeneration cost is low, only a small amount of NaOH is needed, and the damage degree of the material in the desorption regeneration process is small.
(4) The environment-friendly derivative carbon and nano titanate material are not easy to migrate and convert in water environment, and the material is titanate and does not introduce any toxic substances.
Drawings
FIG. 1 is a transmission electron micrograph of a metal-free CTCs composite material supported on a derived carbon prepared from a ZIF-8 metal-organic framework obtained in example 1 of the present invention;
FIG. 2 is a graph showing the effect of the CTCs composite material with the derived carbon as the carrier obtained in example 1 of the present invention on 4-CP adsorption removal and photocatalytic degradation (material synchronous regeneration);
FIG. 3 shows the synergy of the non-doped metal CTCs composite material with the derived carbon prepared by MIL-88A metal organic framework as the carrier obtained in example 2 of the invention and Pb in water 2+ And natural organic matters, and material photocatalytic regeneration and acid-base regeneration effect patterns;
FIG. 4 is a graph showing the effect of the single metal (Mn, fe, co) doped derivative carbon/titanate composite material obtained in example 3 of the present invention on adsorbing and removing perfluorooctanoic acid from water and realizing photocatalytic degradation and deep detoxification;
FIG. 5 is a graph showing the effect of the binary metal (Mn-Co, mn-Cu, co-Cu) doped derivative carbon/titanate composite material obtained in example 4 of the present invention on adsorbing and removing perfluorooctanoic acid in water and realizing photocatalytic degradation and deep detoxification.
Detailed Description
The present invention is further illustrated below by reference to examples, which are only illustrative of the present invention and do not limit the scope of applicability of the invention.
Example 1
According to the invention, 4-chlorophenol in water is removed from CTCs material taking derived carbon prepared by calcining ZIF-8 metal organic framework material as a carrier.
The synthetic material is used for treating sewage containing 4-chlorophenol (4-CP), the concentration of 4-chlorophenol in the sewage is 8mg/L, the pH of the sewage is neutral, and the method comprises the following steps:
(1) CTCs materials were synthesized using derivatized carbon as a carrier;
(a) Calcining ZIF-8 metal organic framework serving as a raw material at a high temperature (900 ℃) for 3 hours in a tube furnace under a nitrogen atmosphere to prepare derivative carbon;
(b) Titanium dioxide (P25 type, 80% anatase and 20% rutile, degussa company, germany) and the derived carbon are mixed according to a mass ratio of 1:1, and 10mol/L NaOH solution is added for ultrasonic dispersion for 24 hours;
(c) Hydrothermal reaction: placing the mixed solution into a reaction kettle, heating for 72 hours at 130 ℃, and cooling to obtain gray or black precipitate;
(d) Rinsing and drying: repeatedly cleaning the precipitate with deionized water to neutrality, and drying at 80 ℃ to obtain the CTCs material without doping other metal elements.
(2) The synthetic material is put into water at a dosage of 0.2g/L and the material is uniformly dispersed, and the concentration and the removal rate of pollutants in the water are monitored after 30 minutes;
(3) Separating materials by gravity natural sedimentation, transferring CTCs materials into a material photo-regeneration reactor for photo-catalytic reaction, degrading 4-CP and realizing material regeneration at the same time, wherein the illumination time is 4 hours, the selected light is ultraviolet band (254 nm), and the illumination intensity is 13mW/cm 2 ；
(4) The methanol heating extraction mode is used for extracting 4-CP adsorbed by the material in the photocatalysis process, and the pollutant degradation efficiency is measured through the residual quantity of the 4-CP (the step aims at testing the photocatalysis performance of the material and is not a necessary step in application);
(5) The steps (2) and (3) were repeated 5 times in succession to test the stability of the material.
(6) Activated carbon (activated carbon from Carlsberg, USA) was selected instead of the derived carbon, and an activated carbon/titanate composite was prepared and compared with the derived carbon/titanate composite in performance using the method described in this example (1).
The results of fig. 2 show that the adsorption capacity for 4-CP, particularly the derivatized carbon, is significantly improved after the activated carbon is composited with the derivatized carbon and titanate material. In addition, the derivative carbon/titanate composite material has strong photocatalytic activity, and can remove more than 99% of 4-CP pollutants in 30 minutes through adsorption, degrade about 96% of pollutants under 4-hour photocatalytic conditions and realize material regeneration. In contrast, although the activated carbon/titanate can efficiently adsorb pollutants in water, the photocatalytic performance of the activated carbon/titanate can be obviously reduced, the 4-CP removal efficiency for 4 hours is only 73%, in addition, the adsorption removal rate of 4-CP is still up to 97% after 5 times of cyclic experiments on the carbon/titanate composite material derived from the same batch of material, and the material has excellent regeneration effect and practical value.
Example 2
In the invention, the CTCs composite material taking the derived carbon prepared by calcining the MIL-88A metal organic framework material as the carrier cooperatively removes lead ions (Pb) 2+ ) With Natural Organic Substances (NOMs)
Treatment of high natural organic matter sewage containing lead ions by using synthetic material, and Pb in sewage 2+ The concentration is 50mg/L, the pH=5 in the sewage, the natural organic matter concentration is 10mg/L as TOC, the use includes the following steps:
synthesizing CTCs material by using derivative carbon prepared by calcining MIL-88A metal organic framework material as a carrier; the synthesis step comprises (a) calcining MIL-8A metal organic framework as raw material at high temperature (900 ℃) in a tube furnace under nitrogen atmosphere for 3 hours to prepare derivative carbon, mixing titanium dioxide (P25 type, 80% anatase and 20% rutile, degussa company, germany) with the derivative carbon according to the mass ratio of 1:1, and adding 10mol/L NaOH solution for ultrasonic dispersion for 24 hours. And placing the mixed solution into a reaction kettle, performing hydrothermal reaction for 24 hours at the temperature of 150 ℃, and cooling to obtain black precipitate. Repeatedly cleaning the precipitate with deionized water to neutrality, and oven drying at 80deg.C.
(1) The composite material was put into water at a dose of 0.2g/L and the material was uniformly dispersed, and Pb in the water was monitored after 60 minutes 2+ And NOMs concentration changes;
(2) Separating materials by gravity natural sedimentation, transferring CTCs materials into a material photo-regeneration reactor for photo-catalytic reaction for 24 hours, degrading NOMs and realizing regeneration of material organic adsorption sites;
(3) Extracting NOMs from materials in a photocatalysis process by using a sodium hydroxide heating extraction mode to measure the degradation efficiency of the NOMs on a solid phase (the step aims at testing the photocatalysis performance of the materials and is not a necessary step in application);
(4) Then regenerating the metal cation adsorption sites, and putting the synthetic material CTCs into a nitric acid solution with the concentration of 0.1mol/L, and soaking for 2 hours; washing with water to neutrality, adding into 0.1mol/L sodium hydroxide solution, soaking for 2 hours to supplement sodium sites, and after acid washing and alkali washing, testing Pb ion concentration and measuring material regeneration efficiency (the step is aimed at testing material regeneration performance and is not a necessary step in application);
(5) Supplement Na + And (3) repeating the steps (2) to (5) after the site, recycling the materials, continuously repeating the steps (2) and (3) for 5 times, and testing the stability of the materials.
In the lead-containing sewage of high natural organic matters treated by the derivative carbon/titanate composite material, the Pb removal rate is up to 99%, and the NOMs adsorption efficiency is 91.6%, in addition, in the material regeneration process unit, about 86% of NOMs pre-enriched on the surface of the material are degraded by photocatalysis, and the adsorbed Pb ions have about 95% of resolution after acid-base regeneration, so that the overall regeneration effect of the material is proved to be excellent. After 5 continuous experiments, the pollutant removal capability and the material regeneration capability of the derivative carbon/titanate composite material are still excellent. For example, the removal rate of Pb ions is still up to 97%, the adsorption rate of NOM is also up to 89%, the performance of the new material is not obviously reduced, meanwhile, the regeneration performance of the material is excellent, 92% of Pb ions are resolved after acid-base regeneration, and 86% of NOM is degraded after photocatalytic regeneration.
Example 3
According to the invention, derivative carbon prepared by high-temperature calcination of ZIF-67 metal organic framework material is used as a carrier, titanate material modification is carried out, and then perfluoro caprylic acid (PFOA) pollutants in water are removed by doping single metal doped CTCs composite materials doped with metals such as manganese, cobalt, copper and the like.
The preparation method of the CTCs composite material doped with different metals comprises the following steps: the preparation method of the CTCs composite material without doping metal comprises the steps of preparing a CTCs composite material without doping metal according to the method of the embodiment 1, dissolving manganese chloride, cobalt nitrate, copper chloride and the like in water or ammonia water, adding sodium carboxymethyl cellulose with the molecular weight of 10000, which is 5 times of the mass of metal salt, and carrying out ultrasonic treatment for 1 hour to obtain a high-dispersion aqueous solution of the metal cations, wherein the concentration of the metal cations such as manganese, cobalt, copper and the like in the final solution is 10mmol/L. Adding undoped CTCs materials into water for mixing, wherein the adding amount of the CTCs is 100 times of the mass of the metal element to be doped; after 4 hours of mixing reaction, solid-liquid separation of the materials is carried out, drying is carried out at 60 ℃, then calcination is carried out at 300 ℃ for 3 hours in nitrogen or argon atmosphere (first-stage annealing), after dissolved impurities on the surfaces of the materials are washed out by water and the materials are dried, second-stage high-temperature annealing is carried out in argon atmosphere for 4 hours, and the temperature is 550 ℃, thus obtaining the derivative carbon/nano titanate composite material doped with different metals.
PFOA with a concentration of 100. Mu.g/L in water, neutral pH, is treated with synthetic material, comprising the steps of:
(1) The synthetic material is put into water at a dosage of 1g/L and the material is uniformly dispersed, and the concentration change of PFOA in the water is monitored after 30 minutes;
(2) Separating material by gravity natural sedimentation, transferring CTCs material into material photo-regeneration reactor, and performing photocatalytic reaction (under irradiation of 254nm ultraviolet light source for 4 hr, the light intensity of material surface is about 10 mW)/cm 2 ) The PFOA is degraded and the material regeneration is realized at the same time;
(3) The methanol heating extraction mode is used for PFOA extraction of the material in the photocatalysis process so as to measure the degradation efficiency of PFOA (the step aims at testing the photocatalysis performance of the material and is not a necessary step in application);
(4) In contrast, the activated carbon/titanate composite (preparation method as described in example 1) was also used for PFOA removal experiments.
As shown in FIG. 4, the activated carbon/titanate composite material, the non-doped derived carbon/titanate composite material and the derived carbon/titanate composite material doped with different metals such as manganese, cobalt and copper can be adsorbed and removed with high efficiency, the removal rate is over 99 percent, wherein the adsorption performance of the manganese-doped CTCs material is optimal, the PFOA adsorption removal rate is up to 99.8 percent, which is mainly caused by the strong hydrophobicity of PFOA, and in addition, the initial concentration of PFOA in the experiment is lower (100 mug/L) and is intended to simulate the pollution degree in a real water environment. The difference in properties of the above materials is mainly manifested in terms of photocatalytic performance. Wherein, the photocatalysis performance of the active carbon/titanate composite material is the worst, about 40 percent of PFOA is only degraded in 4 hours, and the defluorination rate is only 23 percent. The defluorination rate is used as an important index for measuring the degradation and detoxification of the perfluoro/polyfluoroalkyl compounds, can characterize the degree of PFOA deep mineralization, and has more evaluation significance than the degradation rate of pollutants. In addition, the derivative carbon/titanate composite material has good PFOA degradation performance, and the degradation rate and defluorination rate respectively reach 64% and 37%. After metal doping, the photocatalytic performance of the composite material further improves the PFOA degradation rate of the composite material doped with manganese, cobalt and copper to be more than 85%, and the defluorination rate of the composite material is more than 60%, wherein the manganese doped CTCs show the most excellent photocatalytic performance, the PFOA degradation rate reaches 91%, and the PFOA defluorination rate reaches more than 63%.
Example 4
According to the invention, the derivative carbon prepared by high-temperature calcination of the ZIF-67 metal organic framework material is used as a carrier, the titanate material is modified, binary metal doping is carried out, and PFOA in water is removed.
Following the procedure in example 3, a derivatized carbon/titanate composite material was prepared without metal doping, and a highly dispersed metal cation solution was prepared at a concentration of 10mmol/L. Firstly, preparing a derived carbon/titanate composite material with binary doping of Mn and Co, wherein the mass ratio of Mn to Co is 1:2, carrying out material synthesis, wherein the mass of Mn is 1% of that of the undoped derivative carbon/titanate composite material. The undoped derivative carbon/titanate composite material is added into a manganese solution, is rapidly stirred for 30 minutes, is subjected to solid-liquid separation, and is subjected to primary annealing (300 ℃ C., 3 hours and nitrogen atmosphere) after being dried. After washing out the soluble impurities of the material, putting the material into cobalt solution, rapidly stirring for 30 minutes, performing solid-liquid separation, drying the material, and performing secondary annealing (300 ℃ for 3 hours and nitrogen atmosphere). And washing out soluble impurities again, drying the material, and then carrying out third annealing (550 ℃ C., 4 hours, argon atmosphere) to obtain the Mn-Co binary doped derivative carbon/titanate composite material. Secondly, preparing Mn-Cu binary doped derivative carbon/titanate composite materials, co-Cu binary doped derivative carbon/titanate composite materials and other materials by the same method. When Mn and Cu are subjected to binary doping, the mass ratio of Mn to Cu is 1: the doping amount of 2, mn is 1% of the total mass of the material. When Co and Cu are subjected to binary doping, the mass ratio of Co to Cu is 1: the doping amount of the Co is 1 percent of the total mass of the material.
The binary metal doped composite material is used for treating sewage containing PFOA, the PFOA concentration in the sewage is 100 mug/L, the pH of the sewage is neutral, and the using method is the same as that of the example 3.
As shown in fig. 5, the capability of removing PFOA by adsorption is still outstanding, and the photocatalytic performance is further remarkably improved under the same condition compared with the CTCs material doped with single metal. The PFOA adsorption removal rate of binary doped CTCs materials such as Mn-Co, mn-Cu, co-Cu and the like is higher than 99.5%, wherein the Mn-Cu binary metal doped composite material has the most outstanding photocatalytic capability, the PFOA removal rate is up to 99%, and the defluorination rate is up to 91%. Compared with single metal doped CTCs material, the PFOA photocatalytic degradation rate is improved by about 10%, but the defluorination rate is improved by about 30%. This shows that PFOA degradation products remain as relatively high molecular weight and relatively high toxicity products when single metal doped CTCs are used, whereas PFOA degradation products are mainly mineralized products when binary metal doped CTCs are used, and carbon dioxide and fluoride ions are far less toxic than macromolecular products. Therefore, the degradation of PFOA by using binary metal doped CTCs is a safer, efficient and green treatment scheme.
Comparative example 1
The preparation condition optimization process of the metal-free doped CTCs material and the influence on the material structure and performance:
1. when the concentration of NaOH is lower than 2mol/L, the titanium dioxide cannot realize crystal form reconstruction, titanate is difficult to form, when the concentration of NaOH is in the range of 8-10 mol/L, the overall performance of the material is best, when the concentration of NaOH is 8mol/L, the performance of the material for absorbing heavy metals is best, and when the concentration of NaOH is 10mol/L, the photocatalytic performance of the material is best;
2. when the hydrothermal temperature and the reaction time are not matched, the reaction time can be influenced:
(a) The ratio of conversion of titanium dioxide to titanate, possibly forming a mixture of titanium dioxide and titanate;
(b) The microcosmic appearance of the titanate, for example, when the reaction temperature is too low and the reaction duration is short, the titanate exists in a nano-sheet mode, or when the reaction temperature is too high and the reaction duration is too long, the interlayer spacing of the titanate is small, (200) crystal face exposure is weakened, the mass transfer process of pollutants and the photocatalysis performance of the titanate are affected, and the material performance is optimal only when materials are prepared at optimal hydrothermal temperatures and duration collocations (such as 130 ℃/72 hours, 150 ℃/48 hours and 180 ℃/12 hours);
3. the distribution of functional groups on the surface of different carbon raw materials is different from the properties such as specific surface area, and the mass ratio of titanium dioxide to derived carbon is different when the materials are prepared. For example, when the adding amount of titanium dioxide is too high, a large amount of titanium element can be resolved in the application of the material, pollution is caused, when the adding amount of derived carbon is too high, the heavy metal removing capability of the material is reduced, the regeneration rate of the material is slowed down, and the recycling efficiency of the material is seriously affected.
Comparative example 2
The optimization process of the preparation conditions of the single metal doped CTCs material and the influence on the material structure and performance:
1. the metal cation solution for doping must be added with sodium carboxymethyl cellulose as dispersant with molecular weight of 3000-15000 for dispersion, mn, co and Cu are distributed in the form of ultra-small clusters with diameter of about 2nm, and the quantum effect is obvious, thus greatly promoting the electron transmission and light absorption capacity of the material. If the dispersing agent or the dispersing agent with too small molecular weight is not added, the metal in the final preparation material exists in the form of particles with the size of about 20-100 nm, so that the quantum effect of Mn, co and Cu ultra-small clusters is lost, and the catalytic performance of the material is reduced, for example, mn doped CTCs material without adding the dispersing agent can only degrade 67% of PFOA after 4 hours, the catalytic performance of the material is similar to that of non-metal doped CTCs material, if the molecular weight of the dispersing agent is too high, the porous structure of the material is blocked, the specific surface area of the material is greatly reduced, and the adsorption capacity and the photocatalytic capacity of the material are simultaneously inhibited;
2. the material must be prepared by two-stage annealing, and the temperature, duration and gas atmosphere need to be controlled accurately. The first annealing at lower temperature is to realize the preliminary anchoring of the high-dispersion cations, avoid the agglomeration of the cations to form large particles, and simultaneously, the added sodium carboxymethyl cellulose can be converted into impurities with smaller molecular weight, so that the sodium carboxymethyl cellulose is convenient to clean and remove. The second high-temperature annealing is to thoroughly embed the metal ultra-small clusters into the crystal lattice of the titanate material, so as to improve the electron transfer capability of the material and promote the improvement of the photocatalytic performance. If only the first low-temperature annealing is carried out, metal elements doped in the material are easy to separate out, the material cannot be used for a plurality of times for a long time, if only the second high-temperature annealing is carried out, the dispersing agent can be converted into ultra-small carbon particles to block the pore channel structure of CTCs, and if the annealing is carried out in air (instead of argon or nitrogen), the metal with the highest total load can be in the form of metal oxide, which is also unfavorable for the photocatalytic performance of the material. For example, when Mn-loaded CTCs material is subjected to only low temperature annealing treatment, the degradation rate of PFOA is reduced by about 27% compared to new material in the second cycle, and for example, when Mn-loaded CTCs material is subjected to only high temperature annealing treatment, the PFOA adsorption kinetics is significantly slowed down and the PFOA photocatalytic degradation rate is reduced to 40% (4 hours reaction time). For another example, when annealing is performed in an air atmosphere, the photocatalytic performance of the prepared Mn-doped CTCs material is also obviously reduced, and a large amount of smoke generation can be observed during preparation, which is probably caused by decomposition of partial derivative carbon materials, so that the stability of the material is greatly improved.
Comparative example 3
The preparation condition optimization process of the binary metal doped CTCs material and the influence on the material structure and performance:
1. the binary metal doping must be divided into two steps to carry out the distribution doping of the two metals, the two metals cannot be mixed with each other and then doped at the same time, and the doping sequence of the two metals does not significantly influence the material performance. For example, when preparing Mn-Cu doped CTCs, if Mn and Cu cations are directly mixed and dispersant is added for preparation, mn-Cu alloy particles with large spatial distribution difference and uneven size distribution can appear in the synthesized material instead of ultra-small Mn clusters and Cu clusters with uniform distribution and size less than 2nm, and the defluorination rate of PFOA of the material by photocatalytic degradation is only 70 percent and is obviously lower than the optimal material performance. The core mechanism of improving CTCs by binary metal doping is to arrange ultra-small clusters of different transition metals in order, so that the d orbits of Mn element and Cu are mutually influenced, the coordination environment of a second area is changed, and the quantum effect is further improved;
when transition metals such as Mn, co, cu and the like are doped, the doping proportion and the doping amount need to be strictly controlled, and the main reason is to realize more orderly distribution of binary ultra-small metal clusters; for example, when Mn-Co is subjected to binary doping, when the mass ratio of Mn to Co is 1:8 and the doping amount of Mn is equal to 2.5% of the mass of the material, the 4-hour defluorination rate of the material for degrading PFOA is reduced to 61%, because the excessively high doping amount and the excessively high Co doping ratio cause tunneling effect, so that Co becomes a reaction center for photo-generated hole-electron pair recombination, and the generation amount of active species for degrading PFOA in the system is reduced. For another example, when Mn-Cu binary doping is carried out, the doping amount of Mn is maintained to be 1% of the mass of the material, but the mass ratio of Mn to Cu is 2:1, the prepared material is used for removing PFOA, the defluorination rate of the photocatalytic reaction for 4 hours is 83%, and the material is obviously lower than the material with the optimal proportion.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (10)
1. A method for preparing a derivative carbon/nano titanate composite material, which is characterized by comprising the following steps:
mixing titanium dioxide, derived carbon and NaOH solution as raw materials, performing hydrothermal reaction for 3-96 hours at the temperature of 110-210 ℃, performing solid-liquid separation, washing precipitate, and drying to obtain the derived carbon/nano titanate composite material; the derivative carbon is prepared by calcining a metal organic framework material at a high temperature, and the metal organic framework material is one or more of ZIF-8, ZIF-67 and MIL-88A.
2. The method according to claim 1, wherein the high-temperature calcination is performed in an inert atmosphere of nitrogen or argon at 550 to 1000 ℃ and the calcination is performed for 2 hours after the temperature reaches a predetermined temperature by using a three-stage gradient temperature-increasing method.
3. The preparation method according to claim 1, wherein the mass ratio of the titanium dioxide to the derived carbon is 1:5 to 10:1; and/or the concentration of the NaOH solution is 0.5-10 mol/L.
4. A method of preparing according to any one of claims 1 to 3, further comprising: adding the metal salt solution into the prepared derivative carbon/nano titanate composite material, uniformly mixing, standing, separating solid from liquid, drying, and calcining at high temperature in an inert atmosphere for the second time to obtain the metal-doped derivative carbon/nano titanate composite material.
5. The preparation method according to claim 4, wherein the addition amount of CTCs is 10 to 200 times the mass of the metal element to be doped; wherein the doped metal element comprises one or more of manganese, cobalt and copper.
6. The preparation method according to claim 5, wherein when Mn and Co are binary doped, the mass ratio of Mn to Co is 1: 2-1: 4, when Mn and Cu are subjected to binary doping, the mass ratio of Mn to Cu is 1: 2-1: 5, when Co and Cu are subjected to binary doping, the mass ratio of Co to Cu is 1:1 to 1:5.
7. the derivatized carbon/nano titanate composite material prepared by the preparation method according to any one of claims 1 to 6.
8. The use of the derivatized carbon/nanotitanate composite material of claim 7 for the synergistic removal of heavy metals and organic contaminants in water.
9. A method of water treatment or remediation, wherein the method employs the derivatized carbon/nanotitanate composite of claim 7 to treat water.
10. The method of water treatment or remediation according to claim 9 wherein the derivatized carbon/nanotitanate composite is used in a dosage range of 0.01 to 200kg/m 3 ；
And/or the concentration of contaminants in the water is greater than 20ng/L;
and/or, the applicable pH range is pH >2.8;
and/or, a suitable temperature is less than 50 ℃.
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| CN112736234A (en) * | 2021-01-15 | 2021-04-30 | 辽宁大学 | Novel lithium ion battery cathode material based on biomass/carbon nanotube composite modified lithium titanate and application thereof |
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