CN112661233A - System and process for removing heavy metal ions in water - Google Patents
System and process for removing heavy metal ions in water Download PDFInfo
- Publication number
- CN112661233A CN112661233A CN202011534234.6A CN202011534234A CN112661233A CN 112661233 A CN112661233 A CN 112661233A CN 202011534234 A CN202011534234 A CN 202011534234A CN 112661233 A CN112661233 A CN 112661233A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- adsorption
- metal ions
- carbon material
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a system and a process for removing heavy metal ions from water, wherein the system is provided with a first adsorption bed and a second adsorption bed which are connected in series, and the first adsorption bed and the second adsorption bed are filled with different adsorbents. The adsorption system and process can achieve removal of heavy metal ions at an economical cost.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a system and a process for removing heavy metal ions in water.
Background
With the rapid development of the industry in China, heavy metal pollution caused by industrial wastewater and industrial waste residue is increasingly serious. The heavy metal pollution of the water body is serious, and the heavy metal substances discharged into natural water bodies such as rivers, lakes, reservoirs, oceans and the like and water bodies such as industrial water, domestic water and the like processed by human exceed the self-cleaning capacity of the water body environment, so that the property and the composition of the water body are changed, the application of the water is influenced and destroyed, the common life and the living environment of the human are seriously influenced, the health of the human is harmed, and even the life of the human is harmed. In recent years, with the rapid development of industry, agriculture and social economy, the pollution of heavy metals in various water environments is more and more serious, and people pay more and more attention. The harm of heavy metal to human body is direct, not only can cause pollution in the aspect of environment, but also can cause threat to human health in food safety and cosmetics.
The treatment of heavy metal wastewater is paid attention by all countries in the world, heavy metal pollution has serious harm, and a lot of heavy metal wastewater is caused by industrial development, so that the heavy metal wastewater has great harm to the environment and human bodies. The heavy metal has stability and nondegradable property, has certain difficulty in treating heavy metal wastewater, cannot be decomposed and destroyed in structure, and can only change the existing form or position through some chemical reactions or physical actions. For example, the heavy metal existing in the form of ions is converted into a compound which is difficult to dissolve by a chemical precipitation method and is transferred out by a physical method such as precipitation filtration; transferring heavy metal from the solution to the surface and the inside of the adsorption material by using a physical adsorption method and adopting the adsorption material with macropores and specific surface area; the ion exchange method is used for absorbing and storing heavy metal ions and the like by using ion exchange resin.
CN104003462A discloses a heavy metal adsorption device, which comprises a shell, wherein a liquid inlet is arranged at the top of the shell, a liquid outlet is arranged at the bottom of the shell, at least two layers of microporous plates are detachably arranged in the shell, the microporous plates are horizontally arranged, the peripheral walls of the microporous plates are connected with the inner wall of the shell, and the diameters of the upper holes of the microporous plates are 0.1 um-0.1 mm; and adsorbents are paved on each layer of the microporous plate respectively.
CN103755113B discloses a sludge heavy metal ion adsorption and solid separation method, which comprises the steps of sludge dehydration, sludge drying, sludge deodorization, sterilization, crushing and adsorption and solid separation, and sludge heavy metal is decomposed by a microcrystal adsorption and solid separation method synthesized by natural clinoptilolite, a stabilizing agent and low-crystalline minerals.
CN103553173A discloses a method for removing heavy metal ions in wastewater by cyclone adsorption, which comprises the following steps: step 1: the mixed liquid of the adsorbent and the wastewater containing the heavy metal ions enters the micro-extraction sequencing coupling unit through the pressure and flow provided by the power unit, the adsorbent and the heavy metal ions fully perform adsorption, after the heavy metal ions are effectively extracted by a solid phase, the axial flow enters a micro-particle sequencing process, and sequencing is performed according to the particle size of adsorption particles; step 2: sorted extraction particles and waste water.
CN106186615A discloses a device for treating heavy metal cadmium in sludge. The device comprises a cadmium leaching module, a cadmium precipitation module and a cadmium adsorption module, and the method has the advantages of secondary removal, high cadmium removal rate and no introduction of new pollutants.
CN106045181A discloses a heavy metal industrial wastewater treatment device, heavy metal industrial wastewater treatment device comprises solid-liquid separation pond, intake pump, water intaking valve, smart filter tank, electrolysis jar, evaporating pot, calcium carbonate modified diatomaceous earth adsorption tank and drainage valve, the intake pump passes through the water intaking valve and links to each other with solid-liquid separation pond, and intake pump bottom and smart filter tank top link to each other, and the electrolyzing tank top links to each other with smart filter tank bottom, and the evaporating pot top links to each other with the electrolysis jar bottom, and the evaporating pot top links to each other with calcium carbonate modified diatomaceous earth adsorption tank top, and drainage valve establishes on calcium carbonate modified diatomaceous earth adsorption tank.
CN102815831A discloses a device and a method for treating heavy metal wastewater and recovering heavy metals, wherein the device comprises an aeration flocculation-adsorption tank, a sedimentation tank, a filter tank, a chelation reaction device and an electrolytic tank. After the organic flocculation and the inorganic adsorption, the wastewater containing heavy metal is treated, so that the treated wastewater is recycled.
CN104150480A discloses a preparation method of activated carbon with ultra-high specific surface area for adsorbing heavy metals, which comprises the steps of drying and crushing a biomass raw material into 60-100 meshes, putting the crushed biomass raw material into a microwave reactor, and introducing N2And controlling the microwave power and the carbonization temperature to carry out microwave carbonization, and cooling after 50-100 min of microwave carbonization to obtain the carbonized material. Grinding and uniformly mixing the carbonized material and an organic alkoxide activating agent according to the mass ratio of 1: 1-10, putting the mixture into an atmosphere furnace, heating to 800-1000 ℃, preserving heat for 100-300 min, cooling to room temperature, taking out, washing with hydrochloric acid, washing with water to be neutral, and drying to obtain the activated carbon.
"research progress of activated sludge for adsorbing heavy metal ions", shengxiang and so on, industrial water and wastewater, in 2006, 04 th, starting from the current situation of treating wastewater containing heavy metal ions, the research briefly describes surface organic complexation, ion exchange and other mechanisms in the process of adsorbing heavy metal ions by activated sludge, discusses the influence of factors such as temperature, time, pH value, sludge type, pretreatment, heavy metal ion concentration and so on the adsorption of heavy metal ions by activated sludge, discusses the desorption mode, summarizes the latest research results of activated sludge for adsorbing heavy metal ions at home and abroad at present, and points out that the research for further enhancing the adsorption mechanism and immobilization technology to improve the applicability of activated sludge is the future direction.
In the above-mentioned documents and other prior arts, the removal of heavy metal ions is usually performed by using a single adsorbent or adsorbent bed, resulting in either poor adsorption effect or high adsorbent cost. There is a need in the art for an integrated adsorption system and process that provides good adsorption of heavy metal ions at low cost.
Disclosure of Invention
In order to solve the above problems, the present inventors have made extensive system studies and extensive experiments to provide a system (i.e., an apparatus system) and a process for removing heavy metal ions from water, which effectively solve the above technical problems by using an adsorbent having a relatively low adsorption efficiency at a low cost in synergistic combination with an adsorbent having a relatively high adsorption efficiency at a low cost.
In one aspect of the invention, a system for removing heavy metal ions from water is provided having first and second adsorption beds in series packed with different adsorbents, the first adsorption bed being upstream of the second adsorption bed in the direction of flow of the aqueous solution.
Preferably, the first adsorption bed is filled with a carbon material. More preferably, the carbon material is biochar.
Preferably, the second adsorbent is filled with a surface-modified carbon material, preferably a surface-modified biochar. The biochar used for modification is preferably the same as the carbon material of the first adsorption bed.
For the purposes of the present invention, the surface of the surface-modified biochar contains nitrogen atoms which can complex with heavy metals.
Preferably, the system comprises a water inlet, an upper pressure plate, an uniform water distribution plate, an upper fixed pore plate, a protective bed, a first adsorption bed, a second adsorption bed, a lower fixed pore plate, a lower pressure plate and a water outlet which are sequentially arranged from upstream to downstream. Sampling ports may be provided at the sides of the first adsorption bed and the second adsorption bed.
The heavy metal ion may be selected from Cu2+、Pb2+、Cd2+、Cr6+One or more of (a).
In another aspect of the present invention, there is provided a process for removing heavy metal ions using the above system, which comprises passing an aqueous solution containing heavy metal ions sequentially through first and second adsorption beds of the system.
Preferably, the total residence time of the aqueous solution containing heavy metal ions in the first adsorption bed and the second adsorption bed is from 30min to 90 min. Also preferably, wherein the pH of the aqueous solution containing heavy metal ions is adjusted to 6 to 8 before adsorption.
In this process, the pressure of the aqueous solution is preferably 0.1 to 0.5 MPa.
The guard bed is preferably filled with a material selected from the group consisting of diatomaceous earth, molecular sieves, alumina, silica, preferably with diatomaceous earth.
The guard bed, the first adsorption bed and the second adsorption bed can be separated by a partition plate or a diaphragm.
In a particularly preferred embodiment, the carbon material packed in the first adsorption bed and the carbon material used to prepare the surface modification in the second adsorption bed can be prepared by a process comprising the steps of: (1) crushing cotton straws into fine particles, wherein the longest particle size of the crushed cotton straws is less than 2.0 mm; (2) soaking fine particles of cotton straw powder in NH4Soaking in Cl solution at 50-80 deg.C for 1-5 hr; (3) taking out the soaked cotton straw fine particles in the step (2) through filtration, and airing; (4) placing the dried fine particles of the cotton straws in a container, introducing water vapor with the temperature of 300-650 ℃, and heating for 2-10 h; (5) then cooling to room temperature, fully washing the carbonized product with hydrochloric acid solution, washing with distilled water until the pH of the washing solution is 6-7, preferably 6.5, and drying to obtain the carbon material. The carbon material may be filled inAn adsorbent bed and can be used for preparing carbon materials with subsequent surface modification.
Preferably, the water vapor (also referred to as steam) is free of oxygen.
The water vapour preferably comprises 10-50% by volume of water vapour of nitrogen.
In the process of the invention, the NH4The Cl solution is an aqueous solution, and the concentration of the Cl solution is 0.1-0.5 mol/L.
Preferably, the temperature of the water vapor is 500 ℃.
The cotton straw and NH4The mass ratio of the Cl solution is preferably 1:2 to 1: 5.
Optionally and preferably, before the step (1), the method further comprises the step of pretreating the cotton stalks, wherein the pretreatment comprises removing cotton leaves and cotton hulls on the cotton stalks.
The container may be a charring container. The charring vessel is preferably a tube furnace or a tunnel heating vessel.
Compared with the carbon prepared by the commonly adopted dry distillation (thermal decomposition) or decomposition by adopting inert gas such as nitrogen as carrier gas, the carbon material prepared by the method has rich pore structure due to the high permeability of high-temperature steam, relatively low carbonization temperature and short carbonization time.
The method can also obtain higher carbon yield, and the yield of the carbon material of the method is 50-70%, preferably 65%. In contrast, in the method of thermal decomposition using nitrogen as a carrier gas, the char yield or char yield was about 40%.
Further, the present inventors have also developed a novel activator represented by the following formula (I) which can replace NH4Cl activator:
the compound has good pore-forming effect, can be particularly favorable for forming macropores in a carbon material, and has an activation effect superior to that of NH4Cl and zinc chloride.
The activator of formula (I) can be prepared by the following method: adding imidazole and 1-bromobutane into a DMF solution according to a stoichiometric ratio, heating and refluxing for 1-3h, cooling to room temperature, filtering, decompressing the filtrate to remove the DMF solvent, adding a cold hydrochloric acid solution, stirring for 1-2h at room temperature, and decompressing and concentrating to obtain a yellow oily substance, namely the activating agent shown in the formula (I).
By using activators of the formula (I) with NH4Compared with the activator of Cl, the proportion of macropores can be improved by 20-30 percent, and the catalyst is compared with ZnCl2Compared with the prior art, the proportion of macropores can be increased by 5-10%, which is more beneficial to improving the adsorption capacity.
Compared with the simple steam carbonization, the invention has the advantages that the existence of the nitrogen can improve the heat value of the carbonization medium and the heating efficiency, thereby improving the carbonization efficiency, simultaneously saving the consumption of the steam, and in addition, the required steam partial pressure can be adjusted by adding the nitrogen, so that the process operation is more flexible.
In the step (4), the water vapor pressure is preferably 0.1 to 0.5 MPa.
In a preferred embodiment, the BET specific surface area (S) of the carbon material of the present inventionBET) 500-1900m2/g, preferably 1800-2(ii) in terms of/g. At P/P0The total pore volume Vtotal measured below is 0.90-1.25cm3(ii)/g, the average pore diameter D is 2.30-2.65 nm. The carbon material of the present invention has an average particle diameter of 30 to 1000nm, preferably 50 to 500 nm.
More preferably, the carbon material of the present invention is enriched in oxygen-containing functional groups, particularly hydroxyl groups, on the surface. The oxygen-containing functional group is rich in favor of the subsequent modification, for example, the hydroxyl group may be partially or completely reacted with aminopropyltriethoxysilane.
The surface-modified carbon material packed in the second adsorption bed may be represented by the following formula (II):
wherein the N atom can complex with a heavy metal. The steric structure formed by the two ortho hydroxyl groups provides good selectivity for the adsorbent, so that the adsorbent is particularly beneficial to Pb2+Or Cd2+Adsorption of, in particular, Pb2+And Cr6+Adsorption of (3). In addition, the electron-withdrawing action of the hydroxyl groups also enhances the coordination ability of N to heavy metals.
The modification method preferably comprises the steps of:
(1) adding carbon material (such as carbon material obtained by carbonizing straw such as cotton straw) into toluene solution, adding aminopropyltriethoxysilane, heating and refluxing for 24 hr under slow stirring, cooling to room temperature, taking out sludge particles, and washing with petroleum ether to obtain sludge particles with silanized surface. Wherein the weight ratio of the carbon material to the toluene is preferably 1 (3-20); the weight ratio of the carbon material to the aminopropyltriethoxysilane is 1 (0.0001-0.2), preferably 1: 0.001.
(2) And (2) adding the carbon material obtained in the step (1) into absolute ethyl alcohol, slowly adding 2, 6-dihydroxybenzaldehyde under the protection of nitrogen, refluxing for 1-2h, cooling to room temperature, filtering, washing with distilled water, and drying under reduced pressure to obtain the surface-modified carbon material. The surface modified carbon material can be used as a heavy metal ion adsorbent. The drying under reduced pressure is preferably carried out at 40 to 80 ℃.
The surface modified carbon material obtained by the method has the advantages of high adsorption capacity and selectivity and low manufacturing cost.
Drawings
FIG. 1 is an SEM image of a surface modified carbon material obtained according to a method;
FIG. 2 is a schematic diagram of a system according to the present invention; wherein 1: a water inlet; 2: an upper pressure plate; 3: a uniform water distribution plate; 4: an upper fixed orifice plate; 5: a protective bed; 6: a first adsorption bed; 7: a second adsorption bed; 8: a sampling port; 9: a lower fixed orifice plate; 10: a lower pressing plate; 11: and (7) a water outlet.
Detailed description of the preferred embodiments
The present invention will be described in further detail below with reference to the following examples and comparative examples, but the embodiments of the present invention are not limited thereto.
Example 1
The system for removing heavy metal ions in water comprises a water inlet 1, an upper pressure plate 2, an uniform water distribution plate 3, an upper fixed pore plate 4, a protective bed 5, a first adsorption bed 6, a second adsorption bed 7, a lower fixed pore plate 9, a lower pressure plate 10 and a water outlet 11 which are sequentially arranged from upstream to downstream. The side parts of the first adsorption bed 6 and the second adsorption bed 7 are provided with sampling ports 8. The first adsorption bed and the second adsorption bed are arranged in series, the first adsorption bed is filled with carbon materials, and the second adsorbent is filled with surface modified carbon materials.
Example 2
Preparation of the carbon material used in example 1: the cotton stalks are taken from Taixian county in Henan, the mature cotton stalks harvested in the year are taken, the leaves and the shells are removed, the lateral branches do not need to be removed, and the cotton stalks are stored in a laboratory for ventilation and shade for standby. Crushing cotton straws into fine particles, wherein the longest particle size of the crushed cotton straws is less than 2.0 mm; soaking the fine particles of the cotton stalks in 0.2mol/L NH4Soaking in Cl solution at 60 deg.C for 4 hr, taking out the soaked cotton stalk fine particles, and air drying; placing the dried cotton straw fine particles in a container, introducing water vapor with the temperature of 500 ℃, heating for 6h, cooling to room temperature, fully washing the carbonized product with a dilute hydrochloric acid solution, washing with distilled water until the pH of the washing solution is 6-7, and drying to obtain the carbon material, wherein the carbon material can be filled in the first adsorption bed in the embodiment 1 and can be reserved for subsequent surface modification.
Example 3
Preparing a surface modified carbon material: adding the carbon material prepared in the example 2 into a toluene solution, then adding aminopropyltriethoxysilane, heating and refluxing for 24 hours under slow stirring, cooling to room temperature, taking out sludge particles, and washing with petroleum ether to obtain sludge particles with silanized surfaces. Wherein preferably, the weight ratio of the carbon material to the toluene is 1: 8; the weight ratio of the carbon material to the aminopropyltriethoxysilane is 1: 0.05; adding the obtained carbon material into absolute ethyl alcohol, slowly adding 2, 6-dihydroxy-4-benzaldehyde under the protection of nitrogen, refluxing for 2h, cooling to room temperature, filtering, washing with distilled water, and drying under reduced pressure at 60 ℃ to obtain a surface-modified carbon material, wherein the surface-modified carbon material can be used as a filling material of the second adsorption bed in example 1.
Example 4
Using the system of example 1, the first adsorbent bed was packed with the carbon material obtained in example 2, and the second adsorbent bed was packed with the surface-modified carbon material obtained in example 3. Use of the system for Pb2+The aqueous solution of (1) has a concentration of 0.06mg/L, a maximum pressure of 0.2MPa, and contains Pb2+The total residence time of the aqueous solution in the first adsorption bed and the second adsorption bed was 45 min. Through testing, the water outlet Pb2+The concentration of (3) was 0.0001 mg/L. In addition, the detection shows that Pb in the water solution entering the second adsorption bed2+The concentration of (B) was 0.019 mg/L. Most Pb on the surface2+The ions are removed by the first adsorption bed, and the second adsorption bed enables Pb in the aqueous solution to be removed due to the strong adsorption capacity of the second adsorption bed2+The concentration is reduced to a lower value so that it meets the required criteria.
Comparative example 1
The operation of example 4 was repeated except that the carbon materials of the first adsorption bed and the second adsorption bed were each the carbon material obtained in example 2 without surface modification. Through testing, the water outlet Pb2+The concentration of (2) was 0.015 mg/L.
As can be seen from the above examples and comparative examples, the surface-modified carbon material obtained by the method of the present invention has a high heavy metal ion adsorption capacity, particularly for the most harmful Pb2+Has very good adsorption selectivity. And the second adsorption bed does not actually bear a major portion of Pb2+Thereby prolonging the service life of the second adsorption bed with higher cost, and realizing the best comprehensive economic benefit.
This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. All citations referred to herein are incorporated herein by reference to the extent that no inconsistency is made.
Claims (10)
1. A system for removing heavy metal ions from water has first and second adsorption beds in series packed with different adsorbents, the first adsorption bed being upstream of the second adsorption bed in the direction of flow of the aqueous solution.
2. The system of claim 1, the first adsorbent bed being packed with a carbon material.
3. The system of claim 2, the carbon material being biochar.
4. The system of any one of the preceding claims, the second adsorbent being filled with a surface-modified carbon material.
5. The system of claim 4, wherein the surface of the surface-modified biochar comprises nitrogen atoms that can complex with heavy metals.
6. The system of claim 1 or 2, wherein the heavy metal ions are selected from Cu2+、Pb2+、Cd2+、Cr6+One or more of (a).
7. A process for removing heavy metal ions using a system according to any preceding claim, the process comprising passing an aqueous solution containing heavy metal ions sequentially through first and second adsorption beds of the system.
8. The process according to claim 7, wherein the total residence time of the aqueous solution containing heavy metal ions in the first and second adsorption beds is from 30min to 90 min.
9. The process according to claim 7 or 8, wherein the pH of the aqueous solution containing heavy metal ions is adjusted to 6 to 8.
10. The process according to claim 7 or 8, wherein the pressure of the aqueous solution is between 0.1 and 0.5 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011534234.6A CN112661233A (en) | 2020-12-22 | 2020-12-22 | System and process for removing heavy metal ions in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011534234.6A CN112661233A (en) | 2020-12-22 | 2020-12-22 | System and process for removing heavy metal ions in water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112661233A true CN112661233A (en) | 2021-04-16 |
Family
ID=75407936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011534234.6A Pending CN112661233A (en) | 2020-12-22 | 2020-12-22 | System and process for removing heavy metal ions in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112661233A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55159835A (en) * | 1979-05-30 | 1980-12-12 | Unitika Ltd | High selective heavy metal ion adsorbing agent, and method of preparation and adsorption thereof |
| CN101486498A (en) * | 2008-01-18 | 2009-07-22 | 罗门哈斯公司 | Adsorbent bed for water treatment |
| CN104003462A (en) * | 2014-06-14 | 2014-08-27 | 济南米铎碳新能源科技有限公司 | Heavy metal adsorption device |
| CN104475065A (en) * | 2014-12-16 | 2015-04-01 | 湖南科技大学 | Efficient heavy-metal-ion absorbent material and preparation method thereof |
| CN104785212A (en) * | 2014-01-21 | 2015-07-22 | 中国科学院过程工程研究所 | Biomass adsorbent, and preparation method and applications thereof |
| CN104941589A (en) * | 2015-06-15 | 2015-09-30 | 西部矿业股份有限公司 | Preparation method of porous biological carbon heavy metal adsorbing material based on cotton straw |
| CN105253946A (en) * | 2015-11-05 | 2016-01-20 | 中国电建集团华东勘测设计研究院有限公司 | Multistage activated carbon adsorption bed system based on selective adsorptive purification theory and preparation method of multistage activated carbon adsorption bed system |
| CN105413624A (en) * | 2015-12-09 | 2016-03-23 | 中国科学院新疆理化技术研究所 | Preparation method for modified silicone absorption materials for treating anionic dye in waste water |
| CN206108968U (en) * | 2016-08-19 | 2017-04-19 | 农业部环境保护科研监测所 | Water heavy metal ion's three -dimensional adsorption bed |
| WO2018007150A1 (en) * | 2016-07-06 | 2018-01-11 | Clariant International Ltd | Low cost lignin-based adsorption materials for water treatment |
-
2020
- 2020-12-22 CN CN202011534234.6A patent/CN112661233A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55159835A (en) * | 1979-05-30 | 1980-12-12 | Unitika Ltd | High selective heavy metal ion adsorbing agent, and method of preparation and adsorption thereof |
| CN101486498A (en) * | 2008-01-18 | 2009-07-22 | 罗门哈斯公司 | Adsorbent bed for water treatment |
| CN104785212A (en) * | 2014-01-21 | 2015-07-22 | 中国科学院过程工程研究所 | Biomass adsorbent, and preparation method and applications thereof |
| CN104003462A (en) * | 2014-06-14 | 2014-08-27 | 济南米铎碳新能源科技有限公司 | Heavy metal adsorption device |
| CN104475065A (en) * | 2014-12-16 | 2015-04-01 | 湖南科技大学 | Efficient heavy-metal-ion absorbent material and preparation method thereof |
| CN104941589A (en) * | 2015-06-15 | 2015-09-30 | 西部矿业股份有限公司 | Preparation method of porous biological carbon heavy metal adsorbing material based on cotton straw |
| CN105253946A (en) * | 2015-11-05 | 2016-01-20 | 中国电建集团华东勘测设计研究院有限公司 | Multistage activated carbon adsorption bed system based on selective adsorptive purification theory and preparation method of multistage activated carbon adsorption bed system |
| CN105413624A (en) * | 2015-12-09 | 2016-03-23 | 中国科学院新疆理化技术研究所 | Preparation method for modified silicone absorption materials for treating anionic dye in waste water |
| WO2018007150A1 (en) * | 2016-07-06 | 2018-01-11 | Clariant International Ltd | Low cost lignin-based adsorption materials for water treatment |
| CN206108968U (en) * | 2016-08-19 | 2017-04-19 | 农业部环境保护科研监测所 | Water heavy metal ion's three -dimensional adsorption bed |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jiang et al. | Removal and recovery of phosphate from water by Mg-laden biochar: batch and column studies | |
| CN104289185A (en) | Granular filtering material for adsorbing and removing heavy metals in water and preparation method thereof | |
| CN111686694B (en) | MIL-101 material preparation method and application | |
| CN108380214B (en) | A kind of preparation of modified meerschaum and method applied to wastewater treatment | |
| CN114160098B (en) | Preparation method of alkali/bimetallic salt water heat activated sludge biochar for removing norfloxacin in water | |
| CN102897894B (en) | Combined unit type equipment for treating industrial wastewater by ozone catalyzing method | |
| CN107010709B (en) | Method for purifying high-concentration phenol-containing wastewater in production process of o/hydroquinone | |
| CN113042004B (en) | Preparation method and application of modified carbon-based material | |
| CN106943835A (en) | The method that a kind of utilization sludge and feces of livestock and poultry prepare material for air purification and composite fertilizer | |
| CN112892476A (en) | Biochar composite material and preparation method and application thereof | |
| CN114160136B (en) | Preparation method of copper-iron-attapulgite-chitosan catalyst applied to heterogeneous Fenton-like system under condition of wide pH range | |
| CN101104141A (en) | Technique method for preparing active carbon-oxide composite absorbing material and polysilicate-aluminium from coal gangue | |
| CN106552615A (en) | The preparation method of Concave-convex clay rod composite catalyzing material | |
| CN110523378B (en) | Application of cyanobacteria mud in algae-water separation station in preparation of biomass activated carbon and in tail water algal toxin adsorption | |
| CN105271221B (en) | A kind of method that activated carbon is prepared using shell | |
| CN112661233A (en) | System and process for removing heavy metal ions in water | |
| CN111268758A (en) | Treatment method of phenol wastewater | |
| CN111298761A (en) | Modified sepiolite adsorbent and preparation method and application thereof | |
| CN114409009A (en) | Method for adsorbing hydroquinone based on polymer PIM-1 | |
| CN110876918B (en) | Preparation method of efficient nitrate radical treating agent | |
| CN109289783B (en) | Arsenic-removing compound adsorbing material prepared from garlic straw waste and using method | |
| CN109647336B (en) | Composite adsorbent for efficiently removing heavy metal ions in wastewater and preparation method thereof | |
| CN101717147B (en) | Method for removing ammonia nitrogen in water by utilizing synergism of ozone and leaves | |
| CN110876919A (en) | Preparation method of high-salinity wastewater nitrate radical adsorbent | |
| CN106139724B (en) | For removing the filter device of 4-TBP in drinking water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20230228 |