CN105802631B - Transition state iron-based heavy metal immobilized reagent and preparation method thereof - Google Patents
Transition state iron-based heavy metal immobilized reagent and preparation method thereof Download PDFInfo
- Publication number
- CN105802631B CN105802631B CN201610277720.1A CN201610277720A CN105802631B CN 105802631 B CN105802631 B CN 105802631B CN 201610277720 A CN201610277720 A CN 201610277720A CN 105802631 B CN105802631 B CN 105802631B
- Authority
- CN
- China
- Prior art keywords
- iron
- solution
- substrate material
- powder
- acid solution
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a transition state iron-based heavy metal immobilized reagent and a preparation method thereof. The immobilized reagent can stably fix the heavy metal in the soil for a long time.
Description
Technical Field
The invention belongs to the field of soil heavy metal pollution remediation, and particularly relates to a transition-state iron-based heavy metal immobilized reagent and a preparation method thereof.
Background
With the increasing world population, the problems of food production and safety are urgent, and the Chinese agriculture is the first time. The farmland pollution is an important restriction factor of high yield of grains, so that the comprehensive agricultural production capacity is reduced, the sustainability of agricultural production, the quality of agricultural products and the national ecological environment safety of China are influenced, and the wide attention of people is attracted. Among many factors of farmland pollution, chemical fertilizers, pesticides, sewage irrigation and the like are main causes of farmland pollution. Heavy metal pollution is particularly remarkable due to the difficulty and great harm of heavy metal pollution treatment. According to preliminary statistics, the irrigation area of the national sewage reaches 5400 mu of ten thousand, 100 hundred million kilograms of grains are reduced due to heavy metal pollution every year, 120 hundred million kilograms of grains with standard pollution exceed the standard, and the total economic loss exceeds 200 million yuan; more than 4000 million people live in the sewage irrigation area for a long time, 2.5 hundred million people are directly threatened by polluted cultivated land, and the physical health of 13 hundred million people in China is concerned by the pollution of the cultivated land.
At present, the following approaches are mainly used for repairing the heavy metal pollution of soil: firstly, the existence state of heavy metals in soil is changed, and the mobility and bioavailability of the heavy metals in the environment are reduced (immobilization technology); secondly, removing heavy metals from the soil by using a biological or engineering technical method; thirdly, the planting system is changed, and heavy metals are prevented from entering the human body through the food chain transmission. The immobilization technology is a soil pollution remediation technology which is earliest in research, wider in application, mature and complete in technology at present.
The immobilization of the heavy metals in the nanometer zero-valent iron series is a new immobilization technology in the prior immobilization technology. According to the traditional nano zero-valent iron immobilized reagent, nano zero-valent iron is loaded on a substrate material through surface modification, on one hand, the nano zero-valent iron has strong adsorption activity and can adsorb heavy metal or form a compound on the surface of the zero-valent nano iron, meanwhile, the zero-valent iron can generate hydroxide ions through oxygen absorption reaction, and the hydroxide ions can promote the heavy metal to be precipitated; on the other hand, the substrate material generally has a certain pore structure and a certain specific surface area, and can not only disperse the nano zero-valent iron, but also generate the synergistic effect of adsorbing heavy metal ions with the nano zero-valent iron.
However, the realization of the immobilization of heavy metal ions with zero-valent nano-iron or base materials has its drawbacks not negligible. The fixed heavy metal ions are easy to be released again along with the change of the environment because the fixed heavy metal ions cannot form stable bonding action with the curing agent (for example, when the concentration of the heavy metal ions in the farmland is reduced due to the replacement of the water body or the pH of the water body is reduced, the fixed heavy metal ions are likely to be released again).
Disclosure of Invention
The invention aims to solve the problems of the traditional nano zero-valent iron immobilized reagent and provides a transition-state iron-based heavy metal immobilized reagent which can efficiently, permanently and stably fix heavy metals in soil.
The invention also aims to provide a transitional iron-based heavy metal immobilization reagent which has simple preparation process and can efficiently, permanently and stably immobilize heavy metals in soil.
The technical scheme of the invention is as follows:
a preparation method of a transition state iron-based heavy metal immobilized reagent comprises the steps of loading nanometer zero-valent iron on the surface of a substrate material, adding the substrate material loaded with the nanometer zero-valent iron into a weak acid solution for reaction, converting the nanometer zero-valent iron loaded on the surface of the substrate material into transition state iron, washing and drying to obtain the immobilized reagent.
The invention further comprises the following preferred technical scheme:
in a preferred scheme, the solid-liquid mass ratio of the base material loaded with the nano zero-valent iron to the weak acid solution is 1:20-1: 50.
In a preferred embodiment, the reaction is carried out at 10 to 30 ℃.
In a preferred scheme, the weak acid solution is an acetic acid solution, and the mass percentage concentration of the weak acid solution is 2% -5%.
In a preferred embodiment, the reaction time is 2-10 min.
In a preferred scheme, the process of loading the nano zero-valent iron on the surface of the substrate material comprises the following steps: dispersing a substrate material in deionized water, performing ultrasonic treatment, adding the dispersed powder suspension into a hydrochloric acid solution for acid treatment, washing and drying to obtain powder I, dispersing the powder I in a soluble iron salt solution, washing and drying to obtain powder II, further dispersing the powder II in a reducing agent solution for reduction reaction, washing and drying to obtain the substrate material loaded with the nano zero-valent iron.
In a preferred scheme, the substrate material is one or more of attapulgite, kaolin, sepiolite, montmorillonite, diatomite and halloysite.
In a preferred scheme, the reducing agent is potassium borohydride or hydrazine hydrate; the mass percentage concentration of the hydrochloric acid solution is 1-10%, and the mass ratio of the dispersed powder suspension to the hydrochloric acid solution is 1:20-1: 50.
In a preferred scheme, the solid-liquid mass ratio of the powder I to the soluble iron salt solution is 1:20-1:50, and the soluble iron salt solution is FeCl2Or FeCl3The pH value of the solution is 6-8, and the mass percentage of Fe in the soluble ferric salt to the powder I is 4-12%. In the preferred scheme, the mass percentage concentration of the potassium borohydride solution or the hydrazine hydrate solution is 1-10%, the solid-liquid mass ratio of the powder II to the potassium borohydride solution or the hydrazine hydrate solution is 1:20-1:50, and the reduction reaction temperature is 10-30 ℃.
The invention further relates to a transition state iron-based heavy metal immobilization reagent prepared by the method.
Further preferably, the preparation method comprises the following steps:
1) dispersing attapulgite powder in deionized water, and performing ultrasonic treatment for 5-10min at a solid-liquid mass ratio of 1:20-1:50 to obtain a well dispersed powder suspension;
2) adding the dispersed powder suspension into a hydrochloric acid solution, and stirring at the temperature of 10-50 ℃ for 1-3 h;
3) washing with deionized water and anhydrous ethanol, and drying at 30-50 deg.C;
4) dispersing the dried powder I in a soluble ferric salt solution and continuously stirring, wherein the reaction temperature is 30-80 ℃, and the reaction time is 1-12 h;
5) cooling, washing with deionized water and anhydrous ethanol respectively, filtering, and drying at 30-50 deg.C;
6) dispersing the dried powder II into a potassium borohydride solution for reaction for 10-30 min;
7) washing with deionized water and anhydrous ethanol respectively, filtering, and drying at 10-30 deg.C;
8) further dispersing in acetic acid solution for secondary acid treatment;
9) washing with deionized water and absolute ethyl alcohol, drying at 20-40 deg.C to obtain immobilized reagent.
The invention has the advantages of
In the preparation process, firstly, strong acid is used for activating the surface of the attapulgite to form a large number of broken bonds, and then iron is used for modifying. Then reducing the iron ions absorbed by the attapulgite into zero-valent iron by using a reducing agent. And then treating with weak acid solution to remove zero-valent iron in the composite structure of zero-valent iron-transition state iron-attapulgite and leave the transition state iron fixed on the surface of the attapulgite.
Wherein the soluble iron salt is preferably FeCl2Or FeCl3。
Compared with the traditional iron modified complex reagent, the invention has the following essential differences:
the immobilized reagent can efficiently and stably fix the heavy metal in the soil for a long time.
The immobilization of the heavy metals in the nanometer zero-valent iron series is a new immobilization technology in the prior immobilization technology. But the fixed heavy metal is easy to be released again along with the change of the environment (for example, when the concentration of the heavy metal ions in the farmland is reduced due to the replacement of the water body or the pH value of the water body is reduced, the fixed heavy metal ions are likely to be released again). In contrast, the inventors have found that the effect of stably fixing the heavy metal in the soil for a long time can be achieved unexpectedly by adding the substrate material loaded with the nano zero-valent iron into a weak acid solution for treatment and then using the substrate material for treating the soil polluted by the heavy metal.
The invention is just the opposite, and the loaded zero-valent iron is further treated by weak acid solution, the zero-valent iron in the composite structure of the zero-valent iron-transition state iron-base material is removed, and the transition state iron fixed on the surface of the base material is left.
The transition state iron forms a bond with the matrix material, and can adsorb heavy metal ions in the solution and react with the heavy metal ions to generate an Fe-O-M structure (M is heavy metal), thereby achieving the purpose of fixing the heavy metal ions. Compared with the adsorption of zero-valent iron on heavy metal ions, the bonding of transition state iron and the heavy metal ions is more beneficial to the fixation of the heavy metal.
Although surface-loaded zero-valent iron can be used to immobilize heavy metals, such immobilization is susceptible to re-release by environmental influences, particularly pH changes; removing zero-valent iron seems to reduce the fixing effect on heavy metals, and the heavy metals are actually fixed on transition state iron, so that the permanent fixation of the heavy metals is realized.
In addition, since the clay mineral has a formable property, the immobilizing agent of the present invention can be prepared in a specific shape to facilitate permanent removal of immobilized heavy metals from soil.
Drawings
FIG. 1 is a photograph of the iron-based heavy metal-immobilizing reagent in the transition state obtained in example 1.
FIG. 2 is an FTIR spectrum of the transition iron-based heavy metal immobilization reagent obtained in example 1. 982 and 1039cm can be seen from the figure-1Belonging to the Fe-O vibration of Si-O-Fe.
Detailed Description
The following is an example of a specific embodiment of the present invention, but the present invention is not limited to the following embodiment.
Example 1
The preparation method of the immobilized reagent comprises the following steps:
1. dispersing attapulgite powder in deionized water, and treating with ultrasonic wave for 5min at a solid-liquid mass ratio of 1:20 to obtain well dispersed powder suspension;
2. adding the dispersed powder suspension into a hydrochloric acid solution for acid treatment, wherein the mass percentage concentration of the hydrochloric acid solution is 5%, the stirring temperature is 30 ℃, the stirring time is 1h, and the mass ratio of the dispersed powder suspension to the hydrochloric acid solution is 1: 20;
3. washing the powder after acid treatment with deionized water and absolute ethyl alcohol twice respectively, filtering and drying, wherein the drying temperature is 30 ℃;
4. dispersing the dried powder I in a soluble iron salt solution and continuously stirring, wherein the solid-liquid mass ratio of the powder I to the iron salt solution is 1:20, the pH value of the solution is 6, and the soluble iron salt is FeCl3The mass percent of Fe and the powder I is 4 percent, the reaction temperature is 40 ℃, and the reaction time is 4 hours;
5. naturally cooling the reacted sample, washing with deionized water and absolute ethyl alcohol twice, filtering and drying, wherein the drying temperature is 30 ℃;
6. dispersing the dried powder II into a reducing agent solution for reaction, wherein the reducing agent solution is potassium borohydride, the mass percentage concentration of the potassium borohydride solution is 4%, the solid-liquid mass ratio of the powder II to the reducing agent solution is 1:20, the reaction temperature is 30 ℃, and the reaction time is 10 min;
7. washing with deionized water and absolute ethyl alcohol twice, filtering and drying, wherein the drying temperature is 30 ℃;
8. further dispersing the mixture into an acetic acid solution for secondary acid treatment, wherein the mass percentage concentration of the acetic acid solution is 5%, the solid-liquid mass ratio of the base material loaded with the nano zero-valent iron to the acetic acid solution is 1:20, the reaction temperature is 15 ℃, and the reaction time is 5 min;
9. washing with deionized water and absolute ethyl alcohol twice, filtering and drying to obtain the final immobilized reagent, wherein the drying temperature is 30 ℃.
Comparative example 1
Example 1 was followed except that steps 8-9 were not included.
Immobilization experiment
1.0g of the sample prepared in example 1 was added to 100mL of a simulated soil leacheate with a pH of 7 and a Cd concentration of 52ug/mL and stirring was continued at room temperature for 12h, reducing the Cd concentration to 3.5 ug/mL. And (3) adjusting the pH value of the simulated soil leacheate to be 4 by using hydrochloric acid, continuously stirring for 6h, increasing the concentration of Cd to be 5ug/mL, and continuously stirring for 6h, wherein the Cd content is unchanged at 5.4 ug/mL.
Taking 1.0g of a sample prepared in a control group (comparative example 1), adding the sample into a simulated soil leacheate with the concentration of Cd being 52ug/mL and the pH value being 7 of 100mL, continuously stirring at room temperature for 12h, reducing the concentration of Cd to 8.5ug/mL, adjusting the pH value of the simulated soil leacheate to 4 by hydrochloric acid, continuously stirring for 6h, increasing the concentration of Cd to 15ug/mL, and continuously stirring for 6h, wherein the concentration of Cd is increased to 25 ug/mL.
1.0g of the sample prepared in example 1 was added to 100mL of a simulated soil leacheate having a pH of 7 and a Pd concentration of 28ug/mL and the mixture was stirred at room temperature for 12h, and the Cd concentration was reduced to 2.3 ug/mL. And (3) adjusting the pH value of the simulated soil leacheate to 4 by using hydrochloric acid, continuously stirring for 6h, increasing the concentration of Cd to 2.6ug/mL, and continuously stirring for 6h, wherein the Cd content is unchanged at 2.8 ug/mL.
Taking 1.0g of a sample prepared in a control group (comparative example 1), adding the sample into a simulated soil leacheate with the concentration of 28ug/mL of Pd and the pH value of 7 at 100mL, continuously stirring at room temperature for 12h, reducing the concentration of Cd to 2.5ug/mL, adjusting the pH value of the simulated soil leacheate to 4 by using hydrochloric acid, continuously stirring for 6h, increasing the concentration of Cd to 7.6ug/mL, and continuously stirring for 6h, wherein the concentration of Cd is increased to 8.9 ug/mL.
As can be seen from the above immobilization experiments, the immobilization reagent of the present invention can achieve a more efficient, long-lasting and stable immobilization effect.
Claims (7)
1. A preparation method of a transition state iron-based heavy metal immobilized reagent is characterized in that nano zero-valent iron is loaded on the surface of a substrate material, the substrate material loaded with the nano zero-valent iron is added into a weak acid solution for reaction, the nano zero-valent iron loaded on the surface of the substrate material is converted into transition state iron, and the transition state iron is washed and dried to obtain the immobilized reagent;
the solid-liquid mass ratio of the substrate material loaded with the nano zero-valent iron to the weak acid solution is 1:20-1:50;
the weak acid solution is acetic acid solution, and the mass percentage concentration of the weak acid solution is 2-5%;
the process of loading the nano zero-valent iron on the surface of the substrate material comprises the following steps: dispersing a substrate material in deionized water, performing ultrasonic treatment, adding the dispersed powder suspension into a hydrochloric acid solution for acid treatment, washing and drying to obtain powder I, dispersing the powder I in a soluble iron salt solution, washing and drying to obtain powder II, further dispersing the powder II in a reducing agent solution for reduction reaction, washing and drying to obtain the substrate material loaded with the nano zero-valent iron.
2. The preparation method according to claim 1, characterized in that the substrate material loaded with the nano zero-valent iron is added into a weak acid solution for reaction, and the reaction is carried out at 10-30 ℃.
3. The preparation method according to claim 1 or 2, wherein the substrate material is one or more of attapulgite, kaolin, sepiolite, montmorillonite, diatomite and halloysite.
4. The production method according to claim 1, wherein the reducing agent is potassium borohydride or hydrazine hydrate; the mass percentage concentration of the hydrochloric acid solution is 1-10%, and the mass ratio of the dispersed powder suspension to the hydrochloric acid solution is 1:20-1: 50.
5. The preparation method according to claim 1, wherein the solid-liquid mass ratio of the powder I to the soluble iron salt solution is 1:20-1:50, and the soluble iron salt solution is FeCl2Or FeCl3Solutions ofThe pH value is 6-8, and the mass percentage of Fe in the soluble ferric salt and the powder I is 4-12%.
6. The preparation method according to claim 4, wherein the mass percentage concentration of the potassium borohydride solution or the hydrazine hydrate solution is 1-10%, the solid-liquid mass ratio of the powder II to the potassium borohydride solution or the hydrazine hydrate solution is 1:20-1:50, and the reduction reaction temperature is 10-30 ℃.
7. The transition-state iron-based heavy metal immobilization agent prepared by the preparation method according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610277720.1A CN105802631B (en) | 2016-04-29 | 2016-04-29 | Transition state iron-based heavy metal immobilized reagent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610277720.1A CN105802631B (en) | 2016-04-29 | 2016-04-29 | Transition state iron-based heavy metal immobilized reagent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105802631A CN105802631A (en) | 2016-07-27 |
| CN105802631B true CN105802631B (en) | 2020-10-02 |
Family
ID=56457985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610277720.1A Active CN105802631B (en) | 2016-04-29 | 2016-04-29 | Transition state iron-based heavy metal immobilized reagent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105802631B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108372202A (en) * | 2018-04-03 | 2018-08-07 | 格丰科技材料有限公司 | A method of the reparation medicament for administering heavy-metal contaminated soil and its improvement heavy-metal contaminated soil |
| CN108640206A (en) * | 2018-06-08 | 2018-10-12 | 湖南农业大学 | One Yeasts carry the preparation method of nano zero valence iron |
| CN109554180B (en) * | 2018-11-29 | 2021-02-09 | 广州草木蕃环境科技有限公司 | Heavy metal contaminated soil remediation agent and remediation method |
| CN109652080B (en) * | 2019-01-09 | 2020-05-05 | 中国农业大学 | Soil remediation agent and preparation method thereof |
| CN111019663A (en) * | 2019-12-24 | 2020-04-17 | 甘肃瀚兴环保科技有限公司 | Heavy metal passivation material of nano zero-valent iron composite attapulgite, preparation method and application thereof |
| CN111019664A (en) * | 2019-12-26 | 2020-04-17 | 甘肃瀚兴环保科技有限公司 | Method for preparing soil heavy metal passivation material by using palygorskite loaded with nano zero-valent iron |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5975798A (en) * | 1997-09-02 | 1999-11-02 | Ars Technologies, Inc. | In-situ decontamination of subsurface waste using distributed iron powder |
| US6242663B1 (en) * | 1998-01-15 | 2001-06-05 | Penn State Research Foundation | Powerful reductant for decontamination of groundwater and surface streams |
| WO2003101541A1 (en) * | 2002-05-29 | 2003-12-11 | Nasa | Contaminant removal from natural resources |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344194B (en) * | 2011-06-14 | 2013-01-02 | 中国科学院新疆理化技术研究所 | Method for preparing montmorillonite in situ intercalation type nanoscale zero-valent iron |
| CN103394703B (en) * | 2013-08-05 | 2016-04-27 | 中国科学技术大学 | A kind of Coal gangue load-type zero-valent iron nanocomposite and preparation method thereof |
| CN103464102A (en) * | 2013-09-23 | 2013-12-25 | 北京师范大学 | Porous composite adsorbing agent for removing stream substrate sludge contamination and preparation process of agent |
| CN104773806B (en) * | 2015-04-08 | 2017-12-12 | 中国科学院化学研究所 | A kind of preparation method of strong reducing property nano material and its application in underground water pollution processing |
| CN105251995B (en) * | 2015-11-05 | 2017-10-10 | 北京化工大学 | A kind of preparation method of the nanometer nulvalent iron particle of spacetabs type |
-
2016
- 2016-04-29 CN CN201610277720.1A patent/CN105802631B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5975798A (en) * | 1997-09-02 | 1999-11-02 | Ars Technologies, Inc. | In-situ decontamination of subsurface waste using distributed iron powder |
| US6242663B1 (en) * | 1998-01-15 | 2001-06-05 | Penn State Research Foundation | Powerful reductant for decontamination of groundwater and surface streams |
| WO2003101541A1 (en) * | 2002-05-29 | 2003-12-11 | Nasa | Contaminant removal from natural resources |
Non-Patent Citations (2)
| Title |
|---|
| Optimization of Cd (II) removal from aqueous solution by ascorbic acid-stabilized zero valent rion nanoparticles using response surface methodology;Mohadden etal;《Journal of Industrial and Engineering Chemistry》;20140616;第21卷(第25期);第1403-1409页 * |
| 粘土矿物负载型复合催化剂的研究进展;何曦等;《材料导报A：综述篇》;20110731;第25卷(第7期);第86-90页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105802631A (en) | 2016-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105802631B (en) | Transition state iron-based heavy metal immobilized reagent and preparation method thereof | |
| Krstić et al. | A review on adsorbents for treatment of water and wastewaters containing copper ions | |
| CN109504398B (en) | Humic acid nano zero-valent iron soil Cr pollution remediation agent and preparation method thereof | |
| WO2017147979A1 (en) | Method for preparing iron silicon sulfur multi-element composite biochar soil heavy metal conditioner | |
| CN110184065B (en) | Layered double hydroxide and alkali activated biochar composite material and preparation method and application thereof | |
| CN109174026B (en) | Composite microalgae biological adsorbent microsphere and method for adsorbing chromium in wastewater by using composite microalgae biological adsorbent microsphere | |
| CN108126657B (en) | Magnetic pig manure biochar and preparation method thereof | |
| CN109082277B (en) | Cadmium-arsenic composite pollution remediation agent and preparation method and application thereof | |
| CN110586030B (en) | Preparation method of modified charcoal capable of adsorbing and fixing cadmium and copper in soil by cyclic utilization of heat | |
| CN106378094A (en) | Preparation method of amino iron-carrying composite modified biochar | |
| Idris et al. | Introduction of adsorption techniques for heavy metals remediation | |
| CN106943835B (en) | Method for preparing air purification material and compound fertilizer by using sludge and livestock and poultry manure | |
| CN103301803A (en) | Preparation method of attapulgite-modified clay for ammonia-nitrogen wastewater treatment | |
| CN112547024A (en) | Magnetic carbon composite material for repairing heavy metal contaminated soil and preparation method thereof | |
| CN103773375A (en) | Arsenic-contaminated soil repairing and retaining agent based on microbe catalytic synthesis, and preparation and application thereof | |
| CN110125161A (en) | A kind of heavy metal soil-repairing agent and method cooperateing with compost based on magnesia-montmorillonite composite material | |
| CN111570494B (en) | Heavy metal contaminated soil remediation method | |
| CN110653248A (en) | Composite passivation material suitable for arsenic, cadmium and lead polluted rice field 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 | |
| CN113912182B (en) | Application of plant-based solid-liquid mixed carbon source | |
| CN108772038B (en) | Adsorbent for removing lead ions in water and preparation method and application thereof | |
| Zhu et al. | Phosphorus-based nanomaterials as a potential phosphate fertilizer for sustainable agricultural development | |
| CN112774625A (en) | Zirconium oxide doped magnetic high-surface active carbon composite material, preparation method and application | |
| CN111548802A (en) | Long-acting heavy metal contaminated soil remediation agent and preparation method thereof | |
| CN110575812A (en) | environment-friendly adsorbing material for efficient phosphorus removal of argil/pyrolusite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 410100 No. 59 Nanzhuyuan Road, Changsha Economic and Technological Development Zone, Changsha City, Hunan Province Applicant after: AEROSPACE KAITIAN ENVIRONMENTAL TECHNOLOGY Co.,Ltd. Address before: 410100 Xingsha Road, Changsha Economic Development Zone, Hunan, No. 15 Applicant before: KAITIAN ENVIRONMENTAL TECH. Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |