CN105709697B - A kind of cerium salt is modified the preparation method of shell-fish waste adsorbent - Google Patents
A kind of cerium salt is modified the preparation method of shell-fish waste adsorbent Download PDFInfo
- Publication number
- CN105709697B CN105709697B CN201610127526.5A CN201610127526A CN105709697B CN 105709697 B CN105709697 B CN 105709697B CN 201610127526 A CN201610127526 A CN 201610127526A CN 105709697 B CN105709697 B CN 105709697B
- Authority
- CN
- China
- Prior art keywords
- shell
- fish waste
- modified
- cerium salt
- hours
- 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.)
- Expired - Fee Related
Links
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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of cerium salt is modified the preparation method of shell-fish waste adsorbent, includes the following steps：(1) shell-fish waste is placed in HCl solution and is impregnated, cleaning, drying obtains pretreated feedstock；(2) pretreated feedstock is immersed in potassium hydroxide solution, is passed through nitrogen, is reacted 1.5~2 hours at 700~800 DEG C；(3) it is soaked in HCl solution, filters after cooling down step (2) products therefrom, clean, drying；(4) step (3) products obtained therefrom is placed in cerous nitrate solution and is impregnated, be cooled to room temperature filtering, obtain solid particle；(5) it is heat-treated after drying solid particle, after cooling wash with distilled water, drying, system to cerium salt is modified shell-fish waste adsorbent.The present invention prepares shell-fish waste adsorbent by cerium salt modification, which has higher heavy metal removing rate than common shell-fish waste.
Description
Technical field
The present invention relates to a kind of preparation methods for the shell-fish waste adsorbent being modified by cerium salt, belong to adsorbent system
Standby technical field.
Background technology
Water body is is one of the main natural resources on which mankind depends, with industrialized continuous development, in particular with
The development of the industries such as smelting, mining, plating, chemical industry, plating, electronics and the unreasonable landfill of solid waste and stacking so that
Various heavy metal contaminants enter water body, since heavy metal has enriching, so that it is enriched in animal and plant body, accumulate on vegetable
In dish, meat, fish, seafood, health and the existence of the mankind and other biological have been seriously threatened.Currently, heavy metal in water is dirty
Dye has become one of the environmental problem of global upper most serious, and how scientificlly and effectively to solve heavy metal to the pollution of water body
One of hot spot through being studied as numerous environmental workers.
The method for being presently used for heavy-metal ion removal mainly has precipitation, ion exchange, membrane technology etc., but these skills
The application of art by technique, economy and its will produce secondary pollution and limited sometimes.Absorption method has efficient, easy and selectivity
The advantages that good, it is widely used in heavy metal containing wastewater treatment.But the industrial adsorbent generally used is expensive, becomes system
Therefore the about principal element of absorption method develops a kind of important side that adsorbent cheap, that absorption property is good is absorption research
To.
The shell-fish such as crab shell, shrimp shell are the industrial solid waste of aquatic products.With the development of the artificial aquaculture in China,
These shell-fish waste quantity are more and more, some enterprises dispose its unreasonable processing, lead to serious environmental pollution.
But since the functional groups such as hydroxyl, amino contained in this kind of shell-fish waste can form stabilization with metal ion in solution
Chelate, can be used to handle heavy metal wastewater thereby, but its adsorption capacity is very low.Therefore, the present invention is according to " treatment of wastes with processes of wastes against one another "
Thinking is modified the shell-fish waste such as crab shell, shrimp shell, prepares a kind of adsorbent economic and environment-friendly, adsorption capacity is high.
Invention content
For deficiency existing for existing shell-fish waste utilization technology, present invention offer one kind is of low cost, technique is simple
Single cerium salt is modified the preparation method of shell-fish waste adsorbent, and this method can prepare the good suitable removal of absorption property
The shell-fish waste adsorbent of Heavy Metals in Waters ion.
The cerium salt of the present invention is modified the preparation method of shell-fish waste adsorbent, includes the following steps：
(1) shell-fish waste (crab shell, shrimp shell) is placed in the HCl solution of concentration 1mol/L and impregnates 4~6 hours, so
It is 6.0~7.0 to be cleaned repeatedly with clear water afterwards to pH value, and drying obtains pretreated feedstock；
(2) pretreated feedstock is reacted 1~1.5 hour at 400~600 DEG C, then presses pretreated feedstock and potassium hydroxide
Mass ratio 1:2~1:3 ratio immerses in the potassium hydroxide solution that mass concentration is 50%~80% 10~15 hours, with 0.5
~0.8m3The flow of/hour is passed through nitrogen, and 700~800 DEG C of temperature is heated to 10~20 DEG C/min of heating rate, reaction
1.5~2 hours, close nitrogen；
(3) it by after the raw material cooling of step (2) processing, is soaked at 50~60 DEG C in a concentration of 6% HCl solution simultaneously
Be stirred continuously, after 2~4 hours, filtering then is cleaned with 70~80 DEG C of distilled water, finally wash with distilled water to pH value 6.5~
7.0, drying；
(4) under the conditions of 40 DEG C~60 DEG C, by step (3) products obtained therefrom with mass ratio for 2:1~4:1 ratio is placed in matter
It measures and is impregnated in the cerous nitrate solution of concentration 8%~12%, 3~6 hours, be cooled to room temperature filtering, obtain solid particle；
(5) solid particle is 20~25 hours dry at 60~70 DEG C, it is subsequently heat-treated, after cooling wash with distilled water,
Drying, system to cerium salt are modified shell-fish waste adsorbent.
The ratio of shell-fish waste (crab shell, shrimp shell) and HCl solution is 1g in the step (1):15mL~25mL.
Drying temperature in the step (1), step (3) and step (5) is 65~75 DEG C.
A concentration of the 60% of potassium hydroxide solution in the step (2).
Pretreated feedstock in the step (2) reacts 1.5 hours at 500 DEG C, and it is small to be passed through after nitrogen the reaction 2 at 800 DEG C
When.
Raw material in the step (3) is 1 according to mass ratio:10~20 ratio is soaked in HCl solution.
Heat treatment refers to being heat-treated 30~60 minutes for 100~120 DEG C under protection of argon gas in the step (5), in air
In 80~100 DEG C be heat-treated 60~90 minutes.
It is 120 DEG C that heat treatment, which refers to heat treatment temperature under protection of argon gas, in the step (5), heat treatment time 45
Minute；Aerial heat treatment temperature is 100 DEG C, and heat treatment time is 60 minutes.
The present invention prepares shell-fish waste adsorbent by cerium salt modification, and the adsorbent is than common shell-fish waste
With higher heavy metal removing rate.The present invention has following features：
(1) raw material shell-fish waste used by derives from a wealth of sources, cheap, and biodegradable, environment attribute is good
It is good, it can effectively reduce the processing cost of waste water.
(2) the shell-fish waste adsorbent prepared significantly improves the adsorption effect of heavy metal compared with raw material, right
Have great importance in the processing of heavy metal industrial effluent and the improvement of water environment.
(3) it is modified shell-fish waste using cerium salt and prepares adsorbent, can be provided for the comprehensive utilization of shell-fish waste
New approach reduces the environmental pollution caused by waste discharge.
Specific implementation mode
Embodiment 1
(1) 50g crab shells are placed in 1000mL in the HCl solution of 1mol/L to impregnate 5 hours, are then cleaned repeatedly with clear water
It is 6.0 to pH value, is placed in 70 DEG C of baking ovens and dries, obtain pretreated feedstock.
(2) pretreated feedstock is reacted 1.2 hours at 500 DEG C, then presses pretreated feedstock with potassium hydroxide quality than 1:2
It immerses in the potassium hydroxide solution that mass concentration is 50%, dip time is 15 hours, with 0.7m3The flow of/hour is passed through nitrogen
Gas is heated to 700 DEG C of temperature with 20 DEG C/min of heating rate, reacts 2 hours, closes nitrogen.
(3) product cooling after, at 50 DEG C according to mass ratio be 1:10 ratio is soaked in a concentration of 6% HCl solution
In and be stirred continuously, after 3 hours, filtering then is cleaned 3 times with 80 DEG C of distilled water, finally wash with distilled water to pH value 6.5,70
It is dry under DEG C temperature condition.
(4) under the conditions of 50 DEG C, by the said goods with mass ratio for 2:1 ratio is placed in the nitric acid that mass concentration is 10%
It is impregnated 4 hours in cerium solution.
(5) above-mentioned mixed liquor is cooled to room temperature, is filtered, solid particle is placed in Constant Temp. Oven, temperature control
After 20 hours dry at 70 DEG C, it is heat-treated 30 minutes for 100 DEG C, is heat-treated 60 minutes for 80 DEG C in air under protection of argon gas, it is cold
But, wash with distilled water, it is placed in 70 DEG C of baking ovens and dries, obtains cerium salt and be modified crab shell adsorbent (CAC1).
0.2g CAC1 are placed in the arsenic-containing waste water (pH 5.5) of a concentration of 2mg/L of 100mL, is placed on shaking table and vibrates,
Rotating speed is 120 revs/min.After 24 hours, supernatant is extracted, 0.45 μm of PTFE film filtering is passed through, uses atomic absorption spectrophotometry
Remaining arsenic ion concentration in photometric determination filtrate, it is 0.924mg/g to the adsorption capacity of arsenic to obtain CAC1.
Embodiment 2
(1) 50g fresh-water turtle shells 750mL is placed in the HCl solution of 1mol/L to impregnate 6 hours, it is then repeatedly clear with clear water
It is 7.0 to be washed till pH value, is placed in 65 DEG C of baking ovens and dries, obtains pretreated feedstock.
(2) pretreated feedstock is reacted 1 hour at 600 DEG C, then presses pretreated feedstock with potassium hydroxide quality than 1:2.5
It immerses in the potassium hydroxide solution that mass concentration is 60%, dip time is 12 hours, with 0.5m3The flow of/hour is passed through nitrogen
Gas is heated to 800 DEG C of temperature with 10 DEG C/min of heating rate, reacts 1.5 hours, closes nitrogen.
(3) product cooling after, at 60 DEG C according to mass ratio be 1:20 ratio is soaked in a concentration of 6% HCl solution
In and be stirred continuously, after 2 hours, filtering then is cleaned 3 times with 70 DEG C of distilled water, finally wash with distilled water to pH value 6.8,65
It is dry under DEG C temperature condition.
(4) under the conditions of 60 DEG C, by the said goods with mass ratio for 4:1 ratio is placed in the nitric acid that mass concentration is 8%
It is impregnated 6 hours in cerium solution.
(5) above-mentioned mixed liquor is cooled to room temperature, is filtered, solid particle is placed in Constant Temp. Oven, temperature control
After 23 hours dry at 65 DEG C, it is heat-treated 45 minutes for 120 DEG C, is heat-treated 80 minutes for 100 DEG C in air under protection of argon gas, it is cold
But, wash with distilled water, it is placed in 65 DEG C of baking ovens and dries, obtains cerium salt and be modified fresh-water turtle shell adsorbent (CAC2).
0.2g CAC1 are placed in the arsenic-containing waste water (pH value 6.0) of a concentration of 2mg/L of 100mL, is placed on shaking table and shakes
It swings, rotating speed is 120 revs/min.After 36 hours, supernatant is extracted, 0.45 μm of PTFE film filtering is passed through, uses Atomic absorption
Remaining arsenic ion concentration in spectrophotometric determination filtrate, it is 0.936mg/g to the adsorption capacity of arsenic to obtain CAC1.
Embodiment 3
(1) 50g shrimp shells are placed in 1250mL in the HCl solution of 1mol/L to impregnate 4 hours, are then cleaned repeatedly with clear water
It is 6.5 to pH value, is placed in 75 DEG C of baking ovens and dries, obtain pretreated feedstock.
(2) pretreated feedstock is reacted 1.5 hours at 400 DEG C, then presses pretreated feedstock with potassium hydroxide quality than 1:3
It immerses in the potassium hydroxide solution that mass concentration is 80%, dip time is 10 hours, with 0.8m3The flow of/hour is passed through nitrogen
Gas is heated to 750 DEG C of temperature with 15 DEG C/min of heating rate, reacts 1.8 hours, closes nitrogen.
(3) product cooling after, at 55 DEG C according to mass ratio be 1:15 ratio is soaked in a concentration of 6% HCl solution
In and be stirred continuously, after 4 hours, filtering, then 3 times are cleaned with 75 DEG C of distilled water, finally wash with distilled water to 7,75 DEG C of pH value
It is dry under temperature condition.
(4) under the conditions of 40 DEG C, by the said goods with mass ratio for 3:1 ratio is placed in the nitric acid that mass concentration is 12%
It is impregnated 3 hours in cerium solution.
(5) above-mentioned mixed liquor is cooled to room temperature, is filtered, solid particle is placed in Constant Temp. Oven, temperature control
After 25 hours dry at 60 DEG C, it is heat-treated 60 minutes for 110 DEG C, is heat-treated 90 minutes for 90 DEG C in air under protection of argon gas, it is cold
But, wash with distilled water, it is placed in 75 DEG C of baking ovens and dries, obtains cerium salt and be modified shrimp shell adsorbent (CAC3).
0.2g CAC1 are placed in the arsenic-containing waste water (pH 6.5) of a concentration of 2mg/L of 100mL, is placed on shaking table and vibrates,
Rotating speed is 120 revs/min.After 36 hours, supernatant is extracted, 0.45 μm of PTFE film filtering is passed through, uses atomic absorption spectrophotometry
Remaining arsenic ion concentration in photometric determination filtrate, it is 0.922mg/g to the adsorption capacity of arsenic to obtain CAC1.
Claims (8)
1. a kind of cerium salt is modified the preparation method of shell-fish waste adsorbent, characterized in that include the following steps：
(1) shell-fish waste is placed in the HCl solution of concentration 1mol/L and is impregnated 4~6 hours, then cleaned repeatedly with clear water
It is 6.0~7.0 to pH value, drying obtains pretreated feedstock；
(2) pretreated feedstock is reacted 1~1.5 hour at 400~600 DEG C, then presses pretreated feedstock and potassium hydroxide quality
Than 1:2~1:3 ratio immerses in the potassium hydroxide solution that mass concentration is 50%~80% 10~15 hours, with 0.5~
0.8m3The flow of/hour is passed through nitrogen, and 700~800 DEG C of temperature is heated to 10~20 DEG C/min of heating rate, reaction
1.5~2 hours, close nitrogen；
(3) it by after the raw material cooling of step (2) processing, is soaked in a concentration of 6% HCl solution and stirs at 50~60 DEG C
It mixes, after 2~4 hours, filtering, then cleaned with 70~80 DEG C of distilled water, finally dried wash with distilled water to pH value 6.5~7.0
It is dry；
(4) under the conditions of 40 DEG C~60 DEG C, by step (3) products obtained therefrom with mass ratio for 2:1~4:It is dense that 1 ratio is placed in quality
It is impregnated in the cerous nitrate solution of degree 8%~12%, 3~6 hours, is cooled to room temperature filtering, obtains solid particle；
(5) solid particle is 20~25 hours dry at 60~70 DEG C, it is subsequently heat-treated, after cooling wash with distilled water, drying,
It makes cerium salt and is modified shell-fish waste adsorbent.
2. cerium salt according to claim 1 is modified the preparation method of shell-fish waste adsorbent, characterized in that the step
Suddenly the ratio of shell-fish waste and HCl solution is 1g in (1):15mL~25mL.
3. cerium salt according to claim 1 is modified the preparation method of shell-fish waste adsorbent, characterized in that the step
Suddenly the drying temperature in (1), step (3) and step (5) is 65~75 DEG C.
4. cerium salt according to claim 1 is modified the preparation method of shell-fish waste adsorbent, characterized in that the step
Suddenly in (2) potassium hydroxide solution a concentration of 60%.
5. cerium salt according to claim 1 is modified the preparation method of shell-fish waste adsorbent, characterized in that the step
Suddenly the pretreated feedstock in (2) reacts 1.5 hours at 500 DEG C, is passed through after nitrogen and is reacted 2 hours at 800 DEG C.
6. cerium salt according to claim 1 is modified the preparation method of shell-fish waste adsorbent, characterized in that the step
Suddenly the raw material in (3) is 1 according to mass ratio:10~20 ratio is soaked in HCl solution.
7. cerium salt according to claim 1 is modified the preparation method of shell-fish waste adsorbent, characterized in that the step
Suddenly heat treatment refers to being heat-treated 30~60 minutes for 100~120 DEG C under protection of argon gas in (5), in air at 80~100 DEG C of heat
Reason 60~90 minutes.
8. cerium salt according to claim 1 is modified the preparation method of shell-fish waste adsorbent, characterized in that the step
Suddenly it is 120 DEG C that heat treatment, which refers to heat treatment temperature under protection of argon gas, in (5), and heat treatment time is 45 minutes；In air
Heat treatment temperature be 100 DEG C, heat treatment time be 60 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610127526.5A CN105709697B (en) | 2016-03-07 | 2016-03-07 | A kind of cerium salt is modified the preparation method of shell-fish waste adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610127526.5A CN105709697B (en) | 2016-03-07 | 2016-03-07 | A kind of cerium salt is modified the preparation method of shell-fish waste adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105709697A CN105709697A (en) | 2016-06-29 |
| CN105709697B true CN105709697B (en) | 2018-08-17 |
Family
ID=56156395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610127526.5A Expired - Fee Related CN105709697B (en) | 2016-03-07 | 2016-03-07 | A kind of cerium salt is modified the preparation method of shell-fish waste adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105709697B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111672476A (en) * | 2020-06-24 | 2020-09-18 | 黑龙江省科学院大庆分院 | Preparation method and application of modified hemp extraction waste adsorption material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708461A (en) * | 2009-12-01 | 2010-05-19 | 辽宁石油化工大学 | Adsorbent of immobilized rare earth metal cerium and preparation method thereof |
| CN102500337A (en) * | 2011-11-21 | 2012-06-20 | 大连理工大学 | Phosphorus removal adsorbent for modifying oyster shell with iron salt and preparation method as well as application thereof |
| CN103394325A (en) * | 2013-08-14 | 2013-11-20 | 山东建筑大学 | Method for preparing arsenic removal adsorbent by use of marine product waste |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3672855B2 (en) * | 2001-08-29 | 2005-07-20 | Ｊｆｅプラント＆サービス株式会社 | Fluorine adsorbent and fluorine removal method using the same |
-
2016
- 2016-03-07 CN CN201610127526.5A patent/CN105709697B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708461A (en) * | 2009-12-01 | 2010-05-19 | 辽宁石油化工大学 | Adsorbent of immobilized rare earth metal cerium and preparation method thereof |
| CN102500337A (en) * | 2011-11-21 | 2012-06-20 | 大连理工大学 | Phosphorus removal adsorbent for modifying oyster shell with iron salt and preparation method as well as application thereof |
| CN103394325A (en) * | 2013-08-14 | 2013-11-20 | 山东建筑大学 | Method for preparing arsenic removal adsorbent by use of marine product waste |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105709697A (en) | 2016-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104941574B (en) | A kind of inorganic ions modified zeolite composite and its application | |
| CN102935352B (en) | Method for absorbing and removing heavy metal and hexavalent chromium from waste liquid by using mangosteen slag | |
| CN111298770B (en) | Method for simultaneously purifying organic arsenic and inorganic arsenic composite polluted wastewater | |
| CN106237985A (en) | A kind of straw base selectivity removal of mercury material and its preparation method and application | |
| Bamukyaye et al. | Performance of egg-shell and fish-scale as adsorbent materials for chromium (VI) removal from effluents of tannery industries in Eastern Uganda | |
| CN1850637A (en) | Method for preparing efficient heavy metalion adsorbent carbon hydroxy apatite | |
| CN103920461A (en) | Magnetic biochar quantum dot composite adsorbent as well as preparation method and using method thereof | |
| CN104826597A (en) | Method for preparing adsorbent by attapulgite clay organic modification | |
| CN104084221B (en) | In a kind of biological adsorption solution, heavy metal ion prepares the method for catalysis material | |
| CN110433772A (en) | A kind of preparation method and application of mulberry tree bar charcoal/Fe-Mn compound adsorbent | |
| CN111804276A (en) | Preparation method and application of zirconium hydroxide modified magnetic biochar adsorbing material | |
| CN105289490A (en) | Loaded-type bamboo shell adsorbent used for absorbing and separating rhenium as well as preparation method thereof | |
| CN110560154A (en) | Method for preparing FeMn-ZSM-5 catalyst by extracting ferromanganese from nonferrous metal tailings | |
| CN105709697B (en) | A kind of cerium salt is modified the preparation method of shell-fish waste adsorbent | |
| CN105944688A (en) | Preparation method for improved pineapple peel magnetic adsorbing material and method for removing heavy metal from wastewater | |
| CN104057096A (en) | Method for preparing ultrafine powder material from valuable metal ions in biological adsorption solution | |
| CN113856623A (en) | Preparation method and application of magnesium chloride modified eucalyptus biochar adsorbent | |
| Delali et al. | Valorisation of waste Mussel Shells as Biosorbent for an azo dye elimination | |
| Budin et al. | The ability of crab and cockle shell to adsorb lead and chromium from industrial effluent | |
| CN103964534A (en) | Method for treating heavy metal zinc pollution in water | |
| KR19980045823A (en) | Soil modifier using natural minerals and its manufacturing method | |
| CN111346606A (en) | Process for preparing arsenic adsorbent from coal slag | |
| CN104448008A (en) | Low-cost peanut shell adsorbing material and preparation method thereof | |
| CN112239259B (en) | Chemical remover for heavy metal polluted wastewater treatment and preparation method and application thereof | |
| CN109248648B (en) | Modified bauxite for adsorbing heavy metal ions in wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Sun Cuizhen Inventor after: Sun Caijuan Inventor after: Zhao Yang Inventor after: Zhang Zhibin Inventor after: Chen Dongchen Inventor after: Zhang Xiaorui Inventor after: Qiu Jinwei Inventor after: Zhang Yanhao Inventor after: Zhang Hui Inventor before: Sun Cuizhen Inventor before: Zhao Yang Inventor before: Zhang Zhibin Inventor before: Chen Dongchen Inventor before: Zhang Xiaorui Inventor before: Qiu Jinwei Inventor before: Zhang Yanhao Inventor before: Zhang Hui |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180817 Termination date: 20190307 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |