CN106084218A - A kind of melamine class macromolecular material and in the application processed in terms of heavy metal and preparation method - Google Patents

A kind of melamine class macromolecular material and in the application processed in terms of heavy metal and preparation method Download PDF

Info

Publication number
CN106084218A
CN106084218A CN201610569495.9A CN201610569495A CN106084218A CN 106084218 A CN106084218 A CN 106084218A CN 201610569495 A CN201610569495 A CN 201610569495A CN 106084218 A CN106084218 A CN 106084218A
Authority
CN
China
Prior art keywords
heavy metal
macromolecular material
melamine class
class macromolecular
preparation
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.)
Granted
Application number
CN201610569495.9A
Other languages
Chinese (zh)
Other versions
CN106084218B (en
Inventor
王平山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Xilin Environmental Protection Material Co Ltd
Original Assignee
Hunan Xilin Environmental Protection Material Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hunan Xilin Environmental Protection Material Co Ltd filed Critical Hunan Xilin Environmental Protection Material Co Ltd
Priority to CN201610569495.9A priority Critical patent/CN106084218B/en
Publication of CN106084218A publication Critical patent/CN106084218A/en
Application granted granted Critical
Publication of CN106084218B publication Critical patent/CN106084218B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
    • 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)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention discloses a kind of melamine class macromolecular material and the application in terms of processing heavy metal thereof and preparation method；Melamine class macromolecular material is carried out polycondensation reaction by tripolycyanamide and pyrrole aldehyde and obtains, this melamine class macromolecular material energy adsorption and oxidation state heavy metal and elemental heavy metal simultaneously, can efficiently remove each heavy metal species in waste water, waste water is made to reach discharging standards, can efficiently remove again the heavy metal in industrial smoke, reach the purpose of purifying smoke, also can effectively process or heavy metal in curing soil, reach the purpose of soil remediation.

Description

A kind of melamine class macromolecular material and in the application processed in terms of heavy metal and Preparation method
Technical field
The present invention relates to a kind of melamine class macromolecular material and its preparation method and application, particularly to a kind of trimerization The application in terms for the treatment of and purification industrial smoke, waste water and heavy metal in soil of the cyanamide family macromolecule material, belongs to heavy metal-polluted Dye Treatment process field.
Background technology
Heavy metal pollution for ecological impact by common people cognition, especially have highly toxic heavy metal such as hydrargyrum, silver, Cadmium, copper, lead, nickel, zinc etc. cannot decompose in nature voluntarily, it is necessary to be treated as single-element by the method such as physics, chemistry Or metallic compound.At present, the method administering heavy metal-containing waste water has a lot, and the most most widely used is at chemical precipitation method Reason heavy metal-containing waste water, this kind of medicament belongs to chemicals such as sodium hydroxide, calcium hydroxide etc. more, and its production process inherently can be right Environment, and when administering effluent containing heavy metal ions, the produced precipitum containing heavy metal is unstable, the most molten Solution causes secondary pollution.Chemical precipitation method process effluent containing heavy metal ions actually used during due to different heavy metals Ion generates optimal pH difference during hydroxide precipitation, and some heavy metal ion may be with other ions in solution Forming complex (adding its dissolubility in water), treatment effect is undesirable.It addition, heavy metal ion is in alkaline medium The hydroxide precipitation generated, one part can be redissolved in water along with the reduction of pH value in discharge.Existing its Its heavy metal absorbent also tends to optionally react with some heavy metal, and has stink and toxicity.
The method utilizing activated carbon to adsorb metal ion is also to use more processing method.Acticarbon The absorption of heavy metal is mainly physical absorption, and adsorption effect has a greater change with temperature and other environmental condition.But it is active Charcoal cost is expensive, service life is short, operating cost is high, be not easy to regeneration (regeneration cost is high).
Additionally, biotechnology is also the popular research topic of current heavy metal pollution regulation field, such as phytoremediation technology And biosorption technology.Phytoremediation technology has operability, low cost, the advantage of non-secondary pollution, but shortcoming is place Reason rate is low, processes heavy metal pollution kind single.
At present both at home and abroad the purification techniques of known heavy metal in flue gas mainly use wet scrubbing, sodium sulfide injection and The modes such as modified activated carbon (sulfur loaded element).Its pluses and minuses are as follows:
1, wet scrubbing: the oxidation state huge sum of money that the method using water (solution) to spray can highly desirable be removed in flue gas Belong to, but the most poor to the removal effect of elementary gas heavy metal, and also wet scrubbing process produces substantial amounts of containing heavy metal Waste water, brings bigger difficulty to follow-up sewage treatment process, and secondary pollution is serious.
2, physical absorption: use and spray physisorption material in flue gas or install adsorption tower after cleaner Method.Wherein, activated carbon and molecular sieve belong to and are most widely used and ripe adsorbing material, can well adsorb in flue gas Oxidation state heavy metal；But, the adsorption effect for elementary gas heavy metal is poor.Existing documents and materials show, if from unit Element heavy metal concentration is 10ug/m3Removing the element heavy metal of 90% in flue gas, the amounts of activated carbon of required injection is equivalent to unit 3000 times～18000 times of element heavy metal concentration.Therefore, method its cost of control element heavy metal of physical absorption is used very Expensive.It addition, the element heavy metal after activated carbon adsorption will reenter environment after landfill stabilization, cause secondary pollution.
3, sodium sulfide injection: utilize sodium sulfide and oxidation state heavy metal (predominantly chlorination heavy metal) to have good reaction Property, effectively chlorination heavy metal can be converted into the heavy metal of particulate form, thus purified by cleaner；But, the method The clean-up effect of element heavy metal is generally below 30%.
4, modified activated carbon (sulfur loaded element): up-to-date occurring in that utilizes element sulphur load type active carbon to improve unit in the U.S. The experimental technique of element heavy metal purification efficiency, can relatively efficiently purify element state heavy metal, but for gaseous state chlorination weight The removal effect of metal is undesirable.
And, the above common technique is often suitable only for the heavy metal of oxidation state in purifying smoke.
Summary of the invention
The defect existed for prior art, it is an object of the invention to be to provide one simultaneously miscellaneous containing pyrroles and triazines The cross-linked type macromolecule polymeric material of azo-cycle construction unit, this macromolecule polymer material is to oxidation state heavy metal and simple substance State heavy metal all has stronger absorbability.
Another object of the present invention is to be to provide a kind of simple to operate, low cost to prepare described melamine class high score The method of sub-material.
Third object of the present invention is to be to provide described melamine class macromolecular material as heavy metal absorbent Application, it can apply to efficient absorption and removes oxidation state or elemental heavy metal, is particularly well-suited to Adsorption soil, cigarette Heavy metal in gas or waste water.
In order to realize above-mentioned technical purpose, the invention provides a kind of melamine class macromolecular material, this melamine Amine macromolecular material has formula 1 constitutional repeating unit:
Present invention also offers the preparation method of a kind of melamine class macromolecular material, the method is tripolycyanamide and pyrrole Cough up formaldehyde and carry out polycondensation reaction, to obtain final product.
Preferably scheme, the mol ratio of tripolycyanamide and pyrrole aldehyde is 1:(1.2～2)；Most preferably 1:1.5.
More preferably scheme, polycondensation reaction reacts 8～20h at a temperature of 100～150 DEG C.
Further preferred scheme, in polycondensation reaction employing dimethyl sulfoxide, dimethylformamide, dimethyl acetylamide at least A kind of as solvent.
The synthetic route of the melamine class macromolecular material of the present invention is as follows:
Present invention also offers the application of a kind of described melamine class macromolecular material, by described melamine class Macromolecular material is applied to adsorption and oxidation state heavy metal and/or elemental heavy metal as heavy metal absorbent.
Preferably scheme, melamine class macromolecular material is applied to adsorb in flue gas as heavy metal absorbent, water-soluble Oxidation state heavy metal in liquid or in soil and/or elemental heavy metal.
The heavy metal of the present invention includes any heavy metal well known in the art.
Hinge structure, the Advantageous Effects that technical scheme is brought:
1, in technical solution of the present invention, melamine class macromolecular material contains pyrroles and triazine heterocyclic structure simultaneously Unit, azacyclo-structure heavy metal has stronger Coordination Adsorption effect, greatly strengthen the energy of adsorption of oxidation state heavy metal Power, meanwhile, melamine class macromolecular material is crosslinking polymer, is to be piled up by pyrrole unit and 5-triazine units stripping and slicing to construct Becoming three-dimensional network loose structure, this loose structure has stronger physisorption to elemental heavy metal, and porous is tied Structure makes whole polymer specific surface area increase, and internal azacyclo-structure exposes, and makes coordination site increase, is more beneficial for oxidation state The absorbability of heavy metal.
2, melamine class macromolecular material energy efficient absorption oxidation state heavy metal and list simultaneously in technical solution of the present invention Matter state heavy metal, is particularly well-suited to heavy-metal contaminated soil, heavy metal containing heavy metal flue gas and heavy metal polluted waste water is gone Remove, can effectively remove each heavy metal species in waste water, make waste water reach discharging standards, also can effectively remove in industrial smoke Heavy metal, reach the purpose of purifying smoke, also can process or heavy metal in curing soil, reach the purpose of soil remediation.
3, the melamine class macromolecular material preparation method of the present invention is simple, low cost, meets industrialized production.
Accompanying drawing explanation
[Fig. 1] is the Infrared Characterization collection of illustrative plates of the melamine class macromolecular material of embodiment 1 preparation；
[Fig. 2] is the appearing diagram of the melamine class macromolecular material of embodiment 1 preparation.
Detailed description of the invention
Following example are intended to further illustrate present invention rather than limit the protection model of the claims in the present invention Enclose.
Embodiment 1
Macromolecular material is that tripolycyanamide is polymerized, in dimethyl sulfoxide (DMSO), the macromolecule obtained with pyrrole aldehyde.Specifically Synthesis step be: in the low flask of the circles of 500 milliliters, add 100 grams of tripolycyanamide and 100 grams of pyrrole aldehydes, be subsequently adding 250 milliliters of dimethyl sulfoxide solutions, mixture is heated and stirred 15 hours under 130 degrees Celsius and nitrogen atmosphere.Cooled and filtered goes out Flaxen solid, is dried with after water and washing with alcohol, and secure satisfactory grades sub-cross linked polymer 189 grams.
Embodiment 2
Macromolecular material is that tripolycyanamide is polymerized, in dimethylformamide (DMF), the macromolecule obtained with pyrrole aldehyde. Concrete synthesis step is: add 100 grams of tripolycyanamide and 113.1 grams of pyrrole aldehydes in the low flask of the circles of 500 milliliters, then Adding 300 milliliters of dimethyl formamide solutions, mixture stirs 12 hours at 110 degrees Celsius and heated under nitrogen.Mistake after cooling Leaching flaxen solid, be dried with after water and washing with alcohol, secure satisfactory grades sub-cross linked polymer 191 grams.
Embodiment 3
Macromolecular material is that tripolycyanamide is polymerized, in dimethyl acetylamide (DMAC), the macromolecule obtained with pyrrole aldehyde. Concrete synthesis step is: adds 100 grams of tripolycyanamide and 120 grams of pyrrole aldehydes in the low flask of the circles of 500 milliliters, then adds Entering 250 milliliters of dimethylacetamide solutions, mixture was 150 degrees Celsius of lower heated and stirred 8 hours.Cooled and filtered goes out white Solid, is dried with after water and washing with alcohol, and secure satisfactory grades sub-cross linked polymer 190 grams.
Embodiment 4
The macromolecule material of 0.3g above-described embodiment 1 preparation is added in containing the 1000mL waste water that ion concentration of mercury is 20mg/L Material, adds flocculant and filter at 50 DEG C after stirring 20 minutes, in processed waste water, mercury ion content is 0.01mg/L.
Embodiment 5
The macromolecule material of 0.2g above-described embodiment 2 preparation is added in containing the 1000mL waste water that plumbum ion concentration is 10mg/L Material, stirring at normal temperatures adds flocculant and filters after 30 minutes, in processed waste water, lead ion content is 0.02mg/L.
Embodiment 6
Being 20mg/L containing concentration of cadmium ions, ion concentration of mercury is 10mg/L, and plumbum ion concentration is the 1000mL of 15mg/L Adding the macromolecular material of 0.8g above-described embodiment 3 preparation in waste water, stirring at normal temperatures adds flocculant and filters after 30 minutes, place After reason, removal of Cadmium from wastewater concentration is respectively 0.03mg/L, and ion concentration of mercury is 0.01mg/L, and plumbum ion concentration is 0.03mg/L.
Embodiment 7
In a closed system, containing gaseous mercury (Hg0) concentration is 300 μ g/Nm3The gas of (300 micrograms/standard cubic meter) Body is at room temperature by the quartz ampoule (diameter 10mm) of a macromolecular material filling 0.5g embodiment 2 preparation.Produce through Germany VM-3000 detection process after mercury content in gas be 3.0 μ g/Nm3。
Embodiment 8
In a closed system, containing gaseous mercury (Hg0) concentration is 250 μ g/Nm3The gas of (250 micrograms/standard cubic meter) Body is by the quartz ampoule (diameter 10mm) of a macromolecular material filling 0.5g embodiment 1 preparation, and quartz ampoule is placed on one Add and heat pipe is heated to 100 DEG C.After the VM-3000 detection process that Germany produces, the mercury content in gas is 2.0 μ g/Nm3。
Embodiment 9
At 1 kilogram of (2.5mg) Han heavy metal Hg, in the soil of lead (11mg) and zinc (9mg), add embodiment 3 preparation Macromolecular material 10 grams.After being sufficiently mixed, taking 50 grams of soil and add 100 milliliters of water furnishing pulpous states, heating 1 is little at 80 degrees celsius Time.Cooling takes supernatant test after standing.Result is: hydrargyrum (0.02mg/L), lead (0.03mg/L) and zinc (0.2mg/L).

Claims (7)

1. a melamine class macromolecular material, it is characterised in that: there is formula 1 constitutional repeating unit:
2. the preparation method of the melamine class macromolecular material described in claim 1, it is characterised in that: tripolycyanamide and pyrroles Formaldehyde carries out polycondensation reaction, to obtain final product.
The preparation method of melamine class macromolecular material the most according to claim 2, it is characterised in that: tripolycyanamide and The mol ratio of pyrrole aldehyde is 1:(1.2～2).
4. according to the preparation method of the melamine class macromolecular material described in Claims 2 or 3, it is characterised in that: described Polycondensation reaction reacts 8～20h at a temperature of 100～150 DEG C.
The preparation method of melamine class macromolecular material the most according to claim 4, it is characterised in that: described polycondensation In reaction employing dimethyl sulfoxide, dimethylformamide, dimethyl acetylamide, at least one is as solvent.
6. the application of the melamine class macromolecular material described in claim 1, it is characterised in that: should as heavy metal absorbent For adsorption and oxidation state heavy metal and/or elemental heavy metal.
7. the application of the melamine class macromolecular material described in claim 6, it is characterised in that: should as heavy metal absorbent For adsorbing the oxidation state heavy metal in flue gas, in aqueous solution or in soil and/or elemental heavy metal.
CN201610569495.9A 2016-07-19 2016-07-19 A kind of melamine class high molecular material and its application in terms of handling heavy metal and preparation method Active CN106084218B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610569495.9A CN106084218B (en) 2016-07-19 2016-07-19 A kind of melamine class high molecular material and its application in terms of handling heavy metal and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610569495.9A CN106084218B (en) 2016-07-19 2016-07-19 A kind of melamine class high molecular material and its application in terms of handling heavy metal and preparation method

Publications (2)

Publication Number Publication Date
CN106084218A true CN106084218A (en) 2016-11-09
CN106084218B CN106084218B (en) 2018-10-12

Family

ID=57220744

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610569495.9A Active CN106084218B (en) 2016-07-19 2016-07-19 A kind of melamine class high molecular material and its application in terms of handling heavy metal and preparation method

Country Status (1)

Country Link
CN (1) CN106084218B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108310955A (en) * 2018-01-30 2018-07-24 湖南西林环保材料有限公司 A method of mercury is recycled in situ from non-ferrous metal metallurgy mercury fume
CN109880085A (en) * 2019-01-16 2019-06-14 大连理工大学 High richness nitrogen micropore organic polymer and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104684850A (en) * 2011-11-29 2015-06-03 新加坡科技研究局 Melamine aldehyde polymers
CN105348462A (en) * 2015-12-14 2016-02-24 武汉工程大学 Triazinyl organic mesoporous polymer as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104684850A (en) * 2011-11-29 2015-06-03 新加坡科技研究局 Melamine aldehyde polymers
CN105348462A (en) * 2015-12-14 2016-02-24 武汉工程大学 Triazinyl organic mesoporous polymer as well as preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108310955A (en) * 2018-01-30 2018-07-24 湖南西林环保材料有限公司 A method of mercury is recycled in situ from non-ferrous metal metallurgy mercury fume
CN109880085A (en) * 2019-01-16 2019-06-14 大连理工大学 High richness nitrogen micropore organic polymer and preparation method thereof
CN109880085B (en) * 2019-01-16 2021-08-20 大连理工大学 High nitrogen-rich microporous organic polymer and preparation method thereof

Also Published As

Publication number Publication date
CN106084218B (en) 2018-10-12

Similar Documents

Publication Publication Date Title
Hafshejani et al. Removal of nitrate from aqueous solution by modified sugarcane bagasse biochar
Rao et al. Removal of Cr6+ and Ni2+ from aqueous solution using bagasse and fly ash
EP3672721A1 (en) New composites for extraction of metal or contaminating chemical species
CN108310955B (en) Method for in-situ recovery of mercury from mercury-containing flue gas in non-ferrous metal metallurgy
CN109647850B (en) Treatment system for co-treating waste incineration fly ash and waste leachate
Pietrelli et al. Removal and recovery of heavy metals from tannery sludge subjected to plasma pyro-gasification process
CN114160098B (en) Preparation method of alkali/bimetallic salt water heat activated sludge biochar for removing norfloxacin in water
Namasivayam et al. Kinetic studies of adsorption of thiocyanate onto ZnCl2 activated carbon from coir pith, an agricultural solid waste
CN112569900B (en) Preparation method and application of municipal sludge biochar
Qu et al. A combined system of microwave-functionalized rice husk and poly-aluminium chloride for trace cadmium-contaminated source water purification: Exploration of removal efficiency and mechanism
Gupta et al. Adsorption of Cr (VI) by a low-cost adsorbent prepared from neem leaves
Yang et al. Tailored construction of β-cyclodextrin covalently-supported tannic acid polymer nanosponge towards highly selective lead recovery
CN113634228A (en) Sludge biochar loaded magnesium-iron oxide composite material for removing lead and cadmium in water and preparation method and application thereof
CN106084218B (en) A kind of melamine class high molecular material and its application in terms of handling heavy metal and preparation method
Alakhras Biosorption of Cd (II) ions from aqueous solution using chitosan-iso-vanillin as a low-cost sorbent: equilibrium, kinetics, and thermodynamic studies
Murugesan et al. Kinetic studies and isotherm modeling for the removal of Ni2+ and Pb2+ ions by modified activated carbon using sulfuric acid
Luo et al. Enhanced adsorption complexation of biochar by nitrogen-containing functional groups
Chu et al. Magnesium oxide nanoparticles modified biochar derived from tea wastes for enhanced adsorption of o-chlorophenol from industrial wastewater
Fu et al. Adsorption of Acid Red 73 on copper dithiocarbamate precipitate-type solid wastes
CN117443911A (en) Treatment method for reutilization of waste incineration fly ash
Li et al. Fabrication of abundantly functionalized dendritic biochar composites as adsorbents for the high-efficiency removal of heavy metal ions and dyes
JP2008264627A (en) Waste treatment material and treatment method for detoxifying fly ash (soot and dust) and burned ash or the like
Chen et al. Enhanced adsorption performance of methylene blue from aqueous solutions onto modified adsorbents prepared from sewage sludge
Al-Balushi et al. Preparation of activated carbon from date seeds and evaluation of its applications
JP2002177770A (en) Heavy metal adsorbent and method of preparing the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant