CN108993397A - A kind of chemical pharmaceutical waste is the magnetic active carbon and preparation method of raw material - Google Patents

A kind of chemical pharmaceutical waste is the magnetic active carbon and preparation method of raw material Download PDF

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Publication number
CN108993397A
CN108993397A CN201810998428.8A CN201810998428A CN108993397A CN 108993397 A CN108993397 A CN 108993397A CN 201810998428 A CN201810998428 A CN 201810998428A CN 108993397 A CN108993397 A CN 108993397A
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active carbon
magnetic
carbon
magnetic active
raw material
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翟超
李建生
王雪
祖晓冬
刘炳光
李仕增
张泽江
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Tianjin Vocational Institute
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (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)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention relates to magnetic active carbons and preparation method that a kind of D-pHPG production waste residue is raw material, the inorganic activator prepared using soluble ferric iron salt as magnetic material presoma and active carbon, improve its acid resistance with newborn carbon atom coated magnetic material, obtain the chemical composition of magnetic active carbon are as follows: carbon content 91%-95%, oxygen content 4%-6%, iron content is 2%-4%, specific surface area 1000-1500m2The rate of recovery of/g, methylene blue adsorption value 120-150mg/g, magnetic active carbon are greater than 99%, and the inorganic activator is the mixture of soluble ferric iron salt and alkali metal salt.The present invention prepares magnetic active carbon using chemical pharmaceutical waste as raw material, realizes the comprehensive utilization of waste；Iron oxide magnetic material in magnetic active carbon is coated and is firmly combined by newborn carbon atom, its magnetism can be made persistently to improve with cycle performance.

Description

A kind of chemical pharmaceutical waste is the magnetic active carbon and preparation method of raw material
Technical field
The present invention relates to magnetic active carbons and preparation method that a kind of chemical pharmaceutical waste is raw material, especially to hydroxyl Base phenylglycine produces the magnetic active carbon and preparation method that waste residue is raw material, belongs to chemical industry and Material Field.
Background technique
Using D-pHPG (4-Hydroxyphenylglycine) produce antibiotic drug mainly have Ah Amdinocillin, amoxycillin Clavulanate, amoxycillin cephalo, amoxycillin azoles cephalo, cefoperazone, cefatrizine etc..D- D-pHPG industrially by glyoxalic acid, phenol and sulfamic acid carries out condensation reaction at present, and to synthesize DL- para hydroxybenzene sweet Then propylhomoserin obtains D-pHPG by chemical resolution；It can also be carried out being condensed by glyoxalic acid, phenol and urea anti- 4-Hydroxyphenyl hydantoin should be synthesized, D-pHPG is then biologically converted into.No matter taking that technology path, D- is to hydroxyl The total recovery of base phenylglycine synthesis is 45%-50%, generates a large amount of reluctant phenols wastes.
China is DL-p-hydroxyphenylglycine major producing country in the world, since production scale constantly expands and produce receipts Rate is relatively low, not only causes a large amount of wastage of material, but also increases production treatment cost of waste liquor and pollution pressure.With increasingly Severe environmental regulation and stringent government's environmental protection supervision, DL-p-hydroxyphenylglycine production liquid waste processing problem are taken seriously, Fairly large DL-p-hydroxyphenylglycine manufacturing enterprise has used at present is concentrated in vacuo synthesis mother liquid, crystallisation by cooling, centrifugation Isolated a large amount of solid slags, the then method of burning disposal.But DL-p-hydroxyphenylglycine produces at solid slag burning The cost of reason is very high, and there are secondary pollution risk, needs to research and develop method of comprehensive utilization.
For the difficult problem of environmental protection present in enterprise's production, researchs and develops and utilized chemical pharmaceutical phenols waste residue preparation synthesis tree The method of rouge, it is quasi- to be applied to coating and adhesive field, and relevant enterprise expectation is further developed as high performance active carbon, For example, the Magnaglo active carbon of phenolic wastewater treatment.
Powdered Activated Carbon is widely used in pharmaceutical waste water advanced treating, can effectively adsorb average molecular in waste water Quality is 500 ~ 3000 organic pollutant, but often occurs sieve blocking when being separated by filtration Powdered Activated Carbon, leads to activity Charcoal, which is lost serious and production efficiency, to be reduced.It can be efficiently separated using its magnetism using magnetic active carbon, be to solve powder to live Property the simple and effective approach of charcoal recycling problem.
Magnetic active carbon preparation method is divided into one-step method and two step method.One-step method is just introduced in process for preparing active carbon Magnetic material or its presoma, magnetic material are embedded in active carbon molecular structure or are coated by carbon atom newborn in active carbon Fixed, than stronger, stability and cycle performance are improved for the combination of magnetic material and Activated carbon matrix.Two step method is by magnetic Property material or its presoma and active carbon the methods of to bond, mix, adsorb or grind to combine composite material is made, in certain journey The requirement of magnetic adsorbent is met on degree, but its magnetic persistence is poor, influence regenerating active carbon and be recycled.
It is disclosed in patent using timber, shell, biomass, coal and phenolic resin as carbon raw material, it is magnetic by addition Material precursor one-step method prepares the technique of magnetic active carbon, but the acid resistance of obtained magnetic active carbon and magnetic persistence Not good enough, magnetic material loses magnetism quickly because of dissolution in acidic aqueous solution, limits its scope of application.
Summary of the invention
The industrial process of D-pHPG is the glyoxylic acid solution for being 40% by mass concentration, is delayed under stiring It is slow to be added in the aqueous solution containing phenol and sulfamic acid, raw material molar ratio are as follows: glyoxalic acid: phenol: sulfamic acid=1: 1.0-1.2:2.5-3.5, reaction temperature are 65-75 DEG C, and cooling reaction solution is added in concentrated ammonia liquor to room temperature after the completion of condensation reaction PH with reaction solution is 3.5-4.0, has a large amount of DL-p-hydroxyphenylglycine crystallizations to be precipitated at once, isolated after the completion of crystallization DL-p-hydroxyphenylglycine product, is then transferred to and splits process production D-pHPG product, and DL- para hydroxybenzene is sweet The molar yield of propylhomoserin production is 60%-65%.
D-pHPG produces o-hydroxy glycine, D-pHPG, hydroxyl containing by-product in mother liquor The organic pollutants such as mandelic acid, phenol also contain a large amount of ammonium sulfate and Amcide Ammate inorganic matter.By reaction mother liquor hydroxide It is 6-7 that sodium solution, which is further neutralized to pH, and organic pollutant is precipitated out after evaporation and concentration produces as D-pHPG Waste residue containing phenol, moisture content 30%-35%.
The chemical composition of the waste residue containing phenol dried is analyzed, wherein containing o-hydroxy glycine 60%-70%, hydroxyl Mandelic acid 10%-20%, D-pHPG 5%-10%, phenol 5%-10% and other unknown component 3%-5%.The sweet ammonia of o-hydroxy Acid accounts for 60% of total amount or more, it is formed by glyoxalic acid, phenol and sulfamic acid termolecular reaction；Ortho position or contraposition hydroxyl Mandelic acid is formed by glyoxalic acid and phenol bimolecular reaction；D-pHPG and phenol are the product being mingled with and original Material.
The object of the present invention is to provide the magnetic active carbons that a kind of chemical pharmaceutical waste is raw material, especially to hydroxyl Phenylglycine produces the magnetic active carbon that waste residue is raw material, prepares using soluble ferric iron salt as magnetic material presoma and active carbon Inorganic activator, its acid resistance, the chemical group of acquired magnetic active carbon are improved with newborn carbon atom coated magnetic material Become: carbon content 91%-95%, oxygen content 4%-6%, iron content 2%-4%, specific surface area 1000-1500m2/ g, methylene Blue adsorptive value is 120-150mg/g, and the rate of recovery of magnetic active carbon is greater than 99%；The inorganic activator is soluble ferric iron salt With the mixture of alkali carbonate.
It is special it is a further object of the present invention to provide the preparation method for the magnetic active carbon that chemical pharmaceutical waste is raw material Sign is that the technical scheme comprises the following steps:
(1) D-pHPG is produced into waste residue containing phenol, solid formaldehyde, soluble ferric iron salt and alkali metal salt with mass ratio are as follows: 1:0.12-0.18:0.01-0.02:0.7-2 being uniformly mixed, 1-2h is smashed and ground, waste residue containing phenol and formaldehyde have been opened in the process Begin to carry out the mixture that condensation reaction generates phenol resin oligomer and inorganic activator, the iron ion in inorganic activator with point Carboxyl functional group in son combines, the phenolic hydroxyl group functional groups in sodium ion and molecule, the interior activation as active carbon preparation Agent；
(2) mixture of phenol resin oligomer and inorganic activator is heated into 0.5-2h at 110-150 DEG C, waste residue containing phenol and The condensation reaction of formaldehyde is completed, and further crosslinking is the phenolic resin cured of high molecular weight, is then crushed to 100-200 Mesh, in the process phenolic resin carbon raw material uniform load on inorganic activator, be conducive to subsequent carbonization-activation react into Row；
(3) by it is smashed it is phenolic resin cured be put into crucible, be placed in the box-type high-temperature furnace of logical nitrogen protection, with 5-10 DEG C/heating speed of min is warming up to 700 DEG C, and the heat preservation activation 1-2h at 650-750 DEG C, then stop heating and starts to drop Temperature, phenolic resin pyrolysis and thermal polycondensation are reacted while being carried out, the C- in molecular resin under the action of inorganic activator O, C-N, c h bond fracture reduce oxygen, nitrogen and hydrogen atom constantly, and the formation of fused ring compound mentions the phosphorus content of carbide constantly Height, inorganic activator etching carbide form a large amount of micropores；
(4) stop being passed through nitrogen when cooling to 450-500 DEG C, carbide naturally cools to room temperature in the presence of the air, herein In the process, iron oxide magnetic material is oxidized to by the iron oxide that carbide restores again, is assigned to active carbon magnetic；
(5) deionized water is added by several times into activated material after cooling, dipping dissolution activator 3 times, impregnate molten at 70-80 DEG C Liquid is recycled after being concentrated by evaporation as inorganic activator；What the hydrochloric acid solution dipping for being then 0.5% with mass concentration was isolated Active carbon, the inorganic activator dissolution for adsorbing activated carbon surface, it is 6-8 that pH, which is finally washed with deionized, in 110-120 Drying obtains magnetic active carbon at DEG C, and chemical composition is carbon content 91%-95%, oxygen content 4%-6%, iron content 2%-4%, Specific surface area is 1000-1500m2/ g, methylene blue adsorption value 120-150mg/g, the magnetic active carbon rate of recovery are greater than 99%.
Waste residue containing phenol in the present invention is mainly o-hydroxy glycine, contains phenolic hydroxyl group, carboxyl, amino in its molecule With multiple active function groups such as active hydrogen atom, the especially ortho position of phenolic hydroxyl group and all active hydrogen of contraposition, can contract with formaldehyde Conjunction forms phenolic resin.It can carry out under acid, alkalinity and neutrallty condition under phenol formaldehyde condensation reaction room temperature, be selected in the present invention It carries out under alkaline condition, using alkali carbonate inorganic activator as condensation catalyst.Phenol formaldehyde condensation reaction can be with It is carried out in liquid phase, solid phase and gas phase, in order to simplify synthesis technology, present invention selection carries out in solid phase, and with solid formaldehyde For condensing agent.Solid formaldehyde additional proportion is sweet using hydroxy benzenes can form linear phenolic resin with phenol organic matter Curing agent of the amino as phenolic resin in propylhomoserin molecule.
Higher with oxygen content in the phenolic resin molecule of the synthesis of waste residue containing phenol in the present invention, the carboxyl functional group contained can be with Interior activator is formed in conjunction with iron ion and sodium ion in inorganic activator, so, carbonization-activation is more anti-than phenol and formaldehyde The pure phenolic resin that should be formed is easier to carry out, and required inorganic activator can be reduced suitably, activation temperature and activation time It can also suitably reduce.
The soluble ferric iron salt used in the present invention serves not only as magnetic material presoma, and the nothing as active carbon preparation Machine activator plays dual function.Soluble ferric iron salt includes chloride, nitrate or sulfate, is also possible to acylate.Iron There are optimum ranges for the mass ratio of salt and carbon raw material.The adding proportion of molysite is very big on preparation process and product quality influence, Molysite can be combined into salt with the carboxyl in polymer monomer molecule, become the interior activator of polymer carbonization-activation, have relatively strong Activation capacity.Molysite adding proportion is excessive to will lead to active carbon activation excessively, and micropore ratio is reduced, absorption property decline and receipts Rate is greatly reduced.
For molysite as transistion metal compound, the CO small molecule that can be generated with thermal decomposition forms ligand in the present invention, Make the fragrant ring-methylated of phenolic compound, further polycondensation forms condensed ring macromolecular.Molysite plays bone when carbide activates Frame effect provides crystal seed and carrier for new life Carbon deposition, is gradually coated by newborn carbon atom, form the magnetic of Fe/C core-shell structure Property material.The iron atom being wrapped by, which could only be dissolved when strongly acidic aqueous solution impregnates, to lose magnetism, in neutral or faintly acid It is able to maintain that its magnetism in aqueous solution, is convenient for magnetic suck separation.
Magnetic material can be with Fe, Fe in the present invention3C and Fe3O4Form exist, by control high-temperature oxidation process, make it By Fe3O4As main form, the acid resistance and stability of magnetic active carbon are improved.
There is stronger alkalinity as the alkali carbonate of inorganic activator in the present invention, promote phenol in carbonization process The thermal decomposition of urea formaldehyde and thermal polycondensation, are reduced to sodium oxide molybdena and sodium atom by carbide in activation process, have to carbide Pore-creating effect is etched, carbide porosity and surface area are improved.Alkali carbonate is soluble easily in water, can use deionized water dipping It is recycled after dissolution, is the preferred inorganic activator of Activated Carbon Production.
D-pHPG production waste residue is from Hebei Shijiazhuang and Henan enterprise DL- to hydroxyl in the present invention Phenylglycine industrial production equipment；Other chemical raw material formaldehyde, frerrous chloride, hydrochloric acid, sodium hydroxide, potassium hydroxide and potassium carbonate It is commercially available chemical reagent.The technical indicators such as specific surface area, ash content, the methylene blue adsorption value of high performance active carbon powder are referring to water purification It is measured with active carbon standard GB/T 13803.2-1999 and GB/T7701.2-2008 method.The magnetic active carbon rate of recovery is by 1g Magnetic active carbon is dispersed in 1000mL deionized water, attracts fixed magnetic active carbon quality in beaker bottom using permanent magnet Account for the percentage of the magnetic active carbon quality in investment deionized water.
The advantages of the present invention are embodied in:
(1) magnetic active carbon is prepared as raw material using the phenolic resin that chemical pharmaceutical waste synthesizes, realizes the comprehensive benefit of waste With；
(2) inorganic activator that soluble ferric iron salt is prepared as magnetic material presoma and active carbon, plays dual function；
(3) the iron oxide magnetic material in magnetic active carbon is coated and is firmly combined by newborn carbon atom, it can be made magnetic persistently It is improved with cycle performance.
Specific embodiment
The purpose of the present invention is what is realized in the following ways, is described in detail below with reference to embodiment.
Embodiment 1
D-pHPG is produced into the 100g of waste residue containing phenol, solid formaldehyde 18g, frerrous chloride 2.0g and potassium carbonate 200g respectively It is added in pulverizer and smashes and grinds 1h, then the crucible equipped with mixture is put into baking oven, 2h is heated at 125 DEG C, be crosslinked For the phenolic resin cured of high molecular weight, after cooling it be crushed to 200 mesh again, obtain cured phenolic resin and inorganic activation Agent composition 270g.
Smashed phenolic resin cured and inorganic activation agent composition 90g is put into crucible, logical nitrogen protection is placed in Box-type high-temperature furnace in, be warming up to 700 DEG C with the heating speed of 10 DEG C/min, and at 650-750 DEG C heat preservation activation 2h, then Stop heating and start to cool down, stops being passed through nitrogen when cooling to 450-500 DEG C, carbide natural cooling in the presence of the air To room temperature.Deionized water 1000mL is added by several times into activated material after cooling, dipping dissolution activator 3 times at 70-80 DEG C, Then the hydrochloric acid solution 100mL for being 0.5% with mass concentration impregnates the active carbon isolated, and pH is finally washed with deionized For 6-8, drying obtains 10.2 g of magnetic active carbon at 110-120 DEG C, and chemical composition is carbon content 95%, oxygen content 5%, iron Content is 4%, specific surface area 1500m2/ g, methylene blue adsorption value are 150 mg/g, and the magnetic active carbon rate of recovery is greater than 99%.
Embodiment 2
D-pHPG is produced into the 100g of waste residue containing phenol, solid formaldehyde 12g, frerrous chloride 1.0g and sodium carbonate 100g respectively It is added in pulverizer and smashes and grinds 1h, then the crucible equipped with mixture is put into baking oven, 2h is heated at 130 DEG C, be crosslinked For the phenolic resin cured of high molecular weight, after cooling it be crushed to 100 mesh again, obtain cured phenolic resin and inorganic activation Agent composition 180g.
Smashed phenolic resin cured and inorganic activation agent composition 60g is put into crucible, logical nitrogen protection is placed in Box-type high-temperature furnace in, be warming up to 700 DEG C with the heating speed of 5 DEG C/min, and at 650-750 DEG C heat preservation activation 2h, then Stop heating and start to cool down, stops being passed through nitrogen when cooling to 450-500 DEG C, carbide natural cooling in the presence of the air To room temperature.Deionized water 600mL is added by several times into activated material after cooling, dipping dissolution activator 3 times at 70-80 DEG C, Then the hydrochloric acid solution 100mL for being 0.5% with mass concentration impregnates the active carbon isolated, and pH is finally washed with deionized For 6-8, drying obtains 11.4 g of magnetic active carbon at 110-120 DEG C, and chemical composition is carbon content 91%, oxygen content 6%, iron Content is 2%, specific surface area 1100m2/ g, methylene blue adsorption value are 130 mg/g, and the magnetic active carbon rate of recovery is greater than 99%.

Claims (2)

1. the present invention relates to the magnetic active carbons that a kind of chemical pharmaceutical waste is raw material, it is characterised in that with the sweet ammonia of para hydroxybenzene Acid production waste residue is raw material, the inorganic activator prepared using soluble ferric iron salt as magnetic material presoma and active carbon, with new Raw carbon atom coated magnetic material improves its acid resistance, the chemical composition of acquired magnetic active carbon are as follows: carbon content 91%- 95%, oxygen content 4%-6%, iron content 2%-4%, specific surface area 1000-1500m2/ g, methylene blue adsorption value 120- The rate of recovery of 150 mg/g, magnetic active carbon are greater than 99%, and the inorganic activator is soluble ferric iron salt and alkali carbonate Mixture.
2. the present invention relates to a kind of preparation methods for the magnetic active carbon that chemical pharmaceutical waste is raw material, it is characterised in that technology Scheme the following steps are included:
(1) D-pHPG is produced into waste residue containing phenol, solid formaldehyde, soluble ferric iron salt and alkali metal salt with mass ratio are as follows: 1:0.12-0.18:0.01-0.02:0.7-2 being uniformly mixed, 1-2h is smashed and ground, generates phenol resin oligomer and inorganic activation The mixture of agent；
(2) mixture of phenol resin oligomer and inorganic activator is heated into 0.5-2h at 110-150 DEG C, waste residue containing phenol and The condensation reaction of formaldehyde is completed, and further crosslinking is the phenolic resin cured of high molecular weight, is then crushed to 100-200 Mesh；
(3) by it is smashed it is phenolic resin cured be put into crucible, be placed in the box-type high-temperature furnace of logical nitrogen protection, with 5-10 DEG C/heating speed of min is warming up to 700 DEG C, and the heat preservation activation 1-2h at 650-750 DEG C, then stop heating and starts to drop Temperature；
(4) stop being passed through nitrogen when cooling to 450-500 DEG C, carbide naturally cools to room temperature in the presence of the air, by charcoal The iron oxide of compound reduction is oxidized to iron oxide magnetic material again, assigns to active carbon magnetic；
(5) deionized water is added by several times into activated material after cooling, dipping dissolution activator 3 times, are then used at 70-80 DEG C The hydrochloric acid solution that mass concentration is 0.5% impregnates the active carbon isolated, and it is 6-8 that pH, which is finally washed with deionized, in 110- Drying obtains magnetic active carbon, chemical composition at 120 DEG C are as follows: carbon content 91%-95%, oxygen content 4%-6%, iron content 2%- 4%；Its specific surface area is 1000-1500m2/ g, methylene blue adsorption value are 120-150 mg/g, and the magnetic active carbon rate of recovery is big In 99%.
CN201810998428.8A 2018-08-29 2018-08-29 A kind of chemical pharmaceutical waste is the magnetic active carbon and preparation method of raw material Pending CN108993397A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110064366A (en) * 2019-04-27 2019-07-30 天津市职业大学 A kind of phenols waste residue is magnetic active carbon and its preparation and the application of raw material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10046884B4 (en) * 1999-09-24 2007-04-12 Honda Giken Kogyo K.K. Process for the pretreatment of activated carbon for a polarized electrode
CN103706328A (en) * 2014-01-17 2014-04-09 湖南大学 Nitrogen hybridized magnetic ordered mesoporous carbon adsorbent, and preparation method and application thereof
CN107774232A (en) * 2017-10-27 2018-03-09 东莞市联洲知识产权运营管理有限公司 A kind of magnetic active carbon mixture of the ball containing charcoal and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10046884B4 (en) * 1999-09-24 2007-04-12 Honda Giken Kogyo K.K. Process for the pretreatment of activated carbon for a polarized electrode
CN103706328A (en) * 2014-01-17 2014-04-09 湖南大学 Nitrogen hybridized magnetic ordered mesoporous carbon adsorbent, and preparation method and application thereof
CN107774232A (en) * 2017-10-27 2018-03-09 东莞市联洲知识产权运营管理有限公司 A kind of magnetic active carbon mixture of the ball containing charcoal and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110064366A (en) * 2019-04-27 2019-07-30 天津市职业大学 A kind of phenols waste residue is magnetic active carbon and its preparation and the application of raw material

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Application publication date: 20181214