CN107673436A - The method for preparing by iron-carbon micro-electrolysis offal treatment sewage and subsequently catalysis nitro reducing catalyst - Google Patents

The method for preparing by iron-carbon micro-electrolysis offal treatment sewage and subsequently catalysis nitro reducing catalyst Download PDF

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CN107673436A
CN107673436A CN201710952975.8A CN201710952975A CN107673436A CN 107673436 A CN107673436 A CN 107673436A CN 201710952975 A CN201710952975 A CN 201710952975A CN 107673436 A CN107673436 A CN 107673436A
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iron
antimony
electrolysis
carbon
adsorbent
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CN107673436B (en
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孙宏滨
王婧婷
艾永建
牛盾
左卫雄
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Northeastern University China
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid 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 surface properties or porosity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention belongs to environmental protection, chemical field, be related to it is a kind of by iron-carbon micro-electrolysis offal treatment sewage and subsequently prepare catalysis nitro reducing catalyst method.Raw material is that Fe-C Micro Electrolysis Method handles caused iron carbon waste residue during sewage, activated by soda acid, high temperature sintering, co-precipitation, drying obtain porous material absorption agent, for adsorbing heavy metal in waste water antimony, filtered reclaim of adsorbent after absorption antimony must contain antimony waste residue, antimony waste residue will be contained by drying, calcine technology, nitro reducing catalyst is prepared into, the catalyst has catalytic effect to nitro-reduction reaction, can be reused as catalyst.There can be preferable treatment effect to sewage using the adsorbent obtained by the present invention, catalyst activity made of follow-up is also very high, technique is simple simultaneously, strong operability, disclosure satisfy that industry requirement, it is a kind for the treatment of of wastes with processes of wastes against one another, the process for the recycling turned waste into wealth, and has preferable application prospect.

Description

Prepare by iron-carbon micro-electrolysis offal treatment sewage and subsequently catalysis nitro reduction catalystses The method of agent
Technical field
The invention belongs to environmental protection, chemical field, is related to one kind by iron-carbon micro-electrolysis offal treatment sewage and subsequently prepares It is catalyzed the method for nitro reducing catalyst.
Background technology
Iron-carbon micro-electrolysis is a kind of conventional method of water treatment field, and its principle is that the electrochemical corrosion based on metal is former Reason, the waste water with certain electric conductivity being served as into electrolyte, the Fe of the low potential and C of high potential produces potential difference in waste water, Infinite multiple small galvanic cells are formed in waste water, so as to produce electrode reaction, electric field can be formed during the course of the reaction, band in water The contaminant molecule of electricity shifts to the electrode of opposite charges, and adsorb and aoxidize at the electrode surface in the presence of electric field force Reduction reaction, it is degraded into small-molecule substance.Redox reaction, production can occur with the pollutant in solution for the product of electrode reaction The effects such as raw absorption, flocculation, precipitation, so as to reach the purpose for removing pollutant.One shortcoming of this method can exactly produce greatly The sludge of amount, this be a kind of iron content and inertia carbon granules (such as:Graphite, activated carbon, coal etc.) solid waste.Its processing and Recycling is an important topic in field of Environment Protection.
The content of the invention
It is an object of the invention to provide one kind to prepare by iron-carbon micro-electrolysis offal treatment sewage and subsequently catalysis nitro The method of reducing catalyst, there can be preferable treatment effect to sewage using the adsorbent obtained by the present invention, subsequently be made Catalyst activity it is also very high, while technique is simple, strong operability, disclosure satisfy that industry requirement.
The technical scheme is that:
It is a kind of by iron-carbon micro-electrolysis offal treatment sewage and subsequently prepare catalysis nitro reducing catalyst method, raw material For Fe-C Micro Electrolysis Method handle sewage during caused iron carbon waste residue, activated by soda acid, high temperature sintering, co-precipitation, drying Porous material absorption agent is obtained, for adsorbing heavy metal in waste water antimony, antimony must be contained by adsorbing filtered reclaim of adsorbent after antimony Waste residue, antimony waste residue will be contained by drying, calcine technology, be prepared into nitro reducing catalyst.
It is described by iron-carbon micro-electrolysis offal treatment sewage and the method that subsequently prepares catalysis nitro reducing catalyst, acid Alkali activation condition is:Iron carbon waste residue mass fraction is 5%~10% NaOH aqueous solution soakings, in 40~60 DEG C of heating stirrings Then 10~30min is rinsed to neutrality repeatedly with removing the greasy dirt on surface with distilled water;It is 1%~10% with volume fraction Dilute sulfuric acid soaks 0.5~1h, removes the oxidizing component on surface, increases its surface area and activity;Sedimentation 1~4 is small after acidifying When, it is standby that supernatant is that iron-containing liquor pours out, and residue is rinsed to neutrality, vacuum drying repeatedly with deionized water.
It is described by iron-carbon micro-electrolysis offal treatment sewage and the method that subsequently prepares catalysis nitro reducing catalyst, it is high Warm sintering condition is residue:The mass ratio of melamine or urea is 0.1~1:5, calcining heat is with 3~7 DEG C/min speed Rate is warming up to 500~560 DEG C, and calcination time is 3~5 hours, is prepared into the carbon nitride material containing active carbon granule.
It is described by iron-carbon micro-electrolysis offal treatment sewage and the method that subsequently prepares catalysis nitro reducing catalyst, will Carbon nitride material containing active carbon granule mixes with the iron-containing liquor extracted before, is co-precipitated with ammoniacal liquor, obtains having porous knot The C@C of structure3N4@Fe2O3Adsorbent.
It is described by iron-carbon micro-electrolysis offal treatment sewage and the method that subsequently prepares catalysis nitro reducing catalyst, give up In 50~200mg/L, the pH value of waste water is 4~8 for antimony concentration in water, and adsorbent amount is 0.5~2g/L, adsorption temp 25 ~40 DEG C, duration of oscillation is 1~4 hour.
It is described by iron-carbon micro-electrolysis offal treatment sewage and the method that subsequently prepares catalysis nitro reducing catalyst, nitre Base reducing catalyst is carbon iron antimony composite catalyst.
It is described by iron-carbon micro-electrolysis offal treatment sewage and the method that subsequently prepares catalysis nitro reducing catalyst, by The method that the adsorbent of recovery prepares nitro reducing catalyst:The adsorbent that Magneto separate is reclaimed, after being dried at 70~90 DEG C, It is placed in Muffle furnace and is calcined 1~5 hour at 200~350 DEG C, the antimony of absorption is become antimony oxide, and and other components With reference to formation composite oxides, its structure is C@C3N4@Fe2O3·mSb2O3, that is, it is changed into nitro reducing catalyst.
The present invention design philosophy be:
Antimony is a kind of noxious pollutant, it turned out that there is toxicity and carcinogenicity to human body and biology, due to mankind's activity and Antimony containing compounds widely use, and substantial amounts of antimony is entered environment, cause antimony concentration abnormality in environment, antimony pollution starts in recent years Attract people's attention.In the antimony ore exploitation in China and dyeing, because production technology falls behind, a large amount of stibium-containing wastewaters are not Surface water body is directly discharged into through any processing, serious pollution is caused to local water environment, neighbouring resident's health is caused Serious harm, there is an urgent need to develop some cheap, efficient antimony sewage disposal technologies.Currently for the processing skill of stibium-containing wastewater Using the metal oxide adsorption effect such as iron, manganese it is optimal in art, therefore the present invention is based on the thinking of " treatment of wastes with processes of wastes against one another ", iron carbon is micro- After iron carbon waste residue caused by electrolysis carries out appropriate working process, preparation turns into a kind of efficient antimony adsorbent, for removing sewage In heavy metal antimony.
Aromatic amine is the important source material and intermediate for preparing dyestuff, pigment, agricultural chemicals, polymer, insecticide and medicine.Obtain The main path of arylamine, it is the corresponding fragrant nitro compound of reduction, main method includes active metal reducing process at present, catalysis adds Hydrogen method and hydrazine hydrate reduction method etc..Wherein, hydrazine hydrate reduction method accessory substance is nitrogen and water, has the excellent of safety and environmental protection Point.Because the iron carbon waste residue after absorption antimony has good activity to hydrazine hydrate reduction virtue nitro compound, the present invention will contain antimony Iron carbon waste residue secondary use, be processed into catalyst, be catalyzed nitro-reduction reaction.
Advantages of the present invention and beneficial effect are:
1st, the present invention provides a kind of offal treatment sewage, and by the method for its secondary use, by being produced in water treatment field Raw iron-carbon micro-electrolysis discarded object is processed into antimony adsorbent, again by waste residue secondary operation into catalyst after absorption, and is used for nitro Reduction reaction, the not only treatment of wastes with processes of wastes against one another, the recycling target of " turning waste into wealth " is more realized, there is preferable application prospect.
2nd, the present invention prepares antimony adsorbent with iron carbon waste residue, and the adsorbent adsorption capacity of preparation is high, and scavenging effect is good, there is magnetic Property, it can be reclaimed after absorption by Magneto separate.
3rd, caused waste residue containing antimony is used to be prepared into catalyst after present invention processing sewage, by the waste residue containing antimony after absorption Secondary use, it is processed into nitro reducing catalyst.It the experiment proved that, the catalyst has good catalytic effect to reaction, no Only there is universality to various nitro compounds, and also have for the reduction reaction of the compound of this difficult reduction of paranitrophenol There is excellent activity, reaction controlling can react complete within 1h.And the catalyst reusing is high, can repeatedly circulate makes With there is magnetic, be easy to Magneto separate to reclaim.
Embodiment
In specific implementation process, the present invention provides a kind of to be urged by iron-carbon micro-electrolysis offal treatment sewage and subsequently preparing Change the method for nitro reducing catalyst, it is specific as follows:
Waste residue caused by iron-carbon micro-electrolysis is subjected to soda acid activation first, actual conditions is:Iron carbon waste residue (desiccation):Alkali (meter of folding hundred):The ratio of acid (meter of folding hundred) is 1:(5%~10% mass fraction):(1%~10% volume fraction).Wherein, it is sour For sulfuric acid, alkali is sodium hydroxide.Soda acid activation temperature is 40~60 DEG C, and the aqueous slkali soaking time is 10~30min, and acid solution soaks The bubble time is 0.5~1h.The composition of iron carbon waste residue includes iron containing compoundses, inertia carbon granules and organic matter, and some mineral matters And water.The greasy dirt and impurity on surface can be removed with aqueous slkali soaking, the oxidizing component on surface then can be removed with dilute sulfuric acid immersion, Increase its surface area and activity, while also can extract soluble iron, and to being activated in the microstructure of the discarded object. Sedimentation 1~4 hour, supernatant (iron-containing liquor) pour out standby after acidifying, and residue is rinsed to neutrality repeatedly with distilled water.
The preparation method of adsorbent:Residue and melamine or urea mixed calcining after soda acid is activated, specific reaction Condition is mass of residue (after soda acid activation):Melamine quality (urea)=(0.1~1):5, calcining heat is 500~560 DEG C, calcination time is 3~5 hours, and calcination procedure is 3~7 DEG C/min, is prepared into the carbon nitride material containing active carbon granule.Again will It is mixed with the iron-containing liquor extracted before, is co-precipitated with ammoniacal liquor, obtains the C C with loose structure3N4@Fe2O3Absorption Agent.
The method of sorbent treatment waste water:The best effort pH scopes of the adsorbent are 4~8, and stibium-containing wastewater concentration is 50 ~200mg/L, according to the difference of Antimony in Waste Water content, 0.5~2g/L of adsorbent is added, is shaken 1~4 hour at 25~40 DEG C Afterwards, adsorbent is withdrawn by Magneto separate.
The method that nitro reducing catalyst is prepared by the adsorbent reclaimed:The adsorbent that Magneto separate is reclaimed, at 80 DEG C Drying, is then placed in Muffle furnace and is calcined 1~5 hour at 200~350 DEG C, the antimony of absorption is become antimony oxide, and with Other components combine, and form composite oxides, its structure is C@C3N4@Fe2O3·mSb2O3, that is, it is changed into nitro reduction catalystses Agent.
With reference to example, the present invention is further described, but the embodiment of the present invention is not limited to following implementation Example, include any combination of various embodiments.
Embodiment 1:
In the present embodiment, the side of catalysis nitro reducing catalyst is prepared by iron-carbon micro-electrolysis offal treatment sewage and subsequently Method is as follows:
The preparation of adsorbent:Iron carbon waste residue 10g caused by iron-carbon micro-electrolysis water treating method is taken, is 7.5% (matter with concentration Amount) NaOH aqueous solution soakings, 30min or so is stirred at 40 DEG C, solid slag S1 is filtered to obtain, waste residue is repeatedly rinsed with distilled water S1 is to neutrality.The iron carbon waste residue S1 after washing is immersed in 1h in the dilute sulfuric acid that concentration is 5.5% (volume) again, sedimentation 0.5h is obtained Residue H1 and supernatant L1, supernatant L1 is transferred to stand-by in another beaker.Residue H1 is rinsed near repeatedly with deionized water Neutral (pH=5~7), then dry at 80 DEG C.The residue H1 that 0.1g is dried is taken, itself and 5g melamines are sufficiently mixed, It is put into Muffle furnace Program to heat up 3 DEG C/min, calcines 4h at such a temperature after reaching 530 DEG C, obtain solid P1, then by solid P1 Mixed with reserved supernatant L1, add ammoniacal liquor thereto, 4h is co-precipitated at 80 DEG C, obtain nitrogenizing the iron carbon composite oxygen of carbon doping Compound, its structural formula are C@C3N4@Fe2O3, as adsorbent A 1;
The absorption of antimony:Adsorbent (A1) 0.5g is weighed, is added to 1000mL containing (pH value is advance in the water sample that antimony is 50mg/L It is adjusted to 4), vibrates 1 hour at 32.5 DEG C, antimony content remaining in water is less than 20mg/L after testing, and clearance is up to 60%.Use magnetic Iron reclaims adsorbent, obtains used adsorbent B 1;
Catalyst preparation and application:Adsorbent B 1 is dried at 90 DEG C, is then transferred in Muffle furnace, at 200 DEG C 3h is calcined, obtains catalyst C1.14mg catalyst C1,1mmol p-nitrophenol, 2mL isopropanols is taken to be added in tube sealing 2.5mmol hydrazine hydrates, react 1 hour at 110 DEG C.Reaction takes product to be detected with liquid chromatogram after terminating, and conversion ratio reaches 100%, product purity reaches 99%.
Embodiment 2:
In the present embodiment, the side of catalysis nitro reducing catalyst is prepared by iron-carbon micro-electrolysis offal treatment sewage and subsequently Method is as follows:
The preparation of adsorbent:Iron carbon waste residue 10g caused by iron-carbon micro-electrolysis water treating method is taken, is 5% (quality) with concentration NaOH aqueous solution soakings, 10min or so is stirred at 50 DEG C, solid slag S2 is filtered to obtain, is repeatedly rinsed to neutrality with distilled water. Again by the iron carbon waste residue S2 after washing be immersed in concentration be 1% (volume) dilute sulfuric acid in 0.5h, sedimentation 2.5h obtain residue H2 and Supernatant L2, supernatant L2 is transferred to stand-by in another beaker.Residue H2 is rinsed to weakly acidic pH (pH=repeatedly with deionized water 5~7), then dry at 80 DEG C.The residue H2 that 1g is dried is taken, itself and 5g melamines are sufficiently mixed, are put into Muffle furnace 7 DEG C/min of temperature programming, 5h is calcined at such a temperature after reaching 500 DEG C, obtains solid P2, then by solid P2 and reserved supernatant Liquid L2 is mixed, and adds ammoniacal liquor thereto, 4h is co-precipitated at 80 DEG C, obtains nitrogenizing the iron carbon composite oxides of carbon doping, its structure Formula is C@C3N4@Fe2O3, as adsorbent A 2;
The absorption of antimony:Adsorbent (A2) 1.25g is weighed, is added to 1000mL containing (pH value is pre- in the water sample that antimony is 125mg/L First it is adjusted to 6), vibrates 4 hours at 25 DEG C, antimony content remaining in water is less than 25mg/L after testing, and clearance reaches 80%.Magnetic point From reclaiming used adsorbent B 2;
Catalyst preparation and application:Adsorbent B 2 is dried at 70 DEG C, is then transferred in Muffle furnace, at 275 DEG C 1h is calcined, obtains catalyst C2.14mg catalyst C2,1mmol p-nitrophenol, 2ml isopropanols is taken to be added in tube sealing 2.5mmol hydrazine hydrates, react 1 hour at 110 DEG C.Reaction takes product to be detected with liquid chromatogram after terminating, and conversion ratio reaches 100%, product purity reaches 99%.
Embodiment 3:
In the present embodiment, the side of catalysis nitro reducing catalyst is prepared by iron-carbon micro-electrolysis offal treatment sewage and subsequently Method is as follows:
The preparation of adsorbent:Iron carbon waste residue 10g caused by iron-carbon micro-electrolysis water treating method is taken, is 10% (quality) with concentration NaOH aqueous solution soakings, 20min or so is stirred at 60 DEG C, solid slag S3 is filtered to obtain, is repeatedly rinsed to neutrality with distilled water. Again by the iron carbon waste residue S3 after washing be immersed in concentration be 10% (volume) dilute sulfuric acid in 0.75h, sedimentation 4h obtain residue H3 and Supernatant L3, supernatant L3 is transferred to stand-by in another beaker.Residue H3 is rinsed to weakly acidic pH (pH=repeatedly with deionized water 5~7), then dry at 80 DEG C.The residue H3 that 0.55g is dried is taken, itself and 5g melamines are sufficiently mixed, are put into Muffle Stove Program heats up 5 DEG C/min, calcines 3h at such a temperature after reaching 560 DEG C, obtains solid P3, then by solid P3 with it is reserved Supernatant L3 is mixed, and adds ammoniacal liquor thereto, 4h is co-precipitated at 80 DEG C, obtains nitrogenizing the iron carbon composite oxides of carbon doping, its Structural formula is C@C3N4@Fe2O3, as adsorbent A 3;
The absorption of antimony:Adsorbent (A3) 2g is weighed, is added to 1000mL containing (pH value is advance in the water sample that antimony is 200mg/L It is adjusted to 8), is vibrated at 40 DEG C 2.5 hours, antimony content remaining in water is that clearance is up to 90% less than 20mg/L after testing. Magneto separate, reclaim used adsorbent B 3;
Catalyst preparation and application:Adsorbent B 3 is dried at 80 DEG C, is then transferred in Muffle furnace, at 350 DEG C 5h is calcined, obtains catalyst C3.14mg catalyst C2,1mmol p-nitrophenol, 2mL isopropanols is taken to be added in tube sealing 2.5mmol hydrazine hydrates, react 1 hour at 110 DEG C.Reaction takes product to be detected with liquid chromatogram after terminating, and conversion ratio reaches 100%, product purity reaches 99%.
Comparative example 1:
With reference to embodiment 1, by iron-carbon micro-electrolysis discarded object directly as adsorbent A 0, the absorption of antimony is carried out:Weigh absorption Agent (A0) 0.5g, 1000mL is added to containing (pH value is adjusted to 4~8 in advance) in the water sample that antimony is 50mg/L, is vibrated 2 hours, through inspection It is 49mg/L to survey remaining antimony content in water, clearance 2%.The adsorbent containing antimony is reclaimed, calcines 3 hours, obtains at 250 DEG C To catalyst C0.1mmol p-nitrophenols, 14mg catalyst C0,2.5mmol hydrazine hydrates are taken in tube sealing, adds isopropanol 2mL, react 1 hour at 110 DEG C.Reaction measures conversion ratio with high performance liquid chromatography after terminating and reaches 30%.
Comparative example 2:
With reference to embodiment 1, iron-carbon micro-electrolysis discarded object is subjected to soda acid processing through same condition, the waste residue after processing H1 is directly used as adsorbent A 4;Adsorbent (A4) 0.5g is weighed, is added to 1000mL containing (pH value is pre- in the water sample that antimony is 50mg/L First it is adjusted to 4~8), vibrate 2 hours, antimony content remaining in water is 8mg/L after testing, clearance 84%.Recovery is adsorbed containing antimony Agent, calcined 3 hours at 250 DEG C, obtain catalyst C4.Take 1mmol p-nitrophenols, 14mg catalyst C4,2.5mmol hydration Hydrazine adds isopropanol 2mL, reacted 1 hour at 110 DEG C in tube sealing.React and measure conversion ratio with high performance liquid chromatography after terminating Only 20%.
Comparative example 3:
With reference to embodiment 1, after mixing melamine calcining acquisition P1, no longer it is co-precipitated, directly using P1 as adsorbent A 5.Take 0.5gA5,1000mL is added to containing (pH value is adjusted to 4~8 in advance) in the water sample that antimony is 50mg/L, is vibrated 2 hours, water after testing Middle remaining antimony content is 5mg/L, clearance 90%.Recovery contains antimony adsorbent, calcines 3 hours, is catalyzed at 250 DEG C Agent C5.1mmol p-nitrophenols, 14mg catalyst C4,2.5mmol hydrazine hydrates are taken in tube sealing, adds isopropanol 2mL, 110 DEG C Lower reaction 1 hour.It is only 25% that reaction measures conversion ratio after terminating with high performance liquid chromatography.
Comparative example 4:
With reference to embodiment 1, the adsorbent A 1 of preparation is not used in absorption antimony, directly as catalyst C6 catalysis nitro reduction Reaction.Catalytic reaction condition takes 1mmol p-nitrophenols, 14mg catalyst C6,2.5mmol hydrazine hydrates in envelope with embodiment 1 Guan Zhong, isopropanol 2mL is added, is reacted 1 hour at 110 DEG C.It is 30% that reaction measures conversion ratio after terminating with high performance liquid chromatography.
Comparative example 5:
With reference to embodiment 1, after B1 is obtained, without subsequent operations such as calcining and activatings, directly as catalyst C7, catalysis Reaction condition takes 1mmol p-nitrophenols, 14mg catalyst C7,2.5mmol hydrazine hydrates in tube sealing, added different with embodiment 1 Propyl alcohol 2mL, react 1 hour at 110 DEG C.Reaction uses magnet separating catalyst after terminating, and reaction solution revolving is dried to obtain into production Thing, utilize high performance liquid chromatography detection conversion ratio to 25%.
Embodiment and comparative example result show that adsorbent of the present invention is one kind by the caused micro- electricity of iron carbon in water treatment field Discarded object is solved, its processing and its method for recycling specifically can be described as:By the processing of iron-carbon micro-electrolysis discarded object soda acid Mix with melamine or urea, through calcining, being co-precipitated, the step such as drying, be processed into for adsorbing heavy metal ion antimony afterwards Adsorbent, adsorb antimony after adsorbent have catalytic effect to nitro-reduction reaction after the techniques such as calcining and activating again, can conduct Catalyst reuses.

Claims (7)

1. it is a kind of by iron-carbon micro-electrolysis offal treatment sewage and subsequently prepare catalysis nitro reducing catalyst method, its feature Be, raw material be Fe-C Micro Electrolysis Method handle sewage during caused iron carbon waste residue, activated by soda acid, high temperature sintering, altogether Precipitation, drying obtain porous material absorption agent, for adsorbing heavy metal in waste water antimony, adsorb filtered time of adsorbent after antimony Antimony waste residue must be contained by receiving, and will be contained antimony waste residue by drying, calcine technology, and be prepared into nitro reducing catalyst.
2. it is according to claim 1 by iron-carbon micro-electrolysis offal treatment sewage and subsequently prepare catalysis nitro reduction catalystses The method of agent, it is characterised in that soda acid activation condition is:Iron carbon waste residue mass fraction is 5%~10% NaOH aqueous solution Immersion, in 40~60 DEG C of 10~30min of heating stirring to remove the greasy dirt on surface, is then rinsed to neutrality repeatedly with distilled water; Soak 0.5~1h with the dilute sulfuric acid that volume fraction is 1%~10%, remove the oxidizing component on surface, increase its surface area and Activity;Sedimentation 1~4 hour after acidifying, it is standby that supernatant is that iron-containing liquor pours out, and residue is rinsed into repeatedly with deionized water Property, vacuum drying.
3. it is according to claim 2 by iron-carbon micro-electrolysis offal treatment sewage and subsequently prepare catalysis nitro reduction catalystses The method of agent, it is characterised in that high temperature sintering condition is residue:The mass ratio of melamine or urea is 0.1~1:5, calcining Temperature is to be warming up to 500~560 DEG C with 3~7 DEG C/min speed, and calcination time is 3~5 hours, is prepared into containing active carbon granule Carbon nitride material.
4. it is according to claim 3 by iron-carbon micro-electrolysis offal treatment sewage and subsequently prepare catalysis nitro reduction catalystses The method of agent, it is characterised in that the carbon nitride material containing active carbon granule is mixed with the iron-containing liquor extracted before, uses ammoniacal liquor Co-precipitation, obtains the C@C with loose structure3N4@Fe2O3Adsorbent.
5. it is according to claim 1 by iron-carbon micro-electrolysis offal treatment sewage and subsequently prepare catalysis nitro reduction catalystses The method of agent, it is characterised in that antimony concentration in waste water is in 50~200mg/L, and the pH value of waste water is 4~8, and adsorbent amount is 0.5~2g/L, adsorption temp are 25~40 DEG C, and duration of oscillation is 1~4 hour.
6. it is according to claim 1 by iron-carbon micro-electrolysis offal treatment sewage and subsequently prepare catalysis nitro reduction catalystses The method of agent, it is characterised in that nitro reducing catalyst is carbon iron antimony composite catalyst.
7. it is according to claim 1 by iron-carbon micro-electrolysis offal treatment sewage and subsequently prepare catalysis nitro reduction catalystses The method of agent, it is characterised in that the method that nitro reducing catalyst is prepared by the adsorbent reclaimed:The absorption that Magneto separate is reclaimed Agent, after being dried at 70~90 DEG C, it is placed in Muffle furnace and is calcined 1~5 hour at 200~350 DEG C, the antimony of absorption is become three Two antimony are aoxidized, and are combined with other components, form composite oxides, its structure is C@C3N4@Fe2O3·mSb2O3, that is, it is changed into Nitro reducing catalyst.
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CN108854959A (en) * 2018-07-04 2018-11-23 湖南农业大学 A kind of preparation method and applications of nano zero valence iron sludge based biomass charcoal
CN110252425A (en) * 2019-07-03 2019-09-20 中国科学院生态环境研究中心 A kind of activation method inactivating iron-carbon micro-electrolysis filler

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US3197419A (en) * 1962-06-11 1965-07-27 Standard Oil Co Mixed antimony oxide-iron oxide oxidation catalyst
CN101183631A (en) * 2007-11-16 2008-05-21 武汉大学 Method of producing carbon nano-tube array field emission cathode
CN106944075A (en) * 2017-04-20 2017-07-14 东北大学 A kind of method that nitro reducing catalyst is prepared by reduced iron powder waste residue
CN107008486A (en) * 2017-05-19 2017-08-04 西安工业大学 A kind of preparation method of carbonitride/stibium doping stannic oxide hetero-junctions

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US3197419A (en) * 1962-06-11 1965-07-27 Standard Oil Co Mixed antimony oxide-iron oxide oxidation catalyst
CN101183631A (en) * 2007-11-16 2008-05-21 武汉大学 Method of producing carbon nano-tube array field emission cathode
CN106944075A (en) * 2017-04-20 2017-07-14 东北大学 A kind of method that nitro reducing catalyst is prepared by reduced iron powder waste residue
CN107008486A (en) * 2017-05-19 2017-08-04 西安工业大学 A kind of preparation method of carbonitride/stibium doping stannic oxide hetero-junctions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108854959A (en) * 2018-07-04 2018-11-23 湖南农业大学 A kind of preparation method and applications of nano zero valence iron sludge based biomass charcoal
CN110252425A (en) * 2019-07-03 2019-09-20 中国科学院生态环境研究中心 A kind of activation method inactivating iron-carbon micro-electrolysis filler

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