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 PDFInfo
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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
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 48
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 36
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 title claims abstract description 36
- 239000010865 sewage Substances 0.000 title claims abstract description 32
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 25
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 53
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003463 adsorbent Substances 0.000 claims abstract description 48
- 239000002699 waste material Substances 0.000 claims abstract description 37
- 238000010521 absorption reaction Methods 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 229910017112 Fe—C Inorganic materials 0.000 claims abstract description 3
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 4
- VXWFVRYBEIIXJE-UHFFFAOYSA-N [Sb].[Fe].[C] Chemical group [Sb].[Fe].[C] VXWFVRYBEIIXJE-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 150000002828 nitro derivatives Chemical class 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- B01J20/28054—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 surface properties or porosity
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- 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)
- 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
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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Cited By (2)
| 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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|---|---|---|---|---|
| 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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2017
- 2017-10-13 CN CN201710952975.8A patent/CN107673436B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| 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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