CN109604624A - A kind of method and application preparing nano zero valence iron using water treatment plant's iron containing sludge - Google Patents
A kind of method and application preparing nano zero valence iron using water treatment plant's iron containing sludge Download PDFInfo
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- CN109604624A CN109604624A CN201910016833.XA CN201910016833A CN109604624A CN 109604624 A CN109604624 A CN 109604624A CN 201910016833 A CN201910016833 A CN 201910016833A CN 109604624 A CN109604624 A CN 109604624A
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- sludge
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 82
- 239000010802 sludge Substances 0.000 title claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 230000015556 catabolic process Effects 0.000 claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 claims abstract description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 3
- 239000003570 air Substances 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 16
- 229960003405 ciprofloxacin Drugs 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000701 coagulant Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000004917 polyol method Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZBJWWKFMHOAPNS-UHFFFAOYSA-N loretin Chemical compound C1=CN=C2C(O)=C(I)C=C(S(O)(=O)=O)C2=C1 ZBJWWKFMHOAPNS-UHFFFAOYSA-N 0.000 description 1
- 229950010248 loretin Drugs 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/33—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/30—Organic compounds
Abstract
The present invention provides a kind of methods using water treatment plant's iron containing sludge preparation zeroth order ferrum nano material.To be derived from water treatment plant's clarifier sludge through filter-press dehydration, air-dry and crush after, pre-process to obtain dry iron cement particle by high temperature drying, and grind, sieve and obtain iron cement sample；Again by the way that under inert gas shielding, high-temperature calcination is pyrolyzed to obtain magnetic Nano zeroth order iron material.The application of the nano zero valence iron activation of catalyst persulfate oxidation degradation organic pollutants of the present invention prepared according to the above method.The resource reclaim of method of the invention based on water treatment plant's production sludge, the catalyst of preparation has efficient catalytic degradation effect, it separates and recovers and recycles easily from water phase under externally-applied magnetic field, and raw material environmental protection is easy to get, preparation method is simple, economical, the effect of realization turns waste into wealth, controls " waste water " with " waste " has biggish actual application prospect.
Description
Technical field
The invention belongs to nano material preparation and water-treatment technology fields, and in particular to a kind of to utilize water treatment plant's iron containing sludge
Prepare the method and application of nano zero valence iron.
Background technique
Nano zero valence iron has biggish specific surface area, preferable adsorptivity, extremely strong reproducibility, thus to certain mistakes
Oxide (such as: persulfate etc.) there are efficient catalysis characteristics；Meanwhile Zero-valent Iron has good magnetic characteristic, can lead to
It crosses externally-applied magnetic field mode and is separated from the water recycling, can be used for organic pollutant in catalytic degradation removal water environment, be considered as one
Kind has the catalysis material of broad prospect of application, is widely paid close attention in recent years.The preparation for the nano zero valence iron reported at present
Method mainly has chemical method and physical method, and physical method mainly has vapor condensation method and ball-milling method, and wherein vapor condensation method needs height
Warm hyperbaric environment, and need to consume a large amount of coolants, energy consumption is high, and ball-milling method needs special equipment, and energy consumption is also relatively high；Change
Method mainly has liquid phase reduction, carbothermy, polyol process, the reducing agent sodium borohydride that wherein liquid phase reduction uses, price
Valuableness, and strong toxicity, are unfavorable for industrialization and water treatment applications；Carbothermy is compound as reducing agent synthesis Fe-C using inorganic carbon
Material, but due to preparation method complexity, chemical reagent used is more, is unfavorable for being mass produced；And polyol process need to use corruption
Corrosion reagent, limits its scope of application.With the enhancing of recycling and sustainable development idea, it is necessary to make full use of for we
Existing waste researches and develops a kind of inexpensive, efficient, environmentally protective catalysis material by resource utilization.
Water treatment plant's production iron cement has the physicochemical property of synthesis Zero-valent Iron predecessor.Molysite [e.g.FeCl3, FeCl2,
FeSO4·7H2O, poly-ferric chloride (PFCl) etc. are widely used in technique of harnessing the river as coagulant, cause largely to generate useless
Water and sludge by-product.Purification plant sludge produces waste water, including sludge from sedimentation tank water and spent filter backwash water from it.According to
Report, China will have 1.5~2.4 million tons of dry mud to generate every year.For clean water sludge processing method there are mainly three types of, one
It is to be directly discharged into neighbouring water body and river, aluminium can constitute ecological threat to aquatile in spoil disposal water, cause the lift in riverbed
Height, while also will affect the shipping in river and ability of controlling flood and draining flooded fields；Second is that being discharged into Municipal pipe network, it is directly entered drainpipe
Road is transported to sewage treatment plant and is uniformly processed, due to containing the sediments such as a large amount of sand, the row of will cause in water inlet sludge
The blocking of waterpipe, while also will increase the processing load of sewage treatment plant；Third is that carrying out the independent of sludge after sludge dewatering
Disposition, such as carry out soil improvement, recycling metal, the fertilizer as construction material or crops, these dirts turned waste into wealth
Mud method of disposal is the Main Trends of The Development of the following sludge treatment.Since wastewater zero discharge implements the increasing of dynamics, water factory's production
It is imperative that Sewage treatment recycles.If effective component in precipitating sludge centralized recovery and can rationally recycle, not only
Added amount of chemical can be effectively reduced, while also reducing wastewater treatment and sludge treatment expense.
The substance that water-purifying process is removed is mainly colloidal solid, bacterium and micro-content organism, therefore generated sludge
Composition is based on the substances such as solid particle, metal hydroxides, humus, coagulant ingredient and a small amount of algae bacterium, packet
The inexpensive raw material that can be considered preparation Zero-valent Iron containing ingredient, possess biggish recycling potential.If can be simple just with one kind
Prompt method handles iron cement, prepares nano zero valence iron, can not only turn waste into wealth, synthesizing efficient catalyst, effectively
Reduction prepares cost of material, while can also reduce sludge treatment expense.
Summary of the invention
It is an object of the invention to be unfavorable for for current Zero-valent Iron preparation process is complicated, energy consumption is high, cost of material is higher
Extensive industrial application, while in order to more preferably realize the problems such as water treatment plant's production recycling sludge, high efficiente callback recycle, it mentions
For a kind of method and application for preparing nano zero valence iron using water treatment plant's iron containing sludge, the nano zero valence iron being prepared has height
The catalytic performance of effect and preferable magnetism, can be applied to the height of activation persulfate catalyzing oxidizing degrading organic pollutants
Grade oxidation technology.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A method of nano zero valence iron being prepared using water treatment plant's iron containing sludge, specific step is as follows for the method:
Step 1: iron containing sludge is pre-processed: first by iron containing sludge natural air drying, is then smashed, then will crushed
Sludge afterwards, which is put into air dry oven, to be dried, and is then further ground and by obtaining dry dirt after 200 meshes point
Mud sample product；
Step 2: high-temperature calcination is carried out to dewatered sludge: weighing dewatered sludge sample and is put into crucible, then the earthenware that mud sample will be held
Crucible is put into tube furnace, first leads to inert gas or air original in tube furnace is discharged nitrogen, is then opened tube furnace and is carried out
Calcination processing, calcination process specifically: from room temperature to 800 DEG C, then keep the temperature 2h, then cool down, take out black powder sample
Product are put into drying basin and are sealed；It is fired in cooling whole process using inert gas or nitrogen as protecting.
A kind of application of the nano zero valence iron of above-mentioned preparation, the nano zero valence iron are applied to be catalyzed as catalyst
Sulfate degradation organic pollutants.
The beneficial effect of the present invention compared with the existing technology is:
(1) Zero-valent Iron Fe is prepared by one-step calcination method0Effective catalyst, it is inexpensive, environmentally protective, realize waste resource
Change；
(2) rationally magnetic Nano material, Yi Huishou are prepared, realization is recycled for multiple times using the higher source of iron of content in sludge；
(3) water factory's waste reclamation reduces wastewater treatment and sludge treatment expense, slows down the secondary dirt to water environment, soil
Dye；
(4) sludge recycling modification is convenient, and synthesis preparation method is simple, and yield is high, possesses very high industrialization potential, can be extensive
Apply in practical water treatment technology.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph using nano zero valence iron prepared by water treatment plant's iron containing sludge；
Fig. 2 is the transmission electron microscope picture using nano zero valence iron prepared by water treatment plant's iron containing sludge；
Fig. 3 is the X-ray crystallogram of former iron containing sludge and the Fe-series catalyst of preparation under different calcination temperatures；
Fig. 4 is permonosulphuric acid potassium (PMS), nano zero valence iron (Fe0) and the two combination to the drop of Ciprofloxacin organic matter in water
Solve efficiency chart；
Fig. 5 is the adsorption/desorption curve figure of Fe-series catalyst prepared under different calcination temperatures；
Fig. 6 is the hysteresis loop figure of Fe-series catalyst prepared under different calcination temperatures；
Fig. 7 is that Fe-series catalyst prepared under different calcination temperatures activates permonosulphuric acid potassium (PMS) oxidative degradation Ciprofloxacin
Efficiency figure.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawings and examples, and however, it is not limited to this,
It is all that modifying or equivalently replacing the technical solution of the present invention, without departing from the spirit and scope of the technical solution of the present invention,
It should all cover within the protection scope of the present invention.
The principle of the present invention are as follows: water treatment plant's iron containing sludge is that hydrolysis occurs in flocculated stage by iron salt coagulant, together
Shi Fasheng is electrically neutralized and net catches volume and sweeps to act on and particulate matter in raw water and natural organic matter are flocculated and precipitated together, therefore iron cement
In include Fe (OH)3Hydrolysate, there are also a certain amount of organic matters；High-temperature calcination carbonisation can be in an inert atmosphere
By Fe (OH)3It loses and water is combined to form ferriferous oxide Fe3O4, after further increasing temperature, carbon containing organic components in iron cement
By autoreduction, by Fe3O4Also original production Zero-valent Iron Fe0。
Specific embodiment 1: what present embodiment recorded is a kind of to prepare nano zero valence iron using water treatment plant's iron containing sludge
Method, specific step is as follows for the method:
Step 1: iron containing sludge is pre-processed: first by iron containing sludge natural air drying to moisture content be 5% ~ 10%, then into
Row smashes, then smashed sludge is put into air dry oven, is dried 24 hours at a temperature of 105 DEG C, then carries out
It further grinds and by obtaining dewatered sludge sample after 200 meshes point；The iron containing sludge source are as follows: water treatment plant's coagulation/wadding
Solidifying processing unit is using molysite (including iron chloride, ferric sulfate, poly-ferric chloride, polymerized ferric-aluminum chloride etc. is containing ferron) as wadding
Solidifying agent by obtaining high concentration spoil disposal water after coagulation-precipitation process, then adds polyacrylamide, passes through sheet frame after stirring centrifugation
Formula filter press is dehydrated, its moisture content is made to be reduced to 75% or so.
Step 2: high-temperature calcination is carried out to dewatered sludge: weighing 10g dewatered sludge sample and is put into crucible, then sludge will be held
The crucible of sample is put into tube furnace, first leads to inert gas or air original in tube furnace is discharged nitrogen, then opens pipe
Formula furnace carries out calcination processing, calcination process specifically: from room temperature to 800 DEG C, then keeps the temperature 2h, then cools down, takes out black
Color powder sample, is put into drying basin and is sealed；It is fired in cooling whole process using inert gas or nitrogen as guarantor
Shield, avoids iron in sludge from being oxidized by oxygen.When calcination temperature is 400 DEG C, combination water, organic matter volatilization loss in iron cement,
But significant change does not occur for Iron speciation, and gained catalyst is denoted as Fe (OH)3-400；When calcination temperature is 600 DEG C, four oxidations are obtained
Three-iron/silicon dioxide composite material, is denoted as Fe3O4-600；When calcination temperature is 800 DEG C, it is compound to obtain Zero-valent Iron/silica
Material is denoted as Fe0-800。
Specific embodiment 2: a kind of described in specific embodiment one prepare nano zero-valence using water treatment plant's iron containing sludge
The method of iron, in step 2, the inert gas is argon gas.
Specific embodiment 3: a kind of described in specific embodiment one or two prepare nanometer using water treatment plant's iron containing sludge
The method of Zero-valent Iron, in step 2, the flow velocity of the inert gas or nitrogen is 160 mL/min；In calcination process, inertia
The flow velocity of gas or nitrogen is 100 mL/min.
Specific embodiment 4: a kind of described in specific embodiment one or two prepare nanometer using water treatment plant's iron containing sludge
The method of Zero-valent Iron, in step 2, the tube furnace is heated up with the rate of 4 DEG C/min；Temperature-fall period are as follows: with 10 °C/min's
Rate is cooled to 100 DEG C, then natural cooling at room temperature.
Specific embodiment 5: a kind of described in specific embodiment three prepare nano zero-valence using water treatment plant's iron containing sludge
The method of iron, in step 2, the tube furnace is heated up with the rate of 4 DEG C/min；Temperature-fall period are as follows: with the rate of 10 DEG C/min
100 DEG C are cooled to, then natural cooling at room temperature.
Specific embodiment 6: a kind of nano zero valence iron of specific embodiment one to five any specific embodiment preparation
Application, the nano zero valence iron is applied to catalysis persulfate as catalyst and degrades organic pollutants, specific to walk
Suddenly are as follows: configure antibiotic organic wastewater, initial concentration is 10 mg/L, and adjusting pH is 7 ± 0.5, according to the dense of 10 mg/L
Degree requires that nano zero-valence iron catalyst is added into solution, 0.5 g/L of persulfate is added after mixing, in room temperature (25
± 1 DEG C) under the conditions of, it is catalysis reaction 60min in 180 rmp shaking tables in revolving speed.High performance liquid chromatography measurement is anti-after reaction
Organic matter residual concentration after answering, and calculate removal efficiency.
Specific embodiment 7: the application of nano zero valence iron described in specific embodiment six, the persulfate are
Permonosulphuric acid potassium PMS.
Embodiment 1
(1) iron cement sampling and pretreatment:
Water treatment plant is using molysite as coagulant, by obtaining high concentration spoil disposal water after coagulation-precipitation process, then adds polyacrylamide
Amine is dehydrated after stirring centrifugation by plate and frame type filter-press, and making its moisture content will be 75% or so.
Using water treatment plant's iron containing sludge as raw material, then progress natural air drying first is smashed, then by smashed sludge
It is put into air dry oven, is dried 24 hours at 105 DEG C, after then further being ground and being divided by 200 meshes
Obtain dewatered sludge sample.
(2) preparation of magnetic Nano zero-valent iron composite material:
It weighs 10g dewatered sludge sample to be put into crucible, then the crucible for holding mud sample is put into tube furnace, first lead to 1h argon gas
Air original in tube furnace is discharged, argon gas flow velocity is 160 mL/min；Then tube furnace is opened, with the rate of 4 DEG C/min
800 DEG C are warming up to, in 800 DEG C of temperature lower calcination 2h；100 DEG C are cooled to 10 DEG C of rate, it is naturally cold at room temperature
But, black powder sample is taken out after cooling, is put into drying basin and is sealed.It is fired in cooling whole process and is made with argon gas
For protection, iron in sludge is avoided to be oxidized by oxygen.
The surface sweeping Electronic Speculum of the zero-valent iron material prepared using iron containing sludge calcining is as shown in Figure 1, transmission electron microscope such as Fig. 2
It is shown, it can be seen that nano zero valence iron shows the bead that partial size is 20 ~ 30 nm, and dispersibility is preferably.Crystal structure diffraction maximum
For XRD as shown in Fig. 3 figure, the catalyst for calcining 800 DEG C of preparations has apparent Zero-valent Iron characteristic peak.
Embodiment 2
The present embodiment is the application of magnetic Nano zero-valent iron composite material catalysis persulfate degradation organic pollutants, including
Following steps:
(1) 3 groups of 100 mL of organic wastewater containing antibiotic ciprofloxacin are configured, number is~, initial concentration is 10 mg/
L, adjusting pH is 7 ± 0.5.
(2) toPermonosulphuric acid potassium PMS (Oxone, KHSO are only added in number beaker5·0.5 KHSO4·0.5
K2SO4) 0.5 g/L；ToPrepared nano zero valence iron Fe is only added in number beaker010 mg/L of -800 heterogeneous catalysis；
To0.5 g/L of permonosulphuric acid potassium PMS and prepared 10 mg/L of nano zero valence iron are added in number beaker.In room temperature (25 ± 1
°C) under the conditions of, it is to carry out 60 min of catalysis reaction in 180 rmp shaking tables simultaneously in revolving speed.
(3) separately sampled in specific time node, organic matter residual concentration after being reacted by high performance liquid chromatography measurement,
And removal efficiency is calculated, compare its degradation effect to Ciprofloxacin.
Degradation effect is as shown in Figure 4, it can be seen that for the Ciprofloxacin organic pollutant of 10mg/L, independent mistake one
The removal rate of 60 min of sulfuric acid nak response is less than 20%；Individually adding nano zero valence iron reaction 60min can to the removal rate of organic matter
Up to 40% or so；And 30 min are reacted to the removal rate of organic matter just more than 99% when the two combination, it can be seen that utilize water treatment plant
The nano zero valence iron of iron containing sludge preparation has obviously effect to catalysis persulfate degradable organic pollutant.
Embodiment 3
The present embodiment is the different calcination temperatures (400 DEG C, 600 DEG C, 800 DEG C) of research to ferrous magnetic material physicochemical properties
It influences.The following steps are included:
The present embodiment is with 1 difference of embodiment: tube furnace calcination temperature is respectively 400 DEG C and 600 DEG C in step (2), other
Step is same as Example 1；
The adsorption/desorption curve for the catalyst material prepared under three kinds of different calcination temperatures is as shown in Figure 5, it can be seen that with
The raising of calcination temperature, catalyst gradually form meso-hole structure, the nano zero valence iron in comparison formed under 800 DEG C of calcination temperatures
There is maximum specific surface area, exposing more active point would be even more beneficial to promote catalysis reaction.
The hysteresis loop for the catalyst material prepared under three kinds of different calcination temperatures is as shown in Figure 6, it can be seen that with
The magnetism of the raising of calcination temperature, catalyst gradually increases, and the nano zero valence iron in comparison formed under 800 DEG C of calcination temperatures has
Maximum saturation magnetization (30 emu/g), show that catalyst can realize well separation of solid and liquid by externally-applied magnetic field, have
Conducive to recycling and reusing and reduce fine catalyst secondary pollution caused by aqueous solution.
Embodiment 4
The present embodiment is to study the activation of catalyst mistake prepared under former iron cement and different calcination temperatures (400 DEG C, 600 DEG C, 800 DEG C)
The influence of oxide sulfate degradation Ciprofloxacin.
(1) 4 groups of 100 mL of organic wastewater containing antibiotic ciprofloxacin are configured, number is~, initial concentration is 10
Mg/L, adjusting pH is 7 ± 0.5.
(2)10 mg/L original iron cements and 0.5 g/L permonosulphuric acid potassium PMS are added in number beaker；
10 mg/L Fe (OH) are added in number beakerx- 400 and 0.5 g/L permonosulphuric acid potassium PMS；
10 mg/L Fe are added in number beaker3O4- 600 and 0.5 g/L permonosulphuric acid potassium PMS；
10 mg/L Fe are added in number beaker0- 800 and 0.5 g/L permonosulphuric acid potassium PMS.
It (3) is to carry out 60 min of catalysis reaction in 180 rmp shaking tables simultaneously in revolving speed under the conditions of room temperature (25 ± 1 DEG C).
It is separately sampled in specific time node, by organic matter residual concentration after high performance liquid chromatography measurement reaction, and calculate removal effect
Rate compares its degradation effect to Ciprofloxacin.
In comparison 4 groups of catalyzing oxidizing degrading efficiency rate of exchange under 800 DEG C of calcination temperatures as shown in fig. 7, it can be seen that form
Nano zero valence iron have efficient catalytic efficiency.
Claims (7)
1. a kind of method for preparing nano zero valence iron using water treatment plant's iron containing sludge, it is characterised in that: the method specifically walks
It is rapid as follows:
Step 1: iron containing sludge is pre-processed: first by iron containing sludge natural air drying, is then smashed, then will crushed
Sludge afterwards, which is put into air dry oven, to be dried, and is then further ground and by obtaining dry dirt after 200 meshes point
Mud sample product；
Step 2: high-temperature calcination is carried out to dewatered sludge: weighing 10g dewatered sludge sample and is put into crucible, then mud sample will be held
Crucible be put into tube furnace, first lead to inert gas or nitrogen and air original in tube furnace be discharged, then open tube furnace
Carry out calcination processing, calcination process specifically: from room temperature to 800 DEG C, then keep the temperature 2h, then take out black powder after cooling
Last sample, is put into drying basin and is sealed；It is fired in cooling whole process using inert gas or nitrogen as protecting.
2. a kind of method for preparing nano zero valence iron using water treatment plant's iron containing sludge according to claim 1, feature exist
In: in step 2, the inert gas is argon gas.
3. a kind of method for preparing nano zero valence iron using water treatment plant's iron containing sludge according to claim 1 or 2, feature
Be: in step 2, the flow velocity of the inert gas or nitrogen is 160 mL/min；In calcination process, inert gas or nitrogen
The flow velocity of gas is 100 mL/min.
4. a kind of method for preparing nano zero valence iron using water treatment plant's iron containing sludge according to claim 1 or 2, feature
Be: in step 2, the tube furnace is heated up with the rate of 4 DEG C/min；Temperature-fall period are as follows: cooled down with the rate of 10 DEG C/min
To 100 DEG C, then natural cooling at room temperature.
5. a kind of method for preparing nano zero valence iron using water treatment plant's iron containing sludge according to claim 3, feature exist
In: in step 2, the tube furnace is heated up with the rate of 4 DEG C/min；Temperature-fall period are as follows: be cooled to the rate of 10 DEG C/min
100 DEG C, then natural cooling at room temperature.
6. a kind of application of the nano zero valence iron of claim 1 ~ 5 any claim preparation, it is characterised in that: the nanometer
Zero-valent Iron is applied to catalysis persulfate degradation organic pollutants as catalyst.
7. the application of nano zero valence iron according to claim 6, it is characterised in that: the persulfate is permonosulphuric acid
Potassium PMS.
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