CN116891276A - Iron-carbon filler and preparation method and application thereof - Google Patents
Iron-carbon filler and preparation method and application thereof Download PDFInfo
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- CN116891276A CN116891276A CN202311045926.8A CN202311045926A CN116891276A CN 116891276 A CN116891276 A CN 116891276A CN 202311045926 A CN202311045926 A CN 202311045926A CN 116891276 A CN116891276 A CN 116891276A
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- 239000000945 filler Substances 0.000 title claims abstract description 95
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010802 sludge Substances 0.000 claims abstract description 95
- 239000011812 mixed powder Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000002351 wastewater Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 235000009566 rice Nutrition 0.000 claims abstract description 8
- 239000010902 straw Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 240000007594 Oryza sativa Species 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 19
- 238000006555 catalytic reaction Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 238000004062 sedimentation Methods 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000004065 wastewater treatment Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000010903 husk Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004043 dyeing Methods 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 241000209094 Oryza Species 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000010842 industrial wastewater Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005842 biochemical reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005728 strengthening Methods 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides an iron-carbon filler, a preparation method and application thereof. The iron-carbon filler comprises sludge mixed powder, wherein the sludge mixed powder is selected from Fenton dewatered sludge and/or biochemically dewatered sludge, and the sludge mixed powder comprises the following components in percentage by weight: 35-45% of C element, 25-35% of Fe element, 5-15% of Al element and the balance of other conventional components and unavoidable impurities in the sludge. The preparation method comprises the steps of mixing and granulating the sludge mixed powder with a binder, and obtaining the iron-carbon filler through a heating procedure and a cooling procedure. The Fenton sludge, the biochemical sludge, the straw/rice husk and other solid wastes are used as raw materials for recycling, so that iron resources in the Fenton sludge are effectively recovered, the iron-carbon filler with the catalytic oxidation effect is prepared, and the iron-carbon filler has wide applicability and high COD removal rate for industrial refractory wastewater and has high application value.
Description
Technical Field
The invention relates to the technical fields of recycling and recycling of industrial solid wastes and catalytic oxidation degradation of industrial wastewater, in particular to an iron-carbon filler and a preparation method and application thereof.
Background
Along with the strengthening of the national environmental protection treatment force, the emission standard of industrial wastewater is also improved. The Fenton technology has excellent performance of decoloring and removing refractory organic matters, and is widely applied to the fields of papermaking wastewater, printing and dyeing wastewater, coking wastewater and the like. However, the process generates a large amount of Fenton sludge, which not only increases the sewage treatment cost, but also threatens the ecological environment. Conventional treatment means for Fenton sludge include: the dehydration landfill and the drying incineration occupy land resources, the underground water is polluted, the incineration process is high in cost and secondary pollution is possible, and the two treatment processes can not effectively recycle the iron resources in the sludge, so that the resource waste is caused.
The invention aims to prepare an iron-carbon filler with catalytic oxidation effect by recovering iron resources in Fenton sludge, which is used for advanced treatment of industrial wastewater.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide an iron-carbon filler, a preparation method and use thereof, to prepare the iron-carbon filler by recycling waste, and to apply the iron-carbon material to the advanced treatment of industrial wastewater.
To achieve the above and other related objects, a first aspect of the present invention provides an iron-carbon filler comprising a sludge mixed powder selected from Fenton dewatered sludge and/or biochemically dewatered sludge, wherein the sludge mixed powder comprises the following components in percentage by weight: the content of the C element is 35-45%, such as 35-40% or 40-45%; the Fe element is 25-35%, such as 25-30% or 30-35%; the Al element is 5-15%, such as 5-10% or 10-15%, and the balance is other conventional components and unavoidable impurities in the sludge.
In a possible embodiment, the iron-carbon filler further comprises: the mass ratio of the sludge mixed powder to the binder is (85-95): (15-5), for example, the mass ratio of the added amount of the binder is about 5-15%, for example, 5-10% or 10-15% of the total mass.
Preferably, the binder is one or more of clay and kaolin.
In a possible embodiment, the particle size of the sludge mixed powder is 0.1 to 0.3mm, such as 0.1 to 0.2mm or 0.2 to 0.3mm.
In a possible embodiment, the sludge mixed powder is a mixture of Fenton dewatered sludge and biochemical dewatered sludge. The mass ratio of Fenton dewatered sludge to biochemical dewatered sludge is 1 (0.6-1.2), such as 1 (0.6-1.0) or 1 (1.0-1.2).
In a possible embodiment, the iron carbon filler is a porous structure having a pore size of 10 to 100 microns, for example 10 to 30 microns, 30 to 50 microns, 50 to 70 microns or 70 to 100 microns. The porous structure is obtained by adding a pore-forming agent into a filler precursor and calcining, wherein the pore-forming agent is one or more of straw activated carbon powder, rice hull sawdust waste and other materials.
In a possible embodiment, the diameter of the iron carbon filler is 0.5 to 2cm, such as 0.5 to 1cm, 1 to 1.5cm, or 1.5 to 2cm.
The second aspect of the invention provides a preparation method of the iron-carbon filler, which comprises the steps of mixing and granulating sludge mixed powder with a binder, and obtaining the iron-carbon filler after a heating procedure and a cooling procedure.
In a possible embodiment, the method specifically includes the following steps:
1) Providing Fenton dewatered sludge and/or biochemical dewatered sludge, mixing one or two of the Fenton dewatered sludge and/or biochemical dewatered sludge, grinding and sieving to obtain sludge mixed powder;
2) Mixing the sludge mixed powder, a binder and a pore-forming agent, and granulating to obtain spherical raw filler;
3) And (3) passing the spherical raw filler through a heating procedure to obtain the iron-carbon filler.
More specifically, in step 1), at least one of the following technical features is included:
1a) The mass ratio of Fenton dewatered sludge to biochemical dewatered sludge is 1 (0.6-1.2), such as 1 (0.6-1.0) or 1 (1.0-1.2).
1b) The Fenton dewatered sludge is sourced from a sludge dewatering workshop, the water content is 75-85%, and the Fenton dewatered sludge is obtained after drying;
1c) The biochemical dewatered sludge is sourced from a sludge dewatering workshop, the water content is 75-85%, and the biochemical dewatered sludge is obtained after drying;
1d) Grinding by a ball mill;
1e) Grinding and sieving, wherein the mesh number of the sieve is 80-110 meshes;
1f) The composition of each element in the sludge mixed powder is as follows: 30 to 40 percent of C element, such as 35 to 40 percent or 40 to 45 percent; 20 to 30 percent of Fe element, such as 25 to 30 percent or 30 to 35 percent; al element 5-10%, such as 5-10% or 10-15%; the balance of other conventional components and unavoidable impurities in the sludge.
More specifically, in step 2), at least one of the following technical features is included:
2a) The mass ratio of the sludge mixed powder to the binder to the pore-forming agent is (77-94): 15-5): 1:8; specifically, the binder is one or more of clay and kaolin, and the addition amount of the binder accounts for about 5-15% of the total mass, for example 5-10% or 10-15%; the pore-forming agent is one or more of straw activated carbon powder, rice hull sawdust waste and other materials, and the addition mass ratio of the pore-forming agent is about 1-8%, for example 1-5% or 5-8%. The choice is made according to the actual process or the number or size of holes to be made.
2d) Granulating by a granulator;
2e) The particle size of the spherical raw filler is 1-4 cm, such as 1-2 cm, 2-3 cm or 3-4 cm.
More specifically, in step 3), the heating program and the cooling program include:
3a) Drying and shaping the spherical raw filler in a drying box at 50-100 ℃ for 4-12 hours at low temperature; the drying temperature is 50-70 ℃, 70-90 ℃ or 90-100 ℃; the drying time can be 4-6 hours, 6-8 hours or 8-12 hours.
3b) Calcining the filler treated in the step 3 a) in a calciner at 200-300 ℃ for 0.5-1 hour in an anaerobic manner; the calcination temperature is, for example, 200-250℃or 250-300 ℃.
3c) Calcining the filler treated in the step 3 b) in a high-temperature calciner at 600-800 ℃ for 0.5-1 hour in an anaerobic manner; the calcination temperature is 600-650deg.C, 650-700deg.C, 700-750deg.C or 750-800deg.C.
3d) And 3) cooling the filler in the step 3 b) to room temperature to obtain the iron-carbon filler.
The third aspect of the invention provides the use of the iron-carbon filler described above or the iron-carbon filler obtained by the preparation method described above in wastewater treatment.
In a fourth aspect, the present invention provides a method of wastewater treatment comprising the steps of:
1) Providing the iron-carbon filler or the iron-carbon filler prepared by the preparation method of the iron-carbon filler;
2) Placing the iron-carbon filler in the step 1) into a reaction device, wherein the volume proportion of the iron-carbon filler is 30-50%, such as 30-40% or 40-50%, of the total volume.
3) The pH value of the water quality of the inlet water is adjusted to be 2.5-4.5, such as 2.5-3.0,3.0-4.0 or 4.0-4.5. The acid-base modifier is dilute sulfuric acid, and the concentration of the sulfuric acid is about 10-20wt%.
4) Controlling the water inflow rate to ensure that the hydraulic retention time is 0.5 to 1.5 hours, such as 0.5 to 1.0 hour or 1.0 to 1.5 hours.
5) The pH value of the effluent water is adjusted to be 6.0-7.0, such as 6.0-6.5 or 6.5-7.0. After precipitation and filtration, the reaction is completed.
The fifth aspect of the invention provides a wastewater process system comprising an acidification adjusting tank, an iron-carbon catalytic reaction tank, a neutralization tank and a sedimentation tank which are sequentially in fluid communication; the iron-carbon catalytic reaction tank is internally loaded with the iron-carbon filler or the iron-carbon filler prepared by the iron-carbon filler preparation method.
In a possible embodiment, at least one of the following technical features is further included:
c1 The acidification adjusting tank is provided with a wastewater input pipeline;
c2 One end of the first conveying pipeline is communicated with the lower side of the acidification adjusting tank, the other end of the first conveying pipeline is communicated with the lower side of the iron-carbon catalytic reaction tank, and a metering pump is arranged on the first conveying pipeline;
c3 The device also comprises a clean water tank which is arranged at the downstream of the sedimentation tank and is communicated with the sedimentation tank;
c4 A blow-down pipe is arranged at the bottom of the iron-carbon catalytic reaction tank.
As described above, the invention has at least one of the following advantageous effects:
1) The Fenton sludge, biochemical sludge, straw/rice husk and other solid wastes are used as raw materials for recycling, so that iron resources in the Fenton sludge are effectively recovered, and the iron-carbon filler with the catalytic oxidation effect is prepared.
2) The filler provided by the invention has the catalytic effect of MBC (magnetic biochar), has a better pore structure, has wide applicability and higher COD removal rate for industrial refractory wastewater due to the micro-electrolysis reaction of the iron-carbon coupled with Fenton reagent, and has a stronger application value.
Drawings
FIG. 1 is a flow chart showing a method for preparing an iron-carbon filler in example 1 of the present invention.
FIG. 2 is a schematic diagram of a wastewater treatment system according to example 2 of the present invention.
Detailed Description
The invention is further illustrated below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods and reagents not specifying the formulation in the following examples were carried out or configured under conventional conditions or conditions suggested by the manufacturer.
Example 1
Referring to fig. 1:
step (1), preparing 1 part of Fenton dehydrated sludge and 1 part of biochemical dehydrated sludge (secondary sedimentation tank sludge after biochemical reaction) respectively after Fenton process treatment of wastewater in a printing and dyeing factory, drying, dehydrating, grinding by a ball mill, sieving by a 110-mesh sieve, and mixing according to a mass ratio of 1:1 to obtain sludge mixed powder. The weight percentages of the elements in the sludge mixed powder are as follows: 38% of C element, 28% of Fe element, 8% of Al element and 26% of other components.
And (2) mixing the sludge powder, the binder and the pore-forming agent according to a mass ratio of 80:15:5, and preparing spherical raw filler with a diameter of about 1cm by a granulator. The binder is kaolin, the pore-forming agent is a mixture of straw activated carbon powder and rice hulls, and the mass ratio is 2:1.
Step (3), (3 a) the spherical raw filler is dried in a drying box at 80 ℃ for 8 hours;
(3b) Feeding the filler treated in the step (3 a) into a tube furnace, heating the tube furnace to 200 ℃ at a heating rate of 5 ℃/min, then keeping the temperature constant, and performing anaerobic calcination at the constant temperature of 200 ℃ for 1 hour;
(3c) Continuously heating the tubular furnace to 800 ℃ at a heating rate of 5 ℃/min by the filler treated in the step (3 b), keeping the temperature constant, and calcining the filler at the high temperature of 800 ℃ for 1 hour in an anaerobic manner;
(3d) And (3) cooling the filler in the step (3 c) to room temperature to obtain the iron-carbon filler. The iron-carbon filler is of a porous structure, and the size of the porous pore diameter is generally 10-100 microns.
Example 2
Referring to fig. 2:
the wastewater process system comprises an acidification adjusting tank 2, an iron-carbon catalytic reaction tank 5, a neutralization tank 6 and a sedimentation tank 7 which are sequentially in fluid communication; the iron-carbon catalytic reaction tank 5 is internally loaded with iron-carbon packing 4, wherein fluid communication is that each tank is directly communicated or communicated through a pipeline, a metering pump or a control valve is arranged on each communicating pipeline according to requirements, and the acidification adjusting tank 2 is provided with a wastewater input pipeline 1 communicated with the top of the acidification adjusting tank 2. Specifically, the process system includes a first conveying pipeline, one end of a first conveying pipe is communicated with the lower side of the acidification adjusting tank 2, the other end of the first conveying pipe is communicated with the lower side of the iron-carbon catalytic reaction tank 5, and a metering pump 3 and a control valve 10 are arranged on the first conveying pipe . More specifically, the process system further comprises a clean water tank 8 arranged downstream of the sedimentation tank 7 and communicated with the sedimentation tank 7.
Example 3
Step (1), filling 1.5L of the iron-carbon filler prepared in the example 1 into the iron-carbon catalytic reaction tank 5, wherein the total volume of the iron-carbon catalytic reaction tank 5 is about 5L;
step (2) taking 15L of printing and dyeing mill wastewater, and adjusting the pH value of the wastewater to 3.5 by adopting 15% dilute sulfuric acid;
and (3) adjusting the water inflow rate to 83mL/min, continuously feeding water and discharging water for reaction, adjusting the pH value of discharged water to 6.5 by adopting sodium hydroxide, performing water discharge sampling detection after precipitation, wherein the sampling time is 1 hour, 2 hours and 3 hours, and the average value of COD removal rate can reach more than 85 percent.
Example 4
Referring to fig. 1:
and (1) preparing 1 part of Fenton dehydrated sludge and 1 part of biochemical dehydrated sludge (biochemical sludge in a secondary sedimentation tank after biochemical reaction) treated by a Fenton process in a printing and dyeing factory, drying, dehydrating, grinding by a ball mill, sieving by a 100-mesh sieve, and mixing according to a mass ratio of 1:1 to obtain sludge mixed powder. The weight percentage of each element in the sludge mixed powder is as follows: 40% of C element, 27% of Fe element, 8% of Al element and 25% of other elements.
And (2) mixing the sludge powder, the binder and the pore-forming agent according to the mass ratio of 79:15:6, and preparing spherical raw filler with the diameter of about 1cm by a granulator. The binder is kaolin, the pore-forming agent is a mixture of straw activated carbon powder and rice hulls, and the mass ratio is 2:1.
Step (3),
(3a) Drying the spherical raw filler in a drying box at 80 ℃ for 8 hours;
(3b) Feeding the filler treated in the step (3 a) into a tube furnace, heating the tube furnace to 250 ℃ at a heating rate of 6 ℃/min, keeping the temperature, and performing anaerobic calcination at the constant temperature of 250 ℃ for 1 hour;
(3c) Continuously heating the tubular furnace to 850 ℃ at the heating rate of 6 ℃/min by the filler treated in the step (3 b), keeping the temperature constant, and calcining the filler at the high temperature of 850 ℃ for 1 hour in an anaerobic manner;
(3d) And (3) cooling the filler in the step (3 c) to room temperature to obtain the iron-carbon filler.
Example 5
Step (1), filling 1.5L of the iron-carbon filler prepared in the example 1 into the iron-carbon catalytic reaction tank 5, wherein the total volume of the iron-carbon catalytic reaction tank 5 is about 5L;
step (2) taking 15L of printing and dyeing mill wastewater, and adjusting the pH value of the wastewater to 3.5 by adopting 15% dilute sulfuric acid;
and (3) adjusting the water inflow rate to 83mL/min, continuously feeding water and discharging water for reaction, adjusting the pH value of discharged water to 6.5 by adopting sodium hydroxide, performing water discharge sampling detection after precipitation, wherein the sampling time is 1 hour, 2 hours and 3 hours, and the average value of COD removal rate can reach more than 87%.
Example 6
Referring to fig. 1:
and (1) preparing 1 part of Fenton dehydrated sludge and 1 part of biochemical dehydrated sludge (biochemical sludge in a secondary sedimentation tank after biochemical reaction) treated by a Fenton process in a printing and dyeing factory, drying, dehydrating, grinding by a ball mill, sieving by a 100-mesh sieve, and mixing according to a mass ratio of 1:1.2 to obtain sludge mixed powder. The weight percentage of each element in the sludge mixed powder is as follows: 35% of C element, 30% of Fe element, 10% of Al element and 25% of other elements.
And (2) mixing the sludge powder, the binder and the pore-forming agent according to a mass ratio of 80:15:5, and preparing spherical raw filler with a diameter of about 1cm by a granulator. The binder is kaolin, the pore-forming agent is a mixture of straw activated carbon powder and rice hulls, and the mass ratio is 2:1.
Step (3),
(3a) Drying the spherical raw filler in a drying box at 80 ℃ for 8 hours;
(3b) Feeding the filler treated in the step (3 a) into a tube furnace, heating the tube furnace to 200 ℃ at a heating rate of 5 ℃/min, then keeping the temperature constant, and performing anaerobic calcination at the constant temperature of 200 ℃ for 1 hour;
(3c) Continuously heating the tubular furnace to 800 ℃ at a heating rate of 5 ℃/min by the filler treated in the step (3 b), keeping the temperature constant, and calcining the filler at the high temperature of 800 ℃ for 1 hour in an anaerobic manner;
(3d) And (3) cooling the filler in the step (3 c) to room temperature to obtain the iron-carbon filler.
Example 7
Step (1), filling 1.5L of the iron-carbon filler prepared in the example 1 into the iron-carbon catalytic reaction tank 5, wherein the total volume of the iron-carbon catalytic reaction tank 5 is about 5L;
step (2) taking 15L of printing and dyeing mill wastewater, and adjusting the pH value of the wastewater to 3.5 by adopting 15% dilute sulfuric acid;
and (3) adjusting the water inflow rate to 90mL/min, continuously feeding water and discharging water for reaction, adjusting the pH value of discharged water to 6.5 by adopting sodium hydroxide, performing discharged water sampling detection after precipitation, wherein the sampling time is 1 hour, 2 hours and 3 hours, and the average value of COD removal rate can reach more than 90%. The above examples are provided to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, many modifications and variations of the methods and compositions of the invention set forth herein will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the present invention.
Claims (10)
1. An iron-carbon filler for wastewater treatment, comprising a sludge mixed powder, wherein the sludge mixed powder is selected from Fenton dewatered sludge and/or biochemical dewatered sludge, and comprises the following components in percentage by weight:
35-45% of C element, 25-35% of Fe element, 5-15% of Al element and the balance of other conventional components and unavoidable impurities in the sludge.
2. The iron-carbon filler of claim 1, further comprising at least one of the following technical features:
a1 The iron-carbon filler further comprises: the mass ratio of the sludge mixed powder to the binder is (85-95) and (15-5);
a2 The grain diameter of the sludge mixed powder is 0.1-0.3 mm;
a3 The sludge mixed powder is a mixture of Fenton dehydrated sludge and biochemical dehydrated sludge;
a4 The iron-carbon filler is of a porous structure;
a5 The diameter of the iron-carbon filler is 0.5-2 cm.
3. The iron-carbon filler of claim 2, further comprising at least one of the following technical features:
a11 The binder is clay and/or kaolin;
a31 The mass ratio of Fenton dehydrated sludge to biochemical dehydrated sludge is 1 (0.6-1.2);
a41 The pore size of the porous structure is 10-100 micrometers.
4. The preparation method of the iron-carbon filler is characterized by comprising the steps of mixing and granulating sludge mixed powder and a binder, and obtaining the iron-carbon filler after a heating procedure, and comprises the following steps:
1) Providing Fenton dewatered sludge and/or biochemical dewatered sludge, mixing one or two of the Fenton dewatered sludge and/or biochemical dewatered sludge, grinding and sieving to obtain sludge mixed powder;
2) Mixing the sludge mixed powder, a binder and a pore-forming agent, and granulating to obtain spherical raw filler;
3) And (3) passing the spherical raw filler through a heating procedure to obtain the iron-carbon filler.
5. The method for producing an iron-carbon filler according to claim 4, characterized by comprising at least one of the following technical features:
1a) The mass ratio of Fenton dehydrated sludge to biochemical dehydrated sludge is 1 (0.6-1.2);
1b) The Fenton dewatered sludge is sourced from a sludge dewatering workshop, the water content is 75-85%, and the Fenton dewatered sludge is obtained after drying;
1c) The biochemical dewatered sludge is sourced from a sludge dewatering workshop, the water content is 75-85%, and the biochemical dewatered sludge is obtained after drying;
1d) Grinding by a ball mill;
1e) Grinding and sieving, wherein the mesh number of the sieve is 80-110 meshes;
1f) The composition of each element in the sludge mixed powder is as follows: 30-40% of C element, 20-30% of Fe element, 5-10% of Al element and the balance of other conventional components and unavoidable impurities in the sludge;
2a) The mass ratio of the sludge mixed powder to the binder to the pore-forming agent is (77-94): 15-5): 1:8;
2b) The binder is clay and/or kaolin;
2c) The pore-forming agent is selected from straw activated carbon powder and/or rice hull sawdust waste;
2d) Granulating by a granulator;
2e) The particle size of the spherical raw filler is 1-4 cm.
6. The method of producing an iron-carbon filler according to claim 4, wherein in step 3), the heating process and the cooling process include:
3a) Drying and shaping the spherical raw filler in a drying box at 50-100 ℃ for 4-12 hours at low temperature;
3b) Calcining the filler treated in the step 3 a) in a calciner at 200-300 ℃ for 0.5-1 hour in an anaerobic manner;
3c) Calcining the filler treated in the step 3 b) in a high-temperature calciner at 600-800 ℃ for 0.5-1 hour in an anaerobic manner;
3d) And 3) cooling the filler in the step 3 b) to room temperature to obtain the iron-carbon filler.
7. Use of the iron-carbon filler according to any one of claims 1 to 3 or the iron-carbon filler prepared by the iron-carbon filler preparation method according to any one of claims 4 to 6 in wastewater treatment.
8. A method for wastewater treatment comprising the steps of:
1) Providing an iron-carbon filler according to any one of claims 1 to 3, or an iron-carbon filler prepared by the iron-carbon filler preparation method according to any one of claims 4 to 6;
2) Placing the iron-carbon filler in the step 1) into a reaction device, wherein the volume proportion of the iron-carbon filler is 30-50% of the total volume;
3) The pH value of the water quality of the inlet water is adjusted to be 2.5-4.5;
4) Controlling the water inflow rate to ensure that the hydraulic retention time is 0.5-1.5 h;
5) The pH value of the effluent water is regulated to be 6.0-7.0.
9. A wastewater process system is characterized by comprising an acidification adjusting tank (2), an iron-carbon catalytic reaction tank (5), a neutralization tank (6) and a sedimentation tank (7) which are sequentially in fluid communication; the iron-carbon catalytic reaction tank (5) is internally loaded with the iron-carbon filler (4) according to any one of claims 1 to 3 or the iron-carbon filler prepared by the iron-carbon filler preparation method according to any one of claims 4 to 8.
10. The wastewater treatment system of claim 9, further comprising at least one of the following features:
c1 The acidification adjusting tank (2) is provided with a wastewater input pipeline (1);
c2 The device comprises a first conveying pipeline (10), one end of the first conveying pipeline (10) is communicated with the lower side of the acidification adjusting tank (2), the other end of the first conveying pipeline is communicated with the lower side of the iron-carbon catalytic reaction tank (5), and a metering pump (3) is arranged on the first conveying pipeline (10);
c3 The device also comprises a clean water tank (8) which is arranged at the downstream of the sedimentation tank (7) and is communicated with the sedimentation tank (7);
c4 The bottom (5) of the iron-carbon catalytic reaction tank is provided with a blow-down pipe (9).
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| CN101734826A (en) * | 2008-11-18 | 2010-06-16 | 南京理工大学 | Process method for treating coking wastewater |
| CN109851002A (en) * | 2019-02-12 | 2019-06-07 | 陕西煤业化工技术研究院有限责任公司 | A kind of micro-electrolysis stuffing and its preparation method and application for realizing iron cement recycling |
| CN114478058A (en) * | 2022-01-10 | 2022-05-13 | 中国石化集团南京化学工业有限公司 | Sludge carbon-based micro-electrolysis filler for improving biochemical property of chemical wastewater and preparation method and application thereof |
| WO2023077882A1 (en) * | 2021-11-05 | 2023-05-11 | 同济大学 | Method for preparing sludge conditioner from water supply sludge and application of sludge conditioner |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734826A (en) * | 2008-11-18 | 2010-06-16 | 南京理工大学 | Process method for treating coking wastewater |
| CN109851002A (en) * | 2019-02-12 | 2019-06-07 | 陕西煤业化工技术研究院有限责任公司 | A kind of micro-electrolysis stuffing and its preparation method and application for realizing iron cement recycling |
| WO2023077882A1 (en) * | 2021-11-05 | 2023-05-11 | 同济大学 | Method for preparing sludge conditioner from water supply sludge and application of sludge conditioner |
| CN114478058A (en) * | 2022-01-10 | 2022-05-13 | 中国石化集团南京化学工业有限公司 | Sludge carbon-based micro-electrolysis filler for improving biochemical property of chemical wastewater and preparation method and application thereof |
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