CN110040901A - It is a kind of can sludge reuse light electrolysis/heterogeneous Fenton fluidized-bed process and device - Google Patents
It is a kind of can sludge reuse light electrolysis/heterogeneous Fenton fluidized-bed process and device Download PDFInfo
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- CN110040901A CN110040901A CN201910392472.9A CN201910392472A CN110040901A CN 110040901 A CN110040901 A CN 110040901A CN 201910392472 A CN201910392472 A CN 201910392472A CN 110040901 A CN110040901 A CN 110040901A
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- 239000010802 sludge Substances 0.000 title claims abstract description 191
- 238000000034 method Methods 0.000 title claims abstract description 58
- 230000008569 process Effects 0.000 title claims abstract description 44
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 308
- 239000002245 particle Substances 0.000 claims abstract description 192
- 229910052742 iron Inorganic materials 0.000 claims abstract description 155
- 239000002351 wastewater Substances 0.000 claims abstract description 85
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000007767 bonding agent Substances 0.000 claims abstract description 37
- 230000018044 dehydration Effects 0.000 claims abstract description 27
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 27
- 238000010992 reflux Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 81
- 238000003756 stirring Methods 0.000 claims description 35
- 238000005189 flocculation Methods 0.000 claims description 34
- 230000016615 flocculation Effects 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- 238000012856 packing Methods 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 25
- 238000003763 carbonization Methods 0.000 claims description 22
- 238000005243 fluidization Methods 0.000 claims description 22
- 238000004062 sedimentation Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 238000005469 granulation Methods 0.000 claims description 20
- 230000003179 granulation Effects 0.000 claims description 20
- 238000005273 aeration Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000010348 incorporation Methods 0.000 claims description 14
- 238000005255 carburizing Methods 0.000 claims description 11
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 10
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 10
- 241001330002 Bambuseae Species 0.000 claims description 10
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 10
- 239000011425 bamboo Substances 0.000 claims description 10
- 229920005610 lignin Polymers 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 241000196324 Embryophyta Species 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000005276 aerator Methods 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 abstract description 16
- 230000009467 reduction Effects 0.000 abstract description 16
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000003513 alkali Substances 0.000 description 12
- 239000011949 solid catalyst Substances 0.000 description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 8
- 235000003891 ferrous sulphate Nutrition 0.000 description 7
- 239000011790 ferrous sulphate Substances 0.000 description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 7
- 238000007885 magnetic separation Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 4
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 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
- 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
- C02F1/46—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
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses it is a kind of can sludge reuse light electrolysis/heterogeneous Fenton fluidized-bed process and its device, which includes: (1) in fluidized-bed reactor, carries out micro-electrolysis reaction and handles waste water；Or it carries out heterogeneous Fenton's reaction and handles waste water；(2) treated waste water goes out iron containing sludge dehydration through precipitation and separation, and dewatered remaining biochemical sludge and bonding agent is added；(4) it after being granulated drying and other treatment, places into and carries out carbonizing reduction in carbide furnace；(5) porous iron carbon particle obtained/porous carbon load iron particle is thrown in reflux fluidized bed reactor and is recycled.Light electrolysis provided by the invention/heterogeneous Fenton fluidized-bed process and its device, the iron containing sludge that can be generated is prepared into porous iron carbon particle/porous carbon load iron particle, again reaction is participated in investment fluidized-bed reactor, even zero-emission is recycled to realize sludge, and cost of material and sludge treatment cost are declined to a great extent.
Description
Technical field
The present invention relates to waste water treatment process and relevant device device field, more particularly to it is a kind of can sludge reuse micro- electricity
Solution/heterogeneous Fenton fluidized-bed process and device.
Background technique
Iron-carbon micro-electrolysis is exactly to utilize the electricity for forming 1.2V caused by primary battery in waste water between fe and simple substance carbon
Potential difference carries out electrolysis processing to waste water, is current processing high concentrated organic wastewater to have the function that degradable organic pollutant
A kind of ideal technology, also known as internal electrolysis.
Traditional iron-carbon micro-electrolysis is using fixed bed, and there are following some problems: first is that inefficient, reaction speed is not
Fastly；Second is that bed body is easy to harden, short circuit and dead zone are caused；Third is that the sludge quantity that generates is larger after light electrolysis flocculation, sludge treatment at
This height.These there are the problem of also limit popularization of the iron-carbon micro-electrolysis technology on engineering of water treatment.
Fenton's reaction is a kind of common advanced oxidation waste water treatment process, the catalysis by ferrous ion to hydrogen peroxide
Effect generates the extremely strong hydroxyl radical free radical of oxidisability (OH) and carrys out the reluctant organic matter of the other techniques of oxygenolysis.Fenton
Technique has advantage easy to operate, equipment investment is small in all advanced oxidation processes, but due to adding divalent into waste water
Iron ion produces additional waste sludge, to considerably increase the sludge treatment cost of Fenton technology.
It is generated to reduce the iron containing sludge of Fenton technology, develops a kind of new heterogeneous catalytic oxidation Fenton technology,
Deliquescent ferrous salt is substituted using solid catalyst to carry out catalysis oxidation with hydrogen peroxide.Solid catalyst generally selects more
The oxide of the carrier loaded iron ion in hole, iron simple substance or iron is prepared, and some even directly uses certain iron ores.
The above-mentioned heterogeneous Fenton's reaction using solid catalyst will lack compared to the iron containing sludge that common Fenton technology generates,
However, there remains reacting in acid condition, iron-containing sludge still can be generated, and with the consumption of ferro element, catalyst
Particle needs to regularly replace, and which increases additional costs.The presence of these problems greatly limits Fenton and heterogeneous
The application and popularization of Fenton technology, it would be highly desirable to further technology.
Summary of the invention
The present invention is to solve the problems, such as that current iron-carbon micro-electrolysis and Fenton and heterogeneous Fenton's reaction exist, and proposes that one kind can
The light electrolysis of sludge reuse/heterogeneous Fenton fluidized-bed process and device.
To achieve the above object, the invention adopts the following technical scheme:
The first aspect of the invention be to provide it is a kind of can sludge reuse light electrolysis/heterogeneous Fenton fluidized-bed process,
Comprising steps of
(1) in the fluidized-bed reactor of bottom in and top out, using porous iron carbon particle as fluidized packing material, while to waste water
In add acid carry out micro-electrolysis reaction processing waste water；Or using porous carbon load iron particle as catalyst fluidization particle, simultaneously
Acid is added into waste water and hydrogen peroxide carries out heterogeneous Fenton's reaction processing waste water；Using aeration or water outlet circulation in reaction process
Reflux carries out fluidisation stirring；
(2) waste water after fluidized-bed reactor reaction treatment enters magnetic separating apparatus, captures the iron that recycling is flowed out downstream
The little particle of content > 10%, and neutralization flocculation sedimentation is carried out to the water outlet of magnetic separating apparatus and goes out iron containing sludge；
(3) iron containing sludge after step (2) flocculation sedimentation is subjected to mechanical dehydration, and added into dewatered iron containing sludge
The dewatered remaining biochemical sludge and suitable bonding agent for entering proper proportion, are uniformly mixed；
(4) step (3) mixed sludge after granulation, desiccation, crushing and screening, is placed into carbide furnace and is carbonized
Reduction loads iron particle to get porous iron carbon particle/porous carbon；
(5) porous iron carbon particle made from step (4)/porous carbon load iron particle is thrown into back step (1) fluidized-bed reaction
It is recycled in device.
Further, in step (3), the iron containing sludge is mixed with the dewatered remaining biochemical sludge of proper proportion
Afterwards, accounting of the ferro element in mixture in over dry sludge gross mass is 10~50%.
Further, in step (3), the iron containing sludge and the remaining biochemical sludge are uniform by mediating stirring realization
Mixing, incorporation time are not less than 15min, bonding agent are added in sludge mixed process and is uniformly mixed jointly.
Further, in step (3), the bonding agent includes but is not limited to pitch, tar, resinae bonding agent, modification
One of bamboo powder, lignin and its derivative are a variety of, and adding proportion is not higher than the 5% of over dry sludge total amount.
Further, in step (4), described be granulated is granulated mode using extrusion granulation or roller, made particle through drying,
Partial size is 0.5~3mm after broken, screening；The carburizing temperature is 570~820 DEG C, and carbonization time is greater than 1h.
It is further preferred that in step (4), when temperature controls 570~750 DEG C, ferro element in the particle that is sintered
It mixes and deposits with two valence states of zeroth order and divalent, referred to as porous carbon loads iron particle, is used for heterogeneous Fenton fluidized-bed process；
When temperature controls 750~820 DEG C, ferro element is almost all zeroth order, referred to as porous iron carbon particle in the particle that is sintered,
For microelectrolytic fluidized bed technique.In order to obtain porous structure as high as possible, carburizing temperature should not be arranged excessively high.
Further, in step (1), bulk density of the porous carbon load iron particle in the fluidized-bed reactor
For 0.8~1.2g/cm3。
Further, in step (1), packing volume of the porous carbon load iron particle in the fluidized-bed reactor
Ratio is 10~30%.
The second aspect of the invention be to provide it is a kind of can sludge reuse iron-carbon microelectrolytic fluidized bed technique, including step
It is rapid:
(1) in the fluidized-bed reactor of bottom in and top out, using porous iron carbon particle as fluidized packing material, while to waste water
In add acid carry out iron-carbon micro-electrolysis reaction treatment waste water；Fluidisation is carried out using aeration or water outlet circulating reflux in reaction process to stir
It mixes；
(2) waste water after fluidized-bed reactor reaction treatment enters magnetic separating apparatus, captures the iron that recycling is flowed out downstream
The little particle of content > 10%, and neutralization flocculation sedimentation is carried out to the water outlet of magnetic separating apparatus and goes out iron containing sludge；
(3) iron containing sludge after step (2) flocculation sedimentation is subjected to mechanical dehydration, and added into dewatered iron containing sludge
The dewatered remaining biochemical sludge and suitable bonding agent for entering proper proportion, are uniformly mixed；
(4) it by step (3) mixed sludge after being granulated drying and other treatment, places into and carries out carbonizing reduction in carbide furnace,
Up to porous iron carbon particle；
(5) porous iron carbon particle made from step (4) is thrown back in step (1) fluidized-bed reactor and is recycled.
Further, in step (3), the iron containing sludge is mixed with the dewatered remaining biochemical sludge of proper proportion
Afterwards, accounting of the ferro element in mixture in over dry sludge gross mass is 10~50%.
Further, in step (3), the iron containing sludge and the remaining biochemical sludge are uniform by mediating stirring realization
Mixing, incorporation time are not less than 15min, bonding agent are added in sludge mixed process and is uniformly mixed jointly.
Further, in step (3), the bonding agent includes but is not limited to pitch, tar, resinae bonding agent, modification
One of bamboo powder, lignin and its derivative are a variety of, and adding proportion is not higher than the 5% of over dry sludge total amount.
Further, in step (4), described be granulated is granulated mode using extrusion granulation or roller, after made particle drying
Partial size is 0.5~3mm；The carburizing temperature is 750~820 DEG C, and carbonization time is greater than 1h.
Further, in step (1), bulk density of the porous iron carbon particle in the fluidized-bed reactor is
0.8~1.2g/cm3。
Further, in step (1), packing volume ratio of the porous iron carbon particle in the fluidized-bed reactor
For no more than 30%.
The third aspect of the invention be to provide it is a kind of can sludge reuse heterogeneous Fenton fluidized-bed process, including step
It is rapid:
(1) in the fluidized-bed reactor of bottom in and top out, using porous carbon load iron particle be used as solid catalyst, to give up
Sour and hydrogen peroxide is added in water and carries out Fenton's reaction processing waste water, is flowed in reaction process using aeration or water outlet circulating reflux
Change stirring；
(2) waste water after fluidized-bed reactor reaction treatment enters magnetic separating apparatus, captures the iron that recycling is flowed out downstream
The little particle of content > 10%, and neutralization flocculation sedimentation is carried out to the water outlet of magnetic separating apparatus and goes out iron containing sludge；
(3) waste water after reaction in step (2) fluidized-bed reactor is subjected to mechanical dehydration, and dirty to dewatered iron content
The dewatered remaining biochemical sludge and suitable bonding agent of proper proportion are added in mud, is uniformly mixed；
(4) it by step (3) mixed sludge after being granulated drying and other treatment, places into and carries out carbonizing reduction in carbide furnace,
Iron particle is loaded up to porous carbon；
(5) load of porous carbon made from step (4) iron particle is thrown back in step (1) fluidized-bed reactor and is recycled.
Further, in step (2), the iron containing sludge is mixed with the dewatered remaining biochemical sludge of proper proportion
Afterwards, accounting of the ferro element in mixture in over dry sludge gross mass is 10~50%.
Further, in step (2), the iron containing sludge and the remaining biochemical sludge are uniform by mediating stirring realization
Mixing, incorporation time are not less than 15min, bonding agent are added in sludge mixed process and is uniformly mixed jointly.
Further, in step (2), the bonding agent includes but is not limited to pitch, tar, resinae bonding agent, modification
One of bamboo powder, lignin and its derivative are a variety of, and adding proportion is not higher than the 5% of over dry sludge total amount.
Further, in step (3), described be granulated is granulated mode using extrusion granulation or roller, made particle through drying,
Partial size is 0.5~3mm after broken, screening；The carburizing temperature is 570~750 DEG C, and carbonization time is greater than 1h.
Further, in step (1), bulk density of the porous carbon load iron particle in the fluidized-bed reactor
For 0.8~1.2g/cm3。
Further, in step (1), packing volume of the porous carbon load iron particle in the fluidized-bed reactor
Ratio is no more than 30%.
The fourth aspect of the invention be to provide it is a kind of can sludge reuse light electrolysis/heterogeneous Fenton fluidized bed plant,
The bottom of fluidized-bed reactor including bottom in and top out structure, the fluidized-bed reactor is disposed with support plate from bottom to top
(5), aerator (8), water distributor (6) and fluidized particles (15), the water distributor (6) are connected to water inlet pipe (1)；Middle part is provided with
Fluidized particles feed opening (10) is provided with wastewater effluent pipeline (14) at top delivery port；Wherein, the wastewater effluent pipeline
(14) it is installed on magnetic separating apparatus (13), the bottom of the magnetic separating apparatus (13) passes through pipeline and the fluidized-bed reactor
Middle part or bottom connection.
Further, up flow type fluidized-bed reactor top be equipped with it is parallel to each other and in 45~60 ° inclination
Baffle, the baffle length be not less than 50cm.
Further, along the water outlet for being not higher than fluidized-bed reactor on the baffle；
Further, the volume of fluidized particles is no more than the 30% of volume in the up flow type fluidized-bed reactor.
Further, in order to reduce loss of the effective catalyst particle in exiting water process, the magnetic separating apparatus (13)
The little particle of iron content > 10% is retained, and the little particle of retention circulation is returned into fluidized bed.
The particle of 10% or more iron content is considered as effective particle in water outlet, is captured by magnetic separating apparatus；Iron content 10% with
Under particle be considered as spent granules, with water outlet be discharged.The effective particle being captured backs into fluidized bed and continues to use.The Magneto separate is set
The standby loss for further avoiding effective particle, improves the whole service life of fluidized particles.
The present invention by adopting the above technical scheme, compared with prior art, has the following technical effect that
It is of the invention can sludge reuse light electrolysis/heterogeneous Fenton fluidized-bed process and its device, can be generated
Iron containing sludge be prepared into porous iron carbon or porous carbon load iron particle, again put into fluidized-bed reactor in participate in reaction, from
And realize the even zero-emission that recycles of sludge, cost of material and sludge treatment cost are declined to a great extent；It utilizes simultaneously
Fluidized particles as iron gradually uses up remaining porous carbon and specific gravity gradually lightens, partial size gradually becomes smaller, while catalyst failure
Feature is arranged inclined baffle on fluidized-bed reactor top, can lead back to the fluidized particles being streamed at baffle in reactor,
And the minor diameter fluidized particles row's fluidized bed being exhausted substantially goes out reactor, is discharged after magnetic separation system screens, thus
Guarantee the continuous and steady operation of fluidized-bed reactor.
Detailed description of the invention
Fig. 1 be one kind of the present invention can sludge reuse light electrolysis/heterogeneous Fenton fluidized bed plant structural schematic diagram；
Fig. 2 be one kind of the present invention can in light electrolysis/heterogeneous Fenton fluidized bed plant of sludge reuse water distributor structure
Schematic diagram；
Wherein, each appended drawing reference are as follows:
1- water inlet pipe, 2- acid adding interface, 3- add hydrogen peroxide interface, 4- pipe-line mixer, 5 support plates, -6- water distributor, 7-
Exhausting pipeline, 8- aerator, 9- manhole, 10- fluidized particles feed opening, 11- empty three-way valve, 12- baffle, 13- Magneto separate
Equipment, 14- wastewater effluent mouth, 15- fluidized particles, the first pH of 16- probe, the 2nd pH of 17- probe, 18- single-screw (single screw) pump, 19- are cut
Only valve.
Specific embodiment
One aspect of the present invention provide it is a kind of can sludge reuse iron-carbon microelectrolytic fluidized bed technique, it is useless that processing may be implemented
The sludge circulation generated when water utilizes, main technical schemes are as follows: (1) the up flow type fluidized-bed reactor of bottom in and top out is used,
Fluidisation stirring is carried out using aeration or effluent recycling circulation in reactor；(2) 0.5 is added in iron-carbon microelectrolytic fluidized bed reactor
~3mm partial size porous iron carbon particle, granular pile density are not more than 1.2g/cm3, reactor volume is accounted for no more than 30%, with porous
Iron carbon particle can be fluidized sufficiently；(3) iron-carbon micro-electrolysis reaction only adds acid into waste water, uses porous iron in acid condition
Galvanic interaction occurs for carbon particle and waste water, and the waste water after the reaction of iron carbon enters magnetic separation system, and retention is taken out of effective downstream
Porous iron carbon particle is sent back to iron-carbon microelectrolytic fluidized bed, and water outlet becomes the ferro element being introduced into water using adding alkali neutralization precipitating
Iron containing sludge is separated from waste water；(4) iron containing sludge after flocculation sedimentation is fabricated to porous iron carbon particle as raw material.
(5) the porous iron carbon particle throwing of iron-carbon microelectrolytic fluidized bed iron containing sludge preparation, which returns in fluidized-bed reactor, recycles, can
To reduce the sludge yield of system or even realize sludge zero discharge.
Specifically, this programme can realize the microelectrolytic fluidized bed technique that sludge circulation utilizes, comprising steps of
(1) in the fluidized-bed reactor of bottom in and top out, using porous iron carbon particle as fluidized packing material, while to waste water
In add acid and carry out iron-carbon micro-electrolysis reaction treatment waste water, using being aerated or water outlet circulating reflux carries out fluidisation and stirs in reaction process
It mixes；
(2) water outlet enters magnetic separation system, retains the effective porous iron carbon particle (iron content > 10%) taken out of downstream, so
After carry out flocculation sedimentation, be settled out iron containing sludge；
(3) iron containing sludge after step (2) flocculation sedimentation is subjected to mechanical dehydration, and added into dewatered iron containing sludge
The dewatered remaining biochemical sludge and suitable bonding agent for entering proper proportion, are uniformly mixed；
(4) it by step (3) mixed sludge after being granulated drying and other treatment, places into and carries out carbonizing reduction in carbide furnace,
Up to porous iron carbon particle；
(5) porous iron carbon particle made from step (4) is thrown back in step (1) fluidized-bed reactor and is recycled.
This programme the step of in (3), the iron containing sludge is mixed with the dewatered remaining biochemical sludge of proper proportion
Afterwards, accounting of the ferro element in mixture in over dry sludge gross mass is not more than 50%；Preferably, the ferro element in mixture
Accounting in over dry sludge gross mass is 20~40%；It is highly preferred that the ferro element in mixture is in over dry sludge gross mass
In accounting be 30-40%.The iron containing sludge and the remaining biochemical sludge are by mediating stirring realization uniformly mixing, mixing
Time is not less than 15min, and bonding agent is added in sludge mixed process and is uniformly mixed jointly.The bonding agent includes but is not limited to drip
One of blueness, tar, resinae bonding agent, modified bamboo powder, lignin and its derivative are a variety of, and adding proportion is not high
In the 5% of over dry sludge total amount.
This programme the step of in (4), described be granulated is granulated mode using extrusion granulation or roller, and made particle is through doing
Partial size is 0.5~3mm after dry, broken, screening；The carburizing temperature is 750~820 DEG C, and carbonization time is greater than 1h.It is preferred that
Ground, porous iron carbon particle diameter are 1.2~2.5mm；Carburizing temperature is 770~800 DEG C, carbonization time 1-5h；It is more highly preferred to
Ground, porous iron carbon particle diameter are 1.6~2.0mm；Carburizing temperature is 790~810 DEG C, carbonization time 1.5-3h, so that more
Ferro element in the iron carbon particle of hole is with the presence of zeroth order valence state.Carbonizing apparatus is preferably external heat type rotary furnace, both can continous way disengaging
Material, but can batch be carbonized.To avoid aoxidizing, the iron carbon particle temperature after carbonization is come out of the stove after should being down to 200 DEG C or less.
This programme the step of in (1), bulk density of the porous iron carbon particle in the fluidized-bed reactor is
0.8~1.2g/cm3.Packing volume ratio of the porous iron carbon particle in the fluidized-bed reactor is 10~30%.
Another aspect of the present invention provide it is a kind of can sludge reuse heterogeneous Fenton fluidized-bed process, may be implemented to handle
Generated sludge recycles when waste water, main technical schemes are as follows: (1) anti-using the up flow type fluidized bed of bottom in and top out
Device is answered, is recycled in reactor using aeration or effluent recycling and carries out fluidisation stirring；(2) it is thrown in heterogeneous Fenton fluidized-bed reactor
The porous carbon of 0.5~3mm partial size is added to load iron particle, catalyst granules bulk density is not more than 1.2g/cm3, account for reactor body
Product is no more than 30%, to guarantee that catalyst granules can be fluidized sufficiently；(3) heterogeneous Fenton's reaction only added into waste water acid and
Hydrogen peroxide does not add ferrous sulfate, is carried out in acid condition using porous carbon supported ferric catalyst particle substitution ferrous sulfate
Catalytic action, the waste water after fluidized-bed reaction enter magnetic separation system, the effective catalyst particle taken out of downstream are retained, particle
Send Fenton fluidized bed back to, water outlet divides using adding alkali neutralization precipitating that the ferro element being introduced into water is become iron containing sludge from waste water
It separates out and；(4) porous carbon supported iron catalyst is made by the iron containing sludge of neutralization precipitation using the water outlet of heterogeneous Fenton fluidized bed
Particle；(5) the porous carbon supported ferric catalyst throwing of heterogeneous Fenton fluidized bed iron containing sludge preparation returns in fluidized-bed reactor
It recycles, it is possible to reduce the sludge yield of system even realizes sludge zero discharge.
Specifically, this programme can realize the heterogeneous Fenton fluidized-bed process that sludge circulation utilizes, comprising steps of
(1) in the fluidized-bed reactor of bottom in and top out, using porous carbon load iron particle be used as solid catalyst, to give up
Sour and hydrogen peroxide is added in water and carries out Fenton's reaction processing waste water, is flowed in reaction process using aeration or water outlet circulating reflux
Change stirring；
(2) water outlet enters magnetic separation system, retains the effective catalyst particle (iron content > 10%) taken out of downstream, then
Flocculation sedimentation is carried out, iron containing sludge is settled out；
(3) iron containing sludge after step (2) flocculation sedimentation is subjected to mechanical dehydration, and added into dewatered iron containing sludge
The dewatered remaining biochemical sludge and suitable bonding agent for entering proper proportion, are uniformly mixed；
(4) step (3) mixed sludge after granulation, desiccation, crushing and screening, is placed into carbide furnace and is carbonized
Reduction loads iron particle to get porous carbon；
(5) load of porous carbon made from step (4) iron particle is thrown back in step (1) fluidized-bed reactor and is recycled.
This programme the step of in (3), the iron containing sludge is mixed with the dewatered remaining biochemical sludge of proper proportion
Afterwards, accounting of the ferro element in mixture in over dry sludge gross mass is not more than 50%；Preferably, the ferro element in mixture
Accounting in over dry sludge gross mass is 10~40%；It is highly preferred that the ferro element in mixture is in over dry sludge gross mass
In accounting be 15~30%.The iron containing sludge and the remaining biochemical sludge are mixed by mediating stirring realization uniformly mixing
The conjunction time is not less than 15min, and bonding agent is added in sludge mixed process and is uniformly mixed jointly.The bonding agent includes but is not limited to
One of pitch, tar, resinae bonding agent, modified bamboo powder, lignin and its derivative are a variety of, and adding proportion is not
Higher than the 5% of over dry sludge total amount.
This programme the step of in (4), described be granulated is granulated mode using extrusion granulation or roller, and made particle is through doing
Partial size is 0.5~3mm after dry, broken, screening；The carburizing temperature is 570~750 DEG C, and carbonization time is greater than 1h.It is preferred that
Ground, porous carbon load iron particle diameter are 1.2~2.5mm；Carburizing temperature is 640~720 DEG C, carbonization time 1-5h；More
Preferably, porous carbon load iron particle diameter is 1.6~2.0mm；Carburizing temperature is 650~700 DEG C, carbonization time 1.5-
3h not only improves heterogeneous Fenton's reaction and urges so that the ferro element in catalyst granules exists with divalent and zeroth order mixed valence
The performance of catalyst particles effect, and the energy cost in preparation process can be saved.Carbonizing apparatus is preferably external heat type rotary furnace,
Not only can continous way input and output material, but also can batch be carbonized.To avoid aoxidizing, the particle temperature after carbonization should be down to 200 DEG C with
It comes out of the stove after lower.
This programme the step of in (1), accumulation of the porous carbon load iron particle in the fluidized-bed reactor is close
Degree is 0.8~1.2g/cm3.Packing volume ratio of the porous carbon load iron particle in the fluidized-bed reactor is 10
~30%.
Another aspect of the present invention provide it is a kind of can sludge reuse light electrolysis/heterogeneous Fenton fluidized bed plant, such as Fig. 1 institute
Show, the fluidized-bed reactor of the up flow type including bottom in and top out structure, the bottom of the fluidized-bed reactor is from bottom to top successively
Support plate 5, aerator 8, water distributor 6 and fluidized particles 15 are provided with, the water distributor 6 is connected to water inlet pipe 1；Middle part is provided with
Fluidized particles feed opening 10 is provided with manhole 9 used for overhaul below fluidized particles feed opening 10；It is provided at top delivery port
Wastewater effluent pipeline 14；Wherein, magnetic separating apparatus 13 is installed on the wastewater effluent pipeline 14, the magnetic separating apparatus 13
Bottom is connected to by pipeline with the middle part of the fluidized-bed reactor or bottom.Aerator 8 or water distributor 6 are convenient for aeration or water outlet
Circulating reflux realizes the fluidisation stirring in reactor, and the fluidized particles feed opening 10 at middle part is for adding porous iron carbon particle/more
Hole carbon carries iron particle.
In the present embodiment, as shown in fig.1, fluidized-bed reactor top surrounding is equipped with being parallel to each other and is in
45~60 ° of inclined baffles 12,12 length of baffle are not less than 50cm.Along anti-not higher than the fluidized bed on the baffle 12
Answer the water outlet on device.Since inclined baffle 12 reduces the fluidization in upper part region, when the iron member in fluidized particles
Cellulose content is sufficiently high, and when granularity is larger, the particle for being streamed to baffle top will sink rapidly under the effect of gravity, along inclination
The slope of baffle 12 is returned in reactor by interval and continues to participate in reaction.When fluidized particles because fluidisation collision becomes increasingly
Small, also largely reaction is exhausted ferro element, and in the case that residual components are mainly porous carbon, particle will lighten and be difficult to sink
Drop flows out together with waste water from water outlet.It is higher that partial particulate iron content is had in the little particle of outflow, in fluidized bed rear end
Magnetic separation system is set, and the particle of 10% or more iron content is considered as effective particle in water outlet, is captured by magnetic separation system；Iron content
10% particle below is considered as spent granules, is discharged with water outlet.The effective particle being captured backs into fluidized bed and continues to use.
As a preferred embodiment, connect as shown in Figure 1, being disposed with acid adding on the water inlet pipe 1 of the water distributor 6
Mouthfuls 2 and plus hydrogen peroxide interface 3 add and be additionally provided with the on the water inlet pipe 1 after hydrogen peroxide interface 3 for adding acid and hydrogen peroxide
One pH probe 16 controls acid adding amount by pH value；And as shown in Fig. 2, the water distributor 6 is in rich font structure.
In the present embodiment, as shown in fig.1, the lower middle part with the fluidized-bed reactor of the magnetic separating apparatus 13 or
It is successively set on the pipeline of bottom connection and is installed with single-screw (single screw) pump 18, shut-off valve 19 and emptying three-way valve 11.It is visited by the 2nd pH
The consumption of first 17 mistake pH value variation real time monitoring fluidized particles 15 and wastage.Through the magnetic separating apparatus 13, treated
Waste water is discharged from wastewater effluent mouth 14, and carries out flocculation treatment to the waste water of discharge, is settled out iron containing sludge and carries out mechanical de-
Water.The magnetic separating apparatus 13 retains the little particle of iron content > 10%, and the little particle of retention is returned fluidized bed by pipeline
Reactor.
In the present embodiment, as shown in fig.1, the bottom of the up flow type fluidized-bed reactor is provided with exhausting pipeline 7.
The fluidized particles 15 are that porous iron carbon particle or porous carbon load iron particle.In the present solution, fluidized particles in reactor
The volume of particle is no more than the 30% of volume, sufficiently to fluidize under the action of aeration or water pumparound, has with waste water
Effect contact and reaction.
The present invention is described in more detail below by specific embodiment, for a better understanding of the present invention,
But following embodiments are not intended to limit the scope of the invention.
Embodiment 1
There is provided it is a kind of can sludge reuse microelectrolytic fluidized bed technique, include the following steps:
(1) in the fluidized-bed reactor of bottom in and top out, using porous iron carbon particle as fluidized particles, porous iron carbon
The heap density 0.9g/cm of grain3, packing volume ratio of the porous iron carbon particle in the fluidized-bed reactor is 20%；
(2) acid is only added into waste water to pH=3, is carried out iron-carbon micro-electrolysis reaction treatment waste water, is used in reaction process
Aeration or water outlet circulating reflux carry out fluidisation stirring；
(3) hydraulic detention time 20min of the waste water in fluidized bed；Treated waste water through fluidized-bed reactor water outlet into
Enter magnetic separating apparatus, water outlet plus alkali pH are transferred to 8, and flocculation sedimentation goes out iron containing sludge；
(4) sludge after step (3) flocculation is subjected to mechanical dehydration, and by the iron containing sludge proper proportion after mechanical dehydration
Dewatered remaining biochemical sludge realize uniformly mixing by mediating stirring, incorporation time 20min, the iron member in mixture
Accounting of the element in over dry sludge gross mass is 35%, and resinae bonding agent is added in mixed process and is uniformly mixed jointly, resin
The adding proportion of class bonding agent is the 4% of over dry sludge total amount；
(5) then by granulations, desiccation, sieve partial size be 1.5~2mm particle, place into carbide furnace it is interior in 750~
780 DEG C of progress carbonizing reductions, carbonization time are 1h to get porous iron carbon particle；
(6) porous iron carbon particle made from step (5) is thrown back in step (1) fluidized-bed reactor and is recycled, it is described
Bulk density of the porous iron carbon particle in the fluidized-bed reactor is 0.9g/cm3, the porous iron carbon particle is in the stream
Packing volume ratio in fluidized bed reactor is 20%.
Embodiment 2
There is provided it is a kind of can sludge reuse microelectrolytic fluidized bed technique, include the following steps:
(1) in the fluidized-bed reactor of bottom in and top out, using porous iron carbon particle as fluidized particles, porous iron carbon
Heap density 1g/cm3, packing volume ratio of the porous iron carbon particle in the fluidized-bed reactor is 10%；
(2) acid is only added into waste water to pH=4, is carried out iron-carbon micro-electrolysis reaction treatment waste water, is used in reaction process
Aeration or water outlet circulating reflux carry out fluidisation stirring；
(3) hydraulic detention time 30min of the waste water in fluidized bed；Treated waste water through fluidized-bed reactor water outlet into
Enter magnetic separating apparatus, water outlet plus alkali pH are transferred to 7.5, and flocculation sedimentation goes out iron containing sludge；
(4) sludge after step (1) flocculation is subjected to mechanical dehydration, and by the iron containing sludge proper proportion after mechanical dehydration
Dewatered remaining biochemical sludge realize uniformly mixing by mediating stirring, incorporation time 20min, the iron member in mixture
Accounting of the element in over dry sludge gross mass is 50%, and resinae bonding agent is added in mixed process and is uniformly mixed jointly, resin
The adding proportion of class bonding agent is the 4% of over dry sludge total amount；
(5) then by granulations, desiccation, sieve partial size be 1.5~2mm particle, place into carbide furnace it is interior in 780~
800 DEG C of progress carbonizing reductions, carbonization time are 1h to get porous iron carbon particle；
(6) porous iron carbon particle made from step (5) is thrown back in step (1) fluidized-bed reactor and is recycled, it is described
Bulk density of the porous iron carbon particle in the fluidized-bed reactor is 1g/cm3, and its filling in fluidized-bed reactor
Volume ratio is 10%.
Embodiment 3
There is provided it is a kind of can sludge reuse microelectrolytic fluidized bed technique, include the following steps:
(1) in the fluidized-bed reactor of bottom in and top out, using porous iron carbon particle as fluidized particles, porous iron carbon
Heap density 0.95g/cm3, packing volume ratio of the porous iron carbon particle in the fluidized-bed reactor is 30%；
(2) acid is only added into waste water to pH=3.5, is carried out iron-carbon micro-electrolysis reaction treatment waste water, is adopted in reaction process
Fluidisation stirring is carried out with being aerated or being discharged circulating reflux；
(3) hydraulic detention time 20min of the waste water in fluidized bed；Treated waste water through fluidized-bed reactor water outlet into
Enter magnetic separating apparatus, water outlet plus alkali pH are transferred to 8.5, and flocculation sedimentation goes out iron containing sludge；
(4) sludge after step (1) flocculation is subjected to mechanical dehydration, and by the iron containing sludge proper proportion after mechanical dehydration
Dewatered remaining biochemical sludge realize uniformly mixing by mediating stirring, incorporation time 20min, the iron member in mixture
Accounting of the element in over dry sludge gross mass is 40%, and resinae bonding agent is added in mixed process and is uniformly mixed jointly, resin
The adding proportion of class bonding agent is the 4% of over dry sludge total amount；
(5) then by granulations, desiccation, sieve partial size be 1.5~2mm particle, place into carbide furnace it is interior in 800~
820 DEG C of progress carbonizing reductions, carbonization time are 1h to get porous iron carbon particle；
(6) porous iron carbon particle made from step (5) is thrown back in step (1) fluidized-bed reactor and is recycled, it is described
Bulk density of the porous iron carbon particle in the fluidized-bed reactor is 0.95g/cm3, and it is in fluidized-bed reactor
Packing volume ratio is 30%.
Embodiment 4
There is provided it is a kind of can sludge reuse microelectrolytic fluidized bed technique, include the following steps:
(1) in the fluidized-bed reactor of bottom in and top out, using porous iron carbon particle as fluidized particles, porous iron carbon
The heap density 0.85g/cm of grain3, packing volume ratio of the porous iron carbon particle in the fluidized-bed reactor is 20%.
(2) acid is only added into waste water to pH=4, is carried out iron-carbon micro-electrolysis reaction treatment waste water, is used in reaction process
Aeration or water outlet circulating reflux carry out fluidisation stirring；
(3) hydraulic detention time 40min of the waste water in fluidized bed；Treated waste water through fluidized-bed reactor water outlet into
Enter magnetic separating apparatus, water outlet plus alkali pH are transferred to 8, and flocculation sedimentation goes out iron containing sludge；
(4) sludge after step (1) flocculation is subjected to mechanical dehydration, and by the iron containing sludge proper proportion after mechanical dehydration
Dewatered remaining biochemical sludge realize uniformly mixing by mediating stirring, incorporation time 20min, the iron member in mixture
Accounting of the element in over dry sludge gross mass is 30%, and modified bamboo powder is added in mixed process and is uniformly mixed jointly, modified bamboo
The adding proportion of wood powder is the 4% of over dry sludge total amount；
(5) then by granulations, desiccation, sieve partial size be 1.5~2mm particle, place into carbide furnace it is interior in 780~
800 DEG C of progress carbonizing reductions, carbonization time are 1h to get porous iron carbon particle；
(6) porous iron carbon particle made from step (5) is thrown back in step (1) fluidized-bed reactor and is recycled, it is described
Bulk density of the porous iron carbon particle in the fluidized-bed reactor is 0.85g/cm3, and it is in fluidized-bed reactor
Packing volume ratio is 20%.
Embodiment 5
There is provided it is a kind of can sludge reuse microelectrolytic fluidized bed technique, include the following steps:
(1) in the fluidized-bed reactor of bottom in and top out, using porous iron carbon particle as fluidized particles, porous iron carbon
The heap density 0.95g/cm of grain3, packing volume ratio of the porous iron carbon particle in the fluidized-bed reactor is 25%.
(2) acid is only added into waste water to pH=3, is carried out iron-carbon micro-electrolysis reaction treatment waste water, is used in reaction process
Aeration or water outlet circulating reflux carry out fluidisation stirring；
(3) hydraulic detention time 30min of the waste water in fluidized bed；Treated waste water through fluidized-bed reactor water outlet into
Enter magnetic separating apparatus, water outlet plus alkali pH are transferred to 8, and flocculation sedimentation goes out iron containing sludge；
(4) sludge after step (1) flocculation is subjected to mechanical dehydration, and by the iron containing sludge proper proportion after mechanical dehydration
Dewatered remaining biochemical sludge realize uniformly mixing by mediating stirring, incorporation time 20min, the iron member in mixture
Accounting of the element in over dry sludge gross mass is 40%, and lignin is added in mixed process and is uniformly mixed jointly, lignin adds
Adding ratio is the 4% of over dry sludge total amount；
(5) then by granulations, desiccation, sieve partial size be 1.5~2mm particle, place into carbide furnace it is interior in 800~
810 DEG C of progress carbonizing reductions, carbonization time are 1h to get porous iron carbon particle；
(6) porous iron carbon particle made from step (4) is thrown back in step (1) fluidized-bed reactor and is recycled, it is described
Bulk density of the porous iron carbon particle in the fluidized-bed reactor is 0.95g/cm3, and it is in fluidized-bed reactor
Packing volume ratio is 25%.
The test result of the 1 microelectrolytic fluidized bed technique of embodiment 1-5 of table
Embodiment 6
There is provided it is a kind of can sludge reuse heterogeneous Fenton fluidized-bed process, include the following steps:
(1) porous using porous carbon load iron particle as solid catalyst in the fluidized-bed reactor of bottom in and top out
The heap density 0.8g/cm of carbon load iron3, packing volume ratio of the porous carbon load iron particle in the fluidized-bed reactor
It is 20%；
(2) acid is only added into waste water to pH=3 and 0.05% hydrogen peroxide, is not added ferrous sulfate, is carried out heterogeneous sweet smell
Pause reaction treatment waste water, carries out fluidisation stirring using aeration or water outlet circulating reflux in reaction process；
(3) hydraulic detention time 1h of the waste water in fluidized bed；Treated, and waste water enters through fluidized-bed reactor water outlet
Magnetic separating apparatus, water outlet plus alkali pH are transferred to 7.5, and flocculation sedimentation goes out iron containing sludge；
(4) sludge after step (3) flocculation is subjected to mechanical dehydration, and by the iron containing sludge proper proportion after mechanical dehydration
Dewatered remaining biochemical sludge realize uniformly mixing by mediating stirring, incorporation time 20min, the iron member in mixture
Accounting of the element in over dry sludge gross mass is 20%, and resinae bonding agent is added in mixed process and is uniformly mixed jointly, resin
The adding proportion of class bonding agent is the 3.5% of over dry sludge total amount；
(5) then by granulations, desiccation, sieve partial size be 1.5~2mm particle, place into carbide furnace it is interior in 650~
680 DEG C of progress carbonizing reductions, carbonization time are 1h to get porous carbon load iron particle；
(6) load of porous carbon made from step (5) iron particle is thrown back in step (1) fluidized-bed reactor and is recycled,
Bulk density of the porous carbon load iron particle in the fluidized-bed reactor is 0.8g/cm3, the porous carbon load iron
Packing volume ratio of the particle in the fluidized-bed reactor is 20%.
Embodiment 7
There is provided it is a kind of can sludge reuse heterogeneous Fenton fluidized-bed process, include the following steps:
(1) porous using porous carbon load iron particle as solid catalyst in the fluidized-bed reactor of bottom in and top out
The heap density 1g/cm of carbon load iron3, porous carbon loads packing volume ratio of the iron particle in the fluidized-bed reactor and is
10%；
(2) acid is only added into waste water to pH=4 and 0.05% hydrogen peroxide, is not added ferrous sulfate, is carried out heterogeneous sweet smell
Pause reaction treatment waste water, carries out fluidisation stirring using aeration or water outlet circulating reflux in reaction process；
(3) hydraulic detention time 1h of the waste water in fluidized bed；Treated, and waste water enters through fluidized-bed reactor water outlet
Magnetic separating apparatus, water outlet plus alkali pH are transferred to 8, and flocculation sedimentation goes out iron containing sludge；
(4) sludge after step (1) flocculation is subjected to mechanical dehydration, and by the iron containing sludge proper proportion after mechanical dehydration
Dewatered remaining biochemical sludge realize uniformly mixing by mediating stirring, incorporation time 20min, the iron member in mixture
Accounting of the element in over dry sludge gross mass is 30%, and resinae bonding agent is added in mixed process and is uniformly mixed jointly, resin
The adding proportion of class bonding agent is the 3.5% of over dry sludge total amount；
(5) then by granulations, desiccation, sieve partial size be 1.5~2mm particle, place into carbide furnace it is interior in 680~
700 DEG C of progress carbonizing reductions, carbonization time are 1h to get porous carbon load iron particle；
(6) load of porous carbon made from step (5) iron particle is thrown back in step (1) fluidized-bed reactor and is recycled,
Bulk density of the porous carbon load iron particle in the fluidized-bed reactor is 1g/cm3, and it is in fluidized-bed reactor
Interior packing volume ratio is 10%.
Embodiment 8
There is provided it is a kind of can sludge reuse heterogeneous Fenton fluidized-bed process, include the following steps:
(1) porous using porous carbon load iron particle as solid catalyst in the fluidized-bed reactor of bottom in and top out
The heap density 0.8g/cm of carbon load iron3, packing volume ratio of the porous carbon load iron particle in the fluidized-bed reactor
It is 30%；
(2) acid is only added into waste water to pH=3.5 and 0.08% hydrogen peroxide, is not added ferrous sulfate, is carried out heterogeneous
Fenton's reaction handles waste water, and aeration or water outlet circulating reflux is used to carry out fluidisation stirring in reaction process；
(3) hydraulic detention time 0.5h of the waste water in fluidized bed；Treated waste water through fluidized-bed reactor water outlet into
Enter magnetic separating apparatus, water outlet plus alkali pH are transferred to 8.5, and flocculation sedimentation goes out iron containing sludge；
(4) sludge after step (1) flocculation is subjected to mechanical dehydration, and by the iron containing sludge proper proportion after mechanical dehydration
Dewatered remaining biochemical sludge realize uniformly mixing by mediating stirring, incorporation time 20min, the iron member in mixture
Accounting of the element in over dry sludge gross mass is 20%, and resinae bonding agent is added in mixed process and is uniformly mixed jointly, resin
The adding proportion of class bonding agent is the 3.5% of over dry sludge total amount；
(4) then by granulations, desiccation, sieve partial size be 1.5~2mm particle, place into carbide furnace it is interior in 640~
650 DEG C of progress carbonizing reductions, carbonization time are 1h to get porous carbon load iron particle；
(7) load of porous carbon made from step (6) iron particle is thrown back in step (1) fluidized-bed reactor and is recycled,
Bulk density of the porous carbon load iron particle in the fluidized-bed reactor is 0.8g/cm3, and it is in fluidized-bed reaction
Packing volume ratio in device is 30%.
Embodiment 9
There is provided it is a kind of can sludge reuse heterogeneous Fenton fluidized-bed process, include the following steps:
(1) porous using porous carbon load iron particle as solid catalyst in the fluidized-bed reactor of bottom in and top out
The heap density 1.1g/cm of carbon load iron3, packing volume ratio of the porous carbon load iron particle in the fluidized-bed reactor
It is 10%；
(2) acid is only added into waste water to pH=4 and 0.05% hydrogen peroxide, is not added ferrous sulfate, is carried out heterogeneous sweet smell
Pause reaction treatment waste water, carries out fluidisation stirring using aeration or water outlet circulating reflux in reaction process；
(3) hydraulic detention time 0.5h of the waste water in fluidized bed；Treated waste water through fluidized-bed reactor water outlet into
Enter magnetic separating apparatus, water outlet plus alkali pH are transferred to 8, and flocculation sedimentation goes out iron containing sludge；
(4) sludge after step (1) flocculation is subjected to mechanical dehydration, and by the iron containing sludge proper proportion after mechanical dehydration
Dewatered remaining biochemical sludge realize uniformly mixing by mediating stirring, incorporation time 20min, the iron member in mixture
Accounting of the element in over dry sludge gross mass is 35%, and modified bamboo powder is added in mixed process and is uniformly mixed jointly, modified bamboo
The adding proportion of wood powder is the 3.5% of over dry sludge total amount；
(5) then by granulations, desiccation, sieve partial size be 1.5~2mm particle, place into carbide furnace it is interior in 620~
630 DEG C of progress carbonizing reductions, carbonization time are 1h to get porous carbon load iron particle；
(6) load of porous carbon made from step (5) iron particle is thrown back in step (1) fluidized-bed reactor and is recycled,
Bulk density of the porous carbon load iron particle in the fluidized-bed reactor is 1.1g/cm3, and it is in fluidized-bed reaction
Packing volume ratio in device is 10%.
Embodiment 10
There is provided it is a kind of can sludge reuse heterogeneous Fenton fluidized-bed process, include the following steps:
(1) porous using porous carbon load iron particle as solid catalyst in the fluidized-bed reactor of bottom in and top out
The heap density 0.8g/cm of carbon load iron3, packing volume ratio of the porous carbon load iron particle in the fluidized-bed reactor
It is 25%；
(2) acid is only added into waste water to pH=3.5 and 0.1% hydrogen peroxide, is not added ferrous sulfate, is carried out heterogeneous sweet smell
Pause reaction treatment waste water, carries out fluidisation stirring using aeration or water outlet circulating reflux in reaction process；
(3) hydraulic detention time 1h of the waste water in fluidized bed；Treated, and waste water enters through fluidized-bed reactor water outlet
Magnetic separating apparatus, water outlet plus alkali pH are transferred to 8.5, and flocculation sedimentation goes out iron containing sludge；
(4) sludge after step (1) flocculation is subjected to mechanical dehydration, and by the iron containing sludge proper proportion after mechanical dehydration
Dewatered remaining biochemical sludge realize uniformly mixing by mediating stirring, incorporation time 20min, the iron member in mixture
Accounting of the element in over dry sludge gross mass is 20%, and lignin is added in mixed process and is uniformly mixed jointly, lignin adds
Adding ratio is the 3.5% of over dry sludge total amount；
(5) then by granulations, desiccation, sieve partial size be 1.5~2mm particle, place into carbide furnace it is interior in 640~
650 DEG C of progress carbonizing reductions, carbonization time are 1h to get porous carbon load iron particle；
(6) load of porous carbon made from step (5) iron particle is thrown back in step (1) fluidized-bed reactor and is recycled,
Bulk density of the porous carbon load iron particle in the fluidized-bed reactor is 1g/cm3, and it is in fluidized-bed reactor
Interior packing volume ratio is 25%.
The test result of the heterogeneous Fenton fluidized bed waste water treatment process of 2 embodiment 6-10 of table
| Serial number | COD removal rate | Chroma removal rate | B/C lifting values |
| Embodiment 6 | 65% | 81% | 0.17→0.41 |
| Embodiment 7 | 56% | 78% | 0.17→0.34 |
| Embodiment 8 | 67% | 83% | 0.17→0.45 |
| Embodiment 9 | 52% | 75% | 0.17→0.31 |
| Embodiment 10 | 67% | 83% | 0.17→0.46 |
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. one kind can sludge reuse light electrolysis/heterogeneous Fenton fluidized-bed process, which is characterized in that comprising steps of
(1) it in the fluidized-bed reactor of bottom in and top out, using porous iron carbon particle as fluidized packing material, while being thrown into waste water
Acid adding carries out micro-electrolysis reaction and handles waste water；Or using porous carbon load iron particle as catalyst fluidization particle, while to give up
Acid is added in water and hydrogen peroxide carries out heterogeneous Fenton's reaction processing waste water；Using aeration or water outlet circulating reflux in reaction process
Carry out fluidisation stirring；
(2) waste water after fluidized-bed reactor reaction treatment enters magnetic separating apparatus, capture iron content that recycling flows out downstream >
10% little particle, and neutralization flocculation sedimentation is carried out to the water outlet of magnetic separating apparatus and goes out iron containing sludge；
(3) iron containing sludge after step (2) flocculation sedimentation is subjected to mechanical dehydration, and is added and fits into dewatered iron containing sludge
When the dewatered remaining biochemical sludge of ratio and suitable bonding agent, it is uniformly mixed；
(4) it by step (3) mixed sludge after granulation, desiccation, crushing and screening, places into carbide furnace and be carbonized also
Original loads iron particle to get porous iron carbon particle/porous carbon；
(5) porous iron carbon particle made from step (4)/porous carbon load iron particle is thrown back in step (1) fluidized-bed reactor
It recycles.
2. light electrolysis according to claim 1/heterogeneous Fenton fluidized-bed process, which is characterized in that in step (3), institute
State iron containing sludge and proper proportion dewatered remaining biochemical sludge mix after, the ferro element in mixture is total in over dry sludge
Accounting in quality is 10~50%.
3. light electrolysis according to claim 1/heterogeneous Fenton fluidized-bed process, which is characterized in that in step (3), institute
It states iron containing sludge and the remaining biochemical sludge and realizes uniformly mixing by mediating stirring, incorporation time is not less than 15min, sludge
Bonding agent is added in mixed process to be uniformly mixed jointly.
4. light electrolysis according to claim 1/heterogeneous Fenton fluidized-bed process, which is characterized in that in step (3), institute
Stating bonding agent includes but is not limited to one in pitch, tar, resinae bonding agent, modified bamboo powder, lignin and its derivative
Kind is a variety of, and adding proportion is not higher than the 5% of over dry sludge total amount.
5. light electrolysis according to claim 1/heterogeneous Fenton fluidized-bed process, which is characterized in that in step (4), institute
It states granulation and mode is granulated using extrusion granulation or roller, made particle partial size after drying, broken, screening is 0.5~3mm；Institute
Stating carburizing temperature is 570~820 DEG C, and carbonization time is greater than 1h.
6. light electrolysis according to claim 1/heterogeneous Fenton fluidized-bed process, which is characterized in that in step (1), institute
Stating porous iron carbon particle/bulk density of the porous carbon load iron particle in the fluidized-bed reactor is 0.8~1.2g/cm3。
7. light electrolysis according to claim 1/heterogeneous Fenton fluidized-bed process, which is characterized in that in step (1), institute
Stating porous iron carbon particle/packing volume ratio of the porous carbon load iron particle in the fluidized-bed reactor is 10~30%.
8. it is a kind of for as described in claim any one of 1-7 technique can sludge reuse light electrolysis/heterogeneous Fenton fluidisation
Bed apparatus, which is characterized in that the fluidized-bed reactor including bottom in and top out structure, the bottom of the fluidized-bed reactor from lower and
On be disposed with support plate (5), aerator (8), water distributor (6) and fluidized particles (15), the water distributor (6) and water inlet pipe
(1) it is connected to；Middle part is provided with fluidized particles feed opening (10), and wastewater effluent pipeline (14) are provided at top delivery port；Wherein,
Be installed with magnetic separating apparatus (13) on the wastewater effluent pipeline (14), the bottom of the magnetic separating apparatus (13) by pipeline with
The middle part of the fluidized-bed reactor or bottom connection.
9. light electrolysis according to claim 8/heterogeneous Fenton fluidized bed plant, which is characterized in that the fluidized bed is anti-
Device top is answered to be equipped with parallel to each other and be in 45~60 ° of inclined baffles (12), baffle (12) length is not less than 50cm,
Along the water outlet for being not higher than fluidized-bed reactor on the baffle (12).
10. light electrolysis according to claim 8/heterogeneous Fenton fluidized bed plant, which is characterized in that the Magneto separate is set
Standby (13) are used to retain the little particle for iron content > 10% having in fluidized-bed reactor water outlet, and the little particle of retention is followed
Ring returns fluidized-bed reactor.
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