CN118993182B - A Fenton fluidized bed rapid crystallization control system and method - Google Patents
A Fenton fluidized bed rapid crystallization control system and method Download PDFInfo
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- CN118993182B CN118993182B CN202410740975.1A CN202410740975A CN118993182B CN 118993182 B CN118993182 B CN 118993182B CN 202410740975 A CN202410740975 A CN 202410740975A CN 118993182 B CN118993182 B CN 118993182B
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- 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
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
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- 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
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- 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
- C02F2001/5218—Crystallization
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- 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
- C02F2209/40—Liquid flow rate
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- 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
- C02F2209/44—Time
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- 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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Abstract
The invention discloses a Fenton fluidized bed rapid crystallization control system and method, comprising an input unit, a flowmeter, a timer, a crystal discharging period unit, a reflux unit, a ferrous sulfate adding unit and a control unit, wherein raw water flow, crystal particle size and starting time in the Fenton fluidized bed crystallization process are collected, the crystal discharging period is obtained according to the crystal particle size and the starting time, the hydrogen peroxide dosing reflux amount and the ferrous sulfate dosing reflux amount are obtained according to the crystal discharging period and the raw water flow, and the ferrous sulfate adding amount is obtained according to the ratio of the ferrous sulfate adding amount to the chemical oxygen demand and the crystal particle size.
Description
Technical Field
The invention relates to a Fenton fluidized bed rapid crystallization control system and a Fenton fluidized bed rapid crystallization control method, and belongs to the technical field of system control.
Background
The advanced oxidation is a common treatment technology for organic wastewater, especially refractory industrial organic wastewater, fenton is a homogeneous chemical oxidation water treatment technology as a precursor of the advanced oxidation technology, and the reaction conditions are easy to obtain, high temperature and high pressure are not needed, so that the method has the advantages of simple equipment and rapid reaction. Fenton has been widely used in the treatment of industrial wastewater such as petroleum industry, textile industry, paper industry, wood processing industry, brewing industry, landfill leachate, etc. The traditionally accepted Fenton chain reaction mechanism is that the hydroxyl radicals generated by the reaction of Fenton reagent Fe 2+ and H 2O2 are utilized for oxidative decomposition of organic pollutants, wherein the related reaction formula and the reaction rate constant are as follows:
Fe2++H2O2→Fe3++OH-+•OH;k1=40~80（L·mol-1·s-1） （1）
Fe3++H2O2→Fe2++•O2H+H+;k2=0.001~0.02（L·mol-1·s-1） （2）
In the Fenton reaction, the return of Fe 3+ to Fe 2+ is a speed limiting step, the rate constant k2 of the reaction is far lower than the conversion rate k1 of Fe 2+ to Fe 3+, which can cause accumulation of Fe 3+ in the system, the transfer of chain reaction is difficult to realize, and finally the degradation rate of organic matters is reduced. Although the organic degradation rate can be improved by increasing the addition amount of Fe 2+ and H 2O2 so as to improve the concentration of generated hydroxyl radicals, the dosage and the mud yield of the Fenton reagent can be greatly increased, meanwhile, fe 2+ and H 2O2 in the reaction can be used as a hydroxyl radical scavenger to consume.OH and generate HO 2 with lower activity, the H 2O2 can be decomposed in an ineffective way, so that the utilization rate of the Fenton reagent is reduced, and the wastewater treatment cost is increased.
The Fenton fluidized bed system belongs to a reaction system widely applied in Fenton-like oxidation, and is a process combining the traditional Fenton method and a fluidized bed crystallizer. The conventional fluidized bed crystallizer is a columnar reactor, water is generally fed into the bottom of the reactor, the reactor is filled with seed crystal materials, the seed crystal materials are expanded and fluidized through internal circulation, and the seed crystal carriers are subjected to heterogeneous crystallization in the process of fully contacting with the solution, so that the effect of removing target substances in wastewater is achieved. Compared with the traditional precipitation method, the crystallization method has low water content of the obtained crystallization product, and is beneficial to subsequent sludge treatment.
Compared with the traditional Fenton, the Fenton fluidized bed has obvious advantages on the removal rate of organic matters and the utilization rate of Fenton reagent, but because the iron crystallization process is easy to be disturbed, such as reaction pH, iron ion concentration, hydraulic conditions, organic intermediate products, complex interference ions and the like, the crystallization debugging time of the reactor is long, usually 3-6 months or longer is needed, the adjustment of the adding amount of ferric salt in the crystallization process is not based, the adjustment and the operation can only be manually judged and carried out, a large amount of manpower and material resources are consumed in the operation process, the crystallization efficiency is low, the stable operation of Fenton organic matter oxidation reaction is not facilitated, and the practical successful application cases are few.
How to reduce the speed limiting influence of the fluidized bed, reduce the Fenton reagent amount and improve the reagent utilization rate, how to intelligently control the crystallization process and the treatment water quality of the fluidized bed, and the Fenton fluidized bed application method which is easy to control, low in cost and quick in crystallization is a problem to be solved in the industrial degradation-resistant organic wastewater treatment industry.
Disclosure of Invention
The invention aims to solve the problems that the dosage of ferric salt is not regulated in the crystallization process and the Fenton reagent dosage is low in utilization rate.
The technical scheme adopted by the invention is as follows:
A Fenton fluidized bed rapid crystallization control method comprises the following steps:
step 1, collecting raw water flow, crystal particle size and starting time in the Fenton fluidized bed crystallization process.
And 2, establishing a crystal discharge period model according to the measured grain size of the crystal grains and the starting time, and further obtaining the crystal discharge period.
And 3, establishing a reflux quantity model according to the crystal discharging period and the raw water flow quantity, and obtaining the hydrogen peroxide dosing reflux quantity and the ferrous sulfate dosing reflux quantity through the reflux quantity model.
And 4, setting the ratio of the addition amount of ferrous sulfate to the chemical oxygen demand. And establishing a ferrous sulfate addition model according to the ferrous sulfate addition and the chemical oxygen demand ratio and the crystal particle size to obtain the ferrous sulfate addition.
And 5, carrying out hydrogen peroxide reflux dosing on the Fenton fluidized bed raw water according to the hydrogen peroxide dosing reflux quantity obtained in the step 3. And (3) carrying out ferrous sulfate reflux dosing on the Fenton fluidized bed raw water according to the ferrous sulfate dosing reflux quantity obtained in the step (3). And (3) adding ferrous sulfate to the Fenton fluidized bed backwater water according to the adding amount of the ferrous sulfate obtained in the step (4).
Preferably, the crystal-arranging period model is as follows:
;
Wherein, The crystal arrangement period is represented by the period of crystal arrangement,The particle diameter of the crystal particles is shown,Indicating the start-up time.
Preferably, the reflux quantity model is as follows:
;
;
Wherein, The back flow of the hydrogen peroxide is indicated,Represents the flow rate of raw water,Indicating the dosing reflux quantity of ferrous sulfate.
Preferably, the ferrous sulfate addition model comprises the following steps:
;
Wherein, The addition amount of the ferrous sulfate is represented,Represents the Chemical Oxygen Demand (COD),Indicating that the adding amount of ferrous sulfate and the chemical oxygen demand ratio are set,Indicating the crystal grain size.
Preferably, the crystal grain size is measured by periodic sampling.
Preferably before each seeding cycle comesAnd S, stopping the raw water pump, the reflux pump and the water outlet valve. After the crystal arrangement is finishedAnd s, opening the raw water pump, the reflux pump and the water outlet valve.
Preferably: In the range of 50-70s, In the range of 15-20s.
A Fenton fluidized bed rapid crystallization control system comprises an input unit, a flowmeter, a timer, a crystal discharge period unit, a reflux unit, a ferrous sulfate adding unit and a control unit, wherein:
The input unit is used for inputting the grain size of crystal grains and setting the ratio of the adding amount of ferrous sulfate to the chemical oxygen demand.
The flowmeter is used for measuring the raw water flow in the raw water pipe.
The timer is used for timing the system to start crystallization to obtain starting time.
The crystal discharging period unit is used for obtaining the crystal discharging period through a crystal discharging period model according to the measured grain size of the crystal grains and the starting time.
The reflux quantity unit is used for obtaining the hydrogen peroxide dosing reflux quantity and the ferrous sulfate dosing reflux quantity through a reflux quantity model according to the crystal discharging period and the raw water flow quantity.
The ferrous sulfate adding unit is used for obtaining the ferrous sulfate adding amount through a ferrous sulfate adding amount model according to the ferrous sulfate adding amount and the chemical oxygen demand ratio and the crystal particle size.
And the control unit carries out hydrogen peroxide reflux dosing on the Fenton fluidized bed raw water according to the obtained hydrogen peroxide dosing reflux quantity. And carrying out ferrous sulfate reflux dosing on the Fenton fluidized bed raw water according to the obtained ferrous sulfate dosing reflux quantity. And adding ferrous sulfate into the Fenton fluidized bed reflux water according to the obtained ferrous sulfate adding amount.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, the crystal discharging period is obtained by measuring the grain size of crystal particles and the starting time, the dosing reflux quantity of hydrogen peroxide and the dosing reflux quantity of ferrous sulfate are obtained by measuring the raw water flow quantity in the crystal discharging period, the dosing reflux quantity of ferrous sulfate is obtained by measuring the ratio of the ferrous sulfate to the chemical oxygen demand and the grain size of crystal particles, and then the Fenton fluidized bed is controlled, so that the dosing quantity of the dosing reflux quantity of hydrogen oxide, the dosing reflux quantity of ferrous sulfate and the dosing quantity of ferrous sulfate in the crystallization process is more accurate, the normal growth metabolism system of crystals is maintained, the rapid and stable growth of crystals is facilitated, and meanwhile, the utilization rate of Fenton reagent quantity is improved.
Drawings
FIG. 1 is a schematic flow chart of a Fenton fluidized bed rapid crystallization control method.
Fig. 2 is a block diagram of the fast crystallization control system of the Fenton fluidized bed.
Detailed Description
The present application is further illustrated in the accompanying drawings and detailed description which are to be understood as being merely illustrative of the application and not limiting of its scope, and various equivalent modifications to the application will fall within the scope of the application as defined in the appended claims after reading the application.
The invention designs a Fenton fluidized bed rapid crystallization control method, which is shown in figure 1 and comprises the following steps:
Step 1, collecting raw water flow, crystal particle size and starting time in the Fenton fluidized bed crystallization process. In another embodiment, the crystal grain size is measured by periodic sampling.
And 2, establishing a crystal discharge period model according to the measured grain size of the crystal grains and the starting time, and further obtaining the crystal discharge period.
The dimension is removed through the grain diameter of crystal grains, the starting time and the crystal discharge period, and a crystal discharge period model is established:
;
Wherein, The crystal arrangement period is represented by the period of crystal arrangement,The particle diameter of the crystal particles is shown,Indicating the start-up time.
In another embodiment, before each seeding cycle comesAnd S, stopping the raw water pump, the reflux pump and the water outlet valve. After the crystal arrangement is finishedAnd s, opening the raw water pump, the reflux pump and the water outlet valve. In a further embodiment of the present invention,In the range of 50-70s,In the range of 15-20s.
And 3, establishing a reflux quantity model according to the crystal discharging period and the raw water flow quantity, and obtaining the hydrogen peroxide dosing reflux quantity and the ferrous sulfate dosing reflux quantity through the reflux quantity model.
The dimension is removed through the raw water flow, the crystal discharging period, the hydrogen peroxide dosing reflux quantity and the ferrous sulfate dosing reflux quantity, and a reflux quantity model is established:
;
;
Wherein, The back flow of the hydrogen peroxide is indicated,Represents the flow rate of raw water,Indicating the dosing reflux quantity of ferrous sulfate.
According to different particle sizes, different reflux amounts are regulated, so that the requirements of different reflux amounts of hydrogen peroxide dosing reflux amount and ferrous sulfate dosing reflux amount are met, the crystal growth speed is further increased, and the crystal stability of the system is improved.
And step 4, setting the ratio of the addition amount of ferrous sulfate to the chemical oxygen demand, wherein COD refers to the chemical oxygen demand. And establishing a ferrous sulfate addition model according to the ferrous sulfate addition and the chemical oxygen demand ratio and the crystal particle size to obtain the ferrous sulfate addition.
And setting parameters such as the addition amount of ferrous sulfate, the chemical oxygen demand ratio, the crystal particle size, the addition amount of ferrous sulfate and the like to remove dimension, and establishing a reflux quantity model.
The ratio of the addition amount of the ferrous sulfate to the chemical oxygen demand is as follows:
;
Wherein, To set the ratio of the adding amount of ferrous sulfate to the chemical oxygen demand,For the initial addition amount of the ferrous sulfate,Is chemical oxygen demand.
After a period of reaction, the relation between the addition amount of ferrous sulfate after reaction, the chemical oxygen demand ratio and the grain diameter of crystal grains is as follows:
;
Wherein, The ratio of the added amount of the reacted ferrous sulfate to the chemical oxygen demand,Is the grain diameter of crystal grain.
The ratio of the added amount of the ferrous sulfate to the chemical oxygen demand after the reaction is as follows:
;
Wherein, In order to achieve this, the first and second,The adding amount of the reacted ferrous sulfate is adopted,Is chemical oxygen demand.
At this time, the required added amount of the added ferrous sulfate is as follows:
;
;
And then obtain:
;
Wherein, The addition amount of the ferrous sulfate is represented,Represents the Chemical Oxygen Demand (COD),Indicating that the adding amount of ferrous sulfate and the chemical oxygen demand ratio are set,The particle size of the crystal particles is shown, the particle size of the crystal is gradually increased after the reaction, the adding amount of ferrous sulfate is gradually reduced, and the particle size of the crystal particles is generally the sameThe range of the value is 0.2-4mm, and the crystal discharge is started when the value is more than 4 mm.
By monitoring the grain size of the crystal particles in real time, the ferrous sulfate addition amount required to be supplemented for the return water is obtained on the basis of the set ferrous sulfate addition amount and the chemical oxygen demand ratio, and the use of the ferrous sulfate addition amount is reduced by the accurate control.
And 5, carrying out hydrogen peroxide reflux dosing on the Fenton fluidized bed raw water according to the hydrogen peroxide dosing reflux quantity obtained in the step 3. And (3) carrying out ferrous sulfate reflux dosing on the Fenton fluidized bed raw water according to the ferrous sulfate dosing reflux quantity obtained in the step (3). And (3) adding ferrous sulfate to the Fenton fluidized bed backwater water according to the adding amount of the ferrous sulfate obtained in the step (4).
A Fenton fluidized bed rapid crystallization control system, as shown in figure 2, comprises an input unit, a flowmeter, a timer, a crystal discharging period unit, a reflux amount unit, a ferrous sulfate adding amount unit and a control unit, wherein:
The input unit is used for inputting the grain size of crystal particles, the chemical oxygen demand and setting the ratio of the addition amount of ferrous sulfate to the chemical oxygen demand.
The flowmeter is used for measuring the raw water flow in the raw water pipe.
The timer is used for timing the system to start crystallization to obtain starting time.
The crystal discharging period unit is used for obtaining the crystal discharging period through a crystal discharging period model according to the measured grain size of the crystal grains and the starting time.
The reflux quantity unit is used for obtaining the hydrogen peroxide dosing reflux quantity and the ferrous sulfate dosing reflux quantity through a reflux quantity model according to the crystal discharging period and the raw water flow quantity.
The ferrous sulfate adding unit is used for obtaining the ferrous sulfate adding amount through a ferrous sulfate adding amount model according to the ferrous sulfate adding amount and the chemical oxygen demand ratio and the crystal particle size.
And the control unit carries out hydrogen peroxide reflux dosing on the Fenton fluidized bed raw water according to the obtained hydrogen peroxide dosing reflux quantity. And carrying out ferrous sulfate reflux dosing on the Fenton fluidized bed raw water according to the obtained ferrous sulfate dosing reflux quantity. And adding ferrous sulfate into the Fenton fluidized bed reflux water according to the obtained ferrous sulfate adding amount.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The Fenton fluidized bed rapid crystallization control method is characterized by comprising the following steps of:
step 1, collecting raw water flow, crystal particle size and starting time in the Fenton fluidized bed crystallization process;
Step 2, establishing a crystal discharging period model according to the measured grain size of the crystal grains and the starting time, so as to obtain a crystal discharging period;
The crystal-arranging period model is as follows:
;
Wherein, The crystal arrangement period is represented by the period of crystal arrangement,The particle diameter of the crystal particles is shown,Indicating the start time;
step 3, establishing a reflux quantity model according to the crystal discharging period and the raw water flow quantity, and obtaining the hydrogen peroxide dosing reflux quantity and the ferrous sulfate dosing reflux quantity through the reflux quantity model;
The reflux quantity model is as follows:
;
;
Wherein, The back flow of the hydrogen peroxide is indicated,Represents the flow rate of raw water,The adding reflux amount of ferrous sulfate is represented;
Setting a ferrous sulfate addition amount model according to the ferrous sulfate addition amount and the chemical oxygen demand ratio and the crystal particle size to obtain the ferrous sulfate addition amount;
And 5, carrying out hydrogen peroxide reflux dosing on the Fenton fluidized bed raw water according to the hydrogen peroxide dosing reflux quantity obtained in the step 3, carrying out ferrous sulfate reflux dosing on the Fenton fluidized bed raw water according to the ferrous sulfate dosing reflux quantity obtained in the step 3, and carrying out ferrous sulfate dosing on the Fenton fluidized bed reflux water according to the ferrous sulfate dosing quantity obtained in the step 4.
2. The Fenton fluidized bed rapid crystallization control method according to claim 1, wherein the ferrous sulfate addition model is as follows:
;
Wherein, The addition amount of the ferrous sulfate is represented,Represents the Chemical Oxygen Demand (COD),Indicating that the adding amount of ferrous sulfate and the chemical oxygen demand ratio are set,Indicating the crystal grain size.
3. A method for controlling the rapid crystallization of a Fenton fluidized bed according to claim 2, wherein the particle size of the crystal particles is measured by periodic sampling.
4. A method for controlling fast Fenton fluidized bed crystallization according to claim 3, wherein before each crystallization period comesS, stopping the raw water pump, the reflux pump and the water outlet valve, and after the crystal discharge is finishedAnd s, opening the raw water pump, the reflux pump and the water outlet valve.
5. The Fenton fluidized bed rapid crystallization control method according to claim 4, wherein: In the range of 50-70s, In the range of 15-20s.
6. A Fenton fluidized bed rapid crystallization control system is characterized by comprising an input unit, a flowmeter, a timer, a crystal discharge period unit, a reflux amount unit, a ferrous sulfate adding amount unit and a control unit, wherein:
the input unit is used for inputting the grain size of crystal particles and setting the ratio of the addition amount of ferrous sulfate to the chemical oxygen demand;
the flowmeter is used for measuring the raw water flow in the raw water pipe;
The timer is used for timing the system to start crystallization to obtain starting time;
the crystal discharging period unit is used for obtaining a crystal discharging period through a crystal discharging period model according to the measured grain size of the crystal grains and the starting time;
The reflux quantity unit is used for obtaining the hydrogen peroxide dosing reflux quantity and the ferrous sulfate dosing reflux quantity through a reflux quantity model according to the crystal discharging period and the raw water flow quantity;
The reflux quantity model is as follows:
;
;
Wherein, The back flow of the hydrogen peroxide is indicated,Represents the flow rate of raw water,The adding reflux amount of ferrous sulfate is represented;
The ferrous sulfate adding unit is used for obtaining the ferrous sulfate adding amount through a ferrous sulfate adding amount model according to the ferrous sulfate adding amount and the chemical oxygen demand ratio and the crystal particle size;
The control unit carries out hydrogen peroxide reflux dosing on the Fenton fluidized bed raw water according to the obtained hydrogen peroxide dosing reflux quantity, carries out ferrous sulfate reflux dosing on the Fenton fluidized bed raw water according to the obtained ferrous sulfate dosing reflux quantity, and carries out ferrous sulfate dosing on the Fenton fluidized bed reflux water according to the obtained ferrous sulfate dosing quantity.
7. The Fenton fluidized bed rapid crystallization control system according to claim 6, wherein the ferrous sulfate addition model is as follows:
;
Wherein, The addition amount of the ferrous sulfate is represented,Represents the Chemical Oxygen Demand (COD),Indicating that the adding amount of ferrous sulfate and the chemical oxygen demand ratio are set,Indicating the crystal grain size.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192979A (en) * | 2014-09-23 | 2014-12-10 | 南京大学 | Fenton fluidized bed biochemical tail water advanced treatment method |
| CN108298725A (en) * | 2018-02-11 | 2018-07-20 | 吉林建筑大学 | A kind of batch-type Fenton oxidation reactor reagent adds course control method for use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192979A (en) * | 2014-09-23 | 2014-12-10 | 南京大学 | Fenton fluidized bed biochemical tail water advanced treatment method |
| CN108298725A (en) * | 2018-02-11 | 2018-07-20 | 吉林建筑大学 | A kind of batch-type Fenton oxidation reactor reagent adds course control method for use |
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