CN215403265U - Device for treating wastewater containing fluoroborate - Google Patents

Device for treating wastewater containing fluoroborate Download PDF

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Publication number
CN215403265U
CN215403265U CN202120779815.XU CN202120779815U CN215403265U CN 215403265 U CN215403265 U CN 215403265U CN 202120779815 U CN202120779815 U CN 202120779815U CN 215403265 U CN215403265 U CN 215403265U
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Prior art keywords
reaction chamber
water
wastewater
fluoroborate
pump
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CN202120779815.XU
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Chinese (zh)
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赵俊光
姚仕奇
殷仕颖
丁昀
杨庆
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Lanzhou Jiaotong University
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Lanzhou Jiaotong University
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Abstract

本实用新型公开了一种可用于处理含氟硼酸根废水的装置,该装置包括反应室、加热室和水泵,所述加热室包裹在所述反应室的外壁上,所述水泵的入水口通过水管与所述加热室连接,所述水泵的出水口通过水管与所述反应室内连接。本实用新型的装置可以充分利用原料反应过程中产生的热量来加热氟硼酸根废水,无需额外的热源,具有占地面积小、能源利用率高的优点。

Figure 202120779815

The utility model discloses a device which can be used for treating fluoroborate-containing wastewater. The device comprises a reaction chamber, a heating chamber and a water pump, the heating chamber is wrapped on the outer wall of the reaction chamber, and the water inlet of the water pump passes through The water pipe is connected with the heating chamber, and the water outlet of the water pump is connected with the reaction chamber through the water pipe. The device of the utility model can fully utilize the heat generated in the raw material reaction process to heat the fluoroborate wastewater without additional heat source, and has the advantages of small footprint and high energy utilization rate.

Figure 202120779815

Description

Device for treating wastewater containing fluoroborate
Technical Field
The utility model belongs to the field of wastewater treatment, and particularly relates to a device for treating wastewater containing fluoroborate, in particular to a device for treating wastewater containing fluoroborate and fluoride ions simultaneously.
Background
With the rapid development of fluorine-containing processing industries such as oil refining, electroplating and organic fluorine lubricating oil manufacturing, a series of fluorine pollution problems are brought about. In addition, BF is adopted in petrochemical industry3Produced as a catalyst due to BF contained in discharged wastewater4 -Will slowly hydrolyze and release a large amount of F-Increasing the difficulty of wastewater treatment. Since the fluorine ions have strong electronegativity and are easily combined with other elements, if excessive fluorine ions are absorbed by human bodies, health problems are caused. In order to control the concentration of fluorine ions in industrial wastewater, the first-level discharge standard in Integrated wastewater discharge Standard (GB 8978-1996) of China stipulates F-The ion concentration is less than 10 mg/L. Currently, BF is commonly used4-The removal method adopts a potassium salt precipitation method and utilizes K+And BF4-After insoluble precipitate is generated, supernatant is taken and hydrolyzed at medium and high temperature (75-95 ℃) to be removed. F-The precipitation of F is usually carried out by calcium salt precipitation-With Ca2+Production of CaF2Precipitating, and removing F by solid-liquid separation-The purpose of (1). The common BF at present4-Hydrolysis uses waste industrial heat as a concentrated heat source for heating, however this cannot be achieved in some regions.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide a device for treating wastewater containing fluoroborate.
In order to achieve the purpose, the technical scheme adopted by the utility model is as follows:
an apparatus for treating wastewater containing fluoroborate, comprising a reaction chamber 10, a heating chamber 20 and a water pump 30, characterized in that: the heating chamber 20 is wrapped on the outer wall of the reaction chamber 10, the water inlet of the water pump 30 is connected with the heating chamber 20 through a water pipe, and the water outlet of the water pump 30 is connected with the inside of the reaction chamber 10 through a water pipe.
Preferably, the device is provided with a PLC control system, the reaction chamber is provided with a temperature sensor 13, and the temperature sensor 13 and the water pump 30 are respectively connected with the PLC control system. The PLC control system controls the water pump 30 to be turned on according to a signal from the temperature sensor 13.
Preferably, the apparatus is provided with a drain pump 40, and a water inlet of the drain pump 40 is connected with the inside of the reaction chamber 10 through a water pipe.
More preferably, the end of the water pipe connected to the water inlet of the drain pump is provided with a filter screen 41.
More preferably, fluoroborate detection electrode 14 is disposed within the reaction chamber.
More preferably, the side wall of the reaction chamber is provided with a level gauge 18.
More preferably, the liquid level meter 18, the fluoroborate detection electrode 14 and the drain pump 40 are respectively connected with a PLC control system. The PLC control system controls the opening or closing of the drain pump 40 according to signals from the fluoroboric acid detecting electrode 14 and the liquid level gauge 18.
Preferably, the bottom of the reaction chamber is provided with a slag discharge port 17.
Preferably, a gate valve is installed at the slag discharge port 17.
More preferably, a fluorine ion detecting electrode 15 is provided in the reaction chamber.
A method of treating wastewater containing fluoroborate, comprising:
adding fluorine-containing borate wastewater into a reaction chamber of the device, and adding self-heating filler into a heating chamber of the device, wherein the self-heating filler mainly comprises calcium oxide, iron, carbon and electrolyte;
adding water into the heating chamber to react with the self-heating filler to release heat;
and pumping the water in the heating chamber into the reaction chamber to be mixed and reacted with the fluorine-containing borate wastewater when the temperature of the fluorine-containing borate wastewater in the reaction chamber reaches over 75 ℃.
Preferably, the fluorine-containing borate wastewater also contains fluorine ions.
Preferably, the potassium salt or the potassium salt and the calcium salt are added to the fluorine-containing borate wastewater for precipitation treatment before the water in the heating chamber is pumped into the reaction chamber.
More preferably, the potassium salt is added first and the calcium salt is added.
More preferably, the potassium salt is potassium chloride and the calcium salt is calcium chloride.
Preferably, the self-heating filler further contains aluminum.
More preferably, the autothermal packing further comprises an adsorbent.
The adsorbent is diatomite. The adsorption effect of the diatomite and the coke powder is utilized to adsorb the heating reactant in the porous structures inside the diatomite and the coke powder, so that the diatomite and the coke powder are fully contacted and carry out chemical reaction.
Preferably, the electrolyte is sodium chloride, and the electrolyte forms a salt bridge required by an aluminum-carbon primary battery reaction and an iron-carbon primary battery reaction.
Most preferably, the self-heating filler is composed of calcium oxide, aluminum, iron, carbon, electrolyte and adsorbent according to a mass ratio of 4-5: 1-1.2: 2-2.6: 1.2-1.5: 1-2: 0.5-1.
The principle of the utility model is as follows:
calcium oxide in the self-heating filler reacts with water to generate calcium hydroxide and rapidly release a large amount of heat, iron and carbon form an iron-carbon primary battery to generate micro-electrolysis in the environment of generated calcium hydroxide electrolyte solution, a large amount of heat is continuously released, the released heat is transferred into a chamber through the outer wall of the reaction chamber to heat wastewater, when the wastewater is heated to a certain temperature, supernate containing calcium and iron ions in the heating chamber is pumped into the reaction chamber, fluoroborate is rapidly hydrolyzed into FeF under the action of the iron ions at a high temperature6 3-Boric acid, calcium ions form a CaF which is insoluble in fluorine ions in wastewater2And (4) precipitating.
The water-soluble potassium salt is used for precipitating the wastewater containing the fluoroborate in advance, so that on one hand, partial fluoroborate can be precipitated, and on the other hand, the calcium ions and the fluoride ions are promoted to be condensed into CaF by taking a potassium fluoroborate crystal nucleus as a center2Precipitation, preferably in a mass ratio of K: BF4 -Adding water-soluble potassium salt such as potassium chloride in a ratio of 6.5-9:1, wherein the removal rate of the fluoroborate can reach 55-65% after the pre-precipitation treatment.
3BF4 - +2Fe3++9H2O= 2[FeF6]3-+3H3BO3+9H +Formula 1
CaO+H2O = Ca(OH)2Formula 2
Ca 2++2F- = CaF2↓3
K++BF4 -= KBF4 ↓4
The iron-carbon micro-electrolysis reaction process is as follows:
anode: fe-2e → Fe2+Formula 5
Cathode:
2H+ + 2e → H2(acidic conditions) formula 6
O2 + 2H2O+4e→4OH- (basic conditions) formula 7
The aluminum-carbon micro-electrolysis reaction process is as follows:
anode: al-3 e → Al3+Formula 8
Cathode:
2H+ + 2e → H2℃ (acidic condition) formula 9
O2 + 2H2O+4e→4OH-(basic conditions) formula 10
The reaction process for converting Fe2+ into Fe3+ is as follows:
12Fe2+ + 3O2 +6H2O= 4Fe(OH) 3↓+8Fe3+formula 11
Compared with the prior art, the device provided by the utility model has the advantages that the heat generated in the raw material reaction process is fully utilized to heat the fluoroborate wastewater, no additional heat source is needed, the occupied area is small, and the energy utilization rate is high. The device is also suitable for the waste liquid containing the fluoroborate and the fluoride ions at the same time, and is beneficial to improving the treatment efficiency of the waste liquid.
Drawings
FIG. 1 is a schematic view of an apparatus for treating wastewater containing fluoroborate according to the present invention.
Fig. 2 is a schematic structural diagram of a PLC control system.
The system comprises a reaction chamber 10, a stirrer 11, a motor 12, a temperature sensor 13, a fluoroborate detection electrode 14, a fluoride ion detection electrode 15, a pH detection electrode 16, a slag discharge port 17, a liquid level meter 18, a heating chamber 20, self-heating filler 21, a temperature sensor 22, a water pump 30, a water discharge pump 40 and a filter screen 41.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
As shown in FIG. 1, the apparatus for treating waste water containing fluoroborate according to the present invention has an inner and outer double-shell structure, wherein the inner shell forms a wall of the reaction chamber 10, and the cavity between the inner shell and the outer shell forms a heating chamber 20.
The inner shell, namely the wall body of the reaction chamber, is made of thin-wall carbon steel with good heat conduction performance, so that the corrosion resistance of the wall body is further improved, the surface of the carbon steel can be sprayed with a silicon carbide coating with corrosion resistance and high heat conduction efficiency, the outer shell is made of hard phenolic plastic with good heat insulation performance, and rock wool is wrapped to reduce heat loss.
The cavity of the heating chamber 20 is filled with self-heating filler 21, and the self-heating filler reacts with tap water in the cavity to release heat.
The device is provided with a water pump 30, the water inlet of the water pump 30 is connected with the heating chamber 20 through a water pipe, and the water outlet is connected with the reaction chamber 10 through a water pipe. The supernatant in the heating chamber 20 is pumped into the reaction chamber 10 by the water pump 30, and the supernatant containing calcium ions and iron ions is reacted with the waste water containing fluoroborate.
The reaction chamber 10 is provided with a temperature sensor 13 for monitoring the temperature of the wastewater in the reaction chamber.
The heating chamber 20 is provided with a temperature sensor 22 for monitoring the temperature of the supernatant in the heating chamber.
The device is also provided with a drainage pump 40, wherein the water inlet of the drainage pump 40 is connected with the inside of the reaction chamber 10 through a water pipe and is used for discharging the treated wastewater reaching the standard out of the reaction chamber 10. In order to prevent the waste residue in the reaction chamber from being sucked into the drain pump 40, a filter 41 is provided at the end of a water pipe connected to the water inlet of the drain pump 40.
A fluoborate detection electrode 14 is arranged in the reaction chamber and used for monitoring the concentration of fluoborate in the wastewater.
And a fluorine ion detection electrode 15 and a pH detection electrode 16 are also arranged in the reaction chamber and are respectively used for monitoring the concentration of fluorine ions in the wastewater and the pH value of the wastewater.
The bottom of the reaction chamber 10 is provided with a slag discharge port 17 penetrating through the heating chamber 20 for discharging generated waste slag, and the slag discharge port 17 is provided with a gate valve.
The side wall of the reaction chamber is provided with a liquid level meter 18 for monitoring the level of wastewater in the reaction chamber.
The device is also provided with a PLC (Programmable Logic Controller) control system, and the temperature sensors (13, 22), the fluoroborate detection electrode 14, the fluoride ion detection electrode 15, the pH detection electrode 16, the liquid level meter 18, the gate valve of the slag discharge port 17, the motor 12, the water pump 30 and the drainage pump 40 are respectively connected with the PLC control system. A typical structural schematic diagram of the PLC control system is shown in fig. 2, the PLC control system obtains data signals from the temperature sensors (13, 22), the fluoroborate detection electrode 14, the fluoride ion detection electrode 15, the pH detection electrode 16, and the liquid level meter 18 through the input module, and after running a program set by the programming device through the CPU, the PLC control system realizes automatic start or stop of the gate valve of the slag discharge port 17, the motor 12, the water pump 30, and the drain pump 40 through the output module.
Example 2
Meanwhile, the method for treating the wastewater containing the fluoroborate and the fluoride ions comprises the following steps:
adding fluorine-containing borate wastewater into a reaction chamber 10 of the device in example 1, and adding self-heating filler 21 into a heating chamber 20 of the device, wherein the self-heating filler is CaO, Al, Fe, coke powder, NaCl, diatomite and the like in a mass ratio of 4-5: 1-1.2: 2-2.6: 1.2-1.5: 1-2: 0.5-1;
pretreatment: starting the stirrer 11, and feeding the mixture into the reaction chamber 10 according to the mass ratio K: BF4 -Adding potassium chloride according to the proportion of =6.5-9:1, wherein the total adding amount of the potassium chloride is not more than 35g/100ml, adding anhydrous calcium chloride according to the molar ratio of Ca: F =1.5:2 after potassium fluoborate precipitates, and BF in the step4 -The removal rate of the catalyst can reach 55 to 65 percent, F-The removal rate can reach 85-90%, and the specific adding amount of potassium chloride and calcium chloride is determined according to the detection results of the concentration of fluoroborate and fluoride ions;
then, tap water is added into the heating chamber 20, and the tap water and the self-heating filler 21 are in contact reaction to release a large amount of heat, so that the wastewater in the reaction chamber 10 is heated;
when the temperature of the wastewater in the reaction chamber 10 reaches above 75 ℃ (preferably above 85 ℃), the water pump 30 is started, and the supernatant in the heating chamber 20 is pumped into the reaction chamber 10 to be mixed and reacted with the wastewater;
after the concentration of the fluoroborate and the fluorine ions in the wastewater in the reaction chamber 10 reaches the discharge standard, the drainage pump 40 is started to discharge the standard wastewater, when the water level of the wastewater is reduced to the lowest point, the drainage pump 40 is closed, the gate valve of the slag discharge port 17 is opened, and the waste slag is discharged.
It should be noted that, for those skilled in the art, modifications to the technical solutions described in the above embodiments or equivalent replacements of some technical features thereof should be considered as the protection scope of the present invention without departing from the technical principle of the present invention.

Claims (13)

1. The utility model provides a can be used to handle device that contains fluoride borate waste water, the device includes reaction chamber, heating chamber and water pump, its characterized in that: the heating chamber is wrapped on the outer wall of the reaction chamber, a water inlet of the water pump is connected with the heating chamber through a water pipe, and a water outlet of the water pump is connected with the inside of the reaction chamber through a water pipe.
2. The apparatus of claim 1, wherein: the device is provided with a PLC control system, the reaction chamber is provided with a temperature sensor, and the temperature sensor and the water pump are respectively connected with the PLC control system.
3. The apparatus of claim 1 or 2, wherein: the device is provided with a drainage pump, and a water inlet of the drainage pump is connected with the inside of the reaction chamber through a water pipe.
4. The apparatus of claim 3, wherein: and a filter screen is arranged at the tail end of the water pipe connected with the water inlet of the drainage pump.
5. The apparatus of claim 3, wherein: and a fluoborate detection electrode is arranged in the reaction chamber.
6. The apparatus of claim 5, wherein: and a liquid level meter is arranged on the side wall of the reaction chamber.
7. The apparatus of claim 6, wherein: the liquid level meter, the fluoborate detection electrode and the draining pump are respectively connected with the PLC control system.
8. The apparatus of any one of claims 1, 2, 4 to 7, wherein: and a slag discharge port is arranged at the bottom of the reaction chamber.
9. The apparatus of claim 8, wherein: and a gate valve is arranged at the slag discharge hole.
10. The apparatus of claim 3, wherein: and a slag discharge port is arranged at the bottom of the reaction chamber.
11. The apparatus of claim 10, wherein: and a gate valve is arranged at the slag discharge hole.
12. The apparatus of any one of claims 1, 2, 4 to 7, wherein: and a fluorine ion detection electrode is arranged in the reaction chamber.
13. The apparatus of claim 3, wherein: and a fluorine ion detection electrode is arranged in the reaction chamber.
CN202120779815.XU 2021-04-16 2021-04-16 Device for treating wastewater containing fluoroborate Expired - Fee Related CN215403265U (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113060802A (en) * 2021-04-16 2021-07-02 兰州交通大学 A device and method for treating fluoroborate wastewater

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113060802A (en) * 2021-04-16 2021-07-02 兰州交通大学 A device and method for treating fluoroborate wastewater
CN113060802B (en) * 2021-04-16 2025-01-28 兰州交通大学 A device and method for treating fluoroborate-containing wastewater

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