CN103482797A - Process and device for removing hypophosphites and phosphites by advanced oxidation coupling technique - Google Patents
Process and device for removing hypophosphites and phosphites by advanced oxidation coupling technique Download PDFInfo
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- CN103482797A CN103482797A CN201310477879.4A CN201310477879A CN103482797A CN 103482797 A CN103482797 A CN 103482797A CN 201310477879 A CN201310477879 A CN 201310477879A CN 103482797 A CN103482797 A CN 103482797A
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Abstract
The invention relates to industrial wastewater treatment, particularly a process and device for removing hypophosphites and phosphites by an advanced oxidation coupling technique in industrial wastewater treatment. The invention provides a process for removing hypophosphites and phosphites by an advanced oxidation coupling technique, which comprises the following steps: S1. injecting ozone and hydrogen peroxide into wastewater to oxidate hypophosphites and phosphites into orthophosphates by coupling the ozone and hydrogen peroxide; and S2. in the presence of ozone, adding ferrous sulfate into the wastewater to continue oxidate the residual hypophosphites and phosphites and remove the orthophosphates. The invention also provides a device for removing hypophosphites and phosphites by an advanced oxidation coupling technique. The process and device provided by the invention have the advantages of high reaction speed, favorable removal effect, simple technical process, no need of regulating pH value, and low sludge production quantity.
Description
Technical field
The present invention relates to Industrial Wastewater Treatment, a kind of advanced oxidation coupling technique related in particular in Industrial Wastewater Treatment is removed technique and device inferior, phosphite.
Background technology
Electroplate and the water quality complexity of board wastewater, except the heavy metal ion such as the chromium that contains, copper, nickel, cadmium, zinc, gold and silver and prussiate, phosphorus, nitrogen, organism etc. in addition.Wherein, the source of phosphorus is mainly the reduzate phosphite of hypophosphite, and also has the unemployed hypophosphite of part.
At present, very ripe for heavy metal ion, organic removal technology, processing cost is lower, and can guarantee that stable water outlet is up to standard.For inferior, phosphite, the present normal multiple-stage treatment method that adopts: the first step under acidic conditions by oxygenant will be inferior, phosphite is oxidized to orthophosphoric acid salt, the second stage adds lime, under alkaline condition, orthophosphoric acid salt is transformed into to calcium phosphate precipitation.Oxygenant often adopts clorox.
Although current most of engineering all adopts this technique to carry out removal inferior, phosphite, there is the treatment scheme complexity in this technique, the residence time is long, the pH regulator expense is high, sludge output is high, treatment effect is difficult to the problems such as assurance.
Summary of the invention
In order to solve the problems of the prior art, the invention provides a kind of advanced oxidation coupling technique and remove technique and device inferior, phosphite.
The invention provides a kind of advanced oxidation coupling technique and remove technique inferior, phosphite, comprise the following steps:
S1, to waste water injection of ozone and hydrogen peroxide, by ozone and hydrogen peroxide, hypophosphite, phosphite are oxidized to orthophosphoric acid salt;
Under S2, the condition that exists at ozone, to waste water, add ferrous sulfate, continue oxidation remaining hypophosphite, phosphite and also remove orthophosphoric acid salt.
As a further improvement on the present invention, also comprise step S3, by sludge settling by the indissoluble particle separation in waste water and remove orthophosphoric acid salt.
As a further improvement on the present invention, in step S2, continue to the waste water injection of ozone.
As a further improvement on the present invention, carry out step S2 in step S1 reaction after 3-10 minute.
As a further improvement on the present invention, carry out step S2 in step S1 reaction after 5-8 minute.
As a further improvement on the present invention, carry out step S2 in step S1 reaction after 6 minutes.
The present invention also provides a kind of advanced oxidation coupling technique to remove device inferior, phosphite, comprise I section reaction tank, II section reaction tank, hydrogen peroxide injection device, ozone injection device and ferrous sulfate injection device, described I section reaction tank is communicated with described II section reaction tank, described I section reaction tank is provided with water-in, described ozone injection device is connected with described I section reaction tank, described ozone injection device is connected with described I section reaction tank, and described ferrous sulfate injection device is connected with described II section reaction tank.
As a further improvement on the present invention, described ozone injection device is connected with described II section reaction tank.
As a further improvement on the present invention, described ozone injection device comprises ozonizer, the first gas meter, the second gas meter, the first aeration head and the second aeration head, described the first aeration head is arranged on the bottom of described I section reaction tank, described the second aeration head is arranged on the bottom of described II section reaction tank, described ozonizer respectively with described the first aeration head, the second aeration head connects, described the first gas meter is connected to described ozonizer, between the first aeration head, described the second gas meter is connected to described ozonizer, between the second aeration head.
As a further improvement on the present invention, described I section reaction tank is connected with the waste water injection device by water-in, described waste water injection device comprises intake pump and first liquid under meter, described intake pump is connected with the water-in of described I section reaction tank, and described first liquid under meter is connected between the water-in of described intake pump, I section reaction tank.
As a further improvement on the present invention, described hydrogen peroxide injection device comprises hydrogen peroxide storage pool, second liquid under meter and the first impeller pump, the input terminus of described the first impeller pump is connected with described hydrogen peroxide storage pool, the described first centrifugal delivery side of pump is connected with described I section reaction tank, and described second liquid under meter is connected between described hydrogen peroxide storage pool, the first impeller pump.
As a further improvement on the present invention, described ferrous sulfate injection device comprises ferrous sulfate storage pool, the 3rd liquid meter and the second impeller pump, the input terminus of described the second impeller pump is connected with described ferrous sulfate storage pool, the described second centrifugal delivery side of pump is connected with described II section reaction tank, and described the 3rd liquid meter is connected between described ferrous sulfate storage pool, the second impeller pump.
As a further improvement on the present invention, described II section reaction tank is communicated with mudpan, and the saliva plane, pond of described II section reaction tank is higher than the saliva plane, pond of described mudpan, and described mudpan is provided with water port and mud discharging mouth.
As a further improvement on the present invention, described advanced oxidation coupling technique is removed, and device inferior, phosphite also comprises the ozone tail gas destructor, and described I section reaction tank, II section reaction tank, mudpan are connected with described ozone tail gas destructor respectively.
The invention has the beneficial effects as follows: pass through such scheme, by ozone and hydrogen peroxide, hypophosphite, phosphite are oxidized to orthophosphoric acid salt, under the condition existed at hydrogen peroxide, ozone is active to be increased, easily be excited and produce the extremely strong free radical of oxidation capacity, newborn O
3-and HO
2can continue to cause a series of radical chain reaction, produce a large amount of OH, thereby significantly improve the oxidation capacity of independent ozone or independent hydrogen peroxide, rapidly hypophosphite, phosphite are oxidized to the ortho-phosphoric acid root, under the ozone existence condition, add ferrous sulfate, produce free radical by ferrous catalysis ozone on the one hand, continue oxidation remaining time, phosphite, on the other hand, utilize the ferrous ortho-phosphoric acid root produced in newborn ferric iron precipitation removal system of ozone Simultaneous Oxidation, because the pH value of reaction system is lower, ferrous oxidation efficiency under general dissolved oxygen environment is lower, and the existence of ozone can significantly improve newborn ferric generation speed, thereby increase the binding ability of iron ion and phosphate radical, and the growth velocity of crystal, the final removal ability that improves orthophosphoric acid salt, speed of response is fast, removal effect is good, technical process is simple, without pH, adjust, sludge output is low.
The accompanying drawing explanation
Fig. 1 is that a kind of advanced oxidation coupling technique removal of the present invention is inferior, the schema of the technique of phosphite;
Fig. 2 is that a kind of advanced oxidation coupling technique removal of the present invention is inferior, the structural representation of the device of phosphite.
Embodiment
Below in conjunction with accompanying drawing explanation and embodiment, the present invention is further described.
Drawing reference numeral in Fig. 1 to Fig. 2 is: intake pump 1; First liquid under meter 2; Hydrogen peroxide storage pool 3; Second liquid under meter 4; The first impeller pump 51; The second impeller pump 52; Ozonizer 6; The first aeration head 71; The second aeration head 72; The first gas meter 81; The second gas meter 82; The 3rd liquid meter 9; Ferrous sulfate storage pool 10; Ozone tail gas destructor 11; Mudpan 12; I section reaction tank 13; II section reaction tank 14.
As shown in Figure 1, technique inferior, phosphite that a kind of advanced oxidation coupling technique is removed comprises the following steps:
S1, to waste water injection of ozone and hydrogen peroxide, by ozone and hydrogen peroxide, hypophosphite, phosphite are oxidized to orthophosphoric acid salt;
S2, under the ozone existence condition, (this step can adopt and continue to injection of ozone in waste water with reinforced effects, also can utilize step S1 remnants' ozone), add ferrous sulfate to waste water, continue oxidation remaining hypophosphite, phosphite and remove orthophosphoric acid salt;
S3, by sludge settling by the indissoluble particle separation in waste water and remove orthophosphoric acid salt.
Wherein, carry out step S2 in step S1 reaction after 3-10 minute.
A kind of advanced oxidation coupling technique removal provided by the invention is inferior, the principle of the technique of phosphite is as follows:
The first, by ozone and hydrogen peroxide, hypophosphite, phosphite are oxidized to orthophosphoric acid salt, under the condition existed at hydrogen peroxide, ozone is active to be increased, and easily is excited and produces the extremely strong free radical of oxidation capacity, and its reaction formula is: H
2o
2→ HO
2 -+ H
+, newborn O
3-and HO
2can continue to cause a series of radical chain reaction, produce a large amount of OH, thereby significantly improve the oxidation capacity of independent ozone or independent hydrogen peroxide, rapidly hypophosphite, phosphite are oxidized to the ortho-phosphoric acid root;
Second, after reaction 3-10min, under the ozone existence condition, add ferrous sulfate, produce free radical by ferrous catalysis ozone on the one hand, continue oxidation remaining time, phosphite, on the other hand, utilize the ferrous ortho-phosphoric acid root produced in newborn ferric iron precipitation removal system of ozone Simultaneous Oxidation, because the pH value of reaction system is lower, ferrous oxidation efficiency under general dissolved oxygen environment is lower, and the existence of ozone can significantly improve newborn ferric generation speed, thereby increase the binding ability of iron ion and phosphate radical, and the growth velocity of crystal, the final removal ability that improves orthophosphoric acid salt,
The 3rd, by sludge settling by Fe-P indissoluble particle separation, thereby reach the purpose of removing the ortho-phosphoric acid root, owing to there being a large amount of electronegative phosphate radicals in system, whole reaction system is electronegative; And the hydroxo complex that the ferric iron hydrolysis produces is under low pH condition, on schedule, on the basis of charge neutrality, the existence of a large amount of complex compounds can reduce the Zeta potential of whole reaction system to most of band, thereby improve the coagulation separation efficiency of system, improve the separation efficiency of Fe-P particulate matter.
As shown in Figure 2, a kind of advanced oxidation coupling technique is removed inferior, the device of phosphite, comprise I section reaction tank 13, II section reaction tank 14, the hydrogen peroxide injection device, ozone injection device and ferrous sulfate injection device, described I section reaction tank 13 is communicated with described II section reaction tank 14, described I section reaction tank 13 is provided with water-in, described ozone injection device respectively with described I section reaction tank 13, II section reaction tank 14 connects (wherein, described ozone injection device can only be connected with I section reaction tank 13), described ozone injection device is connected with described I section reaction tank 13, described ferrous sulfate injection device is connected with described II section reaction tank 14, wherein, I section reaction tank 13 can be reactor, II section reaction tank 14 can be also reactor.
As shown in Figure 2, described ozone injection device comprises ozonizer 6, the first gas meter 81, the second gas meter 82, the first aeration head 71 and the second aeration head 72, described the first aeration head 71 is arranged on the bottom of described I section reaction tank 13, described the second aeration head 72 is arranged on the bottom of described II section reaction tank 14, described ozonizer 6 respectively with described the first aeration head 71, the second aeration head 72 connects, be used for to I section reaction tank 13, II section reaction tank 14 injection of ozones, described the first gas meter 81 is connected to described ozonizer 6, between the first aeration head 71, described the second gas meter 82 is connected to described ozonizer 6, between the second aeration head 72, wherein, the first gas meter 81 is for controlling the flow of the ozone injected to I section reaction tank 13, the second gas meter 82 is for controlling the flow of the ozone injected to II section reaction tank 14, described the first aeration head 71 has a plurality of and is distributed on the bottom of described I section reaction tank 13, described the second aeration head 72 has a plurality of and is distributed on the bottom of described II section reaction tank 72.
As shown in Figure 2, described I section reaction tank 13 is connected with the waste water injection device by water-in, described waste water injection device comprises intake pump 1 and first liquid under meter 2, described intake pump 1 is connected with the water-in of described I section reaction tank 13, described first liquid under meter 2 is connected between the water-in of described intake pump 1, I section reaction tank 13, described first liquid under meter 2, for controlling the flow of former water (being trade effluent), can inject former water to I section reaction tank 13 by intake pump 1.
As shown in Figure 2, described hydrogen peroxide injection device comprises hydrogen peroxide storage pool 3, second liquid under meter 4 and the first impeller pump 51, store hydrogen peroxide in hydrogen peroxide storage pool 3, the input terminus of described the first impeller pump 51 is connected with described hydrogen peroxide storage pool 3, the output terminal of described the first impeller pump 51 is communicated with described I section reaction tank 13 by pipeline, described second liquid under meter 4 is connected to described hydrogen peroxide storage pool 3, between the first impeller pump 51, the hydrogen peroxide that can will be stored in hydrogen peroxide storage pool 3 by the first impeller pump 51 is added in I section reaction tank 13.
As shown in Figure 2, described ferrous sulfate injection device comprises ferrous sulfate storage pool 10, the 3rd liquid meter 9 and the second impeller pump 52, the input terminus of described the second impeller pump 52 is connected with described ferrous sulfate storage pool 10, the output terminal of described the second impeller pump 52 is communicated with described II section reaction tank 14 by pipeline, described the 3rd liquid meter 9 is connected between described ferrous sulfate storage pool 10, the second impeller pump 52, and the ferrous sulfate that can will be stored in ferrous sulfate storage pool 10 by the second impeller pump 52 is added in II section reaction tank 14.
As shown in Figure 2, described II section reaction tank 14 is communicated with mudpan 12(referred to as settling tank), the saliva plane, pond of described II section reaction tank 14 is higher than the saliva plane, pond of described mudpan 12, the water that can prevent mudpan 12 refluxes, described mudpan 12 is provided with water port and mud discharging mouth, described water port is arranged on the top of described mudpan 12, and described mud discharging mouth is arranged on the bottom of described mudpan 12.
As shown in Figure 2, described advanced oxidation coupling technique is removed, and device inferior, phosphite also comprises ozone tail gas destructor 11, described I section reaction tank 13, II section reaction tank 14, mudpan 12 are connected with described ozone tail gas destructor 11 respectively, wherein, ozone tail gas destructor 11 is for absorbing the ozone do not utilized, and pollutes avoiding.
As shown in Figure 2, described I section reaction tank 13, II section reaction tank 14, mudpan 12 all are arranged in same sealed vessel, II section reaction tank 14 is between I section reaction tank 13, mudpan 12, described I section reaction tank 13, II section reaction tank 14 are separated by the first division plate, both saliva planes, pond are identical, II section reaction tank 14, mudpan 12 are separated by the second division plate, and the saliva plane, pond of mudpan 12 is lower than the saliva plane, pond of II section reaction tank 14.
A kind of advanced oxidation coupling technique removal provided by the invention is inferior, the principle of work of the device of phosphite is:
Pretreated former water (being trade effluent) enters in I section reaction tank 13 under the effect of intake pump 1, and flow is controlled by first liquid under meter 2;
The ozone that ozonizer 6 produces enters I section reaction tank 13 through the first aeration head 71, and flow is controlled by the first gas meter 81;
The first impeller pump 51 is pumped into the hydrogen peroxide in hydrogen peroxide storage pool 3 in I section reaction tank 13, and flow is controlled by second liquid under meter 4;
The former water that enters I section reaction tank 13 is reacted with ozone, hydrogen peroxide, ozone is evenly distributed in I section reaction tank 13 by the first aeration head 71, the first gas meter 81 is for metering and control the ozone amount that ozonizer 6 enters I section reaction tank 13,4, second liquid under meter is for metering and control the flow of the hydrogen peroxide added, along with the injection of former water, I section reaction tank 13 overflows rear water body will flow into II section reaction tank 14;
The ozone that ozonizer 6 produces enters II section reaction tank 14 through the second aeration head 72, and flow is controlled by the second gas meter 82;
The second impeller pump 52 is pumped into the ferrous sulfate in ferrous sulfate storage pool 10 in II section reaction tank 14, and flow is controlled by the 3rd liquid meter 9, and the 3rd liquid meter 9 is for measuring and control the flow of the ferrous sulfate added;
The water body that enters II section reaction tank 14 through I section reaction tank 13 is reacted with ozone, ferrous sulfate;
II section reaction tank 14 overflows rear water body will flow into mudpan 12, carry out sludge settling, and final, the water body that completes processing flows out through water port.
A kind of advanced oxidation coupling technique provided by the invention is removed device inferior, phosphite and is had the following advantages:
1, speed of response is fast.Ozone and hydrogen peroxide co-oxidation ability are strong than clorox, are conducive to Quick Oxidation inferior, phosphite.
2, removal effect is good.Ozone and hydrogen peroxide can faster be oxidized to orthophosphoric acid salt thoroughly by inferior, phosphite, remaining time, phosphite can be under ozone and ferrous effect further complete oxidation, and the ferric iron generated and orthophosphoric acid salt can reacts and generate tertiary iron phosphate and precipitate, inferior, phosphite can efficiently be removed.
3, technical process is simple.The present invention only can complete removal inferior, phosphite by three sections structures, simple far beyond common process.
4, without pH, adjust.This technique is adaptable, under the condition that is 3-10 at former water pH, all can efficiently complete, and without the pH of traditional technology, regulates back and forth expense.
5, sludge output is low.Due to the medicament that will add without pH regulator, sludge output is low.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. an advanced oxidation coupling technique is removed technique inferior, phosphite, it is characterized in that, comprises the following steps:
S1, to waste water injection of ozone and hydrogen peroxide, by ozone and hydrogen peroxide, hypophosphite, phosphite are oxidized to orthophosphoric acid salt;
Under S2, the condition that exists at ozone, to waste water, add ferrous sulfate, continue oxidation remaining hypophosphite, phosphite and also remove orthophosphoric acid salt.
Advanced oxidation coupling technique according to claim 1 remove time, the technique of phosphite, it is characterized in that: also comprise step S3, by sludge settling by the indissoluble particle separation in waste water and remove orthophosphoric acid salt.
3. advanced oxidation coupling technique according to claim 1 is removed technique inferior, phosphite, it is characterized in that: in step S1 reaction, after 3-10 minute, carry out step S2.
4. an advanced oxidation coupling technique is removed device inferior, phosphite, it is characterized in that: comprise I section reaction tank, II section reaction tank, hydrogen peroxide injection device, ozone injection device and ferrous sulfate injection device, described I section reaction tank is communicated with described II section reaction tank, described I section reaction tank is provided with water-in, described ozone injection device is connected with described I section reaction tank, described ozone injection device is connected with described I section reaction tank, and described ferrous sulfate injection device is connected with described II section reaction tank.
5. advanced oxidation coupling technique according to claim 4 is removed device inferior, phosphite, and it is characterized in that: described ozone injection device is connected with described II section reaction tank.
6. advanced oxidation coupling technique according to claim 5 is removed inferior, the device of phosphite, it is characterized in that: described ozone injection device comprises ozonizer, the first gas meter, the second gas meter, the first aeration head and the second aeration head, described the first aeration head is arranged on the bottom of described I section reaction tank, described the second aeration head is arranged on the bottom of described II section reaction tank, described ozonizer respectively with described the first aeration head, the second aeration head connects, described the first gas meter is connected to described ozonizer, between the first aeration head, described the second gas meter is connected to described ozonizer, between the second aeration head.
7. advanced oxidation coupling technique according to claim 4 is removed device inferior, phosphite, it is characterized in that: described I section reaction tank is connected with the waste water injection device by water-in, described waste water injection device comprises intake pump and first liquid under meter, described intake pump is connected with the water-in of described I section reaction tank, and described first liquid under meter is connected between the water-in of described intake pump, I section reaction tank.
8. advanced oxidation coupling technique according to claim 4 is removed device inferior, phosphite, it is characterized in that: described hydrogen peroxide injection device comprises hydrogen peroxide storage pool, second liquid under meter and the first impeller pump, the input terminus of described the first impeller pump is connected with described hydrogen peroxide storage pool, the described first centrifugal delivery side of pump is connected with described I section reaction tank, and described second liquid under meter is connected between described hydrogen peroxide storage pool, the first impeller pump.
9. advanced oxidation coupling technique according to claim 4 is removed device inferior, phosphite, it is characterized in that: described ferrous sulfate injection device comprises ferrous sulfate storage pool, the 3rd liquid meter and the second impeller pump, the input terminus of described the second impeller pump is connected with described ferrous sulfate storage pool, the described second centrifugal delivery side of pump is connected with described II section reaction tank, and described the 3rd liquid meter is connected between described ferrous sulfate storage pool, the second impeller pump.
10. advanced oxidation coupling technique according to claim 4 is removed device inferior, phosphite, it is characterized in that: described II section reaction tank is communicated with mudpan, the saliva plane, pond of described II section reaction tank is higher than the saliva plane, pond of described mudpan, described mudpan is provided with water port and mud discharging mouth, described advanced oxidation coupling technique is removed, and device inferior, phosphite also comprises the ozone tail gas destructor, and described I section reaction tank, II section reaction tank, mudpan are connected with described ozone tail gas destructor respectively.
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| CN104761042A (en) * | 2015-03-19 | 2015-07-08 | 丁建林 | Hydrogen peroxide-phosphoric acid mixture, and preparation method and application thereof |
| CN105084453A (en) * | 2015-08-15 | 2015-11-25 | 苏州湛清环保科技有限公司 | Method for treating high-concentration chemical nickel waste liquid by using ultraviolet light |
| CN105983563A (en) * | 2015-02-07 | 2016-10-05 | 浙江新安化工集团股份有限公司 | Method for treating phosphate solid wastes |
| CN106186427A (en) * | 2016-08-16 | 2016-12-07 | 深圳市福田区环境技术研究所有限公司 | The process technique of a kind of chemical nickel plating waste solution and device |
| CN107804933A (en) * | 2017-11-24 | 2018-03-16 | 广州益方田园环保股份有限公司 | One kind is containing hypophosphites, phosphite sewage treatment equipment |
| CN112551732A (en) * | 2020-11-03 | 2021-03-26 | 浙江海拓环境技术有限公司 | Hypophosphite treatment device and method for preventing iodine loss |
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| CN105983563A (en) * | 2015-02-07 | 2016-10-05 | 浙江新安化工集团股份有限公司 | Method for treating phosphate solid wastes |
| CN104761042A (en) * | 2015-03-19 | 2015-07-08 | 丁建林 | Hydrogen peroxide-phosphoric acid mixture, and preparation method and application thereof |
| CN105084453A (en) * | 2015-08-15 | 2015-11-25 | 苏州湛清环保科技有限公司 | Method for treating high-concentration chemical nickel waste liquid by using ultraviolet light |
| CN106186427A (en) * | 2016-08-16 | 2016-12-07 | 深圳市福田区环境技术研究所有限公司 | The process technique of a kind of chemical nickel plating waste solution and device |
| CN107804933A (en) * | 2017-11-24 | 2018-03-16 | 广州益方田园环保股份有限公司 | One kind is containing hypophosphites, phosphite sewage treatment equipment |
| CN112551732A (en) * | 2020-11-03 | 2021-03-26 | 浙江海拓环境技术有限公司 | Hypophosphite treatment device and method for preventing iodine loss |
| CN112551732B (en) * | 2020-11-03 | 2022-07-12 | 浙江海拓环境技术有限公司 | Hypophosphite treatment device and method for preventing iodine loss |
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