CN209456086U - A kind of system of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium - Google Patents
A kind of system of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium Download PDFInfo
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Abstract
The utility model provides a kind of system of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium, belongs to the waste water comprehensive reutilization of environmental technology field；Including the pretreatment unit for removing a large amount of suspended material of desulfurization wastewater and sulfate ion, the oxalic acid precipitation calcium ion unit for further being separated to desulfurization wastewater calcium ions and magnesium ions, for carrying out the recovery of oxalic acid unit of recycling and reusing to oxalic acid and being used to prepare the magnesium hydroxide preparation unit of magnesium hydroxide products；The pretreatment unit includes the water tank for collecting power plant desulfurization wastewater, the pretreatment flocculation basin that the pretreatment reaction pond and top being connected to by connecting tube and the water tank are connected with the pretreatment reaction bottom of pond portion；Booster pump is provided in connecting tube between the water tank and the pretreatment reaction pond；The pretreatment flocculation bottom of pond portion is provided with pretreatment mud drainage slot；The utility model had both accomplished the decrement emission reduction of waste water, while realizing the resource utilization of waste water.
Description
Technical field
The utility model belongs to technical field of waste water processing, and in particular to a kind of oxalate precipitation method recycling power plant desulfurization wastewater
The system of calcium and magnesium.
Background technique
Coal-burning power plant is industrial water rich and influential family, and it is industry that water consumption and displacement, which account for 40% of industrial water consumption or more,
Interior water-saving important link.In existing power plant process, constituent parts are able to achieve circulation benefit with water by power plant's cascade utilization
With, but there are still the waste water such as a part of example desulfurization wastewater to efficiently use.
Power plant desulfurization wastewater refers to that absorbent is being recycled when the operation of wet desulfurization of flue gas by limestone-gypsum method system
The impurity concentrations such as salinity and suspended matter are higher and higher in the process, to make impurity concentration be no more than the design upper limit, need to arrange from system
This effluent part of effluent part out, discharge is known as desulfurization wastewater.
Desulfurization waste water quality is mainly characterized by: (1) waste water is mainly weakly acidic, water quality chloride ion and sulfate radical content compared with
Height has certain corrosivity to pipeline；(2) containing the suspended matter that a large amount of particles are tiny in waste water, main component is lime stone lime, stone
Cream particle and silica etc.；(3) calcium ions and magnesium ions and silicon ion concentration are higher in waste water, easily form dirt in the duct.
The high salinity and high suspended matter concentration of desulfurization wastewater make its more difficult implementation in terms of circulating and recovering, traditional at present
Desulfurization wastewater processing mode is wet slag removal, coal yard sprinkling and the processing of three headers etc..Wet slag removal refers to desulfurization wastewater without place
Reason is used for wet slag removal system, but its existing corrosion and washing slag water bring secondary environmental problems make it be difficult to be truly realized zero
Discharge.Coal yard sprinkling then needs to accomplish that Anti-seeping technology, the penetrating fluid of sprinkling be easy to cause underground water heavy metal pollution, equally can band
Carry out secondary environmental problems.Three header methods are after simply neutralizing, flocculating and precipitating clarification, though suspended solid, again can be effectively removed
The pollutants such as metal ion, but the technique is difficult to effectively remove Na+、Cl-、SO4 2-、Ca2+And Mg2+Plasma, water outlet salt content is still
It is very high.
Desulfurization wastewater zero-emission is a kind of waste water comprehensive treatment technique newly proposed in recent years, and main meaning is will be in waste water
Various foreign ion components and suspended matter extract, the desalted water of generation carries out reuse, and concentrate passes through a series of steaming
Hair crystallization, finally reaches curing process for the dissolving salt of ionic state, without the technique of any liquid form discharge.It is mature
Desulfurization wastewater processing technique route be " pretreatment unit+concentration be reduced unit+solidified cell ".But due to taking for softening medicament
With higher, and the evaporative crystallization of concentration and solidified cell needs a large amount of energy consumption, keeps its operating cost larger, therefore constrains zero
The development of draining technology.
Due to containing a large amount of calcium ions and magnesium ions in desulfurization wastewater, general power plant desulfurization wastewater calcium ions and magnesium ions content is up to 0.1-
The direct discharging of waste water of 0.3mol/L, such high-concentration Ca content of magnesium not only waste resource, and are easy that equipment is made to generate knot
Dirt.The utility model is recycled the calcium ions and magnesium ions in desulfurization wastewater, both desulfurization wastewater can be carried out sofening treatment, and made
Calcium ions and magnesium ions are separated in waste water, while using magnesium hydroxide and calcium sulfate precipitation as Product recycling, being created for power plant certain
Economic benefit.
Utility model content
The utility model is directed to the defect of prior art, provides a kind of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium
System, not only handled waste water, but also bring certain economic benefits.
Used technical solution is as follows to solve above-mentioned technical problem for the utility model:
A kind of system of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium, including largely hanged for removing desulfurization wastewater
The pretreatment unit of floating object matter and sulfate ion, the oxalic acid precipitation calcium for further being separated to desulfurization wastewater calcium ions and magnesium ions
Ion unit, the recovery of oxalic acid unit for carrying out recycling and reusing to oxalic acid and it is used to prepare the hydrogen-oxygens of magnesium hydroxide products
Change magnesium preparation unit.
The pretreatment unit includes the storage for collecting power plant desulfurization wastewater as a further improvement of the utility model,
Water tank, the pretreatment reaction pond and top being connected to by connecting tube and the water tank are connected with the pretreatment reaction bottom of pond portion
Logical pretreatment flocculation basin；Booster pump is provided in connecting tube between the water tank and the pretreatment reaction pond；It is described
Pretreatment flocculation bottom of pond portion is provided with pretreatment mud drainage slot.
The oxalic acid precipitation calcium ion unit includes flocculating with the pretreatment as a further improvement of the utility model,
The oxalic acid precipitation reaction tank and be set to the oxalic acid precipitation mud drainage slot that the oxalic acid precipitation reacts bottom of pond portion that pond is connected.
The recovery of oxalic acid unit includes and the oxalic acid precipitation mud drainage slot phase as a further improvement of the utility model,
The recycling oxalic acid reaction tank of connection, the mixed acid being connected with the recycling oxalic acid reaction tank prepare pond and are set to described return
Receive the recycling oxalic acid mud drainage slot of oxalic acid reaction bottom of pond portion；The recycling oxalic acid reaction tank passes through reflux line and the oxalic acid precipitation
Reaction tank is connected.
The magnesium hydroxide preparation unit includes reacting with the oxalic acid precipitation as a further improvement of the utility model,
The magnesium hydroxide reaction tank and the magnesium hydroxide plate and frame filter press that bottom of pond portion is connected is reacted with the magnesium hydroxide that pond is connected.
The utility model further includes calcium sulfate plate and frame filter press as a further improvement of the utility model, the pre- place
Reason mud drainage slot and recycling oxalic acid mud drainage slot are connect with calcium sulfate plate and frame filter press respectively.
A kind of application method of the system of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium, includes the following steps:
Step 1: power plant desulfurization wastewater is sent to water tank, and pretreatment reaction pond is transported in water transport under the promotion of booster pump,
Calcium chloride and anion-polyacrylamide flocculant, bottom connection pretreatment flocculation basin, reaction are added in pretreatment reaction pond
Bottom calcium sulfate precipitation is collected by pretreatment mud drainage slot afterwards, and clear liquid is sent to oxalic acid precipitation reaction tank.
During this, since desulfurization wastewater concentration of suspension is higher, flocculation treatment is carried out to desulfurization wastewater first.Flocculation can
With suspended particulates such as the lime stones, gypsum particle and silica that effectively remove desulfurization wastewater.Chlorine is additionally added in preprocessing process
Change calcium, a large amount of calcium ion effectively can generate precipitating in conjunction with the sulfate radical in water by flocculation, calcium ion, be subsequent oxalic acid
Precipitating calcium ion pre-processes.
During this, the dosage of calcium chloride is added according to sulfate radical content in desulfurization wastewater, meets n (Ca2+):n
(SO4 2-)=1:1, reaction equation are as follows:
Ca2++SO4 2-→CaSO4↓ (1)
Step 2: calcium oxalate crystal seed is added in oxalic acid precipitation reaction tank and promotes precipitating, bottom calcium oxalate precipitation is sunk by oxalic acid
Shallow lake mud drainage slot collect, after send to recycling oxalic acid reaction tank, by mixed acid preparation pond preparation oxalic acid sulfuric acid mixture liquid add to return
Oxalic acid reaction tank is received, the calcium sulfate precipitation that recycling oxalic acid reaction tank generates is collected by recycling oxalic acid mud drainage slot, clear liquid reuse to grass
Sour precipitation reaction pond.Pretreatment reaction precipitating mud drainage slot and the calcium sulfate precipitation for recycling the generation of oxalic acid mud drainage slot are sent to plate compression
Machine is dried.
The dosage of this process mesoxalic acid is added according to the calcium ion content of water quality after reacting in step 1, meets n
(H2C2O4):n(Ca2+)=1:1 mainly further separates calcium ions and magnesium ions using oxalic acid, is first added in sedimentation basin before precipitating
Calcium oxalate crystal seed is to promote to precipitate, reaction equation are as follows:
Ca2++C2O4 2-→CaC2O4↓ (2)
The addition of crystal seed increases the collision opportunity between crystal and crystal, produces more secondary nucleus, that is, promotes
The generation of precipitating；Enough crystal seeds are added can accelerate the growth rate of crystal simultaneously, when the growth rate of crystal be greater than at
When core rate, obtained crystal grain is larger, and sedimentation effect is better.Related experiment shows that crystal seed amount is excessive, will cause solid-liquid point
It is excessively high from machine utilization, influence separating effect；And the too small rush sedimentation effect of crystal seed amount is unobvious, therefore this technique chooses 1.5wt ‰
For crystal seed amount is most preferably added.
Recovery of oxalic acid principle is to prepare organic monoacid oxalic acid by inorganic acid sulfuric acid, and the oxalic acid generated after the reaction was completed returns
It receives and recycles.Reaction equation are as follows:
H2SO4+CaC2O4·H2O+H2O→H2C2O4+CaSO4·2H2O (3)
Recovery of oxalic acid rate is up to 75% or more during this；The gypsum by-product is pretreatment reaction and recycling oxalic acid
Unit style obtains, and gypsum by-product purity is 65% or more.
Step 3: the magnesium ion clear liquid that oxalic acid precipitation reaction tank (6) generates is sent to magnesium hydroxide reaction tank (11), with hydrogen-oxygen
Change sodium solution to be added simultaneously, the magnesium hydrate precipitate of generation is discharged by bottom, is connected to plate and frame filter press (12) and place is dried
Reason.
Sodium hydroxide solution injected volume is added according to magnesium ion content in desulfurization wastewater during this, meets n (NaOH): n
(Mg2+)=1:1 mainly uses sodium-hydroxide method, reaction equation using magnesium hydroxide is prepared are as follows:
Mg2++2OH-→Mg(OH)2↓ (4)
The technical effect of the utility model is as follows:
The utility model provides a set of system for proposing to carry out separating calcium and magnesium using oxalic acid, and the system is single by pretreatment
Member, oxalic acid precipitation calcium ion unit, recovery of oxalic acid unit and magnesium hydroxide preparation unit, recycle calcium and magnesium respectively.Calcium turns
Calcium sulfate gypsum by-product is turned to, magnesium is converted into magnesium hydroxide products recycling, while oxalic acid has carried out circulation benefit in the process
With both having mitigated the pressure to subsequent processing desulfurization wastewater, realized simultaneously while carrying out to power plant desulfurization wastewater sofening treatment
The resource utilization of waste.
The utility model reduces the reagent cost of sofening treatment early period compared to technique of zero discharge, and final process generates
Water be mainly monovalent salt sodium chloride, divalent salts are removed.In addition, the utility model had both solved generation to the recycling of magnesium and calcium
Scale problems, while realizing the recycling of waste water.While the utility model is that power plant brings certain economic benefit,
Bring good environment and social benefit.
Detailed description of the invention
Fig. 1 is that oxalate precipitation method recycles power plant desulfurization wastewater calcium and magnesium process device figure；
Fig. 2 is that oxalate precipitation method recycles power plant desulfurization wastewater calcium and magnesium process flow chart；
Fig. 1 label declaration: 1- water tank；2- booster pump；3- pretreatment reaction pond；4- pre-processes flocculation basin；5- pretreatment
Mud drainage slot；6- oxalic acid precipitation reaction tank；7- oxalic acid precipitation mud drainage slot；8- mixed acid prepares pond；9- recycles oxalic acid reaction tank；10-
Recycle oxalic acid mud drainage slot；11- magnesium hydroxide reaction tank；12- magnesium hydroxide plate and frame filter press；13- calcium sulfate plate and frame filter press.
Fig. 1 solid line is the flow direction of water, and dotted line is the flow direction of sludge.
Specific embodiment
For the purpose of this utility model, technical matters is more clearly understood, with shown in Fig. 1 device figure and Fig. 2 flow chart,
This technique is described in further details according to specific embodiment.
As shown in Figure 1, system described in the utility model include for remove a large amount of suspended material of desulfurization wastewater and
The pretreatment unit of sulfate ion, the oxalic acid precipitation calcium ion unit for further being separated to desulfurization wastewater calcium ions and magnesium ions,
For carrying out the recovery of oxalic acid unit of recycling and reusing to oxalic acid and being used to prepare the magnesium hydroxide preparation of magnesium hydroxide products
Unit.
The pretreatment unit includes the water tank 1 for collecting power plant desulfurization wastewater, passes through connecting tube and the water storage
The pretreatment flocculation basin 4 that the pretreatment reaction pond 3 and top that case 1 is connected to are connected with 3 bottom of pretreatment reaction pond；Institute
It states and is provided with booster pump 2 in the connecting tube between water tank 1 and the pretreatment reaction pond 3；4 bottom of pretreatment flocculation basin
It is provided with pretreatment mud drainage slot 5.
The oxalic acid precipitation calcium ion unit includes the oxalic acid precipitation reaction tank 6 being connected with the pretreatment flocculation basin 4
With the oxalic acid precipitation mud drainage slot 7 for being set to 6 bottom of oxalic acid precipitation reaction tank.
The recovery of oxalic acid unit includes the recycling oxalic acid reaction tank 9 being connected with the oxalic acid precipitation mud drainage slot 7 and institute
State the mixed acid preparation pond 8 and the recycling for being set to recycling 9 bottom of oxalic acid reaction tank that recycling oxalic acid reaction tank 9 is connected
Oxalic acid mud drainage slot 10；The recycling oxalic acid reaction tank 9 is connected by reflux line with the oxalic acid precipitation reaction tank 6.
The magnesium hydroxide preparation unit includes the magnesium hydroxide reaction tank 11 being connected with the oxalic acid precipitation reaction tank 6
The magnesium hydroxide plate and frame filter press 12 being connected with 11 bottom of magnesium hydroxide reaction tank.
The utility model further includes calcium sulfate plate and frame filter press 13, the pretreatment mud drainage slot 5 and recycling oxalic acid mud drainage slot
10 connect with calcium sulfate plate and frame filter press 13 respectively.
As shown in Fig. 2, the application method of system described in the utility model, includes the following steps:
Step 1: power plant desulfurization wastewater is sent to water tank 1, and pretreatment reaction is transported in water transport under the promotion of booster pump 2
Pond 3, is added calcium chloride and anion-polyacrylamide flocculant in pretreatment reaction pond, bottom connection pretreatment flocculation basin 4,
Bottom calcium sulfate precipitation is collected by pretreatment mud drainage slot 5 after reaction, and clear liquid is sent to oxalic acid precipitation reaction tank 6.
During this, since desulfurization wastewater concentration of suspension is higher, flocculation treatment is carried out to desulfurization wastewater first.Flocculation can
With suspended particulates such as the lime stones, gypsum particle and silica that effectively remove desulfurization wastewater.Chlorine is additionally added in preprocessing process
Change calcium, a large amount of calcium ion effectively can generate precipitating in conjunction with the sulfate radical in water by flocculation, calcium ion, be subsequent oxalic acid
Precipitating calcium ion pre-processes.
During this, the dosage of calcium chloride is added according to desulfurization wastewater sulfate ion content situation, meets n (Ca2 +):n(SO4 2-)=1:1, reaction equation are as follows:
Ca2++SO4 2-→CaSO4↓
Flocculant uses anion-polyacrylamide, flocculant usage 20mg/L.3 mixing speed of pretreatment reaction pond
For 40r/min, pretreatment 4 digestion time of flocculation basin is 30min, and temperature of reaction system is room temperature, since the flocculant is in pH
There is preferable flocculating effect when 4-8, so process section does not adjust pH value.
Step 2: calcium oxalate crystal seed is added in oxalic acid precipitation reaction tank 6 and promotes precipitating, bottom calcium oxalate precipitation is sunk by oxalic acid
Shallow lake mud drainage slot 7 is collected, after send to recycling oxalic acid reaction tank 9, by the oxalic acid sulfuric acid mixture liquid for preparing of mixed acid preparation pond 8 add to
Oxalic acid reaction tank 9 is recycled, the calcium sulfate precipitation that recycling oxalic acid reaction tank 9 generates is collected by recycling oxalic acid mud drainage slot 10, and clear liquid returns
With to oxalic acid precipitation reaction tank 6.Pretreatment reaction precipitating mud drainage slot 5 and the calcium sulfate precipitation for recycling the generation of oxalic acid mud drainage slot 10 are sent
It is dried to plate and frame filter press 13.
Mainly calcium ions and magnesium ions are further separated using oxalic acid during this, oxalic acid is first added before precipitating in sedimentation basin
Calcium crystal seed is to promote to precipitate, reaction equation are as follows:
Ca2++C2O4 2-→CaC2O4↓
Other technological parameters are as follows: pH control is in 7-8, and the dosage of this process mesoxalic acid is according to water quality after reacting in step 1
Calcium ion content add, meet n (H2C2O4):n(Ca2+)=1:1, mixing speed 40r/min, mixing time 30min,
Digestion time is 2h, and temperature of reaction system is room temperature.
The addition of crystal seed increases the collision opportunity between crystal and crystal, produces more secondary nucleus, that is, promotes
The generation of precipitating；Enough crystal seeds are added can accelerate the growth rate of crystal simultaneously, when the growth rate of crystal be greater than at
When core rate, obtained crystal grain is larger, and sedimentation effect is better.Related experiment shows that crystal seed amount is excessive, will cause solid-liquid point
It is excessively high from machine utilization, influence separating effect；And the too small rush sedimentation effect of crystal seed amount is unobvious, therefore this technique chooses 1.5wt ‰
For crystal seed amount is most preferably added.
Recovery of oxalic acid principle is to prepare organic monoacid oxalic acid by inorganic acid sulfuric acid, and the oxalic acid generated after the reaction was completed returns
It receives and recycles.Reaction equation are as follows:
H2SO4+CaC2O4·H2O+H2O→H2C2O4+CaSO4·2H2O
Specific process parameter are as follows: the concentrated sulfuric acid: oxalic acid dihydrate=4:1 mass ratio preparation reaction mixed acid, calcium oxalate precipitation
For the solidliquid mixture of water content 99.5%, mixing speed 100r/min, mixing time 30min, digestion time 1h,
Temperature of reaction system is room temperature.
The concentrated sulfuric acid and oxalic acid dihydrate that the mixed acid is mass ratio 4:1 react mixed acid, the oxalic acid that mud drainage slot is collected
Calcium precipitate is the solidliquid mixture of water content 99.5%.Reaction mixing time is 30min, digestion time 1h, and system temperature is
Room temperature.
The gypsum by-product be pretreatment reaction and recycling oxalic acid unit style obtain, gypsum by-product purity 65% with
On, the recovery of oxalic acid rate is up to 75% or more.
Step 3: the magnesium ion clear liquid that oxalic acid precipitation reaction tank 6 generates is sent to magnesium hydroxide reaction tank 11, with sodium hydroxide
Solution is added simultaneously, and the magnesium hydrate precipitate of generation is discharged by bottom, is connected to plate and frame filter press 12 and is dried.
Application prepares magnesium hydroxide and mainly uses sodium-hydroxide method, reaction equation during this are as follows:
Mg2++2OH-→MgOH2↓
Specific process parameter are as follows: sodium hydroxide solution injected volume is added according to magnesium ion content in desulfurization wastewater, meets n
(NaOH):n(Mg2+)=1:1, dosing method are that stoste and sodium hydroxide solution inject in sodium hydroxide reactor simultaneously, are reacted
Temperature is 50 DEG C, pH value of reaction system 11, mixing speed 40r/min, mixing time 30min, digestion time 1h.
Embodiment described above is only that the preferred embodiment of the utility model is described, not to the utility model
Range is defined, and under the premise of not departing from the spirit of the design of the utility model, those of ordinary skill in the art are practical new to this
The various changes and improvements that the technical solution of type is made should all fall into the protection scope that the utility model claims book determines
It is interior.
Claims (2)
1. a kind of system of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium, which is characterized in that it includes for removing desulfurization
The pretreatment unit of a large amount of suspended material of waste water and sulfate ion, for further being separated to desulfurization wastewater calcium ions and magnesium ions
Oxalic acid precipitation calcium ion unit, for oxalic acid carry out recycling and reusing recovery of oxalic acid unit and be used to prepare hydroxide
The magnesium hydroxide preparation unit of magnesium products；
The pretreatment unit includes passing through connecting tube and the water tank for collecting the water tank of power plant desulfurization wastewater (1)
(1) the pretreatment flocculation basin that the pretreatment reaction pond (3) and top being connected to are connected with pretreatment reaction pond (3) bottom
(4)；Booster pump (2) are provided in connecting tube between the water tank (1) and the pretreatment reaction pond (3)；The pre- place
Reason flocculation basin (4) bottom is provided with pretreatment mud drainage slot (5)；
The oxalic acid precipitation calcium ion unit includes the oxalic acid precipitation reaction tank (6) being connected with pretreatment flocculation basin (4)
With the oxalic acid precipitation mud drainage slot (7) for being set to oxalic acid precipitation reaction tank (6) bottom；
The recovery of oxalic acid unit includes the recycling oxalic acid reaction tank (9) being connected with the oxalic acid precipitation mud drainage slot (7) and institute
State mixed acid preparation pond (8) and be set to recycling oxalic acid reaction tank (9) bottom that recycling oxalic acid reaction tank (9) is connected
Recycling oxalic acid mud drainage slot (10)；The recycling oxalic acid reaction tank (9) passes through reflux line and the oxalic acid precipitation reaction tank (6)
It is connected；
The magnesium hydroxide preparation unit includes the magnesium hydroxide reaction tank (11) being connected with the oxalic acid precipitation reaction tank (6)
The magnesium hydroxide plate and frame filter press (12) being connected with magnesium hydroxide reaction tank (11) bottom.
2. a kind of system of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium according to claim 1, which is characterized in that
Further include calcium sulfate plate and frame filter press (13), the pretreatment mud drainage slot (5) and recycling oxalic acid mud drainage slot (10) respectively with sulfuric acid
Calcium plate and frame filter press (13) connection.
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| CN109095483A (en) * | 2018-10-30 | 2018-12-28 | 华北电力大学（保定） | A kind of system and its application method of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109095483A (en) * | 2018-10-30 | 2018-12-28 | 华北电力大学（保定） | A kind of system and its application method of oxalate precipitation method recycling power plant desulfurization wastewater calcium and magnesium |
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