CN110773093A - Gas dispersion machine for producing polyferric chloride and production method - Google Patents

Gas dispersion machine for producing polyferric chloride and production method Download PDF

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CN110773093A
CN110773093A CN201911052085.7A CN201911052085A CN110773093A CN 110773093 A CN110773093 A CN 110773093A CN 201911052085 A CN201911052085 A CN 201911052085A CN 110773093 A CN110773093 A CN 110773093A
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reaction tank
ferric chloride
reaction
top cover
gas
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王爱国
徐锡刚
白晓光
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Tangshan Darunda Environmental Protection Technology Co Ltd
Tangshan Darun Da Dangerous Waste Treatment Co Ltd
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Tangshan Darunda Environmental Protection Technology Co Ltd
Tangshan Darun Da Dangerous Waste Treatment Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/10—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00099—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor the reactor being immersed in the heat exchange medium

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Abstract

The invention discloses a gas dispersion machine for producing poly-ferric chloride and a production method thereof, wherein the gas dispersion machine utilizes pickling waste liquid as a raw material, changes waste into valuable, ensures that the poly-ferric chloride generation reaction can be carried out under the normal pressure condition, has no latent explosion hazard, and can increase O 2With FeCl 2The contact area, the oxidation speed is high, the time is saved, the equipment investment is less, and the cost is low; the production method is simple, the ferric oxyhydroxide precipitate cannot be generated, the purity of the obtained polymeric ferric chloride is high, and the nitrogen oxide gas generated by the reaction can be absorbed by sodium hydroxide solution withoutThe environment can be polluted; and carrying out reduced pressure concentration on the poly ferric chloride solution by adopting a 120 ℃ oil bath, adding iron oxyhydroxide, cooling and solidifying to obtain the solid PFC, and the method is simple and easy to implement and is easy for large-scale production.

Description

Gas dispersion machine for producing polyferric chloride and production method
Technical Field
The invention relates to the technical field of waste liquid treatment, in particular to a gas dispersion machine for producing polyferric chloride and a production method.
Background
In the production process of the steel product industry, iron oxide and other iron rust on the surface of steel needs to be removed for pickling, and the pickling generally adopts sulfuric acid or hydrochloric acid. Sulfuric acid is expensive, so acid washing is often performed with cheap hydrochloric acid. A large amount of pickling waste liquid is generated in the pickling process. The pickling waste liquid belongs to high-risk waste liquid and pollutes the environment. The hydrochloric acid pickling waste liquid contains a large amount of ferrous chloride, and the ferrous chloride is recycled and treated, so that waste is changed into valuable, and a large amount of research is carried out in various countries in the world. Among them, the most established scale is to use it to make ferric trichloride solution, even solid ferric trichloride (FeCl) 3·6H 2O), poly-ferric chloride (PFC for short) is also prepared by using ferrous chloride solution in the pickling waste liquid. Most of human FeCl 2The PFC is prepared by using O under pressure 2Or air oxidation of FeCl 2However, explosion often occurs under high temperature and high pressure conditions, and the pressure valve has no time to release pressure, so that potential safety hazards exist.
Further, O is used 2Oxidizing FeCl in pickling waste liquid 2When the solution is formed into a poly-ferric chloride solution, NaNO is generally added 2As a catalyst, nitrogen oxide gas can be generated and directly discharged, which can pollute the environment and harm human health. And with O 2Oxidized FeCl 2In the solution process, because the acidity is insufficient, FeOOH precipitates are often generated, how to effectively remove the precipitates and how to improve the purity of the poly ferric chloride solution are also a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a gas dispersion machine for producing poly-ferric chloride and a production method thereofThe iron generation reaction can be carried out under normal pressure, has no latent explosion hazard, and can increase O 2With FeCl 2The contact area, the oxidation speed is high, the time is saved, the equipment investment is less, and the cost is low; the production method is simple, the ferric oxyhydroxide precipitate cannot be generated, the purity of the obtained polyferric chloride is high, and meanwhile, the nitrogen oxide gas generated by the reaction can be absorbed by sodium hydroxide solution, so that the environment cannot be polluted; and carrying out reduced pressure concentration on the poly ferric chloride solution by adopting a 120 ℃ oil bath, adding iron oxyhydroxide, cooling and solidifying to obtain the solid PFC, and the method is simple and easy to implement and is easy for large-scale production.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
(A) a gas disperser for producing poly ferric chloride, comprising: the reaction tank is provided with a top cover and a tank body which are matched with each other; the bottom of the tank body is provided with supporting legs, the top cover is provided with a sampling port, the center of the top cover is provided with a shaft hole, a hollow rotating shaft is assembled in the shaft hole, and the hollow rotating shaft comprises an outer shaft and an inner shaft which are coaxial;
the upper end of the hollow rotating shaft penetrates through the shaft hole and is connected with a motor, and the lower end of the hollow rotating shaft extends into the tank body and is close to the bottom of the tank body; the lower end of the inner shaft is provided with a movable impeller, and the lower end of the outer shaft is fixed with a cover plate and is provided with a stationary impeller;
an exhaust port is formed in the top cover, a stop valve is arranged at the exhaust port, and the exhaust port is communicated with an exhaust pipe;
the intake pipe passes the top cap and stretches into it is internal to the jar, there is the funnel through the pipeline intercommunication in the intake pipe, be provided with the stop valve on the pipeline.
Preferably, an outlet of the air inlet pipe penetrates through the cover plate and is arranged between the movable impeller and the stationary impeller.
Preferably, the number of the outlets of the air inlet pipe is two, and the two outlets are symmetrically arranged between the movable impeller and the stationary impeller along the hollow rotating shaft.
Preferably, the reaction tank further comprises a water bath, and the reaction tank is placed in the water bath through support legs.
Preferably, the reaction tank is a transparent reaction tank.
Preferably, a thermometer is arranged on the top cover, and the thermometer extends into the reaction tank.
Preferably, the top cover is further provided with an acidity detector, and the acidity detector extends into the reaction tank.
Preferably, the number of the reaction tanks is two, and the exhaust pipe of one reaction tank is communicated with the air inlet pipe of the other reaction tank.
(II) a production method of polyferric chloride, which comprises the following steps:
step 1, opening a top cover, adding pickling waste liquid, a stabilizer and sodium hydroxide into a tank body, and covering the top cover;
step 2, adding a secondary catalyst into the reaction tank through a funnel, turning on a motor, enabling an inner shaft of a hollow rotating shaft to rotate, then automatically sucking air into the reaction tank from an air inlet pipe, fully breaking and dispersing the air through the matching of a stationary impeller and a movable impeller, and heating the reaction tank through water in a water bath tank;
step 3, introducing oxygen into the reaction tank through the air inlet pipe, dropwise adding a main catalyst into the reaction tank through a funnel, and reacting to obtain a poly ferric chloride solution and a nitrogen oxide gas; wherein the nitrogen oxide gas is discharged from the exhaust port.
Preferably, the method further comprises a step 4 of discharging the nitrogen oxide gas from the exhaust port through an exhaust pipe into a next reaction tank, sufficiently breaking the nitrogen oxide gas through the cooperation of the stationary impeller and the movable impeller, and reacting the nitrogen oxide gas with the sodium hydroxide solution in the reaction tank to generate the sodium nitrite.
Preferably, the method further comprises a step 5 of adopting an oil bath at the temperature of 120-150 ℃ to perform reduced pressure concentration on the poly ferric chloride solution, adding iron oxyhydroxide, cooling and solidifying to obtain solid poly ferric chloride.
More preferably, the time for the concentration under reduced pressure is 3 to 4 hours.
Further preferably, the amount of the iron oxyhydroxide used is based on the amount of the poly-ferric chloride solution1/2 for mass; the specific surface area of the hydroxyl ferric oxide is more than or equal to 200m 2The pore volume is more than or equal to 0.25 mL/g.
Preferably, in step 1, before the waste pickle liquor is added, the acidity of the waste pickle liquor is adjusted by hydrochloric acid according to the basicity of the polymeric ferric chloride.
Further preferably, the calculation formula of the basicity W (%) of the poly-ferric chloride is as follows:
wherein A is the mole number of ferrous chloride in the pickling waste liquid; b, the mole number of free acid in the pickling waste liquid.
Preferably, in step 1, the stabilizer is ammonium dihydrogen phosphate or sodium citrate.
Preferably, in step 2, the secondary catalyst is nitric acid.
Preferably, in step 3, the main catalyst is a sodium nitrite solution.
Preferably, the stabilizer accounts for 0.1-0.5% of the mass of the pickling waste liquid, and the mass ratio of the stabilizer to the sodium hydroxide is 20: 1.
Preferably, the dosage of the secondary catalyst is 30-50mL, and the dosage of the main catalyst is 10-50 g.
Preferably, in the step 3, the reaction temperature is 50-70 ℃, and the reaction time is 40-80 min.
Preferably, the oxygen in step 3 is replaced by air, and in the case of air, the reaction time is 3 to 5 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) the gas dispersion machine has the advantages of simple structure, convenience in installation and operation and low cost, and can be used for connecting O 2Or extremely fine air dispersion, can significantly increase O 2With FeCl 2Fe in solution 2+The contact area of (2) is very fast under the condition of normal pressure, and 4 tons of 2.5mol/L FeCl 2The solution can be completely oxidized within 90min, explosion can not occur, and the safety is high; and can be either pureO 2Air can also be used for oxidation reaction; by the use of O 2The oxidation reaction only needs about 1.5 hours, the oxidation speed is high, and the production efficiency of the polyferric chloride is high; the air oxidation reaction is adopted for about 4 hours, and the production cost is low.
(2) Two reaction tanks are adopted, wherein one reaction tank is used for reacting the pickling waste liquid with a main catalyst, a secondary catalyst and oxygen to generate a polyferric chloride solution; the other reaction tank is used for absorbing nitrogen oxide gas generated by the reaction by adopting NaOH solution, can generate sodium nitrite for cyclic utilization, and can prevent the nitrogen oxide gas from being directly discharged into the environment, thereby avoiding the pollution to the environment.
(3) The production method of the poly-ferric chloride is simple, the pickling waste liquid can be fully utilized, the waste is changed into the valuable, and the cost is low; using NaNO 2As the main catalyst, nitric acid (HNO) 3) The catalyst is a secondary catalyst, the main catalyst and the secondary catalyst are matched with each other, and the production efficiency of the poly-ferric chloride is higher. The storage of PFC is facilitated by using sodium dihydrogen phosphate as a stabilizer, phosphate ions are introduced into the sodium dihydrogen phosphate, but experiments show that the PFC not only can eliminate the phosphorus introduced into the PFC, but also can remove the phosphorus inherent in water!
(4) The input amount of the hydrochloric acid is determined according to the basicity formula, any poly-ferric chloride with the basicity within the range of 5-30% can be prepared, the generation of FeOOH can be effectively avoided, and the purity of the poly-ferric chloride solution is improved.
(5) The solid PFC is obtained by performing reduced pressure concentration on the poly ferric chloride solution by adopting a 120 ℃ oil bath, adding the iron oxyhydroxide, cooling and solidifying, the preparation method is simple and easy to implement, the large-scale production is easy, spray drying equipment is not needed, the investment is small, and the complex cost and the equipment maintenance cost are avoided. The solid PFC is beneficial to long-distance transportation, the sale range of the PFC is expanded, and the function of the liquid PFC is not only maintained in performance, but also the effect is better.
Drawings
The invention is described in further detail below with reference to the figures and specific embodiments.
FIG. 1 is a perspective sectional view of a gas disperser for producing polymeric ferric chloride according to the present invention;
FIG. 2 is a schematic view showing the arrangement of two gas dispersers for producing poly (ferric chloride) of FIG. 1, which are connected in series for treating nitrogen oxide gas.
In the above figures: 1, a reaction tank; 101, a top cover; 102 a tank body; 103 supporting legs; 104 a sampling port; 2, a hollow rotating shaft; 201 an inner shaft; 202 an outer shaft; 3, a motor; 4, moving impellers; 5, a stationary impeller; 6, covering a plate; 7, air inlet pipes; 8, exhausting the pipe; 9, a funnel; 10 water bath; 11 thermometer.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Referring to fig. 1 to 2, a gas disperser for producing poly-ferric chloride according to an embodiment of the present disclosure includes: the reaction tank comprises a reaction tank 1 and an air inlet pipe 7, wherein the reaction tank 1 is provided with a top cover 101 and a tank body 102 which are matched with each other; the bottom of the tank body 102 is provided with a supporting leg 103, the top cover 101 is provided with a sampling port 104, the center of the top cover 101 is provided with a shaft hole, a hollow rotating shaft 2 is assembled in the shaft hole, and the hollow rotating shaft 2 comprises an outer shaft 202 and an inner shaft 201 which are coaxial; the upper end of the hollow rotating shaft 2 penetrates through the shaft hole and is connected with a motor 3, and the lower end of the hollow rotating shaft 2 extends into the tank body 102 and is close to the bottom of the tank body 102; wherein, the lower end of the inner shaft 201 is provided with a movable impeller 4, the lower end of the outer shaft 202 is fixed with a cover plate 6 and is provided with a stationary impeller 5; an exhaust port is formed in the top cover 101, a stop valve is arranged at the exhaust port, and the exhaust port is communicated with an exhaust pipe 8; the air inlet pipe 7 penetrates through the top cover 101 and extends into the tank body 102, the air inlet pipe 7 is communicated with a funnel 9 through a pipeline, and a stop valve is arranged on the pipeline.
In the above embodiment, the reaction tank 1 is the corrosion-resistant reaction tank 1, the pickling waste liquid is placed in the reaction tank 1, and the main catalyst and the sub-catalyst are added into the reaction tank 1 through the funnel 9. The motor 3 (the motor 3 is provided with a gear reduction box) drives the movable impeller 4 to rotate, and negative pressure is generated in the reaction tank 1Oxygen or air is sucked into the reaction tank 1 through the air inlet pipe 7, the pickling waste liquid bypassing the movable impeller 4 forms two rows of opposite-rotating vortexes, the vortexes suck the air to the vortex center to form bubbles, the formed bubbles are dispersed into smaller bubbles under the action of dynamic pressure and shearing force generated by turbulent pulsation speed, and the bubbles farther away from the impeller are dispersed into smaller bubbles. The cover plate 6 and the stationary impeller 5 form a stator which plays roles of flow guiding and stabilizing. The gas is sufficiently dispersed in the reaction tank 1 by the movable impeller 4 and the stationary impeller 5, and O is increased 2With FeCl 2The contact area of the acid pickling agent is increased, the acid pickling agent and the ferrous chloride solution in the acid pickling waste liquid are fully reacted, the production efficiency of the poly ferric chloride is improved, the reaction can be carried out under the normal pressure condition, explosion is avoided, and the safety is high. The nitrogen oxide gas generated by the reaction can be directly discharged from the exhaust port.
Referring to fig. 1-2, according to an embodiment of the present invention, an outlet of the intake pipe 7 passes through the cover plate 6 and is disposed between the movable impeller 4 and the stationary impeller 5.
In the above embodiment, the intake pipe 7 is provided between the movable impeller 4 and the stationary impeller 5 so as to be O 2Or the outlet position of the air just serves as the stirring position of the impeller 4, so that the gas dispersing effect is better, the contact area between the gas and the liquid is increased, and the reaction efficiency is accelerated.
According to one embodiment of the invention, the number of the outlets of the air inlet pipe 7 is two, and the two outlets are symmetrically arranged between the movable impeller 4 and the stationary impeller 5 along the hollow rotating shaft 2.
In the above embodiment, the outlet of the air inlet pipe 7 has two ports, which can stir and disperse the gas on both sides of the center idle shaft 2, further increase the contact area between the gas and the liquid, and increase the reaction efficiency.
Referring to fig. 1-2, according to an embodiment of the present invention, further comprising a water bath 10, the reaction tank 1 is placed in the water bath 10 by means of support legs 103.
In the above embodiment, the water bath 10 is provided with the heating means for heating the water in the water bath 10 and further heating the reaction tank 1 to maintain the temperature required for the reaction in the tank.
According to one embodiment of the present invention, the reaction tank 1 is a transparent reaction tank 1.
In the above embodiment, the transparent reaction tank 1 facilitates observation of the conditions inside the reaction tank 1, and is convenient and intuitive, and also facilitates reading of the thermometer 11 and the acidity detector in the later period.
Referring to fig. 1 to 2, according to an embodiment of the present invention, a thermometer 11 is provided on the top cover 101, and the thermometer 11 is inserted into the reaction tank 1.
In the above embodiment, the water bath 10 heats the reaction tank 1, and there is a temperature transfer error, and the thermometer 11 can visually read the actual temperature of the reaction tank 1.
According to an embodiment of the present invention, an acidity detector is further disposed on the top cover 101, and the acidity detector extends into the reaction tank 1.
In the above embodiment, the acidity detector is used to measure the acidity in the reaction tank 1, and according to the detected speed value, the corresponding acid supplement amount is determined in combination with the set basicity, so as to ensure the reaction to be fully performed and avoid the generation of iron oxyhydroxide.
Referring to fig. 2, according to an embodiment of the present invention, the reaction tank 1 is two, wherein the exhaust pipe 8 of one reaction tank 1 is communicated with the intake pipe 7 of the other reaction tank 1.
In the above embodiments, one is a main reaction tank 1, which is used for reacting the pickling waste liquid with the main catalyst, the secondary catalyst and oxygen to generate a poly ferric chloride solution; the other is a side reaction tank 1, which is used for absorbing the nitrogen oxide gas generated by the reaction by adopting NaOH solution, can generate sodium nitrite for cyclic utilization, and can prevent the nitrogen oxide gas from being directly discharged into the environment, thereby avoiding the pollution to the environment.
Example 1
A method for producing poly-ferric chloride comprises the following steps:
step 1, filtering the waste pickle liquor by 747 filter cloth, and adding 2400mL of waste pickle liquor (containing 2.77mol/L FeCl in the waste pickle liquor) according to a calculation formula of the basicity of the polymeric ferric chloride salt 2And 1.31mol/LHCl) with 330mL concentrated hydrochloric acid(concentration: 11.75mol/L) to obtain a mixed solution having a total mass of 4000 g.
Wherein, the calculation formula of the basicity W (%) of the polyferric chloride is as follows:
wherein A is the mole number of ferrous chloride in the pickling waste liquid; b moles of free acid (including additional hydrochloric acid) in the pickle liquor.
Step 2, opening the top cover, adding the mixed solution into the reaction tank, and then adding 120g NaH 2PO 4·2H 2O and 6g sodium hydroxide (NaOH), and the top cap was closed.
Step 3, adding 36mL of HNO into the reaction tank through a funnel 3And the secondary catalyst is started, the inner shaft of the hollow rotating shaft rotates, then air is automatically sucked into the reaction tank from the air inlet pipe, the air is fully broken through the matching of the stationary impeller and the movable impeller, and meanwhile, the reaction tank is heated to 60 ℃ through water in the water bath tank, and the water bath heating is stopped.
Step 3, introducing O into the reaction tank through the air inlet pipe 2，O 2Introducing at a flow rate of 2L/min for 15 min; dropwise adding NaNO into the reaction tank through a funnel 2Main catalyst (NaNO) 2Concentration 20% and dropping rate 1 drop/second) until no Fe is present 2+(about 45min) 14g of NaNO was used 2Obtaining a poly ferric chloride solution and a nitrogen oxide gas, and measuring Fe in the poly ferric chloride solution 3+9.39% and 5.29% basicity. Wherein the nitrogen oxide gas is discharged from the exhaust port.
Wherein, NaNO 2Will also react with HCl to produce HNO 2，HNO 2Is unstable and easy to decompose to generate NO and NO 2The nitrogen is oxidized into gas by the following specific formula:
NaNO 2+HCl＝HNO 2+NaCl
2HNO 2＝H 2O+NO↑+NO 2↑
and 4, discharging the nitrogen oxide gas from the exhaust port, entering a next reaction tank through the exhaust pipe, fully breaking and dispersing the nitrogen oxide gas through the matching of the static impeller and the movable impeller, reacting with 20% sodium hydroxide solution in the reaction tank to generate sodium nitrite, and recycling the sodium nitrite when the pH value of the NaOH solution is reduced to 9.27 to continuously serve as a main catalyst for the polyferric chloride generation reaction.
Step 5, carrying out reduced pressure concentration on the poly ferric chloride solution to Fe by adopting a 120 ℃ oil bath 3+When the content is 30 percent, the time of decompression concentration is 4 hours, FeOOH (more than or equal to 200 m) accounting for 1/2 of the polyferric chloride solution is added 2And the pore volume is more than or equal to 0.25mL/g), cooling and solidifying, mixing by a mixer and packaging to obtain the solid PFC.
Example 2
A method for producing poly-ferric chloride comprises the following steps:
step 1, filtering the waste pickle liquor by 747 filter cloth, and adding 2.11mol/L FeCl in the waste pickle liquor into 2725mL according to a calculation formula of the basicity of the poly (ferric chloride) 2And 0.73mol/L HCl) was added with 226mL of concentrated hydrochloric acid (concentration: 11.75mol/L) to obtain a mixed solution.
Step 2, opening the top cover, adding the mixed solution into the reaction tank, and then adding 120g NaH 2PO 4·2H 2O and 6g sodium hydroxide (NaOH), and the top cap was closed.
Step 3, adding 36mL of HNO into the reaction tank through a funnel 3And the secondary catalyst is started, the inner shaft of the hollow rotating shaft rotates, then air is automatically sucked into the reaction tank from the air inlet pipe, the air is fully broken through the matching of the stationary impeller and the movable impeller, and meanwhile, the reaction tank is heated to 60 ℃ through water in the water bath tank, and the water bath heating is stopped.
Step 3, introducing O into the reaction tank through the air inlet pipe 2，O 2Introducing at a flow rate of 2L/min for 15 min; dropwise adding NaNO into the reaction tank through a funnel 2Main catalyst (NaNO) 2Concentration 20% and dropping rate 1 drop/second) until no Fe is present 2+(70min) 30g of NaNO was used 2Obtaining a poly ferric chloride solution and a nitrogen oxide gas, and measuring Fe in the poly ferric chloride solution 3+8.22% and basicity7.40 percent. Wherein the nitrogen oxide gas is discharged from the exhaust port.
And 4, discharging the nitrogen oxide gas from the exhaust port, entering a next reaction tank through the exhaust pipe, fully breaking and dispersing the nitrogen oxide gas through the matching of the static impeller and the movable impeller, reacting with 20% sodium hydroxide solution in the reaction tank to generate sodium nitrite, and recycling the sodium nitrite when the pH value of the NaOH solution is reduced to 9.27 to continuously serve as a main catalyst for the polyferric chloride generation reaction.
Step 5, carrying out reduced pressure concentration on the poly ferric chloride solution to Fe by adopting a 120 ℃ oil bath 3+When the content is 28 percent, the time of decompression concentration is 4 hours, and FeOOH (more than or equal to 200 m) accounting for 1/2 of the polyferric chloride solution is added 2And the pore volume is more than or equal to 0.25mL/g), cooling and solidifying, mixing by a mixer and packaging to obtain the solid PFC.
Example 3
A method for producing poly-ferric chloride comprises the following steps:
step 1, taking 3000mL of acid pickling waste liquid (the acid pickling waste liquid contains 2.11mol/L FeCl 2And 0.95mol/L HCl), the pickle liquor was filtered through a 747 filter cloth.
Step 2, opening the top cover, adding the filtered pickling waste liquid into the reaction tank, and then adding 120g NaH 2PO 4·2H 2O and 6g sodium hydroxide (NaOH), and the top cap was closed.
Step 3, adding 36mL of HNO into the reaction tank through a funnel 3And the secondary catalyst is started, the inner shaft of the hollow rotating shaft rotates, then air is automatically sucked into the reaction tank from the air inlet pipe, the air is fully broken through the matching of the stationary impeller and the movable impeller, and meanwhile, the reaction tank is heated to 60 ℃ through water in the water bath tank, and the water bath heating is stopped.
Step 3, introducing O into the reaction tank through the air inlet pipe 2，O 2Introducing at a flow rate of 2L/min for 15 min; dropwise adding NaNO into the reaction tank through a funnel 2Main catalyst (NaNO) 2Concentration 20% and dropping rate 1 drop/second) until no Fe is present 2+(70min) 40g of NaNO was used 2Obtaining a poly ferric chloride solution and a nitrogen oxide gas, and measuring polyFe in solution of iron chloride 3+10.07% and basicity 15.2%. Wherein the nitrogen oxide gas is discharged from the exhaust port.
And 4, discharging the nitrogen oxide gas from the exhaust port, entering a next reaction tank through the exhaust pipe, fully breaking and dispersing the nitrogen oxide gas through the matching of the static impeller and the movable impeller, reacting with 20% sodium hydroxide solution in the reaction tank to generate sodium nitrite, and recycling the sodium nitrite when the pH value of the NaOH solution is reduced to 9.27 to continuously serve as a main catalyst for the polyferric chloride generation reaction.
Step 5, concentrating the poly ferric chloride solution to Fe under reduced pressure by adopting 150 ℃ oil bath 3+The content is 32 percent, the time of decompression concentration is 3 hours, FeOOH (more than or equal to 200 m) accounting for 1/2 of the polyferric chloride solution is added 2And the pore volume is more than or equal to 0.25mL/g), cooling and solidifying, mixing by a mixer and packaging to obtain the solid PFC.
Example 4
A method for producing poly-ferric chloride comprises the following steps:
step 1, with solid FeCl 2·4H 2O into 3000mL FeCl 2Solution (in which FeCl 2The concentration was 2.22mol/L and the hydrochloric acid concentration was 0.2 mol/L).
Step 2, opening the top cover, adding prepared FeCl into the reaction tank 2Adding 120g NaH into the solution 2PO 4·2H 2O and 6g NaOH, and the top cover is closed.
Step 3, adding 36mL of HNO into the reaction tank through a funnel 3And the secondary catalyst is started, the inner shaft of the hollow rotating shaft rotates, then air is automatically sucked into the reaction tank from the air inlet pipe, the air is fully broken through the matching of the stationary impeller and the movable impeller, and meanwhile, the reaction tank is heated to 60 ℃ through water in the water bath tank, and the water bath heating is stopped.
Step 3, introducing O into the reaction tank through the air inlet pipe 2，O 2Introducing at a flow rate of 2L/min for 15 min; dropwise adding NaNO into the reaction tank through a funnel 2Main catalyst (NaNO) 2Concentration 20% and dropping rate 1 drop/second) until no Fe is present 2+(65min) 30g of NaNO was used 2Obtaining a poly ferric chloride solution and a nitrogen oxide gas, and measuring Fe in the poly ferric chloride solution 3+10.47% and basicity 24.6%. Wherein the nitrogen oxide gas is discharged from the exhaust port.
And 4, discharging the nitrogen oxide gas from the exhaust port, entering a next reaction tank through the exhaust pipe, fully breaking and dispersing the nitrogen oxide gas through the matching of the static impeller and the movable impeller, reacting with 20% sodium hydroxide solution in the reaction tank to generate sodium nitrite, and recycling the sodium nitrite when the pH value of the NaOH solution is reduced to 9.27 to continuously serve as a main catalyst for the polyferric chloride generation reaction.
By the use of O 2Oxidized FeCl 2The solution tends to precipitate FeOOH due to insufficient acidity. Mainly because the residual hydrochloric acid in the pickling waste liquid is not accurately measured and is often higher, because the pickling waste liquid not only contains FeCl 2Interference indicator color change due to FeCl 3To produce Fe (OH) 3The precipitation interferes more with the indicator color change, so less make-up acid results, resulting in FeOOH precipitation. Before oxidation, hydrochloric acid is added into the pickling waste liquid, and the amount of the supplemented hydrochloric acid is determined according to the basicity, so that excessive hydrochloric acid is not added, waste is avoided, and FeOOH precipitation is not generated.
Test of
1) Test conditions
1000mL of pure water respectively contains 2mg of elements to be tested, 0.3g of solid PFC (or 0.6g of liquid PFC) is used for treating the elements to be tested, the PH value is adjusted to about 7.0 by 0.1M NaOH at the rotating speed of 150r/min, and then the elements are dispersed for 1min at the rotating speed of 300 r/min; transferring the mixture into a 1000mL measuring cylinder, standing and clarifying for more than 5 h; filtering, and collecting appropriate amount of clear liquid.
2) And (3) test results: as shown in table 1.
TABLE 1
Figure BDA0002255567920000131
As can be seen from Table 1, the removal rates of the liquid PFC and the solid PFC on kaolin turbidity solution with the turbidity of 0.02% reach 96% and 99%, respectively, and the removal effect is good.
Although the present invention has been described in detail in this specification with reference to specific embodiments and illustrative embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the present invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A gas dispersion machine for producing poly ferric chloride, characterized by comprising: the reaction tank comprises a reaction tank (1) and an air inlet pipe (7), wherein the reaction tank (1) is provided with a top cover (101) and a tank body (102) which are matched with each other; the bottom of the tank body (102) is provided with supporting legs (103), the top cover (101) is provided with a sampling port (104), the center of the top cover (101) is provided with a shaft hole, a hollow rotating shaft (2) is assembled in the shaft hole, and the hollow rotating shaft (2) comprises an outer shaft (202) and an inner shaft (201) which are coaxial;
the upper end of the hollow rotating shaft (2) penetrates through the shaft hole and is connected with a motor (3), and the lower end of the hollow rotating shaft (2) extends into the tank body (102) and is close to the bottom of the tank body (102); wherein, the lower end of the inner shaft (201) is provided with a movable impeller (4), the lower end of the outer shaft (202) is fixed with a cover plate (6) and is provided with a stationary impeller (5);
an exhaust port is formed in the top cover (101), a stop valve is arranged at the exhaust port, and the exhaust port is communicated with an exhaust pipe (8);
the air inlet pipe (7) penetrates through the top cover (101) and extends into the tank body (102), the air inlet pipe (7) is communicated with a funnel (9) through a pipeline, and a stop valve is arranged on the pipeline.
2. The gas disperser for producing polymeric ferric chloride according to claim 1, characterized in that it further comprises a water bath (10), and the reaction tank (1) is placed in the water bath (10) by means of support legs (103).
3. The gas disperser for producing polymeric ferric chloride according to claim 1, characterized in that said reaction tank (1) is a transparent reaction tank (1), said top cover (101) is provided with a thermometer (11), and said thermometer (11) extends into said reaction tank (1).
4. The gas disperser for producing polymeric ferric chloride according to any of claims 1 to 3, characterized in that said reaction tanks (1) are two in number, wherein the gas outlet pipe (8) of one reaction tank (1) is in communication with the gas inlet pipe (7) of the other reaction tank (1).
5. A method for producing poly-ferric chloride is characterized by comprising the following steps:
step 1, opening a top cover, adding pickling waste liquid, a stabilizer and sodium hydroxide into a tank body, and covering the top cover;
step 2, adding a secondary catalyst into the reaction tank through a funnel, turning on a motor, enabling an inner shaft of a hollow rotating shaft to rotate, then automatically sucking air into the reaction tank from an air inlet pipe, fully breaking and dispersing the air through the matching of a stationary impeller and a movable impeller, and heating the reaction tank through water in a water bath tank;
step 3, introducing oxygen into the reaction tank through the air inlet pipe, dropwise adding a main catalyst into the reaction tank through a funnel, and reacting to obtain a poly ferric chloride solution and a nitrogen oxide gas; wherein the nitrogen oxide gas is discharged from the exhaust port.
6. The method for producing polymeric ferric chloride according to claim 5, further comprising a step 4 of discharging nitrogen oxide gas from the gas outlet through the gas outlet pipe into the next reaction tank, sufficiently breaking the nitrogen oxide gas by the cooperation of the stationary impeller and the movable impeller, and reacting with sodium hydroxide solution in the reaction tank to generate sodium nitrite.
7. The method for producing polymeric ferric chloride as claimed in claim 6, further comprising the step 5 of concentrating the polymeric ferric chloride solution under reduced pressure by using an oil bath at 150 ℃ of 120-; the specific surface area of the hydroxyl ferric oxide is more than or equal to 200m 2The pore volume is more than or equal to 0.25 mL/g.
8. The method for producing polymeric ferric chloride according to claim 6, wherein in the step 1, before the acid waste liquid is added, the acidity of the acid waste liquid is adjusted by hydrochloric acid according to the basicity of the polymeric ferric chloride; wherein, the calculation formula of the basicity W of the polyferric chloride is as follows:
wherein A is the mole number of ferrous chloride in the pickling waste liquid; b, the mole number of free acid in the pickling waste liquid.
9. The method for producing polymeric ferric chloride according to claim 6, wherein the stabilizer is ammonium dihydrogen phosphate, sodium citrate; the secondary catalyst is nitric acid; the main catalyst is sodium nitrite solution.
10. The method for producing polymeric ferric chloride according to claim 6, wherein in the step 3, the reaction temperature is 50-70 ℃ and the reaction time is 40-80 min; the oxygen in step 3 can be replaced by air, and when the oxygen is air, the reaction time is 3-5 hours.
CN201911052085.7A 2019-10-31 2019-10-31 Gas dispersion machine for producing polyferric chloride and production method Pending CN110773093A (en)

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