CN112359366B - Two-stage roasting regeneration device and method for waste mixed acid - Google Patents

Two-stage roasting regeneration device and method for waste mixed acid Download PDF

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CN112359366B
CN112359366B CN202011078952.7A CN202011078952A CN112359366B CN 112359366 B CN112359366 B CN 112359366B CN 202011078952 A CN202011078952 A CN 202011078952A CN 112359366 B CN112359366 B CN 112359366B
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CN112359366A (en
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陈晓平
徐劲松
马吉亮
刘道银
梁财
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
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    • C01B21/42—Preparation from nitrates

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Abstract

本发明公开了一种废混酸两级焙烧再生装置和方法。废混酸两级焙烧再生装置包括预过滤器、文丘里预浓缩器、一级反应炉、旋风分离器、二级反应炉、金属氧化物料仓、吸收塔、洗涤塔、冷却塔、氧化塔、碱洗塔。一级反应炉的炉内温度控制在150°，用于将废混酸中的硝酸盐尽可能全部分解为NO2、O2和金属氧化物，并防止NO2的进一步分解，以提高HNO3的回收率。二级反应炉的炉内温度控制在750°，用于将所述一级反应炉内排出的固体废料进一步焙烧分解，以将其中剩余的氟化盐焙烧分解为HF气体和金属氧化物。本发明可大幅提高NO2的生成量，从而有效提高硝酸回收率。同时，还可有效降低系统能耗。

Figure 202011078952

The invention discloses a waste mixed acid two-stage roasting regeneration device and method. The waste mixed acid two-stage roasting regeneration device includes pre-filter, Venturi pre-concentrator, primary reactor, cyclone separator, secondary reactor, metal oxide silo, absorption tower, washing tower, cooling tower, oxidation tower, alkali wash tower. The furnace temperature of the first-stage reactor is controlled at 150°, which is used to decompose the nitrate in the waste mixed acid into NO 2 , O 2 and metal oxides as much as possible, and prevent the further decomposition of NO 2 , so as to improve the HNO 3 Recovery rate. The furnace temperature of the secondary reactor is controlled at 750°, which is used to further roast and decompose the solid waste discharged from the primary reactor, so as to roast and decompose the remaining fluoride salt into HF gas and metal oxide. The invention can greatly increase the generation amount of NO 2 , thereby effectively improving the recovery rate of nitric acid. At the same time, it can effectively reduce the energy consumption of the system.

Figure 202011078952

Description

Two-stage roasting regeneration device and method for waste mixed acid
Technical Field
The invention belongs to the technical field of harmless treatment and regeneration of waste mixed acid, and particularly relates to a waste mixed acid two-stage roasting regeneration device and method.
Background
In the annealing and pickling process of stainless steel, HF + HNO is generally used3And (3) pickling with mixed acid to remove an iron oxide layer and a chromium-poor layer generated on the surface of the stainless steel during hot rolling and annealing, and passivating the surface. Fe in pickling solution in pickling process2+The concentration is gradually increased and the concentration of free acid is gradually reduced when Fe2+The pickling solution must be replaced after reaching a certain concentration. The waste mixed acid belongs to dangerous waste, can not be directly discharged, and HF and HNO3Is expensive, so the waste mixed acid needs to be innoxious andand (7) carrying out retreatment.
HF+HNO3The common harmless and regeneration treatment methods for waste mixed acid mainly comprise a spray roasting method and a fluidized bed method. The difference is that the spray roasting method sprays acid liquor into the roasting furnace through a spray gun and atomizes the acid liquor into acid mist for roasting, the generated iron oxide is powdery and has high requirements on the components and the water quality of the waste acid, the fluidized bed method sends the acid liquor into the reaction furnace through an acid pipe for reaction, and the generated iron oxide is granular and has no requirements on the waste acid and the water quality.
The existing fluidized bed method is mainly to inject waste acid into a high-temperature furnace (more than 750 ℃) through an acid pipe for roasting, so that the problems of high system energy consumption, more NO gas generation amount, low nitric acid recovery rate and the like caused by high temperature in the furnace exist, and the method can effectively solve the problems.
The nitrate starts to decompose and generate NO at about 125 DEG C2And NO2The decomposition is started to generate NO when the temperature is higher than about 150 ℃, and the decomposition is completely decomposed into NO and O when the temperature is about 650 DEG2The decomposition temperature of fluoride salt is at least above 300 ℃, the iron fluoride starts to decompose between 300 ℃ and 400 ℃, the temperature in the furnace of the prior fluidized bed method is above 750 ℃, nitrogen in nitrate is completely decomposed to generate NO, the treatment difficulty and cost of roasting waste gas are increased, and the recovery rate of nitric acid is obviously reduced.
Disclosure of Invention
The invention aims to solve the technical problems that the temperature in a furnace is higher in the traditional fluidized bed acid regeneration method, so that a large amount of NO is generated, the waste gas treatment cost is increased, the nitric acid recovery rate is reduced, and the energy consumption is higher. The device and the method for regenerating the waste mixed acid (waste nitric acid and waste hydrofluoric acid) by two-stage roasting can greatly reduce the generation amount of NO, improve the recovery rate of nitric acid and greatly reduce the energy consumption of a system.
The invention adopts the following technical scheme for solving the technical problems:
the utility model provides a useless miscarriage two-stage calcination regenerating unit, includes prefilter, venturi preconcentrator, one-level reacting furnace, one-level cyclone, second grade reacting furnace, second grade cyclone, metal oxidation material storehouse, absorption tower, scrubbing tower, cooling tower, oxidation tower, alkali wash tower, wherein:
the feed inlet of the pre-filter can flow into waste mixed acid to be treated, and the discharge outlet is connected with the feed inlet of the Venturi pre-concentrator through a pipeline; the pre-filter can filter the inflowing waste mixed acid to be treated so as to remove solid particles and insoluble residues in the waste mixed acid to be treated; the filtered waste mixed acid to be treated flows into the Venturi preconcentrator through the discharge hole of the prefilter and the feed inlet of the Venturi preconcentrator in sequence;
in the Venturi preconcentrator, a waste gas outlet is sequentially connected with an absorption tower, a washing tower, a cooling tower, an oxidation tower and an alkaline washing tower through pipelines, and a discharge hole is connected with a feed inlet of a primary reaction furnace through a pipeline; the Venturi preconcentrator can concentrate the waste mixed acid to be treated after being filtered by the prefilter; the waste mixed acid to be treated after the concentration treatment flows into the first-stage reaction furnace through a discharge hole of the Venturi preconcentrator and a feed hole of the first-stage reaction furnace in sequence;
the first-stage reaction furnace can only roast and decompose the nitrate in the concentrated waste mixed acid to be treated, and the nitrate in the waste mixed acid to be treated flowing into the first-stage reaction furnace can be decomposed into NO2, O2 and metal oxide by controlling the temperature in the first-stage reaction furnace; a waste gas discharge port of the first-stage reaction furnace is connected with a feed port of the first-stage cyclone separator through a pipeline, and a return outlet and a slag discharge port are respectively connected with the second-stage reaction furnace through pipelines; in the roasting process of the first-stage reaction furnace, the residue in the first-stage reaction furnace needs to be sampled and detected at regular time, and when the detection result shows that the mass percentage of the fluoride salt in the sample exceeds 95%, the residue in the first-stage reaction furnace is discharged into the second-stage reaction furnace through a slag discharge port of the first-stage reaction furnace;
the primary cyclone separator can perform gas-solid separation on waste gas discharged from a waste gas outlet of the primary reaction furnace; the solid material outlet of the primary cyclone separator is connected with the secondary reaction furnace through a pipeline, and the gas outlet is connected with the Venturi preconcentrator through a pipeline;
the secondary reaction furnace can roast and decompose materials in the furnace, and promote fluoride salt in the materials in the furnace to roast and decompose into HF gas and metal oxide by controlling the temperature in the secondary reaction furnace, and nitrate is roasted and decomposed into metal oxide, NO and O2; a slag discharge port of the secondary reaction furnace is connected with a metal oxide bin through a pipeline, and a waste gas discharge port is connected with the secondary cyclone separator through a pipeline;
the secondary cyclone separator can perform solid-gas separation on waste gas discharged from a waste gas outlet of the secondary reaction furnace; the feed opening of the secondary cyclone separator is connected with the secondary reaction furnace through a pipeline, and the gas outlet is connected with the Venturi preconcentrator through a pipeline; the solid part separated by the secondary cyclone separator returns to the secondary reaction furnace through a feed opening arranged on the secondary cyclone separator, and the gas part separated by the secondary cyclone separator is output to the Venturi preconcentrator through a gas outlet arranged on the secondary cyclone separator.
Further, the furnace temperature of the primary reaction furnace is controlled to be 150 degrees; the temperature in the secondary reaction furnace is controlled at 750 degrees.
Further, the operation temperature of the absorption tower is controlled between 80 DEG and 85 DEG, and the absorption tower absorbs HF gas in the waste gas discharged from the waste gas outlet of the Venturi preconcentrator by internally filling an absorption ring, so that the mass ratio of the HF gas in the waste gas flowing out of the absorption tower is not more than 10%.
Further, the scrubbing tower is internally filled with an absorption ring to absorb HF gas in the waste gas discharged from the absorption tower, so that the mass ratio of the HF gas in the waste gas flowing out of the scrubbing tower is promoted to be not more than 3%.
Further, the cooling tower output gas temperature is not higher than 50 °.
Further, the oxidation tower can oxidize NO contained in the exhaust gas treated by the cooling tower to generate NO 2; the oxidation column is also capable of absorbing NO2 to produce nitric acid.
The invention also aims to provide a waste mixed acid two-stage roasting regeneration method, which is realized based on the waste mixed acid two-stage roasting regeneration device and comprises the following steps:
the method comprises the following steps: pre-filtering the waste mixed acid through a pre-filter to separate solid particles and insoluble residues;
step two: the filtered waste mixed acid enters a Venturi preconcentrator to be preheated to 90 degrees, so that free acid and moisture in the waste mixed acid are evaporated;
step three: the waste mixed acid treated by the Venturi preconcentrator is sent into a primary reaction furnace to be roasted and decomposed, and the temperature in the primary reaction furnace is controlled to ensure that nitrate in the waste mixed acid is heated and decomposed in the furnace to generate NO2、O2And metal oxide, in the process, the waste gas discharged from the first-stage reaction furnace enters a first-stage cyclone separator for gas-solid separation treatment, the solid part separated by the first-stage cyclone separator and the solid material and the return material discharged from the first-stage reaction furnace are introduced into a second-stage reaction furnace for further roasting and decomposition, and the furnace temperature of the second-stage reaction furnace is controlled at 750 ℃;
step four: in the second-stage reaction furnace, fluoride salt contained in the waste mixed acid is roasted and decomposed to generate HF gas and metal oxide, meanwhile, nitrate which is not roasted and decomposed in the first-stage reaction furnace is roasted and decomposed in the second-stage reaction furnace to generate NO gas and O2And a metal oxide; waste slag discharged from a slag discharge port of the secondary reaction furnace is directly introduced into the metal oxidation material bin; the waste gas discharged from the secondary reaction furnace enters a secondary cyclone separator for gas-solid separation, and the separated solid particles return to the secondary reaction furnace;
step five: the waste gas treated by the secondary cyclone separator and the waste gas treated by the primary cyclone separator enter a Venturi preconcentrator and exchange heat with acid liquor to evaporate free acid and moisture in the waste mixed acid;
step six: the waste gas enters an absorption tower from a Venturi preconcentrator, acid liquid is sprayed from the top, gas enters from the bottom, and an absorption ring is filled in the absorption tower, wherein more than 90 percent of HF gas is absorbed, the temperature of the waste gas is cooled to be between 80 and 85 degrees, and the generated regenerated acid is supplied to an acid pickling line for recycling;
step seven: waste gas enters a washing tower from an absorption tower, acid liquor is sprayed from the top, gas enters from the bottom, an absorption ring is filled in the washing tower, the residual 10% of HF gas is absorbed, more than 97% of HF gas is completely absorbed, and absorbed regenerated acid enters the absorption tower to absorb the HF gas;
step eight: the waste gas enters a cooling tower from a washing tower for cooling, industrial fresh water is sprayed from the top, and gas enters from the bottom to absorb residual water vapor and NO in the waste gas2And simultaneously, the absorbed regenerated acid enters a washing tower to absorb HF gas.
Step nine: the waste gas enters the oxidation tower from the cooling tower, industrial fresh water is sprayed from the top, hydrogen peroxide is added, the gas enters from the bottom, and high-density filling material is arranged in the oxidation tower to oxidize a small amount of NO contained in the gas into NO2Simultaneously to NO2Absorbing and recovering HNO3And the absorbed regenerated acid solution enters a washing tower to absorb HF gas.
Step ten: and the waste gas enters an alkaline washing tower from the oxidation tower, and the residual acid gas in the waste gas is removed.
Compared with the prior art, the invention adopting the technical scheme has the following technical effects:
compared with the existing one-stage high-temperature roasting regeneration device, the two-stage roasting regeneration device and method for waste mixed acid (waste nitric acid and waste hydrofluoric acid) provided by the invention have the advantages that waste acid is roasted twice, the temperature in the one-stage reaction furnace is about 150 ℃, and almost all nitrates can be decomposed into NO2、O2And metal oxides, and prevention of NO2Further decomposing into NO, greatly improving the recovery rate of nitric acid, decomposing nitrate almost in the first-stage reaction furnace and decomposing water in the waste mixed acid in the first-stage reaction furnace, greatly reducing the energy consumption of the system, and solving the problems that in the prior art, the furnace is high, the pyrolysis product of nitrate almost contains NO and metal oxide, the recovery rate of nitric acid is low, and the energy consumption of the system is high. The invention improves the recovery rate of nitric acid, reduces the reaction energy consumption and simultaneously reduces NOXThe emission is more environment-friendly, and the method has a wide industrial application prospect.
Drawings
FIG. 1 is a flow chart of the overall apparatus in this embodiment;
in the figure, 1, prefiltering; 2. a venturi preconcentrator; 3. a first-stage reaction furnace; 4. a primary vortex separator; 5. a secondary reaction furnace; 6. a metal oxidation material bin; 7. a secondary cyclone separator; 8. an absorption tower; 9. a washing tower; 10. a cooling tower; 11. an oxidation tower; 12. and (4) an alkaline washing tower.
Detailed Description
The technical scheme of the invention is further explained in detail by combining the attached drawings:
the invention relates to a waste mixed acid two-stage roasting regeneration device, which comprises a step 1 and a step 1, wherein the step 1 and the step are connected in sequence; 2. a venturi preconcentrator; 3. a first-stage reaction furnace; 4. a primary vortex separator; 5. a secondary reaction furnace; 6. a metal oxidation material bin; 7. a secondary cyclone separator; 8. an absorption tower; 9. a washing tower; 10. a cooling tower; 11. an oxidation tower; 12. and (4) an alkaline washing tower. Wherein the waste mixed acid is acid liquor prepared from waste nitric acid and hydrofluoric acid according to a certain mass ratio.
Wherein the pre-filtering 1 is used for filtering the waste mixed acid to separate solid particles and undissolved residues.
The venturi preconcentrator 2 is used for evaporating partial water and free acid in the waste mixed acid.
The first-stage reaction furnace 3 is used for roasting the waste acid treated by the Venturi preconcentrator 2, takes natural gas as fuel, controls the temperature at about 150 ℃, and mainly carries out roasting decomposition on nitrate in waste mixed acid to decompose the nitrate into NO2、O2And metal oxides. The main reaction is as follows:
Figure DEST_PATH_IMAGE002
the primary cyclone separator 4 performs gas-solid separation on the waste gas discharged from the primary reaction furnace 3 to separate metal oxide powder, salt and other solid impurities.
The secondary reaction furnace 5 is used for further roasting and decomposing the solid materials (containing fluoride salt, metal oxide, partial undecomposed nitrate and other solid impurities) discharged from the primary reaction furnace 3 and the solid materials separated by the primary cyclone separator 4. The secondary reaction furnace 5 takes natural gas as fuel and appropriately supplements water according to the situation, the temperature in the furnace is controlled at about 750 ℃, the roasting decomposition of fluoride salt and part of undecomposed nitrate is realized, and the main reaction is as follows:
Figure DEST_PATH_IMAGE004
and solid materials such as metal oxides and the like generated by roasting the secondary reaction furnace 5 are discharged from the bottom of the reaction furnace, enter a metal oxide bin 6 and are recycled.
The secondary cyclone separator 7 performs gas-solid separation on the waste gas discharged from the secondary reaction furnace 5, and the separated solid material returns to the secondary reaction furnace 5.
The venturi preconcentrator 2 evaporates free acid and part of water in the waste mixed acid by using high-temperature flue gas which is discharged from the secondary reaction furnace 5 and subjected to gas-solid separation by the secondary cyclone separator 7 and flue gas which is discharged from the primary reaction furnace 3 and subjected to gas-solid separation by the primary cyclone separator 4.
The absorption tower 8 absorbs the waste gas generated after the treatment of the Venturi preconcentrator 2, acid liquid in the tower is sprayed from the top, gas enters from the bottom, an absorption ring is filled in the tower, the operation temperature is controlled between 80 degrees and 85 degrees, and more than 90 percent of HF gas in the waste gas is absorbed.
The washing tower 9 washes the waste gas treated by the absorption tower 8, acid liquid in the tower is sprayed from the top, gas enters from the bottom, and an absorption ring is filled in the tower, so that more than 97% of HF gas is completely absorbed.
The cooling tower 10 cools the exhaust gas treated by the scrubber 9 to reduce the temperature to about 50 ° and absorbs the water vapor remaining in the exhaust gas.
The oxidation tower 11 oxidizes part of NO contained in the exhaust gas treated by the cooling tower 10 to generate NO2Then, a large amount of NO originally present in the composition2And small amount of NO formed by oxidation2Absorbing to recover nitric acid.
The caustic washing tower 12 removes acid gases contained in the exhaust gas absorbed by the oxidation tower 11.
Example 1;
the two-stage roasting regeneration method of waste mixed acid described in this embodiment is realized based on the above two-stage roasting regeneration device of waste mixed acid, and includes the following steps:
the method comprises the following steps: mixing the prepared waste mixed acid (F)-28.4% by mass of NO3 -56.5% by mass and other H+And a mass fraction of metal ions of 15.1%) was subjected to prefiltration 1 at a rate of 1kg per hour to separate solid particles and undissolved residues therefrom.
Step two: the filtered waste mixed acid enters the Venturi preconcentrator 2 to be preheated to about 90 ℃, and part of free acid and water are evaporated.
Step three: the waste mixed acid treated by the Venturi preconcentrator 2 is sent into a first-stage reaction furnace 3 for roasting and decomposition, the temperature of the first-stage reaction furnace 3 is controlled at 130 ℃, and most of nitrate is heated and decomposed in the furnace to generate NO2、O2And metal oxides, and the waste gas enters the primary cyclone separator 4 for treatment. And the treated gas is sampled and detected, and the detection result shows that NO in the waste gas2Volume content of NO and NO2The total volume content of HF is 80.1%, the volume content of NO is 2.0%, and the volume content of HF is 17.9% (HF is mainly free hydrofluoric acid in waste acid evaporated), metal oxide powder, salt and other solid impurities separated by the primary cyclone 4 and solid materials and return materials discharged from the primary reaction furnace 3 enter the secondary reaction furnace 5 for further roasting decomposition, and the detection result shows that the content of fluoride salt accounts for 81.3% of the total content of fluoride salt and nitrate (a part of nitrate is still not decomposed).
Step four: the temperature in the secondary reaction furnace 5 is controlled at about 750 ℃, the main decomposition reaction in the furnace is fluoride salt and partial nitrate, a large amount of HF gas and a small amount of HF gas are generatedMeasuring NO gas, O2And metal oxide, it is found through the detection that in the secondary reaction furnace 5, the decomposition speed of fluoride salt is obviously accelerated, probably because most of water in the waste acid is evaporated and most of nitrate is decomposed in the primary reaction furnace 3, so that fluoride salt can reach the problem required by the reaction more quickly, and fluoride salt exists in a crystal form and contains crystal water, and the reaction can also be carried out more quickly when the reaction temperature is reached. Wherein the metal oxide is discharged into a metal oxide bin 6 through a slag discharge port, the waste gas enters a secondary cyclone separator 7 for gas-solid separation, the separated solid particles return to a secondary reaction furnace 5, the waste gas treated by the secondary cyclone separator is detected, and the detection result shows that the volume content of HF accounts for 82.4% of the total volume content of HF and NO.
Step five: the waste gas treated by the secondary cyclone separator 7 and the waste gas treated by the primary cyclone separator 4 enter the Venturi preconcentrator 2 and exchange heat with the acid liquor to evaporate free acid and part of water in the waste mixed acid.
Step six: the waste gas enters the absorption tower 8 from the Venturi preconcentrator 2, the acid liquid is sprayed from the top, the gas enters from the bottom, and an absorption ring is filled in the absorption tower, wherein more than 90 percent of HF gas is absorbed, the temperature of the waste gas is cooled to be between 80 and 85 degrees, and the generated regenerated acid is supplied to the pickling line for recycling.
Step seven: the waste gas enters the washing tower 9 from the absorption tower 8, the acid liquid is sprayed from the top, the gas enters from the bottom, and an absorption ring is filled in the absorption tower, wherein the residual 10 percent of HF gas is absorbed, so that more than 97 percent of HF gas is completely absorbed, and the absorbed regenerated acid enters the absorption tower 8 to absorb the HF gas.
Step eight: the waste gas enters a cooling tower 10 from a washing tower 9 for cooling, industrial fresh water is sprayed from the top, gas enters from the bottom to absorb water vapor remained in the waste gas, and the absorbed regenerated acid enters the washing tower 9 to absorb HF gas.
Step nine: the waste gas enters the oxidation tower 11 from the cooling tower 10, the industrial fresh water is sprayed from the top, the hydrogen peroxide is added, the gas enters from the bottom, and the high-density filling material is arranged in the gasContaining a small amount of NO oxidized to NO2Simultaneously to NO2Absorbing and recovering HNO3And the absorbed regenerated acid solution enters a washing tower 9 to absorb HF gas.
Step ten: the waste gas enters an alkaline washing tower 12 from an oxidation tower 11, and the residual acid in the waste gas is removed
And (4) a sex gas.
Example 2;
the two-stage roasting regeneration method of waste mixed acid described in this embodiment is realized based on the above two-stage roasting regeneration device of waste mixed acid, and includes the following steps:
the method comprises the following steps: mixing the prepared waste mixed acid (F)-28.4% by mass of NO3 -56.5% by mass and other H+And a mass fraction of metal ions of 15.1%) was subjected to prefiltration 1 at a rate of 1kg per hour to separate solid particles and undissolved residues therefrom.
Step two: the filtered waste mixed acid enters the Venturi preconcentrator 2 to be preheated to about 90 ℃, and part of free acid and water are evaporated.
Step three: the waste mixed acid treated by the Venturi preconcentrator 2 is sent into a first-stage reaction furnace 3 for roasting and decomposition, the temperature in the first-stage reaction furnace 3 is controlled at 150 ℃, and most of nitrate is heated and decomposed in the furnace to generate NO2、O2And metal oxides, and the waste gas enters the primary cyclone separator 4 for treatment. And the treated gas is sampled and detected, and the detection result shows that NO in the waste gas2Volume content of NO and NO2The total volume content of HF is 92.4%, the volume content of NO is 5.1%, the volume content of HF is 2.5%, wherein the total gas content is higher than that of the gas when the temperature in the first-stage reaction furnace 3 is set to 130 ℃, metal oxide powder, salt and other solid impurities separated by the first-stage cyclone separator 4 and the discharged solid material and returned material of the first-stage reaction furnace 3 enter the second-stage reaction furnace 5 for further roasting and decomposition, the solid material discharged from the first-stage reaction furnace is detected, and the detection result shows that the fluoride salt content accounts for 94.0% of the total fluoride salt and nitrate content.
Step four: temperature control in secondary reaction furnace 5The temperature is about 750 ℃, fluoride salt mainly takes place in the furnace for decomposition reaction, the nitrate content is little, and a large amount of HF gas, partial NO gas and O are generated2And metal oxides, and the detection shows that the decomposition speed of the fluoride salt is obviously shortened, which effectively reduces the energy consumption of the secondary reaction furnace 5. Wherein the metal oxide is discharged into a metal oxide bin 6 through a slag discharge port, the waste gas enters a secondary cyclone separator 7 for gas-solid separation, the separated solid particles return to a secondary reaction furnace 5, the waste gas treated by the secondary cyclone separator is detected, and the detection result shows that the volume content of HF accounts for 94.7% of the total volume content of HF and NO.
Step five: the waste gas treated by the secondary cyclone separator 7 and the waste gas treated by the primary cyclone separator 4 enter the Venturi preconcentrator 2 and exchange heat with the acid liquor to evaporate free acid and part of water in the waste mixed acid.
Step six: the waste gas enters the absorption tower 8 from the Venturi preconcentrator 2, the acid liquid is sprayed from the top, the gas enters from the bottom, and an absorption ring is filled in the absorption tower, wherein more than 90 percent of HF gas is absorbed, the temperature of the waste gas is cooled to be between 80 and 85 degrees, and the generated regenerated acid is supplied to the pickling line for recycling.
Step seven: the waste gas enters the washing tower 9 from the absorption tower 8, the acid liquid is sprayed from the top, the gas enters from the bottom, and an absorption ring is filled in the absorption tower, wherein the residual 10 percent of HF gas is absorbed, so that more than 97 percent of HF gas is completely absorbed, and the absorbed regenerated acid enters the absorption tower 8 to absorb the HF gas.
Step eight: the waste gas enters a cooling tower 10 from a washing tower 9 for cooling, industrial fresh water is sprayed from the top, gas enters from the bottom to absorb water vapor remained in the waste gas, and the absorbed regenerated acid enters the washing tower 9 to absorb HF gas.
Step nine: the waste gas enters the oxidation tower 11 from the cooling tower 10, the industrial fresh water is sprayed from the top, the hydrogen peroxide is added, the gas enters from the bottom, and the high-density filling material is arranged in the oxidation tower to oxidize a small amount of NO contained in the gas into NO2Simultaneously to NO2Absorbing and recovering HNO3The absorbed regenerated acid solution enters a washing tower 9Absorbing the HF gas.
Step ten: the waste gas enters an alkaline washing tower 12 from an oxidation tower 11, and the residual acid in the waste gas is removed
And (4) a sex gas.
Example 3;
the two-stage roasting regeneration method of waste mixed acid described in this embodiment is realized based on the above two-stage roasting regeneration device of waste mixed acid, and includes the following steps:
the method comprises the following steps: mixing the prepared waste mixed acid (F)-28.4% by mass of NO3 -56.5% by mass and other H+And a mass fraction of metal ions of 15.1%) was subjected to prefiltration 1 at a rate of 1kg per hour to separate solid particles and undissolved residues therefrom.
Step two: the filtered waste mixed acid enters the Venturi preconcentrator 2 to be preheated to about 90 ℃, and part of free acid and water are evaporated.
Step three: the waste mixed acid treated by the Venturi preconcentrator 2 is sent into a first-stage reaction furnace 3 for roasting and decomposition, the temperature in the first-stage reaction furnace 3 is controlled at 170 ℃, and most of nitrate is heated and decomposed in the furnace to generate NO2、NO、O2And metal oxides, and the waste gas enters the primary cyclone separator 4 for treatment. And the treated gas is sampled and detected, and the detection result shows that NO in the waste gas2Volume content of NO and NO2The total volume content of HF is 75.0%, the volume content of NO is 23.4%, the volume content of HF is 1.6%, wherein the total gas content is higher than that of the gas when the temperature in the first-stage reaction furnace 3 is set to be 150 ℃, metal oxide powder, salt and other solid impurities separated by the first-stage cyclone separator 4, solid materials and return materials discharged from the first-stage reaction furnace 3 enter the second-stage reaction furnace 5 for further roasting and decomposition, the solid materials discharged from the first-stage reaction furnace are detected, and the detection result shows that the fluoride salt content accounts for 96.1% of the total fluoride salt and nitrate content.
Step four: the temperature in the secondary reaction furnace 5 is controlled at about 750 ℃, the decomposition reaction in the furnace mainly takes place of fluoride salt, the content of nitrate is little, and a large amount of HF gas, partial NO gas and O gas are generated2And metal oxide, the decomposition speed of fluoride salt in the secondary reaction furnace 5 is obviously shortened through detection, which can effectively reduce the energy consumption of the secondary reaction furnace 5. Wherein the metal oxide is discharged into a metal oxide bin 6 through a slag discharge port, the waste gas enters a secondary cyclone separator 7 for gas-solid separation, the separated solid particles return to a secondary reaction furnace 5, the waste gas treated by the secondary cyclone separator is detected, and the detection result shows that the volume content of HF accounts for 96.5% of the total volume content of HF and NO.
Step five: the waste gas treated by the secondary cyclone separator 7 and the waste gas treated by the primary cyclone separator 4 enter the Venturi preconcentrator 2 and exchange heat with the acid liquor to evaporate free acid and part of water in the waste mixed acid.
Step six: the waste gas enters the absorption tower 8 from the Venturi preconcentrator 2, the acid liquid is sprayed from the top, the gas enters from the bottom, and an absorption ring is filled in the absorption tower, wherein more than 90 percent of HF gas is absorbed, the temperature of the waste gas is cooled to be between 80 and 85 degrees, and the generated regenerated acid is supplied to the pickling line for recycling.
Step seven: the waste gas enters the washing tower 9 from the absorption tower 8, the acid liquid is sprayed from the top, the gas enters from the bottom, and an absorption ring is filled in the absorption tower, wherein the residual 10 percent of HF gas is absorbed, so that more than 97 percent of HF gas is completely absorbed, and the absorbed regenerated acid enters the absorption tower 8 to absorb the HF gas.
Step eight: the waste gas enters a cooling tower 10 from a washing tower 9 for cooling, industrial fresh water is sprayed from the top, gas enters from the bottom to absorb water vapor remained in the waste gas, and the absorbed regenerated acid enters the washing tower 9 to absorb HF gas.
Step nine: the waste gas enters the oxidation tower 11 from the cooling tower 10, the industrial fresh water is sprayed from the top, the hydrogen peroxide is added, the gas enters from the bottom, and the high-density filling material is arranged in the oxidation tower to oxidize a small amount of NO contained in the gas into NO2Simultaneously to NO2Absorbing and recovering HNO3And the absorbed regenerated acid solution enters a washing tower 9 to absorb HF gas.
Step ten: the waste gas enters an alkaline washing tower 12 from an oxidation tower 11, and the residual acid in the waste gas is removed
And (4) a sex gas.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modifications made on the basis of the technical scheme according to the technical idea of the present invention fall within the protection scope of the present invention. While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.

Claims (7)

1.一种废混酸两级焙烧再生装置，其特征在于：包括预过滤器、文丘里预浓缩器、一级反应炉、一级旋风分离器、二级反应炉、二级旋风分离器、金属氧化物料仓、吸收塔、洗涤塔、冷却塔、氧化塔、碱洗塔，其中：1. a waste mixed acid two-stage roasting regeneration device is characterized in that: comprise pre-filter, Venturi pre-concentrator, one-level reactor, one-level cyclone, two-level reactor, two-level cyclone, metal Oxide silo, absorption tower, washing tower, cooling tower, oxidation tower, alkali washing tower, among which: 所述的预过滤器，进料口能够流入待处理废混酸，出料口通过管道与文丘里预浓缩器的进料口连接；所述的预过滤器能够对流入的待处理废混酸进行过滤，以除去待处理废混酸中的固体颗粒以及不溶残留物；过滤后的待处理废混酸依次经预过滤器的出料口、文丘里预浓缩器的进料口流入文丘里预浓缩器；In the pre-filter, the feed port can flow into the waste mixed acid to be treated, and the discharge port is connected with the feed port of the Venturi pre-concentrator through a pipeline; the pre-filter can filter the inflow of the waste mixed acid to be treated. , to remove solid particles and insoluble residues in the waste mixed acid to be treated; the filtered waste mixed acid to be treated flows into the Venturi preconcentrator through the discharge port of the prefilter and the feed port of the Venturi preconcentrator in turn; 所述的文丘里预浓缩器，废气排口通过管道依次与吸收塔、洗涤塔、冷却塔、氧化塔以及碱洗塔连接，出料口则通过管道与一级反应炉的进料口连接；所述的文丘里预浓缩器能够对预过滤器过滤后的待处理废混酸进行浓缩处理；浓缩处理后的待处理废混酸依次经文丘里预浓缩器的出料口、一级反应炉的进料口流入一级反应炉；In the Venturi pre-concentrator, the waste gas discharge port is connected with the absorption tower, the washing tower, the cooling tower, the oxidation tower and the alkali washing tower in turn through the pipeline, and the discharge port is connected with the feed port of the primary reaction furnace through the pipeline; The Venturi pre-concentrator can concentrate the waste mixed acid to be treated after being filtered by the pre-filter; The feed port flows into the primary reactor; 所述的一级反应炉，仅能够对浓缩处理后的待处理废混酸中的硝酸盐进行焙烧分解，并通过控制一级反应炉中的炉内温度，促使流入一级反应炉的待处理废混酸中的硝酸盐能够分解成NO2、O2和金属氧化物；一级反应炉的废气排口通过管道与一级旋风分离器的进料口连接，返料出口以及排渣口分别通过管道与二级反应炉连接；在一级反应炉进行焙烧的过程中，需要对一级反应炉中的残渣定时取样检测，当检测结果表明样品中氟化盐的质量占比超过95%时，通过一级反应炉的排渣口将一级反应炉中的残渣排入二级反应炉中；The first-stage reaction furnace can only roast and decompose the nitrate in the waste mixed acid to be treated after the concentration treatment, and by controlling the temperature in the furnace in the first-stage reaction furnace, the waste to be treated that flows into the first-stage reaction furnace is promoted. Nitrate in mixed acid can be decomposed into NO 2, O 2 and metal oxides; the waste gas outlet of the primary reactor is connected with the feed inlet of the primary cyclone separator through a pipeline, and the return material outlet and the slag discharge outlet are respectively through the pipeline It is connected to the secondary reaction furnace; during the roasting process of the primary reaction furnace, the residue in the primary reaction furnace needs to be regularly sampled and tested. The slag discharge port of the primary reactor discharges the residue in the primary reactor into the secondary reactor; 所述的一级旋风分离器，能够对一级反应炉的废气排口排出的废气进行气固分离；一级旋风分离器的固体物料出口通过管道与二级反应炉连接，气体出口则通过管道与文丘里预浓缩器连接；The first-stage cyclone separator can perform gas-solid separation on the waste gas discharged from the waste gas outlet of the first-stage reaction furnace; the solid material outlet of the first-stage cyclone separator is connected to the second-stage reaction furnace through a pipeline, and the gas outlet is connected through a pipeline Connected to a Venturi pre-concentrator; 所述的二级反应炉，能够对炉内物料进行焙烧分解，并通过控制二级反应炉的炉内温度，促使炉内物料中的氟化盐焙烧分解为HF气体和金属氧化物，硝酸盐焙烧分解为金属氧化物、NO和O2；二级反应炉的排渣口通过管道与金属氧化物料仓连接，废气排口通过管道与二级旋风分离器连接；The secondary reaction furnace can roast and decompose the materials in the furnace, and by controlling the temperature in the secondary reactor, the fluoride salts in the materials in the furnace can be roasted and decomposed into HF gas, metal oxides, and nitrates. Roasting is decomposed into metal oxides, NO and O 2 ; the slag discharge port of the secondary reaction furnace is connected to the metal oxide silo through a pipeline, and the exhaust gas discharge port is connected to the secondary cyclone separator through a pipeline; 所述的二级旋风分离器，能够对二级反应炉的废气排口排出的废气做固气分离；二级旋风分离器的下料口通过管道与二级反应炉连接，气体出口则通过管道与文丘里预浓缩器连接；二级旋风分离器分离出的固体部分通过二级旋风分离器上所设置的下料口返回二级反应炉，二级旋风分离器分离出的气体部分则通过二级旋风分离器上所设置的气体出口输出至文丘里预浓缩器。The secondary cyclone separator can separate solid gas from the waste gas discharged from the waste gas outlet of the secondary reaction furnace; the discharge port of the secondary cyclone separator is connected to the secondary reaction furnace through a pipeline, and the gas outlet is connected through a pipeline It is connected with the venturi pre-concentrator; the solid part separated by the secondary cyclone separator is returned to the secondary reactor through the feeding port set on the secondary cyclone separator, and the gas part separated by the secondary cyclone separator is passed through the secondary cyclone separator. The gas outlet set on the stage cyclone is output to the venturi preconcentrator. 2.根据权利要求1所述的一种废混酸两级焙烧再生装置，其特征在于：所述一级反应炉的炉内温度控制在150℃；二级反应炉的炉内温度控制在750℃。2. a kind of waste mixed acid two-stage roasting regeneration device according to claim 1, is characterized in that: the temperature in the furnace of described first-level reaction furnace is controlled at 150 ℃; The temperature in the furnace of two-stage reaction furnace is controlled at 750 ℃ . 3.根据权利要求1所述的一种废混酸两级焙烧再生装置，其特征在于：所述吸收塔的运行温度控制在80℃到85℃之间，且吸收塔通过内部填充吸收环，以吸收文丘里预浓缩器废气排口所排出废气中的HF气体，促使流出吸收塔的废气中HF气体的体积占比不超过10%。3. A kind of waste mixed acid two-stage roasting regeneration device according to claim 1, is characterized in that: the operating temperature of described absorption tower is controlled between 80 ℃ to 85 ℃, and the absorption tower is filled with absorption ring through the inside, to The HF gas in the exhaust gas discharged from the exhaust gas outlet of the Venturi pre-concentrator is absorbed, so that the volume ratio of the HF gas in the exhaust gas flowing out of the absorption tower does not exceed 10%. 4.根据权利要求1所述的一种废混酸两级焙烧再生装置，其特征在于：所述洗涤塔通过内部填充吸收环，以吸收吸收塔所排出的废气中的HF气体，促使流出洗涤塔的废气中，HF气体的体积占比不超过3%。4. a kind of waste mixed acid two-stage roasting regeneration device according to claim 1, is characterized in that: described washing tower is filled with absorption ring inside, to absorb the HF gas in the exhaust gas discharged from absorption tower, impels outflow washing tower In the exhaust gas, the volume of HF gas does not exceed 3%. 5.根据权利要求1所述的一种废混酸两级焙烧再生装置，其特征在于：所述冷却塔输出气体温度不高于50℃。5 . The two-stage roasting and regenerating device for waste mixed acid according to claim 1 , wherein the output gas temperature of the cooling tower is not higher than 50° C. 6 . 6.根据权利要求1所述的一种废混酸两级焙烧再生装置，其特征在于：所述氧化塔能够将所述冷却塔处理过的废气中含有的NO进行氧化生成NO2；所述氧化塔还能够吸收NO2以生成硝酸。6 . The two-stage roasting and regenerating device for waste mixed acid according to claim 1 , wherein the oxidation tower is capable of oxidizing NO contained in the exhaust gas treated by the cooling tower to generate NO 2 ; The tower is also capable of absorbing NO2 to generate nitric acid . 7.一种废混酸两级焙烧再生方法，基于权利要求1所述的废混酸两级焙烧再生装置而实现，其特征在于，包括以下步骤：7. a waste mixed acid two-stage roasting regeneration method, realizes based on the waste mixed acid two-stage roasting regeneration device according to claim 1, is characterized in that, comprises the following steps: 步骤一：将主要成分为硝酸铁的废混酸通过预过滤器进行预过滤，将其中的固体颗粒和不溶解的残留物分离出来；Step 1: the waste mixed acid whose main component is ferric nitrate is pre-filtered through a pre-filter, and the solid particles and insoluble residues therein are separated; 步骤二：过滤后的废混酸进入文丘里预浓缩器中被预热到90℃，使得废混酸中的游离酸和水份被蒸发；Step 2: The filtered waste mixed acid enters the Venturi pre-concentrator and is preheated to 90°C, so that the free acid and water in the waste mixed acid are evaporated; 步骤三：文丘里预浓缩器处理后的废混酸被送入一级反应炉中焙烧分解，通过控制一级反应炉的炉内温度在150℃，使得废混酸中的硝酸盐在炉内受热分解生成NO2、O2和金属氧化物, 在此过程中，一级反应炉排出的废气进入一级旋风分离器进行气固分离处理，一级旋风分离器分离出的固体部分以及一级反应炉排出的固体物料和返料均被导入二级反应炉中进一步焙烧分解，二级反应炉的炉内温度控制在750℃；Step 3: The waste mixed acid treated by the Venturi pre-concentrator is sent to the primary reactor for roasting and decomposing, and the temperature in the primary reactor is controlled at 150°C, so that the nitrate in the waste mixed acid is thermally decomposed in the furnace. NO 2 , O 2 and metal oxides are generated. During this process, the waste gas discharged from the primary reactor enters the primary cyclone for gas-solid separation treatment. The solid part separated by the primary cyclone and the primary reactor The discharged solid materials and returned materials are all introduced into the secondary reactor for further roasting and decomposition, and the temperature in the secondary reactor is controlled at 750°C; 步骤四：二级反应炉中，废混酸所包含的氟化盐经焙烧分解后，产生HF气体和金属氧化物，同时，在一级反应炉中未完成焙烧分解的硝酸盐，在二级反应炉中焙烧分解NO气体、O2以及金属氧化物；二级反应炉的排渣口所排出的废渣直接导入金属氧化物料仓中；二级反应炉排出的废气进入二级旋风分离器进行气固分离，分离下来的固体颗粒返回二级反应炉；Step 4: In the secondary reaction furnace, after the fluoride salt contained in the waste mixed acid is decomposed by roasting, HF gas and metal oxides are generated. At the same time, the nitrate that has not been roasted and decomposed in the primary The NO gas, O 2 and metal oxides are decomposed by roasting in the furnace; the waste slag discharged from the slag discharge port of the secondary reactor is directly introduced into the metal oxide silo; the waste gas discharged from the secondary reactor enters the secondary cyclone for gas-solidification Separation, the separated solid particles are returned to the secondary reactor; 步骤五：经二级旋风分离器处理后的废气以及经一级旋风分离器处理后的废气进入文丘里预浓缩器，并与酸液进行热交换，蒸发废混酸中的游离酸和水份；Step 5: The waste gas treated by the secondary cyclone separator and the waste gas treated by the primary cyclone separator enter the Venturi pre-concentrator, and conduct heat exchange with the acid liquid to evaporate the free acid and water in the waste mixed acid; 步骤六：废气从文丘里预浓缩器进入吸收塔，酸液从顶部喷洒，气体从底部进入，并且内部填充吸收环，其中90%以上的HF气体被吸收，此时废气温度冷却到80°到85°之间，生成的再生酸将供给酸洗线循环使用；Step 6: The exhaust gas enters the absorption tower from the Venturi pre-concentrator, the acid liquid is sprayed from the top, the gas enters from the bottom, and the absorption ring is filled inside, and more than 90% of the HF gas is absorbed. At this time, the temperature of the exhaust gas is cooled to 80° to Between 85°, the generated regenerated acid will be supplied to the pickling line for recycling; 步骤七：废气从吸收塔进入洗涤塔，酸液从顶部喷洒，气体从底部进入，并且内部填充吸收环，其中剩余10%HF气体被吸收，确保97%以上的HF气体被彻底吸收，吸收的再生酸将进入吸收塔吸收HF气体；Step 7: The waste gas enters the washing tower from the absorption tower, the acid liquid is sprayed from the top, the gas enters from the bottom, and the absorption ring is filled inside, and the remaining 10% of the HF gas is absorbed to ensure that more than 97% of the HF gas is completely absorbed. The regenerated acid will enter the absorption tower to absorb HF gas; 步骤八：废气从洗涤塔进入冷却塔，进行冷却，将工业新水从顶部喷洒，气体从底部进入，吸收废气中残留的水蒸气以及NO2，同时吸收的再生酸进入洗涤塔吸收HF气体；Step 8: The exhaust gas enters the cooling tower from the scrubbing tower for cooling, and industrial fresh water is sprayed from the top, and the gas enters from the bottom to absorb the residual water vapor and NO 2 in the exhaust gas, and at the same time, the absorbed regenerated acid enters the scrubbing tower to absorb HF gas; 步骤九：废气从冷却塔进入氧化塔，将工业新水从顶部喷洒，并加入双氧水，气体从底部进入，且内部设置了高密度填充料，将其中含有的少量NO氧化为NO2,同时对NO2进行吸收，回收HNO3，吸收的再生酸溶液，进入洗涤塔吸收HF气体；Step 9: Exhaust gas enters the oxidation tower from the cooling tower, sprays new industrial water from the top, and adds hydrogen peroxide. The gas enters from the bottom, and a high-density filler is set inside to oxidize a small amount of NO contained in it to NO 2 . NO 2 is absorbed, HNO 3 is recovered, and the absorbed regenerated acid solution enters the scrubber to absorb HF gas; 步骤十：废气从氧化塔进入碱洗塔，脱除废气中剩余的酸性气体。Step 10: The waste gas enters the alkali washing tower from the oxidation tower to remove the remaining acid gas in the waste gas.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5980850A (en) * 1995-11-27 1999-11-09 Andritz-Patentverwaltungs-Gesellschaft M.B.H. Process and plant for extraction or recovery of acids from solutions of these acids
EP1521864A1 (en) * 2002-07-10 2005-04-13 UVK Engineering GmbH Method and device for recycling metal pickling baths
CN104831298A (en) * 2015-04-22 2015-08-12 鞍山创新废酸除硅再生工程有限公司 Method and device for regeneration of stainless steel mixed acid pickling waste acid by spray roasting process
CN109553152A (en) * 2018-11-30 2019-04-02 中冶南方工程技术有限公司 A kind of stainless steel mixed acid waste liquor regenerated acid technique
CN109721038A (en) * 2019-02-19 2019-05-07 眉山顺应动力电池材料有限公司 A kind of nitrate pyrolysis recycling method of nitric acid and apparatus system
CN211004576U (en) * 2019-09-27 2020-07-14 眉山顺应动力电池材料有限公司 A device system for preparing nitric acid by thermal decomposition of metal nitrate

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT409373B (en) * 1997-08-06 2002-07-25 Andritz Ag Maschf METHOD AND DEVICE FOR WINNING OR RECOVERY OF ACIDS FROM SOLUTIONS
AT407757B (en) * 1999-03-22 2001-06-25 Andritz Patentverwaltung METHOD FOR RECOVERY OF ACIDS FROM METAL SOLUTIONS OF THESE ACIDS
AT508774B1 (en) * 2010-04-20 2011-04-15 Key Technologies Ind Gmbh METHOD OF GAINING BZW. RECOVERY OF SALPETIC ACID AND FLUIC ACID FROM SOLUTIONS OF STAINLESS STEEL INSERTS

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5980850A (en) * 1995-11-27 1999-11-09 Andritz-Patentverwaltungs-Gesellschaft M.B.H. Process and plant for extraction or recovery of acids from solutions of these acids
EP1521864A1 (en) * 2002-07-10 2005-04-13 UVK Engineering GmbH Method and device for recycling metal pickling baths
CN104831298A (en) * 2015-04-22 2015-08-12 鞍山创新废酸除硅再生工程有限公司 Method and device for regeneration of stainless steel mixed acid pickling waste acid by spray roasting process
CN109553152A (en) * 2018-11-30 2019-04-02 中冶南方工程技术有限公司 A kind of stainless steel mixed acid waste liquor regenerated acid technique
CN109721038A (en) * 2019-02-19 2019-05-07 眉山顺应动力电池材料有限公司 A kind of nitrate pyrolysis recycling method of nitric acid and apparatus system
CN211004576U (en) * 2019-09-27 2020-07-14 眉山顺应动力电池材料有限公司 A device system for preparing nitric acid by thermal decomposition of metal nitrate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Absorption of NOx into nitric acid solution in rotating packed bed";Yu Li et al.;《Chinese journal of chemical engineering》;20100831;第18卷(第2期);第244-248页 *
鞍钢联众不锈钢混酸再生技术改进;徐向东等;《鞍钢技术》;20171212(第06期);第61-64页 *

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