CN109467065B - Stainless steel mixed acid waste liquid regenerated acid equipment - Google Patents
Stainless steel mixed acid waste liquid regenerated acid equipment Download PDFInfo
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- CN109467065B CN109467065B CN201811456886.5A CN201811456886A CN109467065B CN 109467065 B CN109467065 B CN 109467065B CN 201811456886 A CN201811456886 A CN 201811456886A CN 109467065 B CN109467065 B CN 109467065B
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- C01B21/00—Nitrogen; Compounds thereof
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- C01B21/38—Nitric acid
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Abstract
The invention belongs to the technical field of mixed acid waste liquid regeneration, and in particular relates to stainless steel mixed acid waste liquid regeneration acid equipment, which comprises a reaction furnace, an absorption tower and a pre-concentration replacement device for carrying out hydrofluoric acid and nitrate replacement reaction and pre-concentration treatment on mixed acid waste liquid; the mixed acid waste liquid inlet of the pre-concentration displacement device is communicated with the mixed acid waste liquid inlet pipe, the concentrated solution outlet of the pre-concentration displacement device is communicated with the concentrated solution inlet of the reaction furnace, the flue gas outlet of the reaction furnace is communicated with the flue gas inlet of the pre-concentration displacement device, and the flue gas outlet of the pre-concentration displacement device is communicated with the flue gas inlet of the absorption tower; the top of the absorption tower is communicated with the spray water pipe, and the bottom of the absorption tower is communicated with the regenerated acid outlet pipe. The stainless steel mixed acid waste liquid regenerated acid equipment provided by the invention performs pre-concentration treatment and nitric acid replacement reaction in the pre-concentration replacement device, and more HNO is released in the pre-concentration replacement device 3 Improves the recovery rate of nitric acid and reduces NO x And the production of the catalyst reduces the running cost.
Description
Technical Field
The invention belongs to the technical field of mixed acid waste liquid regeneration, and particularly relates to stainless steel mixed acid waste liquid regeneration acid equipment.
Background
The steel and mechanical processing industry generally adopts mixed liquor of nitric acid and hydrofluoric acid to carry out chemical acid washing on stainless steel so as to remove iron scales and chromium-poor layers, and the following reactions generally occur when matrix metals, the chromium-poor layers and metal oxides are dissolved:
Fe + HNO 3 = Fe(NO 3 ) 3 + NO+ 2H 2 O
Fe(NO 3 ) 3 + 3HF→FeF 3 + 3HNO 3
Fe 2 O 3 + 6HNO 3 = 2Fe(NO 3 ) 3 + 3H 2 O
FeO + 4HNO 3 = 2Fe(NO 3 ) 3 + 2H 2 O + NO 2
Fe 3 O 4 + 10HNO 3 = 3Fe(NO 3 ) 3 + 5H 2 O + NO 2
Fe(NO 3 ) 3 +3HF = FeF 3 + 3HNO 3
Me x O y + HNO 3 → Me(NO 3 ) z +H 2 O
Me x O y + HF → MeF z +H 2 O
……
(Me means other metal elements than iron)
The mixed acid waste liquid after acid washing contains a large amount of metal nitrate, metal fluoride and nitric acid and hydrofluoric acid which are not completely reacted. At present, a spray roasting method (or a fluidized bed method) is commonly adopted to regenerate the stainless steel waste mixed acid waste liquid, the regeneration process is to supply fuel gas and combustion air to a reaction furnace, supply a combustion heat source to the reaction furnace through combustion, spray the concentrated mixed acid waste liquid into the reaction furnace, and perform the following decomposition reaction in the high-temperature furnace:
H 2 o (liquid) =h 2 O (gas)
HNO 3 (aqueous solution) =hno 3 (gas); evaporation of nitric acid
HF (aqueous) =hf (gas); evaporation of hydrofluoric acid
2FeF 3 + 3H 2 O = Fe 2 O 3 + 6HF
2Fe(NO 3 ) 3 + 3H 2 O= Fe 2 O 3 + 6HNO 3 ；
MeF x + H 2 O→ Me y O z +hf; fluoride decomposition
Me(NO 3 ) x + H 2 O → Me y O z + HNO 3 The method comprises the steps of carrying out a first treatment on the surface of the Nitrate fractionSolution
2 HNO 3 (air) =no 2 (gas) +H 2 O (gas) +O 2 (gas); nitric acid decomposition
NO 2 = NO+ 1/2O 2
……
(Me means other metal elements than iron)
The gas of the reaction furnace is composed of water vapor, HF and NO x The gas and the combustion waste gas leave from the top of the reaction furnace and enter the pre-concentrator, and the mixed acid waste liquid is sprayed from the top after being sprayed from the bottom of the pre-concentrator, so as to form a loop. In the preconcentrator, the high-temperature reaction furnace gas is directly contacted with the circulating spray liquid of the preconcentrator to perform heat exchange, and part of HNO in the mixed acid waste liquid is 3 (nitric acid) is evaporated into the flue gas in heat exchange with the high temperature flue gas, and the evaporation of part of the acid liquor allows the circulating acid liquor to be concentrated. The flue gas containing nitric acid gas enters an absorption tower after dust is separated, and is absorbed by water to form regenerated acid.
By adopting the process, because the mixed acid waste liquid directly enters the preconcentrator for concentration, part of free nitric acid is evaporated in the preconcentrator, and the waste liquid sprayed into the reaction furnace is mainly metal nitrate and fluoride. Nitrate is decomposed into NO in the roasting process of the reaction furnace x Contains NO x The flue gas is cooled and then oxidized and recycled to part of HNO by an oxidation tower 3 NO is to x The conversion to nitric acid requires a lower temperature, and the conversion efficiency is low and the recovery rate of nitric acid is low. While NO is not recovered x The flue gas needs to be heated and converted into N in a denitration reactor 2 Not only a large amount of cooling water and fuel gas but also a large amount of denitration agent (ammonia water or urea) are consumed, and the running cost is increased.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide stainless steel mixed acid waste liquid regenerating acid equipment which can effectively improve the recovery rate of nitric acid and reduce the consumption of ammonia water or urea serving as a denitration agent.
In order to achieve the above purpose, the technical scheme of the invention is that the stainless steel mixed acid waste liquid regenerating acid equipment comprises a reaction furnace, an absorption tower and a pre-concentration replacement device for carrying out hydrofluoric acid and nitrate replacement reaction and pre-concentration treatment on the mixed acid waste liquid; the mixed acid waste liquid inlet of the pre-concentration replacement device is communicated with a mixed acid waste liquid inlet pipe, the concentrated solution outlet of the pre-concentration replacement device is communicated with the concentrated solution inlet of the reaction furnace, the flue gas outlet of the reaction furnace is communicated with the flue gas inlet of the pre-concentration replacement device, and the flue gas outlet of the pre-concentration replacement device is communicated with the flue gas inlet of the absorption tower; the top of the absorption tower is communicated with the spray water pipe, and the bottom of the absorption tower is communicated with the regenerated acid outlet pipe.
Further, the pre-concentration replacement device comprises a nitric acid replacement tower and a pre-concentrator, wherein a flue gas inlet of the pre-concentrator is communicated with a flue gas outlet of the reaction furnace, a concentrated solution outlet of the pre-concentrator is communicated with a concentrated solution inlet of the reaction furnace, and a flue gas outlet of the nitric acid replacement tower is communicated with a flue gas inlet of the absorption tower.
Further, the bottom of the pre-concentrator is communicated with a spray liquid pipe at the top of the pre-concentrator through a pre-concentrator circulating pump, and the spray end of the spray liquid pipe is positioned below a flue gas inlet of the pre-concentrator.
As an implementation mode, the nitric acid replacement tower and the preconcentrator are of split type structures, and the mixed acid waste liquid inlet pipe is communicated with a mixed acid waste liquid inlet at the top of the nitric acid replacement tower; the mixed acid waste liquid outlet of the nitric acid replacement tower is communicated with the mixed acid waste liquid inlet of the pre-concentrator, and the flue gas outlet of the pre-concentrator is communicated with the flue gas inlet of the nitric acid replacement tower.
As one embodiment, the nitric acid replacement column and the pre-concentrator are in an integrated structure, and the nitric acid replacement column is positioned above the pre-concentrator.
Further, the mixed acid waste liquid inlet pipe is communicated with a mixed acid waste liquid inlet of the pre-concentrator, and a mixed acid waste liquid outlet of the pre-concentrator is communicated with a mixed acid waste liquid inlet at the top of the nitric acid replacement tower.
Further, the mixed acid waste liquid inlet pipe is communicated with a mixed acid waste liquid inlet at the top of the nitric acid replacement tower.
Further, the mixed acid waste liquid outlet of the pre-concentrator is communicated with the mixed acid waste liquid inlet at the top of the nitric acid replacement tower.
Further, the bottom of the reaction furnace is connected with an oxide conveying device.
Further, a flue gas outlet of the absorption tower is sequentially connected with a Venturi dust remover, a spray cooling tower, an oxidation tower and a denitration reactor.
Compared with the prior art, the invention has the beneficial effects that:
(1) The stainless steel mixed acid waste liquid regenerated acid equipment provided by the invention performs pre-concentration treatment and nitric acid replacement reaction in the pre-concentration replacement device, and more HNO is released in the pre-concentration replacement device 3 The recovery rate of nitric acid is improved;
(2) The stainless steel mixed acid waste liquid regenerating acid equipment provided by the invention realizes that hydrofluoric acid and metal nitrate in mixed acid waste liquid undergo a displacement reaction to generate nitric acid and fluoride salt through the added nitric acid displacement tower, and avoids the decomposition of the metal nitrate into NO in the roasting furnace x The load of the denitration device is increased, the denitration agent and the energy consumption are increased, and the operation cost is reduced.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a stainless steel mixed acid waste liquid regenerating acid device provided in a fourth embodiment of the present invention;
fig. 2 is a schematic diagram of a stainless steel mixed acid waste liquid regenerating acid device provided in a fifth embodiment of the present invention;
FIG. 3 is a schematic diagram of a stainless steel mixed acid waste liquid regenerating acid device according to a sixth embodiment of the present invention;
fig. 4 is a schematic diagram of a stainless steel mixed acid waste liquid regenerating acid device provided in embodiment seven of the present invention;
in the figure: 1. the device comprises a reaction furnace, 2, an oxide conveying device, 3, a preconcentrator, 4, a first preconcentrator circulating pump, 5, a second preconcentrator circulating pump, 6, a mixed acid waste liquid flow regulating valve, 7, an absorption tower, 8, a venturi dust remover, 9, a venturi dust remover circulating pump, 10, a spray cooling tower, 11, a spray cooling tower heat exchanger, 12, a spray cooling tower circulating pump, 13, an exhaust gas fan, 14, an oxidation tower, 15, an oxidation tower heat exchanger, 16, an oxidation tower circulating pump, 17, a denitration reactor, 18, a chimney, 19, a nitric acid replacement tower, 20 and a nitric acid replacement tower flow regulating valve.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
As shown in fig. 1-4, the embodiment of the invention provides a stainless steel mixed acid waste liquid regenerating acid process, wherein mixed acid waste liquid enters a pre-concentration replacement device for pre-concentration treatment and nitric acid replacement reaction; HF gas in the high-temperature flue gas is absorbed by water to form hydrofluoric acid, and the hydrofluoric acid and metal nitrate in the mixed acid waste liquid undergo a displacement reaction to generate nitric acid and fluoride salt; the mixed acid waste liquid is directly contacted with high-temperature flue gas generated by high-temperature decomposition in the reaction furnace 1 for heat exchange, hydrofluoric acid and nitric acid in the mixed acid waste liquid are evaporated into the high-temperature flue gas, a concentrated solution of the mixed acid waste liquid is obtained, and solid particles in the high-temperature flue gas are washed and separated; the concentrated solution of the mixed acid waste liquid enters the reaction furnace 1 again for pyrolysis; the high-temperature flue gas after dust separation enters an absorption tower 7, and is leached by water spraying, and HF gas and HNO in the high-temperature flue gas are removed 3 The gas is absorbed by water to form regenerated acid. The stainless steel mixed acid waste liquid regenerating acid process provided by the embodiment releases more HNO in the pre-concentration replacement device 3 The recovery rate of nitric acid is improved; rather than decomposing metal nitrate into NO in a roasting furnace x Then the mixture is cooled down by subsequent cooling, and part of HNO is oxidized and recovered by an oxidation tower 14 3 Thereby reducing NO in the system x The production of the denitration device is reduced, the consumption of the denitration agent and the energy consumption are reduced, and the operation cost is reduced.
The high-temperature flue gas leaving from the top of the reaction furnace 1 enters a pre-concentration displacement device, mixed acid waste liquid enters the pre-concentration displacement device through a mixed acid waste liquid flow regulating valve 6, and the mixed acid waste liquid in the pre-concentration displacement device is pumped out by a pre-concentrator circulating pump 4 and is sprayed in from the top of a pre-concentrator 3 to form a loop. In the pre-concentration replacement device, HF gas is absorbed by water to form hydrofluoric acid, and the hydrofluoric acid and metal nitrate in the mixed acid waste liquid undergo a replacement reaction to generate nitric acid and fluoride salt; the gas of the high-temperature reaction furnace 1 is directly contacted with the mixed acid waste liquid sprayed into the pre-concentration displacement device for heat exchange, and the circulating acid liquid is concentrated due to the evaporation of partial nitric acid and hydrofluoric acid; meanwhile, the solid oxide particles remained in the gas are washed by the mixed acid waste liquid to generate Fe (NO) 3 ) 3 And part of nitric acid in the mixed acid waste liquid is evaporated into the flue gas in heat exchange with the high-temperature flue gas.
In the preconcentration displacement device, the following reactions occur:
HF (gas) →hf (aqueous solution); absorption of hydrofluoric acid
Fe(NO 3 ) 3 +3HF→FeF 3 +3HNO 3 The method comprises the steps of carrying out a first treatment on the surface of the Replacement with nitric acid
HNO 3 (aqueous solution) →HNO 3 (gas); evaporation of nitric acid
Fe 2 O 3 + 6HNO 3 → 2Fe(NO 3 ) 3 + 3H 2 O; (the metal oxides in the flue gas are dissolved)
Me x O y + HNO 3 → Me(NO 3 ) z +H 2 O
The gas after cooling and dust separation enters an absorption tower 7, is sprayed and leached by water, is sent from the bottom of the absorption tower 7, and HF gas and HNO in the flue gas are in a countercurrent process 3 The gas is absorbed by the water to form regenerated acid.
HNO 3 (gas) →HNO 3 (aqueous solution); partial absorption of nitric acid
HF (gas) →hf (aqueous solution); absorption of hydrofluoric acid
Further, the high-temperature flue gas generated by pyrolysis in the reaction furnace 1 contains water vapor, HF gas and HNO 3 Gas, NO x And (3) gas. As shown in fig. 2 to 4, by supplying fuel gas and combustion air to the reaction furnace 1, a combustion heat source is supplied to the reaction furnace 1 by combustion, and concentrated mixed acid waste liquid is injected into the reaction furnace 1 by the reaction furnace feed pump 5, and decomposition reaction occurs in the high-temperature furnace. The temperature of the high-temperature flue gas generated in the reaction furnace is 200-300 ℃, and the high-temperature flue gas enters a pre-concentration replacement device to exchange heat with the mixed acid waste liquid, so that nitric acid in the mixed acid waste liquid is evaporated into the flue gas.
Further, the main component generated by pyrolysis is Fe 2 O 3 The metal oxide solid powder is sent to an oxide bin for storage through an oxide conveying device 2 connected with the bottom of the reaction furnace 1.
Further, the flue gas from the absorption tower 7 enters the venturi dust remover 8 for spray washing and purification, then enters the spray cooling tower 10 for spray cooling, the cooled flue gas enters the oxidation tower 14 for oxidation treatment, then enters the denitration reactor 17 for denitration treatment, and is discharged into the atmosphere after reaching the standard.
The flue gas from the absorber 7 contains combustion tail gas and trace amounts of acid and NO x The polluted water vapor tail gas passes through a Venturi dust remover 8, and is washed and purified by circulating spray liquid pumped out by a Venturi dust remover circulating pump 9, so that the metal oxide dust and the acid content in the polluted water vapor tail gas are reduced; then the flue gas enters a spray cooling tower 10, the circulating spray liquid pumped by a spray cooling tower circulating pump 12 is sprayed and cooled, and the heat of the circulating spray liquid is indirectly connected with external cooling water through a spray cooling tower heat exchanger 11Carrying out heat exchange; the cooled tail gas is pumped into an oxidation tower 14 through an exhaust fan 13 for oxidation, and partial nitric acid is generated in the oxidation tower 14 through the following reaction:
NO 2+ H 2 O = 2HNO 3 + NO
NO+1/2O 2 =NO 2
the generated nitric acid is sprayed and absorbed by the circulating spray liquid pumped by the oxidation tower circulating pump 16, and redundant reaction heat and absorption heat are carried out by the oxidation tower heat exchanger 15 through indirect heat exchange with external cooling water;
then the flue gas after the oxidation reaction enters a denitration reactor 17, and denitration agent (ammonia water or urea) is sprayed to perform denitration treatment, and the chemical reaction is as follows:
NO+ NO 2 + 2NH 3 =2N 2 + 3H 2 O
4NO + 4NH 3 + O 2 =4N 2 + 6H 2 O
2NO 2 + 4NH 3 + O 2 =4N 2 + 6H 2 O
the tail gas reaching the standard after denitration treatment is discharged into the atmosphere through a chimney 18.
Example two
As shown in fig. 2 and fig. 4, the embodiment of the invention provides a stainless steel mixed acid waste liquid regenerating acid process, mixed acid waste liquid enters a nitric acid displacement tower 19 of a pre-concentration displacement device in a spraying manner, HF gas in high-temperature flue gas is absorbed by water to form hydrofluoric acid, the hydrofluoric acid and metal nitrate in the mixed acid waste liquid undergo displacement reaction, generated nitric acid and fluoride salt enter the mixed acid waste liquid, then the mixed acid waste liquid enters a pre-concentrator 3 of the pre-concentration displacement device in a spraying manner and directly contacts with high-temperature flue gas generated in a reaction furnace 1 for heat exchange, nitric acid in the mixed acid waste liquid is evaporated into the high-temperature flue gas, a concentrated solution of the mixed acid waste liquid is obtained, and solid particles in the high-temperature flue gas are washed and separated; the concentrated solution of the mixed acid waste liquid enters the reaction furnace 1 again for pyrolysis; the high-temperature flue gas after dust separation enters an absorption tower 7, and is leached by water spraying, and HF gas and HNO in the high-temperature flue gas are removed 3 Gas is absorbed by waterTo form regenerated acid. In the stainless steel mixed acid waste liquid acid regeneration process provided in the embodiment, a nitric acid replacement tower 19 is added between the preconcentrator 3 and the absorption tower 7 in the preconcentrator 3, and is used for pre-absorbing part of the HF gas regenerated by the reaction furnace 1, and meanwhile, pre-absorbing hydrofluoric acid is used for removing Fe (NO) in the mixed acid waste liquid 3 ) 3 Replacement is carried out to release HNO 3 Further improves HNO in the flue gas before entering the absorption tower 7 3 The concentration of the gas further forms regenerated acid containing nitric acid with higher concentration in the absorption tower 7, and excessive nitrate is prevented from entering the reaction furnace 1 to be roasted to generate NO x Affecting nitric acid recovery, further reducing NO in subsequent spray cooling tower 10 and oxidation tower 14 x Concentration, reduced workload of the oxidation tower 14, further reduced consumption of cooling circulating water, and reduced NO not recovered in the denitration reactor 17 x The concentration further reduces the consumption of the denitration agent (ammonia water or urea) and the consumption of the fuel gas required by the heating medium, thereby reducing the running cost.
In the embodiment, the mixed acid waste liquid is input into a nitric acid displacement tower 19 through a mixed acid waste liquid flow regulating valve 6, is sprayed from the top, and is used for pre-absorbing part of HF gas and displacing HNO 3 The nitric acid displacement column 19 may be a hollow column or an absorption column 7 with packing. The flow rate of the mixed acid waste liquid sprayed into the nitric acid replacement tower 19 can be moderately adjusted according to the condition of the mixed acid waste liquid so as to ensure that the replacement reaction of hydrofluoric acid and nitrate is smoothly carried out. And meanwhile, high-temperature flue gas generated by the reaction furnace 1 leaves from the top of the reaction furnace 1 and enters the pre-concentrator 3, mixed acid waste liquid directly enters the pre-concentrator 3 through a mixed acid waste liquid flow regulating valve 6, and is pumped out by a pre-concentrator circulating pump 4 and is sprayed in through the top of the pre-concentrator 3 to form a loop. The gas of the high-temperature reaction furnace 1 is directly contacted with the circulating spray liquid of the pre-concentrator 3 for heat exchange, and the circulating acid liquid is concentrated due to the evaporation of part of the acid liquid; at the same time, the solid oxide particles remained in the gas are washed by the circulating acid liquid to generate Fe (NO) 3 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the Part of the nitric acid in the mixed acid waste liquid is evaporated into the flue gas in heat exchange with the high-temperature flue gas.
The newly added nitric acid replacement tower 19 can be arranged independently of the pre-concentrator 3 and is connected through a flue gas pipeline; or may be combined with the pre-concentrator 3 and placed above the pre-concentrator 3. In this example, the reaction in the nitric acid displacement column 19 and the preconcentrator 3 was the same as that in the preconcentration displacement apparatus of example one, and the principle was the same.
As an implementation manner, as shown in fig. 4, after the generated nitric acid and fluoride salt enter the mixed acid waste liquid, the mixed acid waste liquid enters the nitric acid replacement tower 19 from a branch pipe connected with an outlet pipeline of the pre-concentrator circulating pump 4, and the branch pipe is provided with a flow regulating valve 20 of the nitric acid replacement tower, and the mixed acid waste liquid enters the nitric acid replacement tower 19 in a spraying manner to carry out a replacement reaction. The flow rate of the mixed acid waste liquid sprayed into the nitric acid replacement tower 19 can be regulated by the mixed acid waste liquid flow regulating valve 6 and the nitric acid replacement tower flow regulating valve 20 together according to the condition of the mixed acid waste liquid so as to ensure that the hydrofluoric acid and nitrate replacement reaction can be smoothly carried out.
Further, in order to ensure smooth pre-absorption, displacement and evaporation, the inlet flue gas temperature of the nitric acid displacement tower 19 is 85-95 ℃ and the outlet flue gas temperature is 65-85 ℃.
The method and principle of treatment of the flue gas exiting through the absorber 7 in this embodiment are the same as those in the first embodiment.
Example III
As shown in fig. 3, the mixed acid waste liquid enters a preconcentrator 3 of the preconcentration displacement device in a spraying manner and is in direct contact with high-temperature flue gas generated in the reaction furnace 1 for heat exchange, nitric acid in the mixed acid waste liquid is evaporated into the high-temperature flue gas, a concentrated solution of the mixed acid waste liquid is obtained, and solid particles in the high-temperature flue gas are washed and separated; the concentrated solution of the mixed acid waste liquid enters the reaction furnace 1 again for pyrolysis; then the high-temperature flue gas enters a nitric acid displacement tower 19 of the pre-concentration displacement device, the sprayed mixed acid waste liquid is washed, HF gas in the high-temperature flue gas is absorbed by water to form hydrofluoric acid, the hydrofluoric acid and metal nitrate in the mixed acid waste liquid undergo displacement reaction, and the generated nitric acid and fluoride salt enter the mixed acid waste liquid and then return to the pre-concentrator 3 for pre-concentration treatment. In the stainless steel mixed acid waste liquid regenerating acid process provided in the embodiment, a nitric acid replacement tower 19 is added between the preconcentrator 3 and the absorption tower 7 in the preconcentrator 3, and is used for pre-absorbing part of HF gas regenerated by the reaction furnace 1, and the same asWhen the pre-absorbed hydrofluoric acid is used for treating Fe (NO) in the mixed acid waste liquid 3 ) 3 Replacement is carried out to release HNO 3 Avoiding excessive nitrate from entering the reaction furnace 1 to be roasted to generate NO x Affecting nitric acid recovery.
In the embodiment, high-temperature flue gas generated by the reaction furnace 1 leaves from the top of the reaction furnace 1 and enters the pre-concentrator 3, and mixed acid waste liquid directly enters the pre-concentrator 3 through a mixed acid waste liquid flow regulating valve 6 and is pumped out by a pre-concentrator circulating pump 4 and is sprayed in from the top of the pre-concentrator 3 to form a loop. The gas of the high-temperature reaction furnace 1 is directly contacted with the circulating spray liquid of the pre-concentrator 3 for heat exchange, and the circulating acid liquid is concentrated due to the evaporation of part of the acid liquid; at the same time, the solid oxide particles remained in the gas are washed by the circulating acid liquid to generate Fe (NO) 3 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the Part of HNO in mixed acid waste liquid 3 (nitric acid) is evaporated into the flue gas in heat exchange with the high temperature flue gas. Meanwhile, the mixed acid waste liquid in the pre-concentrator 3 is connected with a branch pipe from an outlet pipeline of a pre-concentrator circulating pump 4 at the bottom of the pre-concentrator 3 to a nitric acid replacement tower 19, a nitric acid replacement tower flow regulating valve 20 is arranged on the branch pipe, the mixed acid waste liquid is sprayed from the top and used for pre-absorbing part of HF gas and replacing nitric acid, and the nitric acid replacement tower 19 can be a hollow tower or an absorption tower 7 with a filler.
The newly added nitric acid replacement tower 19 can be arranged independently of the pre-concentrator 3 and is connected through a flue gas pipeline; or may be combined with the pre-concentrator 3 and placed above the pre-concentrator 3. In this example, the reaction in the nitric acid displacement column 19 and the preconcentrator 3 was the same as that in the preconcentration displacement apparatus of example one, and the principle was the same.
Further, in order to ensure smooth pre-absorption, displacement and evaporation, the inlet flue gas temperature of the nitric acid displacement tower 19 is 85-95 ℃ and the outlet flue gas temperature is 65-85 ℃. The flow rate sprayed into the nitric acid replacement tower 19 can be moderately adjusted according to the condition of the mixed acid waste liquid through the nitric acid replacement tower flow rate adjusting valve 20 so as to ensure that the hydrofluoric acid and nitrate replacement reaction can be smoothly carried out.
The method and principle of treatment of the flue gas exiting through the absorber 7 in this embodiment are the same as those in the first embodiment.
Example IV
As shown in fig. 2-4, the embodiment provides a stainless steel mixed acid waste liquid regenerating acid device, which comprises a reaction furnace 1, an absorption tower 7 and a pre-concentration replacement device for performing a hydrofluoric acid and nitrate replacement reaction and pre-concentration treatment on the mixed acid waste liquid; the mixed acid waste liquid inlet of the pre-concentration replacement device is communicated with a mixed acid waste liquid inlet pipe, the concentrated solution outlet of the pre-concentration replacement device is communicated with the concentrated solution inlet of the reaction furnace 1, the flue gas outlet of the reaction furnace 1 is communicated with the flue gas inlet of the pre-concentration replacement device, and the flue gas outlet of the pre-concentration replacement device is communicated with the flue gas inlet of the absorption tower 7; the top of the absorption tower 7 is communicated with a spray water pipe, and the bottom of the absorption tower 7 is communicated with a regenerated acid outlet pipe. The stainless steel mixed acid waste liquid regenerated acid equipment provided by the invention performs pre-concentration treatment and nitric acid replacement reaction in the pre-concentration replacement device, and more HNO is released in the pre-concentration replacement device 3 The recovery rate of nitric acid is improved; meanwhile, the metal nitrate in the hydrofluoric acid and mixed acid waste liquid is subjected to displacement reaction to generate nitric acid and fluoride salt, so that the metal nitrate is prevented from being decomposed into NO in the roasting furnace x The load of the denitration device is increased, the denitration agent and the energy consumption are increased, and the operation cost is reduced.
Further, the pre-concentration replacement device comprises a nitric acid replacement tower 19 and a pre-concentrator 3, wherein a flue gas inlet of the pre-concentrator 3 is communicated with a flue gas outlet of the reaction furnace 1, a concentrated solution outlet of the pre-concentrator 3 is communicated with a concentrated solution inlet of the reaction furnace 1, and a flue gas outlet of the nitric acid replacement tower 19 is communicated with a flue gas inlet of the absorption tower 7.
Further, the bottom of the pre-concentrator 3 is communicated with a spray liquid pipe at the top of the pre-concentrator 3 through a pre-concentrator circulating pump 4, and the spray end of the spray liquid pipe is positioned below a flue gas inlet of the pre-concentrator 3, so that the mixed acid waste liquid is fully in direct contact with high-temperature flue gas to perform heat exchange, and more nitric acid and hydrofluoric acid in the mixed acid waste liquid are evaporated into the high-temperature flue gas.
Further, the reaction furnace 1The bottom is connected with an oxide delivery device 2. The main component generated by pyrolysis is Fe 2 O 3 Is sent to an oxide bin for storage through an oxide conveying device 2 at the bottom of the reaction furnace 1.
In this embodiment, the mixed acid waste liquid inlet pipe is provided with a mixed acid waste liquid flow regulating valve 6, and the mixed acid waste liquid flow sprayed into the nitric acid displacement tower 19 is regulated by the mixed acid waste liquid flow regulating valve 6, so as to ensure the smooth proceeding of the displacement reaction of hydrofluoric acid and nitrate.
Further, a flue gas outlet of the absorption tower 7 is sequentially connected with a venturi dust remover 8, a spray cooling tower 10, an oxidation tower 14 and a denitration reactor 17, and the flue gas is discharged after being denitrated to reach the standard.
As an implementation manner, the flue gas outlet of the absorption tower 7 is communicated with the flue gas inlet of the venturi dust collector 8, the liquid outlet at the bottom of the venturi dust collector 8 is communicated with the spray liquid pipe at the top of the venturi dust collector 8 through the venturi dust collector circulating pump 9, the spray end of the spray liquid pipe is positioned below the flue gas inlet of the venturi dust collector 8, and the flue gas outlet of the venturi dust collector 8 is communicated with the flue gas inlet. Circulating liquid in the venturi dust collector 8 enters the top of the venturi dust collector 8 in a spraying mode through a venturi dust collector circulating pump 9, is in direct contact with flue gas entering through a flue gas inlet of the venturi dust collector 8, sprays and removes dust, removes solid particles in the flue gas, and the flue gas subjected to dust removal enters a spray cooling tower 10.
As an implementation manner, the liquid outlet of the spray cooling tower 10 is communicated with a spray liquid pipe at the top of the spray cooling tower 10 through a circulation pipeline of the spray cooling tower 10, the spray end of the spray liquid pipe is positioned below a flue gas inlet of the spray cooling tower 10, and the flue gas outlet of the spray cooling tower 10 is communicated with a flue gas inlet of the oxidation tower 14. The spray cooling tower 10 circulating pipeline is provided with a spray cooling tower circulating pump 12 and a spray cooling tower heat exchanger 11, and cooling water of the spray cooling tower heat exchanger 11 is fed in and discharged out from top to bottom. The circulating liquid in the spray cooling tower 10 is pumped out by the Venturi dust collector circulating pump 9 and then subjected to heat exchange by the spray cooling tower heat exchanger 11, then enters the top of the spray cooling tower 10 in a spray mode, directly contacts with the flue gas entering from the flue gas inlet of the spray cooling tower 10, performs spray cooling, and the cooled flue gas enters the oxidation tower 14.
As an implementation manner, the liquid outlet of the oxidation tower 14 is communicated with a spray liquid pipe at the top of the oxidation tower 14 through a circulation pipeline of the oxidation tower 14, the spray end of the spray liquid pipe is positioned above the flue gas inlet of the oxidation tower 14, and the flue gas outlet of the oxidation tower 14 is communicated with the flue gas inlet of the denitration reactor 17. An oxidation tower circulating pump 16 and an oxidation tower heat exchanger 15 are arranged on a circulating pipeline of the oxidation tower 14, and cooling water of the oxidation tower heat exchanger 15 is fed in and discharged out from top to bottom. The circulating liquid in the oxidation tower 14 is pumped out by the Venturi dust collector circulating pump 9 and then subjected to heat exchange by the oxidation tower heat exchanger 15, then enters the top of the oxidation tower 14 in a spraying mode, directly contacts with the flue gas entering from the flue gas inlet of the oxidation tower 14, is subjected to spraying cooling, and enters the denitration reactor 17 for denitration after cooling.
As an implementation manner, a flue gas outlet of the denitration reactor 17 is communicated with a chimney 18, and the denitration reactor 17 is provided with a denitration agent inlet; the flue gas entering the denitration reactor 17 reacts with a denitration agent (ammonia water or urea) to generate nitrogen and water, and the flue gas reaching the standard is discharged into the atmosphere through a chimney 18.
The reaction principle of this example is the same as that of example one.
Example five
As shown in fig. 2, the embodiment provides a stainless steel mixed acid waste liquid regenerating acid device, which comprises a reaction furnace 1, an absorption tower 7, a nitric acid replacement tower 19 and a preconcentrator 3, wherein the nitric acid replacement tower 19 and the preconcentrator 3 are of a split structure, and a mixed acid waste liquid inlet pipe is communicated with a mixed acid waste liquid inlet at the top of the nitric acid replacement tower 19; the mixed acid waste liquid outlet of the nitric acid replacement tower 19 is communicated with the mixed acid waste liquid inlet of the pre-concentrator 3, and the flue gas outlet of the pre-concentrator 3 is communicated with the flue gas inlet of the nitric acid replacement tower 19; the flue gas inlet of the preconcentrator 3 is communicated with the flue gas outlet of the reaction furnace 1, the concentrated solution outlet of the preconcentrator 3 is communicated with the concentrated solution inlet of the reaction furnace 1, and the flue gas outlet of the nitric acid replacement tower 19 is communicated with the flue gas inlet of the absorption tower 7; the top of the absorption tower 7 is sprayed withThe water drenching pipe is communicated, and the bottom of the absorption tower 7 is communicated with a regenerated acid outlet pipe. In the stainless steel mixed acid waste liquid acid regenerating device provided in this embodiment, a nitric acid replacement tower 19 is added between the preconcentrator 3 and the absorption tower 7 in the preconcentrator 3, and is used for pre-absorbing part of the HF gas regenerated by the reaction furnace 1, and meanwhile, pre-absorbing hydrofluoric acid is used for absorbing Fe (NO 3 ) 3 Replacement is carried out to release HNO 3 Further improves HNO in the flue gas before entering the absorption tower 7 3 The concentration of the gas further forms regenerated acid containing nitric acid with higher concentration in the absorption tower 7, and excessive nitrate is prevented from entering the reaction furnace 1 to be roasted to generate NO x Affecting the recovery rate of nitric acid and further reducing the running cost.
The transport of the pyrolysis produced metal oxide, the pre-concentration and the subsequent treatment of the flue gas from the absorber 7 in this example are all the same as in example four. The reaction principle of this example is the same as that of the example.
Example six
As shown in fig. 3, the embodiment provides a stainless steel mixed acid waste liquid regenerating acid device, which comprises a reaction furnace 1, an absorption tower 7, a nitric acid replacement tower 19 and a preconcentrator 3, wherein the nitric acid replacement tower 19 and the preconcentrator 3 are in an integrated structure, the nitric acid replacement tower 19 is positioned above the preconcentrator 3, a mixed acid waste liquid inlet pipe is communicated with a mixed acid waste liquid inlet of the preconcentrator 3, a mixed acid waste liquid outlet of the preconcentrator 3 is communicated with a mixed acid waste liquid inlet at the top of the nitric acid replacement tower 19, a flue gas inlet of the preconcentrator 3 is communicated with a flue gas outlet of the reaction furnace 1, a concentrated solution outlet of the preconcentrator 3 is communicated with a concentrated solution inlet of the reaction furnace 1, and a flue gas outlet of the nitric acid replacement tower 19 is communicated with a flue gas inlet of the absorption tower 7; the top of the absorption tower 7 is communicated with a spray water pipe, and the bottom of the absorption tower 7 is communicated with a regenerated acid outlet pipe. In the stainless steel mixed acid waste liquid acid regenerating device provided in this embodiment, a nitric acid replacement tower 19 is added between the preconcentrator 3 and the absorption tower 7 in the preconcentrator 3, and is used for pre-absorbing part of the HF gas regenerated by the reaction furnace 1, and meanwhile, pre-absorbing hydrofluoric acid is used for absorbing Fe (NO 3 ) 3 Substitution is carried out to release HNO 3 Further improves HNO in the flue gas before entering the absorption tower 7 3 The concentration of the gas; meanwhile, the nitric acid replacement tower 19 and the preconcentrator 3 are of an integrated structure, the integration level of the whole equipment is high, and the occupied area is saved. The flue gas in the preconcentrator 3 enters a nitric acid replacement tower 19, and the mixed acid waste liquid in the nitric acid replacement tower 19 enters the preconcentrator 3.
Further, a flow regulating valve 20 of the nitric acid replacement tower is arranged on a pipeline, which is communicated with the mixed acid waste liquid outlet of the pre-concentrator 3 and the mixed acid waste liquid inlet at the top of the nitric acid replacement tower 19. The flow rate of the mixed acid waste liquid sprayed into the nitric acid displacement tower 19 is regulated by the flow regulating valve 20 of the nitric acid displacement tower and the flow regulating valve 6 of the mixed acid waste liquid.
The transport of the pyrolysis produced metal oxide, the pre-concentration and the subsequent treatment of the flue gas from the absorber 7 in this example are all the same as in example four. The reaction principle of this example is the same as that of the example.
Example seven
As shown in fig. 4, the embodiment provides a stainless steel mixed acid waste liquid regenerating acid device, which comprises a reaction furnace 1, an absorption tower 7, a nitric acid replacement tower 19 and a preconcentrator 3, wherein the nitric acid replacement tower 19 and the preconcentrator 3 are in an integrated structure, the nitric acid replacement tower 19 is positioned above the preconcentrator 3, a mixed acid waste liquid inlet pipe is communicated with a mixed acid waste liquid inlet at the top of the nitric acid replacement tower 19, a flue gas inlet of the preconcentrator 3 is communicated with a flue gas outlet of the reaction furnace 1, a concentrated solution outlet of the preconcentrator 3 is communicated with a concentrated solution inlet of the reaction furnace 1, and a flue gas outlet of the nitric acid replacement tower 19 is communicated with a flue gas inlet of the absorption tower 7; the top of the absorption tower 7 is communicated with a spray water pipe, and the bottom of the absorption tower 7 is communicated with a regenerated acid outlet pipe. In the stainless steel mixed acid waste liquid regenerating acid equipment provided in the embodiment, a nitric acid replacement tower 19 is added between the preconcentrator 3 and the absorption tower 7 in the preconcentrator 3, and the preabsorbed hydrofluoric acid is utilized to treat Fe (NO) in the mixed acid waste liquid 3 ) 3 Replacement to release HNO 3 The recovery rate of nitric acid is improved; meanwhile, the nitric acid replacement tower 19 and the preconcentrator 3 are of an integrated structure, the integration level of the whole equipment is high, and the occupied area is saved.The flue gas in the preconcentrator 3 enters a nitric acid replacement tower 19, and the mixed acid waste liquid in the nitric acid replacement tower 19 enters the preconcentrator 3.
Further, the mixed acid waste liquid outlet of the preconcentrator 3 is communicated with the mixed acid waste liquid inlet at the top of the nitric acid replacement tower 19, and a flow regulating valve 20 of the nitric acid replacement tower is arranged on a pipeline for communicating the mixed acid waste liquid outlet and the mixed acid waste liquid inlet. The flow rate of the mixed acid waste liquid sprayed into the nitric acid displacement tower 19 is regulated by the flow regulating valve 20 of the nitric acid displacement tower and the flow regulating valve 6 of the mixed acid waste liquid.
The transport of the pyrolysis produced metal oxide, the pre-concentration and the subsequent treatment of the flue gas from the absorber 7 in this example are all the same as in example four. The reaction principle of this example is the same as that of the example.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. The utility model provides a stainless steel mixes sour waste liquid regeneration acid equipment which characterized in that: comprises a reaction furnace, an absorption tower and a pre-concentration replacement device for carrying out a hydrofluoric acid and nitrate replacement reaction and pre-concentration treatment on mixed acid waste liquid; the mixed acid waste liquid inlet of the pre-concentration replacement device is communicated with a mixed acid waste liquid inlet pipe, the concentrated solution outlet of the pre-concentration replacement device is communicated with the concentrated solution inlet of the reaction furnace, the flue gas outlet of the reaction furnace is communicated with the flue gas inlet of the pre-concentration replacement device, and the flue gas outlet of the pre-concentration replacement device is communicated with the flue gas inlet of the absorption tower; the top of the absorption tower is communicated with a spray water pipe, and the bottom of the absorption tower is communicated with a regenerated acid outlet pipe; the pre-concentration replacement device comprises a nitric acid replacement tower and a pre-concentrator, wherein a flue gas inlet of the pre-concentrator is communicated with a flue gas outlet of the reaction furnace, a concentrated solution outlet of the pre-concentrator is communicated with a concentrated solution inlet of the reaction furnace, and a flue gas outlet of the nitric acid replacement tower is communicated with a flue gas inlet of the absorption tower.
2. A stainless steel mixed acid waste liquid regenerating acid apparatus as defined in claim 1, wherein: the bottom of the pre-concentrator is communicated with a spray liquid pipe at the top of the pre-concentrator through a circulating pump of the pre-concentrator, and the spray end of the spray liquid pipe is positioned below a flue gas inlet of the pre-concentrator.
3. A stainless steel mixed acid waste liquid regenerating acid apparatus as defined in claim 1, wherein: the nitric acid replacement tower and the preconcentrator are of split type structures, and the mixed acid waste liquid inlet pipe is communicated with a mixed acid waste liquid inlet at the top of the nitric acid replacement tower; the mixed acid waste liquid outlet of the nitric acid replacement tower is communicated with the mixed acid waste liquid inlet of the pre-concentrator, and the flue gas outlet of the pre-concentrator is communicated with the flue gas inlet of the nitric acid replacement tower.
4. A stainless steel mixed acid waste liquid regenerating acid apparatus as defined in claim 1, wherein: the nitric acid replacement tower and the pre-concentrator are of an integrated structure, and the nitric acid replacement tower is positioned above the pre-concentrator.
5. A stainless steel mixed acid waste liquid regenerating acid apparatus as defined in claim 4, wherein: the mixed acid waste liquid inlet pipe is communicated with the mixed acid waste liquid inlet of the pre-concentrator, and the mixed acid waste liquid outlet of the pre-concentrator is communicated with the mixed acid waste liquid inlet at the top of the nitric acid replacement tower.
6. A stainless steel mixed acid waste liquid regenerating acid apparatus as defined in claim 4, wherein: and the mixed acid waste liquid inlet pipe is communicated with a mixed acid waste liquid inlet at the top of the nitric acid replacement tower.
7. The stainless steel mixed acid waste liquid recycling acid equipment as set forth in claim 6, wherein: and the mixed acid waste liquid outlet of the preconcentrator is communicated with the mixed acid waste liquid inlet at the top of the nitric acid replacement tower.
8. A stainless steel mixed acid waste liquid regenerating acid apparatus as defined in claim 1, wherein: the bottom of the reaction furnace is connected with an oxide conveying device.
9. A stainless steel mixed acid waste liquid regenerating acid apparatus as defined in claim 1, wherein: the flue gas outlet of the absorption tower is sequentially connected with a Venturi dust remover, a spray cooling tower, an oxidation tower and a denitration reactor.
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| CN201811456886.5A CN109467065B (en) | 2018-11-30 | 2018-11-30 | Stainless steel mixed acid waste liquid regenerated acid equipment |
| PCT/CN2019/106444 WO2020108029A1 (en) | 2018-11-30 | 2019-09-18 | Apparatus for regenerating acid from acid-containing waste liquor of stainless steel |
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| CN201811456886.5A CN109467065B (en) | 2018-11-30 | 2018-11-30 | Stainless steel mixed acid waste liquid regenerated acid equipment |
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| CN109467065B true CN109467065B (en) | 2023-09-19 |
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| CN109467065B (en) * | 2018-11-30 | 2023-09-19 | 中冶南方工程技术有限公司 | Stainless steel mixed acid waste liquid regenerated acid equipment |
| CN109553152B (en) * | 2018-11-30 | 2021-09-10 | 中冶南方工程技术有限公司 | Stainless steel mixed acid waste liquid regenerated acid process |
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| CN109553152B (en) * | 2018-11-30 | 2021-09-10 | 中冶南方工程技术有限公司 | Stainless steel mixed acid waste liquid regenerated acid process |
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| CN109467065A (en) | 2019-03-15 |
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