CN111960392A - Mixed acid waste liquid resource recovery system and process - Google Patents
Mixed acid waste liquid resource recovery system and process Download PDFInfo
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- CN111960392A CN111960392A CN202010807942.6A CN202010807942A CN111960392A CN 111960392 A CN111960392 A CN 111960392A CN 202010807942 A CN202010807942 A CN 202010807942A CN 111960392 A CN111960392 A CN 111960392A
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/46—Purification; Separation ; Stabilisation
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- C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
- C01B13/322—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process of elements or compounds in the solid state
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/40—Preparation by absorption of oxides of nitrogen
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- C—CHEMISTRY; METALLURGY
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- C01B21/00—Nitrogen; Compounds thereof
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Abstract
The invention belongs to the technical field of resource disposal and recycling of waste acid liquid, and particularly relates to a resource recovery system and a resource recovery process of mixed acid waste liquid, which comprises a free acid absorber, an acid concentrator, a high-temperature reactor, a pre-concentrator and an absorber which are sequentially connected through a gas transmission pipeline; the material inlet of the free acid adsorber is communicated with the waste acid inlet pipe, the adsorption recovery acid outlet of the free acid adsorber is communicated with the material inlet of the acid concentrator, and the adsorbed waste acid outlet of the free acid adsorber is communicated with the material inlet of the high-temperature reactor; the concentrated and recovered acid outlet of the acid concentrator is communicated with the material inlet of the absorber, and the material outlet of the absorber is communicated with the regenerated acid outlet pipe. The invention provides a method for recycling mixed acid waste liquidThe recovery system and the recovery process respectively recover the free acid and the combined acid, thereby avoiding HNO in the free acid3Enters a high temperature reactor to be decomposed, so that HNO is further improved3The recovery rate is high, and the amount of the reducing agent consumed by tail gas denitration is saved.
Description
Technical Field
The invention belongs to the technical field of resource disposal and recycling of waste acid liquid, and particularly relates to a resource recycling system and process of mixed acid waste liquid.
Background
In the acid pickling process of the metallurgical industry, a large amount of acid liquor is adopted to carry out acid pickling on plates, rods, wires and the like, a large amount of acid pickling waste liquid is generated in the process, the acid pickling waste liquid contains waste acid, heavy metals and the like, the waste acid, the heavy metals and the like are the most important pollutants of metallurgical enterprises, and the waste acid pickling waste liquid is listed in a national dangerous waste list.
The method aims at the problems that acid pickling waste liquid iron and steel enterprises generally adopt lime to carry out neutralization treatment on the iron and steel enterprises to form neutralized sludge precipitates, the treatment cost is very high, a large amount of heavy metal sludge is generated, the environment is greatly influenced, and resources are greatly wasted. Some enterprises also adopt spray roasting as a treatment method, but because both free acid and combined acid in waste acid are fed into a high-temperature reactor, HNO in free acid3Heated to decompose, even after subsequent procedures such as flue gas oxidation and the like, the HNO3The recovery rate is still not high, especially due to HNO in mixed waste acid generated by pickling stainless steel with mixed acid3Compared with HF, the acid exists in a free acid form more, and the waste of resources is more remarkable。
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a resource recovery system and a resource recovery process for mixed acid waste liquid, which can recover free acid, combined acid and metal oxide in the mixed waste acid to the maximum extent, improve the resource recovery rate and reduce the energy consumption.
In order to achieve the aim, the technical scheme of the invention is a resource recovery system for mixed acid waste liquid, which comprises a free acid absorber, an acid concentrator, a high-temperature reactor, a preconcentrator and an absorber which are sequentially connected through a gas transmission pipeline; the material inlet of the free acid adsorber is communicated with a waste acid inlet pipe, the adsorption recovery acid outlet of the free acid adsorber is communicated with the material inlet of the acid concentrator, and the adsorbed waste acid outlet of the free acid adsorber is communicated with the material inlet of the high-temperature reactor; and a concentrated and recovered acid outlet of the acid concentrator is communicated with a material inlet of the absorber, and a material outlet of the absorber is communicated with a regenerated acid outlet pipe.
In one embodiment, the post-adsorption waste acid outlet of the free acid adsorber is communicated with the material inlet of the pre-concentrator, and the material outlet of the pre-concentrator is communicated with the material inlet of the high-temperature reactor.
Further, the gas outlet of the absorber is sequentially connected with a cooler, a nitric acid converter and a denitration reactor through a gas transmission pipeline.
Furthermore, a cooling circulating pump and a first circulating liquid cooler are connected in series on the cooler, and a water outlet of the first circulating liquid cooler is communicated with a material inlet of the absorber and/or a desorption liquid inlet of the free acid absorber.
Furthermore, a scrubber is arranged between the absorber and the cooler, the air outlet of the absorber is communicated with the air inlet of the scrubber, and the air outlet of the scrubber is communicated with the air inlet of the cooler; the water outlet of the first circulating liquid cooler is communicated with the washer through a branch pipe; the scrubber is connected with a scrubbing pump in series, and the water outlet of the scrubbing pump is communicated with the material inlet of the absorber and/or the desorption liquid inlet of the free acid absorber through a branch pipe.
Furthermore, a conversion circulating pump and a second circulating liquid cooler are connected in series on the nitric acid converter, and a water outlet of the second circulating liquid cooler is communicated with the cooler or the scrubber through a branch pipe.
Further, the cleaning liquid outlet of the acid concentrator is communicated with the desorption liquid inlet of the free acid adsorber.
The invention also provides a resource recycling process of the mixed acid waste liquid, which comprises the following steps:
waste acid enters a free acid adsorber to be adsorbed by free acid;
feeding the adsorbed waste acid into a pre-concentrator to exchange heat with gas containing acidic components conveyed by a high-temperature reactor, so that a large amount of water in the waste acid is evaporated, concentrating the waste acid, conveying the obtained concentrated acid liquor into the high-temperature reactor to perform high-temperature pyrohydrolysis reaction to generate acidic components and metal oxides, or directly feeding the adsorbed waste acid into the high-temperature reactor to perform high-temperature pyrohydrolysis reaction to generate acidic components and metal oxides;
recovering the metal oxide in the high-temperature reactor and discharging the metal oxide; meanwhile, gas containing acid components generated in the high-temperature reactor enters a preconcentrator for heat exchange and then enters an absorber;
desorbing the free acid adsorbed in the free acid adsorber by using desorption liquid, feeding the formed adsorption recovered acid into an acid concentrator for concentration, conveying the generated cleaning liquid into the free acid adsorber as desorption liquid, conveying the generated concentrated recovered acid into the absorber as spraying absorption liquid, spraying and absorbing the gas in the absorber, absorbing acid components in the gas to form regenerated acid, and recovering and discharging the regenerated acid.
As an implementation mode, the residual gas after the spraying absorption in the absorber enters a cooler for cooling, the cooled gas enters a nitric acid converter, and NO in the gasXOxidized to HNO3At the same timeOxidizing the absorbed HNO through a branch pipe on a circulating liquid pipeline of the nitric acid converter3The solution is conveyed into a cooler, mixed with circulating liquid in the cooler and conveyed into an absorber through a branch pipe on a circulating liquid pipeline of the cooler to be used as spraying absorption liquid and/or conveyed into a free acid absorber to be used as desorption liquid;
and (3) enabling the gas oxidized and absorbed in the nitric acid converter to enter a denitration reactor for denitration treatment, and discharging the tail gas after denitration treatment to reach the standard.
As another embodiment, the residual gas after the spraying absorption in the absorber enters a scrubber for spraying dust removal, the gas after dust removal enters a cooler for cooling, and NO in the gas in the cooled gas nitric acid converterXOxidized to HNO3Simultaneously oxidizing and absorbing HNO through a branch pipe on a circulating liquid pipeline of the nitric acid converter3Conveying the solution into a washer to be used as absorption tower spray liquid;
circulating liquid in the cooler is conveyed into the washer through a branch pipe on a circulating liquid pipeline of the cooler, is mixed with washing liquid in the washer and then is conveyed into the absorber through the branch pipe on the circulating liquid pipeline of the washer to be used as spraying absorption liquid and/or is conveyed into the free acid absorber to be used as desorption liquid;
and (3) enabling the gas oxidized and absorbed in the nitric acid converter to enter a denitration reactor for denitration treatment, and discharging the tail gas after denitration treatment to reach the standard.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the mixed acid waste liquid recycling system and process provided by the invention, free acid and combined acid are respectively recycled, so that HNO in the free acid is avoided3Enters a high temperature link to be decomposed, and further improves HNO3The recovery rate is high, and the amount of the reducing agent consumed by tail gas denitration is saved;
(2) the invention adopts the circulating liquid and the acid-concentrated cleaning liquid in the system as the desorption liquid of the free acid adsorber, thereby avoiding the consumption of external water resources and avoiding the waste liquid doubling problem of the traditional free acid adsorption method;
(3) the invention adopts the circulating liquid in the system and the concentrated recovered acid of the acid concentration as the acid absorption liquid in the absorber, thereby realizing HNO3The high-efficiency recovery is realized;
(4) the invention can realize maximum HNO control under the condition of adaptive control by adjusting the proportion of the circulating liquid supply absorber and the free acid absorber in the system3And (4) recovering.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a mixed acid waste liquid resource recovery system provided in an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a mixed acid waste liquid resource recovery system provided in the second embodiment of the present invention;
fig. 3 is a schematic structural diagram of a mixed acid waste liquid resource recovery system provided in the third embodiment of the present invention;
in the figure: 1. a free acid adsorber, 2, an acid concentrator, 3, a high-temperature reactor, 4, a pre-concentrator, 5, an absorber, 6, a scrubber, 7, a cooler, 8, a nitric acid converter, 9, a denitration reactor, 10, a concentration pump, 11, an absorber pump, 12, a washing pump, 13, a first circulating liquid cooler, 14, a cooling circulating pump, 15, a second circulating liquid cooler, 16 and a conversion circulating pump.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature; in the description of the present invention, "a plurality" means two or more unless otherwise specified.
Example one
As shown in fig. 1 and fig. 2, the present embodiment provides a resource recycling system for mixed acid waste liquid, which includes a free acid adsorber 1, an acid concentrator 2, and a high temperature reactor 3, a pre-concentrator 4 and an absorber 5 sequentially connected through a gas transmission pipeline; the material inlet of the free acid adsorber 1 is communicated with a waste acid inlet pipe, the adsorption recovery acid outlet of the free acid adsorber 1 is communicated with the material inlet of the acid concentrator 2, the adsorbed waste acid outlet of the free acid adsorber 1 is communicated with the material inlet of the pre-concentrator 4, and the material outlet of the pre-concentrator 4 is communicated with the material inlet of the high-temperature reactor 3; the concentrated and recovered acid outlet of the acid concentrator 2 is communicated with the material inlet of the absorber 5, and the material outlet of the absorber 5 is communicated with the regenerated acid outlet pipe. In the embodiment, free acid in the waste acid is adsorbed by the free acid adsorber 1, so that HNO in the free acid is avoided3Enters a high temperature link to be decomposed, and further improves HNO3Recovery rate; the waste acid containing the chemical compound acid after adsorption is further concentrated by a preconcentrator 4 and then is subjected to secondary concentrationAnd then conveyed into the high-temperature reactor 3 for high-temperature thermal hydrolysis reaction.
Further, a concentration pump 10 is connected in series to the preconcentrator 4, and a branch pipe of the concentration pump 10 is communicated with the material inlet of the high temperature reactor 3, so as to convey the material between the high temperature reactor 3 and the preconcentrator 4, so that the material in the preconcentrator 4 is conveyed into the high temperature reactor 3 after passing through the concentration pump 10.
The acid concentrator 2 in this embodiment may implement acid concentration by using a technical scheme such as reverse osmosis.
Example two
As shown in fig. 3, the present embodiment provides a resource recycling system for mixed acid waste liquid, which includes a free acid adsorber 1, an acid concentrator 2, and a high temperature reactor 3, a preconcentrator 4, and an absorber 5 sequentially connected through a gas transmission pipeline; the material inlet of the free acid adsorber 1 is communicated with a waste acid inlet pipe, the adsorption recovery acid outlet of the free acid adsorber 1 is communicated with the material inlet of the acid concentrator 2, and the adsorbed waste acid outlet of the free acid adsorber 1 is communicated with the material inlet of the high-temperature reactor 3; the concentrated and recovered acid outlet of the acid concentrator 2 is communicated with the material inlet of the absorber 5, and the material outlet of the absorber 5 is communicated with the regenerated acid outlet pipe. In the embodiment, free acid in the waste acid is adsorbed by the free acid adsorber 1, so that HNO in the free acid is avoided3Enters a high temperature link to be decomposed, and further improves HNO3Recovery rate; when the concentration of the adsorbed waste acid containing the chemical compound acid is very high, the adsorbed waste acid is directly conveyed into the high-temperature reactor 3 for high-temperature pyrohydrolysis reaction, so that the problem of waste acid crystallization caused by the fact that the adsorbed waste acid is concentrated by a pre-concentrator is solved.
Furthermore, the absorber 5 is communicated with the pre-concentrator 4 through a material pipeline and is used for supplying the regenerated acid generated in the absorber 5 into the pre-concentrator 4, so that on one hand, water evaporation loss caused by heat exchange with high-temperature flue gas in the pre-concentrator 4 can be supplemented, and on the other hand, acidic components in the regenerated acid are beneficial to dedusting the high-temperature flue gas.
The acid concentrator 2 in this embodiment may implement acid concentration by using a technical scheme such as reverse osmosis.
EXAMPLE III
In the recycling system of the mixed acid waste liquid provided in the first embodiment or the second embodiment, the gas outlet of the absorber 5 is sequentially connected to the cooler 7, the nitric acid converter 8 and the denitration reactor 9 through a gas transmission pipeline, as shown in fig. 1 and 2.
Furthermore, a cooling circulation pump 14 and a first circulation liquid cooler 13 are connected in series on the cooler 7, and a circulation liquid outlet of the first circulation liquid cooler 13 is communicated with a material inlet of the absorber 5 and/or a desorption liquid inlet of the free acid adsorber 1, and is used for providing spraying absorption liquid into the absorber 5 and providing desorption liquid into the free acid adsorber 1. Adopt cooler 7 to cool down the flue gas in this embodiment, make the vapor condensation in the flue gas be water, the condensate that forms is as the source and the replenishment of the circulating fluid in the cooler, need not outside moisturizing, is favorable to practicing thrift the water consumption.
Furthermore, a conversion circulating pump 16 and a second circulating liquid cooler 15 are connected in series on the nitric acid converter 8, and a water outlet of the second circulating liquid cooler 15 is communicated with the cooler 7 through a branch pipe for communicating HNO generated in the nitric acid converter 83The solution is transported into the absorber 5 through the cooler 7, further increasing the HNO3The recovery rate of (1).
Further, the cleaning liquid outlet of the acid concentrator 2 is communicated with the desorption liquid inlet of the free acid adsorber 1, and is used for supplying the cleaning liquid generated by the acid concentrator 2 into the free acid adsorber 1 as desorption liquid.
Further, an absorber pump 11 is connected to the absorber 5 for conveying the regenerated acid generated in the absorber 5 to the outside.
Example four
In the recycling system of the mixed acid waste liquid provided in the first embodiment or the second embodiment, the gas outlet of the absorber 5 is sequentially connected to the scrubber 6, the cooler 7, the nitric acid converter 8 and the denitration reactor 9 through a gas transmission pipeline, as shown in fig. 3.
Further, a washing pump 12 is connected in series to the washing device 6, and a water outlet of the washing pump 12 is communicated with a material inlet of the absorber 5 and/or a desorption liquid inlet of the free acid adsorber 1 through a branch pipe, and is used for providing a spray absorption liquid into the absorber 5 and providing a desorption liquid into the free acid adsorber 1.
Furthermore, a cooling circulation pump 14 and a first circulation liquid cooler 13 are connected in series on the cooler 7, and the water outlet of the first circulation liquid cooler 13 is communicated with the cooler 7 through a branch pipe.
Furthermore, a conversion circulating pump 16 and a second circulating liquid cooler 15 are connected in series on the nitric acid converter 8, and a water outlet of the second circulating liquid cooler 15 is communicated with the scrubber 6 through a branch pipe for communicating HNO generated in the nitric acid converter 83The solution is transported through a scrubber 6 into an absorber 5 for further HNO enhancement3The recovery rate of (1).
Further, the cleaning liquid outlet of the acid concentrator 2 is communicated with the desorption liquid inlet of the free acid adsorber 1, and is used for supplying the cleaning liquid generated by the acid concentrator 2 into the free acid adsorber 1 as desorption liquid.
Further, an absorber pump 11 is connected to the absorber 5 for conveying the regenerated acid generated in the absorber 5 to the outside.
EXAMPLE five
As shown in fig. 1, this embodiment provides a resource recycling process for mixed acid waste liquid, which includes the following steps:
the waste acid enters a free acid adsorber 1 to be adsorbed by free acid, the free acid is adsorbed in the free acid adsorber 1, the adsorbed waste acid containing the combined acid is supplied to a pre-concentrator 4 to exchange heat with gas containing acidic components conveyed by a high-temperature reactor 3, so that a large amount of water in the waste acid is evaporated, the waste acid is concentrated at the same time, and the obtained concentrated acid solution is conveyed to the high-temperature reactor 3 to be subjected to high-temperature thermal hydrolysis reaction to generate acidic components and metal oxides;
recovering the metal oxide in the high-temperature reactor 3 and discharging it; meanwhile, gas containing acid components generated in the high-temperature reactor 3 enters the preconcentrator 4 for heat exchange and then enters the absorber 5;
desorbing the free acid adsorbed in the free acid adsorber 1 by using desorption liquid, feeding the formed adsorption recovered acid into an acid concentrator 2 for concentration, conveying the generated cleaning liquid into the free acid adsorber 1 as desorption liquid, conveying the generated concentrated recovered acid into an absorber 5 as spray absorption liquid, spraying and absorbing the gas in the absorber 5, absorbing the recoverable effective acidic components in the gas to form regenerated acid, and then recovering and discharging the regenerated acid by an absorber pump 11;
the residual gas after the spraying absorption in the absorber 5 enters a cooler 7 for cooling, the cooled gas enters a nitric acid converter 8, and NO in the gasXOxidized to HNO3At the same time, the absorbed HNO is oxidized by a branch pipe on the circulating liquid pipeline of the nitric acid converter 83The solution is conveyed into a cooler 7, mixed with the circulating liquid in the cooler 7 and conveyed into an absorber 5 through a branch pipe on a circulating liquid pipeline of the cooler 7 to be used as spraying absorbing liquid together with concentrated recovered acid and/or conveyed into a free acid absorber 1 to be used as desorption liquid together with cleaning liquid;
and the gas oxidized and absorbed in the nitric acid converter 8 enters a denitration reactor 9 for denitration treatment, and the tail gas after denitration treatment reaches the standard and is discharged.
EXAMPLE six
As shown in fig. 2, this embodiment provides a resource recycling process for mixed acid waste liquid, which includes the following steps:
the waste acid enters a free acid adsorber 1 to be adsorbed by free acid, the free acid is adsorbed in the free acid adsorber 1, the adsorbed waste acid containing the combined acid is supplied to a pre-concentrator 4 to exchange heat with gas containing acidic components conveyed by a high-temperature reactor 3, so that a large amount of water in the waste acid is evaporated, the waste acid is concentrated at the same time, and the obtained concentrated acid solution is conveyed to the high-temperature reactor 3 to be subjected to high-temperature thermal hydrolysis reaction to generate acidic components and metal oxides;
recovering the metal oxide in the high-temperature reactor 3 and discharging it; meanwhile, gas containing acid components generated in the high-temperature reactor 3 enters the preconcentrator 4 for heat exchange and then enters the absorber 5;
desorbing the free acid adsorbed in the free acid adsorber 1 by using desorption liquid, feeding the formed adsorption recovered acid into an acid concentrator 2 for concentration, conveying the generated cleaning liquid into the free acid adsorber 1 as desorption liquid, conveying the generated concentrated recovered acid into an absorber 5 as spray absorption liquid, spraying and absorbing the gas in the absorber 5, absorbing the recoverable effective acidic components in the gas to form regenerated acid, and then recovering and discharging the regenerated acid by an absorber pump 11;
the residual gas after the spraying absorption in the absorber 5 enters the scrubber 6 for spraying dust removal, the gas after dust removal enters the cooler 7 for cooling, the cooled gas is in the nitric acid converter 8, and NO in the gasXOxidized to HNO3At the same time, the absorbed HNO is oxidized by a branch pipe on the circulating liquid pipeline of the nitric acid converter 83The solution is conveyed into a washer 6 to be used as absorption tower spray liquid;
circulating liquid in the cooler 7 is conveyed into the washer 6 through a branch pipe on a circulating liquid pipeline of the cooler 7, is mixed with washing liquid in the washer 6 and then is conveyed into the absorber 5 through a branch pipe on a circulating liquid pipeline of the washer 6 to be used as spraying absorption liquid together with concentrated recovered acid and/or is conveyed into the free acid absorber 1 to be used as desorption liquid together with cleaning liquid;
and the gas oxidized and absorbed in the nitric acid converter 8 enters a denitration reactor 9 for denitration treatment, and the tail gas after denitration treatment reaches the standard and is discharged.
EXAMPLE seven
As shown in fig. 3, this embodiment provides a resource recycling process for mixed acid waste liquid, which includes the following steps:
the waste acid enters a free acid adsorber 1 to be adsorbed by free acid, the free acid is adsorbed in the free acid adsorber 1, and the adsorbed waste acid containing the combined acid is directly fed into a high-temperature reactor 3 to be subjected to high-temperature pyrohydrolysis reaction to generate acid components and metal oxide;
recovering the metal oxide in the high-temperature reactor 3 and discharging it; meanwhile, gas containing acid components generated in the high-temperature reactor 3 enters the preconcentrator 4 for heat exchange and then enters the absorber 5;
desorbing the free acid adsorbed in the free acid adsorber 1 by using desorption liquid, feeding the formed adsorption recovered acid into an acid concentrator 2 for concentration, conveying the generated cleaning liquid into the free acid adsorber 1 as desorption liquid, conveying the generated concentrated recovered acid into an absorber 5 as spray absorption liquid, spraying and absorbing the gas in the absorber 5, absorbing the recoverable effective acidic components in the gas to form regenerated acid, and then recovering and discharging the regenerated acid by an absorber pump 11;
the residual gas after the spraying absorption in the absorber 5 enters a cooler 7 for cooling, the cooled gas enters a nitric acid converter 8, and NO in the gasXOxidized to HNO3At the same time, the absorbed HNO is oxidized by a branch pipe on the circulating liquid pipeline of the nitric acid converter 83The solution is conveyed into a cooler 7, mixed with the circulating liquid in the cooler 7 and conveyed into an absorber 5 through a branch pipe on a circulating liquid pipeline of the cooler 7 to be used as spraying absorption liquid together with concentrated recovered acid and/or conveyed into a free acid absorber 1 to be used as desorption liquid together with cleaning liquid;
and the gas oxidized and absorbed in the nitric acid converter 8 enters a denitration reactor 9 for denitration treatment, and the tail gas after denitration treatment reaches the standard and is discharged.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The utility model provides a mixed acid waste liquid resource recovery system which characterized in that: comprises a free acid absorber, an acid concentrator, a high-temperature reactor, a preconcentrator and an absorber which are sequentially connected through a gas transmission pipeline; the material inlet of the free acid adsorber is communicated with a waste acid inlet pipe, the adsorption recovery acid outlet of the free acid adsorber is communicated with the material inlet of the acid concentrator, and the adsorbed waste acid outlet of the free acid adsorber is communicated with the material inlet of the high-temperature reactor; and a concentrated and recovered acid outlet of the acid concentrator is communicated with a material inlet of the absorber, and a material outlet of the absorber is communicated with a regenerated acid outlet pipe.
2. The resource recycling system for the mixed acid waste liquid as claimed in claim 1, characterized in that: and the adsorbed waste acid outlet of the free acid adsorber is communicated with the material inlet of the preconcentrator, and the material outlet of the preconcentrator is communicated with the material inlet of the high-temperature reactor.
3. The resource recycling system of the mixed acid waste liquid as claimed in claim 1 or 2, characterized in that: and the air outlet of the absorber is sequentially connected with the cooler, the nitric acid converter and the denitration reactor through a gas transmission pipeline.
4. The resource recycling system for the mixed acid waste liquid as claimed in claim 3, characterized in that: and a cooling circulating pump and a first circulating liquid cooler are connected in series on the cooler, and a water outlet of the first circulating liquid cooler is communicated with a material inlet of the absorber and/or a desorption liquid inlet of the free acid absorber.
5. The resource recycling system for the mixed acid waste liquid as claimed in claim 4, characterized in that: a scrubber is arranged between the absorber and the cooler, an air outlet of the absorber is communicated with an air inlet of the scrubber, and an air outlet of the scrubber is communicated with an air inlet of the cooler; the water outlet of the first circulating liquid cooler is communicated with the washer through a branch pipe; the scrubber is connected with a scrubbing pump in series, and the water outlet of the scrubbing pump is communicated with the material inlet of the absorber and/or the desorption liquid inlet of the free acid absorber through a branch pipe.
6. The resource recycling system for the mixed acid waste liquid as claimed in claim 5, characterized in that: a conversion circulating pump and a second circulating liquid cooler are connected in series on the nitric acid converter, and a water outlet of the second circulating liquid cooler is communicated with the cooler or the scrubber through a branch pipe.
7. The resource recycling system for the mixed acid waste liquid as claimed in claim 1, characterized in that: and a cleaning liquid outlet of the acid concentrator is communicated with a desorption liquid inlet of the free acid adsorber.
8. A resource recycling process of mixed acid waste liquid is characterized in that:
waste acid enters a free acid adsorber to be adsorbed by free acid;
feeding the adsorbed waste acid into a pre-concentrator to exchange heat with gas containing acidic components conveyed by a high-temperature reactor, so that a large amount of water in the waste acid is evaporated, concentrating the waste acid, conveying the obtained concentrated acid liquor into the high-temperature reactor to perform high-temperature pyrohydrolysis reaction to generate acidic components and metal oxides, or directly feeding the adsorbed waste acid into the high-temperature reactor to perform high-temperature pyrohydrolysis reaction to generate acidic components and metal oxides;
recovering the metal oxide in the high-temperature reactor and discharging the metal oxide; meanwhile, gas containing acid components generated in the high-temperature reactor enters a preconcentrator for heat exchange and then enters an absorber;
desorbing the free acid adsorbed in the free acid adsorber by using desorption liquid, feeding the formed adsorption recovered acid into an acid concentrator for concentration, conveying the generated cleaning liquid into the free acid adsorber as desorption liquid, conveying the generated concentrated recovered acid into the absorber as spraying absorption liquid, spraying and absorbing the gas in the absorber, absorbing acid components in the gas to form regenerated acid, and recovering and discharging the regenerated acid.
9. The resource recycling process of the mixed acid waste liquid as claimed in claim 8, characterized in that:
the residual gas after the spraying absorption in the absorber enters a coolerCooling, introducing the cooled gas into a nitric acid converter, and adding NO in the gasXOxidized to HNO3Simultaneously oxidizing and absorbing HNO through a branch pipe on a circulating liquid pipeline of the nitric acid converter3The solution is conveyed into a cooler, mixed with circulating liquid in the cooler and conveyed into an absorber through a branch pipe on a circulating liquid pipeline of the cooler to be used as spraying absorption liquid and/or conveyed into a free acid absorber to be used as desorption liquid;
and (3) enabling the gas oxidized and absorbed in the nitric acid converter to enter a denitration reactor for denitration treatment, and discharging the tail gas after denitration treatment to reach the standard.
10. The resource recycling process of the mixed acid waste liquid as claimed in claim 8, characterized in that:
the residual gas after the spraying absorption in the absorber enters a scrubber for spraying dust removal, the gas after dust removal enters a cooler for cooling, and NO in the gas in a cooled gas nitric acid converterXOxidized to HNO3Simultaneously oxidizing and absorbing HNO through a branch pipe on a circulating liquid pipeline of the nitric acid converter3Conveying the solution into a washer to be used as absorption tower spray liquid;
circulating liquid in the cooler is conveyed into the washer through a branch pipe on a circulating liquid pipeline of the cooler, is mixed with washing liquid in the washer and then is conveyed into the absorber through the branch pipe on the circulating liquid pipeline of the washer to be used as spraying absorption liquid and/or is conveyed into the free acid absorber to be used as desorption liquid;
and (3) enabling the gas oxidized and absorbed in the nitric acid converter to enter a denitration reactor for denitration treatment, and discharging the tail gas after denitration treatment to reach the standard.
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