CN111663044B - Acidic sludge and waste acid recycling device and process - Google Patents

Acidic sludge and waste acid recycling device and process Download PDF

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Publication number
CN111663044B
CN111663044B CN202010407490.2A CN202010407490A CN111663044B CN 111663044 B CN111663044 B CN 111663044B CN 202010407490 A CN202010407490 A CN 202010407490A CN 111663044 B CN111663044 B CN 111663044B
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acid
sludge
gas
temperature
scrubber
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CN111663044A (en
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高俊峰
赵金标
林清鹏
丁煜
赵海
王军
常勤学
郭金仓
吴宗应
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Wisdri Engineering and Research Incorporation Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456Removing acid components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/54Nitrogen compounds
    • B01D53/56Nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14Methods for preparing oxides or hydroxides in general
    • C01B13/32Methods 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
    • C01B13/322Methods 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/20Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/38Nitric acid
    • C01B21/40Preparation by absorption of oxides of nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/13Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • Oil, Petroleum & Natural Gas (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

The invention relates to an acidic sludge and waste acid recycling device which comprises a sludge evaporator, a high-temperature reactor, a negative pressure evaporation concentrator, an absorber and a scrubber which are connected in sequence, wherein the high-temperature reactor is connected with the sludge evaporator; the sludge evaporator is sequentially connected with a grinder, a molecular sieve filter, a solid-liquid mixer and a high-temperature reactor; the negative pressure evaporation concentrator is communicated with the high-temperature reactor; a heat source H is connected to the gas pipeline between the scrubber and the sludge evaporator; by adopting the recovery process of the recovery device, the waste acid and the gas conveyed by the high-temperature reactor are subjected to heat exchange in the negative pressure evaporation concentrator, so that free acid in the waste acid is evaporated and is absorbed with recoverable acid components in the gas conveyed by the high-temperature reactor in the absorber to form regenerated acid, and the waste heat of the tail gas of the scrubber and the heat source H are utilized to evaporate the acid sludge, and then the acid sludge is ground and mixed with solid and liquid to form slurry, and the slurry is conveyed into the high-temperature reactor to react. The invention can simultaneously recycle the free acid, the compound acid and the metal oxide in the waste acid and the acid sludge, and can also reduce the energy consumption by utilizing the waste heat.

Description

Acidic sludge and waste acid recycling device and process
Technical Field
The invention belongs to the technical field of recycling treatment and recycling of acid sludge and waste acid, and particularly relates to a recycling recovery device of acid sludge and waste acid and a recycling recovery process of acid sludge and waste acid by adopting the recycling device.
Background
In the pickling process of the metallurgical industry, a large amount of acid liquor is adopted to pickle plates, bars, wires and the like, a large amount of pickling waste liquor is generated in the process, and a large amount of acid sludge consisting of oxidized iron scales, settled metal acid compounds and the like on the surface of a base material is also generated. The pickling waste liquid and the acid sludge contain waste acid, heavy metals and the like, which are the most important pollutants of metallurgical enterprises and are listed in a dangerous waste list.
Aiming at the pickling waste liquid and the acid sludge, the iron and steel enterprises usually adopt lime to neutralize the pickling waste liquid and the acid sludge to form a neutralized sludge precipitate, the treatment cost is high, a larger amount of heavy metal sludge is generated, the environmental impact is larger, and the resource is wasted greatly.
Some enterprises filter-press the acid sludge into sludge cakes by adopting a filter press, and then intensively convey the sludge cakes into a metallurgical smelting system to be used as a treatment means for mixing and adding raw materials, iron ore and the like. However, because the acid sludge contains a large amount of acid components, severe corrosion is caused to smelting equipment, and equipment damage often results in production influence.
In the industrial preparation process of various products, the generated acid waste liquid containing the nitric acid with extremely strong corrosiveness causes serious pollution to the environment if not reasonably treated, and meanwhile, the acid washing cost is increased due to the fact that the waste acid containing the nitric acid is discharged in a large amount. In the existing waste acid regeneration industry containing free nitric acid, high-temperature thermal hydrolysis is one of the common methods, and a heat source is needed to be used in a tail gas denitration process section of the high-temperature thermal hydrolysis process to meet the temperature requirement of tail gas denitration, but the heat of the part of tail gas which is subjected to heating treatment and reaches the standard is directly lost if the tail gas is directly discharged.
Therefore, it is necessary to design a device and a process for recycling the acid sludge and the waste acid to overcome the above problems.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an acidic sludge and waste acid recycling device and process, which can simultaneously carry out integrated resource recycling treatment on the acidic sludge and waste acid.
In order to achieve the aim, the technical scheme of the invention is that the device for recycling the acid sludge and the waste acid comprises a sludge evaporator, and a high-temperature reactor, a negative pressure evaporation concentrator, an absorber and a scrubber which are connected in sequence through a gas pipeline; the material inlet of the sludge evaporator is communicated with the acid sludge inlet pipe, and the material outlet of the sludge evaporator is connected with the grinder, the molecular sieve filter, the solid-liquid mixer and the high-temperature reactor through material pipelines in sequence; the material inlet of the negative pressure evaporation concentrator is communicated with the waste acid inlet pipe, and the material outlet of the negative pressure evaporation concentrator is communicated with the material inlet of the high-temperature reactor; the material outlet of the absorber is communicated with a regenerated acid outlet pipe; the exhaust port of the scrubber is communicated with the heat source gas inlet of the sludge evaporator through a gas pipeline, and a heat source H is connected to the gas pipeline between the scrubber and the sludge evaporator.
As one of the embodiments, the exhaust port of the scrubber is connected with the nitric acid converter and the denitration reactor sequentially through a gas pipeline, and the exhaust port of the denitration reactor is communicated with the heat source gas inlet of the sludge evaporator through the gas pipeline; and the heat source H is connected with the denitration reactor.
Further, the acid-containing steam outlet of the sludge evaporator is communicated with the gas pipeline between the negative pressure evaporation concentrator and the absorber through the gas pipeline, or the acid-containing steam outlet of the sludge evaporator is communicated with the gas pipeline between the absorber and the scrubber through the gas pipeline.
Further, the sludge evaporator is an indirect heat exchange device.
Further, the high-temperature reactor comprises an upper high-temperature reaction layer and a lower high-temperature reaction layer which is in material communication with the upper high-temperature reaction layer, and a material outlet of the solid-liquid mixer and a material outlet of the negative pressure evaporation concentrator are both communicated with a material inlet on the upper high-temperature reaction layer.
Further, a washing pump is connected in series with the scrubber, and the washing pump is communicated with the absorber through a branch pipe.
Further, a concentration pump is connected in series on the negative pressure evaporation concentrator, and the concentration pump is communicated with a material inlet of the high-temperature reactor through a branch pipe.
Further, the nitric acid converter is connected with a conversion circulating pump and a circulating liquid cooler in series, and the circulating liquid cooler is communicated with the scrubber through a branch pipe.
The invention also provides an acid sludge and waste acid recycling recovery process adopting the recovery device, which comprises the following specific steps:
introducing the waste acid into the negative pressure evaporation concentrator, and carrying out heat exchange on the waste acid and the gas containing the acidic components conveyed by the high-temperature reactor under the action of negative pressure to evaporate a large amount of water and free acid in the waste acid, and concentrating the waste acid at the same time, so that the obtained concentrated acid liquor is conveyed into the high-temperature reactor for carrying out high-temperature thermal hydrolysis reaction to generate the acidic components and the metal oxides;
the acid sludge is fed into the sludge evaporator, the waste heat of tail gas discharged by the scrubber and a heat source H are adopted to evaporate the acid sludge, the dried acid sludge is conveyed into the grinder to be ground into particle powder, the particle powder is filtered by the molecular sieve filter and then is fed into the solid-liquid mixer, the solid-liquid mixer is mixed with configuration liquid to form sludge slurry, and the sludge slurry is conveyed into the high-temperature reactor to be subjected to high-temperature thermal hydrolysis reaction to generate acid components and metal oxides;
recovering the metal oxide in the high temperature reactor and discharging the metal oxide; meanwhile, the free acid generated in the negative pressure evaporation concentrator is mixed with the gas containing acidic components conveyed by the high-temperature reactor, the mixed gas is conveyed into the absorber through a gas conveying pipeline, the acidic components in the gas are absorbed by water to form regenerated acid through water spraying and leaching, and the regenerated acid is recovered and discharged;
and the residual gas in the absorber is conveyed into the scrubber through a gas pipeline to remove dust, and tail gas discharged from the scrubber is heated by the heat source H and then conveyed to the sludge evaporator to heat and discharge the acid sludge.
The invention also provides an acid sludge and waste acid integrated recovery process adopting the recovery device, which comprises the following specific steps:
introducing the waste acid into the negative pressure evaporation concentrator, and carrying out heat exchange on the waste acid and the gas containing the acidic components conveyed by the high-temperature reactor under the action of negative pressure to evaporate a large amount of water and free acid in the waste acid, and concentrating the waste acid at the same time, so that the obtained concentrated acid liquor is conveyed into the high-temperature reactor for carrying out high-temperature thermal hydrolysis reaction to generate the acidic components and the metal oxides;
the acid sludge is fed into the sludge evaporator, the acid sludge is evaporated to dryness by adopting the waste heat of tail gas of the denitration reaction in the denitration reactor, the dried acid sludge is conveyed into the grinder to be ground into particle powder, filtered by the molecular sieve filter and then fed into the solid-liquid mixer, the solid-liquid mixer is mixed with the preparation liquid to form sludge slurry, and the sludge slurry is conveyed into the high-temperature reactor to be subjected to high-temperature thermal hydrolysis reaction to generate acid components and metal oxides;
recovering the metal oxide in the high temperature reactor and discharging the metal oxide; meanwhile, the free acid generated in the negative pressure evaporation concentrator is mixed with the gas containing acidic components conveyed by the high-temperature reactor, the mixed gas is conveyed into the absorber through a gas conveying pipeline, the acidic components in the gas are absorbed by water to form regenerated acid through water spraying and leaching, and the regenerated acid is recovered and discharged;
the residual gas in the absorber is conveyed into the scrubber through a gas pipeline to remove dust, and tail gas discharged by the scrubber enters the nitric acid converter to remove NO in the gas x Oxidation to HNO 3 HNO absorbed by oxidation 3 Delivering the solution to the scrubber to carry HNO in the scrubber 3 The solution is conveyed into the absorber to be used as spray absorption liquid for recycling regenerated acid;
and heating the denitration reactor by adopting the heat source H, simultaneously conveying tail gas discharged by the nitric acid converter into the denitration reactor for denitration treatment, and conveying high-temperature tail gas which can reach the standard after denitration treatment to the sludge evaporator for heating and then discharging acid sludge.
Compared with the prior art, the invention has the following beneficial effects:
(1) The acidic sludge and waste acid recycling device and the process provided by the invention can be used for recycling the acid and the metal oxide in the acidic sludge and the waste acid at the same time, so that the resource recycling is increased;
(2) The acidic sludge and waste acid recycling device and the process provided by the invention can be used for intensively treating the tail gas of the acidic sludge and the waste acid and intensively recycling the acidic components and the metal oxide products;
(3) According to the invention, the temperature area division in the high-temperature reactor is adjusted according to the addition amount of the acid sludge and the waste acid, so that high reaction efficiency is realized and the treatment is ensured to be complete;
(4) The invention reduces the temperature of the gas in the nitric acid converter, causes a large amount of water in the gas to be condensed into the circulating liquid, supplements the circulating liquid, can automatically complete the treatment of waste acid without additional water supplementing, and is beneficial to the discharge of the gas after reaching the standard;
(5) The invention heats and evaporates the acid sludge by utilizing the waste heat of the tail gas of the scrubber or the reaction waste heat of the denitration reactor, and the like, thereby being beneficial to reducing the energy consumption of the system;
(6) According to the invention, the water and free acid in the acid sludge are removed by evaporation, and the sludge is ground, so that the corrosiveness of the sludge to the grinder can be effectively reduced;
(7) The invention adopts a solid-liquid mixing mode, and feeds materials through equipment such as a slurry feeding pump, a slurry spray gun and the like, thereby being beneficial to simplifying the feeding mode of sludge.
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 an acidic sludge and waste acid recycling device according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of an apparatus for recycling acid sludge and waste acid according to a second embodiment of the present invention;
in the figure: 1. the device comprises a sludge evaporator, 2, a grinder, 3, a molecular sieve filter, 4, a solid-liquid mixer, 5, a high-temperature reactor, 6, a negative pressure evaporation concentrator, 7, an absorber, 8, a scrubber, 9, a nitric acid converter, 10, a denitration reactor, 11, a concentration pump, 12, an absorber pump, 13, a scrubber pump, 14, a conversion circulating pump, 15 and a circulating liquid cooler.
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.
In the description of the present invention, it should 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 the orientation or positional relationships shown in the drawings, merely to facilitate describing the present invention and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
The terms "first," "second," and the like, 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 defining "a first", "a second" may include one or more such features, either explicitly or implicitly; in the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
Example 1
As shown in fig. 1, the embodiment provides an acidic sludge and waste acid recycling device, which comprises a sludge evaporator 1, a high-temperature reactor 5, a negative pressure evaporation concentrator 6, an absorber 7 and a scrubber 8, wherein the high-temperature reactor 5, the negative pressure evaporation concentrator 6, the absorber 7 and the scrubber 8 are connected in sequence through a gas pipeline; the exhaust port of the high-temperature reactor 5 is communicated with the air inlet of the negative pressure evaporation concentrator 6 and is used for conveying high-temperature gas containing acidic components into the negative pressure evaporation concentrator 6 and providing heat for the negative pressure evaporation concentrator 6; the exhaust port of the negative pressure evaporation concentrator 6 is communicated with the air inlet of the absorber 7, and is used for conveying the gas containing acidic components in the negative pressure evaporation concentrator 6 into the absorber 7, and absorbing recoverable acidic components in the gas to form regenerated acid and recovering the regenerated acid; the exhaust port of the absorber 7 is communicated with the air inlet of the scrubber 8 and is used for conveying the residual gas in the absorber 7 to the scrubber 8 for scrubbing and dedusting; the material inlet of the sludge evaporator 1 is communicated with an acid sludge inlet pipe and is used for supplying acid sludge into the sludge evaporator 1; the material outlet of the sludge evaporator 1 is connected with a grinder 2, a molecular sieve filter 3, a solid-liquid mixer 4 and a high-temperature reactor 5 through material pipelines in sequence, and is used for supplying sludge slurry into the high-temperature reactor 5 to generate recoverable effective acidic components and metal oxides through high-temperature hydrolysis reaction, wherein the solid-liquid mixer 4 is also communicated with a configuration liquid adding device and is used for supplying configuration liquid configured by water, waste acid and the like into the solid-liquid mixer 4; the material inlet of the negative pressure evaporation concentrator 6 is communicated with a waste acid inlet pipe and is used for supplying waste acid into the negative pressure evaporation concentrator 6; the material outlet of the negative pressure evaporation concentrator 6 is communicated with the material inlet of the high temperature reactor 5, and is used for conveying the acid liquor concentrated in the negative pressure evaporation concentrator 6 into the high temperature reactor 5 for high temperature thermal hydrolysis reaction to generate recoverable effective acidic components and metal oxides; the material outlet of the absorber 7 is communicated with a regenerated acid outlet pipe and is used for discharging generated regenerated acid; the exhaust port of the scrubber 8 is communicated with the heat source gas inlet of the sludge evaporator 1 through a gas transmission pipeline, and a heat source H is connected to the gas transmission pipeline between the scrubber 8 and the sludge evaporator 1 and used for heating the tail gas discharged by the scrubber 8 so as to provide heat for the sludge evaporator 1.
The acid sludge and waste acid recycling device can be used for treating acid washing waste liquid and acid sludge without nitric acid, and the tail gas of the acid sludge and the waste acid is intensively treated, so that acid and metal oxide in the acid sludge and the waste acid can be simultaneously recycled, and the resource recycling is increased; meanwhile, the waste heat of the tail gas discharged by the scrubber 8 and the heat source H are utilized to heat and evaporate the acid sludge, so that the energy consumption of the system is reduced.
In the embodiment, the heat source H is configured on the gas pipeline between the scrubber 8 and the sludge evaporator 1 and is used for heating the tail gas discharged by the scrubber 8, and the temperature of the tail gas introduced into the sludge evaporator 1 is regulated and controlled, so that a better acid sludge evaporation effect is achieved, and a heat source such as an electric heater can be adopted; preferably, the temperature of the tail gas introduced into the sludge evaporator 1 is controlled to 140-250 ℃, the evaporation of the free acid is ensured, and the temperature is further preferably controlled to about 160 ℃.
Example two
As shown in FIG. 2, the embodiment provides an acidic sludge and waste acid recycling device, which comprises a sludge evaporator 1, a high-temperature reactor 5, a negative pressure evaporation concentrator 6, an absorber 7, a scrubber 8, a high-temperature reactor 5, a negative pressure evaporation concentrator 6, an absorber 7 and a scrubber 8, wherein the high-temperature reactor 5, the negative pressure evaporation concentrator 6, the absorber 7 and the scrubber 8 are sequentially connected through a gas pipeline,A nitric acid converter 9 and a denitration reactor 10; the exhaust port of the high-temperature reactor 5 is communicated with the air inlet of the negative pressure evaporation concentrator 6 and is used for conveying high-temperature gas containing acidic components into the negative pressure evaporation concentrator 6 and providing heat for the negative pressure evaporation concentrator 6; the exhaust port of the negative pressure evaporation concentrator 6 is communicated with the air inlet of the absorber 7, and is used for conveying the gas containing acidic components in the negative pressure evaporation concentrator 6 into the absorber 7, and absorbing recoverable acidic components in the gas to form regenerated acid and recovering the regenerated acid; the exhaust port of the absorber 7 is communicated with the air inlet of the scrubber 8 and is used for conveying the residual gas in the absorber 7 to the scrubber 8 for scrubbing and dedusting; the exhaust port of the scrubber 8 is communicated with the air inlet of the nitric acid converter 9 for supplying NO in the residual gas conveyed from the scrubber 8 x Oxidation and conversion to HNO 3 The method comprises the steps of carrying out a first treatment on the surface of the The exhaust port of the nitric acid converter 9 is communicated with the air inlet of the denitration reactor 10, so that the residual gas after NOx recovery enters the denitration reactor 10 for denitration treatment, and finally, high-temperature tail gas which can reach the standard and be discharged is formed; the material inlet of the sludge evaporator 1 is communicated with an acid sludge inlet pipe and is used for supplying acid sludge into the sludge evaporator 1; the material outlet of the sludge evaporator 1 is connected with a grinder 2, a molecular sieve filter 3, a solid-liquid mixer 4 and a high-temperature reactor 5 through material pipelines in sequence, and is used for supplying sludge slurry into the high-temperature reactor 5 to generate recoverable effective acidic components and metal oxides through high-temperature hydrolysis reaction, wherein the solid-liquid mixer 4 is also communicated with a configuration liquid adding device and is used for supplying configuration liquid configured by water, waste acid and the like into the solid-liquid mixer 4; the material inlet of the negative pressure evaporation concentrator 6 is communicated with a waste acid inlet pipe and is used for supplying waste acid into the negative pressure evaporation concentrator 6; the material outlet of the negative pressure evaporation concentrator 6 is communicated with the material inlet of the high temperature reactor 5, and is used for conveying the acid liquor concentrated in the negative pressure evaporation concentrator 6 into the high temperature reactor 5 for high temperature thermal hydrolysis reaction to generate recoverable effective acidic components and metal oxides; the material outlet of the absorber 7 is communicated with a regenerated acid outlet pipe and is used for discharging generated regenerated acid; the exhaust port of the denitration reactor 10 is communicated with the heat source gas inlet of the sludge evaporator 1 through a gas transmission pipeline and is used for providing heat into the sludge evaporatorAn amount of; the heat source H is connected with the denitration reactor 10 and is used for ensuring the required temperature of the denitration reaction.
The acid sludge and waste acid recycling device can be used for treating acid washing waste liquid and acid sludge containing nitric acid, and the tail gas of the acid sludge and the waste acid is intensively treated, so that acid and metal oxide in the acid sludge and the waste acid can be recovered at the same time, and the resource recovery is increased; meanwhile, since the denitration reaction performed in the denitration reactor 10 is exothermic, the acidic sludge is heated and evaporated by utilizing the heat released by the reaction, which is beneficial to reducing the energy consumption of the system.
The denitration reactor 10 of the embodiment is used for carrying out denitration treatment on the gas discharged by the nitric acid converter 9, so as to ensure that the tail gas reaches the emission standard; the denitration reactor 10 is configured with a heat source H for the denitration reaction demand temperature, for example, a heat source such as an electric heater can be adopted; the temperature of the denitration tail gas which is introduced into the sludge evaporator 1 can be regulated and controlled through the heat source H, so that a better acid sludge evaporation effect is achieved, preferably, the temperature of the denitration tail gas which is introduced into the sludge evaporator 1 is controlled to be 140-250 ℃, the evaporation of free acid is ensured, and further, the temperature is controlled to be about 160 ℃.
Further, a conversion circulating pump 14 and a circulating liquid cooler 15 are connected in series with the nitric acid converter 9 and are used for converting NO in the gas in the nitric acid converter 9 x Oxidation to HNO 3 The method comprises the steps of carrying out a first treatment on the surface of the The circulating liquid cooler 15 is communicated with the scrubber 8 through a branch pipe for oxidizing and absorbing HNO 3 The solution is fed to the scrubber 8 and transported through a branch of the scrubber 8 into the absorber 7 for recovery of the regenerated acid. In this embodiment, the temperature of the gas in the nitric acid converter is reduced by the circulating liquid cooler 15, so that a large amount of moisture in the gas is condensed into the circulating liquid, the circulating liquid is supplemented, the circulating liquid enters the scrubber 8 through the branch pipe and then enters the absorber 7 to absorb the recoverable acidic components in the gas to form regenerated acid, the waste acid treatment can be completed without additional water supplementing, and meanwhile, the gas is beneficial to reaching the standard and discharging.
Example III
The acid sludge and waste acid recycling recovery device provided in the first embodiment or the second embodiment is further characterized in that the acid-containing steam outlet of the sludge evaporator 1 is communicated with the gas pipeline between the negative pressure evaporation concentrator 6 and the absorber 7 through the gas pipeline, or the acid-containing steam outlet of the sludge evaporator 1 is communicated with the gas pipeline between the absorber 7 and the scrubber 8 through the gas pipeline, and is used for recovering the recoverable effective acid components evaporated in the negative pressure evaporation concentrator 6. As shown in fig. 1 and 2, the gas containing acidic components evaporated in the sludge evaporator 1 of the present embodiment is conveyed into the absorber 7 through a gas conveying pipeline, and after being sprayed and absorbed, the recoverable effective acidic components in the gas are absorbed by water to form regenerated acid, and then discharged through a regenerated acid outlet pipe; or the gas containing acidic components evaporated in the sludge evaporator 1 is conveyed into the scrubber 8 through a gas conveying pipeline, and after being sprayed and absorbed, the recyclable effective acidic components in the gas are absorbed by water to form regenerated acid, and the regenerated acid is conveyed into the absorber 7 through the scrubbing pump 13 and then discharged through a regenerated acid outlet pipe. In this embodiment, an absorber pump 12 is installed on a regenerated acid outlet pipe communicating with a material outlet of the absorber 7, and is used for conveying and discharging regenerated acid generated in the absorber 7.
The apparatus for recycling acid sludge and waste acid provided in the first embodiment or the second embodiment is characterized in that the sludge evaporator 1 is an indirect heat exchange apparatus, and tail gas discharged from the scrubber 8 or the denitration reactor 10 enters through a heat source gas inlet of the sludge evaporator 1, performs indirect heat exchange with acid sludge in the sludge evaporator 1, and is directly discharged from a cold source gas outlet of the sludge evaporator 1.
The acidic sludge and waste acid recycling device provided in the first or second embodiment is connected with a washing pump 13 in series on the washer 8 to recycle the spray liquid; and the wash pump 13 communicates with the spray absorption liquid inlet of the absorber 7 through a branch pipe for supplying the spray absorption liquid to the absorber 7.
The apparatus for recycling acid sludge and waste acid provided in the first or second embodiment is connected with a concentration pump 11 in series on the negative pressure evaporation concentrator 6, and the concentrated acid solution is concentrated for multiple times; and the concentration pump 11 is communicated with the material inlet of the high-temperature reactor 5 through a branch pipe and is used for conveying concentrated acid liquor in the negative pressure evaporation concentrator 6 into the high-temperature reactor 5 for high-temperature thermal hydrolysis reaction.
The apparatus for recycling acid sludge and waste acid provided in the first or second embodiment is further configured to enable the concentrated acid solution conveyed by the negative pressure evaporation concentrator 6 and the sludge slurry conveyed by the solid-liquid mixer 4 to undergo a high-temperature thermal hydrolysis reaction to generate recoverable effective acid components and metal oxides, so that the metal oxides are recovered, and the gas containing the acid components enters the negative pressure evaporation concentrator 6 to perform heat exchange with the waste acid. The high temperature reactor 5 of the present embodiment may employ a roasting furnace or a high temperature thermal hydrolysis reactor. As shown in fig. 1 and fig. 2, the high-temperature reactor 5 can be divided into an upper layer and a lower layer according to the components, the concentration and the like of the concentrated acid solution, namely, the high-temperature reactor 5 comprises an upper high-temperature reaction layer and a lower high-temperature reaction layer which is in material communication with the upper high-temperature reaction layer, and a material outlet of the solid-liquid mixer 4 and a material outlet of the negative pressure evaporation concentrator 6 are both communicated with a material inlet on the upper high-temperature reaction layer. Concentrated acid liquid conveyed by the negative pressure evaporation concentrator 6 and sludge slurry conveyed by the solid-liquid mixer 4 firstly enter an upper high-temperature reaction layer to enable most of metal compounds to react for recycling, and solid-liquid materials/liquid materials after reaction enter a lower high-temperature reaction layer to enable the rest of metal compounds to react for recycling; the upper high-temperature reaction layer can be connected with the same high-temperature heat source or can be connected with different high-temperature heat sources, and the high-temperature heat sources are selected according to actual reaction conditions, wherein the high-temperature heat sources can be steel rabbet combustible gas and the like. In one embodiment, the upper high temperature reaction layer and the lower high temperature reaction layer both have an operating temperature in the range of 500-850 ℃.
Example IV
The embodiment provides a recycling recovery process for acid sludge and waste acid by adopting the recovery device provided in the first embodiment, as shown in fig. 1, which specifically comprises the following steps:
introducing the waste acid into a negative pressure evaporation concentrator 6, carrying out heat exchange on the waste acid and high-temperature gas containing acidic components conveyed by a high-temperature reactor 5 under the action of negative pressure, evaporating a large amount of water and free acid in the waste acid to recover the free acid, concentrating the waste acid, and conveying the obtained concentrated acid liquor into the high-temperature reactor 5 through a branch pipe on a concentration pump 11 to carry out high-temperature hydrolysis reaction to generate recoverable effective acidic components and metal oxides;
the acid sludge is fed into a sludge evaporator 1, the acid sludge is evaporated to dryness by adopting the waste heat and the heat source H of the tail gas discharged by a scrubber 8, the dried acid sludge is conveyed into a grinder 2 to be ground into particle powder, the particle powder is filtered by a molecular sieve filter 3 and then is fed into a solid-liquid mixer 4, the preparation liquid prepared by water, waste acid and the like is conveyed into the solid-liquid mixer 4 by a preparation liquid feeding device, the powder sludge and the preparation liquid are mixed to form sludge slurry, and the sludge slurry is conveyed into a high-temperature reactor 5 to be subjected to high-temperature hydrolysis reaction, so that recoverable effective acid components and metal oxides are generated; the gas containing acidic components evaporated in the sludge evaporator 1 is conveyed into an absorber 7 through a gas conveying pipeline, the recoverable effective acidic components in the gas after spraying and absorbing are absorbed by water to form regenerated acid and then are discharged through a regenerated acid outlet pipe, or the gas containing acidic components evaporated in the sludge evaporator 1 is conveyed into a scrubber 8 through a gas conveying pipeline, the recoverable effective acidic components in the gas after spraying and absorbing are absorbed by water to form regenerated acid, and then are conveyed into the absorber 7 through a branch pipe of a scrubbing pump 13 and then are discharged through the regenerated acid outlet pipe;
recovering the metal oxide in the high temperature reactor 5 and discharging it; meanwhile, the free acid generated in the negative pressure evaporation concentrator 6 is mixed with the gas containing the recoverable effective acid component conveyed by the high-temperature reactor 5, the mixed gas is conveyed into the absorber 7 through a gas conveying pipeline, and the recoverable effective acid component in the gas is absorbed by water to form regenerated acid through water spraying and leaching, and is recovered and discharged;
the residual gas in the absorber 7 is conveyed into the scrubber 8 through a gas pipeline to remove dust, and tail gas which is discharged from the scrubber 8 and can reach the standard is heated by the heat source H and then conveyed to the sludge evaporator 1 to heat the acid sludge and then discharged.
The acid sludge and waste acid recycling recovery process of the embodiment can be used for treating pickling waste liquid and acid sludge which do not contain nitric acid.
Example five
The embodiment provides a recycling recovery process for acid sludge and waste acid by adopting the recovery device provided in the second embodiment, as shown in fig. 2, which specifically comprises the following steps:
introducing the waste acid into a negative pressure evaporation concentrator 6, carrying out heat exchange on the waste acid and the gas containing the acidic components conveyed by the high-temperature reactor 5 under the action of negative pressure, evaporating a large amount of water and free acid in the waste acid to recover the free acid, concentrating the waste acid, and conveying the obtained concentrated acid liquor into the high-temperature reactor 5 through a branch pipe on a concentration pump 11 to carry out high-temperature thermal hydrolysis reaction to generate recoverable effective acidic components and metal oxides;
the acid sludge is fed into a sludge evaporator 1, the acid sludge is evaporated to dryness by adopting the waste heat of tail gas of the denitration reaction in a denitration reactor 10, the dried acid sludge is conveyed into a grinder 2 to be ground into particle powder, the particle powder is filtered by a molecular sieve filter 3 and then is fed into a solid-liquid mixer 4, a configuration liquid prepared by water, waste acid and the like is conveyed into the solid-liquid mixer 4 through a configuration liquid feeding device, the powder sludge and the configuration liquid are mixed to form sludge slurry, and the sludge slurry is conveyed into a high-temperature reactor 5 to be subjected to high-temperature thermal hydrolysis reaction, so that recoverable effective acid components and metal oxides are generated; the gas containing acidic components evaporated in the sludge evaporator 1 is conveyed into an absorber 7 through a gas conveying pipeline, the recoverable effective acidic components in the gas after spraying and absorbing are absorbed by water to form regenerated acid and then are discharged through a regenerated acid outlet pipe, or the gas containing acidic components evaporated in the sludge evaporator 1 is conveyed into a scrubber 8 through a gas conveying pipeline, the recoverable effective acidic components in the gas after spraying and absorbing are absorbed by water to form regenerated acid, and then are conveyed into the absorber 7 through a branch pipe of a scrubbing pump 13 and then are discharged through the regenerated acid outlet pipe;
recovering the metal oxide in the high temperature reactor 5 and discharging it; meanwhile, the free acid generated in the negative pressure evaporation concentrator 6 is mixed with the gas containing the recoverable effective acid component conveyed by the high-temperature reactor 5, the mixed gas is conveyed into the absorber 7 through a gas conveying pipeline, and the recoverable effective acid component in the gas is absorbed by water to form regenerated acid through water spraying and leaching, and is recovered and discharged;
the residual gas in the absorber 7 is conveyed into the scrubber 8 through a gas pipeline for dust removal, the tail gas discharged from the scrubber 8 enters the nitric acid converter 9, and NO in the gas is discharged through a conversion circulating pump 14 and a circulating liquid cooler 15 which are connected in series on the nitric acid converter 9 x Oxidation to HNO 3 While oxidizing the absorbed HNO through a branch on the circulating fluid cooler 15 3 The solution is sent to a washer 8, and HNO in the washer 8 3 The solution is then conveyed into the absorber 7 through a branch pipe on the washing pump 13 to be used as spray absorption liquid for recycling regenerated acid;
the denitration reactor 10 is heated by a heat source H to provide the denitration reaction demand temperature, and meanwhile, tail gas discharged from the nitric acid converter 9 is conveyed into the denitration reactor 10 for denitration treatment, and high-temperature tail gas which can reach the standard after denitration treatment is conveyed to the sludge evaporator 1 for heating and then is discharged.
The acid sludge and waste acid recycling recovery process of the embodiment can be used for treating acid washing waste liquid and acid sludge containing nitric acid.
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 (6)

1. The recycling recovery process of the acid sludge and the waste acid is characterized by comprising the following specific steps:
introducing the waste acid into a negative pressure evaporation concentrator, carrying out heat exchange on the waste acid and the gas containing the acidic components conveyed by the high-temperature reactor under the action of negative pressure, evaporating a large amount of water and free acid in the waste acid, concentrating the waste acid, and conveying the obtained concentrated acid liquor into the high-temperature reactor for carrying out high-temperature thermal hydrolysis reaction to generate the acidic components and the metal oxides;
the method comprises the steps of feeding acid sludge into a sludge evaporator, evaporating the acid sludge by using waste heat of tail gas of a denitration reaction in a denitration reactor, conveying the dried acid sludge into a grinder to be ground into particle powder, filtering the particle powder by a molecular sieve filter, adding the particle powder into a solid-liquid mixer, mixing the particle powder with a preparation liquid to form sludge slurry, and conveying the sludge slurry into a high-temperature reactor to perform high-temperature thermal hydrolysis reaction to generate acid components and metal oxides;
recovering the metal oxide in the high-temperature reactor and discharging the metal oxide; meanwhile, the free acid generated in the negative pressure evaporation concentrator is mixed with the gas containing acidic components conveyed by the high-temperature reactor, the mixed gas is conveyed into the absorber through a gas conveying pipeline, the acidic components in the gas are absorbed by water to form regenerated acid through water spraying and leaching, and the regenerated acid is recovered and discharged;
the residual gas in the absorber is conveyed into a scrubber through a gas pipeline to remove dust, and tail gas discharged by the scrubber enters a nitric acid converter to oxidize NOx in the gas into HNO 3 HNO absorbed by oxidation 3 The solution is delivered to a scrubber, HNO in the scrubber is removed 3 The solution is conveyed into an absorber to be used as spray absorption liquid for recycling regenerated acid;
and heating the denitration reactor by adopting a heat source H, simultaneously conveying tail gas discharged by the nitric acid converter into the denitration reactor for denitration treatment, and conveying high-temperature tail gas which can reach the standard after denitration treatment to a sludge evaporator for heating and then discharging acid sludge.
2. The acid sludge and waste acid recycling device adopting the process as claimed in claim 1, which is characterized in that: comprises a sludge evaporator, a high-temperature reactor, a negative pressure evaporation concentrator, an absorber and a scrubber which are connected in sequence through a gas pipeline; the material inlet of the sludge evaporator is communicated with the acid sludge inlet pipe, and the material outlet of the sludge evaporator is connected with the grinder, the molecular sieve filter, the solid-liquid mixer and the high-temperature reactor through material pipelines in sequence; the material inlet of the negative pressure evaporation concentrator is communicated with the waste acid inlet pipe, and the material outlet of the negative pressure evaporation concentrator is communicated with the material inlet of the high-temperature reactor; the material outlet of the absorber is communicated with a regenerated acid outlet pipe; the exhaust port of the scrubber is connected with the nitric acid converter and the denitration reactor sequentially through a gas pipeline, and the exhaust port of the denitration reactor is communicated with the heat source gas inlet of the sludge evaporator through the gas pipeline; the heat source H is connected with the denitration reactor; the acid-containing steam outlet of the sludge evaporator is communicated with a gas pipeline between the negative pressure evaporation concentrator and the absorber through a gas pipeline, or the acid-containing steam outlet of the sludge evaporator is communicated with a gas pipeline between the absorber and the scrubber through a gas pipeline; the sludge evaporator is an indirect heat exchange device.
3. The apparatus of claim 2, wherein: the high-temperature reactor comprises an upper high-temperature reaction layer and a lower high-temperature reaction layer which is in material communication with the upper high-temperature reaction layer, and a material outlet of the solid-liquid mixer and a material outlet of the negative pressure evaporation concentrator are both communicated with a material inlet on the upper high-temperature reaction layer.
4. The apparatus of claim 2, wherein: the scrubber is connected with a scrubbing pump in series, and the scrubbing pump is communicated with the absorber through a branch pipe.
5. The apparatus of claim 2, wherein: the negative pressure evaporation concentrator is connected with a concentration pump in series, and the concentration pump is communicated with a material inlet of the high-temperature reactor through a branch pipe.
6. The apparatus of claim 2, wherein: the nitric acid converter is connected with a conversion circulating pump and a circulating liquid cooler in series, and the circulating liquid cooler is communicated with the scrubber through a branch pipe.
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