CN114853242B - Method for recycling acidic wastewater - Google Patents
Method for recycling acidic wastewater Download PDFInfo
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- CN114853242B CN114853242B CN202210495752.4A CN202210495752A CN114853242B CN 114853242 B CN114853242 B CN 114853242B CN 202210495752 A CN202210495752 A CN 202210495752A CN 114853242 B CN114853242 B CN 114853242B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 title claims description 10
- 239000002253 acid Substances 0.000 claims abstract description 128
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000001704 evaporation Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000008020 evaporation Effects 0.000 claims abstract description 42
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000003825 pressing Methods 0.000 claims abstract description 17
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 238000004458 analytical method Methods 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 238000004073 vulcanization Methods 0.000 claims description 25
- 239000002699 waste material Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 13
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002562 thickening agent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- -1 fluorine-chlorine ions Chemical class 0.000 claims description 8
- 239000010802 sludge Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 230000003993 interaction Effects 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 238000005496 tempering Methods 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 abstract description 2
- 238000005987 sulfurization reaction Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/10—Treatment of water, waste water, or sewage by heating by distillation or evaporation by direct contact with a particulate solid or with a fluid, as a heat transfer medium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/16—Treatment of water, waste water, or sewage by heating by distillation or evaporation using waste heat from other processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/03—Pressure
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Physical Water Treatments (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention relates to a method for recycling acid wastewater, which relates to the technical field of wastewater recycling and comprises the steps of carrying out filter pressing and desliming on acid wastewater, recycling part of the acid wastewater after the filter pressing and desliming, and feeding the other part of the acid wastewater into an adiabatic evaporation tower to realize concentration and emission reduction of acid water, wherein the concentrated acid water is subjected to sulfuration and impurity removal, three-effect downstream evaporation and concentration, fluorine-chlorine stripping and fluorine-chlorine analysis tower, and the acid water after analysis is filtered by a filter press or enters a mixed acid tank to be mixed with 98% sulfuric acid produced by a sulfuric acid system to be configured into 93% -93.5% sulfuric acid, and then the acid water is sold or directly used for supplementing water in a dry absorption process of an acid making system to reduce the consumption of new water.
Description
Technical Field
The invention relates to the technical field of wastewater recycling, in particular to a method for recycling acidic wastewater.
Background
The method is characterized in that metal sulfide associated with ores in the smelting process is often mixed in high-temperature dust-containing multicomponent flue gas in the form of sulfur dioxide and sulfur trioxide, the high-temperature dust-containing multicomponent flue gas enters a matched acid making system, sulfuric acid products are produced through a purifying, cooling, dedusting and demisting process, a drying water process and a double-conversion and double-absorption process, a dynamic wave wet washing process is often adopted for flue gas purification, a large amount of harmful substances such as mineral dust, halogen elements and the like enter a liquid phase from a gas phase in a double-membrane contact process, and are continuously enriched in circulating dilute acid, acidity, solid content, heavy metals and the like are gradually increased, and in order to ensure a spray washing effect, the circulating dilute acid is required to be subjected to open-circuit treatment, so that a certain amount of acid wastewater is produced, and the problems of high treatment cost, large wastewater discharge, difficult recovery of valuable metals and water resources and the like exist in the conventional dilute acid process produced in the smelting process at home and abroad.
Disclosure of Invention
The invention aims at: in order to solve the technical problems in the background technology, the invention provides a method for recycling acidic wastewater.
The invention adopts the following technical scheme for realizing the purposes: a method for recycling acidic wastewater, comprising the following steps:
s1, carrying out filter pressing and desliming on acid wastewater, wherein after the acid wastewater is subjected to filter pressing and desliming, one part of the acid wastewater is returned to the system for recycling, the other part of the acid wastewater enters an adiabatic evaporation tower, and the part of the acid wastewater enters the adiabatic evaporation tower adopts a low-temperature flue gas adiabatic evaporation technology, so that a good adiabatic humidifying effect is achieved, concentration and emission reduction of acid water are realized, and the acid sludge is produced by filter pressing and smelted by a heavy tempering system;
concentrating the waste acid concentrated by the adiabatic evaporation tower in the S2S 1 to 41%, then delivering the concentrated waste acid to a vulcanization impurity removal system through a circulating pump, and settling and press-filtering the waste acid by a primary vulcanization reactor, a primary thickener, a secondary vulcanization reactor and a secondary thickener to recycle vulcanized slag, thereby realizing the purification and removal of heavy metal impurities;
s3, evaporating and concentrating the dilute acid vulcanized in the S2 by adopting three-effect concurrent evaporation and concentration;
s4, conveying the waste acid obtained after evaporation and concentration in the S3 to a fluorine-chlorine stripping system, carrying out gas-liquid interaction reaction on hot air and dilute acid in a stripping tower, and improving the acid water temperature so as to reduce the solubility of fluorine-chlorine ions, automatically separating out fluorine-chlorine in a form of hydrogen fluoride and hydrogen chloride molecules in an acidic environment into a gas phase, stripping fluorine and chlorine ions in the waste acid into the gas phase, and finally, entering a tail gas absorption tower, and discharging after further spray washing and absorption;
s5, conveying the acid water after the fluorine and chlorine are blown off in the step S4 to a fluorine and chlorine analysis tower, filtering the analyzed acid water by a filter press or mixing the analyzed acid water with 98% sulfuric acid produced by a sulfuric acid mixing tank and a sulfuric acid system to prepare 93% -93.5% sulfuric acid, and then selling the sulfuric acid or directly using the sulfuric acid to supplement water in a dry absorption process of an acid making system to reduce the consumption of new water.
In order to prevent strong corrosion and easy crystallization in the acid water concentration process, in the step S3, equipment which takes phenolic resin impregnated graphite as a main material is adopted as evaporation equipment.
Further, the heat of the hot air in the step S4 is derived from the heat emitted when the diluted acid and the 98% concentrated acid are mixed in the step S5, and steam is not used, so that the steam consumption can be saved.
Further, the fluorine-chlorine analysis tower in the step S5 adopts a negative pressure vacuum method to control the partial pressure of the sulfuric acid surface at-75 kPa to-80 kPa.
Further, in the mixing process of the acid obtained by filtering the acid water after the analysis in the step S5 by a filter press and 98% sulfuric acid, a large amount of reaction heat can be released, the acid temperature is controlled to be 85-120 ℃, and the fluorine-chlorine analysis efficiency can be improved.
The utility model provides an acid wastewater recycling's system, includes adiabatic vaporization system, vulcanization edulcoration system, triple effect evaporation concentration system, fluorine chlorine stripping system and dilute acid system of mixing, the export of adiabatic vaporization system and the entry intercommunication of vulcanization edulcoration system, the export of vulcanization edulcoration system and the entry intercommunication of triple effect evaporation concentration system, the export of triple effect evaporation concentration system and fluorine chlorine stripping system entry intercommunication, fluorine chlorine stripping system's export and dilute acid system of mixing's entry intercommunication.
The invention has the beneficial effects that: according to the method for recycling the acid wastewater, provided by the invention, the recycling of the acid wastewater is realized through the adiabatic evaporation system, the vulcanization impurity removal system, the triple-effect evaporation concentration system, the fluorine-chlorine stripping system and the dilute acid mixing system, the running cost of the system is effectively reduced, the production amount of the acid wastewater is obviously reduced from the source, the production of dangerous solid wastes is greatly reduced, and the environmental benefit and the social benefit are obvious.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. 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.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
In describing embodiments of the present invention, it should be noted that the directions or positional relationships indicated by the terms "inner", "outer", "upper", etc. are directions or positional relationships based on those shown in the drawings, or those that are conventionally put in place when the inventive product is used, are merely for convenience of description and simplification of description, and are not indicative or implying that the apparatus or element in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Example 1
As shown in fig. 1, a method for recycling acidic wastewater comprises the following steps:
s1, carrying out filter pressing and desliming on acid wastewater, wherein after the acid wastewater is subjected to filter pressing and desliming, one part of the acid wastewater is returned to the system for recycling, the other part of the acid wastewater enters an adiabatic evaporation tower, and the part of the acid wastewater enters the adiabatic evaporation tower adopts a low-temperature flue gas adiabatic evaporation technology, so that a good adiabatic humidifying effect is achieved, concentration and emission reduction of acid water are realized, and the acid sludge is produced by filter pressing and smelted by a heavy tempering system;
concentrating the waste acid concentrated by the adiabatic evaporation tower in the S2S 1 to 41%, then delivering the concentrated waste acid to a vulcanization impurity removal system through a circulating pump, and settling and press-filtering the waste acid by a primary vulcanization reactor, a primary thickener, a secondary vulcanization reactor and a secondary thickener to recycle vulcanized slag, thereby realizing the purification and removal of heavy metal impurities;
s3, evaporating and concentrating the dilute acid vulcanized in the S2 by adopting three-effect concurrent evaporation and concentration;
s4, conveying the waste acid obtained after evaporation and concentration in the S3 to a fluorine-chlorine stripping system, carrying out gas-liquid interaction reaction on hot air and dilute acid in a stripping tower, and improving the acid water temperature so as to reduce the solubility of fluorine-chlorine ions, automatically separating out fluorine-chlorine in a form of hydrogen fluoride and hydrogen chloride molecules in an acidic environment into a gas phase, stripping fluorine and chlorine ions in the waste acid into the gas phase, and finally, entering a tail gas absorption tower, and discharging after further spray washing and absorption;
s5, conveying the acid water after the fluorine and chlorine are blown off in the step S4 to a fluorine and chlorine analysis tower, filtering the analyzed acid water by a filter press or mixing the analyzed acid water with 98% sulfuric acid produced by a sulfuric acid mixing tank and a sulfuric acid system to prepare 93% -93.5% sulfuric acid, and then selling the sulfuric acid or directly using the sulfuric acid to supplement water in a dry absorption process of an acid making system to reduce the consumption of new water.
In order to prevent strong corrosion and easy crystallization in the acid water concentration process, in the step S3, equipment which takes phenolic resin impregnated graphite as a main material is adopted as evaporation equipment.
Further, the heat of the hot air in the step S4 is derived from the heat emitted when the diluted acid and the 98% concentrated acid are mixed in the step S5, and steam is not used, so that the steam consumption can be saved.
Further, the fluorine-chlorine analysis tower in the step S5 adopts a negative pressure vacuum method to control the partial pressure of the sulfuric acid surface at-75 kPa to-80 kPa.
Further, in the mixing process of the acid obtained by filtering the acid water after the analysis in the step S5 by a filter press and 98% sulfuric acid, a large amount of reaction heat can be released, the acid temperature is controlled to be 85-120 ℃, and the fluorine-chlorine analysis efficiency can be improved.
The utility model provides an acid wastewater recycling's system, includes adiabatic vaporization system, vulcanization edulcoration system, triple effect evaporation concentration system, fluorine chlorine stripping system and dilute acid system of mixing, the export of adiabatic vaporization system and the entry intercommunication of vulcanization edulcoration system, the export of vulcanization edulcoration system and the entry intercommunication of triple effect evaporation concentration system, the export of triple effect evaporation concentration system and fluorine chlorine stripping system entry intercommunication, fluorine chlorine stripping system's export and dilute acid system of mixing's entry intercommunication.
Example 2
Carrying out filter pressing and desliming on the acid wastewater of the system, wherein the filter pressing generates acid sludge, and the acid sludge is recycled to the smelting system by a tempering method, and part of filter pressing clear liquid is returned to the system for recycling, and the other part of the clear liquid enters an adiabatic evaporation tower to evaporate concentrated acid; the mixture enters an adiabatic evaporation tower to be evaporated and concentrated to a certain acidity, and then is pumped to a vulcanization impurity removal system by a circulating pump, wherein a vulcanizing agent adopts hydrogen sulfide, and the mixture is subjected to sedimentation and pressure filtration by a primary vulcanization reactor, a primary thickener, a secondary vulcanization reactor and a secondary thickener, so that the vulcanized slag is recovered, and the purification and removal of heavy metal impurities are realized; concentrating the vulcanized waste acid through a three-effect evaporation system, and concentrating and separating different components in the mixed liquid according to different boiling points mainly through steam action; conveying the evaporated and concentrated waste acid to a fluorine-chlorine stripping system, carrying out gas-liquid interaction reaction on hot air and dilute acid in a stripping tower, stripping fluorine and chlorine ions in the waste acid into a gas phase, and finally, entering a tail gas absorption tower, and discharging after further spray washing and absorption; and (3) conveying the acid water after the fluorine-chlorine stripping to a fluorine-chlorine analysis tower, further removing fluorine-chlorine by adopting negative pressure vacuum high temperature, filtering the analyzed acid water by a filter press, and then feeding the filtered acid water into an acid mixing tank to prepare 93-93.5% concentrated sulfuric acid to be used as a finished product for sale.
Example 3
Carrying out filter pressing and desliming on the acid wastewater of the system, wherein the filter pressing generates acid sludge, and the acid sludge is recycled to the smelting system by a tempering method, and part of filter pressing clear liquid is returned to the system for recycling, and the other part of the clear liquid enters an adiabatic evaporation tower to evaporate concentrated acid; the mixture enters an adiabatic evaporation tower to be evaporated and concentrated to a certain acidity, and then is pumped to a vulcanization impurity removal system by a circulating pump, wherein a vulcanizing agent adopts hydrogen sulfide, and the mixture is subjected to sedimentation and pressure filtration by a primary vulcanization reactor, a primary thickener, a secondary vulcanization reactor and a secondary thickener, so that the vulcanized slag is recovered, and the purification and removal of heavy metal impurities are realized; concentrating the vulcanized waste acid through a three-effect evaporation system, and concentrating and separating different components in the mixed liquid according to different boiling points mainly through steam action; conveying the evaporated and concentrated waste acid to a fluorine-chlorine stripping system, carrying out gas-liquid interaction reaction on hot air and dilute acid in a stripping tower, stripping fluorine and chlorine ions in the waste acid into a gas phase, and finally, entering a tail gas absorption tower, and discharging after further spray washing and absorption; and (3) conveying the acid water after the fluorine-chlorine stripping to a fluorine-chlorine analysis tower, further removing fluorine-chlorine by adopting negative pressure vacuum high temperature, filtering the analyzed acid water by a filter press, and directly using the acid water for supplementing water in a dry absorption process of an acid making system, thereby reducing the consumption of new water.
It will be appreciated by those skilled in the art that the present invention can be carried out in other embodiments without departing from the spirit or essential characteristics thereof. Accordingly, the above disclosed embodiments are illustrative in all respects, and not exclusive. All changes that come within the scope of the invention or equivalents thereto are intended to be embraced therein.
Claims (2)
1. The method for recycling the acid wastewater is characterized by comprising the following steps of:
s1, carrying out filter pressing and desliming on acid wastewater, wherein after the acid wastewater is subjected to filter pressing and desliming, one part of the acid wastewater is returned to the system for recycling, the other part of the acid wastewater enters an adiabatic evaporation tower, and the part of the acid wastewater enters the adiabatic evaporation tower adopts a low-temperature flue gas adiabatic evaporation technology, so that a good adiabatic humidifying effect is achieved, concentration and emission reduction of acid water are realized, and the acid sludge is produced by filter pressing and smelted by a heavy tempering system;
concentrating the waste acid concentrated by the adiabatic evaporation tower in the S2S 1 to 41%, then delivering the concentrated waste acid to a vulcanization impurity removal system through a circulating pump, and settling and press-filtering the waste acid by a primary vulcanization reactor, a primary thickener, a secondary vulcanization reactor and a secondary thickener, recovering vulcanized slag, thereby realizing the purification and removal of heavy metal impurities;
s3, evaporating and concentrating the dilute acid vulcanized in the S2 by adopting three-effect concurrent evaporation and concentration;
in order to prevent strong corrosion and easy crystallization in the acid water concentration process, equipment which takes phenolic resin impregnated graphite as a main material is adopted as evaporation equipment;
s4, conveying the waste acid obtained after evaporation and concentration in the S3 to a fluorine-chlorine stripping system, carrying out gas-liquid interaction reaction on hot air and dilute acid in a stripping tower, and improving the acid water temperature so as to reduce the solubility of fluorine-chlorine ions, automatically separating out fluorine-chlorine in a form of hydrogen fluoride and hydrogen chloride molecules in an acidic environment into a gas phase, stripping fluorine and chlorine ions in the waste acid into the gas phase, and finally, entering a tail gas absorption tower, and discharging after further spray washing and absorption;
the heat of the hot air is derived from the heat emitted when the dilute acid and the 98% concentrated acid in the step S5 are mixed, and steam is not used, so that the steam consumption can be saved;
s5, conveying the acid water after the fluorine and chlorine are blown off in the step S4 to a fluorine and chlorine analysis tower, filtering the analyzed acid water by a filter press or mixing the analyzed acid water with 98% sulfuric acid produced by a sulfuric acid mixing tank and a sulfuric acid system to prepare 93% -93.5% sulfuric acid, and then selling the sulfuric acid or directly using the sulfuric acid to supplement water in a dry absorption process of an acid making system to reduce the consumption of new water;
the fluorine-chlorine analysis tower adopts a negative pressure vacuum method to control the partial pressure of the sulfuric acid surface to be between 75kPa and 80kPa;
the acid obtained by filtering the resolved acid water by a filter press releases a great amount of reaction heat in the mixing process of the acid and 98% sulfuric acid, the acid temperature is controlled to be 85-120 ℃, and the fluorine-chlorine resolving efficiency can be improved.
2. The method for recycling acidic wastewater according to claim 1, comprising an adiabatic evaporation system, a vulcanization impurity removal system, a triple effect evaporation concentration system, a fluorine-chlorine stripping system and a dilute acid mixing system, wherein the outlet of the adiabatic evaporation system is communicated with the inlet of the vulcanization impurity removal system, the outlet of the vulcanization impurity removal system is communicated with the inlet of the triple effect evaporation concentration system, the outlet of the triple effect evaporation concentration system is communicated with the inlet of the fluorine-chlorine stripping system, and the outlet of the fluorine-chlorine stripping system is communicated with the inlet of the dilute acid mixing system.
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| US9719179B2 (en) * | 2012-05-23 | 2017-08-01 | High Sierra Energy, LP | System and method for treatment of produced waters |
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