CN107226519A - A kind of recycling sulfurizing treatment method of acid waste water containing heavy metal - Google Patents
A kind of recycling sulfurizing treatment method of acid waste water containing heavy metal Download PDFInfo
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- CN107226519A CN107226519A CN201710553125.0A CN201710553125A CN107226519A CN 107226519 A CN107226519 A CN 107226519A CN 201710553125 A CN201710553125 A CN 201710553125A CN 107226519 A CN107226519 A CN 107226519A
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- waste water
- acid waste
- acid
- heavy metal
- recycling
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- 239000002253 acid Substances 0.000 title claims abstract description 57
- 239000002351 wastewater Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 42
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 35
- 238000004073 vulcanization Methods 0.000 claims abstract description 35
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000002893 slag Substances 0.000 claims abstract description 12
- 239000002699 waste material Substances 0.000 claims abstract description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 31
- 229910052708 sodium Inorganic materials 0.000 claims description 31
- 239000011734 sodium Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000005987 sulfurization reaction Methods 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- CXXPNVHRJBAYGS-UHFFFAOYSA-N [F].[As] Chemical compound [F].[As] CXXPNVHRJBAYGS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000960 colored gold Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000009491 slugging Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0093—Treating solutions by chemical methods by gases, e.g. hydrogen or hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working 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
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Removal Of Specific Substances (AREA)
- Treating Waste Gases (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention is a kind of recycling sulfurizing treatment method of acid waste water containing heavy metal, it is vulcanizing agent by using the hydrogen sulfide gas of synthesis, avoid the high salinization that Traditional Method disposes acid waste water, the efficient removal of heavy metal ion in acid waste water is realized simultaneously, the yield of dangerous waste vulcanized slag is reduced.In the preparation process of vulcanizing agent, the comprehensive utilization of resources of sodium sulfate byproduct is realized.The operating cost of the inventive method is low, to environment non-secondary pollution, can acid waste water during high performance vulcanization metallurgical off-gas acid-making, in industry with dissemination.
Description
Technical field
The invention belongs to pyrometallurgical smelting and chemical industry environmental protection field, and in particular to a kind of recycling, high performance vulcanization processing are smelted
The method of acid waste water during flue gas acid preparing.
Background technology
China's nonferrous metals ore source is numerous, and many metallic ore associations.In recent years because global rich ore is in short supply, smelt
Enterprise is largely using low-grade ore, the plain ore deposit of complicated pluralism and the high miscellaneous ore deposit of arsenic fluorine.During pyrometallurgical smelting non-ferrous metal, in ore
Metal sulfide burning conversion into sulfur dioxide, be mixed in the ash-laden gas of high temperature be discharged into from the equipment such as metallurgical furnace kiln with
Supporting metallurgical gas sulphuric acid system.Into the heavy metal ion of metallurgical gas sulphuric acid system, flue dust, halogen compound
Have an impact etc. harmful substance to the product quality of acid making system, it is necessary in the discharge of acid making system cleaning procedure, the dilute sulfuric acid of discharge
Solution contains these impurity, it is big to environmental hazard, it is necessary to handle it is up to standard after can be discharged into factory's external environment.
The processing up to standard of the efficient of acid waste water, low cost is the problem of flue gas acid preparing system all the time.There is coloured gold at present
Belong to smelting enterprise's acid waste water treatment technology more than 90% using a certain unit of the vulcanization method as its handling process.Vulcanization method
It is directed in acid waste water add vulcanizing agent, makes most of metal ion and vulcanizing agent in acid waste water molten based on various sulfide
The method that degree product is different and generates the separation of insoluble metal sulfide precipitation.Conventional vulcanizing agent is sodium sulfide solution, according to《With much money
Belong to sewage chemical method processing design specification》, the dosing mass fraction of vulcanized sodium need to be controlled within 10%, 10% sodium sulfide solution
Formed by the industrial solid vulcanized sodium dissolving configuration that active ingredient is only 60%.The technique be faced with always curing efficiency it is low, vulcanization
The shortcomings of dangerous waste quantity of slag is big, plant investment is costly, vulcanizing agent does not obtain comprehensive utilization of resources.
The content of the invention
The purpose of the present invention is exactly that there is provided one kind in order to improve problem present in above-mentioned existing acid waste water sulfurization technology
Curing efficiency is high, the vulcanization dangerous waste quantity of slag is small, vulcanization operating cost is low, the acid waste water vulcanization process of vulcanizing agent comprehensive utilization.
The present invention is integrated by vulcanizing agent recycling to be utilized and reaches the purpose for solving prior art bottleneck.
To achieve the above objectives, the present invention uses following technical scheme：A kind of recycling sulphur of acid waste water containing heavy metal
Change processing method, comprise the following steps：（a）It will be poured into after technical grade vulcanized sodium unpacking in vulcanized sodium dissolving tank, in dissolving tank
70-90 DEG C of hot water of injection dissolves it；（b）By step（a）Clear liquid after middle dissolving, i.e. sodium sulfide solution are delivered to gas with pump
Generator, during sodium sulfide solution adds gas generator, sulfuric acid is also added in gas generator simultaneously, sodium sulfide solution
In sodium ions content and sulfuric acid in the ratio between sulfate radical content 2:1, vulcanized sodium reacts with sulfuric acid, is reacted in generator
Generate gaseous hydrogen sulfide and liquid phase metabisulfite solution；（c）The gas-phase product hydrogen sulfide of gas generator is sent into gas buffer tank
Storage, it is used for vulcanization；Liquid phase in gas generator is sent in vacuum desiccator, and metabisulfite solution is in vacuum desiccator
Moisture is evaporated, solid-state sodium sulphate is formed；（d）The sodium sulphate feeding fixed bed reactors of solid-state, are passed through reducing agent, in catalyst
The lower reaction of effect obtains anhydrous sodium sulfide；（e）It is impure during metallurgical off-gas acid-making in acid waste water regulating reservoir
Acid waste water collects after homogenizing, is delivered to pump in vulcanization reaction device, and the hydrogen sulfide in gas buffer tank also feeds vulcanization reaction
Heavy metal and hydrogen sulfide reaction generation metal sulfide precipitation in device, acid waste water；（f）By step（e）Had in middle gas
The complete hydrogen sulfide of unreacted is measured, gas is sent into the alkali liquor absorption tower of postorder by blower fan, with caustic lye of soda by unnecessary vulcanization
Qualified discharge after hydrogen absorbs, the main component of absorbing liquid is soluble vulcanized sodium, is back to the recycling of vulcanized sodium dissolving tank；
（g）Acid waste water after vulcanization enters concentrator and carries out dense thickening, and its bottom liquid is delivered to filter press through slush pump, by filter press
Metal sulfide is separated with acid waste water, filter press gives birth to filter residue for dangerous waste vulcanized slag, and filter residue delivers to hazardous waste processing center, dense
The clear liquid of close machine and filter press is delivered to downstream neutralization step and is further processed.
Further, the step（a）Middle vulcanized sodium dissolving tank is provided with agitator, to improve dissolved efficiency.Inside is not
Molten thing impurity needs periodic cleaning, disposes, is not brought into dangerous waste slag as general solid waste.
Further, the step（b）Middle gas generator outer wall should set high pressure sheath water pipe cooling back installation, with
Constantly persistently cool to gas generator, maintain internal-response to carry out.
Further, the step（b）The h 2 so 4 concentration 75% of gas generator is added, when sulfuric acid raw material is quality
When concentration is 98% concentrated sulfuric acid, first by sulfuric acid dilution device dilute sulphuric acid, sulfuric acid dilution device needs continuous cooling, to remove sulfuric acid
The amount of heat released during dilution.
Further, the step（c）The moisture content evaporated in middle vacuum desiccator is used to dissolve vulcanized sodium after collecting, with
The water consume of reduction system.
Further, the step（d）In reducing agent be hydrogen, the catalyst be vanadic anhydride, three oxidation two
Iron or nickel oxide, controlling reaction temperature is at 550~600 DEG C.
Further, the step（e）In vulcanization reaction device can be set two to three series operations, formed two-stage or three
Level sulfuration process, to improve curing efficiency, this configuration is more suitable for handling the larger system of water.
Further, the step（e）The reaction mass hydrogen sulfide plan vertical of middle vulcanization reaction device enters, acid waste water
Entered by the inverse spray of hydrogen sulfide pipeline with hydrogen sulfide in vulcanization reaction device, to strengthen gas liquid interfacial area, improve vulcanization effect
Rate.
Further, hydrogen sulfide is inflammable and explosive and has stronger toxicity, easily occurs casualty accident, therefore from the system of hydrogen sulfide
It is standby to be carried out to whole vulcanization reaction in closed environment, prevent hydrogen sulfide gas from escaping, while setting hydrogen sulfide to monitor report
Alarm device.
Further, the step（f）Liquid phase heat exchanger is configured with the device of the remaining hydrogen sulfide of alkali liquor absorption, by continuous
For absorbing liquid cooling to ensure assimilation effect, the less plate type heat exchanger of floor space, alkali liquor absorption tower institute may be selected in heat exchanger
It is 32% with the mass concentration of caustic lye of soda.
Compared with existing sulfuration process, beneficial effects of the present invention are embodied in following several respects：
1. the use of hydrogen sulfide, improves the efficiency of acid waste water vulcanization, the consumption of vulcanizing agent is saved more than 20%, reduced
The cost of raw material.
2. the impurity in vulcanized sodium course of dissolution is removed in dissolution phase out of system, it is to avoid is brought vulcanization section into and is become danger
Sulfur waste slugging, the dangerous waste quantity of slag reduces more than 30%, and slag system construction scale is small, and plant investment is low.
3. the sulfuration process that the present invention takes, it is to avoid a large amount of sodium ions enter acid waste water and generate sodium sulphate liquid,
The salinity of acid waste water is reduced, is easy to the processing and reuse of follow-up waste water, it also avoid high-salt wastewater caused by discharging to environment
Secondary pollution.
4. the liquid product of gas generator is converted into after drying, reduction and produces vulcanizing agent in vulcanization process of the present invention
Raw material, substantially waste is used, and reduces the consumption of vulcanized sodium, improves the economy of system.
5. the vulcanization process of the present invention can realize efficiently separating for heavy metal ion, the separative efficiency of ambrose alloy reach 98% with
On, other heavy metals（In addition to nickel）Separation rate up to more than 70%, in the vulcanized slag of generation heavy metal ion grade reach 60% with
On, raw materials recovery valuable metal therein can be used as.
6. the present invention takes efficient sulfuration process, spent acidic is just efficiently eliminated in the primary stage of acid waste water processing
Most of heavy metal ion in water, alleviates follow-up neutralization step and the processing load of advanced treating process, reduces back segment
The consumption and operating cost of process medicament.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
Embodiment 1：Using the acid waste water of cleaning procedure discharge between certain nickel fibers flue gas acid preparing system normal production period as place
Object is managed, the water quality of discharge acid waste water is shown in Table 1：
Specific process step is as follows：
（1）The hot water 1.25kg of 80 DEG C of injection, pours into industrial sodium sulfide in vulcanized sodium dissolving tank（s）250g starts agitating device
It is sufficiently stirred for, 400r/min stirrings make it fully dissolve in 5 minutes, and the turbid solution after dissolving is filtered with filter paper, obtained
100g（Butt）Vulcanize sodium impurity and 10% vulcanized sodium clear liquid 1400g.
（2）55g deionized waters are weighed with beaker, the concentrated sulfuric acid 180g that mass fraction is 98% is slowly added into, 300r/min enters
Row stirring, produces the concentrated sulfuric acid 235g of mass concentration 75%.
（3）Gas generator outer wall high pressure sheath recirculated cooling water is opened, generator cooling is given.By 10% sulphur after dissolving
Change sodium clear liquid 1400g, 75% concentrated sulfuric acid 235g is moved into gas generator, chemically reacted in gas generator respectively,
Gas-phase product hydrogen sulfide（88%）Send into the storage of gas buffer tank；Liquid curing sodium is positioned in beaker, moves to vacuum desiccator,
Dryer temperature is set as 135 DEG C, and vacuum -8kPa, 75 DEG C of vapor (steam) temperature is dried after 24h, obtains solid-state sodium sulphate 255g.
（4）Solid-state sodium sulphate 255g moves into fixed bed reactors, adds catalyst vanadic anhydride 8.0g, and temperature control exists
Between 550 DEG C~600 DEG C, hydrogen is passed through, tolerance is controlled in 15L/min or so, can produce anhydrous sodium sulfide 140g.
（5）Acid waste water 66L is measured, is moved into vulcanization reaction device, by step（3）The hydrogen sulfide of generation is passed through vulcanization reaction
Heavy metal in device, acid waste water carries out fully reaction 25 minutes with hydrogen sulfide, generates sulfide precipitation, is carried out solid-liquid point
From analyzing filtrate, the content of each heavy metal is shown in Table 2 in filtrate.Dried to Washing of Filter Cake and under the conditions of temperature is 120 DEG C
It is dry, solid slag is obtained, 133g is weighed as.
（6）By step（5）The middle complete hydrogen sulfide of excessive unreacted is evacuated by blower fan enters alkali liquor absorption tower, utilizes 32%
Caustic lye of soda by unnecessary hydrogen sulfide absorption, absorbing liquid be back to vulcanized sodium dissolving tank repetitive cycling utilization.
After being handled more than, calculate vulcanization and go the efficiency of removing heavy metals to be：Ni：69.8%、Cu：98.3%、As：99.6%、
Pb：87.6 %、Zn：71.3%、Cd：80.2 %, filtering removes in acid waste water about 91.2% solid content.
Embodiment 2：Using the acid waste water of cleaning procedure discharge between certain copper blast furnace off-gas acid making system normal production period as place
Object is managed, the water quality of discharge acid waste water is shown in Table 3：
Specific process step is as follows：
（1）The hot water 1.5kg of 80 DEG C of injection, pours into industrial sodium sulfide in vulcanized sodium dissolving tank（s）300g starts agitating device
It is sufficiently stirred for, 420r/min stirrings make it fully dissolve in 5 minutes, and the turbid solution after dissolving is filtered with filter paper, obtained
120g（Butt）Vulcanize sodium impurity and 10% vulcanized sodium clear liquid 1680g.
（2）66g deionized waters are weighed with beaker, the concentrated sulfuric acid 215g that mass fraction is 98% is slowly added into, 300r/min enters
Row stirring, produces the concentrated sulfuric acid 281g of mass concentration 75%.
（3）Gas generator outer wall high pressure sheath recirculated cooling water is opened, generator cooling is given.By 10% sulphur after dissolving
Change sodium clear liquid 1680g, 75% concentrated sulfuric acid 281g is moved into gas generator, chemically reacted in gas generator respectively,
Gas-phase product hydrogen sulfide（85%）Send into the storage of gas buffer tank；Liquid curing sodium is positioned in beaker, moves to vacuum desiccator,
Dryer temperature is set as 135 DEG C, and vacuum -8kPa, 75 DEG C of vapor (steam) temperature is dried after 24h, obtains solid-state sodium sulphate 306g.
（4）Solid-state sodium sulphate 306g moves into fixed bed reactors, adds catalyst vanadic anhydride 9.6g, and temperature control exists
Between 550 DEG C~600 DEG C, hydrogen is passed through, tolerance is controlled in 15L/min or so, can produce anhydrous sodium sulfide 168g.
（5）Acid waste water 75L is measured, is moved into vulcanization reaction device, by step（3）The hydrogen sulfide of generation is passed through vulcanization reaction
Heavy metal in device, acid waste water carries out fully reaction 25 minutes with hydrogen sulfide, generates sulfide precipitation, is carried out solid-liquid point
From analyzing filtrate, composition is shown in Table 4.Dried to Washing of Filter Cake and under the conditions of temperature is 120 DEG C, obtain solid slag,
It is weighed as 156g.
（6）By step（5）The middle complete hydrogen sulfide of excessive unreacted is evacuated by blower fan enters alkali liquor absorption tower, utilizes 32%
Caustic lye of soda by unnecessary hydrogen sulfide absorption, absorbing liquid be back to vulcanized sodium dissolving tank repetitive cycling utilization.
After being handled more than, calculate vulcanization and go the efficiency of removing heavy metals to be：Ni：67.4%、Cu：98.5%、As：99.4%、
Pb：83.5%、Zn：70.6%、Cd：79.3 %, filtering removes in acid waste water about 93.1% solid content.
Claims (10)
1. the recycling sulfurizing treatment method of a kind of acid waste water containing heavy metal, it is characterized in that comprising the following steps：
（a）It will be poured into after technical grade vulcanized sodium unpacking in vulcanized sodium dissolving tank, 70-90 DEG C of hot water is injected in dissolving tank makes its molten
Solution；
（b）By step（a）Clear liquid after middle dissolving, i.e. sodium sulfide solution are delivered to gas generator with pump, and sodium sulfide solution adds
During entering gas generator, sulfuric acid is also added in gas generator simultaneously, sodium ions content and sulphur in sodium sulfide solution
The ratio between sulfate radical content in acid is 2:1, vulcanized sodium reacts with sulfuric acid, in generator reaction generation gaseous hydrogen sulfide and
Liquid phase metabisulfite solution；
（c）By the gas-phase product hydrogen sulfide feeding gas buffer tank storage of gas generator, for used in vulcanization；In gas generator
Liquid phase be sent in vacuum desiccator, metabisulfite solution evaporates moisture in vacuum desiccator, forms solid-state sodium sulphate；
（d）The sodium sulphate feeding fixed bed reactors of solid-state, are passed through reducing agent, reaction obtains anhydrous sulphur in the presence of catalyst
Change sodium；
（e）In acid waste water regulating reservoir, impure acid waste water collects after homogenizing during metallurgical off-gas acid-making, uses
Pump is delivered in vulcanization reaction device, and the hydrogen sulfide in gas buffer tank also feeds the heavy metal in vulcanization reaction device, acid waste water
With hydrogen sulfide reaction generation metal sulfide precipitation；
（f）By step（e）There is the complete hydrogen sulfide of excessive unreacted in middle gas, gas is sent into the alkali liquor absorption of postorder by blower fan
Tower, with caustic lye of soda by qualified discharge after unnecessary hydrogen sulfide absorption, the main component of absorbing liquid is soluble vulcanized sodium,
It is back to the recycling of vulcanized sodium dissolving tank；
（g）Acid waste water after vulcanization enters concentrator and carries out dense thickening, and its bottom liquid is delivered to filter press through slush pump, by pressing
Filter separates metal sulfide with acid waste water, and filter press gives birth to filter residue for dangerous waste vulcanized slag, and filter residue is delivered in dangerous waste processing
The clear liquid of the heart, concentrator and filter press is delivered to downstream neutralization step and is further processed.
2. a kind of recycling sulfurizing treatment method of acid waste water containing heavy metal according to claim 1, it is characterised in that：
Step（a）Middle vulcanized sodium dissolving tank is provided with the insoluble matter impurity periodic cleaning inside agitator, groove, at general solid waste
Put, do not bring into dangerous waste slag.
3. a kind of recycling sulfurizing treatment method of acid waste water containing heavy metal according to claim 1, it is characterised in that：
Step（b）Middle gas generator outer wall should set high pressure sheath water pipe cooling back installation.
4. a kind of recycling sulfurizing treatment method of acid waste water containing heavy metal according to claim 1, it is characterised in that
Step（b）The h 2 so 4 concentration 75% of gas generator is added, when sulfuric acid raw material is the concentrated sulfuric acid that mass concentration is 98%, first
By sulfuric acid dilution device dilute sulphuric acid.
5. a kind of recycling sulfurizing treatment method of acid waste water containing heavy metal according to claim 1, it is characterised in that
Step（c）The moisture content evaporated in middle vacuum desiccator is used to dissolve vulcanized sodium after collecting.
6. a kind of recycling sulfurizing treatment method of acid waste water containing heavy metal according to claim 1, it is characterised in that
Step（d）In reducing agent be hydrogen, the catalyst be vanadic anhydride, di-iron trioxide or nickel oxide, control reaction temperature
Degree is at 550~600 DEG C.
7. a kind of recycling sulfurizing treatment method of acid waste water containing heavy metal according to claim 1, it is characterised in that
Step（e）In vulcanization reaction device two to three series operations can be set, form two-stage or three-level sulfuration process.
8. a kind of recycling sulfurizing treatment method of acid waste water containing heavy metal according to claim 1, it is characterised in that
Step（e）The reaction mass hydrogen sulfide plan vertical of middle vulcanization reaction device enters, acid waste water by the inverse spray of hydrogen sulfide pipeline with
Hydrogen sulfide enters in vulcanization reaction device together.
9. a kind of recycling sulfurizing treatment method of acid waste water containing heavy metal according to claim 1, it is characterised in that
Step（f）The mass concentration of caustic lye of soda used in middle alkali liquor absorption tower is 32%.
10. a kind of recycling sulfurizing treatment method of acid waste water containing heavy metal according to claims 1, its feature exists
In step（f）Liquid phase plate type heat exchanger is configured during hydrogen sulfide remaining with alkali liquor absorption.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108706700A (en) * | 2018-04-25 | 2018-10-26 | 中国瑞林工程技术有限公司 | A kind of method and its application of processing waste liquid containing heavy metal ion |
| CN109626656A (en) * | 2019-01-19 | 2019-04-16 | 江钨世泰科钨品有限公司 | A kind of administering method vulcanizing waste water |
| CN109626655A (en) * | 2019-01-19 | 2019-04-16 | 江钨世泰科钨品有限公司 | A method of vulcanization cycling utilization of wastewater |
| CN110182766A (en) * | 2019-06-20 | 2019-08-30 | 江钨世泰科钨品有限公司 | The H of whole non-pollutant discharge2S preparation method |
| CN110203890A (en) * | 2019-06-18 | 2019-09-06 | 江钨世泰科钨品有限公司 | There are two the hydrogen sulfide preparation methods of closed loop for tool |
| CN111003778A (en) * | 2019-12-30 | 2020-04-14 | 上海交通大学 | Heavy metal-containing contaminated acid vulcanization reaction device with gas phase pressure gradient |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108706700A (en) * | 2018-04-25 | 2018-10-26 | 中国瑞林工程技术有限公司 | A kind of method and its application of processing waste liquid containing heavy metal ion |
| CN109626656A (en) * | 2019-01-19 | 2019-04-16 | 江钨世泰科钨品有限公司 | A kind of administering method vulcanizing waste water |
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| CN110182766A (en) * | 2019-06-20 | 2019-08-30 | 江钨世泰科钨品有限公司 | The H of whole non-pollutant discharge2S preparation method |
| CN111003778A (en) * | 2019-12-30 | 2020-04-14 | 上海交通大学 | Heavy metal-containing contaminated acid vulcanization reaction device with gas phase pressure gradient |
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