CN102897885B - The method of sulfuric acid industry Two-way Cycle jet-type arsenic removal - Google Patents
The method of sulfuric acid industry Two-way Cycle jet-type arsenic removal Download PDFInfo
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Abstract
The invention provides the method and apparatus of a kind of vitriol works Two-way Cycle jet-type arsenic removal.Vulcanizing agent is placed in hydrogen sulfide generator, and the hydrogen sulfide of generation enters reactor (3) by pipeline, and ON cycle pump (5) makes the material in reactor (3) carry out internal recycle; Simultaneous reactions still (3) remaining hydrogen sulfide enters reactor (4), and ON cycle pump (6) makes the material in reactor (4) carry out internal recycle.After question response 60 ~ 90min, by pipeline, reactor (3) reacted liquid is placed in storage tank, after leaving standstill 30 ~ 60min, liquid is carried out press filtration, the filter residue obtained can deliver to the recovery that smeltery carries out heavy metal, filtrate is directly discharged, and the waste liquid of reactor (4) then gives over to the reaction solution into next round reactor (3).The clearance of arsenic of the present invention reaches more than 99%, and filter residue arsenic content is high, is conducive to deep processing.
Description
Technical field
The present invention relates to the method and apparatus of a kind of vitriol works waste acid water Two-way Cycle jet-type removing heavy metals, belong to wastewater treatment, field of environment protection.
Background technology
In sulphuric acid process, extensively adopt sulfurous iron ore as raw material roasting, a large amount of arsenic-containing waste waters can be produced in water washing cleaning furnace gas process.A large amount of arsenic serious environment pollutions in waste water, the life health of harm people, and containing contents of many kinds of heavy metal ion in waste water, more increase its harm.How economical and effectively process gas washing in SA production factory containing arsenic spent acid, be numerous gas washing in SA production factory difficult problem urgently to be resolved hurrily.
At present, the method for process acidic arsenic-containing waste water is a lot of both at home and abroad, mainly contains absorption method, electroosmose process, electrolytic process, ion-exchange-resin process, membrane separation process, microorganism treatment, chemical precipitation method etc.Absorption method is exactly the heavy metal in the species adsorbs waste water utilizing the specific surface areas such as gac large, makes it precipitate and reaches the object of removing, and this method cost is high, is not generally used alone.Electroosmose process is the effect utilizing electric field, heavy metal ion is attracted to electrode place, thus reaches separation, concentrated object.The feature of electroosmose process process waste water does not need to consume chemical, and equipment is simple, easy to operate, but the treatment time is long, and treatment capacity is little, is not suitable for extensive process.Electrolytic process is exactly utilize heavy metal ion, on the negative electrode, anode of electrolyzer, redox reaction occurs, its form is changed and makes the method that toxicity reduces or disappears, the method process heavy metal ability is strong, directly can reclaim again heavy metal, shortcoming is exactly that power consumption is large, and the treatment time is long.Ion-exchange-resin process process heavy metal is exactly the object utilizing the active group Adsorption of Heavy Metal Ions in ion exchange resin and reach separation, fixing, enriching heavy metal, but the resin after Adsorption of Heavy Metals needs regeneration, and cost wants high relatively.Membrane separation process utilizes the mould material with a certain size aperture optionally through the material of a certain size molecular weight, them are made to reach separation, purifying, concentrated object, membrane sepn heavy metal is effective, but mould material price, the cleaning of film, safeguard cumbersome.The method of microbiological treatment heavy metal utilizes microorganism in reproductive process, by self oxidation, reductive action, heavy metal is converted into the even nontoxic form of low toxicity, and the material such as polysaccharide compound, protein secreted in microbial reproduction process can Adsorption of Heavy Metals and reach enrichment, transform the object of heavy metal.The method of microbial method process heavy metal is simple, and cost is low, but the treatment time is long, and the factor affecting treatment effect is a lot, and treatment effect is unstable.Relative to above six kinds for the treatment of processs, precipitator method process heavy metal is a kind of ancient, simple, method that scope is wide, and it utilizes heavy metal ion to produce with the precipitation agent added to react, generation indissoluble thing and reach the object of removal.The most frequently used precipitation agent is alkali metalsulphide.The solubility product of the sulfide of heavy metal is all very little, can various heavy in a step process waste water, and therefore the main method of sulfuric acid industry process arsenic-containing waste water is chemical precipitation method at present, and it specifically comprises lime method again, sulfuration method.
Lime method: the method exists the large and secondary pollution problem of the quantity of slag, slightly poor to arsenious treatment effect, and the arsenic in sulfuric acid production wastewater is mainly based on trivalent.The solubleness of Tricalcium arsenate in water is 130mg/L, be equivalent to arsenic content 48mg/L, and the solubleness of calcium arsenite is higher, is about 900mg/L.Therefore, in the water outlet after common lime method directly processes, arsenic content is often difficult to reach emission standard.
Sulfuration method: the sulfide solubility product sodium sulphite of heavy metal etc. obtain vulcanizing agent and are fixed in vulcanized slag by the heavy metal in arsenic-containing waste water, reach the object of removal heavy metal; And the arsenic content in vulcanized slag generally can reach more than 30%, the utilization of resources of its arsenic and the elimination of secondary pollution is made to become possibility.In neutrality or acidic solution, the equation of sulfonium ion and heavy metal ion generation chemical reaction is:
Cd
2++s
2-＝Cds↓Hg
2++s
2-＝Hgs↓
Pb
2++s
2-＝Pbs↓2As
3++3S
2-＝As
2S
3↓
2Gr
6++3S
2-＝2Cr
3++3S↓2Cr
3++3S
2-＝Cr
2S
3↓
Zn
2++s
2-＝ZnS↓Cu
2++s
2-＝CuS↓
Ni
2++s
2-＝Nis↓
But sulfuration method exists again some problems at present: 1. after sulfuration, in water, arsenic content is higher simultaneously, generally at more than 100mg/L, do not reach discharge or circulation standard.2. vulcanizing agent consumption is far longer than theoretical amount, and hydrogen sulfide is escaped in a large number, not only increases processing cost, also affects production plant environment.3. all need before and after the process of most of sulfuration method, with lime treatment, not only to waste raw material, also the acid in spent acid is also neutralized, waste resource, add quantity discharged, and technical process is all more loaded down with trivial details.
Summary of the invention
The object of the invention is to remove for existing sulphide precipitation that vitriol works's arsenic-containing waste water technique vulcanizing agent consumption is large, clearance is not high, produce the hydrogen sulfide of a large amount of contaminate environment, cumbersome, resource can not the problem such as recycle, provides the method and apparatus of a kind of Two-way Cycle jet-type arsenic removal.Level of automation of the present invention is high, and heavy metal removing rate is high, and cost is low.
The present invention is achieved in that and vulcanizing agent is placed in hydrogen sulfide generator, the hydrogen sulfide produced enters the first reactor 3 in Two-way Cycle jet-type by pipeline, opening the first recycle pump 5 makes the material in the first reactor 3 carry out internal recycle reaction, the circulating reaction time is 60 ~ 90 minutes, temperature of reaction is 30 ~ 60 DEG C, and reaction pressure is 0.1 ~ 0.3Mpa; The remaining hydrogen sulfide of first reactor 3 enters the second reactor 4 simultaneously, opening the second recycle pump 6 makes the material in the second reactor 4 carry out internal recycle reaction, the circulating reaction time is 60 ~ 90 minutes, and temperature of reaction is 30 ~ 60 DEG C, and reaction pressure is 0.1 ~ 0.3Mpa; Circulating reaction terminates, and is placed in storage tank by pipeline by the reacted liquid of the first reactor 3, and after leaving standstill 30 ~ 60min, liquid is carried out press filtration, and the filter residue obtained delivers to the recovery that smeltery carries out heavy metal, and filtrate directly fully utilizes, and realizes zero release; Waste liquid after second reactor 4 circulating reaction then gives over to the reaction solution into next round first reactor 3.Arsenic removal rate reaches more than 99%, and filter residue arsenic content is high, is conducive to deep processing.
Described stoste groove, is equipped with the waste water through one-level press filtration.
Described vulcanizing agent comprises a kind of in sodium sulphite, Iron sulfuret, Sodium sulfhydrate, potassium sulphide, ammonium sulfide or their composition, and consumption is 110 ~ 120% of theoretical amount.
Described mineral acid comprises a kind of in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or their composition, and concentration is 20 ~ 60%.
Advantage of the present invention is:
1, the present invention has a hydrogen sulfide generator, the add-on of hydrogen sulfide can be controlled at any time according to the size of pressure, Two-way Cycle jet-type makes responseless hydrogen sulfide stay in system until utilize completely always, therefore hydrogen sulfide does not lose, do not pollute the environment yet, running environment is good, and innovation vulcanization reaction device, vulcanization reaction realizes controlled.
2, react the vulcanized slag arsenic content drawn and reach more than 30%, be conducive to the deep processing of arsenic, realize resource utilization and the commercialization of arsenic, and the quantity of slag be few, one cube of spent acid containing arsenic 2% only obtains the dry slag of sulfuration of 35 ~ 40kg.
3, arsenic removal efficiency is reacted high, filtrate arsenic content can reach 2mg/L, and well below sulfuric acid industry circulation standard 50mg/L, the filtrate be obtained by reacting is without the need to carrying out advanced treatment, be directly used in the dry absorption section of vitriol works, achieve powerlessness waste, free of contamination process for cleanly preparing and wastewater zero discharge.
4, Two-way Cycle sprays and hydrogen sulfide is made full use of, and reduces the consumption of vulcanizing agent, improves the content of arsenic in vulcanized slag; Arsenic can a step eliminate, and eliminates the cumbersome process such as pretreatment and advanced treatment, simple for process.
5, the add-on of hydrogen sulfide can adjust according to the pressure of reactor, easily realizes automatization.
6, whole process unit can close arrangement, and floor space is little.
Accompanying drawing explanation
Fig. 1 is the equipment drawing of the method and apparatus of Two-way Cycle jet-type of the present invention arsenic removal, numbering and title as follows:
1---the first injector; 2---the second injector; 3 first reactors, 4---the second reactor; 5 first recycle pumps; 6---the second recycle pump; 7---stoste groove; 8---hydrogen sulfide generator; 9---interchanger; 10---surge tank.
Fig. 1 finding, the equipment of the method employing of Two-way Cycle jet-type arsenic removal, the lower end comprising the second reactor 4, first reactor 3, first injector 1, second injector 2, first recycle pump 5, second recycle pump 6, stoste groove 7, hydrogen sulfide generator 8, interchanger 9 and surge tank 10, first injector 1 is connected with the first reactor 3 with a pipeline; The lower end of the second injector 2 is connected with the second reactor 4 with a pipeline, the bottom pipeline of the first reactor 3 is communicated with the opening for feed of the first recycle pump 5, the bottom pipeline of the second reactor 4 is communicated with the opening for feed of the second recycle pump 6, the discharge port of the first recycle pump 5 is connected with the top of the first injector 1, the discharge port of the second recycle pump 6 is connected with the top of the second injector 2, connect with pipeline between two injectors, be also connected with pipeline between two reactors; Be connected with the feed end of the first recycle pump 5, second recycle pump 6 respectively with pipeline bottom stoste groove 7; Hydrogen sulfide generator 8 top pipeline is communicated with one end of interchanger 9, and the other end of interchanger 9 is communicated with surge tank 10, and the top pipeline of surge tank 10 is connected with the second injector 2 with the first injector 1.
Fig. 2 is the process flow sheet of the method and apparatus of Two-way Cycle jet-type of the present invention arsenic removal.
Embodiment
Embodiment 1
Get waste water 1 cube (waste water is vitriol works's arsenic-containing waste water, and acid content is 2.53%, and arsenic content is 1.15%), adopt Two-way Cycle jet-type removing heavy metals device, amount of sodium sulfide is 120% of theoretical amount, and circulating temperature is 40 DEG C, 60 minutes cycling time, reaction pressure is 0.2Mpa.Arsenic content 0.0002% (2ppm) after reaction, the clearance of arsenic reaches 99.98%, obtains the dry slag of 22.62Kg, and in dry slag, arsenic content is 34.53%.
Embodiment 2
Get waste water 1 cube (waste water is vitriol works's arsenic-containing waste water, and acid content is 2.53%, and arsenic content is 2.29%), adopt Two-way Cycle jet-type removing heavy metals device, amount of sodium sulfide is 120% of theoretical amount, and circulating temperature is 40 DEG C, 90 minutes cycling time, reaction pressure is 0.2Mpa.Arsenic content 0.0004% (4ppm) after reaction, the clearance of arsenic reaches 99.98%, obtains the dry slag of 39.71Kg, and in dry slag, arsenic content is 34.53%.
Embodiment 3
Get waste water 1 cube (waste water is vitriol works's arsenic-containing waste water, and acid content is 6.03%, and arsenic content is 1.05%), adopt Two-way Cycle jet-type removing heavy metals device, amount of sodium sulfide is 120% of theoretical amount, and circulating temperature is 40 DEG C, 60 minutes cycling time, reaction pressure is 0.2Mpa.Arsenic content 0.0005% (5ppm) after reaction, the clearance of arsenic reaches 99.99%, obtains the dry slag of 20.71Kg, and in dry slag, arsenic content is 32.03%.
Embodiment 4
Get waste water 1 cube (waste water is vitriol works's arsenic-containing waste water, and acid content is 6.03%, and arsenic content is 2.18%), adopt Two-way Cycle jet-type removing heavy metals device, amount of sodium sulfide is 120% of theoretical amount, and circulating temperature is 40 DEG C, 90 minutes cycling time, reaction pressure is 0.2Mpa.Arsenic content 0.0004% (4ppm) after reaction, the clearance of arsenic reaches 99.98%, obtains the dry slag of 37.78Kg, and in dry slag, arsenic content is 31.35%.
Claims (2)
1. the method for Two-way Cycle jet-type arsenic removal, it is characterized in that: vulcanizing agent is placed in hydrogen sulfide generator, be added dropwise to mineral acid, reaction, the hydrogen sulfide produced enters the first reactor (3) in Two-way Cycle jet-type equipment by pipeline, open the first recycle pump (5) and make the material in the first reactor (3) carry out internal recycle reaction, the circulating reaction time is 60 ~ 90 minutes, temperature of reaction is 30 ~ 60 DEG C, and reaction pressure is 0.1 ~ 0.3Mpa; First reactor (3) remaining hydrogen sulfide enters the second reactor (4) simultaneously, opening the second recycle pump (6) makes the material in the second reactor (4) carry out internal recycle reaction, the circulating reaction time is 60 ~ 90 minutes, and temperature of reaction is 30 ~ 60 DEG C, and reaction pressure is 0.1 ~ 0.3Mpa; Circulating reaction terminates, and is placed in storage tank by pipeline by the first reactor (3) reacted liquid, and after leaving standstill 30 ~ 60min, liquid is carried out press filtration, and the filter residue obtained is red arsenic, and filtrate fully utilizes after treatment, realizes zero release; Waste liquid after second reactor (4) circulating reaction then gives over to the reaction solution into next round first reactor (3);
Described vulcanizing agent comprises a kind of in sodium sulphite, Iron sulfuret, Sodium sulfhydrate, potassium sulphide and ammonium sulfide or their composition, and consumption is 110 ~ 120% of theoretical amount;
Described mineral acid comprises a kind of in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or their composition, and concentration is 20 ~ 60%;
The equipment of the method employing of Two-way Cycle jet-type arsenic removal, comprise the second reactor (4), the first reactor (3), the first injector (1), the second injector (2), the first recycle pump (5), the second recycle pump (6), stoste groove (7), hydrogen sulfide generator (8), interchanger (9) and surge tank (10), the lower end of the first injector (1) is connected with the first reactor (3) with a pipeline; The lower end of the second injector (2) is connected with the second reactor (4) with a pipeline, the bottom pipeline of the first reactor (3) is communicated with the opening for feed of the first recycle pump (5), the bottom pipeline of the second reactor (4) is communicated with the opening for feed of the second recycle pump (6), the discharge port of the first recycle pump (5) is connected with the top of the first injector (1), the discharge port of the second recycle pump (6) is connected with the top of the second injector (2), connect with pipeline between two injectors, be also connected with pipeline between two reactors; Stoste groove (7) bottom is connected with the feed end of the first recycle pump (5), the second recycle pump (6) respectively with pipeline; Hydrogen sulfide generator (8) top pipeline is communicated with one end of interchanger (9), and the other end of interchanger (9) is communicated with surge tank (10), and the top pipeline of surge tank (10) is connected with the second injector (2) with the first injector (1).
2. the method for Two-way Cycle jet-type according to claim 1 arsenic removal, is characterized in that: described stoste groove, and the waste water through one-level press filtration is housed.
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| CN103553248B (en) * | 2013-10-23 | 2015-04-08 | 中南大学 | Heavy metal waste acid and wastewater resource recycling method and device |
| CN103880111B (en) * | 2014-03-28 | 2015-01-21 | 中国地质大学（武汉） | Arsenic removal method based on surface in-situ iron plating technology |
| CN105502622B (en) * | 2016-01-15 | 2018-04-06 | 中国瑞林工程技术有限公司 | Waste Water Treatment and method |
| CN105777597A (en) * | 2016-04-08 | 2016-07-20 | 张俊杰 | Method for preparing thioacetamide |
| CN106083678A (en) * | 2016-06-01 | 2016-11-09 | 张俊杰 | A kind of supported catalyst prepares the method for thioacetamide |
| CN113979568B (en) * | 2021-11-26 | 2023-08-11 | 四川匠德环保技术开发有限公司 | Arsenic removal treatment process for high-arsenic strong-acid wastewater |
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| WO2010017652A1 (en) * | 2008-08-11 | 2010-02-18 | Hernandez Pavez Jose Octavio | Process and system for separation, recycling and sustainable environmental stabilisation of acid effluents with arsenic (as) and/or heavy metals which form insoluble sulphides |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5732786A (en) * | 1980-08-02 | 1982-02-22 | Nippon Mining Co Ltd | Method and device for dearsenization |
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Patent Citations (5)
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| JP2002012995A (en) * | 2000-06-30 | 2002-01-15 | Nippon Mining & Metals Co Ltd | Apparatus and method for automatically purifying liquid after copper removal |
| CN101234826A (en) * | 2007-08-29 | 2008-08-06 | 大冶有色金属公司 | Sulfuration recovery processing method and device for high-acidity high-arsenic high-cadmium waste water |
| WO2010017652A1 (en) * | 2008-08-11 | 2010-02-18 | Hernandez Pavez Jose Octavio | Process and system for separation, recycling and sustainable environmental stabilisation of acid effluents with arsenic (as) and/or heavy metals which form insoluble sulphides |
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