CN103789533B - Process for treating iron vanadium slag by virtue of dry-process rotary kiln - Google Patents

Process for treating iron vanadium slag by virtue of dry-process rotary kiln Download PDF

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Publication number
CN103789533B
CN103789533B CN201410047260.4A CN201410047260A CN103789533B CN 103789533 B CN103789533 B CN 103789533B CN 201410047260 A CN201410047260 A CN 201410047260A CN 103789533 B CN103789533 B CN 103789533B
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dry
iron vitriol
vitriol slag
grades
cyclone
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CN103789533A (en
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谭宏斌
马小玲
侯小强
郭从盛
林拉才
郑旭涛
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Shaanxi University of Technology
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Shaanxi University of Technology
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses a process for treating iron vanadium slag by virtue of a dry-process rotary kiln. The process comprises the following steps: breaking the iron vanadium slag, and feeding into a rotary dryer for drying to obtain tail gas with ammonium carbonate, wherein drying hot air is hot air at the tail of the dry-process rotary kiln; grinding deaminized iron vanadium slag, adding a bonder and water, feeding into a multistage cyclone treatment device, and desulfurizing to obtain iron oxide and tail gas; feeding the tail gas generated by the desulfurization of the iron vanadium slag into a sulfuric acid workshop to produce sulfuric acid; washing the iron oxide, recovering valuable metals, and taking the washed iron oxide as a steelmaking material. According to the process, all heat sources are residual heat of the dry-process rotary kiln, so that the economic and environment-friendly benefits are remarkable.

Description

A kind of technique utilizing dry-process rotory kiln Heat Treatment iron vitriol slag
Technical field
The present invention relates to the treatment process that a kind of metallurgy industry is harmful to waste residue.
Background technology
Nearly ten years, the plumbous zinc metallurgy of China maintains the impetus increased fast, and 2010, plumbous zinc ultimate production reached 958.1 ten thousand tons.For the wet processing Sheng electricity zinc factory of annual output 100000 tons, if zinc ore concentrate iron content is in 8%, then the ammonium jarosite slag (abbreviation iron vitriol slag) of annual output is about 5.3 ten thousand tons of [Chen Yongmings, Tang Motang, 19th volume the 7th interim state non-ferrous metal journal Yang Sheng sea etc., NaOH decomposes containing indium iron vitriol slag novel process [J], China YouSe Acta Metallurgica Sinica, 2009,19(7): 1322-1331].The plumbous zinc metal production of China occupies the first in the world for years.While the develop rapidly of product production capacity, the process problem of the ammonium jarosite slag in production process progressively shows especially, is not only related to the comprehensive cyclic utilization of resource, and is more related to the impact on physical environment.
At present, the method for iron vitriol slag process is mainly and adopts high-temperature calcination and alkali decomposition additive process, the complex process of alkaline cleaning, and the waste residue obtained, waste liquid are difficult to process.High-temperature calcination technique is simple, produces without waste residue, waste gas, waste liquid.
Iron vitriol slag high-temperature calcination process is mainly and adopts rotary kiln heating and calcining, according to the thermal properties of ammonium jarosite, in heating up process, thermolysis occurs, and the product that differing temps is decomposed is different; At 290-479 DEG C, the product of decomposition is intermediate product and the ammonia of ferric oxide; More than 650 DEG C, final decomposition obtains ferric oxide and sulfur oxide, and reaction formula is as follows:
[Qiu electricity Yun, Ma Rongjun, hot acid leaches the treatment process [J] of iron vitriol slag in zinc hydrometallurgy, Hunan's nonferrous metals, 1994,10(3): 158-162].Though the recyclable ferric oxide of existing method and sulfur oxide, need external energy to heat iron vitriol slag, ammonia is more difficult with being separated of sulfur oxide, is unfavorable for reclaiming.The crystal grain of iron vitriol slag comparatively thin (1-10 μm) in addition, when desulfurization process, due to deviating from further of sulphur and water, the viscosifying power of crystal grain and crystal grain weakens, and will obtain thinner powder, is unfavorable for being separated of the gas after desulfurization and solid.
Summary of the invention
The object of this invention is to provide a kind for the treatment of process of iron vitriol slag of energy-saving and environmental protection.
For reaching above object, the present invention takes following technical scheme to be achieved:
Utilize a technique for dry-process rotory kiln Heat Treatment iron vitriol slag, it is characterized in that, comprise the steps:
(1) deamination process
After iron vitriol slag fragmentation, send into rotary dryer dry, desiccant hot blast is the hot blast of dry-process rotory kiln kiln tail, and hot blast temperature controls at 300 DEG C, obtains the tail gas containing volatile salt and deamination iron vitriol slag;
(2) desulfurization process
After deamination iron vitriol slag is pulverized, add binding agent and water, after mixing, be prepared into the bead that particle diameter is 1 millimeter, utilize the temperature of dry-process rotory kiln to be three hot blasts of 900 DEG C, in multistage cyclone cylinder treater, carry out desulfurization process, obtain ferric oxide and containing SO 2tail gas, wherein, binding agent is the one in silicon sol, Alumina gel, bauxitic clay, kaolinite, illite, montmorillonite, and add-on is the 5-10% of deamination iron vitriol slag weight; The add-on of water is 30% of deamination iron vitriol slag weight;
(3) what desulfurization process produced contains SO 2tail gas, send into sulfuric acid plant produce sulfuric acid; By ferric oxide after washing, reclaim valuable metal, the ferric oxide after washing is as steelmaking feed.
In aforesaid method, described multistage cyclone cylinder treater is three grades of cyclone cylinder treaters, and desulfurization process concrete steps are as follows:
A, the course of deamination iron vitriol slag bead in cyclone cylinder treater are: pass through charging opening, enter the venting port of secondary rotary air duct, be brought into one cyclonic cylinder, the inwall encountering one cyclonic cylinder falls, enter the venting port of three grades of cyclone cylinders, be brought into secondary rotary air duct, the inwall encountering secondary rotary air duct falls, and is brought into three grades of cyclone cylinders by the wind of tertiary air entrance, the inwall encountering three grades of cyclone cylinders falls, enter cooling room, finally by the rotation of capstan head, discharge from discharge port;
The moving line of b, gas is: hot blast enters three grades of cyclone cylinders by tertiary air entrance, through the vapor pipe on three grades of cyclone cylinder tops, enter secondary rotary air duct, the vapor pipe through secondary rotary air duct top enters one cyclonic cylinder, and the vapor pipe through one cyclonic cylinder top enters discharge; Entered the hot blast of three grades of cyclone cylinders by tertiary air entrance, produce a negative pressure at the top of cooling room, freezing air is sucked from discharge port, slag is cooled.
The bottom of described cyclone cylinder at different levels is provided with tightness system, and solid can move downward, and gas can not move up or down.
Tail gas step (1) gained being contained volatile salt carries out gas and is separated with volatile salt, and spelter works's recycle sent into by the volatile salt obtained, gas qualified discharge.
The washing of described step (3) adopts dilute sulphuric acid washing, and washings enters in the leach liquor of zinc abstraction.
Compared with prior art, thermal source of the present invention adopts the waste heat of dry-process rotory kiln, and namely the hot blast of dry-process rotory kiln kiln tail carries out drying to iron vitriol slag, and rotary kiln tail gas contains a large amount of CO 2, CO 2decompose with iron vitriol slag the ammonia gas react produced, obtain volatile salt, be conducive to recovery and the storage of ammonia, simultaneously also recyclable valuable sulphur and ferric oxide, therefore, present invention process has significant economic benefit and environmental benefit.In addition, binding agent is added in the iron vitriol slag of the present invention after deamination process, be prepared into the bead that particle diameter is 1 millimeter, the temperature of dry-process rotory kiln is utilized to be three hot blasts of 900 DEG C, desulfurization process is carried out in multistage cyclone cylinder treater, be conducive to being separated of gas and solid, reduce the dedusting cost of tail gas further.
Accompanying drawing explanation
Fig. 1 is inventive desulfurization process cyclone cylinder processor structure schematic diagram used.In figure: 1, capstan head; 2, discharge port; 3, cooling room; 4, three grades of cyclone cylinders; 5, tertiary air entrance; 6, secondary rotary air duct; 7, charging opening; 8, one cyclonic cylinder; 9, venting port.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Utilize a technique for dry-process rotory kiln Heat Treatment iron vitriol slag, comprise the steps:
(1) iron vitriol slag deamination process
After iron vitriol slag fragmentation, send into rotary dryer dry, desiccant hot blast is the hot blast of dry-process rotory kiln kiln tail, and hot blast temperature controls at 300 DEG C, obtains the tail gas containing volatile salt; After gas is separated with volatile salt, obtain volatile salt, send into spelter works's recycle, gas qualified discharge.
(2) the desulfurization process of iron vitriol slag
Iron vitriol slag after deamination process is pulverized, adds binding agent and water (filling a prescription see table 1), after mixing, be prepared into the bead that particle diameter is 1 millimeter, join in the cyclone cylinder treater of Fig. 1 and carry out desulfurization process, obtain ferric oxide and tail gas.
(3) by the tail gas that the desulfurization process of iron vitriol slag produces, send into sulfuric acid plant and produce sulfuric acid; By ferric oxide after dilute sulphuric acid washing, reclaim valuable metal, the ferric oxide after washing is as steelmaking feed; Washings enters in the leach liquor of zinc abstraction.
Desulfurization process concrete technology is see Fig. 1, iron vitriol slag after a, deamination process at the moving line of cyclone cylinder treater is: the venting port being entered secondary rotary air duct 6 by charging opening 7, be brought into one cyclonic cylinder 8, the inwall encountering cyclone cylinder 8 falls, enter the venting port of three grades of cyclone cylinders 4, be brought into secondary rotary air duct 6, the inwall encountering cyclone cylinder 6 falls, brought into cyclone cylinder 4 by the wind of tertiary air entrance 5, the inwall encountering cyclone cylinder 4 falls, enter cooling room 3, slag, by the rotation of capstan head 1, is discharged from discharge port 2.The hot blast of tertiary air entrance 5 is the tertiary air of dry-process rotory kiln, and temperature in is 900 degree.Be provided with tightness system in the bottom of cyclone cylinder at different levels, slag can move downward, and gas can not move up or down.The moving line of b, gas is: hot blast is by tertiary air entrance 5, and enter cyclone cylinder 4, through the vapor pipe on cyclone cylinder 4 top, enter cyclone cylinder 6, the vapor pipe through cyclone cylinder 6 top enters cyclone cylinder 8, and the vapor pipe through cyclone cylinder 8 top enters venting port 9.Entered the hot blast of cyclone cylinder 4 by tertiary air entrance 5, produce a negative pressure at the top of cooling room 3, freezing air is sucked from discharge port 2, slag is cooled.
Table 1

Claims (5)

1. utilize a technique for dry-process rotory kiln Heat Treatment iron vitriol slag, it is characterized in that, comprise the steps:
(1) deamination process
After iron vitriol slag fragmentation, send into rotary dryer dry, desiccant hot blast is the hot blast of dry-process rotory kiln kiln tail, and hot blast temperature controls at 300 DEG C, obtains the tail gas containing volatile salt and deamination iron vitriol slag;
(2) desulfurization process
After deamination iron vitriol slag is pulverized, add binding agent and water, after mixing, be prepared into the bead that particle diameter is 1 millimeter, utilize the temperature of dry-process rotory kiln to be three hot blasts of 900 DEG C, in multistage cyclone cylinder treater, carry out desulfurization process, obtain ferric oxide and containing SO 2tail gas, wherein, binding agent is the one in silicon sol, Alumina gel, and add-on is the 5-10% of deamination iron vitriol slag weight; The add-on of water is 30% of deamination iron vitriol slag weight;
(3) what desulfurization process produced contains SO 2tail gas, send into sulfuric acid plant produce sulfuric acid; By ferric oxide after washing, reclaim valuable metal, the ferric oxide after washing is as steelmaking feed.
2. utilize the technique of dry-process rotory kiln Heat Treatment iron vitriol slag as claimed in claim 1, it is characterized in that, described multistage cyclone cylinder treater is three grades of cyclone cylinder treaters, and desulfurization process concrete steps are as follows:
A, the course of deamination iron vitriol slag bead in cyclone cylinder treater are: pass through charging opening, enter the venting port of secondary rotary air duct, be brought into one cyclonic cylinder, the inwall encountering one cyclonic cylinder falls, enter the venting port of three grades of cyclone cylinders, be brought into secondary rotary air duct, the inwall encountering secondary rotary air duct falls, and is brought into three grades of cyclone cylinders by the wind of tertiary air entrance, the inwall encountering three grades of cyclone cylinders falls, enter cooling room, finally by the rotation of capstan head, discharge from discharge port;
The moving line of b, gas is: hot blast enters three grades of cyclone cylinders by tertiary air entrance, through the vapor pipe on three grades of cyclone cylinder tops, enter secondary rotary air duct, the vapor pipe through secondary rotary air duct top enters one cyclonic cylinder, and the vapor pipe through one cyclonic cylinder top enters discharge; Entered the hot blast of three grades of cyclone cylinders by tertiary air entrance, produce a negative pressure at the top of cooling room, freezing air is sucked from discharge port, slag is cooled.
3. utilize the technique of dry-process rotory kiln Heat Treatment iron vitriol slag as claimed in claim 2, it is characterized in that, be provided with tightness system in the bottom of cyclone cylinder at different levels, solid can move downward, and gas can not move up or down.
4. utilize the technique of dry-process rotory kiln Heat Treatment iron vitriol slag as claimed in claim 1, it is characterized in that, tail gas step (1) gained being contained volatile salt carries out gas and is separated with volatile salt, and spelter works's recycle sent into by the volatile salt obtained, gas qualified discharge.
5. utilize the technique of dry-process rotory kiln Heat Treatment iron vitriol slag as claimed in claim 1, it is characterized in that, the washing of described step (3) adopts dilute sulphuric acid washing, and washings enters in the leach liquor of zinc abstraction.
CN201410047260.4A 2014-02-11 2014-02-11 Process for treating iron vanadium slag by virtue of dry-process rotary kiln Expired - Fee Related CN103789533B (en)

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Publication number Priority date Publication date Assignee Title
CN106865504B (en) * 2017-01-09 2018-12-28 西南科技大学 A method of recycling high concentration sulfur oxide gas
CN107324358B (en) * 2017-06-20 2019-03-12 谭宏斌 A kind of iron vitriol slag low-temperature decomposition and the method that resource is separately recovered
CN107840311B (en) * 2017-11-15 2019-10-29 西南科技大学 A kind of method of containing sulphur-slag recycling sulphur

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1340456A (en) * 2000-09-01 2002-03-20 山东鲁北企业集团总公司 Process and equipment for decomposing gypsum
CN101456690A (en) * 2009-01-07 2009-06-17 中国建筑材料科学研究总院 Method and system for preparing active coal gangue
CN202081023U (en) * 2011-05-13 2011-12-21 高玉宗 Cyclone preheater
CN103411424A (en) * 2013-07-29 2013-11-27 攀钢集团攀枝花钢铁研究院有限公司 Powdery material heating device and method
CN103523832A (en) * 2013-09-04 2014-01-22 陕西理工学院 Process for recovering sulfur from ammoniojarosite

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1340456A (en) * 2000-09-01 2002-03-20 山东鲁北企业集团总公司 Process and equipment for decomposing gypsum
CN101456690A (en) * 2009-01-07 2009-06-17 中国建筑材料科学研究总院 Method and system for preparing active coal gangue
CN202081023U (en) * 2011-05-13 2011-12-21 高玉宗 Cyclone preheater
CN103411424A (en) * 2013-07-29 2013-11-27 攀钢集团攀枝花钢铁研究院有限公司 Powdery material heating device and method
CN103523832A (en) * 2013-09-04 2014-01-22 陕西理工学院 Process for recovering sulfur from ammoniojarosite

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