CN102534188A - Method for producing iron pellet with sulfur acid residue containing large contents of impurities and enriching valuable metal - Google Patents
Method for producing iron pellet with sulfur acid residue containing large contents of impurities and enriching valuable metal Download PDFInfo
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Abstract
The invention discloses a method for producing iron pellets with sulfur acid residue containing large contents of impurities and enriching valuable metal. The method comprises the following steps: reducing and calcining under a moderate temperature, preparing the iron pellets, chlorinating and calcining under a high temperature, reducing the temperature of the iron pellets while recycling heat energy, collecting dust in flue gas and purifying the flue gas, adding a reducing agent of which the weight is 6 to 9 percent that of the sulfur acid residue on the condition that the kiln head temperature ranges from 750 to 900 DEG C, the kiln tail temperature ranges from 350 to 500 DEG C, and the reducing and calcining step lasts for 70 to 100 min; calcining sand in a high temperature on the condition that 3 to 5 percent of ferrous chloride, 2 to 3 percent of adhesive, and 2 to 3 percent of lignite and/or coke powder are added; pelletizing; carrying out the high-temperature chlorinating and calcining step after dry pre-heating; and recycling heat energy, collecting dust, and purifying the flue gas to achieve the emission standard. According to the invention, two sections of a rotary kiln are adopted for fulfilling the reducing and calcining step and the high-temperature chlorinating and calcining step respectively, wherein a large quantity of arsenic is extracted, part of zinc is reduced and volatilized, the chlorination calcining ensures the reduction and the volatilization of residual arsenic, zinc, tin, lead and copper are chlorinated and volatilized, and sulphur is oxidized into sulfur dioxide and enters the flue gas, so as to obtain qualified the iron pellets. The method has the advantages that the iron recovery rate is 92 to 95; the arsenic extraction rate is larger than 95 percent; the desulfuration rate is equal to or larger than 90 percent; the volatilization rates of the lead, tin and zinc are 60 to 70 percent; and the volatilization rate of copper is about 30 percent.
Description
Technical field
The invention belongs to the non-ferrous metal metallurgy technical field, especially the tin technical field of metallurgical equipment is specifically related to a kind of process stabilizing, and is easy and simple to handle, can be with the effective production iron ball nodulizing of removing of the various impurity in the high sulfur impurity acid sludge and the method for concentration of valuable metals.
Background technology
Along with the development of Iron And Steel Industry, the natural resources of iron ore is in short supply day by day, and many countries have begun the second stage employ research to iron-containing resource very early.Pyrite is produced boiling furnace slag and the flue dust behind the sulfuric acid, is referred to as " sulfate slag ", because its iron content is higher, foreign matter content is low, becomes the valuable source of second development and utilization for many years always.The country that research and development the earliest utilize is a Japan, just formally uses sulfate slag to be iron-smelting raw material from nineteen fifty, year usage quantity more than 1,000,000 tons, by 1961, the sulfate slag total amount of Japan, West Germany, the use of Britain three states reached 6,720,000 tons.Sulfate slag utilization technology is most representative to be Japanese light and concentrate company exploitation " chloridizing volatilization pelletizing method ", is called for short " light and method "." light and method " processing pyritic sulphur acid sludge of Japan is just learnt to introduce since the sixties in last century by China, and domestic for many years also have many Application Research achievements to occur, and applied for multinomial patent of invention.The irony multi-metal complex of China's non-ferrous metal association is associated minerals altogether; The content of iron is very high in the mine tailing that in ore dressing process, produces; Select sulfurous iron ore during comprehensive utilization of tailing, wherein often contain the metal such as arsenic, zinc, lead, tin, copper of some amount, when producing sulfuric acid; The most of sulfate slag that gets into of above-mentioned metal becomes the impurity that influences the iron-smelting raw material quality.High impurity sulfate cinder iron content higher though (Fe 53 ~ 57%); But zinc (Zn 0.7 ~ 1.5%), copper (Cu 0.5 ~ 0.7%), tin (Sn 0.2 ~ 0.5%), plumbous (Pb 0.1 ~ 0.3%), sulphur (S 0.5 ~ 1.2%) content are also higher; Especially content can be up to 0.5 ~ 1.8% in sulfate slag for arsenic; And the iron ore quality standard is the strictest to the requirement of arsenic content, must be below 0.07%.Just because of the influence of impurity arsenic, limited in the sulfate slag as the comprehensive utilization of fe source, the dearsenification effect is the technology barrier that the high sulfur impurity acid sludge of influence makes full use of, and is the technical barrier that presses for solution.The inventor is through concentrate on studies for many years; A kind of characteristics have been developed to high impurity multielement sulfate slag; Proposed dearsenification from sulfate slag, extracted the method for multiple non-ferrous metals such as zinc, lead, tin, copper simultaneously, when obtaining up-to-standard iron-smelting raw material; Become useful resource to deleterious impurity, the comprehensive utilization of the secondary resource of precious metals is rich in realization.
Summary of the invention
The object of the present invention is to provide a kind of process stabilizing, easy and simple to handle, can the various impurity in the high sulfur impurity acid sludge effectively be removed the method for concentration of valuable metals when producing qualified iron ball nodulizing.
The objective of the invention is to realize like this, warm reducing roasting in comprising, the preparation of iron ball group, high temperature chlorination roasting, the cooling of iron ball group are also reclaimed heat energy, flue gas dust collection and cleaning section, specifically comprise:
A, middle temperature reducing roasting: the weight of pressing sulfate slag adds 6 ~ 9% brown coal and/or coke powder as reductive agent; Control batching basicity is 0.5 ~ 0.67; Control 750 ~ 900 ℃ of preposition rotary kiln end temperature, 350 ~ 500 ℃ of kiln end temperatures, material is roasting 70 ~ 100min under weak reducing environment; Wherein most arsenic and a part of zinc, tin reduction volatilization are got in the flue dust, and iron and copper are then stayed in the calcining;
B, the preparation of iron ball group: hot calcine is sent in the whisking appliance; Add weight ratio 3 ~ 5% iron protochlorides, 2 ~ 3% tackiness agent, 2 ~ 3% brown coal and/or coke powder; Behind stirring and evenly mixing, process the spherolite of particle diameter 20 ~ 30mm; Send into then in the drying and preheating device,, make iron ball group drying and be preheated to 700 ~ 800 ℃ at 400 ~ 1000 ℃ of temperature lower step heating 16 ~ 20min;
C, high temperature chlorination roasting: the iron ball group through preheating sends into rearmounted rotary kiln, 1150 ~ 1300 ℃ of control temperature of kiln head, 850 ~ 1000 ℃ of kiln end temperatures; Make kiln hood keep weakly reducing atmosphere; The kiln tail keeps weak oxide atmosphere, and chloridizing roasting 60 ~ 80min makes remaining arsenic reduction volatilization; Zinc, tin, copper chloridizing volatilization, sulphur are oxidized to sulfurous gas and get into flue gas; And impel the sclerosis of iron ball briquetting knot, improve pellet strength; Kiln tail high-temperature flue gas is introduced the B operation as the work thermal source;
D, the cooling of iron ball group are also reclaimed heat energy: send into cooling apparatus behind the high temperature pelletizing kiln discharge, feed cold wind the high temperature pelletizing is cooled to about 100 ℃, reclaim the work thermal source of the hot blast of its heat energy as the B operation;
E, flue gas dust collection and purification: the ash-laden gas from rotary kiln adopts the dry dust collection system to gather dust, and the oxide compound of collecting arsenic, zinc, lead, tin, copper and/or muriate improve metal recovery rate; Flue gas after the dedusting adopts wet purification, and with the oxide compound and/or the muriate of the sulphur in the flue gas, arsenic, and remaining flue dust collecting makes the flue gas qualified discharge in scavenging solution.
Arsenic in the sulfate slag is with high price arsenic oxide (As
2O
5) and low price arsenic oxide (As
2O
3) the form coexistence, wherein high oxide accounts for 2/3; Other non-ferrous metal impurity also mainly exists with oxide form.Prior art high temperature chlorination roasting methods such as " light and methods "; The avidity that all is based on various metal pair oxygen and chlorine is different with volatilization point; Multiple different process such as reduction, chlorination, oxidizing roasting, high-temperature concretion are concentrated on accomplish in one section rotary kiln; But in fact can not take into account the multiple impurity of different nature of volatilization simultaneously, especially adopt calcium chloride (CaCl
2) as chlorizating agent, though have many good qualities, very unfavorable to dearsenification, because all possibly being cured as arsenic Tricalcium arsenate and can't volatilizing, the oxide compound of any calcium or calcium salt remove.Here it is, and why traditional chloridizing roasting method can handle the low pyrite of foreign matter content " burning slag " effectively, and when handling the high sulfur impurity acid sludge of non-ferro metals debris relieving haperacidity output, can not produce the major cause of qualified iron-smelting raw material.
Usually the content of arsenic in sulfate slag is 1.0 ~ 2.0%, and qualified powdered iron ore (pelletizing) require arsenic necessary≤0.07%, then require the evaporation rate of arsenic to reach more than 95%.Prior art chloridizing roasting technology adopts calcium chloride as chlorizating agent more, and dearsenification and non-ferrous metal chloridizing volatilization are mixed, and makes arsenic oxide arsenoxide chemical combination become Tricalcium arsenate, so arsenic-removing rate is very low.Arsenic oxide (As at a low price in fact
2O
3) boiling point very low, be merely 460 ℃, in setting under the warm reducing roasting condition, as long as can generate As
2O
3, can make most arsenic reduction volatilizations, can satisfy the ironmaking requirement basically.The present invention is directed to the performance characteristics of high sulfur impurity acid sludge; Adopt and divide kiln roasting volatilization technology; Warm reducing roasting volatilization method during arsenic taked to zinc, tin, the plumbous method of then taking to reduce chloridizing roasting, is then taked oxidation chlorination roasting volatilization method to copper; And under oxidizing atmosphere, carry out high-temperature roasting, produce qualified iron ball group.
The present invention adopts brown coal partly or entirely to substitute coke powder as reductive agent, and helping keeping in the kiln is weakly reducing atmosphere, helps the arsenic reduction volatilization.Strongly reducing atmosphere can cause arsenic, iron reduction to become the arsenic iron alloy, and unfavorable volatilization also can cause the knot kiln, makes operation not smooth.If oxidizing atmosphere is unfavorable to the volatilization of arsenic.The present invention utilizes the high characteristics of brown coal fugitive constituent, cooperates the control air quantity, avoids occurring in the kiln oxidizing atmosphere.
Said B operation adopts iron protochloride as chlorizating agent, and purpose is to reduce dearsenification and has met the requirements of under the prerequisite, utilizes the advantage of iron protochloride, further with the abundant chloridizing volatilization of residual non-ferrous metal.The purpose that adds tackiness agent is to guarantee the quality of iron ball group through improving the cohesiveness of material.
Said C operation, the maintenance kiln hood is a weakly reducing atmosphere, the one, in order to make remaining arsenic reduction volatilization, the 2nd, make zinc, tin reduction chloridizing volatilization; Keeping the kiln tail is weak oxide atmosphere, the one, make martial ethiops (Fe
3O
4) be oxidized to high oxide (Fe
2O
3), the 2nd, make sulphur be oxidized to sulfurous gas and get into flue gas, the 3rd, under oxidizing atmosphere, impel copper chloridizing volatilization.
The present invention is directed to that to burn in the slag several kinds of non-ferrous metals different different with volatilization point to the oxygen chloride affinity; With the rotary kiln is roasting volatilization equipment; Adopt different atmosphere, different volatilization temperatures, warm reducing roasting and high temperature chlorination roasting in two sections rotary kilns, carrying out respectively.The leading portion rotary kiln is accomplished the reduction volatilization of most arsenic, and the back segment rotary kiln is mainly accomplished the reduction and the chloridizing volatilization task of zinc, tin, lead, the oxidation removal of the oxidation of copper and chloridizing volatilization, sulphur and the oxidation of iron and pelletizing high-temperature concretion.The iron recovery 92 ~ 95% of the inventive method, arsenic-removing rate>95%, desulfurization degree >=90%, lead, tin, zinc evaporation rate 60 ~ 70%, copper evaporation rate about 30%.
Description of drawings
Accompanying drawing is the present invention's process flow diagram.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described, but never in any form the present invention is limited, any change or improvement based on training centre of the present invention is done all belong to protection scope of the present invention.
Shown in accompanying drawing, warm reducing roasting in the present invention includes, the preparation of iron ball group, high temperature chlorination roasting, the cooling of iron ball group are also reclaimed heat energy, flue gas dust collection and cleaning section, specifically comprise:
A, middle temperature reducing roasting: the weight of pressing sulfate slag adds 6 ~ 9% brown coal and/or coke powder as reductive agent, control batching basicity (CaO/SiO
2) be 0.5 ~ 0.67; Control 750 ~ 900 ℃ of preposition rotary kiln end temperature, 350 ~ 500 ℃ of kiln end temperatures, material is roasting 70 ~ 100min under weak reducing environment; Wherein most arsenic and a part of zinc, tin reduction volatilization are got in the flue dust, and iron and copper are then stayed in the calcining;
B, the preparation of iron ball group: hot calcine is sent in the whisking appliance; Add weight ratio 3 ~ 5% iron protochlorides, 2 ~ 3% tackiness agent, 2 ~ 3% brown coal and/or coke powder; Behind stirring and evenly mixing, process the spherolite of particle diameter 20 ~ 30mm; Send into then in the drying and preheating device,, make iron ball group drying and be preheated to 700 ~ 800 ℃ at 400 ~ 1000 ℃ of temperature lower step heating 16 ~ 20min;
C, high temperature chlorination roasting: the iron ball group through preheating sends into rearmounted rotary kiln, 1150 ~ 1300 ℃ of control temperature of kiln head, 850 ~ 1000 ℃ of kiln end temperatures; Make kiln hood keep weakly reducing atmosphere; The kiln tail keeps weak oxide atmosphere, and chloridizing roasting 60 ~ 80min makes remaining arsenic reduction volatilization; Zinc, tin, copper chloridizing volatilization, sulphur are oxidized to sulfurous gas and get into flue gas; And impel the sclerosis of iron ball briquetting knot, improve pellet strength; Kiln tail high-temperature flue gas is introduced the B operation as the work thermal source;
D, the cooling of iron ball group are also reclaimed heat energy: send into cooling apparatus behind the high temperature pelletizing kiln discharge, feed cold wind the high temperature pelletizing is cooled to about 100 ℃, reclaim the work thermal source of the hot blast of heat energy as the B operation;
E, flue gas dust collection and purification: the ash-laden gas of two sections rotary kilns adopts the dry dust collection system to gather dust, and the oxide compound of collecting arsenic, zinc, lead, tin, copper or muriate improve metal recovery rate; Flue gas after the dedusting adopts wet purification, and with the oxide compound and/or the muriate of the sulphur in the flue gas, arsenic, and remaining flue dust collecting makes the flue gas qualified discharge in scavenging solution.
The weight of pressing sulfate slag in the A operation adds 5 ~ 8% brown coal and/or coke powder, or to use silica powder be 0.55 ~ 0.60 as alkalinity regulator control batching basicity, 800 ~ 850 ℃ of temperature of kiln head, 400 ~ 450 ℃ of kiln end temperatures, middle temperature reducing roasting 80 ~ 90min.
Described tackiness agent is one or more the mixed adhesive in sodium bentonite, the calcium-base bentonite.The content of smectite >=65% in the said wilkinite, pH value 7 ~ 9.
Said B operation whisking appliance mix adopts twin-screw mixing procedure machine or garden tube mixer, and material is fully mixed.
The granulator as garden pan granulator; said drying unit preheating unit in the chain Bi, Bi spheroids in the chain drive 600 ~ 800 ℃ temperature drying and preheating segmentation.Described high temperature iron oxygen pelletizing cooling adopts circular cooler to carry out air-cooled and heat energy is reclaimed in exchange.
Described dry dust collection is gathered dust for the gravity decanter type and cloth bag type gathers dust.
The described cloth bag type temperature of gathering dust is controlled on 160 ~ 180 ℃ of the muriatic dew points, and the described cloth bag that gathers dust is high temperature resistant cloth bag, heatproof >=200 ℃.
The high-temperature flue gas of said preposition rotary kiln is directly sent into system for wet purification after dry dust collection; The high temperature dust flue gas of said rearmounted rotary kiln at first is introduced into the B operation as iron oxygen pelletizing drying and preheating thermal source, gets into dust collecting system again after the heating iron ball group.
Described wet purifying decice adopts high anticorrosion N-D steel to do.
Said preposition rotary kiln length-to-diameter ratio is 12 ~ 15; Obliquity is 4 ~ 5%; Velocity of rotation is 0.8 ~ 1.2 r/min.
Said rearmounted rotary kiln length-to-diameter ratio is 10 ~ 12; Obliquity is 2 ~ 3%; Velocity of rotation is 0.6 ~ 1.0 r/min.
Said rotary kiln is fuel with the producer gas.
Described solid useless comprehensive utilization: obnoxious flavoures such as wet purification system remaining flue dust of absorption and sulfur in smoke, oxynitride, arsenic oxide arsenoxide become slurries; In slurries, adding the multistage neutralization of lime filters; In the filter residue enrichment metals such as zinc, tin, lead; Directly as the raw material of melting, the calcium chloride in the filtrating gets into the high temperature chlorination roasting flow process, to replenish the consumption of chlorizating agent.
Further specify the present invention below in conjunction with embodiment:
Use the raw material sulphuric acid slag ingredient to see table 1:
High sulfur impurity acid sludge instance component list (%) table 1
| Fe | As | S | Zn | Pb | Sn | Cu | SiO 2 | CaO |
| 56.13 | 1.65 | 0.85 | 1.31 | 0.21 | 0.21 | 0.18 | 5.68 | 0.93 |
Embodiment 1
With sulfate slag shown in the table 1 is raw material, in sulfate slag, adds reductive agent 6%, wherein brown coal 4%, coke powder 2%, and control batching basicity is 0.50, behind stirring and evenly mixing, sends into preposition rotary kiln, the rotary kiln length-to-diameter ratio is 12; Obliquity 4 %; Velocity of rotation 0.8 r/min, 800 ~ 850 ℃ of control temperature of kiln head, 400 ~ 450 ℃ of kiln end temperatures, roasting kiln 90min under weakly reducing atmosphere.Calcine directly into the kiln cylinder mixer, add 3% by weight of calcine ferrous chloride and 2.5% sodium bentonite were added after dilution with water, then add 2% of lignite, coke powder 1% and control the material moisture of 11 to 12%, in the blender stir the mixture into the disc granulators, made of 20 ~ 30mm diameter pellets, and then fed into the chain Bi machine 400 ~ 1000 ℃ temperature next rung drying 18min, and preheat to 700 ~ 800 ℃.The iron ball group of preheating sends into rearmounted rotary kiln, and the rotary kiln length-to-diameter ratio is 10; Obliquity 2 %; Velocity of rotation 0.6 r/min; 1200 ~ 1250 ℃ of control temperature of kiln head, 900 ~ 950 ℃ of kiln end temperatures, chloridizing roasting 60min; Sending into circular cooler behind the kiln discharge is cooled to about 100 ℃; Obtain iron ball group, wherein contain Fe 56.72%, As 0.07%, Zn 0.46%, Cu 0.14%, Pb 0.10%, Sn 0.10%, S < 0.10%.The be up to state standards requirement of H55 of the grade of iron, outside the dezincification content overproof, other foreign matter content meets the requirement of iron-smelting raw material fully, and especially arsenic content reaches requirement.The plumbous evaporation rate of tin all about 70%, the evaporation rate about 65% of zinc, the evaporation rate about 30% of copper, iron recovery is more than 81%.Adopt the gravity settling dust collecting system to collect flue dust, the fume centralized after the dedusting adopts wet purifying decice to purify, and obtains precious metals such as zinc, lead, tin, copper, the flue gas qualified discharge.
Embodiment 2
With sulfate slag shown in the table 1 is raw material, in sulfate slag, adds reductive agent 9%, wherein brown coal 4%, coke powder 5%, and control batching basicity is 0.67, behind stirring and evenly mixing, sends into preposition rotary kiln, the rotary kiln length-to-diameter ratio is 15; Obliquity 5 %; Velocity of rotation 1.2 r/min, 850 ~ 900 ℃ of control temperature of kiln head, 450 ~ 500 ℃ of kiln end temperatures, roasting kiln 80min under weakly reducing atmosphere.Calcine kiln cylinder directly into blender, add 4% by weight of calcine ferrous chloride and 1.5% calcium bentonite were added after dilution with water, then add 3% of lignite and control the material moisture 11 to 12%, sufficiently stirred in the mixing machine into the mixing pan granulator, having diameters of 20 ~ 30mm pellets and then fed chain Bi machine temperature 500 ~ 900 ℃ drying steps 18min, and preheated to 700 ~ 800 ℃.The iron ball group of preheating sends into rearmounted rotary kiln, and the rotary kiln length-to-diameter ratio is 12; Obliquity 3 %; Velocity of rotation 1.0 r/min, 1250 ~ 1300 ℃ of control temperature of kiln head, 950 ~ 1000 ℃ of kiln end temperatures; Chloridizing roasting 60min sends into circular cooler and is cooled to about 100 ℃ behind the kiln discharge, obtain iron ball group; Wherein contain Fe 56.53%, As 0.06%, S 0.10%, Zn 0.39%, Cu 0.11%, Pb 0.10%, < 0.10%, the be up to state standards requirement of H55 of the grade of iron is outside the dezincification content overproof for Sn; Other foreign matter content meets the requirement of iron-smelting raw material fully, and especially arsenic content reaches requirement.The plumbous evaporation rate of tin all about 70%, the evaporation rate about 70% of zinc, the evaporation rate about 35% of copper, iron direct yield 79%.Gather dust, cleaning section is with last embodiment, obtains precious metals such as zinc, lead, tin, copper, the flue gas qualified discharge.
Embodiment 3
With sulfate slag shown in the table 1 is raw material, in sulfate slag, adds reductive agent 7%, wherein brown coal 1%, coke powder 6%, and control batching basicity is 0.6, behind stirring and evenly mixing, sends into preposition rotary kiln, the rotary kiln length-to-diameter ratio is 12; Obliquity 6 %; Velocity of rotation 1.1 r/min, 750 ~ 800 ℃ of control temperature of kiln head, 350 ~ 400 ℃ of kiln end temperatures, roasting kiln 100min under weakly reducing atmosphere.Calcine directly into the kiln cylinder mixer, add the calcine 5% by weight of ferrous chloride and 3% sodium bentonite were added after dilution with water, then add 1% of lignite, coke powder 3% and control the material moisture of 11 to 12%, in the blender stir the mixture into the pan granulator, granulating disc mechanism with a particle size of 20 ~ 30mm pellets, and then into the chain Bi machine 600 ~ 800 ℃ temperature cascade dried 18min, and preheat to 700 ~ 800 ℃.The iron ball group of preheating sends into rearmounted rotary kiln, and the rotary kiln length-to-diameter ratio is 11; Obliquity 3%; Velocity of rotation 1.0 r/min, 1150 ~ 1200 ℃ of control temperature of kiln head, 850 ~ 900 ℃ of kiln end temperatures; Chloridizing roasting 70min sends into circular cooler and is cooled to about 100 ℃ behind the kiln discharge, obtain iron ball group; Wherein contain Fe 56.80%, As 0.06%, S 0.10%, Zn 0.45%, Cu 0.12%, Pb 0.10%, < 0.10%, the be up to state standards requirement of H55 of the grade of iron is outside the dezincification content overproof for Sn; Other foreign matter content meets the requirement of iron-smelting raw material fully, and especially arsenic content reaches requirement.The plumbous evaporation rate of tin all about 70%, the evaporation rate about 65% of zinc, the evaporation rate about 30% of copper, iron direct yield 81%.Gather dust, cleaning section obtains with last embodiment, obtains precious metals such as zinc, lead, tin, copper, the flue gas qualified discharge.
Embodiment 4
With sulfate slag shown in the table 1 is raw material, in sulfate slag, adds 9% brown coal as reductive agent, and control batching basicity is 0.55, behind stirring and evenly mixing, sends into preposition rotary kiln, and the rotary kiln length-to-diameter ratio is 11; Obliquity 4%; Velocity of rotation 0.9 r/min, 750 ~ 800 ℃ of control temperature of kiln head, 350 ~ 400 ℃ of kiln end temperatures, roasting kiln 70min under weakly reducing atmosphere.Directly send into behind the calcining kiln discharge in the tube mixer of garden; Add the iron protochloride of calcining weight 3% and 2% calcium base and sodium base mixing wilkinite, all add behind the dilute with water, add coke powder 3% again; And the control material moisture is 11 ~ 12%; Subsequent handling is with embodiment 3, obtain iron ball group contain Fe 56.20%, As 0.06%, S 0.11%, Zn 0.40%, Cu 0.11%, Pb 0.10%, Sn 0.10%, the be up to state standards requirement of H55 of the grade of iron.Gather dust, cleaning section obtains with last embodiment, obtains precious metals such as zinc, lead, tin, copper, the flue gas qualified discharge.
Embodiment 5
With sulfate slag shown in the table 1 is raw material, in sulfate slag, adds 6% brown coal as reductive agent, and control batching basicity is 0.58, behind stirring and evenly mixing, sends into preposition rotary kiln, and the rotary kiln length-to-diameter ratio is 12; Obliquity 5%; Velocity of rotation 1.1 r/min, 850 ~ 900 ℃ of control temperature of kiln head, 400 ~ 450 ℃ of kiln end temperatures, roasting kiln 65min under weakly reducing atmosphere.Directly send into behind the calcining kiln discharge in the tube mixer of garden; Add the iron protochloride of calcining weight 4% and 3% calcium-base bentonite, all add behind the dilute with water, add coke powder 2% again; And the control material moisture is 11 ~ 12%; Subsequent handling is with embodiment 3, obtain iron ball group contain Fe 57.10%, As 0.05%, S 0.09%, Zn 0.36%, Cu 0.10%, Pb 0.10%, Sn 0.10%, the be up to state standards requirement of H55 of the grade of iron.Collect flue dust through the cloth bag type dust collecting system, the fume centralized after the dedusting adopts wet purifying decice to purify, and obtains precious metals such as zinc, lead, tin, copper, the flue gas qualified discharge.
Embodiment 6
With sulfate slag shown in the table 1 is raw material, in sulfate slag, adds 9% coke powder as reductive agent, and control batching basicity is 0.65, behind stirring and evenly mixing, sends into preposition rotary kiln, and the rotary kiln length-to-diameter ratio is 14; Obliquity 5%; Velocity of rotation 1.1 r/min, 750 ~ 800 ℃ of control temperature of kiln head, 400 ~ 450 ℃ of kiln end temperatures, roasting kiln 60min under weakly reducing atmosphere.Directly send into behind the calcining kiln discharge in the tube mixer of garden; Add the iron protochloride of calcining weight 5% and 3% sodium bentonite, all add behind the dilute with water, add brown coal 2%, coke powder 1% again; And the control material moisture is 11 ~ 12%; Subsequent handling is with embodiment 2, obtain iron ball group contain Fe 57.70%, As 0.06%, S 0.13%, Zn 0.42%, Cu 0.12%, Pb 0.10%, Sn 0.10%, the be up to state standards requirement of H55 of the grade of iron.Gather dust, cleaning section is with last embodiment, obtains precious metals such as zinc, lead, tin, copper, the flue gas qualified discharge.
Embodiment 7
With sulfate slag shown in the table 1 is raw material, in sulfate slag, adds 6% coke powder as reductive agent, and control batching basicity is 0.65, behind stirring and evenly mixing, sends into preposition rotary kiln, and the rotary kiln length-to-diameter ratio is 13; Obliquity 4%; Velocity of rotation 1.2 r/min, 700 ~ 850 ℃ of control temperature of kiln head, 350 ~ 400 ℃ of kiln end temperatures, roasting kiln 60min under weakly reducing atmosphere.Directly send into behind the calcining kiln discharge in the tube mixer of garden; Add the iron protochloride of calcining weight 5% and 3% calcium-base bentonite, all add behind the dilute with water, add brown coal 2% again; And the control material moisture is 11 ~ 12%; Subsequent handling is with embodiment 1, obtain iron ball group contain Fe 58.10%, As 0.07%, S 0.12%, Zn 0.43%, Cu 0.11%, Pb 0.10%, Sn 0.10%, the be up to state standards requirement of H55 of the grade of iron.Gather dust, cleaning section is with last embodiment, obtains precious metals such as zinc, lead, tin, copper, the flue gas qualified discharge.
Flue dust collecting result: the cleaning dust collecting system, the flue dust of MOXs such as tin lead that obtained enrichment is through analyzing: Sn7.7%, Pb7.8%, Zn31.3%, Fe8.7%, Cu2.4%.
Claims (10)
1. method of utilizing high sulfur impurity acid sludge to produce iron ball nodulizing and concentration of valuable metals; It is characterized in that: warm reducing roasting in comprising, the preparation of iron ball group, high temperature chlorination roasting, the cooling of iron ball group are also reclaimed heat energy, flue gas dust collection and cleaning section, specifically comprise:
A, middle temperature reducing roasting: the weight of pressing sulfate slag adds 6 ~ 9% brown coal and/or coke powder as reductive agent; Control batching basicity is 0.5 ~ 0.67; Control 750 ~ 900 ℃ of preposition rotary kiln end temperature, 350 ~ 500 ℃ of kiln end temperatures, material is roasting 70 ~ 100min under weak reducing environment; Wherein most arsenic and a part of zinc, tin reduction volatilization are got in the flue dust, and iron and copper are then stayed in the calcining;
B, the preparation of iron ball group: hot calcine is sent in the whisking appliance; Add weight ratio 3 ~ 5% iron protochlorides, 2 ~ 3% tackiness agent, 2 ~ 3% brown coal and/or coke powder; Behind stirring and evenly mixing, process the spherolite of particle diameter 20 ~ 30mm; Send into then in the drying and preheating device,, make iron ball group drying and be preheated to 700 ~ 800 ℃ at 400 ~ 1000 ℃ of temperature lower step heating 16 ~ 20min;
C, high temperature chlorination roasting: the iron ball group through preheating sends into rearmounted rotary kiln, 1150 ~ 1300 ℃ of control temperature of kiln head, 850 ~ 1000 ℃ of kiln end temperatures; Make kiln hood keep weakly reducing atmosphere; The kiln tail keeps weak oxide atmosphere, and chloridizing roasting 60 ~ 80min makes remaining arsenic reduction volatilization; Zinc, tin, copper chloridizing volatilization, sulphur are oxidized to sulfurous gas and get into flue gas; And impel the sclerosis of iron ball briquetting knot, improve pellet strength; Kiln tail high-temperature flue gas is introduced the B operation as the work thermal source;
D, the cooling of iron ball group are also reclaimed heat energy: send into cooling apparatus behind the high temperature pelletizing kiln discharge, feed cold wind the high temperature pelletizing is cooled to about 100 ℃, reclaim the work thermal source of the hot blast of its heat energy as the B operation;
E, flue gas dust collection and purification: the ash-laden gas of two sections rotary kilns adopts the dry dust collection system to gather dust, and the oxide compound of collecting arsenic, zinc, lead, tin, copper or muriate improve metal recovery rate; Flue gas after the dedusting adopts wet purification, and with the oxide compound and/or the muriate of the sulphur in the flue gas, arsenic, and remaining flue dust collecting makes the flue gas qualified discharge in scavenging solution.
2. the method for utilizing high sulfur impurity acid sludge to produce iron ball nodulizing and concentration of valuable metals according to claim 1; It is characterized in that: the weight of pressing sulfate slag in the A operation adds 5 ~ 8% brown coal and/or coke powder; Or use silica powder is 0.55 ~ 0.60 as alkalinity regulator control batching basicity; 800 ~ 850 ℃ of control temperature of kiln head, 400 ~ 450 ℃ of kiln end temperatures, middle temperature reducing roasting 80 ~ 90min.
3. the method for utilizing high sulfur impurity acid sludge to produce iron ball nodulizing and concentration of valuable metals according to claim 1 is characterized in that: said tackiness agent is one or more the mixed adhesive in sodium bentonite, the calcium-base bentonite.
As claimed in claim 1, wherein the acid residue using high impurity production of iron ore pellets and enriched in valuable metals, characterized in that: said disc granulator granulator to park; said drying preheating device is a chain Bi machine spheroids in the chain Bi machine temperature 600 ~ 800 ℃ drying and preheating steps.
5. the method for utilizing high sulfur impurity acid sludge to produce iron ball nodulizing and concentration of valuable metals according to claim 1, it is characterized in that: described dry dust collection is gathered dust for the gravity decanter type and/or cloth bag type gathers dust.
6. the method for utilizing high sulfur impurity acid sludge to produce iron ball nodulizing and concentration of valuable metals according to claim 5 is characterized in that: the described cloth bag type temperature of gathering dust is controlled on 160 ~ 180 ℃ of the muriatic dew points, described cloth bag heatproof >=200 ℃ of gathering dust.
7. the method for utilizing high sulfur impurity acid sludge to produce iron ball nodulizing and concentration of valuable metals according to claim 1, it is characterized in that: the high-temperature flue gas of said preposition rotary kiln is directly sent into system for wet purification after dry dust collection; The high temperature dust flue gas of said rearmounted rotary kiln at first is introduced into the B operation as iron oxygen pelletizing drying and preheating thermal source, gets into dust collecting system again after the heating iron ball group.
8. the method for utilizing high sulfur impurity acid sludge to produce iron ball nodulizing and concentration of valuable metals according to claim 1 is characterized in that: described wet purifying decice adopts high anticorrosion N-D steel to do.
9. the method for utilizing high sulfur impurity acid sludge to produce iron ball nodulizing and concentration of valuable metals according to claim 1, it is characterized in that: said preposition rotary kiln length-to-diameter ratio is 12 ~ 15; Obliquity is 4 ~ 5 %; Velocity of rotation is 0.8 ~ 1.2 r/min.
10. the method for utilizing high sulfur impurity acid sludge to produce iron ball nodulizing and concentration of valuable metals according to claim 1, it is characterized in that: said rearmounted rotary kiln length-to-diameter ratio is 10 ~ 12; Obliquity is 2 ~ 3%; Velocity of rotation is 0.6 ~ 1.0 r/min.
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| CN107739817A (en) * | 2017-10-10 | 2018-02-27 | 北京矿冶研究总院 | Method for calcified chlorination and volatilization comprehensive resource utilization of jarosite slag |
| CN107974559A (en) * | 2017-11-20 | 2018-05-01 | 中国科学院过程工程研究所 | A kind of method that high-quality iron smelting pellets are prepared using pyrite cinder |
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