CN105907969A - Process for producing metal manganese by using submerged arc furnace and rocking furnace - Google Patents

Abstract

The invention discloses a process for producing metal manganese by using a submerged arc furnace and a rocking furnace. In the submerged arc furnace, ferromanganese ores are reduced by cokes; the reducing temperature is controlled below 1500 DEG C; the slag alkalinity omega (CaO)/omega (SiO2) is 0.16; the mass fraction of SiO2 is 18%; the mass fraction of MnO in produced manganese enriched slag is not lower than 70%; meanwhile, a by-product of carbon ferromanganese is generated; then, manganese enriched slag is thermally mixed in the rocking furnace; lime is added for refining and producing blending slag, so that the alkalinity is increased to 2.0, the removal of phosphorus and sulfur is facilitated, and the activity of SiO2 is reduced; and finally, industrial silicon is added in the rocking furnace for reducing manganese in the blending slag to obtain the metal manganese with the manganese mass fraction of not lower than 99%, so that the energy conservation effect is obvious.

Description

The technique that a kind of mineral hot furnace and grate produce manganese metal

Technical field

The invention belongs to the technical field of producing of ferroalloy, particularly to one mineral hot furnace and grate The technique producing manganese metal.

Background technology

The ferroalloy industry is the key industry that national energy-saving reduces discharging, in recent years, and the one of China's the ferroalloy industry A little enterprises carry out scientific and technical innovation, active development and application ferroalloy advanced technologies equipment and achieve substantially Effect, not only energy-saving and cost-reducing, reduce discharging pollution treatment but also add economic benefit.

The industrial process of metal current manganese is mainly electro silicothermic process, electrolysis and aluminothermic process, and these are raw Product method is primarily present the shortcomings such as energy consumption is huge.

Summary of the invention

In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide one mineral hot furnace and Grate produces the technique of manganese metal, electricity saving and energy saving, is substantially reduced production cost, and economic benefit is obvious.

To achieve these goals, the technical solution used in the present invention is:

A kind of mineral hot furnace and grate produce the technique of manganese metal, use reductive coke ferrous manganese ore in mineral hot furnace Stone, controls to be 1,420 1500 DEG C by the temperature of reduction reaction, obtains Mn-rich slag and by-product carbon element manganese Ferrum；Then Mn-rich slag heat is blended in grate, adds Calx refine, remove p and s, and reduce SiO₂ Activity, obtain be in harmonious proportion slag；The last manganese added in grate in industrial silicon reduction mediation slag, it is thus achieved that manganese The mass fraction manganese metal not less than 99%.

Preferably, during using reductive coke ferromanganese Ore in mineral hot furnace, basicity of slag ω_(CaO)/ω_(SiO2) It is 0.16, SiO₂Mass fraction be 18%, in the Mn-rich slag obtained, the mass fraction of MnO is not less than 70%.

Wherein, during using reductive coke ferromanganese Ore in mineral hot furnace, high electric current and low-voltage are used Reach reaction temperature, such as, when mineral hot furnace is 3200kV A, use 90～120V voltages, phase current Difference is less than 30%.

According to the grate production cycle, Mn-rich slag heat is blended in grate.The ferrum mouth of mineral hot furnace goes out carbon element ferromanganese, Cinder notch goes out Mn-rich slag.

Preferably, during adding Calx refine, basicity is made to bring up to 2.0.And Calx is preheating to 500～ 800 DEG C, add refine.

Calculate with every 100Kg ferromanganese Ore: manganese content 40-50%, then coke consumption in ferromanganese Ore 9.5Kg-10.2Kg, lime consumption 39Kg-40Kg, industrial silicon consumption 8.8Kg-9.2Kg.With prior art Comparing, this with reductive coke ferromanganese Ore, is reduced into oxidation at a low price value Mn oxide in mineral hot furnace Thing, it is thus achieved that the MnO mass fraction Mn-rich slag not less than 70%, but have by-product carbon element ferromanganese simultaneously Produce.Then the Mn-rich slag heat being smelt is blended in grate, adds Calx and carry out refine, remove phosphorus, sulfur, It is smelt mediation slag, finally with industry Si reduction in grate.3 steps are run continuously, the accumulation of heat of furnace lining It is fully used, it is possible to save heat energy, reduce consumption.Specifically:

(1) in mineral hot furnace, MnO mass fraction can be produced with reductive coke ferromanganese Ore to be not less than The Mn-rich slag of 70%.

(2) in grate, add Calx removing phosphorus, sulfur, and improve basicity of slag to 2.0, reduce SiO2 in slag Activity.

(3) in grate, add industrial silicon and be reduced into manganese metal, calculate theoretically, 100kg ferromanganese Ore can smelt the manganese mass fraction manganese metal 35.40kg not less than 99%.

(4) mineral hot furnace adds grate method compared with electro silicothermic process, and electricity saving and energy saving, economic benefit is obvious.

Detailed description of the invention

Embodiments of the present invention are described in detail below in conjunction with embodiment.

1, process characteristic

Production technology of the present invention is set up in a basic theoretical basis, in mineral hot furnace with coke step by step also Value Mn oxide in former ferromanganese Ore, formula (1) is shown in reaction.

MnO₂→Mn₂O₃→Mn₃O₄→MnO (1)

Calculating and mensuration shows, in the molten state, the decomposition pressure of MnO is the least.When temperature is 5000K, p(O₂)=101.325kPa, it can be seen that, MnO is stable under the high temperature conditions, is not easily decomposed.With Jiao Charcoal reduction MnO can get the manganese metal in solid solution ferrum liquid, and formula (2) is shown in reaction.

MnO+C=Mn+CO ↑, Δ G⁰=137 400-81.15T (2)

The theoretical reaction starting temperature of formula (2) is 1420 DEG C.In mineral hot furnace, with the rising of furnace temperature, standard Reaction free enthalpy change negative value diminishes, and is more beneficial for reaction and carries out to product direction, therefore, was operating Cheng Zhongwei controls smelting temperature, sets up a rational power supply system extremely important, and, smelt Mn-rich slag The reducing agent (coke) joined is little, and charging resistance rate is very big, and conductive capability is very poor.Therefore, smelting Electric current that Shi Caiyong is high and relatively low voltage, as 3200kV A mineral hot furnace uses 90～120V voltages, three-phase Electrode descending depth is unanimous on the whole, and three-phase current is in a basic balance, and phase differential current is less than 30%.Reaction completes In time Mn-rich slag is proceeded in grate afterwards, to prevent from generating by-product carbon element ferromanganese rather than generating Mn-rich slag, Must strictly control reaction temperature and be less than 1500 DEG C, so can obtain high-quality Mn-rich slag from mineral hot furnace.

Specifically, with manganese, ferrum and the high oxide in reductive coke ferrous manganese ore in mineral hot furnace, by Mn₃O₄ Decompose and be reduced into manganese, FeO is reduced into ferrum, smelting and obtain Mn-rich slag and by-product carbon element ferromanganese, reaction See formula (3)～formula (5).

Mn₃O₄+ C=3MnO+CO ↑ (3)

MnO+C=Mn+CO ↑ (4)

FeO+C=Fe+CO ↑ (5)

Meanwhile, the phosphorus in mineral also reduces in entrance metal, and formula (6) is shown in reaction.

P₂O₅+ 5C=2P+5CO ↑ (6)

In order to refine to obtain high-quality Mn-rich slag in mineral hot furnace, need correctly to control basicity of slag, smelt gold Belonging to manganese is high basicity slag operation, SiO in Mn-rich slag₂Mass fraction the lowest more good, need to add appropriate Silicon stone, it is ensured that the SiO of certain mass mark₂Control the viscosity of slag, such as, adjustable basicity of slag ω_(CaO)/ω_(SiO2)It is 0.16, SiO₂Mass fraction be 18%, make the dynamic conditions of reaction be improved, Smelt the mass fraction of MnO in the Mn-rich slag and be not less than 70%.

Then, Mn-rich slag is blended in grate, and adds a small amount of Calx, it is contemplated that dissolving Calx to absorb heat, According to practical situation, Calx can be preheating to 500～800 DEG C, complete mediation slag and produce and go dephosphorization, sulfur, Next step being smoothed out with industry Si reduction reaction in grate can be made, and need not external heat source.

Wherein Mn-rich slag also needs to improve basicity in grate, and controlling basicity is 1.9～2.2, further up to removal Phosphorus, the purpose of sulfur, control SiO simultaneously₂Activity, complete be in harmonious proportion slag.

Final addition industrial silicon reduction mediation slag in grate, obtains the manganese mass fraction metal not less than 99% Manganese.Formula (7) is shown in reaction.

2 (MnO)+[Si]+2 (CaO)=2 [Mn]+(2CaO SiO₂) (7)

The method and the technics comparing of electro silicothermic process metal smelting manganese, eliminate and smelt with high energy consumption in electric furnace The process of intermediate alloy height silicomanganese.

2 burdening calculation

To the reaction mass in mineral hot furnace, grate produce lime adding amount when being in harmonious proportion slag and reducing metal Industrial silicon addition during manganese calculates.

2.1 mineral hot furnace burdening calculation

Raw material is Australia's import ferrous manganese ore, and its concrete composition is shown in Table 1, and coke and stone ash composition are shown in Table 2.

The main component (mass fraction) of table 1 Australia import ferrous manganese ore

Mn	Fe	SiO2	P	Al2O3	CaO	MgO
							48.5	3.5	7.0	0.103	5.0	2.0	1.0

Table 2 coke and stone ash composition (mass fraction)

The Elemental partition data of burdening calculation and basicity of slag are as follows: manganese enters slag 85%, and manganese enters manganese Ferrum 10%, volatilization 5%；Ferrum enters slag 10%, and ferrum enters ferromanganese 90%；Phosphorus enters slag 5%, and phosphorus enters Enter ferromanganese 70%, volatilization 25%.

Raw material is the lowest with the mass fraction of CaO, FeO in slag, SiO₂Mass fraction higher, This with metal dephosphorization needed for highly basic degree, the condition contrast such as strong oxidizing property, so beneficially phosphorus is abundant Reduction.Most of phosphorus (accounting for the 70% of phosphorus total amount) can generate stable phosphide (Fe₂P、Fe₃P、Mn₃P Deng) enter in by-product carbon element ferromanganese, remaining phosphorus major part (accounting for the 25% of phosphorus total amount) is at high temperature bar With P under part₂O₅Form is volatilized, and a small amount of phosphorus (accounting for the 5% of phosphorus total amount) is with 3FeO P₂O₅With 4CaO P₂O₅ It is present in Mn-rich slag etc. form.Mn-rich slag basicity ω_(CaO)/ω_(SiO2)It is 0.16, SiO in Mn-rich slag₂Quality Fractional domination is 18%.

2.1.1 reducing agent (amount of coke)

Calculating with 100kg ferrous manganese ore, in ferrous manganese ore, the high oxide decomposes of manganese becomes Mn₃O₄, Needed for it continues to be reduced into O, carbonaceous amount is:

Mn₃O₄+ C=3MnO+CO ↑, 100 × 48.5% × 12/165=3.53kg

Needed for the manganese of reduction entrance by-product carbon element ferromanganese and volatilization, carbonaceous amount is:

MnO+C=Mn+CO ↑, 100 × 48.5% × (10%+5%) × 12/55=1.59kg

Needed for FeO is reduced into ferrum, carbonaceous amount is:

FeO+C=Fe+CO ↑, 100 × 3.5% × 90% × 12/56=0.68kg

P₂O₅The carbonaceous amount needed for phosphorus enters ferromanganese that is reduced into is:

P₂O₅+ 5C=2P+5CO ↑, 100 × 0.103% × 70% × 5 × 12/ (2 × 31)=0.07kg

The carbonaceous amount is needed to be:

3.53+1.59+0.68+0.07=5.87kg

The quality of by-product carbon element ferromanganese is:

$\frac{48.5\×0.1+3.5\×0.9}{1-0.065}=8.56Kg$

In formula: 0.065 is other amount of element in carbon element ferromanganese in addition to Mn, Fe.

Molten iron carburizing quality is:

8.56 × 0.06=0.51kg

In formula: 0.06 is that carbon element ferromanganese C content calculates by 6%.

The carbonaceous amount is always needed to be:

5.87+0.51=6.38kg

In dry coke, fixed carbon is 83.700%, and the utilization rate of coke is 95%, and fire door coke burning is 10%, Then required dry coke quality is:

6.38/ (83.700% × 95%) × (1+10%)=8.82kg

Assume that moisture content is 10% in coke, then required coke quality is: 8.82/ (1-10%)=9.8kg

2.1.2 the addition of Silicon stone

Used by 100kg ferrous manganese ore, dry amount of coke is 8.82kg, and in dry coke, ash is 14.100%, the most in fact Border ash quality is 8.82 × 14.100%=1.24kg, and the manganese mass fraction in Mn-rich slag is:

$\mathrm{\ω}(\[Mn\])=\frac{48.5\×0.85}{1.24+15+128\×3.5\%\×10\%+129\×85\%\×48.5\%}\×100\%=59\%$

In formula: 15 is contained SiO in every 100kg manganese ore₂+Al₂O₃The summation of+CaO+MgO, kg, 128, 129 is manganese content criterion calculation equation coefficients in Mn-rich slag.

SiO in Mn-rich slag₂Mass fraction is:

$\mathrm{\ω}\left({\mathrm{SiO}}_2\right)=\frac{7+0.52\×1.24}{1.24+15+128\×3.5\%\×10\%+129\×85\%\×48.5\%}\×100\%=10.94\%$

SiO in slag₂Mass fraction too low time, slag melt temperature drastically raises, and slag is sticky, unfavorable In containing high ferro, the abundant sedimentation of high phosphorus bead, here we are by SiO in Mn-rich slag₂Mass fraction Control is 18%, needs to add Silicon stone.If needing the Silicon stone amount added is that x kg (assumes SiO in Silicon stone₂'s Mass fraction is 100%), then need add Silicon stone quality be:

$\frac{7+0.52\×1.24+x}{69.87+x}=18\%,x=6.0kg$

The SiO that slag is total₂Quality be:

100 × 7.0%+1.24 × 52.000%+6.0=13.66kg

When basicity of slag is 0.16, the quality needing CaO is:

0.16 × 13.66=2.19kg

In slag composition, CaO actual mass is:

100 × 2.0%+1.24 × 33.700%=2.42kg

Therefore, there is no need to additionally add Calx.

(1) calculating of Mn-rich slag composition.CaO、MgO、Al₂O₃Fully enter Mn-rich slag, in Mn-rich slag MnO mass fraction be:

$\mathrm{\ω}(\[Mn\])=\frac{48.5\×0.85}{69.87+6.0}\×100\%=54.34\%,\mathrm{\ω}\left(MnO\right)=54.34\%\×71/55=70.15\%$

FeO mass fraction in Mn-rich slag is:

$\mathrm{\ω}(\[Fe\])=\frac{(3.5\×0.1+0.5915\×\frac{56}{72})}{69.87+6.0}\×100\%=0.52\%,\mathrm{\ω}\left(FeO\right)=0.52\%\×72/56=0.67\%$

In formula: 0.05915 is the mass fraction 4.55 of coke ash FeO and the product entering slag rate 1.3%.

CaO mass fraction in Mn-rich slag is:

$\mathrm{\ω}\left(CaO\right)=\frac{2.42}{69.87+6.0}\×100\%=3.19\%$

MgO mass fraction in Mn-rich slag is:

$\mathrm{\ω}\left(MgO\right)=\frac{1.0+0.0135\×1.24}{69.87+6.0}\×100\%=1.34\%$

Al in Mn-rich slag₂O₃Mass fraction is:

Phosphorus mass fraction in Mn-rich slag is:

$\mathrm{\ω}(\[P\])=\frac{(0.103\×0.05+0.00026\×1.24\×62\×\frac{1}{142})}{69.87+6.0}\×100\%=0.007\%,$

ω(P₂O₅)=0.007% × 142/62=0.016%

Sulfur nutrient in Mn-rich slag is:

$\mathrm{\ω}(\[S\])=\frac{8.82\×0.00480}{69.87+6.0}\×100\%=0.056\%$

SiO in Mn-rich slag₂Mass fraction is 18%.Mn-rich slag composition is shown in Table 3.

Table 3 Mn-rich slag composition (mass fraction)

MnO	FeO	CaO	MgO	Al2O3	P2O5	S	SiO2
								70.15	0.67	3.19	1.34	7.06	0.016	0.056	18

(2) composition of carbon element ferromanganese calculates.The quality of by-product carbon element ferromanganese is 8.56kg；In carbon element ferromanganese The mass fraction of carbon is by 6% calculating；In carbon element ferromanganese, the mass fraction of ferrum is ω (Fe)=100 × 3.5% × 90%/8.56 × 100%=36.80%；In carbon element ferromanganese the mass fraction of manganese be ω (Mn)= 100 × 48.5% × 10%/8.56 × 100%=56.66%；In carbon element ferromanganese the mass fraction of phosphorus be ω (P)= 100 × 0.103% × 70%/8.56 × 100%=0.84%.

2.2 lime adding amounts calculate

The Mn-rich slag that this part mainly produces to the first step and separates adds appropriate Calx, in order to Remove part phosphorus, sulfur, the simultaneously basicity of working the slag, reduce SiO₂Activity, make the 3rd step industrial silicon smelting The reaction of refining manganese metal is quickly carried out more smoothly.Calx can displace MnO SiO₂In MnO, Form more stable compound 2CaO SiO₂, make MnO all in free state, consequently facilitating manganese reduction Reaction carrying out, it is possible to reduce manganese enter slag loss, improve manganese the response rate.Therefore, the alkali to finishing slag Degree must strictly control, and typically chooses basicity CaO/SiO₂It is 1.9～2.2, is identified herein as 2.0.

Except the sulfur in Mn-rich slag, CaO mass required for phosphorus are:

CaO+SO₂=CaSO₃, 8.82 × 0.480% × 56/32=0.074kg

3CaO+P₂O₅=3CaO P₂O₅, 0.016% × (69.87+6.0) × 3 × 56/142=0.014kg

The CaO mass that regulation Mn-rich slag basicity needs increase is:

18% × (69.87+6.0) × 2.0-2.42=24.89kg

Therefore, total CaO mass is:

0.074+0.014+24.89=24.98kg

In Calx, effective CaO quality is:

$\frac{70.66-2.0\×3.29}{100}\×100\%=64.08\%$

Required lime quality is:

24.98/64.08%=38.98kg

2.3 industrial silicon additions calculate

In mediation slag, the quality of manganese oxide is:

M (MnO)=70.15% × (69.87+6.0)=53.22kg

In mediation slag, the quality of elemental iron is:

M (Fe)=0.52% × (69.87+6.0)=0.39kg

Shaking ladle process produces during medium-low carbon ferromanganese, and the response rate of external manganese is 90%～95%, domestic is 80%～81%, during calculating, the response rate of manganese is defined as 85%, the response rate of ferrum is defined as 90%.Assume Reduction process has the industrial silicon loss of 5% and reduces other elements.

Needed for reduction-oxidation manganese, siliceous amount is:

$m\left(Si\right)=\frac{53.22\×85\%\×28}{2\×71}=8.92kg$

Needed for reduction FeO, siliceous amount is:

$m\left(Si\right)=\frac{0.39\×90\%\×28}{56}=0.18kg$

The pure silicon quality is needed to be altogether:

(8.92+0.18) × (1+5%)=8.67kg

In industrial silicon, the mass fraction of silicon is 98%, then required industrial silicon quality is 8.67/98%=8.85kg.

Can obtain manganese metal quality is:

$53.22\×\frac{55}{71}\×85\%\÷99\%=35.40kg$

Comprehensive above 3 steps can obtain, the ferrous manganese ore of 100kg can smelt obtain mass fraction be 99% with On manganese metal 35.40kg.Meanwhile, the consumption of required coke, Calx and industrial silicon is shown in Table 4.

Table 4 coke, Calx, industrial silicon consumption

Coke	Calx	Industrial silicon
			9.8	38.98	8.85

3 economic benefits

Carry out cost calculation by raw material market price, and compare with electro silicothermic process there is obvious economic benefit. Raw material and product price, quality are shown in Table 5.Calculating cost is: 35.40 × 13.5-100 × 2.5-9.8 × 0.5- 38.98 × 0.35-8.85 × 12.5=98.7 (first).I.e. reduction 35.40kg manganese metal is got a profit 98.7 yuan.New method (mineral hot furnace adds grate) manganese metal per ton is profitable is: 98.7 × 1 000/35.40=2 788 (first).

Table 5 raw material and product price, quality

Mine heat furnace smelting Mn-rich slag power consumption is generally 1 100～1 500kW h/t, with furnace volume difference not With, the biggest more power saving.Such as 9 000kV A capacity electric furnaces, running voltage 110V, unit power consumption be about 1 100～ 1 200kW h/t, is calculated as 2 500kW h/t by electric furnace smelting Mn-rich slag power consumption, it is contemplated that grate and other power Power consumption, is smelt manganese metal power consumption and calculates the electricity charge (commercial power is based on 0.6 yuan/kW h) by 3 500kW h/t. It is 10 000kW h that electro silicothermic process smelts the power consumption of 1t manganese metal.Two kinds of method contrasts, electro silicothermic process is with new The economic benefit difference of method is:

2788-3500 × 0.6-13.5 × 1000+10000 × 0.6+ (35.40 × 13.5-98.7) × 1000/35.40=3900 (unit/t)

Obviously, produce the technique using industry Si reduction in Mn-rich slag, grate by mineral hot furnace, for producing high-grade Manganese metal, save the energy explore a Tiao Xin road, comply fully with country 13 planning energy policies, warp Ji benefit is the most notable.

Claims (8)

1. the technique producing manganese metal with mineral hot furnace and grate, it is characterised in that use in mineral hot furnace Reductive coke ferromanganese Ore, controls to be 1,420 1500 DEG C by the temperature of reduction reaction, obtain Mn-rich slag with And by-product carbon element ferromanganese；Then Mn-rich slag heat is blended in grate, adds Calx refine, remove p and s, And reduce SiO₂Activity, obtain be in harmonious proportion slag；The last industrial silicon that adds in grate reduces in mediation slag Manganese, it is thus achieved that the manganese mass fraction manganese metal not less than 99%.

The technique producing manganese metal with mineral hot furnace and grate the most according to claim 1, it is characterised in that During using reductive coke ferromanganese Ore in mineral hot furnace, basicity of slag ω_(CaO)/ω_(SiO2)It is 0.16, SiO₂ Mass fraction be 18%, in the Mn-rich slag obtained the mass fraction of MnO be not less than 70%.

The technique producing manganese metal with mineral hot furnace and grate the most according to claim 1, it is characterised in that During using reductive coke ferromanganese Ore in mineral hot furnace, high electric current and low-voltage is used to reach reaction temperature Degree.

The technique producing manganese metal with mineral hot furnace and grate the most according to claim 3, it is characterised in that Described mineral hot furnace is 3200kV A, uses 90～120V voltages, and phase differential current is less than 30%.

The technique producing manganese metal with mineral hot furnace and grate the most according to claim 1, it is characterised in that Mn-rich slag heat being blended in grate according to the grate production cycle, the ferrum mouth of mineral hot furnace goes out carbon element ferromanganese, cinder notch Go out Mn-rich slag.

The technique producing manganese metal with mineral hot furnace and grate the most according to claim 1, it is characterised in that During adding Calx refine, basicity is made to bring up to 2.0.

The technique producing manganese metal with mineral hot furnace and grate the most according to claim 1, it is characterised in that Calx is preheating to 500～800 DEG C, adds refine.

The technique producing manganese metal with mineral hot furnace and grate the most according to claim 1, it is characterised in that Calculate with every 100Kg ferromanganese Ore: manganese content 40-50%, then coke consumption in ferromanganese Ore 9.5Kg-10.2Kg, lime consumption 39Kg-40Kg, industrial silicon consumption 8.8Kg-9.2Kg.