CN107130116A

CN107130116A - Fused solution high lead slag saves method for smelting reduction of Ni

Info

Publication number: CN107130116A
Application number: CN201610104922.6A
Authority: CN
Inventors: 陈少辉; 陈漫虹; 陈少忠
Original assignee: Guodiankangneng Technology Stock Co Ltd
Current assignee: Guodiankangneng Technology Stock Co Ltd
Priority date: 2016-02-26
Filing date: 2016-02-26
Publication date: 2017-09-05

Abstract

Method for smelting reduction of Ni is saved the invention discloses fused solution high lead slag, fused solution lead skim is reduced directly using reducing agent, the addition of reducing agent is the 3.25~3.5% of fused solution lead skim quality；Reduction temperature is 1200~1225 DEG C；Recovery time is 30~60min.Instant invention overcomes the low problem of lead, zinc recovery under high lead system, flow is simple, high treating effect, the valuable metal such as energy high efficiente callback zinc, solves a large amount of castaway slags and stores up the environmental pollution caused and problem of resource waste.Directly metallurgy melting lead skim of the invention, makes full use of the heat content of molten lead oxidation slag, saves the energy.The smelting process of the present invention uses direct reduction process, improves the utilization rate of carbonaceous reducing agent, saves smelting cost.

Description

Fused solution high lead slag saves method for smelting reduction of Ni

Technical field

The present invention relates to metallurgical technology field, specifically fused solution high lead slag energy-conservation method for smelting reduction of Ni.

Background technology

The lead output and consumption figure of China rank first in the world.Lead skim is usually iron content in the metallurgical slag of pyrometallurgical smelting of lead, lead skim 21-31%, 2-15% containing zinc, leaded 0.02-3%.Current lead skim is largely stored up, and land occupation resource simultaneously pollutes environment.Lead Filler, production glass that the processing of slag focuses primarily upon and reclaims lead zinc and dissipated metal in lead skim, lead skim is made to underground pit Glass and ceramics, the production building materials such as brick and building block cement etc., but substantial amounts of lead is not recycled with zinc resource in lead skim.The use of zinc It is quite varied on the way, occupied an important position in national economy, the fusing point of zinc is relatively low, fluidity of molten is good, there is preferably anti- Corrosive nature, is mainly used in zinc-plated industry, and frequently as the protective layer of steel, such as zinc-plated sheet material pipe fitting, its consumption is accounted for The 50% of world's zinc consumption.And China's lead skim amount is big, the content of Pb＆Zn in slag is high, therefore the lead in lead skim, zinc are provided Source be can yet be regarded as raw material makes up a kind of approach of China's ore resource chronic shortage.Lead, the recovery of zinc resource in current lead skim Using lacking effective method so that lead, zinc resource cannot get high efficiente callback and utilize in lead skim.It may be said that lead in lead skim, The recycling of zinc resource is the metallurgical and mute problem to be solved of environmental area, in the urgent need to one kind energy-conservation, efficient, flow are short Process reclaim lead skim in association resource.

The content of the invention

It is an object of the invention to provide flow is simple, the energy-conservation reduction melting of high treating effect, cost low melt liquid high lead dross Method, to solve the problems mentioned in the above background technology.

To achieve the above object, the present invention provides following technical scheme：

Fused solution high lead slag saves method for smelting reduction of Ni, and fused solution lead skim is reduced directly using reducing agent, reduces The addition of agent is the 3.25~3.5% of fused solution lead skim quality；Reduction temperature is 1200~1225 DEG C；Recovery time is 30~60min.

It is used as further scheme of the invention：Reducing agent uses CO, C, solid coal, H₂Or CH₄。

It is used as further scheme of the invention：Reducing agent uses solid coal.

It is used as further scheme of the invention：Reducing agent uses solid anthracite.

It is used as further scheme of the invention：The slag type that fused solution lead skim is used is CaO/SiO₂Between 0.4~0.8, FeO/SiO₂Between 1.2~1.8.

It is used as further scheme of the invention：FeO/SiO₂=1.5.

Compared with prior art, the beneficial effects of the invention are as follows：

Instant invention overcomes the low problem of lead, zinc recovery under high lead system, flow is simple, and high treating effect can be returned efficiently The valuable metals such as zinc are received, a large amount of castaway slags is solved and stores up the environmental pollution caused and problem of resource waste.The present invention directly smelts Processing melting lead skim, makes full use of the heat content of molten lead oxidation slag, saves the energy.The smelting process of the present invention is using directly also Former method, improves the utilization rate of carbonaceous reducing agent, saves smelting cost.

Brief description of the drawings

Fig. 1 is influence of the iron silicon ratio to the rate of recovery of lead zinc-copper；

Fig. 2 is the influence that iron silicon ratio is distributed lead zinc-copper；

Fig. 3 is the influence that calcium silicon compares the lead zinc-copper rate of recovery；

Fig. 4 is the influence that calcium silicon compares the distribution of lead zinc-copper；

Fig. 5 is influence of the temperature to anthracitic CO2 percent reductions；

Fig. 6 is the impact effect of reducing agent coal Comparability test；

Fig. 7 is the influence that reducing agent coal compares metal recovery rate；

Fig. 8 is influence (time 60min) of the reduction temperature to metal recovery rate；

Fig. 9 is influence (time 30min) of the reduction temperature to metal recovery rate；

Figure 10 is influence (temperature 1200 DEG C) of the recovery time to metal recovery rate；

Figure 11 is influence (temperature 1225 DEG C) of the recovery time to metal recovery rate；

Figure 12 is influence (temperature 1250 DEG C) of the recovery time to metal recovery rate；

Figure 13 is influence of the calcium silicon than 0.45 reduction temperature to metal recovery rate；

Figure 14 is the influence that different calcium silicon compares metal recovery rate；

Figure 15 is influence of the different iron silicon ratios to metal recovery rate.

Embodiment

Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, shown So, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all Belong to the scope of protection of the invention.

Embodiment 1

The experimental study of the slag type selection of 1.1 high lead dross reduction processes

Lead skim is complicated polynary system, is made up of various oxides, they be combined with each other and formed compound, solid solution, Liquid melt and eutectic mixture.Specifically, clinker is by the institute such as silicate, perferrite and aluminate of various metals group Into；In addition, containing a small amount of metal sulfide, metal and gas.SiO₂, FeO and CaO be lead clinker main component, But for other non-ferrous metal clinkers, the characteristics of high CaO, high ZnO content are lead clinker again.To plumbum smelting slag It is required that mainly having：(1) flux consumption minimum requirement when slag composition has to comply with melting；(2) fusing point of clinker is closed It is suitable；(3) viscosity of clinker is small；(4) clinker is smaller than important；(5) surface nature (surface tension, the boundary of clinker Face tension force etc.) separation of clinker and metal or sulfonium is played an important role, in addition, clinker to the corrosion of refractory material also with The surface nature of clinker has larger relation.In order to reduce lead-in-dreg, raw material comprehensive utilization degree and processing high zinc material are improved, Widely used high-zinc high-calcium slag type.In the present invention, clinker intends the fusion using iron calcium-silicate, and selects suitable iron silicon Than with calcium silicon ratio.

1.1.1 the influence that iron silicon ratio is distributed to high lead dross reduction process valuable metal

Fig. 1 is FeO/SiO₂The influence of the lead zinc-copper rate of recovery during comparison high lead dross reduction.As seen from the figure, lead and copper are main It is present in metal phase, zinc is then primarily present in slag.The rate of recovery of lead and copper is in the trend of first increases and then decreases, but two Person's trend has obvious difference.In FeO/SiO₂Ratio is in the range of 1.0-1.8, what the presentation of the Pb rate of recovery grew steadily becomes Gesture, in FeO/SiO₂The highest rate of recovery 84.8% is reached when=1.8, further increases FeO/SiO₂Ratio will cause Pb to return Yield drastically declines.And the Cu rate of recovery is in FeO/SiO₂Peak (81.7%), increase or reduction FeO/SiO are reached when=1.25₂ Than that the rate of recovery will be caused significantly to decline, work as FeO/SiO₂Than increasing to when 2.0 or even will decrease to 20%.In metal Substantially zinc is not detected in phase, illustrates testing detected FeO/SiO₂Zinc mainly enters in slag phase under ratio, therefore zinc The rate of recovery mainly investigated by Zn content in slag.As shown in figure 1, it is with FeO/SiO₂Change is shown and Pb, Cu Opposite trend.Zinc is in FeO/SiO₂For 1.5 when in slag content minimum (75%) increase and reduction FeO/SiO₂It will improve The rate of recovery of zinc, can reach 90%.

Fig. 2 is FeO/SiO₂The influence of behavior is distributed lead zinc-copper during high lead dross reduction.As seen from the figure, with FeO/SiO₂ Increase, lead, the distribution of copper in first increasing the trend that reduces afterwards, and zinc then due to primarily entering slag phase in experiment test FeO/SiO₂In the range of distribution ratio be smoothly maintained near 0.It is worth noting that, different FeO/SiO₂Under ratio, Pb distribution ratio is above Cu, and FeO/SiO₂Compare the influence of Pb distribution ratios clearly.Work as FeO/SiO₂Than increasing from 1 When being added to 1.5, distribution ratio increases to 18.6 from 8.2, and increasing degree reaches 1.2 times, further increases FeO/SiO₂Than then Distribution ratio is caused drastically to decline, FeO/SiO₂Distribution ratio drops to minimum (1.6) when=2.Cu distribution ratios are by FeO/SiO₂ The influence of ratio is relatively small, except FeO/SiO₂When=2.0 distribution ratio be 0.4 outside, under other ratios distribution ratio more than 2, And with the (FeO/SiO of highest distribution ratio 4.9₂=1.5) difference it is little.It is preferably right that these results have with result shown in Fig. 1 Ying Xing, illustrates in FeO/SiO₂Pb, Cu can obtain maximum distribution in metal phase under conditions of=1.5, and zinc is then led To enter in slag, therefore FeO/SiO₂=1.5 be optimum condition.

1.1.2 calcium silicon compares the influence of high lead dross reduction process valuable metal distribution

Fig. 3 is CaO/SiO₂The influence of distribution ratio to recovery rate of valuable metals and in metal, slag phase.Experimental result is as schemed Shown in 2.As seen from the figure, in it can be seen that in high lead dross reduction different calcium silicon than when the lead zinc-copper rate of recovery change.When CaO/SiO₂When changing between 0.4~0.8, lead, the rate of recovery of copper rise and the decline of the rate of recovery of zinc.In CaO/SiO₂=0.8 When, Pb reaches the highest rate of recovery 84.9%, and the Zn rate of recovery is then reduced to minimum at this moment.Continue to improve CaO/SiO₂ Than the rate of recovery for causing Pb is reduced, and the rate of recovery of copper and zinc then may proceed to the trend for keeping rising, and respectively reach most High point (81.3%, 100%), in experiment highest CaO/SiO used₂(1.4) under, lead and copper recovery are greatly reduced, Respectively 51% and 10%.The rate of recovery of zinc is then continually maintained in peak.Fig. 4 is shown using lead zinc during different calcium silicon ratio Distribution ratio of the copper in metal phase and slag phase.As can be seen that CaO/SiO₂For 0.8 when lead, copper distribution ratio reach maximum Value, the distribution ratio of zinc then substantially remains in 0 in whole test scope.In other CaO/SiO₂Than under, lead, point of copper With in 3.8 and 2 or so fluctuations, difference is not notable respectively.It is noted that working as CaO/SiO₂Than for 1.4 when, lead, Copper distribution ratio drops to minimum.In summary, the slag type that liquid high lead dross direct-reduction laboratory is used is CaO/SiO₂ In 0.4~0.8, FeO/SiO₂Between 1.2~1.8.

The comparison of the 1.2 slag types determined and traditional blast furnace smelting slag

Conventional lead agglomerate originally is that, from molten loose porous block, porosity is generally 50%-60%, bulk density 1.8-2.2, lumpiness is generally 50~150mm.The lead existed in agglomerate with lead silicate and free oxidation Lead speciation accounts for total lead 40%-60% is measured, therefore in retailoring of blast furnace, free PbO has largely been reduced at 600 DEG C, various lead silicate Start to melt and reduce at 700~900 DEG C, lead compound is raised in air-flow in fusion zone in other metal oxide melts CO and flux in CaO, FeO reduce and replace, in focal area, C directly take part in and lead silicate reduced from melt In lead.Because lead agglomerate surface area is big, the direct reduction reactor of CO gas-solid reactions and carbon is more active, and reduction process is entered It is very thoroughly capable.It is a kind of leaded high, fine and close lump material that oxygen bottom blown furnace, which obtains high lead slag, and bulk density 3.05 compares table Area is small, and gas (CO) is Gu-(solid-state high lead slag) reduction contact area is small, and reducing power is weak, and agglomerate has very big difference. It is that slag is higher containing ZnO that clinker feature is produced in lead blast furnace reduction melting, usual SiO₂, that FeO, CaO and ZnO sum account for slag is total The 85%-90% of amount.The leaded generally 3%-5% of blast furnace slag, accounts for the 60%-70% of fusion process total losses.Shaft smelting lead Loss form in slag is broadly divided into three classes：1. the chemical loss of silicic acid Lead speciation；2. the thing in slag is dissolved in vulcanized lead Reason loss；3. the mechanical loss being mingled with metallic lead particulate.In general, reduction lead-in-dreg is to improve metal recovery and enterprise The key of economic benefit.General calcium in furnace silicon ratio is w (CaO)/w (SiO₂)=0.4-0.8, w(FeO)/w(SiO₂)=0.6-1.3.The high iron white residue type of the low zinc of liquid reduction clinker calcium, and lead content is comprehensive less than 2% in slag The experiment in face is closed, w (CaO)/w (SiO in liquid reduction slag are primarily determined that₂) ＜ 0.8, w (FeO)/w (SiO₂)=0.6-1.4, it is main If CaO content is relatively low, while iron content is higher.

The solubility behavior of lead oxide and metallic lead in 1.3 reduction finishing slags

Separate in reducing slag has lead oxide phase, lead arsenate phase, zinc ferrite phase, Spinel, silicate phase, testing sulphide And glass phase.Lead mainly has three kinds of loss states in the reducing slag, one is lead oxide phase, two is lead arsenate phase, three be glass Glass phase, the latter is the main loss form of lead, and the comparision contents of lead oxide and lead arsenate in the slag are low.Table 1 is to glass The average content of lead is 2.31% in the sem energy spectrum analysis that glass is mutually carried out, glass phase.

The basic chemical composition (%) of the glass phase of table 1

Measuring point	Na	Al	Si	P	S	Cl	K	Ca	Mn	Fe	Zn	Ba	Pb	O
															1	2.88	5.66	18.50	1.04	0.41	0.29	5.55	7.47	0.82	11.13	4.73	1.86	1.58	38.08
2	3.09	6.02	18.39	0.88	0.04	0.45	4.93	5.89	0.79	9.57	6.20	5.29	1.30	37.16
															3	2.75	6.23	19.05	0.60	0.31	0.41	5.42	7.19	0.73	10.77	4.27	2.52	1.56	38.19
4	3.76	5.97	19.26	0.72	0.46	0.37	4.81	4.89	0.83	7.73	7.34	3.62	2.25	37.99
															5	3.70	5.24	19.36	0.73	0.29	0.46	4.45	5.59	0.59	8.68	6.77	4.57	2.05	37.52
6	3.66	4.46	18.48	0.46	0.30	0.39	4.09	5.88	0.61	9.04	8.04	4.50	3.99	36.10
															7	3.19	5.38	18.56	0.57	0.23	0.44	4.85	6.88	0.80	11.12	6.53	2.33	1.83	37.29
8	3.21	4.60	19.71	0.66	0.04	0.31	4.01	4.74	0.88	9.65	8.85	3.31	2.91	37.12
															9	3.71	3.89	19.08	0.66	0.26	0.51	3.46	6.64	1.00	9.95	5.89	4.23	4.23	36.49
10	3.63	5.15	19.87	0.73	0.33	0.46	4.58	5.35	0.82	7.86	6.02	4.00	3.51	37.69
															11	3.57	4.89	19.23	0.72	0.06	0.32	4.26	6.59	0.50	8.75	6.92	3.26	3.87	37.06
12	3.64	4.26	19.23	0.56	0.07	0.41	4.40	5.86	0.86	9.23	7.54	3.94	3.51	36.49
															13	3.33	4.99	19.72	0.69	0.10	0.31	4.66	6.20	0.79	8.36	6.89	3.56	2.91	37.49
14	2.27	5.04	18.96	0.40	0.26	0.23	4.42	8.74	1.42	11.51	5.50	1.29	2.38	37.58
															15	3.10	5.50	19.56	0.51	0.23	0.30	4.84	5.86	0.87	9.72	5.76	3.16	2.96	37.63
16	3.38	5.54	19.5	0.42	0.24	0.42	5.02	6.28	0.88	10.3	4.76	3.69	1.88	37.69
															17	3.84	6.06	20.37	0.39	0.21	0.39	5.54	5.93	0.67	9.15	4.72	2.57	1.52	38.64
18	3.22	5.02	18.98	0.71	0.34	0.47	4.68	5.60	0.71	8.37	8.65	3.64	2.45	37.16
															19	3.51	5.43	18.76	0.67	0.6	0.42	4.66	6.40	0.83	8.29	6.57	4.28	2.02	37.56
20	3.65	6.62	19.8	0.57	0.35	0.40	5.43	4.79	0.84	7.72	5.26	3.70	2.51	38.36
															21	4.08	5.43	19.15	0.40	0.40	0.48	5.05	4.90	0.32	7.92	7.92	5.24	1.50	37.21
22	3.48	5.53	19.95	0.81	0.27	0.32	5.67	4.69	0.61	7.49	7.04	4.55	1.57	38.02
															23	3.39	7.11	19.03	0.70	0.29	0.53	6.13	5.04	0.42	8.74	5.44	3.64	1.27	38.27
24	4.00	8.16	19.25	0.45	0.23	0.13	6.12	5.74	0.61	8.24	3.86	3.88	0.30	39.03
															25	3.99	5.11	18.69	0.59	0.26	0.42	4.7	5.37	0.46	8.38	8.86	4.34	1.98	36.85
It is average	3.44	5.49	19.22	0.62	0.26	0.39	4.87	5.94	0.75	9.11	6.41	3.64	2.31	37.55

2 breach liquid high lead dross reduction process atmosphere optimal control key technology

2.1 high lead dross reduction process mechanisms

According to Pb-S-O systems oxygen bitmap, the temperature province that lead liquid is stabilized during melting should be higher than that 900 DEG C, while to ensure oxygen The heat request excessively of gas bottom blowing clinker, the temperature province general control of smelting is at 1000-1150 DEG C, and the high lead slag temperature of discharge exists More than 900 DEG C.Lead in high lead slag is main with lead oxide and lead silicate presence, passes through calculation of thermodynamics, CO, C, H₂、CH₄ Reducing agent can be all used as, it is considered to add solid coal as reducing agent.

PbO+C=Pb+CO

PbO+CO=Pb+CO₂

PbO·SiO₂+ C=Pb+CO+SiO₂

PbO·SiO₂+ CO=Pb+CO₂+SiO₂

In reduction melting, lead oxide is its main path by CO reduction, and the reduction of lead silicate must have alkaline oxygen Under compound (CaO and FeO) is participated in, and it is main occur after load melting, its reason is only silicon in the molten state Lead plumbate could have good contact with basic anhydride, reducing agent or CO, so as to complete reduction reaction.

PbO·SiO₂+ CaO+CO=CaOSiO₂+Pb+CO₂

2PbO·SiO₂+ 2CaO+2CO=2CaOSiO₂+2Pb+2CO₂

PbO·SiO₂+ FeO+CO=FeOSiO₂+Pb+CO₂

2PbO·SiO₂+ 2FeO+2CO=2FeOSiO₂+2Pb+2CO₂

2PbO·SiO₂+ CaO+FeO+2CO=CaOFeOSiO₂+2Pb+2CO₂

PbO·Fe₂O₃+ CO=Pb+Fe₂O₃+CO₂

Fe₂O₃+ CO=2FeO+CO₂

Obviously, liquid lead skim direct-reduction with high lead slag ingot bar blast furnace reduction be not both because lead skim enter oven-like state and mode Difference cause.During blast furnace reduction high lead slag ingot bar, when making reducing agent with coke, lead oxide and lead silicate Reduction be to contain to contact with solid (oxide of lead) one of reducing agent solid (coke) or solid (oxide of lead)-gas (CO), arrive Solid (incandescent coke) or liquid (oxide of the lead of melting)-gas (CO) contact process of liquid (oxide of the lead of melting) one.When When high lead slag enters reduction process in a liquid-like manner, because either solid oxidation lead or liquid oxidation lead are all easily reduced Oxide, and the furnace charge melted is conducive to the reduction of lead silicate, so the direct-reduction of liquid lead skim is just apparent.

The regulation and control of 2.2 high lead dross reduction reducing atmospheres

Compare 3.5% in coal, 1250 DEG C of reduction temperature during time 60min, carries out the reduction reaction of lead skim in tube furnace. In temperature-rise period and holding stage, the sampling and composition measurement of gas are carried out, the change of atmosphere in reduction process is specified Journey.

CO has been substantially carried out using Orsat apparatus₂, CO and O₂Analysis determine, the absorbent of oxygen does not have food for Jiao's property The alkaline solution of sub- acid, carbon dioxide is acidic oxide, typically uses caustic alkali (KOH) for absorbent, uses protochloride Copper ammonia solution makees the absorbent of carbon monoxide.Specific testing result is as shown in table 2.As seen from table, with the rise of temperature, Reaction between carbon and oxygen occurs, generation carbon monoxide and carbon dioxide.Carbon monoxide content increases and tended towards stability simultaneously, carbon dioxide Content is reduced and tended towards stability, CO/CO₂Ratio gradually increases.The content of oxygen and nitrogen is basicly stable in reduction process. After 1100 DEG C of temperature, the composition of reducing atmosphere is basicly stable, and CO contents are basic in percent by volume 60% or so.

The composition of gas and change in the lead skim reduction process of table 2

2.3 have carried out high lead dross reduction experiment and zinc beneficiation technologies research

Using high lead slag as raw material, major metal lead, zinc, copper, the trend of iron are investigated in reduction process, and determines to close lab scale For high lead slag raw material, different technical parameters research is carried out, and investigate the trend of major metal lead, zinc, copper, iron.It is determined that Rational Reduction parameter and the slag type for the determination for verifying determination.

2.3.1 the physical and chemical performance research of reducing agent coal

Table 3 is that experiment reducing agent used is the anthracitic composition of solid and Analysis of Physical result reducing agent coal as seen from table Carbon content is high, and ash content is low, and porosity is big.

The anthracite physicochemical analysis of table 3

Table 4 is with CO₂It is used as gas medium, chemical reactivity analysis result of the coal to carbon dioxide.As seen from table, it is various The reactivity of coal weakens with the intensification of degree of coalification.Because carbon and CO₂Reaction is not only carried out in the outer surface of fuel, and Carried out inside fuel on fine-pored capillary wall, porosity is higher, and the surface area of reaction is bigger.Coal with Different Rank The porosity, chemical constitution it is different, therefore its reactivity is different.

The reactivity of lignite is most strong, but when temperature higher (more than 900 DEG C), reactivity, which increases, to be slowed down.Anthracitic reaction Property is most weak, but in higher temperature, raises its reactivity with temperature and significantly increase.Pit ash composition is reacted it with quantity Property also has obvious influence.Alkali and alkaline earth metal ions are to carbon and CO₂Reaction play catalytic action, put forward the reactivity of coal It is high.Fig. 5 is temperature to anthracitic CO₂The influence of percent reduction, as seen from the figure, the CO of coal₂Percent reduction α is raised with temperature And increase, show generation CO amount increases, the chemical reactivity of coal strengthens with the rise of reaction temperature.

The anthracite of table 4 is to CO₂Chemical reactivity

2.3.2 reducing agent coal consumption

Fig. 6 and Fig. 7 are illustrated respectively under the conditions of high lead slag 400g, 1250 DEG C of temperature, time 60min, different reducing agents Anthracite consumption to the reduction effect of high lead slag and the influence of recovery rate of valuable metals, as seen from the figure with coal than increase, lead The weight-loss ratio increase of slag, shows that the various oxides in high lead slag are reduced degree enhancing.Lead content in slag is gradually reduced, Zn content is gradually lowered simultaneously.Iron content in slag is first increased slightly and then gradually reduced.

As shown in Figure 7, the rate of recovery of lead and copper increases with the increase of coal ratio in metal derby.And zinc and iron in reducing slag The rate of recovery is reduced with coal than increasing, and especially coal ratio is after 3.5%, and zinc is due to being volatized into flue gas, iron due to reduction All make zinc in reducing slag, iron content reduction into metal.Calcium silicon ratio is 0.17 in high lead slag raw material, after different coals are than reduction Calcium silicon ratio shows that slag type influences of the CaO and SiO2 contained in reducing agent coal on reducing slag is little substantially also 0.17 or so, The influence of contained chemical composition in reducing agent coal is not considered in being studied below.Experiment shows, when coal is than 3.25%, reduction Lead content 2.41% in slag, now the rate of recovery of lead is 98.11%, and the rate of recovery of zinc is 85.19%.When coal is than 3.5%, Lead content 1.48% in reducing slag, now the rate of recovery of lead is 98.86%, and the rate of recovery of zinc is only 82.91%.Consider It is recommended that coal ratio is 3.25~3.5%.

2.3.3 the influence of reducing agent temperature

Table 5 and table 6 are respectively that during time 60min, different reduction temperatures are gone back to high lead slag in coal ratio 3.25% and 3.5% Former effect.Table 7 in coal than 3.25% and 3.5%, during time 30min, reduction effect of the different reduction temperatures to high lead slag. From table 5, table 6 and Fig. 8, during recovery time 60min, with the rise of reduction temperature, the rate of recovery of lead slightly increases Plus, and lead recovery of the coal than 3.5% than coal than 3.25% is slightly higher, and coal is than high, then reducing atmosphere is high, beneficial to the reduction of lead； The rate of recovery reduction of zinc is obvious, and temperature raises the volatilization for adding zinc.And zinc recovering of the coal than 3.5% than coal than 3.25% Rate is low, and coal is than high, then reducing atmosphere height also increases the volatilization of zinc；The rate of recovery of copper, which is presented, first increases the trend reduced again, At 1225 DEG C, copper recovery is maximum, and copper recovery of the coal than 3.5% than coal than 3.25% is slightly higher；The rate of recovery of iron is with reduction Temperature rise gradually increases, and can be just reduced when ferrous acid lead temperature is high, iron is entered slag phase, and coal ratio with FeO and silicon slag making 3.5% iron recovery than coal than 3.25% is low, and coal is stronger than high then reducing atmosphere, and iron reduction can be made to enter metal phase.

(3.25%) time 60min, coal compares the reduction test situation of the different reduction temperatures of table 5

(3.5%) time 60min, coal compares the reduction test situation of the different reduction temperatures of table 6

From table 7 and Fig. 9, during recovery time 30min, with the rise of reduction temperature, the rate of recovery of lead has increased slightly, And lead recovery of the coal than 3.5% than coal than 3.25% is slightly higher；Zinc the rate of recovery reduction it is obvious, and coal than 3.5% than coal ratio 3.25% zinc recovery is low；The rate of recovery influence of copper is not obvious, and copper recovery of the coal than 3.5% than coal than 3.25% is slightly higher； The rate of recovery of iron gradually increases with reduction temperature rise, and iron recovery of the coal than 3.5% than coal than 3.25% is low.Recovery time It is identical when experimental phenomena is with recovery time 60min during 30min, but the recovery time it is shorter when, the rate of recovery of zinc is of a relatively high, The rate of recovery of iron is relatively low.In addition, when reduction temperature is low, slag gold separating effect is bad in experiment, makes to be mingled with metal phase There is scum silica frost, reduction temperature rise, lead, the rate of recovery of iron have increased slightly, but the rate of recovery reduction of zinc.Consider, it is proposed that Reduction temperature is 1200~1225 DEG C.

The reduction test situation (time 30min) of the different reduction temperatures of table 7

2.3.4 the influence of reducing agent time

8~table of table 10 is respectively that the different recovery times are to high lead dross reduction effect at 1200 DEG C, 1225 DEG C and 1250 DEG C Influence.From table 8 and Figure 10, in 1200 DEG C of temperature, with the extension of recovery time, the rate of recovery of lead slightly increases Plus, and lead recovery of the coal than 3.5% than coal than 3.25% is slightly higher；The rate of recovery of zinc is in a slight decrease, and coal than 3.5% than coal ratio 3.25% zinc recovery is low；The rate of recovery of copper slightly has reduction, and copper recovery of the coal than 3.5% than coal than 3.25% is slightly higher； The rate of recovery of iron gradually increases with recovery time extension, and iron recovery of the coal than 3.5% than coal than 3.25% is low.By the He of table 9 Figure 11 understands that, in 1225 DEG C of temperature, with the extension of recovery time, the rate of recovery of lead has increased slightly, and coal compares 3.5% Lead recovery than coal than 3.25% is slightly higher；The rate of recovery of zinc is in a slight decrease, and zinc recovering of the coal than 3.5% than coal than 3.25% Rate is low；The rate of recovery change of copper is not obvious, and copper recovery of the coal than 3.5% than coal than 3.25% is slightly higher；The rate of recovery of iron with Recovery time extension gradually increases, and iron recovery of the coal than 3.5% than coal than 3.25% is low.

The reduction test situation (1200 DEG C of temperature) of the different recovery times of table 8

From table 10 and Figure 12, in 1250 DEG C of temperature, with the extension of recovery time, to lead, zinc, copper and iron Rate of recovery influence is not obvious, and lead and copper recovery coal are more slightly higher than 3.25% than coal than 3.5%.Zinc and iron recovery coal ratio 3.5% It is more slightly lower than 3.25% than coal.As can be seen here, in 1200 DEG C and 1225 DEG C of temperature as the recovery time extends, lead content in slag Gradually reduce, lead, the rate of recovery of iron are had increased slightly, and the rate of recovery of zinc increases over time gradually to be reduced.In 1250 DEG C of temperature When, rate of recovery influence of the recovery time on lead, zinc, copper and iron be not obvious.Recovery time influences not notable to lead reduction reaction, Slightly has influence to iron and zinc recovery.The recovery time is 30min at a temperature of coal compares 3.5%, 1200 DEG C, and lead-in-dreg is 1.91%, Zinc recovery is 90.85%, and iron recovery is 91.73%；Recovery time is 60min, and lead-in-dreg is 1.83%, zinc recovery For 89.43%, iron recovery is 92.58%.The recovery time is 30min at a temperature of 1225 DEG C, and lead-in-dreg is 1.84%, and zinc is returned Yield is 89.36%, and iron recovery is 92.11%；Recovery time is 60min, and lead-in-dreg is 1.35%, and zinc recovery is 87.95%, iron recovery is 94.21%.The suggestion recovery time is considered for 30~60min.

The reduction test situation (1225 DEG C of temperature) of the different recovery times of table 9

The reduction test situation (1250 DEG C of temperature) of the different recovery times of table 10

2.3.5 calcium silicon than influence

W (CaO)/w (SiO in high lead slag₂) it is 0.17, w (FeO)/w (SiO₂) it is 1.66, relatively conventional slag type, calcium silicon compares It is low.Calcium carbonate is incorporated, the calcium silicon ratio of reducing slag is improved, the influence of different slag types is investigated.In high lead slag 400g, coal compares 3%, Under the conditions of time 60min, reduction effect of the different temperatures to high lead slag when investigating calcium silicon than 0.45.Specific test situation is shown in Table 11.From table 11 and Figure 13, when calcium silicon is than 0.45, as reduction temperature is raised, the content reduction of lead in slag, The rate of recovery of lead and copper increases substantially before 1100 DEG C, as reduction temperature rise is slowly increased after 1100 DEG C, the rate of recovery of zinc Gradually reduce, the rate of recovery of iron slightly has fluctuation.

The test situation of different reduction temperatures when the calcium silicon of table 11 is than 0.45

Table 12 is that, as high lead slag 400g, coal compares 3.5%, 1250 DEG C of temperature, time 60min, w (CaO)/w (SiO in lead skim₂) For 0.17, w (FeO)/w (SiO₂) be 1.66 when, different calcium silicon compare high lead slag reduction effect.Can by table 12 and Figure 14 Know, at 1250 DEG C, with calcium silicon than increase, the content of lead gradually rises in slag, and lead and copper recovery are in a slight decrease, The rate of recovery of zinc there is not influence substantially simultaneously, and the rate of recovery of iron decreases.Pass through above-mentioned result of the test, addition calcium carbonate adjustment The calcium silicon ratio of slag type, due to calcium silicon than increase increase the fusing point of slag, make the lead metal rate of recovery reduction, while also increase also The former quantity of slag.Therefore advise in testing without calcium carbonate, the calcium silicon ratio for keeping reducing slag low.

The different calcium silicon of table 12 than reduction test situation

2.3.6 the influence of iron silicon ratio

Table 13 and Figure 15 are influence of the different iron silicon ratios to the reduction effect of high lead slag.From table 13 and Figure 15, At 1250 DEG C, with the increase of iron silicon ratio, lead, copper and iron recovery are basically unchanged, and the rate of recovery of zinc slightly has reduction.

The test situation of the different iron silicon ratios of table 13

2.4 zinc occurrence in reducing slag

In addition to lead oxide and lead arsenate phase, zinc has all been distributed in each phase of the reducing slag.Zinc is mainly preservation sharp brilliant In stone, zinc ferrite, next to that preservation is in silicate phase, when iron content is higher in silicate phase, when calcic is also higher, and The content of zinc is typically relatively low, and a small amount of zinc preservation is and few with the zincode of testing sulphide output in glass phase.Zinc is in the slag Typical output state is as described below.Spinelle is averagely contained based on Zn-Fe spinelles in its composition in the reducing slag Zn16.77%, Al9.52%, Fe40.26%, O31.44%；Zinc ferrite averagely contains Zn9.57%, Fe51.95%, O30.89%. Silicate phase can be divided into silicate and Fe based on Zn as main silicate by its composition, with containing the silicate based on zinc Contain Zn34.87%, Fe16.42%, Si13.72%, O30.76% in average assay；Silicate based on iron content is averaged into Contain Fe35.53%, Zn7.81%, Ca4.40%, Mn5.72%, Si14.25%, O31.96% in point.

Main separate typical occurrence characteristics in the reducing slag.Spinelle and the temperature of zinc ferrite formation are general higher, in Reduction Body Often crystallized when being temperature drop relatively early, be in euhedral crytal output more especially spinelle, and with certain border ring texture； With the reduction of system temperature, silicate phase is subsequently formed, and what is eventually formed is glass phase, and glass phase constituent is complex, To some extent containing elements such as Zn, Fe, Pb, K, Na, S, Cl.

2.5 liquid high lead dross reduction integrated conditions

Summary reduction test, the basic technological parameters for determining high lead dross reduction are：Reducing agent coal ratio is 3.25~3.5%； Reduction temperature is 1200~1225 DEG C；Recovery time is 30~60min.Now, result of the test can meet performance assessment criteria, slag Middle lead content is less than 2%, and 85% zinc is in slag.Under experiment Y-111 techniques, i.e., coal compares 3.5%, 1225 DEG C of temperature, time During 30min, lead content 1.84% in slag, the rate of recovery 98.57% of lead, the rate of recovery 89.36% of zinc.In experiment Y-97 works Under skill, i.e. coal compares 3.5%, 1225 DEG C of temperature, during time 60min, lead content 1.35% in slag, the rate of recovery 98.97% of lead, The rate of recovery 87.95% of zinc.

It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, and do not carrying on the back In the case of spirit or essential attributes from the present invention, the present invention can be realized in other specific forms.Therefore, no matter from From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power Profit is required rather than described above is limited, it is intended that all in the implication and scope of the equivalency of claim by falling Change is included in the present invention.

Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only included One independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should be by Specification is as an entirety, and the technical solutions in the various embodiments may also be suitably combined, and forming those skilled in the art can With the other embodiment of understanding.

Claims

1. fused solution high lead slag saves method for smelting reduction of Ni, it is characterised in that fused solution lead skim is carried out using reducing agent Direct-reduction, the addition of reducing agent is the 3.25~3.5% of fused solution lead skim quality；Reduction temperature is 1200~1225 DEG C； Recovery time is 30~60min.

2. fused solution high lead slag according to claim 1 saves method for smelting reduction of Ni, it is characterised in that reducing agent is adopted With CO, C, solid coal, H₂Or CH₄。

3. fused solution high lead slag according to claim 2 saves method for smelting reduction of Ni, it is characterised in that reducing agent is adopted Use solid coal.

4. fused solution high lead slag according to claim 3 saves method for smelting reduction of Ni, it is characterised in that reducing agent is adopted Use solid anthracite.

5. method for smelting reduction of Ni is saved according to any described fused solution high lead slags of claim 1-4, it is characterised in that molten The slag type for melting the use of liquid lead skim is CaO/SiO₂Between 0.4~0.8, FeO/SiO₂Between 1.2~1.8.

6. fused solution high lead slag according to claim 5 saves method for smelting reduction of Ni, it is characterised in that FeO/SiO₂=1.5.