CN110117745A - A method of ferrorphosphorus is prepared using mid low grade phosphate rock and copper ashes - Google Patents
A method of ferrorphosphorus is prepared using mid low grade phosphate rock and copper ashes Download PDFInfo
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- CN110117745A CN110117745A CN201910463659.3A CN201910463659A CN110117745A CN 110117745 A CN110117745 A CN 110117745A CN 201910463659 A CN201910463659 A CN 201910463659A CN 110117745 A CN110117745 A CN 110117745A
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- copper ashes
- phosphate rock
- low grade
- ferrorphosphorus
- grade phosphate
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of methods for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes, the following steps are included: mid low grade phosphate rock, copper ashes are first carried out ball milling respectively using ball mill, then it is uniformly mixed with reducing agent, additive and water, under an argon atmosphere, first it is sent into compression moulding in mold, being then fed into drying process to its moisture content in drying box is 0, it is finally re-fed into resistance furnace and is roasted, melting removes residue, ferrorphosphorus is obtained, while the residue produced can be used as the raw material for preparing cement.The present invention carries out comprehensive reutilization to the copper ashes and mid low grade phosphate rock that not yet handle bulk deposition, it prepares with high added value ferrorphosphorus, turn waste into wealth, it improves resource utilization, problems of the prior art are solved, efficiently solve the problems, such as that existing higher cost when the prior art handles mid low grade phosphate rock and copper ashes, pollution weight, energy consumption is high, three wastes quantum of output is big.
Description
Technical field
The invention belongs to energy conservation and environmental protection and technical field of resource comprehensive utilization more particularly to it is a kind of use mid low grade phosphate rock
The method for preparing ferrorphosphorus with copper ashes.
Background technique
Ferrophosphorus is that a kind of iron and phosphorus mix preferable intermetallic compound, and good conductivity, density is larger, under room temperature chemically
Matter is stablized, anti-corrosion, and extensive use, which concentrates on, prepares high-purity FePO4, synthesizing spherical LiFePO4, tertiary sodium phosphate and iron oxide is made
Red product, obtained ferrophosphorus powder etc..Ferrorphosphorus is the important source material of metallurgy and chemical industry, and application is very extensive.In smelting
In golden industry, ferrorphosphorus is mainly as alloy addition, to precisely adjust in metal phosphorus element content to any need
Level, furthermore ferrophosphorus may also function as the effect of deoxidier in smelting process；In chemical industry ferrorphosphorus mainly by with
To synthesize phosphoric acid, phosphate and novel sound insulating material, antirusting paint etc..At present ferrophosphorus mainly from fosfosiderite, thermal phosphoric acid or
It is obtained in the chemical byproducts such as calcium magnesium phosphate.But the excessive use and thermalization phosphoric acid due to ferrophosphorus ore resources have energy consumption it is high,
The deficiencies of high, at high cost to phosphorus ore grade requirement, the development and application of ferrophosphorus are limited, therefore be badly in need of a kind of novel low-cost phosphorus
Process for making iron.
China's steel industry high speed development, but high-quality iron ore resource is fewer and fewer, therefore rationally makes full use of resource,
Alleviate iron ore imports pressure, it has also become Chinese steel looks forward to the major issue to be solved.Copper is electrical, light industry, machine-building, building
With the indispensable important non-ferrous metal in fields such as national defence, there are about 97% copper from copper concentrate pyrometallurgical smelting in China.According to
Refined copper yield 8,440,000 t in China's is calculated within 2016, produces nearly 20,000,000 t of copper ashes per year.In the copper ashes of such flood tide, only have on a small quantity
Valence element is recycled, remaining is all handled by stockpiling.According to statistics, the copper ashes that quantity is more than 1.4 hundred million t, copper are also stored up in the whole nation
Slag has become a fairly large number of industrial solid castoff generated in metallurgy industry.Copper ashes is in pyrometallurgic copper process from copper smelter
The metallurgical slag of discharge is glass phase of the molten state material upper layer through being cooled into copper smelter, mainly contain Fe, Cu, Zn, Pb,
A small amount of noble metal such as a variety of valuable metals such as Co and Ni and Au, Ag, wherein essential mineral is ferrosilicate and magnetic iron oxide, iron
Grade be more than 40%, the iron ore much higher than 29.1% is averaged production-grade, however the iron utilization rate in copper ashes is but not
Foot 1%.Most of copper ashes is dumped that there are cinder fields, can also water body to surrounding and soil generate pollution, cause environmental hazard, and
It is also the huge waste of resource.Therefore, the resource harmless treatment for reinforcing copper ashes is significant and imperative, especially in copper ashes
The recycling of iron resource has certain economic benefit.
There is phosphate rock resource abundant in China, and storage capacity is 193.6 hundred million tons, accounts for about world phosphate resource storage capacity
30%, but rich ore is few, lean ore is more, and average grade is only 17%, the mid low grade phosphate rock (P that cannot directly utilize2O5< 26%) it accounts for
90% or more, it is one of the country that rock phosphate in powder average grade is minimum in the world.The development and utilization of phosphate rock resource are mainly with rich ore
Main, some high-quality phosphate rock resources do not obtain protective mining and scientific and reasonable utilization, the high-quality phosphate rock resource in Guizhou are caused seriously to flow
It loses.In addition, the disposal of waste gas, water and industrial residue difficulty of phosphorous chemical industry end is big, phosphate rock resource comprehensive utilization is insufficient, and technological innovation urgently enhances.
Currently, rich ore has drained off, researcher has to sight to invest the lower phosphorus ore of grade.Based on this, how to make full use of
Mid low grade phosphate rock improves phosphorus ore comprehensive utilization ratio and economic benefit, it appears increasingly important.
Currently, the document about bule gold preparation has, such as:
1, patent application CN201310123248.2 is disclosed and a kind of is prepared phosphorus using high-phosphorus iron ore and mid low grade phosphate rock
The method of ferroalloy is made after mixing the high-phosphor oolitic hematite for being crushed to -3mm in advance and mid low grade phosphate rock by a certain percentage
Block, the briquetting coal after drying make reducing agent and carry out reduction roasting, and maturing temperature is 1150 DEG C~1200 DEG C, and calcining time is
90min~120min, reduction agglomerate after cooling obtain ferrorphosphorus product after mill choosing.The invention is with current utilization not yet in effect
Oolitic hematite inferior, Mid-and low-grade phosphate rock resources still in " dull " state are that raw material directly prepares ferrorphosphorus, technique
Process is short, at low cost, added value of product is high, has broad application prospects.The present invention is easily industrialized.
2, patent application CN201310332335.9, discloses a kind of preparation method of ferrophosphorus, wherein is by weight proportion
Ferrophosphorus slag, high-phosphorus iron ore and the dolomite of 70-85%:10-25%:5-20%, which is placed in smelting furnace, to be smelted, and ferrophosphorus is obtained.
Ferrophosphorus preparation method simple process of the present invention, ferrophosphorus slag utilization rate are up to 98% or more, so that waste phosphorus scum is realized
Resource utilization reduces its pollution on the environment, improves the grade of ferrophosphorus.The invention also discloses one kind by above-mentioned
Ferrophosphorus made from preparation method.
But disclosed currently without pertinent literature and ferrorphosphorus is made in mid low grade phosphate rock, copper ashes, therefore, how to open
It sends out novel low-cost a kind of, make full use of mid low grade phosphate rock and copper ashes, improve phosphorus ore and copper ashes comprehensive utilization ratio and economic effect
Benefit, it appears increasingly important.
Summary of the invention
The present invention a kind of prepares ferrorphosphorus using mid low grade phosphate rock and copper ashes in order to solve the above technical problems, providing
Method.
In order to reach purpose described above, the invention adopts the following technical scheme:
A method of ferrorphosphorus being prepared using mid low grade phosphate rock and copper ashes, comprising the following steps: first use ball milling
Mid low grade phosphate rock, copper ashes are carried out ball milling by machine respectively, are then uniformly mixed with reducing agent, additive and water, in argon atmosphere
Under, it is first sent into compression moulding in mold, being then fed into drying process to its moisture content in drying box is 0, is finally re-fed into electricity
It is roasted in resistance furnace, melting removes residue, obtains ferrorphosphorus.
The residue cleared out after melting can be used as the raw material for preparing cement.
Further, the mid low grade phosphate rock, copper ashes, reducing agent, additive and water are mixed according to following weight
It closes: 25~35 parts of phosphorus ore, 60~80 parts of copper ashes, 15~17 parts of reducing agent, 4~7 parts of additive, 0.4~0.7 part of water.
Further, the ball milling is that material is worn into mesh granularity for 80~120 mesh powders.
Further, the diameter of the mold is 20.01~30mm.
Further, the pressure of the compression moulding is 12~18MPa.
Further, the temperature of the roasting is 1200~1300 DEG C, and the time is 60~90min.
Further, the temperature of the drying is >=120 DEG C, and the time is 2~3h.
Further: the reducing agent is coke powder.
Further, the additive is borax.
Further, the water is distilled water, deionized water or ultrapure water.
Since present invention employs above technical schemes, have the advantages that
(1) present invention is prepared using the copper ashes resource and mid low grade phosphate rock for not yet handling bulk deposition at present as raw material
With high added value ferrorphosphorus material, the comprehensive utilization for this complicated intractable copper ashes and ore resource provides new think of
Road, new method.
(2) present invention reduces the impurity content of ferrorphosphorus during processing, and by the addition of additive, due to
It can effectively improve copper ashes reproducibility, iron crystal grain is promoted to grow up, reduce reduction temperature, reduce costs with high alkalinity,
And the discharge amount that energy consumption can also be reduced, reduce the three wastes；In addition, additive therefor of the present invention is from a wealth of sources, at low cost, it is easy to accomplish
Industrialization large-scale production is particularly adapted to the application of the mid low grade phosphate rock that do not developed and copper ashes resource.
(3) present invention turns waste into wealth by carrying out comprehensive reutilization to mid low grade phosphate rock and copper ashes, improves resource
Utilization rate solves the problems, such as that the application proposes, efficiently solves when the prior art handles mid low grade phosphate rock and copper ashes and exists
Higher cost, pollution weight, the problem that energy consumption is high, three wastes quantum of output is big.
(4) low energy consumption, process flow is short, added value of product is higher, has broad application prospects for the method for the present invention, and
It can preferably realize the comprehensive utilization to mid low grade phosphate rock and copper ashes.
Specific embodiment
Specific embodiments of the present invention will be described in further detail below, but the invention is not limited to these realities
Mode is applied, it is claimed to still fall within the claims in the present invention for any improvement or replacement on the present embodiment essence spirit
Range.
Copper ashes used in the embodiment of the present application is looked forward to from enterprise, Shandong Province, mid low grade phosphate rock from Guizhou Province
Industry, we respectively analyze the chemical component of copper ashes and middle-low grade phosphorus, obtain the mass fraction of copper ashes chemical component such as
The mass fraction of the following table 1, middle-low grade phosphorus chemistry ingredient is as shown in table 2 below.
The chemical component and content of 1 copper ashes of table
The chemical component and content of 2 mid low grade phosphate rock of table
| Ingredient | P2O5 | CaO | Fe2O3 | SiO2 | F | SiO3 | Al2O3 |
| Content (wt%) | 29 | 49 | 2 | 5 | 1.4 | 1.1 | 1 |
Embodiment 1
A method of ferrorphosphorus being prepared using mid low grade phosphate rock and copper ashes, comprising the following steps: first use ball milling
Mid low grade phosphate rock, copper ashes are carried out ball milling by machine respectively, are then uniformly mixed with reducing agent, additive and water, in argon atmosphere
Under, it is first sent into compression moulding in mold, being then fed into drying process to its moisture content in drying box is 0, is finally re-fed into electricity
It is roasted in resistance furnace, melting removes residue, obtains ferrorphosphorus, while the residue produced can be used as the original for preparing cement
Material.
Further, the mid low grade phosphate rock, copper ashes, reducing agent, additive and water are mixed according to following weight
It closes: 25 parts of phosphorus ore, 60 parts of copper ashes, 15 parts of reducing agent, 4 parts of additive, 0.4 part of water；The ball milling is that material is worn into mesh granularity
For 80 mesh powders；The diameter of the mold is 20.01mm；The pressure of the compression moulding is 12MPa；The temperature of the roasting
It is 1200 DEG C, time 60min；The temperature of the drying is >=120 DEG C, time 2h；The reducing agent is coke powder；It is described to add
Adding agent is borax；The water is distilled water.
Embodiment 2
A method of ferrorphosphorus being prepared using mid low grade phosphate rock and copper ashes, comprising the following steps: first use ball milling
Mid low grade phosphate rock, copper ashes are carried out ball milling by machine respectively, are then uniformly mixed with reducing agent, additive and water, in argon atmosphere
Under, it is first sent into compression moulding in mold, being then fed into drying process to its moisture content in drying box is 0, is finally re-fed into electricity
It is roasted in resistance furnace, melting removes residue, obtains ferrorphosphorus, while the residue produced can be used as the original for preparing cement
Material.
Further, the mid low grade phosphate rock, copper ashes, reducing agent, additive and water are mixed according to following weight
It closes: 35 parts of phosphorus ore, 80 parts of copper ashes, 17 parts of reducing agent, 7 parts of additive, 0.7 part of water；The ball milling is that material is worn into mesh granularity
For 120 mesh powders；The diameter of the mold is 30mm；The pressure of the compression moulding is 18MPa；The temperature of the roasting is
1300 DEG C, time 90min；The temperature of the drying is >=120 DEG C, time 3h；The reducing agent is coke powder；The addition
Agent is borax；The water is deionized water.
Embodiment 3
A method of ferrorphosphorus being prepared using mid low grade phosphate rock and copper ashes, comprising the following steps: first use ball milling
Mid low grade phosphate rock, copper ashes are carried out ball milling by machine respectively, are then uniformly mixed with reducing agent, additive and water, in argon atmosphere
Under, it is first sent into compression moulding in mold, being then fed into drying process to its moisture content in drying box is 0, is finally re-fed into electricity
It is roasted in resistance furnace, melting removes residue, obtains ferrorphosphorus, while the residue produced can be used as the original for preparing cement
Material.
Further, the mid low grade phosphate rock, copper ashes, reducing agent, additive and water are mixed according to following weight
It closes: 27 parts of phosphorus ore, 65 parts of copper ashes, 15.5 parts of reducing agent, 5 parts of additive, 0.5 part of water；The ball milling is that material is worn into mesh grain
Degree is 80~120 mesh powders；The diameter of the mold is 22mm；The pressure of the compression moulding is 13MPa；The roasting
Temperature is 1220 DEG C, time 70min；The temperature of the drying is >=120 DEG C, time 2.2h；The reducing agent is coke powder；
The additive is borax；The water is distilled water, deionized water or ultrapure water.
Embodiment 4
A method of ferrorphosphorus being prepared using mid low grade phosphate rock and copper ashes, comprising the following steps: first use ball milling
Mid low grade phosphate rock, copper ashes are carried out ball milling by machine respectively, are then uniformly mixed with reducing agent, additive and water, in argon atmosphere
Under, it is first sent into compression moulding in mold, being then fed into drying process to its moisture content in drying box is 0, is finally re-fed into electricity
It is roasted in resistance furnace, melting removes residue, obtains ferrorphosphorus, while the residue produced can be used as the original for preparing cement
Material.
Further, the mid low grade phosphate rock, copper ashes, reducing agent, additive and water are mixed according to following weight
It closes: 33 parts of phosphorus ore, 75 parts of copper ashes, 16.5 parts of reducing agent, 6 parts of additive, 0.6 part of water；The ball milling is that material is worn into mesh grain
Degree is 110 mesh powders；The diameter of the mold is 28mm；The pressure of the compression moulding is 17MPa；The temperature of the roasting
It is 1280 DEG C, time 80min；The temperature of the drying is >=120 DEG C, time 2.8h；The reducing agent is coke powder；It is described
Additive is borax；The water is distilled water, deionized water or ultrapure water.
Embodiment 5
A method of ferrorphosphorus being prepared using mid low grade phosphate rock and copper ashes, comprising the following steps: first use ball milling
Mid low grade phosphate rock, copper ashes are carried out ball milling by machine respectively, are then uniformly mixed with reducing agent, additive and water, in argon atmosphere
Under, it is first sent into compression moulding in mold, being then fed into drying process to its moisture content in drying box is 0, is finally re-fed into electricity
It is roasted in resistance furnace, melting removes residue, obtains ferrorphosphorus, while the residue produced can be used as the original for preparing cement
Material.
Further, the mid low grade phosphate rock, copper ashes, reducing agent, additive and water are mixed according to following weight
It closes: 30 parts of phosphorus ore, 70 parts of copper ashes, 16 parts of reducing agent, 5.5 parts of additive, 0.55 part of water；The ball milling is that material is worn into mesh grain
Degree is 100 mesh powders；The diameter of the mold is 25mm；The pressure of the compression moulding is 15MPa；The temperature of the roasting
It is 1200~1300 DEG C, time 75min；The temperature of the drying is >=120 DEG C, time 2.5h；The reducing agent is coke
Powder；The additive is borax；The water is distilled water, deionized water or ultrapure water.
Comparative example 1
It is carried out according to the embodiment in patent application CN201310123248.2.
Comparative example 2
It is carried out according to the embodiment in patent application CN201310332335.9.
Chemical component and content analysis are carried out to Copper component made from the embodiment of the present application 1~5 and comparative example 1~2, and remembered
Quan Tie, phosphorus, iron simple substance content in Copper component obtained by distinct methods processing mid low grade phosphate rock and copper ashes are recorded, experimental result is as follows
Shown in table 3.
Table 3
By 3 experimental data of table it is found that ferrophosphorus and gold needed for meeting production can be made in the application method.
In conclusion the present invention using at present not yet handle bulk deposition copper ashes resource and mid low grade phosphate rock as raw material,
The comprehensive utilization with high added value ferrorphosphorus material, for this complicated intractable copper ashes and ore resource is prepared to provide
New methods in working.The present invention reduces the impurity content of ferrorphosphorus during processing, and by the addition of additive,
The reduction for promoting ferro element in the P elements and copper ashes in phosphorus ore combines it more effectively and forms ferrophosphorus material；It can drop simultaneously
Low reduction temperature, reduces costs, and the discharge amount that can also be reduced energy consumption, reduce the three wastes；In addition, additive of the present invention source is wide
It is general, at low cost, it is easy to accomplish industrialization large-scale production is particularly adapted to the mid low grade phosphate rock that do not developed and copper ashes resource
Application.The present invention turns waste into wealth by carrying out comprehensive reutilization to mid low grade phosphate rock and copper ashes, improves the utilization of resources
Rate solves the problems, such as that the application proposes, efficiently solve when the prior art handles mid low grade phosphate rock and copper ashes it is existing at
This higher, pollution weight, the problem that energy consumption is high, three wastes quantum of output is big.Low energy consumption for the method for the present invention, process flow is short, product is additional
Value is higher, has broad application prospects, and can preferably realize the comprehensive utilization to mid low grade phosphate rock and copper ashes.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, nothing
By from the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended
Claim rather than above description limit, it is intended that by the institute in the meaning and scope for the equivalent loins for falling in claim
It changes and includes within protection scope of the present invention.
Claims (10)
1. a kind of method for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes, which comprises the following steps: first
Mid low grade phosphate rock, copper ashes are carried out by ball milling using ball mill respectively, are then uniformly mixed with reducing agent, additive and water,
Under argon atmosphere, it is first sent into compression moulding in mold, being then fed into drying process to its moisture content in drying box is 0, finally
It is re-fed into resistance furnace and is roasted, melting removes residue, obtains ferrorphosphorus.
2. a kind of method for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes according to claim 1, feature
Be: the mid low grade phosphate rock, copper ashes, reducing agent, additive and water are mixed according to following weight: phosphorus ore 25~35
Part, 60~80 parts of copper ashes, 15~17 parts of reducing agent, 4~7 parts of additive, 0.4~0.7 part of water.
3. a kind of method for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes according to claim 1, feature
Be: the ball milling is that material is worn into mesh granularity for 80~120 mesh powders.
4. a kind of method for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes according to claim 1, feature
Be: the diameter of the mold is 20.01~30mm.
5. a kind of method for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes according to claim 1, feature
Be: the pressure of the compression moulding is 12~18MPa.
6. a kind of method for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes according to claim 1, feature
Be: the temperature of the roasting is 1200~1300 DEG C, and the time is 60~90min.
7. a kind of method for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes according to claim 1, feature
Be: the temperature of the drying is >=120 DEG C, and the time is 2~3h.
8. a kind of method for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes according to claim 1, feature
Be: the reducing agent is coke powder.
9. a kind of method for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes according to claim 1, feature
Be: the additive is borax.
10. a kind of method for preparing ferrorphosphorus using mid low grade phosphate rock and copper ashes according to claim 1, feature
Be: the water is distilled water, deionized water or ultrapure water.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113283707A (en) * | 2021-04-27 | 2021-08-20 | 安徽安纳达钛业股份有限公司 | Method for determining mixing ratio of high-phosphorus titanium ore and common titanium ore |
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