CN109971970B - Method for recovering chromium from ferronickel smelting slag and preparing geopolymer - Google Patents

Method for recovering chromium from ferronickel smelting slag and preparing geopolymer Download PDF

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CN109971970B
CN109971970B CN201910354757.3A CN201910354757A CN109971970B CN 109971970 B CN109971970 B CN 109971970B CN 201910354757 A CN201910354757 A CN 201910354757A CN 109971970 B CN109971970 B CN 109971970B
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leaching
chromium
curing
geopolymer
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CN109971970A (en
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彭志伟
张元波
古佛全
李光辉
姜涛
饶明军
苏子键
范晓慧
郭宇峰
杨永斌
李骞
徐斌
杨凌志
易凌云
唐慧敏
杨磊
王连成
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • C04B7/1535—Mixtures thereof with other inorganic cementitious materials or other activators with alkali metal containing activators, e.g. sodium hydroxide or waterglass
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • 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
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

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  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
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  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Treatment Of Sludge (AREA)

Abstract

The invention discloses a method for recovering chromium from ferronickel smelting slag and preparing geopolymer, which comprises two processes of selectively recovering chromium from the ferronickel smelting slag and preparing geopolymer by using leached slag after chromium extraction. And (2) uniformly mixing the fine powder of the ferronickel smelting slag with sodium nitrite and sodium peroxide to obtain a uniform mixture, roasting the uniform mixture, leaching with water to obtain chromium-containing leaching solution and leaching slag, adding water into the leaching slag, pouring, forming and maintaining to obtain the geopolymer. The method has high chromium recovery rate, can realize full-scale utilization of the ferronickel smelting slag, greatly improves the strength of the obtained geopolymer compared with the geopolymer obtained from the ferronickel smelting slag in the prior art, and has important environmental and economic benefits.

Description

Method for recovering chromium from ferronickel smelting slag and preparing geopolymer
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for recovering chromium from ferronickel smelting slag and preparing a geopolymer.
Background
China is the largest chromium resource consuming country in the world, the chromium consumption is over one third of the world chromite yield, but the annual output of the chromite in China is less than 1% of the world annual output, the huge demand makes the chromium become one of the metals with the highest external dependence in China, and the contradiction between supply and demand is quite prominent.
On the other hand, along with the rapid development of the process for smelting ferronickel from laterite-nickel ore, the discharge amount of ferronickel smelting slag is increased sharply, and according to incomplete statistics, the annual production amount of the ferronickel smelting slag in China exceeds 3000 million tons, the utilization rate of the ferronickel smelting slag is less than 10 percent, and the accumulated stockpiling amount is far more than 2 hundred million tons. The ferronickel smelting slag contains heavy metal elements such as chromium (3 percent) and the like, has potential toxic action, and cannot be widely used in the building material industry like a blast furnace. If the chromium in the ferronickel smelting slag can be recycled, the method has important significance for reducing the external dependence of chromium resources in China and improving the resource utilization water level of the ferronickel smelting slag, and is expected to realize the mass use of the slag after chromium extraction in the material industry and reduce the stockpiling amount of the ferronickel smelting slag.
The method for recovering valuable metals from ferronickel smelting slag mainly comprises a wet process, wherein the wet process is to dissolve elements such as nickel, cobalt, chromium and the like in the slag in an ion form by adopting an acid leaching or alkali fusion method, and then separate and purify valuable components from the solution. In order to separate and recover nickel and chromium from ferronickel smelting slag, research is carried out on enriching nickel in magnetic substances in advance by a magnetic separation method, leaving most chromium in non-magnetic substances, extracting nickel from the magnetic substances by normal-pressure acid leaching, and reacting chromium oxide in the non-magnetic substances with sodium carbonate in an alkali fusion mode to generate sodium chromate easily soluble in water. The result shows that the nickel is enriched from 0.26% to 2.57% and the chromium is enriched from 4.55% to 4.61% after magnetic separation; leaching the magnetic substance for 2 hours at the temperature of 110 ℃ by using 220g/L sulfuric acid solution as a leaching agent, wherein the leaching rate of nickel reaches 91.5%; the non-magnetic material is roasted by sodium carbonate to extract chromium, and the leaching rate of the chromium is 94.1 percent under the conditions that the mass ratio of the sodium carbonate to the non-magnetic material is 0.65, the roasting temperature is 1000 ℃ and the roasting time is 1 h. The method realizes the separation and recovery of nickel and chromium in the ferronickel smelting slag. However, a large amount of leaching slag is generated, and the potential secondary pollution problem is serious.
In conclusion, chromium contained in the ferronickel smelting slag is an important factor influencing the application of the ferronickel smelting slag in the building material industry, and the problems of high roasting temperature, low recovery efficiency, secondary pollution of chromium and the like exist in the conventional chromium recovery from the ferronickel smelting slag, so that the development of a more effective recovery process is urgently needed.
Disclosure of Invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a method for recovering chromium from ferronickel smelting slag and for preparing geopolymers.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the invention relates to a method for recovering chromium from ferronickel smelting slag and preparing geopolymer, which comprises the following steps:
step one, recovery of chromium
Mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a uniform mixture, roasting the uniform mixture at the temperature of 300-450 ℃ for 20-80 min, leaching the roasted material with water, and controlling the water leaching time to be less than or equal to 40min to obtain chromium-containing leachate and leached slag, wherein in the uniform mixture, the fine ferronickel smelting slag powder is calculated according to the mass ratio: sodium nitrite: sodium peroxide 1: 0.1-0.5: 0.2 to 1.8;
step two, preparation of geopolymer
And (3) finely grinding the leaching slag obtained in the step one to obtain a leaching slag grinding material, then adding water to obtain slurry, pouring and forming, and maintaining to obtain the geopolymer.
The key point of the technical scheme of the invention is that sodium nitrite and sodium peroxide are used for reacting with the ferronickel smelting slag, the mass ratio of the ferronickel smelting slag to the sodium nitrite and the sodium peroxide and the roasting condition are controlled at the same time, chromium is selectively converted into sodium meta-chromate with good solubility, the separation of water leaching and other components is realized, and silicon dioxide and aluminum oxide in the slag are excited by the sodium nitrite and the sodium peroxide (equivalent to an alkaline exciting agent) to generate water-insoluble polymerized aluminosilicate.
According to the method, the mass transfer process can be promoted by utilizing the characteristics that the sodium nitrite is decomposed into the sodium peroxide and the generated gas at a low melting point and a low temperature, the chromium oxide in the ferronickel smelting slag is selectively converted into the sodium meta-chromate at the low temperature, the high-efficiency excitation of the gelling activity of the ferronickel smelting slag is synchronously realized, the chromium recovery rate is high, the full-scale utilization of the ferronickel smelting slag can be realized, and the strength of the obtained geopolymer is greatly improved compared with that of the geopolymer obtained by the ferronickel smelting slag in the prior art. Has important environmental and economic benefits.
In the present invention, sodium nitrite and sodium peroxide are not substituted for the simultaneous recovery of chromium and the geopolymer obtained, for example, if sodium hydroxide is selected instead of sodium nitrite, although chromium leaching can be achieved by raising the temperature, the temperature is raised on the one hand, and the resulting geopolymer is largely reduced in high temperature strength due to saltpetering.
In the invention, the fine ferronickel smelting slag powder is obtained by finely grinding ferronickel slag, and the particle size of the fine ferronickel smelting slag powder is less than 74 mu m. Namely, the ferronickel slag is finely ground and then is sieved by a 200-mesh sieve, and the sieved substances are taken out.
In the preferred scheme, in the first step, in the uniform mixture, the fine powder of the ferronickel smelting slag is calculated according to the mass ratio: sodium nitrite: sodium peroxide 1: 0.3-0.5: 0.5 to 1.8.
As a further preference, in the first step, in the mixed material, the ferronickel smelting slag fine powder comprises the following components in percentage by mass: sodium nitrite: sodium peroxide 1: 0.3-0.5: 1.2 to 1.8.
As a further preference, in the first step, in the mixture, the fine powder of the ferronickel smelting slag is: sodium nitrite: sodium peroxide 1: 0.5: 1.2 to 1.8.
In the preferred scheme, in the step one, the mixed and uniform material is roasted for 40-60 min at the temperature of 350-400 ℃.
In a preferred scheme, in the first step, the roasted material is ground to 58-74 μm and then is leached by water.
In the invention, the roasting material needs to be further ground, because a small amount of the material is sintered together in the roasting process, the grinding can improve the leaching efficiency and realize quick leaching, but the particle size of the roasting material needs to be effectively controlled, and the roasting material cannot be ground to be too fine (namely the particle size is too small), otherwise the roasting material is easy to agglomerate, the leaching efficiency is influenced, and the forming of the geopolymer is influenced.
In a preferable scheme, in the step one, the leaching time is controlled to be 20-40 min during leaching.
Preferably, the leaching time is controlled to be 30-40 min during leaching.
In the preferred scheme, in the first step, the liquid-solid volume mass ratio of water to the roasted material is 5-8 mL: 1g of the total weight of the composition.
In a preferable scheme, in the first step, the leaching temperature is 25-80 ℃ during leaching.
Preferably, in the second step, the grain size of the leached slag abrasive is less than 37 μm. Sieving with 400 mesh sieve, and collecting the undersize product.
In the second step, the ratio of water to leached slag in the slurry is 0.2-0.3 by mass.
Preferably, in the second step, the ratio of water to the leached slag in the slurry is 0.2-0.25 by mass.
In the preferred scheme, in the second step, the curing process is as follows: curing for more than or equal to 12 hours at room temperature, demolding, putting the obtained sample into a curing box at the temperature of 40-70 ℃ for curing for 24-72 hours, and obtaining the geopolymer.
Preferably, the obtained sample is put into a curing box at 50-60 ℃ for curing for 36-72 h.
The principle and the advantages of the technical scheme of the invention are as follows:
according to the invention, sodium nitrite and sodium peroxide are used as roasting additives of the ferronickel smelting slag for the first time, the selective conversion of chromium oxide into sodium metachromate with good water solubility is realized by cooperatively controlling the addition amounts of the sodium nitrite and the sodium peroxide and the roasting temperature, and the water-insoluble polymerized aluminosilicate is generated from silicon dioxide and aluminum oxide in the slag, so that the selective recovery of chromium and the high-efficiency excitation of slag activity are realized. The inventor discovers through a large number of experiments that the mass ratio of the ferronickel smelting slag to the sodium nitrite to the sodium peroxide is controlled to be 1: (0.1-0.5): (0.2-1.8), uniformly mixing the fine powder of the ferronickel smelting slag with sodium nitrite and sodium peroxide, and then roasting at the temperature of 300-450 ℃ for 20-80 min, wherein the liquid phase generated by the sodium nitrite at low temperature obviously improves the mass transfer process, so that chromium oxide and sodium peroxide in the ferronickel smelting slag can be promoted to rapidly generate water-soluble sodium meta-chromate (NaCrO)2) And at the moment, silicon dioxide and aluminum oxide in the slag generate water-insoluble polymerized aluminosilicate, so that the high-efficiency excitation of slag gelation activity is realized, and therefore, the high-efficiency selective recovery of chromium can be realized by water leaching on the premise of not generating hexavalent chromium, and after the leaching slag is finely ground, the geopolymer can be obtained by simply controlling the abrasive ratio of water to the leaching slag. The method realizes the full-scale efficient utilization of the ferronickel smelting slag, and has great economic value and environmental benefit.
The method has the advantages of simple process, high production efficiency, environmental protection, high product added value and the like, and has good application prospect.
Detailed Description
The present invention will be described in detail with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention are within the scope of the present invention.
In order to avoid repetition, the raw materials related to this specific embodiment are described below in a unified manner, and are not described in detail in the specific embodiment:
the ferronickel smelting slag comprises the following components in percentage by mass:
SiO228.02-45.15 wt%, 25.41-30.33 wt% of MgO, 5.09-10.26 wt% of FeO, and Al2O33.26-14.03 wt% of Cr2O31.18 to 3.22 wt% and 2.40 to 5.36 wt% of CaO.
The purities of the sodium nitrite and the sodium peroxide are more than 95%.
Example 1
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.5: 1.2.
the roasting temperature is 400 ℃.
The roasting time is 60 min.
The leaching temperature was 70 ℃.
The leaching time is 40 min.
The solid-to-liquid ratio of the leaching solution is 8 mL/g.
The calcined sample was ground to an average particle size of 68 μm.
The water to leached residue abrasive ratio was 0.2.
The room temperature curing time is 24 hours.
The curing temperature of the curing box is 50 ℃.
The curing time of the curing box is 72 hours.
The chromium leaching rate in example 1 was 96.75%. The compressive strength of the obtained geopolymer after 7 days is 93.23MPa, and the compressive strength after 28 days is 103.69 MPa.
Example 2
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.5: 0.5.
the roasting temperature is 300 ℃.
The roasting time is 80 min.
The leaching temperature was 25 ℃.
The leaching time is 40 min.
The solid-to-liquid ratio of the leaching solution is 8 mL/g.
The calcined sample was ground to an average particle size of 60 μm.
The water to leached residue abrasive ratio was 0.3.
The room temperature curing time is 36 h.
The curing temperature of the curing box is 70 ℃.
The curing time of the curing box is 72 hours.
In example 2, the chromium leaching rate was 85.56%. The compressive strength of the obtained geopolymer after 7 days is 89.14MPa, and the compressive strength after 28 days is 109.11 MPa.
Example 3
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.1: 1.8.
the roasting temperature is 450 ℃.
The roasting time is 20 min.
The leaching temperature was 25 ℃.
The leaching time is 20 min.
The solid-to-liquid ratio of the leaching solution is 5 mL/g.
The calcined sample was ground to an average particle size of 68 μm.
The water to leached residue abrasive ratio was 0.25.
The room temperature curing time is 12 h.
The curing temperature of the curing box is 40 ℃.
The curing time of the curing box is 24 hours.
In example 3, the chromium leaching rate was 88.26%. The compressive strength of the obtained geopolymer after 7 days is 83.32MPa, and the compressive strength after 28 days is 101.63 MPa.
Example 4
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.5: 1.8.
the roasting temperature is 450 ℃.
The roasting time is 80 min.
The leaching temperature was 80 ℃.
The leaching time is 30 min.
The solid-to-liquid ratio of the leaching solution is 8 mL/g.
The calcined sample was ground to an average particle size of 66 μm.
The water to leached residue abrasive ratio was 0.2.
The room temperature curing time is 30 h.
The curing temperature of the curing box is 60 ℃.
The curing time of the curing box is 48 h.
In example 4, the chromium leaching rate was 94.13%. The compressive strength of the obtained geopolymer after 7 days is 96.44MPa, and the compressive strength after 28 days is 125.97 MPa.
Example 5
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.1: 0.2.
the roasting temperature is 300 ℃.
The roasting time is 20 min.
The leaching temperature was 25 ℃.
The leaching time is 20 min.
The solid-to-liquid ratio of the leaching solution is 4 mL/g.
The calcined sample was ground to 68 μm.
The water to leached residue abrasive ratio was 0.3.
The room temperature curing time is 36 h.
The curing temperature of the curing box is 40 ℃.
The curing time of the curing box is 48 h.
In example 5, the chromium leaching rate was 80.33%. The compressive strength of the obtained geopolymer after 7 days is 73.87MPa, and the compressive strength after 28 days is 90.09 MPa.
Example 6
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.3: 1.2.
the roasting temperature is 300 ℃.
The roasting time is 20 min.
The leaching temperature was 25 ℃.
The leaching time is 30 min.
The solid-to-liquid ratio of the leaching solution is 4 mL/g.
The calcined sample was ground to 68 μm.
The water to leached residue abrasive ratio was 0.3.
The room temperature curing time is 36 h.
The curing temperature of the curing box is 40 ℃.
The curing time of the curing box is 48 h.
In example 6, the chromium leaching rate was 86.02%. The compressive strength of the obtained geopolymer after 7 days is 88.78MPa, and the compressive strength after 28 days is 110.19 MPa.
Example 7
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.4: 0.9.
the roasting temperature is 450 ℃.
The roasting time is 20 min.
The leaching temperature was 80 ℃.
The leaching time is 40 min.
The solid-to-liquid ratio of the leaching solution is 8 mL/g.
The calcined sample was ground to an average particle size of 68 μm.
The water to leached residue abrasive ratio was 0.25.
The room temperature curing time is 36 h.
The curing temperature of the curing box is 40 ℃.
The curing time of the curing box is 48 h.
In example 7, the chromium leaching rate was 90.11%. The compressive strength of the obtained geopolymer after 7 days is 81.47MPa, and the compressive strength after 28 days is 94.36 MPa.
Comparative example 1
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.6: 0.1.
the roasting temperature is 300 ℃.
The roasting time is 20 min.
The leaching temperature was 25 ℃.
The leaching time is 20 min.
The solid-to-liquid ratio of the leaching solution is 4 mL/g.
The calcined sample was ground to an average particle size of 68 μm.
The water to leached residue abrasive ratio was 0.1.
The room temperature curing time is 10 h.
The curing temperature of the curing box is 50 ℃.
The curing time of the curing box is 72 hours.
The leaching rate of chromium of comparative example 1 was 20.41%. The compressive strength of the obtained geopolymer after 7 days is 30.78MPa, and the compressive strength after 28 days is 34.96 MPa.
Comparative example 2
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.5: 0.5.
the roasting temperature is 250 ℃.
The roasting time is 80 min.
The leaching temperature was 80 ℃.
The leaching time is 60 min.
The solid-to-liquid ratio of the leaching solution is 8 mL/g.
The calcined sample was ground to an average particle size of 66 μm.
The water to leached residue abrasive ratio was 0.3.
The room temperature curing time is 12 h.
The curing temperature of the curing box is 30 ℃.
The curing time of the curing box is 72 hours.
The leaching rate of chromium of this comparative example 2 was 22.73%. The compressive strength of the obtained geopolymer after 7 days is 31.02MPa, and the compressive strength after 28 days is 40.21 MPa.
Comparative example 3
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0: 1.8.
the roasting temperature is 450 ℃.
The roasting time is 80 min.
The leaching temperature was 80 ℃.
The leaching time is 60 min.
The solid-to-liquid ratio of the leaching solution is 8 mL/g.
The calcined sample was ground to an average particle size of 60 μm.
The water to leached residue abrasive ratio was 0.25.
The room temperature curing time is 24 hours.
The curing temperature of the curing box is 80 ℃.
The curing time of the curing box is 72 hours.
The leaching rate of chromium in comparative example 3 was 12.61%. The compressive strength of the obtained geopolymer after 7 days is 25.69MPa, and the compressive strength after 28 days is 31.34 MPa.
Comparative example 4
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.05: 0.1.
the roasting temperature is 450 ℃.
The roasting time is 20 min.
The leaching temperature was 80 ℃.
The leaching time is 40 min.
The solid-to-liquid ratio of the leaching solution is 8 mL/g.
The calcined sample was ground to an average particle size of 68 μm.
The water to leached residue abrasive ratio was 0.25.
The room temperature curing time is 36 h.
The curing temperature of the curing box is 40 ℃.
The curing time of the curing box is 48 h.
The leaching rate of chromium of this comparative example 4 was 5.11%. Geopolymers do not gain strength.
Comparative example 5
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.5: 0.
the roasting temperature is 450 ℃.
The roasting time is 20 min.
The leaching temperature was 80 ℃.
The leaching time is 40 min.
The solid-to-liquid ratio of the leaching solution is 8 mL/g.
The calcined sample was ground to an average particle size of 68 μm.
The water to leached residue abrasive ratio was 0.25.
The room temperature curing time is 36 h.
The curing temperature of the curing box is 40 ℃.
The curing time of the curing box is 48 h.
The leaching rate of chromium of this comparative example 5 was 10.21%. The compressive strength of the obtained geopolymer after 7 days is 12.37MPa, and the compressive strength after 28 days is 24.36 MPa.
Comparative example 6
And uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a mixture, roasting in a muffle furnace, grinding a roasted sample, and leaching in water to obtain chromium-containing leaching solution and leaching slag. And (3) milling the leaching slag to-37 mu m in a planetary ball mill, controlling the ratio of water to the leaching slag grinding material, pouring and molding, curing and demolding at room temperature, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.5: 1.8.
the roasting temperature is 450 ℃.
The roasting time is 80 min.
The leaching temperature was 80 ℃.
The leaching time is 60 min.
The solid-to-liquid ratio of the leaching solution is 8 mL/g.
The calcined sample was ground to an average particle size of 61 μm.
The water to leached residue abrasive ratio was 0.2.
The room temperature curing time is 30 h.
The curing temperature of the curing box is 60 ℃.
The curing time of the curing box is 48 h.
In example 4, the chromium leaching rate was 87.43%. The compressive strength of the obtained geopolymer after 7 days is 24.64MPa, and the compressive strength after 28 days is 35.79 MPa.
Comparative example 7
Mixing the fine ferronickel smelting slag powder, sodium nitrite and sodium peroxide uniformly to obtain a mixture, roasting in a muffle furnace, directly grinding a roasted sample to-37 mu m (sieving by a 400-mesh sieve, taking undersize products), and leaching by water to obtain chromium-containing leachate and leaching slag. And adding water into the leaching slag, controlling the ratio of the water to the leaching slag abrasive, pouring and forming, curing at room temperature, demolding, and curing in a curing box to obtain the geopolymer.
The mass ratio of the fine ferronickel smelting slag powder to the sodium nitrite to the sodium peroxide in the uniform mixture is 1: 0.4: 0.9.
the roasting temperature is 450 ℃.
The roasting time is 20 min.
The leaching temperature was 80 ℃.
The leaching time is 40 min.
The solid-to-liquid ratio of the leaching solution is 8 mL/g.
The water to leached residue abrasive ratio was 0.25.
The room temperature curing time is 36 h.
The curing temperature of the curing box is 40 ℃.
The curing time of the curing box is 48 h.
The leaching rate of chromium of this comparative example 7 was 90.11%. The compressive strength of the obtained geopolymer after 7 days is 31.21MPa, and the compressive strength after 28 days is 36.08 MPa.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that the present embodiments be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art will be able to make the description as a whole, and the embodiments in each example may be appropriately combined to form other embodiments that may be understood by those skilled in the art.

Claims (9)

1. A method for recovering chromium from ferronickel smelting slag and preparing geopolymer is characterized in that: the method comprises the following steps:
step one, recovery of chromium
Uniformly mixing the fine ferronickel smelting slag powder with sodium nitrite and sodium peroxide to obtain a uniform mixture, and mixing the uniform mixture at 300-450 DEG CoRoasting at the temperature of C for 20-80 min, grinding the roasted material to 58-74 mu m, leaching with water for less than or equal to 40min to obtain chromium-containing leachate andleaching slag, wherein in the mixed material, fine powder of ferronickel smelting slag is calculated according to the mass ratio: sodium nitrite: sodium peroxide =1: 0.1-0.5: 0.2 to 1.8;
step two, preparation of geopolymer
And (3) finely grinding the leaching slag obtained in the step one to obtain a leaching slag grinding material, then adding water to obtain slurry, pouring and forming, and maintaining to obtain the geopolymer.
2. A method of recovering chromium from ferronickel slag and producing geopolymers according to claim 1, characterized in that: in the mixed material, the fine powder of the ferronickel smelting slag is calculated according to the mass ratio: sodium nitrite: sodium peroxide =1: 0.3-0.5: 0.5 to 1.8.
3. A method of recovering chromium from ferronickel slag and producing geopolymers according to claim 1, characterized in that: in the first step, the uniformly mixed material is placed in a range of 350-400 DEGoAnd roasting at the temperature of C for 40-60 min.
4. A method of recovering chromium from ferronickel slag and producing geopolymers according to claim 1, characterized in that: in the first step, during leaching, the leaching time is controlled to be 20-40 min.
5. A method of recovering chromium from ferronickel slag and producing geopolymers according to claim 1, characterized in that: in the first step, during leaching, the liquid-solid volume mass of water and the roasted material is 5-8 mL: 1g, the leaching temperature is 25-80%oC。
6. A method of recovering chromium from ferronickel slag and producing geopolymers according to claim 1, characterized in that: in the second step, the grain size of the leached slag grinding material is less than 37 mu m.
7. A method of recovering chromium from ferronickel slag and producing geopolymers according to claim 1, characterized in that: in the second step, the ratio of water to leached slag abrasive in the slurry is 0.2-0.3 by mass ratio.
8. A method of recovering chromium from ferronickel slag and producing geopolymers according to claim 1, characterized in that: in the second step, the curing process comprises the following steps: firstly, curing for more than or equal to 12 hours at room temperature, demolding, and putting the obtained sample into a container with the temperature of 40-70 DEG CoC, curing for 24-72 hours by using a curing box to obtain the geopolymer,
9. a method of recovering chromium from ferronickel slag and producing geopolymers according to claim 8, characterized in that: putting the obtained sample into 50-60 partsoAnd C, maintaining the steel plate for 36-72 hours by using a maintaining box.
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CN105776910A (en) * 2016-04-08 2016-07-20 济南大学 Ferronickel slag geopolymer and preparation method thereof

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WO2004083123A1 (en) * 2003-03-19 2004-09-30 Institute Of Process Engineering Chinese Academy Of Sciences Method for production of alkali metal chromates

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Publication number Priority date Publication date Assignee Title
CN101456589A (en) * 2009-01-05 2009-06-17 中南大学 Chromium-containing material strong oxidizing roast technique
CN101824530A (en) * 2010-04-08 2010-09-08 白向南 Process for roasting chromite resources in ring kiln through pure oxygen by using low-temperature method and harmlessly and deeply utilizing chromium residue
CN103121717A (en) * 2013-02-05 2013-05-29 湖北理工学院 Method for preparing sodium chromate by mixing chromite and ferrochrome and device for method
CN105420519A (en) * 2015-12-21 2016-03-23 中南大学 Method for extracting vanadium and chromium from materials containing vanadium or/and chromium
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