CN101543829B - Comprehensive utilization method for recycling manganous carbonate slag - Google Patents

Comprehensive utilization method for recycling manganous carbonate slag Download PDF

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CN101543829B
CN101543829B CN200910061903A CN200910061903A CN101543829B CN 101543829 B CN101543829 B CN 101543829B CN 200910061903 A CN200910061903 A CN 200910061903A CN 200910061903 A CN200910061903 A CN 200910061903A CN 101543829 B CN101543829 B CN 101543829B
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manganous carbonate
slag
carbonate slag
cement
manganous
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CN101543829A (en
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张晓年
李家珍
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Acer Hubei Changyang Environmental Protection Technology Co., Ltd.
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Hubei Shengrong Environmental Protection & Energy Conservation Technology Co Ltd
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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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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Abstract

The invention relates to a comprehensive utilization method for recycling manganous carbonate slag. The method comprises the following steps: (1) screen separation; (2) dilution and agitation; (3) integrated separation; (4) dehydrating and drying; (5) package; and (6) repreparation of cement retarder or mixing and pressing of walling material or repreparation of slag cement. The method has the advantages that about 20 percent of manganous carbonate concentrate, iron and other heavy metals in the manganous carbonate slag reaching mine-entering grade (content of manganese metal is 17 percent) are recycled by using integrated separation technology, and the secondary tailing part remained after the integrated separation replaces plaster to be the cement retarder, or the walling material, or the slag cement; and the method can fundamentally solve the problem of the pollution on the environment caused by the manganous carbonate slag, make full and reasonable use of resources in the manganous carbonate slag, save land resource, improve the comprehensive utilization value of the manganous carbonate slag and completely realize zero discharge of the manganous carbonate slag.

Description

The method of comprehensive utilization that manganous carbonate slag reclaims
Technical field
The present invention relates to the recovery and the comprehensive utilization technique field of industrial residue, the method for comprehensive utilization that a kind of specifically manganous carbonate slag reclaims.
Background technology
Manganese carbonate ore is that the rare Gao Meng of China, high-sulfur, Gao Yin, high plumbous, zinc mix primary manganese ore, after electrolysis is refined, its product can be used for preparing the high-purity manganese carbonate concentrate, be to produce primary raw materials such as manganese sulfate, electrolytic manganese metal, activated manganese dioxide, electrolytic manganese dioxide, four manganese oxide, be widely used in a plurality of fields such as steel and iron industry, aluminium alloy industry, magnetic material industry, chemical industry.
Yet, China's manganese resource poorness, the manganese ore grade is low.Simultaneously, it is huge that electrolytic manganese process is handled the waste residue amount that produces behind the manganese carbonate ore, and 1 ton of manganese metal of every extraction will produce the manganous carbonate slag of 7-8 ton.China's manganese slag annual emissions surpasses 2,000,000 tons at present, and utilization rate is extremely low.For a long time, comprehensive, valid approach all not being found in the processing of manganese slag, is to adopt to pile up or the mode of landfill basically, and thus, the land resource amount that takies increases year by year, the polluted underground water source, and the mineral resources waste is serious, and production cost rises year by year.
How further reclaiming the high-grade manganese carbonate concentrate in the manganous carbonate slag, and to remainder comprehensive utilization, is that people wish the target of making great efforts for a long time.The open name of application for a patent for invention, CN1080950A that the open name of application for a patent for invention, CN1830865A that the open name of CN1837120A is called " cement that utilizes electrolytic manganese residues to produce " is called " utilizing electrolytic manganese residues to produce the method for ecological cementing material " is called the application for a patent for invention of " being the moulded coal of component with the Electrolytic Manganese Metal Residues ", all is that electrolytic manganese residues has been done the trial that partly utilizes.Three patents all are as raw material electrolytic manganese residues, produce cement, ecological cementing material, moulded coal, all the manganese carbonate concentrate that contains in the electrolytic manganese residues is not recycled, thereby do not fully utilize the manganese slag fully, the pollution of heavy metal can not be thoroughly solved, the manganous carbonate slag zero-emission can not be realized environment.
Summary of the invention
The objective of the invention is to develop the method for comprehensive utilization that a kind of manganous carbonate slag reclaims, utilizing the total score selecting technology to reclaim in the manganous carbonate slag about 20% can reach into heavy metal substances such as the manganese carbonate concentrate of ore deposit grade (manganese metal content 17%) and iron, the remaining secondary tailings part of comprehensive sorting, substitute gypsum as cement retarder, or as materials for wall, or as the partly alternative traditional cement of slag cements; Fundamentally solve the pollution problem of manganous carbonate slag to environment, make that resource in the manganous carbonate slag obtains fully, reasonable use, economize the land resource, the comprehensive reutilization that improves manganous carbonate slag is worth, and realizes the zero-emission of manganous carbonate slag.
The present invention proposes on the basis of manganous carbonate slag being carried out assay, and data show according to one's analysis, contain in this manganous carbonate slag: about 2.1%, the alundum (Al (Al of magnesia (MgO) 2O 3) about 9.3%, silica (SiO 2) about 33.1%, sulfur trioxide (SO 3) about 8.2%, the titanium dioxide (TiO of about 23.6%, calcium oxide (CaO) 2) about 0.5%, di-iron trioxide (Fe 2O 3) about 6.8%, the phosphorus pentoxide (P of about 4.8%, manganese oxide (MnO) 2O 5) about 1.8%, potassium oxide (K 2O) about 2.2%, wherein silica and sulfur trioxide content are more, secondly are compounds such as manganese metal, iron, aluminium, magnesium.
The method of comprehensive utilization that manganous carbonate slag of the present invention reclaims, its step is as follows:
(1) screening: manganous carbonate slag after the electrolysis is sieved, adopt screening plant, the granularity of manganous carbonate slag determines that according to the requirement of total score optional equipment granularity is at 10～120 orders/cm 2Between, through screening, remove impurity etc., guaranteed to enter the granularity of total score optional equipment material;
(2) dilution is stirred: add water and dilute stirring, improve its decentralization, impurity and manganous carbonate slag in the manganous carbonate slag are broken away from as far as possible;
(3) comprehensive sorting: adopt the equipment of patent applied for to carry out comprehensive sorting, number of patent application is 200910061341.9, and name is called the permanent-magnet drum eccentric inner surface axial sorting method and apparatus; Number of patent application is 200910061407.4, and name is called the permanent-magnet arc-shaped groove inner surface axial sorting method and apparatus; (manganese mineral belongs to weak magnetic mineral (relative magnetic susceptibility coefficient X=100～600 * 10-6cm to the difference of each ratio of components magnetic susceptibility coefficient in the above equipment utilization manganous carbonate slag 3/ g)), manganous carbonate slag is carried out sorting, reclaim the concentrate part and the heavy metal substance of manganous carbonate slag;
(4) dehydrate: the manganese carbonate concentrate is dehydrated;
(5) packing: reaching into the manganese carbonate ore of ore deposit grade (manganese metal content is 17%) of will sub-electing from manganous carbonate slag packed;
(6) materials for wall or the composite slag cements of making are made in composite produce concrete retardation agent or mixing, compacting:
1. composite produce concrete retardation agent:
Gypsum is one of requisite raw material in the cement production process, and it mainly acts on is that adjusting cement is first, the final set knot time, is the set retarder of cement, SO in the general cement 3Content is 1.5～3.5%, and the main chemical compositions of gypsum is CaSO 42H 2O, SO in theory 3Content 46.5%, the general low-grade gypsum SO of employing during actual the use 3Content is more than 30%, manganous carbonate slag SO 3About content 20%, utilize manganous carbonate slag to substitute gypsum, its incorporation is between 5～15%.
At first, remove harmful components in the manganous carbonate slag.For example titanium pigment makes it convert phosphate to, has eliminated the influence of titanium pigment to manufacture of cement, manganous carbonate slag is done necessary modification, make titanium pigment be transformed into phosphoric acid salt,, influence cement quality because the existence of titanium pigment can cause the instability of cement setting time;
Manganous carbonate slag is substituted gypsum in the ratio between 5～15%, join in the clinker, as cement retarder;
Or 2. mix, suppress and make materials for wall:
Burnt-free walling material, mainly with flyash, lime, gypsum, gather materials and raw material such as small amount of cement by certain proportioning through mixing, making after the compression moulding; Manganous carbonate slag can substitute gypsum and part is gathered materials after the comprehensive sorting in materials for wall, because of its fine size, and contains water about 30%, can be not treated make the burnt-free walling material of various uses behind the direct and flyash, lime, cement mixing;
According to cement: 4-15%, lime: 3-12%, flyash: 15-35%, the burnt-free walling material that the weight ratio of manganous carbonate slag: 30-75% is made after mixing, compression moulding, its intensity can be used as the load bearing wall materials for wall and uses between 20～30Mpa;
Manganous carbonate slag and flyash, lime, cement proportion are made the burnt-free walling material of various uses, if incorporation between 5～70%, the color of brick is a black, and certain decorative effect is arranged;
Or the 3. composite slag cements of making:
Through manganous carbonate slag after the sorting, its main component is dihydrate gypsum CaSO 42H 2O and quartzy SiO 2, activity is extremely low, after proper temperature (600 ℃～900 ℃) calcining, excites its activity, and as gel rubber material part place of cement, the ratio that substitutes is between 5～20%, and every performance indications of cement can not descend.
The advantage of the method for comprehensive utilization that manganous carbonate slag of the present invention reclaims is: utilize the total score selecting technology to reclaim in the manganous carbonate slag about 20% and can reach into heavy metals such as the manganese carbonate concentrate of ore deposit grade (manganese metal content 17%) and iron, save mineral resources; Substitute gypsum as cement retarder by remainder after the sorting of total score selecting technology, in cement production process, can substitute 5～15% gypsum, reduced the consumption of gypsum; Can be used as the production burnt-free walling material by remainder after the sorting of total score selecting technology, in the manufacturing process of burnt-free walling material, can mix 5～75% manganous carbonate slag, the intensity of the burnt-free walling material of making is between 20～30MPa, can be used as load bearing wall or dividing wall uses, traditional relatively non-burning brick, product weight is light, the intensity height; Excite its activity by remainder after the sorting of total score selecting technology, make slag cements, the part place of cement; Fundamentally solve the pollution problem of manganous carbonate slag to environment, make that resource in the manganous carbonate slag obtains fully, reasonable use, economize the land resource, the comprehensive reutilization that improves manganous carbonate slag is worth, and has realized the zero-emission of manganous carbonate slag.
The specific embodiment
Embodiment one
The method of comprehensive utilization that a kind of manganous carbonate slag reclaims, its step is as follows:
(1) screening: manganous carbonate slag after the electrolysis is sieved, adopt screening plant, the granularity of manganous carbonate slag determines that according to the requirement of total score optional equipment granularity is 10～120 orders/cm 2, through screening, remove impurity etc., guaranteed to enter the granularity of total score optional equipment material;
(2) dilution is stirred: add entry and dilute stirring, improve its decentralization, make impurity and manganous carbonate slag maximum disengaging to the greatest extent in the manganous carbonate slag;
(3) comprehensive sorting: adopt the equipment of patent applied for to carry out comprehensive sorting, number of patent application is 200910061341.9, and name is called the permanent-magnet drum eccentric inner surface axial sorting method and apparatus; Number of patent application is 200910061407.4, and name is called the permanent-magnet arc-shaped groove inner surface axial sorting method and apparatus; (manganese mineral belongs to weak magnetic mineral (relative magnetic susceptibility coefficient X=100～600 * 10-6cm to the difference of each ratio of components magnetic susceptibility coefficient in the above equipment utilization manganous carbonate slag 3/ g)), manganous carbonate slag is carried out sorting, reclaim the concentrate part and the heavy metal substance of manganous carbonate slag;
(4) dehydrate: the manganese carbonate concentrate is dehydrated;
(5) packing: reaching into the manganese carbonate ore of ore deposit grade (manganese metal content is 17%) of will sub-electing from manganous carbonate slag packed;
(6) composite produce concrete retardation agent:
Remove the harmful components in the manganous carbonate slag.For example titanium pigment makes it convert phosphate to, has eliminated the influence of titanium pigment to manufacture of cement, promptly manganous carbonate slag is done necessary modification, convert titanium pigment to phosphate, cement is first because the existence of titanium pigment can cause, the instability of final set knot time, influences cement quality;
Manganous carbonate slag is substituted gypsum in the ratio between 5～15%, join in the clinker,, whole set retarder first as cement.
Embodiment two
The method of comprehensive utilization that a kind of manganous carbonate slag reclaims, its step is as follows:
(1) screening: manganous carbonate slag after the electrolysis is sieved, adopt screening plant, the granularity of manganous carbonate slag determines that according to the requirement of total score optional equipment granularity is 10～120 orders/cm 2, through screening, remove impurity etc., guaranteed to enter the granularity of total score optional equipment material;
(2) dilution is stirred: add entry and dilute stirring, improve its decentralization, make impurity and manganous carbonate slag maximum disengaging to the greatest extent in the manganous carbonate slag;
(3) comprehensive sorting: adopt the equipment of patent applied for to carry out comprehensive sorting, number of patent application is 200910061341.9, and name is called the permanent-magnet drum eccentric inner surface axial sorting method and apparatus; Number of patent application is 200910061407.4, and name is called the permanent-magnet arc-shaped groove inner surface axial sorting method and apparatus; (manganese mineral belongs to weak magnetic mineral (relative magnetic susceptibility coefficient X=100～600 * 10-6cm to the difference of each ratio of components magnetic susceptibility coefficient in the above equipment utilization manganous carbonate slag 3/ g)), manganous carbonate slag is carried out sorting, reclaim the concentrate part and the heavy metal substance of manganous carbonate slag;
(4) dehydrate: the manganese carbonate concentrate is dehydrated;
(5) packing: reaching into the manganese carbonate ore of ore deposit grade (manganese metal content is 17%) of will sub-electing from manganous carbonate slag packed;
(6) mix, make materials for wall:
According to cement: 4～15%, lime: 3～12%, flyash: 15～35%, manganous carbonate slag: the burnt-free walling material of 30～75% weight ratio through mixing, making after the compression moulding, its intensity can be used as the load bearing wall materials for wall and uses between 20～30Mpa;
Simultaneously, can change the burnt-free walling material that manganous carbonate slag and flyash, lime, cement proportion are made various uses, if incorporation is 5～70%, the color of brick is a black, and certain decorative effect is arranged.
Embodiment three
The method of comprehensive utilization that a kind of manganous carbonate slag reclaims, its step is as follows:
(1) screening: manganous carbonate slag after the electrolysis is sieved, adopt screening plant, the granularity of manganous carbonate slag determines that according to the requirement of total score optional equipment granularity is 10～120 orders/cm 2, through screening, remove impurity etc., guaranteed to enter the granularity of total score optional equipment material;
(2) dilution is stirred: add entry and dilute stirring, make impurity and manganous carbonate slag maximum disengaging to the greatest extent in the manganous carbonate slag;
(3) comprehensive sorting: adopt the equipment of patent applied for to carry out comprehensive sorting, number of patent application is 200910061341.9, and name is called the permanent-magnet drum eccentric inner surface axial sorting method and apparatus; Number of patent application is 200910061407.4, and name is called the permanent-magnet arc-shaped groove inner surface axial sorting method and apparatus; (manganese mineral belongs to weak magnetic mineral (relative magnetic susceptibility coefficient X=100～600 * 10-6cm to the difference of each ratio of components magnetic susceptibility coefficient in the above equipment utilization manganous carbonate slag 3/ g)), manganous carbonate slag is carried out sorting, reclaim concentrate and heavy metal part in the manganous carbonate slag;
(4) dehydrate: the manganese carbonate concentrate is dehydrated;
(5) packing: reaching into the manganese carbonate ore of ore deposit grade (manganese metal content is 17%) of will sub-electing from manganous carbonate slag packed;
(6) the composite slag cements of making:
Through manganous carbonate slag after the sorting, its main component is dihydrate gypsum CaSO 42H 2O and quartzy SiO 2, activity is extremely low, can excite its activity after temperature (600 ℃～900 ℃) calcining, can partly seek for cement, and alternative ratio is 5～20%, and every performance indications of cement can not descend.

Claims (1)

1. the method for comprehensive utilization that reclaims of a manganous carbonate slag, it is characterized in that: its step is as follows:
(1) screening: manganous carbonate slag after the electrolysis is sieved, adopt screening plant, the granularity of manganous carbonate slag determines that according to the requirement of total score optional equipment the size of sieve aperture is at 10～120 orders/cm 2Between, through screening, remove big stone, leaf, branch, the granularity that has guaranteed to enter total score optional equipment material;
(2) dilution is stirred: add entry and dilute stirring, impurity and manganous carbonate slag in the manganous carbonate slag are broken away from;
(3) comprehensive sorting: manganese mineral belongs to weak magnetic mineral, its relative magnetic susceptibility coefficient X=100～600 * 10-6cm 3/ g utilizes in the manganous carbonate slag difference of each different relative magnetic susceptibility coefficient of forming, and manganous carbonate slag is carried out comprehensive sorting, reclaims the concentrate and the heavy metal part of manganous carbonate slag;
(4) dehydrate: the manganese carbonate concentrate is dehydrated;
(5) packing: reaching into the manganese carbonate ore of ore deposit grade of will sub-electing from manganous carbonate slag packed, and the manganese metal content of going into the ore deposit grade is 17%;
(6) materials for wall or the composite slag cements of making are made in composite produce concrete retardation agent or mixing, compacting:
1. composite produce concrete retardation agent:
At first, remove the harmful components titanium pigment in the manganous carbonate slag,, influence cement quality because the existence of titanium pigment can cause the instability of cement setting time;
Manganous carbonate slag in the ratio instead of gypsum between 5～15%, is joined in the clinker, as cement retarder;
Or 2. mix, suppress and make materials for wall:
According to cement: 4-15%, lime: 3-12%, flyash: 15-35%, the burnt-free walling material of making after the weight ratio mixing of manganous carbonate slag: 30-75%, the compression moulding, its intensity is used as the load bearing wall materials for wall between 20～30Mpa;
Change the proportioning of manganous carbonate slag and flyash, lime, cement, can be made into the burnt-free walling material of various uses, incorporation is between 5～70%, and the color of brick is a black, and certain decorative effect is arranged;
Or the 3. composite slag cements of making:
Through manganous carbonate slag after the sorting, its main component is dihydrate gypsum CaSO 42H 2O and quartzy SiO 2, after 600 ℃～900 ℃ temperature calcining, can excite its activity, but the part place of cement, between the alternative ratio 5～20%, every performance indications of cement can not descend.
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101767978B (en) * 2010-01-21 2011-10-05 中南大学 Manganese slag-solid waste mixed sintering brick making method
CN101864823B (en) * 2010-06-10 2012-01-11 湖北声荣环保节能科技有限公司 Aerated concrete building block produced by heavy metal-removed manganese carbonate tailing and manufacturing method thereof
CN103553378A (en) * 2013-11-12 2014-02-05 宁夏天元锰业有限公司 Method for preparing cement by utilizing electrolytic manganese residue as retarder
CN104532010A (en) * 2015-01-08 2015-04-22 劳淑仪 Comprehensive manganese tailing utilization process
CN112608127B (en) * 2020-12-18 2022-06-21 湖北工业大学 Aqueous manganese carbonate slag-based liquid cementing material and preparation method and application thereof
CN113603377B (en) * 2021-08-23 2023-01-03 广西凭祥市恒宇水泥有限公司 Cement produced by utilizing electrolytic manganese slag and production method thereof
CN116496068A (en) * 2023-06-26 2023-07-28 通友微电(四川)有限公司 Magnetic inductance material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1465538A (en) * 2002-06-08 2004-01-07 叶德敏 Steel slag modification and steel slag cement

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1465538A (en) * 2002-06-08 2004-01-07 叶德敏 Steel slag modification and steel slag cement

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