CN104724958B - Desulfurizing iron is skimmed and washes tail mud modification processing method - Google Patents
Desulfurizing iron is skimmed and washes tail mud modification processing method Download PDFInfo
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- CN104724958B CN104724958B CN201410745118.7A CN201410745118A CN104724958B CN 104724958 B CN104724958 B CN 104724958B CN 201410745118 A CN201410745118 A CN 201410745118A CN 104724958 B CN104724958 B CN 104724958B
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- tail mud
- cement
- washing tail
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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
Abstract
The invention discloses a kind of desulfurizing iron is skimmed, washing tail mud modification processing method, the washing tail mud after dried process is processed with composite reactive modifying agent mixing and ball milling, and modified washing tail mud is used in complex cement production.The present invention with can improve desulfurizing iron skim washing tail mud hydration activity so as to can be used for building material field and do the beneficial effect that active mixed material is used.
Description
Technical field
The present invention relates to field of cement production, specifically a kind of desulfurizing iron is skimmed washing tail mud modification processing method.
Background technology
Molten iron pretreatment desulfurizing technique is indispensable operation in STEELMAKING PRODUCTION flow process, in production, the discharge capacity of desulphurization and slag skimming
Account for the 2%～3% of common slag discharge capacity.Calculate by 5,500,000 tons of molten iron are produced per year, the molten iron pretreatment desulfurizing of annual discharge is skimmed
About 200,000 tons, produce discharged desulphurization and slag skimming and iron is selected through suitable procedure, such as broken → screening → magnetic separation, finally by dry magnetic separation
Magnetic separation ash afterwards proposes iron process further through the ball milling → magnetic separation that adds water again, and the washing tail mud of final discharge, by mud pumping
To filtering ponds.Washing tail mud is in pureed after natural filtration moisture, and moisture content is high.Effectively means are recycled due to lacking, this
Part accounts for the tail mud waste residue of desulphurization and slag skimming total amount 50% and directly transports outward landfill or pile up, and takes a large amount of soils, produces danger to environment
Evil.The utilization rate of washing tail mud how is improved, the best use way is found, becomes problem in the urgent need to address at present.
In washing tail mud after repeatedly carrying iron and processing, thing phase composition is complicated, but contains simple substance carbon, hydrogen-oxygen on the whole
Change calcium, calcium carbonate, calcium sulfate, dicalcium silicate and a small amount of hydrated calcium silicate phase.Washing tail mud powder 28d activity index is only
60%.According to GB/T 2847-2005《For the calcareous addition of volcano in cement》Regulation, 28 days intensity of its cement mortar resist
Compressive Strength ratio is not less than 65%；And press GB/T1596-2005《For the flyash in cement and concrete》Standard regulation, intensity
Activity index is not less than 70%.It can be seen that though washing tail mud powder is with latent hydraulicity, hydration activity is poor.Willow
Dawn et al. (see《Metal mine》7th phase in 2011 " mixing the cement cementitious performance study of desulphurization and slag skimming ground slag " paper) result of study
Show, using non-modified process tailings and cement mixing when, the incorporation of ground slag reduces the gelling of whole gelling system
Performance, so as to significantly reduce the compression strength of mortar.When volume is 30%, strength of cement grade reduces by 2 labels, by 28
Its intensity is reduced to 42.5MPa grade for 625 grades of 69.56MPa.After volume is more than 30%, the intensity of glue sand test block
Start to accelerate to decline.Therefore application of the tailings in manufacture of cement is had a strong impact on.
Content of the invention
The invention aims to solving the deficiency that above-mentioned background technology is present, proposition one kind can improve desulfurizing iron and take off
Pulp water washes the hydration activity of tail mud so as to can be used for building material field do active mixed material using desulfurizing iron skim washing
Tail mud modification processing method.
In order to realize object above, a kind of desulfurizing iron of present invention offer is skimmed and washes tail mud modification processing method, its
It is characterised by：Comprise the steps：
1) washing tail mud is taken natural drying to air-dry or drying and processing is to moisture content less than 5%, using jaw crusher
The largest particles is crushed to less than 10mm；
2) the washing tail mud for having crushed is entered mill using ball mill, and composite reactive modifying agent is added, Ball-milling Time is 20
～30min；
3) by the modified washing tail mud after ball milling and Portland cement P.O42.5 by weight percentage 30%～
45%：55%～70% mixing, mixed cement performance reach the requirement of 32.5 grade of composite Portland cement P.C or with
Clinker, gypsum mix grinding together, is produced by complex cement production technology, the percentage by weight of wherein modified cement tail mud
For 25%～45%, the percentage by weight of gypsum and clinker is 55%～75%, can produce P.C 42.5 or P.C32.5
The composite Portland cement of grade；
Preferably, the composite reactive modifying agent is by the first solid modifier, the second solid modifier and liquid
Modifying agent by weight percentage 87%～94%：5.7%～12%：0.3%～1.0% mixes.
Further, first solid modifier is water-granulated slag micro mist or flyash, water-granulated slag micro mist ratio used
Surface area is not less than 400/kg, and flyash used is that two grades and ratings above do ash discharge.
Closer, second solid modifier is alkali compounds, by alkali metal or alkaline earth metal hydroxide,
One or more in carbonate, silicate is mixed with arbitrary proportion.
Yet further the liquid modifying agent is organic polymer solution, by propane diols, triisopropanolamine, three ethanol
Being mixed with arbitrary proportion for one or more in amine, ethylene glycol, ENST- II.
Beneficial effects of the present invention：It is modified by adding a certain amount of composite modifier in washing tail mud, effectively
Improve the hydration activity of tail mud so as to which active mixed material is changed into by waste residue, incorporation is obtained greatly in complex cement is prepared
Amplitude is improved, and can reach 45%, greatlys save slag and flyash consumption, while decrease tail mud and stacking, filling
Pollution to environment, with good social benefit and economic benefit.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment one：A kind of desulfurizing iron is skimmed and washes tail mud modification processing method, it is characterised in that：Including following step
Suddenly：
1) washing tail mud is taken natural drying to air-dry or drying and processing is to moisture content less than 5%, using jaw crusher
The largest particles is crushed to less than 10mm；
2) the washing tail mud for having crushed is entered mill using ball mill, and composite reactive modifying agent is added, Ball-milling Time is 20
～30min；
3) by the modified washing tail mud after ball milling and Portland cement P.O42.5 by weight percentage 30%～
45%：55%～70% mixing, mixed cement performance reach the requirement of 32.5 grade of composite Portland cement P.C or with
Clinker, gypsum mix grinding together, is produced by complex cement production technology, the percentage by weight of wherein modified cement tail mud
For 25%～45%, the percentage by weight of gypsum and clinker is 55%～75%, can produce P.C 42.5 or P.C32.5
The composite Portland cement of grade；
Above-mentioned first solid modifier is water-granulated slag micro mist or flyash, and water-granulated slag micro mist specific surface area used is not little
In 400/kg, flyash used is that two grades and ratings above do ash discharge.Second solid modifier is alkali compounds, by
Being mixed with arbitrary proportion for one or more in alkali metal or alkaline earth metal hydroxide, carbonate, silicate.The liquid
Modifies dose is organic polymer solution, by the one kind in propane diols, triisopropanolamine, triethanolamine, ethylene glycol, ENST- II
Or multiple mixed with arbitrary proportion.
In the present embodiment, the percentage by weight of modified washing tail mud composition is：Washing tail mud (butt) 95%, composite reactive
Modifier A 5%, Ball-milling Time 25min.The match ratio of wherein composite reactive modifying agent is：(slag is micro- for first solid modifier
Powder, specific surface area are more than 400m2/ kg) 87%, the second solid modifier 12%, liquid modifying agent 1%.
Embodiment two：The percentage by weight of tail mud composition is washed in modification in this enforcement：Washing tail mud (butt) 85%,
Composite reactive modifying agent 15%, Ball-milling Time 25min.The match ratio of wherein composite reactive modifying agent is：First solid modifier
(flyash, two grades of dry ash discharges) 94%, the second solid modifier 5.7%, liquid modifying agent 0.3%.
Embodiment three：The percentage by weight of tail mud composition is washed in modification in this enforcement：Tail mud (butt) washed by cement
75%, composite reactive modifying agent 25%, Ball-milling Time 25min.The match ratio of wherein composite reactive modifying agent C is：First solid
(slag micropowder, specific surface area are more than 400m to modifying agent2/ kg) 90%, the second solid modifier 9%, liquid modifying agent 1%.
With the development in pluralism of cement and concrete, the demand of cement mixture and mineral admixture is increasing.
And the current supply growing tension of the mineral admixture such as the flyash of China, ground slag powder, price also rising steadily.This
In the bright washing tail mud waste residue large dosage application complex cement production that hydration activity is very low, provincialism manufacture of cement may be solved
Dependence to mixing materials such as slag and flyash.Cement product standard in the country's specifies at present, fine coal in Portland fly ash cement
The volume scope of ash is 20%～40%, produce reality volume generally 25%～30%；Mixing material in composite Portland cement
Incorporation scope be 20%～50%, but if the hydration activity from mixing material is low, make when volume is high cement performance decline
Seriously, its volume is restricted.
The technical advance of the present invention is embodied in and is changed by adding a certain amount of composite modifier in washing tail mud
Property, effectively increase the hydration activity of tail mud so as to which active mixed material is changed into by waste residue, incorporation in complex cement is prepared
Being greatly improved, 45% is can reach, slag and flyash consumption being greatlyd save, while decreasing tail mud heap
Put, the pollution to environment is filled, with good social benefit and economic benefit.
In modifying process, as active modifier consumption is few, and consumption is sensitive, is directly incorporated into ball milling in washing tail mud
Easily cause mixing uneven, stability is poor, the small fluctuations of volume can bring the significant fluctuations of quality, affect the later stage profit of tail mud
With.The present invention proposes a small amount of slag of incorporation with flyash for modified technical scheme, one of effect be as multiple modifications
The dispersible carrier of agent, modified masterbatch is suitably amplified, and plays a part of disperse minor additive, when making tail mud modification
Measure control is more accurate, while dispersion of the modifying agent in tail mud is more favorable to, uniform mixing.
Mix slag micropowder and be embodied in the more important function of flyash and fully super with the mud generation of washing tail can be superimposed association
Same effect.It is well known that slag is deposited there is the materials such as calcium hydroxide, calcium carbonate and calcium sulfate with flyash based on glassy state
In case, contained high activity vitreous structure in slag and flyash can be depolymerizated, destroy, and make slag and flyash
Aquation microenvironment improved, accelerate promote its hydration and hardening, can comparatively fast generate drated calcium aluminate and hydrated calcium silicate, so as to
Improve strength of cement.In desulphurization and slag skimming washing tail mud, due to there is a certain amount of calcium hydroxide, calcium carbonate and a small amount of aquation silicon
The components such as sour calcium, add the effect of alkali solid modifying agent, constitute washing tail mud and promote slag micropowder with pulverized burned coal ash hydration
Beneficial composition, can both promote the aquation of slag, flyash, also compensate for washing the not enough shortcoming of active constituent in tail mud, preferably
Achieve synergy.Additionally, by with composite modifier mixing and ball milling, improve washing tail mud particle composition, through 25min
The specific surface area of the modified washing tail mud of ball milling can reach 800/kg, and cement specific surface area is generally 330～360/kg.
In modified washing tail mud, inactive ingredient can be filled between cement granules in cement hydration process, played ultra micro and gathered materials work
With making finer and close inside Behavior of Hardened Cement Paste, reduce so as to reduce the strength of cement that is brought due to high additive.
Basic activated dose, Mcromolecular grinding aid are combined and are added in slag or flyash carrier by the present invention first, are passed through
The complex excitation effect of three, makes the activity index of modified washing tail mud bring up to more than 0.8, higher than flyash and volcanic ash
The activity of matter mixing material.The recombination energy of three kinds of modifying agent advantageously promotes the activity of washing tail mud, is the resource for washing tail mud
Using playing a key effect.
The above, is only presently preferred embodiments of the present invention, not the structure of the present invention is done any pro forma
Limit.Any simple modification, equivalent variations and modification that every technical spirit according to the present invention is made to above example, all
Still fall within the range of technical scheme.
Claims (1)
1. a kind of desulfurizing iron is skimmed and washes tail mud modification processing method, it is characterised in that：Comprise the steps：
1) washing tail mud is taken natural drying to air-dry or drying and processing is to moisture content less than 5%, using jaw crushing crusher machine
10mm is less than to the largest particles；
2) the washing tail mud for having crushed is entered mill using ball mill, and composite reactive modifying agent is added, the composite reactive is modified
Agent is by the first solid modifier, the second solid modifier and liquid modifying agent by weight percentage 87%～94%：5.7%～
12%：0.3%～1.0% mixes, and Ball-milling Time is 20～30min；First solid modifier is that water-granulated slag is micro-
Powder or flyash, water-granulated slag micro mist specific surface area used are not less than 400/kg, and flyash used is two grades and ratings above
Dry ash discharge, second solid modifier are alkali compounds, by alkali metal or alkaline earth metal hydroxide, carbonate, silicic acid
One or more in salt is mixed with arbitrary proportion, the liquid modifying agent be organic polymer solution, by propane diols, three
Being mixed with arbitrary proportion for one or more in isopropanolamine, triethanolamine, ethylene glycol, ENST- II,
3) by the modified washing tail mud after ball milling and Portland cement P.O42.5 by weight percentage 30%～45%：
55%～70% mixing, mixed cement performance reach the requirement of 32.5 grade of composite Portland cement P.C or ripe with cement
Material, gypsum mix grinding together, are produced by complex cement production technology, and the percentage by weight of wherein modified cement tail mud is 25%
～45%, the percentage by weight of gypsum and clinker is 55%～75%, can produce P.C 42.5 or P.C32.5 grade
Composite Portland cement.
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| CN201410745118.7A CN104724958B (en) | 2014-12-05 | 2014-12-05 | Desulfurizing iron is skimmed and washes tail mud modification processing method |
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| KR100816790B1 (en) * | 2001-09-27 | 2008-03-25 | 주식회사 포스코 | Improvement of Skimming Efficiency for De-[S] Slag in Hot Metal Pretreatment |
| CN1566010A (en) * | 2003-07-08 | 2005-01-19 | 鞍钢集团水泥厂 | Deferrization process for steel scoria and application of steel scoria fine powder thereof |
| CN100545115C (en) * | 2007-10-17 | 2009-09-30 | 莱芜钢铁集团有限公司 | Utilize steel slag tailing slurry slag cement of steel slag ball-milling tail mud production and preparation method thereof |
| CN101298079A (en) * | 2008-04-28 | 2008-11-05 | 莱芜钢铁集团泰东实业有限公司 | Environmental protection process method of desulfurizing slag of hot metal |
| CN101492261A (en) * | 2008-12-17 | 2009-07-29 | 武汉钢铁(集团)公司 | Steel scoria tail mud composite slag micro mist agglutination material |
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Effective date of registration: 20170801 Address after: 430083, Hubei Wuhan Qingshan District Factory No. 2 Gate joint stock company organs Patentee after: Wuhan iron and Steel Company Limited Address before: 15, Wuhan, Hubei, Wuchang Friendship Road, No. 999, block A, floor (Wuhan Iron and steel science and technology innovation department) () Patentee before: Wuhan Iron & Steel (Group) Corp. |
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Effective date of registration: 20200619 Address after: 430080 Qingshan District, Hubei, Wuhan Patentee after: Baowu huanke Wuhan Metal Resources Co.,Ltd. Address before: 430083, Hubei Wuhan Qingshan District Factory No. 2 Gate joint stock company organs Patentee before: WUHAN IRON AND STEEL Co.,Ltd. |