CN103274612A - Method for preparing cement clinker additive through using stainless steel production residues - Google Patents
Method for preparing cement clinker additive through using stainless steel production residues Download PDFInfo
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- CN103274612A CN103274612A CN2013102270513A CN201310227051A CN103274612A CN 103274612 A CN103274612 A CN 103274612A CN 2013102270513 A CN2013102270513 A CN 2013102270513A CN 201310227051 A CN201310227051 A CN 201310227051A CN 103274612 A CN103274612 A CN 103274612A
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- stainless steel
- cement clinker
- additive
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- leftover bits
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Abstract
The invention relates to a chemical engineering sludge processing method, and concretely relates to a method for preparing a cement clinker additive through using stainless steel production residues. The method comprises the following steps: naturally airing stainless steel production residues for reducing the mass content of water in the sludge to 20-25%; adding an additive, a reducing agent and a medium temperature binder to the stainless steel production residues, uniformly mixing, and balling; drying the obtained balls by a dryer to the water mass content of 5-8%; and processing the dried balls at 925-1100DEG C for 15-30min. The method has the advantages of less investment, low energy consumption, small occupied area of the system facility, high reliability, low running cost and the like; the purposes of the invention comprise heavy metal harmlessness and waste utilization, so a local harmlessness disposal problem of the stainless steel production residues is effectively solved; and the method has a wide market prospect.
Description
Technical field
The present invention relates to a kind of chemical engineering sludge treatment process, specifically refer to a kind of method with stainless steel sludge producing cement clinker additive.
Technical background
China is a stainless steel big producing country, and annual production has reached 2,000 ten thousand tons, annual all will produce a large amount of stainless steel products, and what be accompanied by in the course of processing is the generation of a large amount of pickling waste waters.And the mud that these waste water produce after treatment contains a large amount of heavy metals and harmful element, if do not deal carefully with, and then can serious environment pollution.
According to the stainless steel tube processing enterprise of Songyang County, Zhejiang, produced Stainless Steel Products in 2011 to reach more than 250,000 tons, these enterprises add deeply at product that have 500,000 tons of pickling waste waterss to produce every year approximately in the acid cleaning process, handle the back with lime method and produce the about 2.8 ten thousand tons/a of mud.The mud (tailings) of getting a foothold after hydrometallurgy extracts chromium nickel heavy metal still contains pollution substances such as certain iron, nickel, chromium, and also genus danger is given up admittedly as dealt with improperly and will bring very big influence to environment.The inventor is according to the analyzing and testing result to the sampling of leftover bits and pieces mud, and the process great deal of experimental, has proposed the leftover bits and pieces mud of heavy metals such as Ni and Cr contained is concentrated the process technology scheme that carries out harmlessness disposing.
Both at home and abroad at present the method that sludge containing heavy metal is disposed is more, mainly is divided into two big classes: one, carry out the resource utilization recycling earlier, after carry out harmlessness disposing; Two, directly carry out harmlessness disposing.Aspect the resource utilization recycling, the branch of pyrometallurgical smelting and hydrometallurgy is arranged again, the pyrometallurgical smelting rate of recovery is higher, but because bottlenecks such as its energy consumption and environmental pollution retrain, is controlled; Though and hydrometallurgy has the lower advantage of its energy consumption, exist leftover bits and pieces mud (tailings) still to belong to useless admittedly this outstanding problem of danger, effective solution is brickmaking or cement processed at present; By vitrifying or lattice distortion method, make heavy metal stabilization; But in the developed area, population collection city especially, as Shanghai City, brick field and cement mill have not allowed to exist; Therefore, how science solves the contradiction of this development and environmental protection, has become numerous environmental protection scientific workers and has paid close attention to jointly, but a historic difficult problem of properly settling is not arranged at present as yet.
And, in producing stainless steel process, contain positively charged ion in the generation leftover bits and pieces mud and be mainly Cr
3+, Ni
2+, Fe
3+, Ca
2+Negatively charged ion is mainly F
-1, NO
3 -1, SO
4 2-, Cl
-1Deng, if heavy metal is unprocessed in leftover bits and pieces mud, then not meeting the regulation of the relevant environmental protection law of China, rules, namely can not discharge.For this reason, the enterprises of producing stainless steel of China also can be handled the leftover bits and pieces mud of its generation, then needs a large amount of energy consumptions in the treating processes, such as adopting pyroprocessing, temperature reaches more than 1000 ℃, could transform by the ion that these are harmful, and finally just discharging or discharge system carry out using in addition.In addition, it is also very huge at present above-mentioned leftover bits and pieces mud to be handled the devices needed investment, and processing cost is very high, causes the production cost of enterprises of producing stainless steel to rise, and finally causes not having competitive power etc.How these things that are regarded as refuse are carried out second stage employ, contaminate environment again neither, can utilize again again is that enterprise, government wish the problem that solves always.
Summary of the invention
The present invention is directed to deficiency of the prior art, propose the method that a kind of less investment, made stainless steel leftover bits and pieces mud that processing cost is low are utilized again.
The present invention is achieved by following technical proposals:
The method of stainless steel sludge producing cement clinker additive is characterized in that comprising the steps:
(1) stainless steel is got a foothold mud natural drying makes the mass content of its moisture content be down to 20%～25%; Because the water content of the leftover bits and pieces mud that comes out in enterprises of producing stainless steel is higher, generally can reach 60～70%, do not reduce processing if do not carry out moisture content, then can bring disadvantageous effect for the energy consumption reduction in the later process technological process, and if drop to moisture content very low by airing, then need time of more growing, bigger place etc., these are from the angle of economy, need take into full account, otherwise in practice, then do not have promotional value, so in the present invention, the moisture content in the leftover bits and pieces mud is down to 20%～25%, after contriver's long-time running, the conclusion that the mixed economy cost draws;
(2) in stainless steel leftover bits and pieces mud, add additive, reductive agent, middle temperature binding agent, mix and balling-up; Because the composition characteristic of stainless steel leftover bits and pieces mud so need in the present invention additive, reductive agent etc. are added in the lump, if these are separated, does not then have effect, enforcement of the present invention is impacted yet;
(3) balling-up drying machine is dried to moisture mass content 5%～8%; In the case, easily by roasting reduction;
(4) balling-up after will drying is handled 15～30min down at 925 ℃～1100 ℃ and is got final product.
As preferably, the additive described in the step (2) of the method for above-mentioned stainless steel sludge producing cement clinker additive is calcium oxide or magnesium oxide or both mixtures, and consumption is 2～3% of leftover bits and pieces shale amount.
As preferably, the reductive agent described in the step (2) of the method for above-mentioned stainless steel sludge producing cement clinker additive is coal, and consumption is 4～6% of leftover bits and pieces shale amount.
As preferably, the middle temperature binding agent described in the step (2) of the method for above-mentioned stainless steel sludge producing cement clinker additive is kaolin, and consumption is 4～6% of leftover bits and pieces shale amount.
As preferably, the process that mixes in the step (2) of the method for above-mentioned stainless steel sludge producing cement clinker additive adopts the treatment process of ball mill pulverizing, and the particle diameter that makes mixture is below the 0.04mm.In the present invention, process by ball milling, pulverizing, can better mix leftover bits and pieces mud and reductive agent, additive, and can attenuate particle diameter, then realize more favourable for reaction process of the present invention, carry out quick, abundant etc., so the contriver in order to obtain better economic benefit, technique effect, has adopted ball mill pulverizing.
As preferably, the balling-up particle diameter in the method for above-mentioned stainless steel sludge producing cement clinker additive is Ф 15～25mm.
As preferably, the balling-up treatment temp in the method for above-mentioned stainless steel sludge producing cement clinker additive is 950 ℃.
In stainless steel leftover bits and pieces mud, contain Cr
3+, Ni
2+, Fe
3+, Ca
2+Deng positively charged ion, negatively charged ion is mainly F
-1, NO
3 -1, SO
4 2-, Cl
-1Deng, by adding additive, then additive can with leftover bits and pieces mud in ion react, its reaction mechanism is: the halogenide of metal and vitriol are replaced as corresponding oxide compound by calcium ions and magnesium ions:
MeR
2+CaO=CaR
2+MeO
MeR
2+MgO=MgR
2+MeO
By above-mentioned reaction as seen: F
-1, Cl
-1And SO
4 2-With additive generation replacement(metathesis)reaction, form metastable calcium, magnesium salts, and displace corresponding metal oxide; Simultaneously, adopting coal as reductive agent in the present invention, also is the problem that has taken into full account energy consumption.In the time of 925 ℃～1100 ℃, the charcoal in the coal is in than activation phase, can give full play of the effect of reductive agent, and metal oxide is reduced to corresponding suboxide:
MeO+CO=Me+CO
2
C+CO
2=2CO
MeO+C=Me+CO
Cr wherein
3+Price reduction is Cr
2+(nontoxic), Ni
2+Price reduction is Ni, Fe
3+Price reduction is Fe
3O
4, the harmless treatment target of the mud of can realizing getting a foothold.
(4) the stainless steel leftover bits and pieces mud after will mixing is handled 15～30min down at 925 ℃～1100 ℃, namely can be made into product.
Beneficial effect: can be converted into the innoxious material that meets national requirements for environmental protection to the heavy metal ion in the leftover bits and pieces mud of stainless steel production generation; Enforcement of the present invention has less investment, energy consumption is low, and system's facility floor space is little, the reliability height, and working cost is low etc.; Innoxious and realize that utilization of waste material is purpose, the problem of harmlessness disposing on the spot of stainless steel sludge but efficient solution is determined with heavy metal among the present invention; Have vast market prospect, had good economic benefit in the stainless steel production base of Songyang, Zhejiang.
Embodiment
Below enforcement of the present invention is specified:
Embodiment 1
130T/ days the amount of leftover bits and pieces mud that enterprises of producing stainless steel produces is carried out airing earlier, after measured, the water content that has just gone out after the production line is 65%, after reaching 25% after the airing, to sneak into additive, reductive agent, middle temperature binding agent in the leftover bits and pieces mud, mix and balling-up; Wherein additive is that calcium oxide, consumption are 3% of leftover bits and pieces shale amount; Reductive agent is coal, and consumption is 5% of leftover bits and pieces shale amount; In warm binding agent be kaolin, consumption is 4% of leftover bits and pieces shale amount; Then balling-up drying machine is dried to moisture mass content 6%; At last balling-up is got final product at 1000 ℃ of following calcination process 25min, obtain the cement clinker additive.
Embodiment 2
The method identical according to embodiment 1,130T/ days the amount of leftover bits and pieces mud that enterprises of producing stainless steel produces is carried out airing earlier, after measured, the water content that has just gone out after the production line is 68%, after reaching 23% after the airing, to sneak into additive, reductive agent, middle temperature binding agent in the leftover bits and pieces mud, mix and balling-up; Wherein additive is that magnesium oxide, consumption are 2% of leftover bits and pieces shale amount; Reductive agent is coal, and consumption is 4% of leftover bits and pieces shale amount; In warm binding agent be kaolin, consumption is 6% of leftover bits and pieces shale amount; And the treatment process of employing ball mill pulverizing, the particle diameter that makes mixture is below the 0.04mm, then balling-up drying machine is dried to moisture mass content 8%; At last balling-up is got final product at 950 ℃ of following calcination process 30min, obtain the cement clinker additive.
Embodiment 3
The method identical according to embodiment 1,130T/ days the amount of leftover bits and pieces mud that enterprises of producing stainless steel produces is carried out airing earlier, after measured, the water content that has just gone out after the production line is 65%, after reaching 20% after the airing, to sneak into additive, reductive agent, middle temperature binding agent in the leftover bits and pieces mud, mix and balling-up; Wherein additive is the mixture of magnesium oxide and calcium oxide, and two kinds of compositions half and half, total consumptions are 3% of leftover bits and pieces shale amount; Reductive agent is coal, and consumption is 5% of leftover bits and pieces shale amount; In warm binding agent be kaolin, consumption is 6% of leftover bits and pieces shale amount; And the treatment process of employing ball mill pulverizing, the particle diameter that makes mixture is below the 0.04mm, then balling-up drying machine is dried to moisture mass content 8%; At last balling-up is got final product at 930 ℃ of following calcination process 30min, obtain the cement clinker additive.
Embodiment 4
The method identical according to embodiment 1,130T/ days the amount of leftover bits and pieces mud that enterprises of producing stainless steel produces is carried out airing earlier, after measured, the water content that has just gone out after the production line is 65%, after reaching 20% after the airing, to sneak into additive, reductive agent, middle temperature binding agent in the leftover bits and pieces mud, mix and balling-up; Wherein additive is the mixture of magnesium oxide and calcium oxide, and two kinds of compositions half and half, total consumptions are 3% of leftover bits and pieces shale amount; Reductive agent is coal, and consumption is 5% of leftover bits and pieces shale amount; In warm binding agent be kaolin, consumption is 6% of leftover bits and pieces shale amount; And the treatment process of employing ball mill pulverizing, the particle diameter that makes mixture is below the 0.04mm, then balling-up drying machine is dried to moisture mass content 8%; At last balling-up is got final product at 950 ℃ of following calcination process 25min, obtain the cement clinker additive.
Claims (7)
1. the method for stainless steel sludge producing cement clinker additive is characterized in that comprising the steps:
(1) stainless steel is got a foothold mud natural drying makes the mass content of its moisture content be down to 20%～25%;
(2) in stainless steel leftover bits and pieces mud, add additive, reductive agent, middle temperature binding agent, mix and balling-up;
(3) balling-up drying machine is dried to moisture mass content 5%～8%;
(4) balling-up after will drying is handled 15～30min down at 925 ℃～1100 ℃ and is got final product.
2. the method for stainless steel sludge producing cement clinker additive according to claim 1 is characterized in that the additive described in the step (2) is calcium oxide or magnesium oxide or both mixtures, and consumption is 2～3% of leftover bits and pieces shale amount.
3. the method for stainless steel sludge producing cement clinker additive according to claim 1 is characterized in that the reductive agent described in the step (2) is coal, and consumption is 4～6% of leftover bits and pieces shale amount.
4. the method for stainless steel sludge producing cement clinker additive according to claim 1 is characterized in that the middle temperature binding agent described in the step (2) is kaolin, and consumption is 4～6% of leftover bits and pieces shale amount.
5. the method for stainless steel sludge producing cement clinker additive according to claim 1 is characterized in that the process that mixes in the step (2) adopts the treatment process of ball mill pulverizing, and the particle diameter that makes mixture is below the 0.04mm.
6. the method for stainless steel sludge producing cement clinker additive according to claim 1 is characterized in that the balling-up particle diameter is Ф 15～25mm.
7. the method for stainless steel sludge producing cement clinker additive according to claim 1 is characterized in that the balling-up treatment temp is 950 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592244A (en) * | 2020-06-02 | 2020-08-28 | 张斌 | Formula and preparation method of solid waste sludge conversion bonding sintering material |
| CN111847955A (en) * | 2020-07-01 | 2020-10-30 | 清远市博发环保科技有限公司 | Manufacturing process of cement clinker additive by using stainless steel acid-washing sludge |
| CN112207117A (en) * | 2020-09-27 | 2021-01-12 | 重庆亿源环保工程有限公司 | Method for preparing building material by using heavy metal contaminated soil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583920A (en) * | 2012-03-12 | 2012-07-18 | 陈启松 | Harmless treatment method for reducing stainless steel leftover sludge at medium temperature |
-
2013
- 2013-06-06 CN CN2013102270513A patent/CN103274612A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583920A (en) * | 2012-03-12 | 2012-07-18 | 陈启松 | Harmless treatment method for reducing stainless steel leftover sludge at medium temperature |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592244A (en) * | 2020-06-02 | 2020-08-28 | 张斌 | Formula and preparation method of solid waste sludge conversion bonding sintering material |
| CN111847955A (en) * | 2020-07-01 | 2020-10-30 | 清远市博发环保科技有限公司 | Manufacturing process of cement clinker additive by using stainless steel acid-washing sludge |
| CN112207117A (en) * | 2020-09-27 | 2021-01-12 | 重庆亿源环保工程有限公司 | Method for preparing building material by using heavy metal contaminated soil |
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Application publication date: 20130904 |