CN103121802B - Method for preparing magnesium-oxy-chloride cement by utilizing chromium slag produced through salt sub-melting technology - Google Patents
Method for preparing magnesium-oxy-chloride cement by utilizing chromium slag produced through salt sub-melting technology Download PDFInfo
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- CN103121802B CN103121802B CN201110369332.3A CN201110369332A CN103121802B CN 103121802 B CN103121802 B CN 103121802B CN 201110369332 A CN201110369332 A CN 201110369332A CN 103121802 B CN103121802 B CN 103121802B
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Abstract
The invention provides a method for preparing magnesium-oxy-chloride cement by utilizing chromium slag produced through a salt sub-melting technology. The method is characterized in that based on the characteristic that the chromium slag produced through the salt sub-melting technology is rich in magnesium oxide, the chromium slag can be used for replacing a part of magnesite light burning powder, thereby reducing the preparation cost of the magnesium-oxy-chloride cement; toxic hexavalent chromium in the chromium slag is reduced by utilizing ferrous iron, thereby eliminating the potential safety hazard; chromium slag produced through the salt sub-melting technology is rich in iron and can generate ferric hydroxide gel when used for preparing the magnesium-oxy-chloride cement, so that the compactness of products can be improved and then the wear resistance and the strength of the products can be further increased; and a modifier is added so as to improve the properties of the products, obtain a good water-resisting effect and eliminate the defects that the products are rimed and halogenated easily. During the preparation of the magnesium-oxy-chloride cement by utilizing the chromium slag produced through the salt sub-melting technology, neither strong acid nor strong base is involved, the method is carried out at normal temperature and normal pressure, the requirements on equipment materials are not high, the utilization rate of raw materials is high, the technological process is simple, and the method is a novel method for preparing the magnesium-oxy-chloride cement and recycling the chromium slag.
Description
Technical field
The present invention relates to the method for magnesia oxychloride cement preparation and chromium slag resource utilization, particularly utilize sub-fused salt technique output chromium slag to prepare magnesia oxychloride cement as raw material, and realize the method for chromium slag resource utilization.
Technical background
Sub-fused salt process using potassium hydroxide and chromite are raw material production chromoxide green, and the chromium slag producing after a series of processing still contains sexavalent chrome and Mg content is higher, and makes its resource utilization become a difficult problem.At present, the improvement method of chromium slag is divided into " watershed management " and " end treatment " two large classes substantially." watershed management " thinking is to reduce by novel method, novel process the generation of chromium slag, belongs to cleaner production, deals with problems not yet at all." sub-fused salt " chromium-salt clean production process that Chinese Academy Of Sciences Process Engineering Research Institute proposes is exactly typical " watershed management ", and built Yima, henan Province ton demonstration project, still exists chromium slag digestive problems.The thinking of " end treatment " is existing chromium slag to process (innoxious) and comprehensive utilization (resource utilization), belongs to recycling economy.Traditional chromium residue detoxifying is processed generally and can be completed voluntarily by chromium slag generation enterprise; Comprehensive utilization generally will be connected with other relevant enterprise (as cement, ironmaking, fused(calcium magnesium)phosphate, glass and ornamental brick, refractory materials etc.) and be supporting, otherwise often makes its comprehensive utilization not have economy because of costs such as transport and protection.The chromic wastes disposal method having proposed at present mainly comprises dry process (chromium slag mixes with coal grain, high temperature reduction roasting), (acidolysis or alkaline hydrolysis, add Na in wet processing
2s, FeSO
4deng reductive agent reduction Cr
6+), solidification method (chromium slag and FeSO
4, mineral acid and cement or pitch, lime, flyash and chemical agent etc. solidify and seal up for safekeeping), microbial method (microorganism direct-reduction Cr
6+the indirect method of enzymatic process and microbial metabolism, complexing, flocculation etc.) and microwave method (microwave exposure removing toxic substances under reductive agent effect) etc.There is the shortcomings such as removing toxic substances is thorough, cost is high, treatment capacity is little, efficiency is low in these methods, does not solve root problem.
Magnesia oxychloride cement is that Sweden scholar Sorel was invented in 1867, is by light-burned MgO, MgCl
2and H
2o three is in harmonious proportion the air hardening cementitious materials forming according to a certain ratio.Magnesia oxychloride cement has plurality of advantages: (1) fast solidifying, and general 1h left and right is coagulable; (2) good physical strength, resistance to compression, the folding strength of general magnesite product can reach 5～10 times of ordinary Portland cement; (3) weakly alkaline and low-corrosiveness; The pH value of magnesia oxychloride cement slurry filtrate fluctuates between 8～9.5, more much lower than the basicity of silicate cement; (4) good wear resistance is 3 times of ordinary Portland cement; (5) cohesiveness is good, and other material except metallic substance is had to good cohesiveness; (6) outstanding flame retardant resistance, MgO and MgCl
2all non-flammable; (7) good thermal insulation, the thermal conductivity of magnesia oxychloride cement is 0.14～0.23W/mK.(8) high temperature resistant, low temperature (30 DEG C～300 DEG C) in various inorganic coagulation materials, only has magnesia oxychloride cement to possess not only high temperature resistant, but also low temperature resistant characteristic simultaneously.(9) lightweight low density, density generally only has 70% of ordinary Portland cement.
But the shortcoming of magnesia oxychloride cement is also clearly: (1) poor water resistance, and general magnesite product soaks its strength decreased 70～80% after 28 days in water; (2) easy damp suction surface halide accumulation under wet environment, there is large water drop in product surface, even globule trickling; (3) in the improper or raw material of proportioning, the too high meeting of activated magnesia causes reaction too fast, and heat release is concentrated, and causes product buckling deformation; (4) hardenite is split up, and shows as thermal discharge large, condenses too fast, and early strength development is fast and later strength is low, is split up as fragment body after meeting water; (5) scum rises whitely, and the small white point of hickie or needle point size appears in product surface, and the time length is longer.The general shortcoming of improving magnesium oxychloride cement product by adding water-fast properties-correcting agent (as phosphoric acid salt, inorganic molysite, high molecular polymer, softening agent etc.) at present.
The problem and the chromium slag resource utilization difficult problem that exist for magnesia oxychloride cement, the present invention utilizes chromium slag to be rich in the feature of magnesium, iron, and the resource utilization of being prepared by magnesia oxychloride cement to modification and chromium slag organically combines, and both can eliminate the environment hidden danger of chromium slag, turns waste into wealth; The consumption that can reduce again magnesite light burnt powder, reduces costs; Also can improve Properties of Magnesium Oxychloride Cement.
Summary of the invention
The present invention relates to the method for magnesia oxychloride cement preparation and chromium slag resource utilization, particularly utilize sub-fused salt technique output chromium slag to prepare magnesia oxychloride cement as raw material, and realize the method for chromium slag resource utilization.
The method of magnesia oxychloride cement preparation of the present invention and chromium slag resource utilization, refer to that utilizing the chromium slag of institute's output in sub-fused salt explained hereafter chromoxide green process is raw material, in conjunction with formation mechanism and the feature of magnesium oxychloride cement product, in reaction process, utilize divalent iron salt to make sexavalent chrome in chromium slag change into nontoxic trivalent chromium, magnesium wherein participates in a small amount of calcium, iron, aluminium etc. the chemical reaction that magnesia oxychloride cement forms, or forms reticulated structure with property-modifying additive; Both reduce the consumption of chlorine oxygen magnesium main raw material magnesite light burnt powder, can improve again structure and the performance of magnesia oxychloride cement; Whole process will be reacted and modification organic coupling, there is no waste discharge, processing condition gentleness, and equipment requirements is not high, and technique and equipment flowsheet are simple; Both can reduce production costs, can realize again the recycling of chromium slag.
The inventive method comprises the key step such as batching, reaction, modification, curing molding and maintenance and goods modification:
A. first, light burnt powder after pulverizing and jevigating (150～200 order), magnesium chloride and water are mixed by a certain percentage in a container that disposes whipping appts, stirring reaction (first adds water magnesium chloride to make solution in actually operating, then add light burnt powder; Mol ratio in light burnt powder between magnesium oxide, magnesium chloride and water is between 6: 1: 15～18);
B. secondly, in the material obtaining to a step, add chromium slag (200～300 orders after a certain amount of pulverizing and jevigating; Chromium slag addition be light burnt powder, magnesium chloride and water three quality sum 10%～30%), add reductive agent (as iron protochloride or ferrous sulfate simultaneously, in the relative chromium slag of reductive agent addition, sexavalent chrome is slightly excessive) or other additive (as fiber, inorganic softening agent etc., addition be a step quality of material 3%～5%), stirring reaction;
C. again, in the material obtaining to step b, add water-fast properties-correcting agent (as conditioning agent, admixture, organic softening agent etc., addition be generally b step gained quality of material 2%～3%), stirring reaction;
D. c step gained material is placed in to mould, in 25～35 DEG C of curing moldings and maintenance, sclerosis is condensed very fast, Collapsible mould after 24h, continue temperature control moisturizing (relative humidity 60%～70%) maintenance 3～5 days, then after the empty maintenance of 28 the Heavenly Stems, goods reach better performance;
E. the polishing of moulded products, equating, cutting edge shaping etc.
Main chemical reactions can be expressed by following equation:
MgO+H
2O →Mg(OH)
2 (1)
5Mg(OH)
2+MgCl
2+13H
2O →5Mg(OH)
2·MgCl
2·8H
2O (2)
3Mg(OH)
2+MgCl
2+13H
2O →3Mg(OH)
2·MgCl
2·8H
2O (3)
5MgO+Mg
2++2Cl
-+13H
2O→5Mg(OH)
2·MgCl
2·8H
2O (4)
3MgO+Mg
2++2Cl
-+11H
2O→3Mg(OH)
2·MgCl
2·8H
2O (5)
3Mg
2++Cl
-+5OH
-+4H
2O→5Mg(OH)
2·MgCl
2·8H
2O (6)
2Mg
2++Cl
-+3OH
-+4H
2O→3Mg(OH)
2·MgCl
2·8H
2O (7)
3Fe
2++Cr
6+→3Fe
3++Cr
3+ (8)
The present invention forms mechanism according to magnesia oxychloride cement, organically combines with the resource utilization of chromium slag.In the device that reaction is stirred at band, carry out.First, magnesite light burnt powder, magnesium chloride solution, chromium slag and reductive agent etc. are added in reaction unit, start stirring, make it fully react (comprising the formation of the main thing phase of chromic reduction and magnesia oxychloride cement); Secondly, add water-fast properties-correcting agent (as phosphoric acid and phosphoric acid salt, high molecular polymer etc.), it is further reacted and structural changes; Again, material is proceeded to particular mold, curing molding, the mould of dismantling after certain hour, late maintaining, further promotes product properties.Experimental results show that the method can obtain the good magnesium oxychloride cement product of performance, resource utilization and the raw material availability of realizing chromium slag are high; The method can reduce the consumption of magnesite light burnt powder, thereby reduces magnesium oxychloride cement product cost; Whole process, because there is no the participation of strong acid, highly basic, requires lower, easy to operation to equipment material.The present invention provides novel method for the resource utilization of magnesia oxychloride cement preparation and sub-fused salt novel process output chromium slag.
Below in conjunction with drawings and Examples, the present invention is further illustrated.
Brief description of the drawings
Fig. 1. the process flow diagram of sub-molten salt method technique output chromium slag method of resource of the present invention.
Fig. 2. the magnesia oxychloride cement of method of the present invention is prepared the schematic diagram of main reaction device used.
Reference numeral
1. reactor 2. electric blender 3. stirring rakes
4. volume pump 5. liquid feeding valve 6. feeding-in solid body valves
7. bleeder valve 8. forming mould 9 thermo detectors
Accompanying drawing structure:
Fig. 2 is that magnesia oxychloride cement is prepared main reaction device schematic diagram used: major parts reactor 1 (being furnished with electric stirring); Electric blender 2 (rotating speed is adjustable, controls material stirring in reactor); Stirring rake 3 (stirring material carries out to react fully); Volume pump 4 (liquid material is pumped into reactor); Liquid feeding valve 5 (controlling liquid phase material adds); Feeding-in solid body valve 6 (controlling solid-phase material adds); Bleeder valve 7 (control material and derive reactor); Forming mould 8 (goods curing molding) and thermo detector 9 (measurement system temperature).
Embodiment
The sub-fused salt technique output chromium slag providing using Yima, henan Province chromium salt factory is as a kind of raw material, and its chemical constitution is as shown in table 1.
The principal element chemical constitution of table 1, the sub-fused salt technique of Yima, henan Province chromium salt factory output chromium slag
Taking Haicheng magnesite light burnt powder as main raw material, its chemical constitution is as shown in table 2.
Table 2, Haicheng magnesite light burnt powder principal element chemical constitution
Goods curing molding mould adopts Cangzhou Samsung building materials testing ISO of instrument plant cement mortar three joint-trial moulds (specification is 40 × 40 × 160, the mm of unit).
The sub-fused salt technique of the present invention output chromium slag is prepared magnesia oxychloride cement method and is made up of processes such as preparation feedback, reduction reaction, modified-reaction and curing molding, maintenance modifications, technical process is referring to accompanying drawing 1, and magnesia oxychloride cement is prepared reaction unit used referring to accompanying drawing 2.
Take a certain amount of magnesium chloride hexahydrate (Tianjin sail chemical reagent Science and Technology Ltd., MgCl
26H
2o > 98%), add a certain amount of deionized water by proportioning, stir, make magnesium chloride solution; Take a certain amount of sub-fused salt technique output chromium slag (cross 300 mesh sieves, form as shown in table 1); Take a certain amount of magnesite light burnt powder (cross 200 mesh sieves, form as shown in table 2); Take a certain amount of FeCl
24H
2o (Shantou Xilong Chemical Factory, FeCl
24H
2o > 99.7%).Light burnt powder, chromium slag are added in reactor 1 through feeding-in solid body valve 6 shown in accompanying drawing 2; Open electric blender 2, adjust certain rotating speed; Iron protochloride is dissolved in to magnesium chloride solution, by volume pump 4 shown in accompanying drawing 2, pump into reactor 1 through liquid feeding valve 5; After reaction certain hour, add property-modifying additive through entering feed valve 5 or 6 shown in accompanying drawing 2, continue reaction certain hour, can measure temperature in system by thermo detector 9 shown in accompanying drawing 2; Open bleeder valve 7 shown in accompanying drawing 2, material is put into forming mould 8 shown in accompanying drawing 2, curing molding; After certain hour, the mould of dismantling, carries out late maintaining; Finally, carry out goods modification, comprise polishing, equating etc., obtain magnesium oxychloride cement product.
Embodiment 1
Experiment batching: Haicheng magnesite light burnt powder (is crossed 200 mesh sieves, forming as shown in table 2) 135g, chromium slag (cross 300 mesh sieves, form as shown in table 1) 70g, magnesium chloride hexahydrate 101.5g, four water iron protochloride 5g, dicalcium phosphate dihydrate 8.5g, deionized water 110ml.
Experiment condition: in magnesite light burnt powder, magnesium oxide and mole proportioning of magnesium chloride and water are that in 6: 1: 18, the relative chromium slag of iron protochloride, theoretical excessive 10%, the chromium slag addition of sexavalent chrome is 20%, and properties-correcting agent secondary calcium phosphate addition is 2%; Room temperature (approximately 28 DEG C), mixing speed 150rpm, reaction times 0.5h, solidified forming time is 24h, and curing time is 5 days, and the water resistance test time is 28 days.
Experimental result: according to cement products ruggedness test standard, measuring its folding strength is 6.10Mpa, and ultimate compression strength is 39.5Mpa.After water resistance test, measuring its folding strength is 5.92Mpa, and ultimate compression strength is 38.7Mpa.
Embodiment 2
Experiment batching: Haicheng magnesite light burnt powder (is crossed 200 mesh sieves, forming as shown in table 2) 135g, chromium slag (cross 300 mesh sieves, form as shown in table 1) 63.5g, magnesium chloride hexahydrate 101.5g, four water iron protochloride 4.5g, dicalcium phosphate dihydrate 7.7g, deionized water 81ml.
Experiment condition: in magnesite light burnt powder, magnesium oxide and mole proportioning of magnesium chloride and water are that in 6: 1: 15, the relative chromium slag of iron protochloride, theoretical excessive 10%, the chromium slag addition of sexavalent chrome is 20%, and secondary calcium phosphate addition is 2%; Room temperature (approximately 28 DEG C), mixing speed 150rpm, reaction times 0.5h, solidified forming time is 24h, and curing time is 5 days, and the water resistance test time is 28 days.
Experimental result: according to cement products ruggedness test standard, measuring its folding strength is 6.25Mpa, and ultimate compression strength is 40.7Mpa.After water resistance test, measuring its folding strength is 6.11Mpa, and ultimate compression strength is 39.8Mpa.
In the inventive method embodiment, gained magnesium oxychloride cement product has following features: (1) water resisting property is good, and the loss of strength after water logging is lower than 5%, well below 70～80% of traditional magnesium oxychloride cement product water logging loss of strength; (2) with containing magnesium chromium slag Substitute For Partial magnesite light burnt powder, both solved chromium slag contaminatedly, reduce again goods cost; (3) there is the total fire prevention temperature resistance of magnesia oxychloride cement, the characteristics such as fast hard lightweight.
Claims (3)
1. utilize sub-fused salt technique output chromium slag to prepare a method for magnesia oxychloride cement, its feature is as follows:
A. first, pulverizing and jevigating to 150～200 object light burnt powder, magnesium chloride and water are mixed by a certain percentage in a container that disposes whipping appts, stirring reaction, wherein first adds water magnesium chloride to make solution, then adds light burnt powder; Mol ratio in light burnt powder between magnesium oxide, magnesium chloride and water is between 6: 1: 15～18;
B. secondly, in the material obtaining to a step, add a certain amount of pulverizing and jevigating to 200～300 order chromium slag, chromium slag addition is 10%～30% of light burnt powder, magnesium chloride and water three quality sum, add iron protochloride or ferrous sulfate simultaneously, in the relative chromium slag of addition, sexavalent chrome is slightly excessive, or inorganic softening agent, addition is 3%～5% of a step quality of material, stirring reaction;
C. again, add water-fast properties-correcting agent to step b in the material obtaining, addition is 2%～3% of b step gained quality of material, stirring reaction;
D. step c gained material is placed in to mould and is cured moulding, maintenance, after dismounting mould, proceed temperature control moisture-keeping maintaining and dry empty maintenance;
E. to steps d resulting product polish, equating, cutting edge, shaping operation, obtains finished product.
2. method according to claim 1, wherein indication chromium slag is that sub-fused salt technique produces chromium slag, indication light burnt powder is Haicheng magnesite light burnt powder.
3. method according to claim 1, wherein indication reaction conditions is normal temperature, normal pressure, and curing temperature is 25～35 DEG C, and maintain humidity is 60～70%, and striking time is greater than 24h, temperature control moisture-keeping maintaining 3～5 days, dry empty curing time is 28 days.
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|---|---|---|---|
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|---|---|---|---|
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| CN107285811A (en) * | 2017-07-18 | 2017-10-24 | 济南大学 | A kind of surface treatment method of magnesia cement decorative panel |
| CN108774043B (en) * | 2018-07-27 | 2021-07-20 | 安溪中科镁基科技有限公司 | High-doping-ratio red mud building material |
| CN115259701B (en) * | 2022-07-18 | 2023-04-14 | 济南大学 | High-sulfur-resistance portland cement clinker, cement and application thereof |
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|---|---|---|---|---|
| JP2007538156A (en) * | 2004-05-18 | 2007-12-27 | ホルシム リミティド | Chromium reduction method for metallurgical slag |
| CN101112647A (en) * | 2007-06-26 | 2008-01-30 | 广州铬德工程有限公司 | Technics for expelling poison for chromic slag |
| CN101265508A (en) * | 2007-03-16 | 2008-09-17 | 天津市大钧科技开发有限公司 | Harmless resource treatment method for chromium slag by using blast furnace iron-making technique |
| CN101288795A (en) * | 2008-05-27 | 2008-10-22 | 李兴 | Chromic salt production and extracting and reducing method of hexavalent chromium from chromic slag left behind society |
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| DE102007006529A1 (en) * | 2007-02-09 | 2008-08-14 | Sms Demag Ag | Process and reduction of a chromium-containing slag in an electric arc furnace |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007538156A (en) * | 2004-05-18 | 2007-12-27 | ホルシム リミティド | Chromium reduction method for metallurgical slag |
| CN101265508A (en) * | 2007-03-16 | 2008-09-17 | 天津市大钧科技开发有限公司 | Harmless resource treatment method for chromium slag by using blast furnace iron-making technique |
| CN101112647A (en) * | 2007-06-26 | 2008-01-30 | 广州铬德工程有限公司 | Technics for expelling poison for chromic slag |
| CN101288795A (en) * | 2008-05-27 | 2008-10-22 | 李兴 | Chromic salt production and extracting and reducing method of hexavalent chromium from chromic slag left behind society |
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