CN101823697B - Method for preparing hydrotalcite-like compounds by flue gas desulfurized waste residue - Google Patents
Method for preparing hydrotalcite-like compounds by flue gas desulfurized waste residue Download PDFInfo
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- CN101823697B CN101823697B CN2010101612242A CN201010161224A CN101823697B CN 101823697 B CN101823697 B CN 101823697B CN 2010101612242 A CN2010101612242 A CN 2010101612242A CN 201010161224 A CN201010161224 A CN 201010161224A CN 101823697 B CN101823697 B CN 101823697B
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Abstract
The invention relates to a method for preparing hydrotalcite-like compounds by flue gas desulfurized waste residue, belonging to the technical field of flue gas desulfurized waste residue recycling and inorganic stratified material preparation. The method comprises the following steps: 1) dissolving NaOH and Al(OH)3 in 150-200 parts of water, regulating pH value of the solution to be 13-14, and heating to boiling point to obtain aluminate solution A; 2) detecting content of each element of the desulfurized waste residue, adding desulfurized waste residue containing Mg in solution A, adding Na2CO3, regulating pH value of the solution to be 11-12, and stirring fully and uniformly to obtain solution B; and stirring fully, vehiclerying out backflow condensation, reacting for 5-8h, leaching, washing to obtain filter liquor C and solid powder D, drying and grinding the solid powder D to obtain hydrotalcite-like compounds, and further utilizing Mg, Al and other elements contained in the filter liquor C to prepare hydrotalcite-like compounds in a cyclic manner. In the invention, filter liquor can be fully utilized in cyclic manner, no high-concentration waste liquor is discharged, and the production technology is environment friendly.
Description
Technical field
The invention belongs to flue gas desulfurization waste slag and recycle field and inorganic lamellar material preparation field, relate to a kind of method of utilizing flue gas desulfurization waste slag to prepare houghite.
Background technology
(Layered Double Hydrotalcides LDHs) is a kind of novel mineral material that is similar to montmorillonite to hydrotalcite, and typical magnalium hydrotalcite chemical formula is: [Mg
6Al
2(OH)
16CO
3] 4H
2O.Mg in hydrotalcite is formed
2+, Al
3+Just constituted when being replaced by other iso-valence metal ion houghite (Hydrotalcite-like compounds, HTLcs).As one type of functional inorganic materials with layer structure, the general formula of hydrotalcite and houghite can be expressed as [M
2+ 1-xM
3+ x(OH)
2] [A
N-]
X/nMH
2O, wherein M
2+Be divalent metal, comprise Mg
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Deng; M
3+Be trivalent metal cation, comprise Al
3+, Fe
3+, Cr
3+Deng.By effective combination of these divalence and trivalent metal ion, can form two, the HTLcs of ternary even quaternary; A
N-For interlayer anion can be inorganic anion such as Cl
-, CO
3 2-Deng, also can be organic anion.Therefore but hydrotalcite has chemical composition and the particular structure and the performance of modulation: the Modulatory character of (1) laminate chemical composition; (2) Modulatory character of interlayer ion kind and quantity; (3) Modulatory character of crystallite dimension and distribution thereof; (4) low-surface-energy.
The main application of hydrotalcite and houghite has: multi-functional filling improver such as fire-retardant, stable, the insulation of macromolecular materials such as (1) plastics, rubber, chemical fibre, painted, uvioresistant.For example, present global fire retardant total flow surpasses 1,000,000 tons, and wherein external inorganic combustion inhibitor has reached 530,000 tons.Domestic halogen-free flame retardants is mainly used in automobile, coating, cable industry, household electrical appliance, plastics, rubber etc., and development potentiality is huge.It is growing that magnalium hydrotalcite substitutes the Pb stabilizer demand as the PVC non-toxic stabilizer; Particularly forbid using some harmful substance in the 2002/95/EC number instruction of European Union at electronic equipment; Directly influence the outlet of China's 1,500 hundred million RMB electronic equipments, caused the great attention of national departments concerned.Realize that as early as possible the magnesium base inorganic particle of environment friendliness and the large-scale production of Halogen material are the effective ways that addresses this problem; (2) dyestuff, coating, paint, printing ink, cosmetics daily-use chemical industry raw material; (3) dyeing and weaving thing waste water treating agent, radioactive wastewater inorganic agent, removing pollutant flocculant etc.Humic acid material in the former water accounts for 50%～90% (mass fraction) of total organic matter in the water, in the chlorination process, can produce the multiple accessory substance haloform that human body is had carcinogenic, teratogenesis, mutagenesis etc." drinking water sanitary standard " (GB 5749-2006) of promulgation in 2006 first haloform etc. to human body have three cause effect DBPs (DBPs) as controlling object.Houghite has good adsorption to humic acid and removes effect; (4) chemical catalyst carrier and aromatized catalyst; (5) improver of multiple material and intermediate etc.
The NaOH that the disposable consumption in reaction of traditional houghite synthetic route is a large amount of also generates NaCl, the NaNO of low value
3Or Na
2SO
4And a large amount of the discharge, cost is higher relatively on the one hand, and (Guo Yu .Mg/Al type houghite and product of roasting thereof are to Cl in the aqueous solution for Wang Junfeng, plum honor to cause environmental pollution on the other hand
-Absorption.Xi'an Polytechnic University's journal, 2008,22 (2): 171-174; Yan Chunyan, Yi Wentao, Ma Peihua, the experimental study of the strong .Mg/Al type of Lee's method houghite attracts boron. ion-exchange and absorption, 2009,25 (3): 233～240).
In addition, main matter is diatomite (silica), excessive magnesium, magnesium hydroxide, carbon dust, magnesium sulfate, magnesium sulfite, calcium oxide, alundum (Al etc. in the magnesia desulfurization residue; At present, magnesia desuifurized processing in coal-burning power plant's has three kinds of directions: (1) byproduct holomorphosis is also produced sulfuric acid, but calcine technology is complicated, and the overall operation expense is also higher; (2) be that the byproduct of main desulfurization directly is used for fertilizer with magnesium sulfite, but added value of product is lower; (3) directly efflux: magnesium salts can cause polluting, and does not meet the requirement of national cleaner production and recycling economy.Therefore, how effectively to utilize magnesia flue gas desulfurization byproduct and obtain high social and economic benefit is a problem demanding prompt solution.
Summary of the invention
The object of the invention provides a kind of method of utilizing flue gas desulfurization waste slag to prepare houghite.
For achieving the above object, the technical scheme that the present invention adopts is: a kind of method of utilizing flue gas desulfurization waste slag to prepare houghite may further comprise the steps:
(1) in the whole process of preparation, be mete-wand with the amount of substance, with Na
2CO
3Amount of substance be 1 part; With NaOH and 2.1～3.3 parts of Al (OH)
3, be dissolved in 150～200 parts of water, through regulating the amount of NaOH, regulator solution pH value is 13～14, is heated to the solution boiling, prepares aluminate solution A;
(2) content of the desuifurized middle element of detection will contain in the desuifurized adding A solution of 5.8～9.3 parts of Mg elements, add 1 part of Na
2CO
3The pH value of regulator solution is 11～12, stirs, and obtains solution B;
(3) fully stirring, under the condition of reflux condensation mode, reacting 5～8 hours, then suction filtration, wash liquor C and pressed powder D; Powder D was descended dry 20～30 hours at 70～100 ℃, grind, obtain houghite;
In the technique scheme, be that benchmark is because the variation of concentration of sodium carbonate can influence the CO in the magnalium hydrotalcite crystal intermediate layer with the amount of substance of sodium carbonate
3 2-Symmetric height and the CO in the intermediate layer
3 2-With the order of hydrone distribution, and then influence the basic layer of magnalium hydrotalcite crystal upward cationic distribution situation and performance.
Further in the technical scheme, elements such as the Mg in the recycle liquor C, Al may further comprise the steps: detect Mg, Al constituent content in the liquor C, OH
-Concentration is replenished Mg, Al raw material, and the preparation houghite specifically may further comprise the steps:
(4) detect Mg, Al constituent content in the liquor C, OH
-Concentration is added Al (OH)
3Making the Al constituent content is 2.1～3.3 parts, and adding water, to make the total amount of water in the solution be 150～200 parts, and adding NaOH, to make pH value of solution be 13～14, is heated to the solution boiling, prepares aluminate solution;
(5) add to step (4) gained aluminate solution and contain the desuifurized of Mg element, making the Mg constituent content contain is 5.8～9.3 parts, adds Na
2CO
3The pH value of regulator solution is 11～12, stirs;
(6) fully stirring, under the condition of reflux condensation mode, reacting 5～8 hours, then suction filtration, wash filtrating and pressed powder; Pressed powder was descended dry 20～30 hours at 70～100 ℃, grind, obtain houghite.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. because the present invention adopts the cleaning synthetic route to prepare magnalium hydrotalcite, and the reaction rear filtrate can all be recycled, no high-concentration waste liquid discharging is the environmental friendliness production technology; And traditional houghite synthetic route consumes a large amount of NaOH in reaction and generate NaCl, the NaNO of low value
3Or Na
2SO
4And a large amount of the discharge, cost is higher relatively on the one hand, causes environmental pollution on the other hand.
2. the present invention utilizes the magnesia flue gas desulfurization byproduct to produce magnesium base class hydrotalcite; Contain elements such as Mg, Al, Ca, Fe, Si; Have than high added value, cost of material is significantly less than like product on the market, has the good market competitiveness and society, ecological environment benefit.
Description of drawings
Fig. 1 is the schematic flow sheet of preparation houghite among the embodiment;
Fig. 2 is the structural representation of houghite among the embodiment one;
Fig. 3 is for containing the desuifurized elementary analysis figure of Mg element among the embodiment one;
Fig. 4 is the elementary analysis figure of embodiment one gained houghite;
Fig. 5 is the XRD figure spectrum of embodiment one gained houghite.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Embodiment one: prepare houghite referring to step shown in the accompanying drawing 1:
The first step takes by weighing 10.4g Al (OH)
3(0.13mol, 3.25 parts) and 12g NaOH (0.3mol, 7.5 parts) put into the 250ml beaker, add the deionized water (6.94mol, 173.5 parts) of 125ml, and the pH value that records solution is 13, are heated to the solution boiling, with preparation aluminate solution A.
In second step, analyzing and testing contains the content of each element in Mg element desuifurized, referring to Fig. 3; Take by weighing 4.3g Na
2CO
3(0.04mol, 1 part) and contain 0.19mol (4.75 parts) Mg element desuifurized joining in the solution A, fully stir, make to mix, obtain solution B, its pH value is 12.
The 3rd step, pour solution B in the there-necked flask of 500ml, under the condition of abundant stirring, reflux condensation mode, reacted 6 hours, suction filtration is washed then, gets liquor C and pressed powder D.Powder D 80 ℃ of dryings 24 hours, is ground, obtain houghite, yield is 44.5%.
In the 4th step, Mg, Al constituent content are respectively 0.155mol and 0.063mol, OH in the detection liquor C
-Concentration is 2.0mol/L.
In the 5th step, take by weighing 5.36g Al (OH)
3(0.067mol) add in the liquor C, replenish deionized water, be heated to the solution boiling, with preparation aluminate solution A ' to 125ml with 0.2g NaOH.
The 6th step is to solution A ' in add the waste residue contain 0.035mol (0.88 part) Mg, adding Na
2CO
3The pH value of regulating mixed solution is about 11, obtains solution B '.
The 7th step, under the condition of abundant stirring, reflux condensation mode, reacted 6 hours, suction filtration is washed then, gets liquor C ' and pressed powder D '.Powder D ' 80 ℃ of dryings 24 hours, is ground, obtain houghite; To the gained houghite carry out elementary analysis (referring to Fig. 4) and XRD analysis (referring to Fig. 5, wherein, (1) magnesium slag; (2) houghite), and in view of the above make the structural representation (referring to Fig. 2) of houghite.
Repeat～the seven step of the 4th step, the preparation houghite.
Relatively the XRD of magnesium slag and houghite composes and can know, the characteristic diffraction peak of magnesium slag is 2 θ=21.93 °, and 26.66 °, 35.88 °; 46.02 ° and 53.88 °, but the intensity of these diffraction maximums weakens in houghite or disappears, and magnalium silicon houghite 003,006 occurred; 111,009,012,015; The characteristic diffraction peak of 018,110 and 113 crystal faces, consistent with bibliographical information; Confirm that products therefrom is that (referring to Wang Junfeng, plum is flourish, and Guo Yu .Mg/Al type hydrotalcite and product of roasting thereof are to Cl in the aqueous solution for magnalium silicon houghite
-Absorption. Xi'an Polytechnic University's journal, 2008,22 (2): 171-173; Yan Chunyan, Yi Wentao, Ma Peihua, the experimental study of the strong .Mg/Al type of Lee's method hydrotalcite attracts boron. ion-exchange and absorption, 2009,25 (3): 233～240).
Embodiment two: referring to preparing houghite shown in the accompanying drawing 1:
The first step takes by weighing 20.8g Al (OH)
3(0.26mol, 6.5 parts) and 24g NaOH (0.6mol, 15 parts) put into the 500ml beaker, add the deionized water (13.88mol, 347 parts) of 250ml, and the pH value that records solution is 14, are heated to the solution boiling, with preparation aluminate solution A.
In second step, take by weighing 8.6g Na
2CO
3(0.08mol, 2 parts) and contain desuifurized the joining in the solution A of 0.38mol (9.5 parts) Mg element fully stir, and make to mix, and obtain solution B, and the pH value of solution B is about 12.
The 3rd step, pour solution B in the there-necked flask of 1000ml, under the condition of abundant stirring, reflux condensation mode, reacted 5 hours, suction filtration is washed then, gets liquor C and pressed powder D.Powder D 100 ℃ of dryings 24 hours, is ground, obtain houghite.
In the 4th step, Mg, Al constituent content are respectively 0.31mol and 0.13mol, OH in the detection liquor C
-Concentration is 1.9mol/L.
In the 5th step, take by weighing 10.5g Al (OH)
3(0.13mol) add in the liquor C with 0.25g NaOH, replenish deionized water to 250ml, the pH value that records solution is 13, is heated to the solution boiling, with preparation aluminate solution A '.
The 6th step is to solution A ' in add the waste residue contain 0.07mol Mg, adding Na
2CO
3, the pH value of regulating mixed solution is about 12, obtains solution B '.
The 7th step, under the condition of abundant stirring, reflux condensation mode, reacted 6 hours, suction filtration is washed then, gets liquor C ' and pressed powder D '.Powder D ' 80 ℃ of dryings 24 hours, is ground, obtain houghite.
Repeat～the seven step of the 4th step, the preparation houghite.
Embodiment three: referring to preparing houghite shown in the accompanying drawing 1:
The first step takes by weighing 20.8g Al (OH)
3(0.26mol, 6.5 parts) and 24g NaOH (0.6mol, 15 parts) put into the 500ml beaker, add the deionized water (13.88mol, 347 parts) of 250ml, record the pH value to 13 of solution, are heated to the solution boiling, with preparation aluminate solution A.
In second step, take by weighing 8.6g Na
2CO
3(0.08mol, 2 parts) and contain desuifurized the joining in the solution A of 1.14mol (28.6 parts) Mg element fully stir, and make to mix, and obtain solution B, and the pH that records solution B is about 12.
The 3rd step, pour solution B in the there-necked flask of 1000ml, under the condition of abundant stirring, reflux condensation mode, reacted 5 hours, suction filtration is washed then, gets liquor C and pressed powder D.Powder D 100 ℃ of dryings 24 hours, is ground, obtain houghite.
In the 4th step, Mg, Al constituent content are respectively 0.49mol and 0.08mol, OH in the detection liquor C
-Concentration is 1.8mol/L.
In the 5th step, take by weighing 14.5g Al (OH)
3(0.18mol) add in the liquor C with 0.4g NaOH, replenish deionized water to 250ml, the pH value that records solution is 13, is heated to the solution boiling, with preparation aluminate solution A '.
The 6th step is to solution A ' in add the waste residue contain 0.65mol Mg, adding Na
2CO
3The pH value of regulating mixed solution is about 12, obtains solution B '.
The 7th step, under the condition of abundant stirring, reflux condensation mode, reacted 6 hours, suction filtration is washed then, gets liquor C ' and pressed powder D '.Powder D ' 80 ℃ of dryings 24 hours, is ground, obtain houghite.
Repeat～the seven step of the 4th step, the preparation houghite.
Embodiment four, and embodiment one gained houghite adsorbs Application humic in the former water: adopt the Static Adsorption method to handle humic acid in the water.
With humic acid (BR) and 0.1mol/L NaOH hot solution (about 60 ℃) preparation HA mother liquor.In washing, the dry 250mL conical flask of crossing, add certain amount of H A mother liquor and one-level ultra-pure water, mix, be mixed with 10mg/LHA solution.In fluid bed, houghite is suspended in the former water to adsorb the humic acid in the former water, saturated back of houghite absorption humic acid and former separated form water through stirring; With solution with 0.45 μ m membrane filtration after, measure HA concentration in the filtrating, do blank (not adding HTlc) experiment simultaneously, according to the change calculations adsorbance (qe) of HA concentration before and after the absorption.HA concentration adopts the UV254 method to measure.Instrument is the UV-7504 ultraviolet-visible spectrophotometer, and wavelength is 254nm, and the mensuration temperature is a room temperature.Wherein, the consumption of houghite is 1～10g/L, and in the adsorption process, temperature is 15～35 ℃, and the humic acid initial concentration is 5～150mg/L, pH value of solution=5～9, and adsorption time is 60～140min.Houghite can reach more than 87% the clearance of HA in the water.
Embodiment five, and embodiment one gained houghite is as the application of synergist fire retarding epoxide resin.
Houghite may further comprise the steps as the method for synergist fire retarding epoxide resin:
Houghite and melamine borate phosphate flame retardants 2.75g are joined in the 10g E-44 epoxy resin; Add the 1g curing agent ethylene diamine after stirring again and be prepared into 110mm * 6mm * 3.5mm standard size, carry out limited oxygen index (LOI) test according to GB/T2406-93 with HC900-2 type limiting oxygen index determination appearance (analysis Instrument equipment factory in the Jiangning District side, Nanjing).The result is as shown in table 1:
Table 1 houghite is to the flame retardant effect of epoxy resin
LOI represents " limit oxygen index value ", and it is to weigh polymer (or mixture) direct indicator of capacity for quenching voluntarily.This numerical value is big more, and then the anti-flammability of polymer is strong more.
Claims (2)
1. a method of utilizing flue gas desulfurization waste slag to prepare houghite is characterized in that, may further comprise the steps:
(1) in the whole process of preparation, be mete-wand with the amount of substance, with Na
2CO
3Amount of substance be 1 part; With NaOH and 2.1～3.3 parts of Al (OH)
3, be dissolved in 150～200 parts of water, through regulating the amount of NaOH, regulator solution pH value is 13～14, is heated to the solution boiling, prepares aluminate solution A;
(2) detect desuifurized in the content of each element, will contain in the desuifurized adding A solution of 5.8～9.3 parts of Mg elements, add 1 part of Na
2CO
3The pH value of regulator solution is 11～12, stirs, and obtains solution B;
(3) fully stirring, under the condition of reflux condensation mode, reacting 5～8 hours, then suction filtration, wash liquor C and pressed powder D; Powder D was descended dry 20～30 hours at 70～100 ℃, grind, obtain houghite;
Said flue gas desulfurization waste slag is the magnesia flue gas desulfurization waste slag.
2. a kind of method of utilizing flue gas desulfurization waste slag to prepare houghite according to claim 1 is characterized in that, the Mg in the recycle liquor C, Al element may further comprise the steps: detect Mg, Al constituent content in the liquor C, OH
-Concentration is replenished Mg, Al raw material, and the preparation houghite specifically may further comprise the steps:
Detect Mg, Al constituent content in the liquor C, OH
-Concentration is added Al (OH)
3Making the Al constituent content is 2.1～3.3 parts, and adding water, to make the total amount of water in the solution be 150～200 parts, and adding NaOH, to make pH value of solution be 13～14, is heated to the solution boiling, prepares aluminate solution; Add to the gained aluminate solution and to contain the desuifurized of Mg element, making the Mg constituent content contain is 5.8～9.3 parts, adds Na
2CO
3The pH value of regulator solution is 11～12, stirs; Fully stirring, under the condition of reflux condensation mode, reacting 5～8 hours, then suction filtration, wash filtrating and pressed powder; Pressed powder was descended dry 20～30 hours at 70～100 ℃, grind, obtain houghite.
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| CN102093525B (en) * | 2010-12-30 | 2013-07-31 | 苏州科技学院 | Method for preparing macromolecular flame retardant containing hydrotalcite-like compounds |
| CN102319714B (en) * | 2011-05-16 | 2013-06-12 | 中冶建筑研究总院有限公司 | Treatment process of dry method or semi-dry method smoke gas desulfurized slag |
| CN102391590B (en) * | 2011-07-11 | 2013-05-29 | 苏州科技学院 | Method for preparing flame-retardant plastic from magnesia mixture desulfurization waste residue |
| CN103553105B (en) * | 2013-10-02 | 2015-10-14 | 中国地质大学（武汉） | A kind of one-step synthesis method peels off the method for hydrotalcite/houghite |
| CN108751237B (en) * | 2018-07-18 | 2020-04-21 | 北京化工大学 | Clean preparation method of layered composite metal hydroxide |
| CN113716588B (en) * | 2021-08-17 | 2023-04-18 | 湖南恒光化工有限公司 | Low-cost preparation method of magnesium-aluminum hydrotalcite |
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