CN101475197A - Method for preparing ultra-fine high dispersing magnesium hydrate flame retardant from saline lake bittern or bischofite - Google Patents
Method for preparing ultra-fine high dispersing magnesium hydrate flame retardant from saline lake bittern or bischofite Download PDFInfo
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- CN101475197A CN101475197A CNA2009100016738A CN200910001673A CN101475197A CN 101475197 A CN101475197 A CN 101475197A CN A2009100016738 A CNA2009100016738 A CN A2009100016738A CN 200910001673 A CN200910001673 A CN 200910001673A CN 101475197 A CN101475197 A CN 101475197A
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Abstract
The invention provides a method for preparing an ultrafine high-dispersion magnesium hydroxide flame retardant by taking salt lake brine or bischofite as a raw material, which comprises the following steps that: the salt lake brine or the bischofite is prepared into a solution with 3 to 4mol/L magnesium chloride, 3 to 14mol/L ammonia water is quickly added into the solution at a temperature of between 25 and 95 DEG C to perform a precipitation reaction, and then an ultrafine high-dispersion magnesium hydroxide flame retardant product can be obtained through washing, filtration and drying. The method has simple process flow and low cost, and can produce the magnesium hydroxide flame retardant with good dispersivity, evenly distributed particle size, and average grain diameter of between 0.5 and 1mu m without adding a dispersing agent and a flocculating agent during the reaction.
Description
Technical field
The invention belongs to materials chemistry, chemical technology field, relate to a kind of preparation technology of magnesium hydroxide, particularly a kind of is the method for feedstock production ultra-fine high dispersing magnesium hydrate flame retardant with salt lake brine or bischofite.
Technical background
Flame retardant of magnesium hydroxide has obtained significant progress as novel interpolation inorganic combustion inhibitor efficient, superior, environmental protection in the inorganic combustion inhibitor field.This product is nontoxic, tasteless, non-corrosiveness.Magnesium hydroxide heat decomposition temperature height, heat decomposition temperature is between 340 ℃～490 ℃, during decomposes, discharge water outlet, absorb a large amount of latent heat simultaneously, this has just reduced resin actual temperature of bearing in flame, has to suppress the cooling effect that superpolymer decomposes and inflammable gas produces, the magnesium oxide that decomposes the back generation promptly is good refractory materials, also can help to improve the ability of resin opposing flame.
Magnesium hydroxide as fire retardant with its superior flame retardant properties, more and more be subjected at present people's favor, but because the consistency of itself and synthetic materials is relatively poor, addition is big, make the mechanical property and the resistance toheat of material all decrease, this also is the weak point of magnesium hydroxide as fire retardant.Therefore, produce the flame retardant of magnesium hydroxide of ultra-fine polymolecularity, the consistency that strengthens itself and synthetic materials becomes one of development trend of flame retardant of magnesium hydroxide.
Chinese patent CN1513761A provides a kind of nanometric magnesium hydroxide preparation method, and it is raw material that this method adopts magnesium salt solution, makes mixed precipitant with sodium hydroxide and ammoniacal liquor, prepares nanometric magnesium hydroxide by the reverse precipitator method.This invention is made mixed precipitant with sodium hydroxide and ammoniacal liquor, unreacted precipitation agent inconvenience completely recycle and reuse, if directly discharging also pollutes the environment, this patent also needs to add ethanol as dispersion agent in reaction process, increases production cost.Chinese patent CN101012382A discloses a kind of preparation method of high-purity high-dispersion magnesium hydroxide fire retardant, is that the salt lake bittern is soluble in water, adds H
2O
2Oxidation foreign ion wherein, and to adjust pH value be 6.5～7.5 leaves standstill to make after 3～10 hours and makes with extra care bittern and mix the mother liquor that is made into density of magnesium chloride 0.5mol/L～3.0mol/L with acetone, produces magnesium hydroxide after adding ammoniacal liquor then.This patent is removed impurity with chemical process, the pH value of solution is required also too harsh, and it is too of a specified duration to produce in the process of refining bittern time of repose, also needs to add acetone as dispersion agent in reaction process, and this patent complex process, production efficiency are lower.Chinese patent CN101066772A discloses the method that a kind of alcohol-water system single stage method prepares nano-magnesium hydrate fire retardant, is to mix by a certain percentage with inorganic magnesium salt, water and ethanol, 50～70 ℃ of water bath with thermostatic control heating; In addition surface treatment agent is added in the precipitation agent ammoniacal liquor, stir thorough mixing, be made into the ammonia soln of surface treatment agent; Then described surface treatment agent ammonia soln is joined in the alcohol solution of magnesium salts, be heated to 80～90 ℃, and isothermal reaction 1.5～2.0h, generate white precipitate, after filtration, oven dry, pulverize, finally make the nano-magnesium hydrate fire retardant of plate crystal.This method temperature in reaction process is higher, and the reaction times is longer, and also needs to add ethanol as dispersion agent, and production cost is higher.CN1718542A is precursor with the magnesium chloride hex-ammoniate, adopts liquid phase production high-purity nm magnesium hydroxide.This method also need add dispersion agent in reaction process just can prepare desired product, and this patent complex process, complex operation, production cost are higher.
China is magnesium resource big country, and the magnesium resource reserves are huge in the especially western salt lake.Because salt lake resources exploitation for a long time mainly concentrates on resources such as potassium, lithium, boron, the exploitation of magnesium resource is only rested on the primary stage.Wherein utilize salt lake resources to produce in the process of potash fertilizer 10 tons of magnesium chlorides of 1 ton of Repone K by-product of every production.Bittern behind the production potash fertilizer is all as waste liquid, be discharged in the salt lake with facilities such as pipeline, channel, pumping plants, cause the Local enrichment of magnesium salts, make balancing each other of salt lake destroyed, this not only causes the wasting of resources, and main is the severe contamination that causes environment and salt lake brine resource.Therefore, in salt lake resources development and use process, handle the relation of potassium, magnesium two large resources well, strengthen the salt lake magnesium resource and utilize technical study, drop into a certain amount of human and material resources, multipath exploitation China magnesium based compound is very important, and makes magnesium products seriation, high-valued, and allowing product take part in international competition as early as possible is problem demanding prompt solution.
Summary of the invention
The object of the invention provides a kind of method of utilizing salt lake brine or bischofite for the feedstock production ultra-fine magnesium hydroxide flame retardant.
The present invention prepares the method for ultra-fine high dispersing magnesium hydrate flame retardant, be that salt lake brine or bischofite are made into the solution that density of magnesium chloride is 3～4mol/L, remove by filter the ammoniacal liquor that quick adding concentration are 3～14mol/L under 25 ℃～95 ℃ behind the insoluble impurities and carry out precipitin reaction 5～20min, then through washing, filter, be drying to obtain the ultra-fine high dispersing magnesium hydrate flame retardant product that meso-position radius is 0.5～1 μ m; The add-on of ammoniacal liquor is controlled at ammoniacal liquor and adds back NH fully
4 +/ Mg
2+In the scope of 1:1～3:1; The adding speed of ammoniacal liquor is 60～100mL/min.
Its reaction equation is as follows:
MgCl
2+NH
4OH→Mg(OH)
2↓+NH
4Cl
The technology that salt lake brine or bischofite is made into magnesium chloride solution is: salt lake brine or bischofite are concentrated or after water dissolution, remove by filter insoluble impurities, promptly get magnesium chloride solution.In order to enhance productivity, reduce production costs, magnesium chloride solution is mixed with concentration in the scope of 3～4mol/L.
In order to make raw material reaction abundant, improve productive rate and make the flame retardant of magnesium hydroxide Granularity Distribution that obtains more even, after finishing, described precipitin reaction continues to stir 1～60min.
For foreign ion in the thorough washing product, obtain the higher flame retardant of magnesium hydroxide product of purity, described washing is adopted to wash and starch again and is washed.
The described dry vacuum-drying of adopting, drying temperature is 60 ℃～120 ℃.
The present invention compared to existing technology, technology is simple, and is easy to operate, flow process is short, production cost is low, the production efficiency height.Salt lake brine or magnesium chloride solution need not in the pre-treatment process through the chemical process removal of impurities, only need just can make the required bittern of reaction to stock liquid through the physics removal of impurities, density of magnesium chloride and ammonia concn are higher in the reaction process, and react in moment, the production efficiency height also need not to add the flame retardant of magnesium hydroxide product that dispersion agent, flocculation agent etc. just can be produced ultra-fine high dispersive in the reaction process.
Description of drawings
Fig. 1 is the embodiment of the invention 1 a product granularity test result distribution plan
Fig. 2 is the embodiment of the invention 2 product granularity test result distribution plans
Fig. 3 is the embodiment of the invention 3 product granularity test result distribution plans
Fig. 4 is the XRD figure of the embodiment of the invention 1,2,3 products
Fig. 5 is the magnesian XRD figure of standard hydrogen
It is narrower to test the magnesium hydroxide particle size distribution range that makes as can be seen from Fig. 1,2,3, and all less than 3 μ m, the homogeneity of product is better for the difference between D98 and the D3.
Fig. 4 is the XRD figure of magnesium hydroxide, and the magnesium hydroxide sample that illustrative experiment is worth belongs to hexagonal system, and characteristic diffraction peak intensity height, peak shape are sharp-pointed, illustrate that the product structure regularity is strong.The position of diffraction peak is consistent with standard magnesium hydroxide XRD figure among Fig. 5, except the characteristic peak of magnesium hydroxide, does not have the characteristic peak of other impurity in the diffracting spectrum, illustrates that magnesium hydroxide sample purity is higher.
Embodiment
Embodiment 1: get a certain amount of water and be placed in the beaker, constantly add the rich bischofite that produces in salt lake under stirring at low speed, till bischofite no longer dissolves, remove by filter insoluble impurities, be made into the magnesium chloride solution that concentration is 3.45mol/L.The magnesium chloride solution 500mL that gets 3.45mol/L joins in the isothermal reaction still, under the 2000rpm stir speed (S.S.), be warming up to 45 ℃, flow adding concentration with 70mL/min under 45 ℃ of constant temperatures is the ammoniacal liquor of 6.68mol/L, the feed time of ammoniacal liquor is 11min, ammoniacal liquor charging fully back continues to react 60min under 45 ℃ of constant temperature and 2000rpm stir speed (S.S.), and then washes and starches that to wash, filter, promptly get after 120 ℃ of vacuum-drying meso-position radius D50 be 0.70 μ m flame retardant of magnesium hydroxide product.The laser particle analyzer test result is as shown in table 1, and size-grade distribution as shown in Figure 1.
Table 1 testing graininess result
| D3:0.36μm | D6:0.41μm | D10:0.45μm | D16:0.49μm | D25:0.54μm | D50:0.70μm |
| D75:1.04μm | D80:1.18μm | D90:1.53μm | D97:1.95μm | D98:2.07μm |
D98 is 2.07 μ m as can be seen from Table 1, D3 be 0.36 μ m particle diameter distribution width less than 2 μ m, the product homogeneity of illustrative experiment gained is better.
Embodiment 2: get a certain amount of water and be placed in the beaker, constantly add the rich bischofite that produces in salt lake under stirring at low speed, till bischofite no longer dissolves, remove by filter insoluble impurities, be made into the magnesium chloride solution that concentration is 3.00mol/L.The magnesium chloride solution 500mL that gets 3.00mol/L joins in the isothermal reaction still, under the 2500rpm stir speed (S.S.), be warming up to 75 ℃, the ammoniacal liquor that under 75 ℃ of constant temperatures, adds 3mol/L with the flow of 80mL/min, the feed time of ammoniacal liquor is 7.37min, ammoniacal liquor charging fully back continues to react 20min under 75 ℃ of constant temperature and 2500rpm stir speed (S.S.), and then washes and starches that to wash, filter, promptly get after 120 ℃ of vacuum-drying meso-position radius be 0.69 μ m magnesium hydroxide products.The laser particle analyzer test result is as shown in table 2, and size-grade distribution as shown in Figure 2.
Table 2 testing graininess result
| D3:0.33μm | D6:0.37μm | D10:0.41μm | D16:0.46μm | D25:0.52μm | D50:0.69μm |
| D75:1.00μm | D80:1.21μm | D90:1.41μm | D97:1.83μm | D98:1.95μm |
D98 is 1.95 μ m as can be seen from Table 2, D3 be 0.33 μ m particle diameter distribution width less than 2 μ m, the product homogeneity of illustrative experiment gained is better.
Embodiment 3: get a certain amount of water and be placed in the beaker, constantly add the rich bischofite that produces in salt lake under stirring at low speed, till bischofite no longer dissolves, remove by filter insoluble impurities, be made into the magnesium chloride solution that concentration is 3.21mol/L.The magnesium chloride solution 500mL that gets 3.21mol/L joins in the isothermal reaction still, under the 2000rpm stir speed (S.S.), be warming up to 60 ℃, the ammoniacal liquor that under 60 ℃ of constant temperatures, adds 6.28mol/L with the flow of 70mL/min, the feed time of ammoniacal liquor is 11min, ammoniacal liquor charging fully back continues to react 60min under 60 ℃ of constant temperature and 2000rpm stir speed (S.S.), and then washes and starches that to wash, filter, promptly get after 120 ℃ of vacuum-drying meso-position radius be 0.87 μ m magnesium hydroxide products.The laser particle analyzer test result is as shown in table 3, and size-grade distribution as shown in Figure 3.
Table 3 testing graininess result
| D3:0.36μm | D6:0.42μm | D10:0.47μm | D16:0.53μm | D25:0.61μm | D50:0.87μm |
| D75:1.36μm | D80:1.50μm | D90:1.89μm | D97:2.55μm | D98:2.75μm |
D98 is 2.75 μ m as can be seen from Table 3, D3 be 0.36 μ m particle diameter distribution width less than 3 μ m, the product homogeneity of illustrative experiment gained is better.
Claims (5)
1, a kind of is the method for feedstock production ultra-fine high dispersing magnesium hydrate flame retardant with salt lake brine or bischofite, it is characterized in that: salt lake brine or bischofite are made into the solution that density of magnesium chloride is 3～4mol/L, remove by filter the ammoniacal liquor that quick adding concentration are 3～14mol/L under 25 ℃～95 ℃ behind the insoluble impurities and carry out precipitin reaction 5～20min, then through washing, filter, be drying to obtain the ultra-fine high dispersing magnesium hydrate flame retardant product that meso-position radius is 0.5～1 μ m; The add-on of ammoniacal liquor is controlled at ammoniacal liquor and adds back NH fully
4 +/ Mg
2+In the scope of 1:1～3:1; The adding speed of ammoniacal liquor is 60～100mL/min.
2, be the method for feedstock production ultra-fine high dispersing magnesium hydrate flame retardant with salt lake brine or bischofite according to claim 1, it is characterized in that: continue to stir 1～60min after described precipitin reaction is finished.
3, be the method for feedstock production ultra-fine high dispersing magnesium hydrate flame retardant with salt lake brine or bischofite according to claim 1, it is characterized in that: described washing is adopted to wash and starch again and is washed.
4, be the method for feedstock production ultra-fine high dispersing magnesium hydrate flame retardant with salt lake brine or bischofite according to claim 1, it is characterized in that: the described dry vacuum-drying of adopting, drying temperature is 60 ℃～120 ℃.
5, be the method for feedstock production ultra-fine high dispersing magnesium hydrate flame retardant with salt lake brine or bischofite according to claim 1, it is characterized in that: salt lake brine or bischofite are concentrated or after water dissolution, remove by filter insoluble impurities and promptly get the magnesium chloride solution that concentration is 3～4mol/L.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712491A (en) * | 2009-10-02 | 2012-10-03 | 达泰豪化学工业株式会社 | Magnesium oxide powder having excellent dispersion properties and method of manufacturing same |
| RU2469843C2 (en) * | 2011-01-13 | 2012-12-20 | Ахмед Ибрагим Шакер Салех | Flame retardant for wood processing |
| CN103011209A (en) * | 2011-09-23 | 2013-04-03 | 但建明 | Ammonium chloride circulation method for producing magnesium hydroxide and calcium chloride from carbide slag and salt lake magnesium chloride |
| CN103140446A (en) * | 2010-09-28 | 2013-06-05 | 达泰豪化学工业株式会社 | Magnesium hydroxide microparticles, magnexium oxide microparticles, and method for producing each |
| CN103130251A (en) * | 2011-11-22 | 2013-06-05 | 中国科学院青海盐湖研究所 | Preparation method of magnesium hydroxide fire retardant |
| CN104529376A (en) * | 2014-12-03 | 2015-04-22 | 中国科学院青海盐湖研究所 | Antifreezing magnesium oxychloride cement and preparation method and application thereof |
| WO2015089685A1 (en) * | 2013-12-16 | 2015-06-25 | 刘登富 | Method for preparation of a flame retardant |
| CN110240184A (en) * | 2019-05-25 | 2019-09-17 | 邢台镁熙环保材料有限公司 | A kind of production technology of high-purity Nano-class magnesia |
| CN113461036A (en) * | 2021-06-30 | 2021-10-01 | 西部矿业股份有限公司 | Method for compounding and rapidly refining high-concentration magnesium chloride solution by using salt lake difficult-to-filter-water chloromagnesite |
| CN115771908A (en) * | 2022-11-23 | 2023-03-10 | 北京化工大学 | Preparation method of low-chlorine magnesium hydroxide |
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2009
- 2009-01-09 CN CN2009100016738A patent/CN101475197B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712491A (en) * | 2009-10-02 | 2012-10-03 | 达泰豪化学工业株式会社 | Magnesium oxide powder having excellent dispersion properties and method of manufacturing same |
| US9061919B2 (en) | 2009-10-02 | 2015-06-23 | Tateho Chemical Industries Co., Ltd. | Magnesium oxide powder having excellent dispersibility and method for producing the same |
| CN103140446A (en) * | 2010-09-28 | 2013-06-05 | 达泰豪化学工业株式会社 | Magnesium hydroxide microparticles, magnexium oxide microparticles, and method for producing each |
| RU2469843C2 (en) * | 2011-01-13 | 2012-12-20 | Ахмед Ибрагим Шакер Салех | Flame retardant for wood processing |
| CN103011209A (en) * | 2011-09-23 | 2013-04-03 | 但建明 | Ammonium chloride circulation method for producing magnesium hydroxide and calcium chloride from carbide slag and salt lake magnesium chloride |
| CN103130251A (en) * | 2011-11-22 | 2013-06-05 | 中国科学院青海盐湖研究所 | Preparation method of magnesium hydroxide fire retardant |
| CN103130251B (en) * | 2011-11-22 | 2016-08-17 | 中国科学院青海盐湖研究所 | The preparation method of flame retardant of magnesium hydroxide |
| WO2015089685A1 (en) * | 2013-12-16 | 2015-06-25 | 刘登富 | Method for preparation of a flame retardant |
| CN104529376A (en) * | 2014-12-03 | 2015-04-22 | 中国科学院青海盐湖研究所 | Antifreezing magnesium oxychloride cement and preparation method and application thereof |
| CN110240184A (en) * | 2019-05-25 | 2019-09-17 | 邢台镁熙环保材料有限公司 | A kind of production technology of high-purity Nano-class magnesia |
| CN113461036A (en) * | 2021-06-30 | 2021-10-01 | 西部矿业股份有限公司 | Method for compounding and rapidly refining high-concentration magnesium chloride solution by using salt lake difficult-to-filter-water chloromagnesite |
| CN115771908A (en) * | 2022-11-23 | 2023-03-10 | 北京化工大学 | Preparation method of low-chlorine magnesium hydroxide |
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