CN100478418C - Preparing composite flame-retardant agent in Al-P-N series from ore tailings of treating bauxite - Google Patents
Preparing composite flame-retardant agent in Al-P-N series from ore tailings of treating bauxite Download PDFInfo
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- CN100478418C CN100478418C CNB2007100349440A CN200710034944A CN100478418C CN 100478418 C CN100478418 C CN 100478418C CN B2007100349440 A CNB2007100349440 A CN B2007100349440A CN 200710034944 A CN200710034944 A CN 200710034944A CN 100478418 C CN100478418 C CN 100478418C
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Abstract
This invention discloses a method for preparing Al-P-N series composite flame retardant from bauxite tailing. The method comprises: reacting phosphoric acid, pyrophosphoric acid, P2O5 and melamine to obtain melamine phosphate, adding ground bauxite tailing into melamine phosphate, stirring or grinding to mix uniformly, drying, and polymerizing in a reaction kettle or crucible at 267-310 deg.C for 4-6 h to obtain the composite flame retardant. The composite flame retardant has such advantages as good flame retardancy, high smoke-eliminating performance, simple process, and high thermal stability (greater than or equal to 260 deg.C), and is environmentally friendly.
Description
Technical field
The present invention relates to a kind of preparation technology and raw material of fire retardant, belong to phosphorus-nitrogen flame retardant technical field.
Background technology
It is big that mineral processing tailing of bauxite has quantum of output, and complex chemical composition such as is difficult to store up at characteristics.Main chemical compositions is aluminum oxide, silicon oxide, and the essential mineral composition is diaspore and clay mineral, and content is more than 80%.Dehydration temperaturre is in 400～600 ℃ scope, mine tailing main component after the dehydration is aluminum oxide and metakaolinite, they have features such as stronger adsorptivity and catalytic and surface properties be adjustable, and these features make mineral processing tailing of bauxite have flame retardant resistance and smoke-suppressing.Yet the heat that absorbs during the mine tailing dehydration is few, and fluid loss is about 15%, so a spot of addition is not enough to play fire retardation, when addition is big, the mechanical property of material is reduced greatly.
In order to improve flame retardant resistance, people usually utilize the synergistic effect between the different flame retardant, with several fire retardant and usefulness with different fire retardations, for example: the synergistic effect between the halogen system/antimony system; Synergistic effect between the phosphorus system/nitrogen system; Synergistic between phosphorus-nitrogen system/metal hydroxides, the metal oxide uses; As the clay class mineral of superpolymer additive also constantly as the synergist of other fire retardants and use.In these flame-retardant systems, halogen system, antimony system, halogen-Sb system fire retardant are because toxicity is big, and corrodibility is strong, and existing rules are forbidden their use.Phosphorus-nitrogen flame retardant and inorganic combustion inhibitor are with advantages such as its low cigarette, low toxicities and enjoy people's favor.Yet, up to the present, these industrialized flame-retardant systems all are to use with the form of mixture, the defective of this mixing flame-retardant system maximum is to distribute inequality between the fire retardant, can not bring into play fire-retardant synergistic to greatest extent, the particularly use that mixes of expanded polystyrene veneer (phosphorus-nitrogen system) fire retardant and metal hydroxides, metal oxide, formed expansion carbon-coating is inhomogeneous, and the degree of uniformity of carbon-coating has determined the height of flame retarding efficiency to a great extent.
Mix uneven problem in order to overcome flame-retardant system, people by physicochemical method with between the different flame retardant with chemical bonded refractory altogether, formation has the flame-retarding characteristic of each single fire retardant and the compound of fire-retardant synergistic characteristic concurrently, so not only overcome the skewness problem, can make fire-retardant synergistic effect perform to maximum again, but also can eliminate some defective of single fire retardant.That has reported at present has combining of metal hydroxides and ammonium polyphosphate or melamine phosphate.For example, Li Bin in its patent (200510010255.7), with metal hydroxides and phosphoric acid, trimeric cyanamide prepared in reaction cation-modified phosphoric melamine salt; Braterman has prepared the binding substances of double-metal hydroxide and polyphosphate in its patent (20060219991).This combination has overcome phosphorus-nitrogen flame retardant poor stability, acid higher in water, the problem that flame retardant properties is low.
Summary of the invention
In order to realize efficiently utilizing on a large scale the purpose of bauxite, realize that trade waste utilizes again, the present invention provides a kind of method that bauxite is prepared into the Al-P-N series composite flame retardant according to the bauxite mineralogy features.
The method of preparing composite flame-retardant agent in Al P-N series from ore tailings for the treatment of bauxite comprises:
(4) with phosphoric acid, tetra-sodium, Vanadium Pentoxide in FLAKES and trimeric cyanamide reaction, obtain phosphoric acid (tetra-sodium) melamine salt, the mole ratio of trimeric cyanamide and phosphorus atom is 0.29～0.68.
(5) mine tailing is put into ball grinder, adds water, with 200r/m wet ball grinding 6～8 hours, levigate mine tailing.
(6) the levigate mine tailing of mud shape is added in phosphoric acid (tetra-sodium) melamine salt, after stirring or grinding are mixed, put into the loft drier drying.The add-on of mine tailing is 30%～50% of a phosphoric melamine salt quality.
(7) desciccate in 267 ℃～310 ℃ polymerizations 4～6 hours, gets powder or block composite flame-retardant agent in reactor or crucible, and block composite flame-retardant agent is ground, and gets the composite flame-retardant agent powder.
The present invention is according to the bauxite mineralogy features, with bauxite and phosphorous, nitrogenous substance reaction, polymerization, prepares and has concurrently fire-retardant and the composite flame-retardant agent smoke elimination dual function.The present invention has realized the utilization of trade waste, and preparation technology is simple, and environmental friendliness is easy to realize industrialization.The composite flame-retardant agent constitutional features of preparation is for containing aluminium-phosphorus-nitrogen bond, the thermostability of composite flame-retardant agent 〉=260 ℃.
Description of drawings
Fig. 1: preparation technology's schema of composite flame-retardant agent.
Embodiment
Embodiment 1
(1) 50g is selected mine tailing put into the porcelain ball grinder, carry out ball milling, get the levigate mine tailing of mud shape with the processing parameter in the table 1;
(2) in the 500ml beaker, add 40g phosphoric acid solution (〉=85%) and 20g trimeric cyanamide, be diluted with water to scale after, heat while stirring, the emulsion in beaker becomes the solution a of transparent homogeneous;
(3) the levigate mine tailing of mud shape is added among the solution a, the heated and stirred evaporating solns is until becoming thick paste;
(4) the thick paste material after will evaporating is spread out on sheet glass, 110 ℃ of dry 5h, dry thing b;
(5) dry thing b is moved in the alumina crucible, compacting, the lid lid, 270 ℃ of polymerization 4h, naturally cooling grinds, and gets the composite flame-retardant agent powder.
Table 1 milling parameters
| The grinding media packing fraction | Grinding media conditions of mixture ratios (Φ 100mm: Φ 50mm) | Rotating speed | Ore milling concentration | The ore grinding time |
| 40％ | 8/2 | 200r/min | 70％ | 6h |
Embodiment 2
(1) mine tailing is put into the porcelain ball grinder, carried out ball milling, get the levigate mine tailing of mud shape with the processing parameter in the table 1;
(2) will add in the levigate mine tailing behind 30g Vanadium Pentoxide in FLAKES and the 20g trimeric cyanamide ball milling 1h, with the processing parameter ball milling 6h of table 1, the gunk that obtains is designated as a again;
(3) with gunk a at 110 ℃ of dry 5h, dry thing b;
(4) dry thing b is moved in the alumina crucible, compacting, the lid lid, 290 ℃ of polymerization 4h, naturally cooling gets the composite flame-retardant agent powder.
(I) adds respectively in polyethylene, the polypropylene system with composite flame-retardant agent that embodiment obtains, and compares with the melamine phosphate (II) that does not contain mine tailing.Adopt JF-3 type limiting oxygen index determination instrument and JCY-1 type smoke density determinator, as shown in table 2 according to the oxygen index and the smoke density of GB2406-80 standard and GB/T8627-1999 standard testing.
Table 2 composite flame-retardant agent (I) compares with fire retardant melamine phosphate (II) flame retardant properties
| Specimen | Oxygen index | Smoke density |
| The PE that does not add fire retardant | 17.2 | 96.3 |
| Add the PE of fire retardant I | 26.8 | 67.8 |
| Add the PE of fire retardant II | 27.1 | 101.2 |
| The PP that does not add fire retardant | 17.0 | 93.5 |
| Add the PP of fire retardant I | 27.2 | 73.1 |
| Add the PP of fire retardant II | 27.8 | 97.6 |
In the polymkeric substance add-on of fire retardant be in mass 26%.
Claims (2)
1. the method for preparing composite flame-retardant agent in Al P-N series from ore tailings for the treatment of bauxite is characterized in that: comprising:
(1) with phosphoric acid or Vanadium Pentoxide in FLAKES and trimeric cyanamide reaction, obtain phosphoric melamine salt, the mole ratio of trimeric cyanamide and phosphorus atom is 0.29～0.68;
(2) the levigate mine tailing of mud shape is added in the phosphoric melamine salt, after stirring or grinding are mixed, drying; The add-on of mine tailing is 30%～50% of a phosphoric melamine salt quality;
(3) desciccate in 267 ℃～310 ℃ polymerizations 4～6 hours, gets composite flame-retardant agent in reactor or crucible.
2. method according to claim 1 is characterized in that: the course of processing of the levigate mine tailing of described mud shape is: mine tailing is put into ball grinder, add water, with 200r/m wet ball grinding 6～8 hours.
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| CNB2007100349440A CN100478418C (en) | 2007-05-18 | 2007-05-18 | Preparing composite flame-retardant agent in Al-P-N series from ore tailings of treating bauxite |
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| CNB2007100349440A CN100478418C (en) | 2007-05-18 | 2007-05-18 | Preparing composite flame-retardant agent in Al-P-N series from ore tailings of treating bauxite |
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| CN100478418C true CN100478418C (en) | 2009-04-15 |
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| CN101884911B (en) * | 2009-12-31 | 2012-01-04 | 中南大学 | Simple adsorbent and preparation method thereof |
| CN110156058A (en) * | 2019-05-30 | 2019-08-23 | 南华大学 | A kind of method that bauxite gangue prepares water purification agent aluminium polychloride |
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Non-Patent Citations (4)
| Title |
|---|
| 一水硬铝石的机械化学处理. 杨华明，胡岳华，杨武国，杜春芳，邱冠周.硅酸盐学报，第33卷第6期. 2005 |
| 一水硬铝石的机械化学处理. 杨华明，胡岳华，杨武国，杜春芳，邱冠周.硅酸盐学报，第33卷第6期. 2005 * |
| 磷、氮体系类复合阻燃剂的研究. 覃文清，李风，戚天游.消防科学与技术，第25卷第1期. 2006 |
| 磷、氮体系类复合阻燃剂的研究. 覃文清，李风，戚天游.消防科学与技术，第25卷第1期. 2006 * |
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