CN1326972C - Prepn of fire retardant of hydrotalcite - Google Patents
Prepn of fire retardant of hydrotalcite Download PDFInfo
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- CN1326972C CN1326972C CNB2006100418840A CN200610041884A CN1326972C CN 1326972 C CN1326972 C CN 1326972C CN B2006100418840 A CNB2006100418840 A CN B2006100418840A CN 200610041884 A CN200610041884 A CN 200610041884A CN 1326972 C CN1326972 C CN 1326972C
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Abstract
The present invention relates to a process for preparing an inorganic fire retardant, and particularly to a process for preparing carbonate radical type hydrotalcite. The present invention comprises that aluminium reacts with a water solution of sodium hydroxide to obtain sodium metaaluminate; the sodium metaaluminate is added to a water solution of sodium carbonate for reaction, and after reaction, the mixture is added with a zinc sulphate solution for reaction; finally, crystallization is carried out after the reaction is finished.
Description
Technical field
The present invention relates to a kind of preparation method of inorganic combustion inhibitor, particularly the preparation method of carbonate type hydrotalcite.
Background technology
Fire retardant is a class additive that stops material to be ignited and suppress the further propagation of flame.In multiple material especially synthetic polymer materials, obtained using widely.The additive flame retardant that uses can be divided into organic type and inorganic type two big classes at present.Organic fire-retardant comprises phosphorus system, halogen-phosphorus system and phosphorus-phosphorus system etc.; Inorganic combustion inhibitor then can be divided into antimony system, phosphorus system and boron system etc.Though these fire retardants have excellent flame-retardant performance, but also there are many problems, not dispersed not good enough as in material, undesirable etc. with the intermiscibility of material, main is to contain elements such as halogen, phosphorus, antimony in the organic fire-retardant, in case material will be discharged by igniting and a large amount of poison gas be arranged and to human body and the deleterious residue of environment.Therefore, the U.S., 2002/95/EC number instruction of Japan and European Union forbid using some objectionable impurities (as lead, cadmium etc.) and organic fire-retardant (Poly Brominated Diphenyl Ethers etc.) in electronics.
Hydrotalcite (LDH) is the novel alternate inorganic combustion inhibitor of a class, this has been carried out comparatively detailed research both at home and abroad, and existing having developed has nontoxic, tasteless, nothing corrosion, has fire-retardant, as to press down cigarette, three kinds of functions of filler hydrotalcite fire retardant concurrently.Facts have proved, this BACN absorbs a large amount of heats and generates the temperature that a certain amount of water vapour has reduced material significantly when pyrolytic decomposition, thereby played flame retardant effect, the more important thing is that the solid product after flame retardant particle decomposes has very big specific surface and very strong alkalescence, in time the sour gas that discharges of absorbing material thermolysis and smog and play the effect that cigarette eliminates smoke that presses down.In preparation process, make the fire retardant super-refinement and make surface organic, strengthened the compatibility and the intermiscibility of fire retardant and body material, thereby improved the over-all properties of material.
But in the report of existing synthetic hydrotalcite, exist the problem of following several respects: (1) is generally avoided using vitriol as raw material in the synthetic field of carbonate type hydrotalcite.Reduce because sulfate radical participates in the product purity of intercalation formula, and the generation of sulfur-bearing poison gas, unfavorable its application are arranged when hindering cigarette and pressing down cigarette; (2) because of preceding problem causes in the prior art nitrate that adopt as reaction raw materials more, but because nitrate and when producing nitrate used nitric acid price higher, make production cost improve greatly, and be unfavorable for that big area promotes.(3) nearly all synthetic in, all adopt mixing salt and mixed base direct mixing method, must make that like this element aluminum need enter with the form of aluminium salt in the reaction raw materials, extensively to put forward the aluminium step too many for the acid system that adopts, and improved production cost.
Summary of the invention
The invention provides a kind of preparation method of new hydrotalcite fire retardant.Method of the present invention can be simplified hydrotalcite fire retardant production technique greatly, and significantly reduces production costs.
Method of the present invention is that aluminium and aqueous sodium hydroxide solution reaction are obtained sodium metaaluminate, adds aqueous sodium carbonate again and react in sodium metaaluminate, adds solution of zinc sulfate after reaction is finished again and react in system, carries out crystallization treatment behind the sufficient reacting.
Among the hydrotalcite preparation method of the present invention, the aluminium that reacts used can be the aluminium ash that bauxitic clay, aluminium slag or aluminium metallurgy produce, and for simplicity, below these aluminium sources is referred to as the aluminium ash.
Relevant test shows, when adopting the aluminium ash to be the aluminium source, the sodium hydroxide quality that adds in when reaction is 1.5～3 times of aluminium quality in the aluminium ash, the concentration of aqueous sodium hydroxide solution is 5%～15%, after finishing, reaction leaches the sodium metaaluminate aqueous solution, adding aqueous sodium carbonate more therein reacts, the yellow soda ash quality that is added is 10～20 times of aluminium ash quality, yellow soda ash is made into saturated or near saturated solution, reaction adds entry after finishing and is diluted to that aluminium content is 4～6g/L in the solution, in system, add equal-volume solution of zinc sulfate solution reaction again, carry out crystallization treatment behind the sufficient reacting.
For the product that uses method preparation of the present invention has higher purity, used aluminium ash should be removed the water solubles earlier before reaction.Its concrete way is the aluminium ash to be washed with water earlier to get final product before reaction.The used zinc sulfate solution of the present invention can make with utilising zinc containing waste residue and sulfuric acid reaction.
Among the preparation method of hydrotalcite fire retardant of the present invention, adopt: concentration is to be that the ratio of 42g/1L adds the aluminium ash in aluminium/alkali lye in 10% the aqueous sodium hydroxide solution, leach liquid Deng reaction after finishing, in the liquid that is leached, add the yellow soda ash saturated aqueous solution again, the yellow soda ash quality that adds is 15 times of aluminium quality, thin up aluminium content to the solution is 5g/L behind the stirring and evenly mixing, be that the solution of zinc sulfate of 37.5g/L reacts with equal-volume zinc content again, carry out crystallization treatment after waiting reaction to finish.Best effect can be arranged like this.
Method of the present invention can add concentration in system when crystallization be 1.0～2.0 times sodium stearate methanol solution of aluminium quality for the 150g/L quality.
Method of the present invention is owing to be that aluminium reaction earlier is sodium aluminate solution, overcome and to have made aluminium be converted into the deficiency that Tai-Ace S 150 further transforms again in the prior art earlier, simplified the preparation process of hydrotalcite greatly, shortened the production cycle, its speed of response is far longer than the speed of response that acid system in the prior art is carried aluminium.
The present invention adopts vitriol as main raw material, with respect to the nitrate of prior art, can obviously reduce production costs.Owing to adopt vitriol as main raw material, having broken domestic and international carbonate synthesis root type hydrotalcite, all to adopt nitrate be the tradition of raw material, solved sulfate radical and be easy to the difficult problem that intercalation influences product purity.
Because aluminium of the present invention source can be for using the aluminium ash, can utilize the locality to become the waste material in important solid pollution source as initial feed, and this method can avoid other foreign metal ion to sneak into, and employed in the present invention solution of zinc sulfate can make with utilising zinc containing waste residue and sulfuric acid reaction simultaneously.Therefore the present invention not only production cost can reduce greatly, can use aluminum and zinc to smelt the waste material that is produced simultaneously, turn waste into wealth, eliminate environmental pollution.
By product of the present invention is nontoxic Na
2SO
4, can say the discharging of the essentially no three wastes of the present invention, can not bring new pollution problem.
Description of drawings
Fig. 1 is that the structure of product is by X-ray powder diffraction (XRD) collection of illustrative plates.Fig. 2 is the infrared spectra of sample.Fig. 3 is the electromicroscopic photograph of the sample of product.
Embodiment
It below is a most preferred embodiment of the present invention.
Used aluminium ash is taken from the aluminum dross after the aluminium metallurgy of Baiyin City, Gansu Province Northwest Lead Zinc factory, and wherein average aluminum content is 28%.The analytical results of the concrete sample of a copy of it is:
Fe：0.14％
Mg：0.38％
SiO2：1.53％
Al：28.07％
Cu, Ca: trace).
Used aluminium ash is washed with water earlier, to remove soluble impurity wherein.In alkaline-resisting retort, drop into 0.8 ton of sodium hydroxide, add water 7.2m
3Dissolving fully, making it concentration is 10%, adds 2.0 tons of aluminium ashes through wash while hot, promptly produces very violently, need not heat and gets final product maintenance system and react.After reaction is finished liquid is promptly got the sodium metaaluminate aqueous solution, the extraction yield of this process can reach 60-70%.
The contriver has adopted the aluminium ash of different grades in experiment, and its aluminium content adopts this method all can obtain being fit to the sodium aluminate solution of production at 10%-33%.
In the sodium metaaluminate aqueous solution, add 2.4 tons of NaOH, 5.0 tons of Na again
2CO
3And 42 tons of mixing solutionss that water forms, behind the stirring and evenly mixing, (get the zinc sulfate stoste 18cm of 118g/L with zinc sulfate solution
3Adding 30 tons of water dilutes) feed main reactor together, in main reactor, after stopping several minutes behind the high-speed stirring apparatus stirring and evenly mixing, promptly flow into the crystallization groove, the methanol solution that adds sodium stearate in the crystallization groove, crystallization 10-12 hour at normal temperatures, product washs through three press filtrations, changes the flash distillation plant drying again over to, gets product.
Zinc sulfate solution is that utilising zinc containing waste residue and the sulfuric acid reaction that produces after the zinc metallurgy of Northwest Lead Zinc factory makes in this embodiment.
The sign of products obtained therefrom and dependence test result are as follows:
Basic chemical constitution: Zn
6Al
2(OH)
16CO
34H
2O
Layer pole structure crystalline phase: more than 98%
Laminate spacing: 0.76nm
Unit cell parameters: a=0.35nm
Laminate thickness: 0.65nm slenderness ratio:
Offspring size: 1-5 μ m (usual way oven dry)
PH value: 7～9
Water ratio: 0.3%
SO
4 2-： ＜0.5％
The structure of product is seen accompanying drawing 1 by X-ray powder diffraction (XRD) collection of illustrative plates.XRD diffraction data table sees Table 1.
| Table 1 | ||
| 2θ(°) | d() | I/I 0 |
| 11.660 | 7.5832 | 100 |
| 18.100 | 4.8970 | 3 |
| 23.400 | 3.7985 | 34 |
| 33.900 | 2.6421 | 7 |
| 34.600 | 2.5903 | 47 |
| 37.280 | 2.4100 | 7 |
| 39.160 | 2.2985 | 28 |
| 43.940 | 2.0589 | 4 |
| 46.660 | 1.9450 | 19 |
| 52.820 | 1.7318 | 6 |
| 56.180 | 1.6359 | 5 |
| 60.200 | 1.5359 | 10 |
| 61.540 | 1.5057 | 12 |
| 63.440 | 1.4651 | 3 |
| 65.520 | 1.4235 | 5 |
See the bigger diffraction peak of three diffracted intensities being arranged from XRD spectra corresponding to (d
003) 0.758 and two senior reflection 0.380nm (d
006), 0.259nm (d
009), the diffraction peak shape is narrow and sharp, and degree of crystallinity is fine, and crystalline phase is single.Interlamellar spacing is 0.758nm, d
110=0.1536nm is to be unit cell parameters a.
The infrared spectra of product sample is seen Fig. 2, and parameter is:
3462cm
-1OH (laminate) absorption of vibrations
1494cm
-1CO
3 2-(interlayer) absorption of vibrations
430cm
-1The skeletal vibration charateristic avsorption band of hydrotalcite-based compound.
The pattern of product is seen accompanying drawing 3.
The present invention adopts low price raw material and new processing method successfully to prepare BACN (carbonate intercal type zinc-aluminium hydrotalcite).Above chemistry and instrumental analysis result show that the product purity under the new process conditions is very high, have identical technical parameter with the product that document has been reported.
Claims (6)
1, a kind of preparation method of carbonate intercal type zinc-aluminium hydrotalcite fire retardant, it is characterized in that aluminium and aqueous sodium hydroxide solution reaction are obtained sodium metaaluminate, the sodium hydroxide quality that adds during reaction is 1.5～3 times of aluminium quality in the aluminium ash, the concentration of aqueous sodium hydroxide solution is 5%～15%, adding aqueous sodium carbonate again in sodium metaaluminate reacts, the yellow soda ash quality that is added is 10～20 times of aluminium ash quality, yellow soda ash is made into saturated or near saturated solution, adding the equal-volume solution of zinc sulfate after reaction is finished again in system reacts, the zinc sulfate content that is added is 30～45g/L, carries out crystallization treatment behind the sufficient reacting.
2, the preparation method of carbonate intercal type zinc-aluminium hydrotalcite fire retardant according to claim 1 is characterized in that the aluminium that reacts used can be the aluminium ash that bauxitic clay, aluminium slag or aluminium metallurgy produce.
3, the preparation method of carbonate intercal type zinc-aluminium hydrotalcite fire retardant according to claim 2, it is characterized in that the reaction of sodium metaaluminate and aqueous sodium carbonate adds entry after finishing and is diluted to that aluminium content is 4～6g/L in the solution, in system, add equal-volume solution of zinc sulfate solution reaction again, carry out crystallization treatment behind the sufficient reacting.
4, according to the preparation method of claim 2 or 3 described carbonate intercal type zinc-aluminium hydrotalcite fire retardants, it is characterized in that used aluminium ash removes the water solubles earlier before reaction, used zinc sulfate solution system makes with utilising zinc containing waste residue and sulfuric acid reaction.
5, the preparation method of a kind of carbonate intercal type zinc-aluminium hydrotalcite fire retardant according to claim 4, it is characterized in that in concentration being to be that the ratio of 42g/1L adds the aluminium ash in aluminium/alkali lye in 10% the aqueous sodium hydroxide solution, leach liquid Deng reaction after finishing, in the liquid that is leached, add the yellow soda ash saturated aqueous solution again, the yellow soda ash quality that adds is 15 times of aluminium quality, thin up aluminium content to the solution is 5g/L behind the stirring and evenly mixing, be that the solution of zinc sulfate of 37.5g/L reacts with equal-volume zinc content again, carry out crystallization treatment after waiting reaction to finish.
6, the preparation method of a kind of carbonate intercal type zinc-aluminium hydrotalcite fire retardant according to claim 5, adding concentration when it is characterized in that crystallization in system is 1.0～2.0 times sodium stearate methanol solution of aluminium quality for the 150g/L quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100418840A CN1326972C (en) | 2006-02-28 | 2006-02-28 | Prepn of fire retardant of hydrotalcite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100418840A CN1326972C (en) | 2006-02-28 | 2006-02-28 | Prepn of fire retardant of hydrotalcite |
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|---|---|
| CN1810926A CN1810926A (en) | 2006-08-02 |
| CN1326972C true CN1326972C (en) | 2007-07-18 |
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| CNB2006100418840A Expired - Fee Related CN1326972C (en) | 2006-02-28 | 2006-02-28 | Prepn of fire retardant of hydrotalcite |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280072B (en) * | 2008-04-25 | 2010-06-09 | 北京化工大学 | Hydrotalcite-like compound as flame-retardant smoke-suppressant agent for engineering plastics and preparation thereof |
| CN104744882B (en) * | 2015-04-08 | 2017-09-26 | 浙江大学 | Nano modification flame-proof phenolic injection molding material and preparation method thereof |
| CN104744883B (en) * | 2015-04-08 | 2017-07-21 | 浙江嘉民塑胶有限公司 | Nano modification flame-proof phenolic plastic and preparation method thereof |
| CN109467109B (en) * | 2018-07-17 | 2021-12-10 | 兰州大学 | Morphology-controllable magnesium-aluminum nano hydrotalcite and preparation method thereof |
| CN112250094B (en) * | 2020-10-13 | 2021-12-24 | 北京化工大学 | High-purity hydrotalcite and preparation method thereof |
| CN115160642A (en) * | 2022-07-07 | 2022-10-11 | 邵阳市富森阻燃材料有限公司 | Method for preparing hydrotalcite flame retardant by taking bean dregs as template |
| CN116178788B (en) * | 2022-12-02 | 2024-08-20 | 中国消防救援学院 | Method for preparing hydrotalcite-containing nano flame retardant by using blast furnace dust and chromium-containing aluminum mud |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5730951A (en) * | 1994-04-29 | 1998-03-24 | Aluminum Company Of America | Two powder synthesis of hydrotalcite and hydrotalcite-like compounds with polyvalent inorganic anions |
| CN1475535A (en) * | 2003-03-25 | 2004-02-18 | 北京化工大学 | Phosphate intercalation water talc and its preparation method and use as fire retardant |
| CN1537807A (en) * | 2003-10-23 | 2004-10-20 | 浙江大学 | Method of preparing bimetal oxide and hydrotalcite |
-
2006
- 2006-02-28 CN CNB2006100418840A patent/CN1326972C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5730951A (en) * | 1994-04-29 | 1998-03-24 | Aluminum Company Of America | Two powder synthesis of hydrotalcite and hydrotalcite-like compounds with polyvalent inorganic anions |
| CN1475535A (en) * | 2003-03-25 | 2004-02-18 | 北京化工大学 | Phosphate intercalation water talc and its preparation method and use as fire retardant |
| CN1537807A (en) * | 2003-10-23 | 2004-10-20 | 浙江大学 | Method of preparing bimetal oxide and hydrotalcite |
Non-Patent Citations (3)
| Title |
|---|
| 水滑石的制备、表征及其在酯交换反应中的作用 吕亮 等，精细石油化工，第2001.1期 2001 * |
| 水滑石的表面改性研究 杨文虎 等，化学工业与工程，第21卷第5期 2004 * |
| 水滑石的表面改性研究 杨文虎 等，化学工业与工程，第21卷第5期 2004;水滑石的制备、表征及其在酯交换反应中的作用 吕亮 等，精细石油化工，第2001.1期 2001 * |
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|---|---|
| CN1810926A (en) | 2006-08-02 |
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