CN1230494C - Inorganic combustion inhibitor and its preparation method - Google Patents
Inorganic combustion inhibitor and its preparation method Download PDFInfo
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- CN1230494C CN1230494C CN 200410017994 CN200410017994A CN1230494C CN 1230494 C CN1230494 C CN 1230494C CN 200410017994 CN200410017994 CN 200410017994 CN 200410017994 A CN200410017994 A CN 200410017994A CN 1230494 C CN1230494 C CN 1230494C
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Abstract
The present invention discloses a fire retardant and a preparation process thereof. The fire retardant is antimony-contained hydrotalcite. Like other hydrotalcite, crystallized water and volatile negative ions are filled among the structural layers of the antimony-contained hydrotalcite, and a large amount of volatilized water is released out through two thermal decomposition reactions when heated, wherein the two thermal decomposition reactions respectively covers a low temperature range and a high temperature range so that the temperature range of fire retardance is widened; at high temperatures, the antimony contained in the structural layers reacts with the halogen contained in an organic synthesized substance or the halogen contained among the layers of the hydrotalcite to form volatile antimony halide serving the assistant function of fire retardance, so that the antimony-contained hydrotalcite has the dual effect of fire retardance. Using a large amount of natural raw mineral materials which have extensive source and low price, the technological process for preparing the antimony-contained hydrotalcite disclosed by the present invention has the advantages of simple technological process and less investment for equipment, so that the antimony-contained hydrotalcite prepared by the present invention has the performance-price ratio obviously superior than that of the existing commercial fire retardant of hydrotalcite and antimonic oxide when used as a fire retardant.
Description
Technical Field
The invention relates to an inorganic flame retardant and a preparation method thereof.
Background
The fire retardant is one of main components of fire-proof paint constructed by steel, fire-proof filler of plastic material and fire-proof filler of cable insulating layer, and its consumption is rapidly increased with the improvement of national industrialization degree and people's living standard. In recent years, due to the wide application of interior decoration materials, the importance of the fire-retardant property of the synthetic material itself to the safety of buildings is increasing. Among various inorganicflame retardants, the magnesium-aluminum hydrotalcite has good thermal stability, has three functions of flame retardance, smoke abatement and filling enhancement, is a high-efficiency, nontoxic and low-smoke high-quality flame retardant, and has higher preparation cost; the antimony oxide flame retardant can generate a great synergistic flame-retardant effect with halogen contained in a synthetic material or a halogen-containing compound used in combination, is a high-efficiency flame-retardant synergist, and can generate a great amount of black smoke during combustion. The invention adopts a new preparation process, integrates the two inorganic flame retardants into a whole, gives full play to the respective advantages of the two inorganic flame retardants, is a brand new synergistic high-efficiency inorganic flame retardant, and has the effects of smoke abatement and filling enhancement.
Disclosure of Invention
The invention aims to provide an inorganic flame retardant and a preparation method thereof.
The inorganic flame retardant is antimony-containing hydrotalcite, wherein the content of antimony in the hydrotalcite is 2-15% by weight, and the chemical structural general formula of the inorganic flame retardant is as follows: [ Mg1-x(Al，Sb)x(OH)2]x+·Ry- x/y·nH2O, wherein x is 0.5-0.17; r is an anion and is CO3 2-、HCO3 -Or Cl-(ii) a y is the valence of the anion; n is 2 to 8.
The preparation method of the inorganic flame retardant comprises the following steps:
1) mixing crushed magnesium hydroxide or magnesium oxide and aluminum hydroxide according to the molar ratio of 1: 1-5: 1, adding the mixture into a ball mill or a rod mill, adding 2-8 times of water, and grinding for 6-24 hours;
2) dehydrating the ground mixture, airing or drying at a temperature lower than 90 ℃, calcining for 2-5 hours at a temperature of 500-750 ℃, and grinding to less than 200 meshes for later use to obtain a product which is a bimetallic oxide and has a chemical structural general formula of Mgm. Aln. Ox, wherein x is m +3 n/2;
3) crushing stibnite ore to be less than 100 meshes, pouring the crushed stibnite ore into a slurry pool, adding soluble sulfide with the weight being 0.8-2.0 times of the amount of antimony metal in the ore, adding water with the weight being 2-8 times of the amount of the antimony metal in the ore, uniformly stirring, and continuously stirring for 0.5-3 hours to dissolve the stibnite therein to form a thioantimonite radical;
4) separating the solution from the residual solid phase by adopting a precipitation, centrifugation or filtration method, adding the bimetallic oxide obtained in the step 2) into the solution, wherein the weight of the bimetallic oxide is 10-20 times of the amount of antimony metal in stibnite, uniformly stirring, and continuously stirring for 4-12 hours;
5) separating the reactant from the solution by precipitation, centrifugation or filtration, air-drying or drying at a temperature lower than 90 ℃, allowing the solid phase to enter the next procedure, and allowing the liquid phase to return to the step 3) for reuse;
6) the solid phase obtained in the step 5) is stripped at the temperature of 500-750 DEG CCalcining for 2-5 hours under the condition to decompose the thioantimonite radical adsorbed by the bimetallic oxide, and fusing the thioantimonite radical into the bimetallic oxide molecules in the form of antimony oxide, SO in the flue gas3Recovering by a water washing mode to obtain sulfuric acid, wherein the calcined residueis still a bimetallic oxide and can enter the next procedure or return to the step 4) for reuse so as to improve the content of antimony in the product;
7) preparing soluble carbonate or hydrochloride into a solution with the concentration of 0.5-2 mole/L, adding the product obtained in the step 6) into the solution according to the proportion of adding 100-300 g of bimetallic oxide into each gram of molecular salt, uniformly mixing, continuously stirring for 3-8 hours, filtering or centrifugally dewatering, washing for 2-3 times with clean water, dewatering, airing or drying at the temperature lower than 90 ℃, and grinding to be less than 200 meshes.
The magnesium hydroxide is a commercial product or natural mineral brucite with the chemical composition of Mg (OH)2(ii) a The magnesium oxide is a commercial product or a calcined product of natural mineral magnesite at 400-600 ℃. The aluminum hydroxide is a commercial product or a natural mineral gibbsite with a chemical composition of Al (OH)3. The soluble sulfide is Na2S、K2S and (NH)4)2One or more of S. The soluble carbonate is one or more of sodium carbonate, sodium bicarbonate or hydrate thereof. The soluble hydrochloride is one or more of sodium chloride, potassium chloride, ammonium chloride, or their hydrates.
The technological process for preparing the antimony-containing hydrotalcite provided by the invention uses a large amount of natural mineral raw materials, and has the advantages of wide source of main raw materials, low price, simple technological process and less equipment investment. Compared with the existing method for preparing the hydrotalcite, the method simplifies the production process, adopts natural mineral raw materials, greatly reduces the cost and consumption, can realize zero emission in the production process, and is beneficial to environmental protection. The antimony-containing hydrotalcite prepared by the method is adopted as a flame retardant, and the cost performance is obviously superior to that of hydrotalcite and antimony oxide flame retardants in the current market.
Detailed Description
Hydrotalcite, also known as Layered Double Hydroxides (LDH), has a Layered structure with a basic structure layer consisting of M2+-OH、M3+-OH octahedra, forming a positively charged layer, filled with anionic layers and water molecules between the structural layers, hence the name anionic clay, whose lamellar crystal structure has good filling reinforcement effect on plastic materials. The most common hydrotalcite is a magnesium aluminum composite hydroxide, which has a representative chemical formula: [ Mg3Al(OH)8]2CO3·nH2And O. When the hydrotalcite is heated to 190-250 ℃, the hydrotalcite is subjected to primary thermal decomposition, crystal water is released in a water vapor form and takes away a large amount of heat, the peak temperature of the reaction is about 210 ℃, the weight loss rate is 12-15%, and the highest endothermic value can be achievedUp to 410J/g or more; when the material is heated to 380-450 ℃, secondary thermal decomposition occurs, hydroxyl and carbonate are released in the form of carbon dioxide and water vapor, the weight loss rate is 29-30%, and the heat absorption value is above 550J/g. Large amount of CO released from hydrotalcite when it is heated to decompose2And water vapor has good foaming flame-retardant effect. The decomposed hydrotalcite is called bimetallic oxide, which keeps the layered structure of hydrotalcite and has smoke eliminating effect during combustion.
The inorganic flame retardant provided by the invention is antimony-containing hydrotalcite. Sb3+The crystal lattice octahedron exists, and Sb-OH octahedrons, Mg-OH octahedrons and Al-OH octahedrons form a basic structure layer of the hydrotalcite crystal. The anions filled between the structural layers can be carbonate, bicarbonate or chloride. The former is suitable for use with plastics, rubbers and paints which contain halogen, and the latter is suitable for use with halogen-free synthetic materials.
During combustion, crystal water existing between the antimony-containing hydrotalcite layers is released at about 200 ℃, a large amount of heat is taken away, and the material is foamed to reduce the thermal conductivity of the material; when the temperature rises to more than 350 ℃, the antimony-containing hydrotalcite is decomposed for the second time, and a large amount of flame-retardant gas is released again and heat is absorbed; at the same time, antimony is organically synthesizedHalogen contained in the matter or halogen at interlayer positions of hydrotalcite reacts to form volatile antimony halide which plays a role in synergistic flame retardance. Therefore, the stibium-containing hydrotalcite has double flame-retardant effects and combines hydrotalcite and Sb2O3Two flame retardants have the advantages.
The antimony-containing hydrotalcite is a double-effect flame retardant. It is like hydrotalcite, and has crystal water and volatile anions filled between the basic structure layers, and when heated, it releases great amount of water vapor and CO via two thermal decomposition reactions2. The two thermal decomposition reactions respectively cover the low-temperature section and the high-temperature section, the flame-retardant temperature range is widened, the lamellar crystal structure can absorb volatile substances generated by the decomposition of the coating at high temperature, and the flame-retardant, smoke-eliminating and filling enhancement functions are realized. Antimony contained in the structural layer reacts with halogen contained in the organic compound or halogen at interlayer positions of hydrotalcite at high temperature to form volatile antimony halide, so that the synergistic flame retardant effect is achieved. Therefore, the stibium-containing hydrotalcite has double flame-retardant effects and combines hydrotalcite and Sb2O3Two flame retardants have the advantages.
The precursors of antimony-containing hydrotalcites are bimetallic oxides. The basis for preparing the bimetallic oxide and the hydrotalcite by taking magnesium hydroxide or magnesium oxide and aluminum hydroxide as raw materials is that the magnesium hydroxide and the oxide have slight solubility, can form a uniform mixture on a molecular scale with the aluminum hydroxide during wet ball milling, form a solid solution during high-temperature calcination, and hydrolyze the solid solution in a salt solution to obtain the magnesium-aluminum type hydrotalcite.
The ratio of magnesium aluminum hydroxide in the raw materials has certain influence on the performance of the final product. Generally, when the former is used in a higher amount, the crystal structure of the product is more stable; when the latter is used in high amount, the product has better adsorption performance. The molar ratio of magnesium hydroxide to aluminum hydroxide is preferably controlled within the range of 2: 1 to 5: 1.
The magnesium hydroxide may be commercially available or may be a natural mineral brucite, the latter component also being Mg (OH)2. Natural brucite deposits are produced in Liaoning places in China. MgO may be used instead of magnesium hydroxideBecause it is easily hydrolyzed, it is ball-milled in a wet processConversion to Mg (OH) in the process2. MgO can be a commercial product, and can also be obtained by calcining natural magnesite at the temperatureof 400-600 ℃. Magnesite is a widely distributed non-metallic mineral and is mainly distributed in Liaoning places in China. The aluminum hydroxide in the raw material can be a commercial product, and is usually an intermediate product of an electrolytic aluminum plant; or gibbsite which is a natural mineral and has a chemical composition of Al (OH)3. Gibbsite is the main component of weathered residual bauxite and is distributed in south China and southwest provinces. The use of natural mineral raw materials is beneficial to reducing the cost, but effective measures are required to ensure the quality of the raw materials.
The water adding amount can be adjusted according to different properties of raw materials, so that the grinding product is preferably viscous and flowable ore pulp. The water consumption is too low, the raw materials are easy to agglomerate during grinding, and the grinding effect is influenced; the water consumption is too high, which greatly increases the energy consumption of the subsequent process and the equipment abrasion. The recommended water consumption is 3-5 times of the feeding amount.
Because magnesium hydroxide and magnesium oxide have slight solubility, wet grinding can ensure that the magnesium hydroxide and the aluminum hydroxide are uniformly mixed on a molecular scale. The optimum milling time depends on the nature of the starting materials. When the raw materials are natural minerals, the grinding time is not less than 12 hours; when a commercially available compound is used as a raw material, the grinding time can be shortened to less than 10 hours, so that the energy consumption can be reduced.
The ground mixture can be dehydrated by filtration, filter pressing or centrifugation, and dried naturally or at a temperature not higher than 90 deg.C to further age the mixture during drying. The mixture is calcined at a temperature not exceeding 750 ℃ for 2 to 5 hours, preferably at a temperature of 550 to 650 ℃. The purpose of calcination is to convert the raw mixture into a solid solution. The calcined product is a bimetallic oxide.
The use of stibnite as a source of antimony is intended to reduce costs and simplify the manufacturing process. The stibnite dissolution is carried out in a cylindrical slurry tank, the depth of the tank is 1-2 times of the diameter of the tank, and a mechanical stirring device is arranged in the middle of the tank so as to keep the ore or ore slurry powder and the sulfide solution to be uniformly mixed. The sulfide used may beIs Na2S、K2S and (NH)4)2One or more of S, but from the comprehensive consideration of cost, benefit and environmental factors, Na is recommended to be used2And S. Stibnite and S in solution2-Ion reaction to form a thioantimonite:
when the reaction is complete, the dissolved stibnite is equal to the number of moles of sulfide in the solution, but the solubility of stibnite in sulfide solution is only about 60% of theoretical value. Therefore, the sulfide is used in excess in practical operation. If Na is used2S, the dosage of the antimony is about equal to the amount of antimony metal in the antimony ore, the antimony ore is incompletely dissolved when the dosage is too low, and the cost is increased when the dosage is too high.
The invention adopts bimetallic oxide to adsorb antimony in solution, and the representative reaction is as follows:
the adsorption of the bimetallic oxide to the antimonous sulfate radical in the solution belongs to chemical adsorption, and the adsorption capacity is controlled by the reaction progress degree. Taking into account residual S in the solution2-、OH-And CO2The amount of the bimetallic oxide is required to be excessive, and the amount of the bimetallic oxide is 10-20 times of the amount of antimony metal in the antimony ore to be treated. After the adsorption reaction, a small amount of SbS still remains in the liquid phase3 3-And S2-And (4) leading the solution back to the slurry pond for recycling.
The bimetallic oxide adsorbed with the thioantimonite radical is grey, and is dried or baked and then sent into a furnace for calcination. The calcination temperature should not exceed 750 ℃, and is preferably controlled between 550 ℃ and 650 ℃. The hearth is relatively closed and is provided with a longer flue so as to cool and recover volatile matters. Representative reactions that occur upon calcination are:
the calcined residue is antimony-containing bimetallic oxide. In order to increase the Sb content in the molecular formula, the calcined product can be adsorbed with the thioantimonite radical again and calcined again.
Hydrolyzing the antimony-containing bimetallic oxide in a carbonate or hydrochloride solution to obtain the antimony-containing hydrotalcite. Representative chemical reactions in solution are:
The carbonate antimony-containing hydrotalcite is suitable for being used with plastics, rubber and paint which contain halogen, and the chloride ion antimony-containing hydrotalcite is suitable for being used with synthetic materials which do not contain halogen.
The present invention is further illustrated by the following examples.
Example 1: bimetallic oxides are prepared from brucite and gibbsite.
1) Weighing 174 kg of brucite and 78 kg of gibbsite, crushing until the lumpiness is less than 2 cm, adding into a ball mill, adding 750 kg of water, and grinding for 18 hours;
2) and (3) putting the ground mixture on a filter cloth, filtering and dehydrating, calcining for 3 hours at 600 ℃ after air drying, cooling and grinding to less than 200 meshes for later use.
Example 2: bimetallic oxides are prepared from magnesite and gibbsite.
1) Weighing 168 kilograms of magnesite, heating to 400 ℃, and keeping the temperature for 3 hours to decompose the magnesite into MgO;
2) weighing 78 kg of gibbsite, crushing the gibbsite until the lumpiness is less than 2 cm, adding the gibbsite and MgO obtained in the previous step into a ball mill, adding 500 kg of water, and grinding for 14 hours;
3) and (3) putting the ground mixture on a filter cloth, filtering and dehydrating, calcining for 3 hours at 650 ℃ after air drying, cooling and grinding to less than 200 meshes for later use.
Example 3: from magnesite and commercial Al (OH)3Preparing the bimetal oxide.
1) Weighing 252 kg of magnesite, heating to 450 ℃, and keeping the temperature for 2 hours to decompose the magnesite into MgO;
2) 78 kg of commercial Al (OH) were weighed3Adding the MgO obtained in the previous step and the MgO into a ball mill, adding 600kg of water, and grinding for 8 hours;
3) and (3) putting the ground mixture on a filter cloth, filtering and dehydrating, calcining for 4 hours at 550 ℃ after air drying, cooling and grinding to less than 200 meshes for later use.
Example 4: from commercial MgO and commercial Al (OH)3Preparing the bimetal oxide.
1) 84 kg of MgO, a commercial product, 78 kg of Al (OH)3Adding the mixture into a ball mill, adding 600kg of water, and grinding for 6 hours;
2) and (3) putting the ground mixture on a filter cloth, filtering and dehydrating, calcining for 2 hours at 700 ℃ after air drying, cooling and grinding to less than 200 meshes for later use.
Example 5: preparation of antimony-containing bimetallic oxide from stibnite lean ore
1) Taking stibnite lean ore from a place, containing 5 percent of stibnite, crushing and grinding the lean ore to be less than 100 meshes, weighing 100Kg of ore powder, pouring the ore powder into an ore pulp pool, adding 5Kg of Na2S, adding 300Kg of water, uniformly stirring, and continuously stirring for 1 hour to dissolve stibnite therein;
2) filtering to separate the solution from the residual solid phase, spraying the solid phase for 2 times, and allowing the leacheate and the solution to enter the next working procedure;
3) adding 80Kg of bimetal oxide into the solution, stirring uniformly, and continuously stirring for 10 hours;
4) filtering the solid phase to separate from the solution, drying at the temperature lower than 80 ℃, enabling the solid phase to enter the next procedure, and returning the liquid phase to the step 1 for reuse;
5) calcining the solid phase obtained in the step 4 at the temperature of 600 ℃ for 3 hours to oxidize the thioantimonite radical adsorbed by the bimetallic oxide and fuse the thioantimonite radical into an adsorbent to obtain the antimony-containing bimetallic oxide; SO in flue gas3Recovering in a water washing mode to obtain sulfuric acid;
6) and (3) returning the antimony-containing bimetallic oxide to the step 3, adsorbing the thioantimonite radical again, and repeating the steps 4-5 to improve the antimony content in the antimony-containing bimetallic oxide.
Example 6: preparation of antimony-containing bimetallic oxide by using antimony concentrate as raw material
1) Weighing 100Kg of antimony concentrate containing 30% of antimony, pouring the antimony concentrate into a slurry pond, and adding 40Kg of K2S, adding 800Kg of water, uniformly stirring, and continuously stirring for 2 hours to dissolve stibnite therein;
2) filtering to separate the solution from the residual solid phase, spraying the solid phase for 2 times, and allowing the leacheate and the solution to enter the next working procedure;
3) adding 400Kg of bimetal oxide into the solution, uniformly stirring, and continuously stirring for 10 hours;
4) filtering the solid phase to separate from the solution, drying at the temperature lower than 80 ℃, enabling the solid phase to enter the next procedure, and returning the liquid phase to the step 1 for reuse;
5) calcining the solid phase obtained in the step 4 at the temperature of 700 ℃ for 2 hours to oxidize the thioantimonite radical adsorbed by the bimetallic oxide and fuse the thioantimonite radical into an adsorbent to obtain the antimony-containing bimetallic oxide; SO in flue gas3And recovering by a water washing mode to obtain sulfuric acid.
Example 7: preparation of antimony-containing bimetallic oxide by using antimony concentrate as raw material
1) Weighing antimony concentrate 100 containing 20% of antimonyPouring the mixture into a slurry pool, adding 600Kg of (NH) with the concentration of 10 percent prepared in advance4)2The S solution is stirred evenly and is continuously stirred for 2 hours, so that the stibnite in the S solution is dissolved;
2) filtering to separate the solution from the residual solid phase, spraying the solid phase for 2 times, and allowing the leacheate and the solution to enter the next working procedure;
3) adding 300Kg of bimetal oxide into the solution, stirring uniformly, and continuously stirring for 10 hours;
4) filtering the solid phase to separate from the solution, drying at the temperature lower than 80 ℃, enabling the solid phase to enter the next procedure, and returning the liquid phase to the step 1 for reuse;
5) calcining the solid phaseobtained in the step 4 at the temperature of 550 ℃ for 4 hours to oxidize the thioantimonite radical adsorbed by the bimetallic oxide and fuse the thioantimonite radical into an adsorbent to obtain the antimony-containing bimetallic oxide; SO in flue gas3And recovering by a water washing mode to obtain sulfuric acid.
Example 8: antimony-containing hydrotalcite is prepared from antimony-containing bimetallic oxides.
1) Weighing 125 kg of sodium carbonate, adding 1 ton of water, fully stirring to completely dissolve the sodium carbonate, adding 350 kg of antimony-containing bimetallic oxide into the solution, uniformly mixing, and continuously stirring for 6 hours;
2) after filtering and dehydrating, adding one ton of water, fully stirring to uniformly mix, filtering again, and repeating the steps;
3) or oven drying at 80 deg.C to obtain antimony-containing hydrotalcite, grinding to less than 200 mesh, and bagging.
Example 9: antimony-containing hydrotalcite is prepared from antimony-containing bimetallic oxides.
1) Weighing 250 kg of sodium bicarbonate, adding 2 tons of water, fully stirring to completely dissolve the sodium bicarbonate, adding 200 kg of antimony-containing bimetallic oxide into the solution, uniformly mixing, and continuously stirring for 8 hours;
2) after filtering and dehydrating, adding one ton of water, fully stirring to uniformly mix, filtering again, and repeating the steps;
3) or drying at 70 deg.C to obtain antimony-containing hydrotalcite, grinding to less than 200 mesh, and bagging.
Example 10: antimony-containing hydrotalcite is prepared from antimony-containing bimetallic oxides.
1) Weighing 180 kg of sodium chloride, adding 1 ton of water, fully stirring to completely dissolve the sodium chloride, adding 200 kg of antimony-containing bimetallic oxide into the solution, uniformly mixing, and continuously stirring for 6 hours;
2) after filtering and dehydrating, adding 1.5 tons of water, fully stirring to uniformly mix, filtering again, and repeating the steps;
3) or drying at 60 deg.C to obtain antimony-containing hydrotalcite, grinding to less than 200 mesh, and bagging.
Example 11: antimony-containing hydrotalcite is prepared from antimony-containing bimetallic oxides.
1) Weighing 200 kg of potassium chloride, adding 1.5 ton of water, fully stirring to completely dissolve the potassium chloride, adding 160 kg of antimony-containing bimetallic oxide into the solution, uniformly mixing, and continuously stirring for 5 hours;
2) after filtering and dehydrating, adding 2 tons of water, fully stirring to uniformly mix, filtering again, and repeating the steps;
3) or oven drying at 80 deg.C, grinding to less than 200 mesh, and packaging.
Example 12: antimony-containing hydrotalcite is prepared from antimony-containing bimetallic oxides.
1) Weighing 200 kg of ammonium chloride, adding 2 tons of water, fully stirring to completely dissolve the ammonium chloride, adding 120 kg of antimony-containing bimetallic oxide into the solution, uniformly mixing, and continuously stirring for 6 hours;
2) after filtering and dehydrating, adding 1 ton of water, fully stirring to uniformly mix, filtering again, and repeating the steps;
3) or oven drying at 60 deg.C, grinding to less than 200 mesh, and packaging.
Claims (7)
1. The inorganic flame retardant is characterized by being antimony-containing hydrotalcite, wherein the content of antimony in the hydrotalcite is 2-15% by weight, and the inorganic flame retardant has a chemical structural general formula as follows: [ Mg1-x(Al，Sb)x(OH)2]x+·Ry- x/y·nH2O, wherein x is 0.5-0.17; r is an anion and is CO3 2-、HCO3 -Or Cl-(ii) a y is the valence of the anion; n is 2 to 8.
2. The preparation method of the inorganic flame retardant is characterized by comprising the following steps:
1) mixing crushed magnesium hydroxide or magnesium oxide and aluminum hydroxide according to the molar ratio of 1: 1-5: 1, adding the mixture into a ball mill or a rod mill, adding 2-8 times of water, and grinding for 6-24 hours;
2) dehydrating the ground mixture, airing or drying at a temperature lower than 90 ℃, calcining for 2-5 hours at a temperature of 500-750 ℃, and grinding to less than 200 meshes for later use to obtain a product which is a bimetallic oxide and has a chemical structural general formula of Mgm. Aln. Ox, wherein x is m +3 n/2;
3) crushing stibnite ore to be less than 100 meshes, pouring the crushed stibnite ore into a slurry pool, adding soluble sulfide with the weight being 0.8-2.0 times of the amount of antimony metal in the ore, adding water with the weight being 2-8 times of the amount of the antimony metal in the ore, uniformly stirring, and continuously stirring for 0.5-3 hours to dissolve the stibnite therein to form a thioantimonite radical;
4) separating the solution from the residual solid phase by adopting a precipitation, centrifugation or filtration method, adding the bimetallic oxide obtained in the step 2) into the solution, wherein the weight of the bimetallic oxide is 10-20 times of the amount of antimony metal in stibnite, uniformly stirring, and continuously stirring for 4-12 hours;
5) separating the reactant from the solution by precipitation, centrifugation or filtration, air-drying or drying at a temperature lower than 90 ℃, allowing the solid phase to enter the next procedure, and allowing the liquid phase to return to the step 3) for reuse;
6) calcining the solid phase obtained in the step 5) for 2-5 hours at 500-750 ℃ to decompose the thioantimonite radical adsorbed by the bimetallic oxide, and fusing the thioantimonite radical into the bimetallic oxide molecules in the form of antimony oxide, SO in the flue gas3Recovering by water washing to obtain sulfuric acid, and calcining residue is still bisThe metal oxide can be used in the next procedure or returned to the step 4) for reuse to increase the antimony content in the product.
7) Preparing soluble carbonate or hydrochloride into a solution with the concentration of 0.5-2 mole/L, adding the product obtained in the step 6) into the solution according to the proportion of adding 100-300 g of bimetallic oxide into each gram of molecular salt, uniformly mixing, continuously stirring for 3-8 hours, filtering or centrifugally dewatering, washing for 2-3 times with clean water, dewatering, airing or drying at the temperature lower than 90 ℃, and grinding to be less than 200 meshes.
3. The method of claim 2, wherein the magnesium hydroxide is commercially available or natural mineral brucite having a chemical composition of Mg (OH)2(ii) a The magnesium oxide is a commercial product or a calcined product of natural mineral magnesite at 400-600 ℃.
4. The method of claim 2, wherein the inorganic flame retardant is prepared byThe aluminum hydroxide is a commercial product or a natural mineral gibbsite with a chemical composition of Al (OH)3。
5. The process for producing an inorganic flame retardant according to claim 2, wherein the soluble sulfide is Na2S、K2S and (NH)4)2One or more of S.
6. The method of claim 2, wherein the soluble carbonate is one or more of sodium carbonate, sodium bicarbonate or their hydrates.
7. The method of claim 2, wherein the soluble hydrochloride is one or more of sodium chloride, potassium chloride, ammonium chloride, or their hydrates.
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| CN100371419C (en) * | 2006-03-13 | 2008-02-27 | 浙江大学 | Composite inorganic flame retardant and its preparation method |
| CN102585845B (en) * | 2010-12-31 | 2014-04-09 | 梁清源 | Inorganic mineral composite flame retardant and preparation method thereof |
| CN103241771B (en) * | 2013-05-20 | 2014-12-03 | 浙江省地质矿产研究所 | Hydrotalcite-like compound-metallic antimony composite material and preparation method thereof |
| CN105950188A (en) * | 2015-12-31 | 2016-09-21 | 洛阳神佳窑业有限公司 | Novel flame retarding agent |
| CN105925274A (en) * | 2015-12-31 | 2016-09-07 | 洛阳神佳窑业有限公司 | Flame retardant with fixed proportion |
| CN107286829A (en) * | 2017-06-29 | 2017-10-24 | 周兰兰 | It is a kind of applied to anti-flaming dope of wood furniture and preparation method thereof |
| CN107129755A (en) * | 2017-06-29 | 2017-09-05 | 周兰兰 | It is a kind of applied to anti-flaming dope of Wood plastic furniture and preparation method thereof |
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| CN1570023A (en) | 2005-01-26 |
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