Preparation method of antimony trioxide composite flame retardant

Abstract

The invention discloses a preparation method of an antimony trioxide composite flame retardant, which is specifically implemented according to the following steps: pretreating a catalytic cracking poising agent to obtain a poising agent solution, and adding antimony trichloride into hydrochloric acid; dropwise adding an antimony trichloride solution into the poising agent solution, and stirring for 3-5 hours to obtain a first mixed solution; standing to enable precipitates in the first mixed solution to settle to the bottom, clarifying supernatant liquid, then pouring out the supernatant liquid, and filtering bottom turbid liquid to obtain a first filter cake; adding water into the first filter cake, dispersing to obtain a first turbid solution, adding an alkaline solution into the first turbid solution, neutralizing to obtain a second turbid solution, filtering the second turbid solution to obtain a second filter cake, washing the second filter cake, and drying to obtain the antimony trioxide composite flame retardant. The preparation method of the antimony trioxide composite flame retardant is simple in process, low in raw material cost, high in additional value and environmentally friendly.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of flame retardant, and relates to a preparation method of antimony trioxide composite flame retardant. BACKGROUND

[0002] Since the 1970s, the application field and application technology of antimony products have been continuously expanded and improved. From the demand for antimony products in industrialized countries, it can be seen that the application of antimony products has developed from metal to its compounds and salt products. Among the compounds of antimony, antimony trioxide applied in the field of flame retardant occupies a dominant position. Since the 1970s, domestic reform of antimony white production process mainly focuses on alkali leaching of antimony concentrate, followed by electrodeposition and crude metal refining, and finally producing antimony white by oxidizing and volatilizing refined antimony. Although this process avoids air pollution, it has high energy consumption, poor working conditions, and also has the problem of reverse processing of metal re-oxidation. Since the 1980s, many domestic units have begun to study the method of directly producing antimony white by acid leaching of antimony concentrate with chloride salt or chlorine water. The main use of Sb2O3 is as a flame-retardant synergist for flammable materials such as plastics, rubber, paint, chemical fiber and cotton and hemp fabrics; as a catalyst in polyester production; as a clarifying agent in the glass industry; as an emulsifying agent in the enamel industry; as a passivation agent in the petroleum cracking industry. In the application field that needs coloring, coarse particle antimony trioxide can reduce the consumption of pigments, which can not only reduce the production cost of the finished product, but also reduce the influence of antimony trioxide on the performance of the finished product. Adding ultra-fine Sb2O3 to plastics, coatings and fibers forms inorganic-organic high molecular composite materials, which can significantly improve the flame-retardant synergistic property and the flame retardancy of Sb2O3 and the whole material, and also significantly improve and enhance the physical and chemical properties of the composite material.

[0003] The output of domestic catalytic cracking equilibrium agent is large and the quality is unstable. Except for part of the regenerated use, most of them are treated as solid waste or hazardous waste, and the generated waste residue is buried in place, causing resource waste and environmental pollution. The equilibrium agent contains a small amount of rare earth elements, which are of high value, and a high content of silicon and aluminum elements, which are of low price. Therefore, it is urgent to find a resource utilization solution.

[0004] In summary, the prior art lacks a method for reasonably recycling and reusing catalytic cracking equilibrium agent. SUMMARY

[0005] The purpose of the present application is to provide a preparation method of antimony trioxide composite flame retardant, which solves the problem of lacking a method for reasonably recycling and reusing catalytic cracking equilibrium agent in the prior art.

[0006] The technical scheme adopted by the present application is a preparation method of antimony trioxide composite flame retardant, which is implemented according to the following steps:

[0007] Step 1: Take the catalytic cracking equilibrium agent, antimony trichloride, hydrochloric acid, and water;

[0008] Step 2: After pretreating the catalytic cracking equilibrium agent to obtain an equilibrium agent solution, add antimony trichloride to hydrochloric acid to obtain an antimony trichloride solution;

[0009] Step 3: Add antimony trichloride solution dropwise to the balancing agent solution and stir for 3-5 hours to obtain the first mixed solution;

[0010] Step 4: Let the mixture stand to allow the precipitate in the first mixed solution to settle to the bottom, and the supernatant to become clear. Then pour out the supernatant and filter the turbid liquid at the bottom to obtain the first filter cake.

[0011] Step 5: After dispersing the first filter cake with water, a first turbid liquid is obtained. After neutralizing the first turbid liquid with an alkaline solution, a second turbid liquid is obtained. The second turbid liquid is filtered to obtain a second filter cake. After washing the second filter cake, it is dried to obtain antimony trioxide composite flame retardant.

[0012] The invention is further characterized by:

[0013] The catalytic cracking equilibrium agent contains molecular sieves and binders, and its microstructure is spherical or ellipsoidal with a particle size of 30μm-120μm.

[0014] The binder is one of kaolin, boehmite, hydrochloric acid, or aluminum molten adhesive; the mass concentration of hydrochloric acid is 10%-20%.

[0015] The specific steps for the pretreatment of the catalytic cracking equilibrium agent in step two are as follows: grind the catalytic cracking equilibrium agent using a grinder, add the ground catalytic cracking equilibrium agent to the activator and activate for 3-6 hours, then add a complexing agent to remove metal ions. When the solution is colorless, the metal ions are completely removed, and the pretreatment is complete.

[0016] The particle size of the ground catalytic cracking equilibrium agent is D50 = 5μm-40μm and D97 = 10μm-120μm; the activator includes acidic activator, basic activator and electrochemical corrosion.

[0017] The alkaline activator is one or a mixture of several of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium peroxide, and the mass concentration of the alkaline activator is 1%-3%.

[0018] The acidic activator is one or a mixture of several of hydrochloric acid, sulfuric acid, and oxalic acid, and the mass concentration of the acidic activator solution is 1%-5%.

[0019] The complexing agent is one of salicylic acid, citric acid, ethylenediaminetetraacetic acid and its sodium salt, thiocyanate, and phenol, with a mass concentration of 0.1%-10%.

[0020] The mass ratio of antimony trichloride to hydrochloric acid in the antimony trichloride solution is 1:(2-5).

[0021] The mass ratio of the balancing agent solution to the antimony trichloride solution in the first mixed solution is 1:(1-7).

[0022] The pH value of the second turbid solution is 7-8; the alkaline solution is a saturated solution containing one or a mixture of several of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and ammonia.

[0023] The particle size of the antimony trioxide composite flame retardant is 5-10 mu m.

[0024] The antimony trioxide composite flame retardant prepared by the method has the advantages that the method is simple, the raw material cost is low, the added value is high, the environment is friendly, and the problem of recycling of the catalytic cracking balancing agent is solved. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 FIG. 1 is a scanning electron microscope image of the antimony trioxide composite flame retardant obtained in Example 1 in the preparation method of the antimony trioxide composite flame retardant of the present application;

[0026] Figure 2 FIG. 2 is a scanning electron microscope image of the antimony trioxide composite flame retardant obtained in Example 2 in the preparation method of the antimony trioxide composite flame retardant of the present application;

[0027] Figure 3 FIG. 3 is a scanning electron microscope image of the antimony trioxide composite flame retardant obtained in Example 3 in the preparation method of the antimony trioxide composite flame retardant of the present application;

[0028] Figure 4 FIG. 4 is a scanning electron microscope image of the antimony trioxide composite flame retardant obtained in Example 4 in the preparation method of the antimony trioxide composite flame retardant of the present application;

[0029] Figure 5 FIG. 5 is a scanning electron microscope image of the antimony trioxide composite flame retardant obtained in Example 5 in the preparation method of the antimony trioxide composite flame retardant of the present application;

[0030] Figure 6 FIG. 6 is a scanning electron microscope image of the antimony trioxide composite flame retardant obtained in Example 6 in the preparation method of the antimony trioxide composite flame retardant of the present application;

[0031] Figure 7 FIG. 7 is a scanning electron microscope image of the antimony trioxide composite flame retardant obtained in Example 7 in the preparation method of the antimony trioxide composite flame retardant of the present application;

[0032] Figure 8is the scanning electron microscope image of the antimony trioxide composite flame retardant obtained in Example 8 in the preparation method of the antimony trioxide composite flame retardant of the present application;

[0033] Figure 9 is the X-ray diffraction pattern of the antimony trioxide composite flame retardant obtained in Examples 1-8 in the preparation method of the antimony trioxide composite flame retardant of the present application. DETAILED DESCRIPTION

[0034] The present application will be described in detail below in conjunction with the drawings and specific embodiments.

[0035] The preparation method of the antimony trioxide composite flame retardant is specifically implemented according to the following steps:

[0036] Step one, take catalytic cracking equilibrium agent, antimony trichloride, hydrochloric acid, and water;

[0037] The catalytic cracking equilibrium agent contains molecular sieve and binder, and its micro-morphology is spherical or ellipsoidal, and its particle size is 30-120 μm; the binder is one of kaolin, pseudo-boehmite, hydrochloric acid, and aluminum sol; the mass concentration of the hydrochloric acid is 10-20%;

[0038] Step two, the catalytic cracking equilibrium agent is pretreated to obtain an equilibrium agent solution, and the antimony trichloride is added to the hydrochloric acid to obtain an antimony trichloride solution;

[0039] The specific steps of the pretreatment of the catalytic cracking equilibrium agent in Step two are as follows: the catalytic cracking equilibrium agent is ground by a grinding machine, the ground catalytic cracking equilibrium agent is added to an activator for activation for 3-6 hours, and then a complexing agent is added to remove metal ions; when the solution is colorless, the metal ions are completely removed, and the pretreatment is completed;

[0040] The particle size of the ground catalytic cracking equilibrium agent is D50=5-40 μm and D97=10-120 μm; the activator includes an acidic activator, an alkaline activator, and electrochemical corrosion.

[0041] The alkaline activator is one or a mixture of several of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium peroxide, and the mass concentration of the alkaline activator is 1-3%;

[0042] The acidic activator is one or a mixture of several of hydrochloric acid, sulfuric acid, and oxalic acid, and the mass concentration of the acidic activator solution is 1-5%;

[0043] The complexing agent is one of salicylic acid, citric acid, ethylenediaminetetraacetic acid and its sodium salt, thiocyanate, and phenol, and the mass concentration of the complexing agent is 0.1-10%;

[0044] The mass ratio of the antimony trichloride to the hydrochloric acid in the antimony trichloride solution is 1:(2-5).

[0045] Step three, drop the antimony trichloride solution into the equilibrium agent solution and stir for 3-5 hours to obtain a first mixed solution;

[0046] The mass ratio of the equilibrium agent solution and the antimony trichloride solution in the first mixed solution is 1:(1-7);

[0047] Step four, let the precipitate in the first mixed solution settle to the bottom, the upper clear liquid is clear, then pour out the upper clear liquid, and filter the bottom turbid liquid to obtain a first filter cake;

[0048] Step five, disperse the first filter cake with water to obtain a first turbid liquid, neutralize the first turbid liquid with an alkaline solution to obtain a second turbid liquid, filter the second turbid liquid to obtain a second filter cake, wash the second filter cake, and dry to obtain a antimony trioxide composite flame retardant.

[0049] The pH value of the second turbid liquid is 7-8; the alkaline solution is a saturated solution containing one or a mixture of several of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and ammonia.

[0050] The particle size of the antimony trioxide composite flame retardant is 5-10 μm, and the micro-morphology is a flower-shaped structure composed of irregular hexahedrons.

[0051] The particle size of the catalytic cracking equilibrium agent is large, easy to settle, and relatively difficult to be coated. The product made of the catalytic cracking equilibrium agent affects the mechanical properties of the sample, and a grinding machine is needed to control the particle size of the catalytic cracking equilibrium agent. The grinding machine can be a jaw crusher, a planetary ball mill, a rotary ball mill, a wet ball mill, and the grinding effect of the rotary ball mill and the wet ball mill is better. The particle size of the catalytic cracking equilibrium agent after grinding should not be too small. If the particle size is too small, the viscosity is large and it is not easy to disperse. The Si-O-Al chemical bond on the surface of the catalytic cracking equilibrium agent is not conducive to the deposition of antimony trioxide, and an activator is needed to activate the surface. The activator refers to a kind of chemical substance that can chemically treat the surface of the catalytic cracking equilibrium agent, expose the pores with physical adsorption or chemical bonding, active functional groups, and increase the polarity of the surface. In a strong acid and strong alkali system, the nickel, iron, copper and other metal elements in the catalytic cracking equilibrium agent are easily precipitated after grinding, which affects the whiteness of the product. Therefore, the catalytic cracking equilibrium agent is soaked in a complexing agent solution to remove metal ions that affect the color of the product. The complexing agent is a reagent that can form a complex with iron ions. The antimony trioxide composite flame retardant can be used as or for the synthesis of white pigments, paints, various resins and synthetic rubbers, and has excellent flame retardant effect.

[0052] Example 1

[0053] The preparation method of the antimony trioxide composite flame retardant is implemented according to the following steps:

[0054] Step one, take catalytic cracking equilibrium agent, antimony trichloride, hydrochloric acid, water;

[0055] The mass concentration of hydrochloric acid is 10%;

[0056] Step two, after the catalytic cracking equilibrium agent is pretreated, an equilibrium agent solution is obtained, and antimony trichloride is added to hydrochloric acid to obtain an antimony trichloride solution;

[0057] The specific steps of pretreatment of the catalytic cracking equilibrium agent in step two are as follows: the catalytic cracking equilibrium agent is ground by using a grinder, the ground catalytic cracking equilibrium agent is added to an activator and activated for 3 hours, a complexing agent is then added to remove metal ions, and when the solution color is colorless, the metal ions are completely removed, and the pretreatment is completed.

[0058] The activator includes an acidic activator, and the acidic activator is hydrochloric acid; the mass concentration of the acidic activator solution is 1%;

[0059] The complexing agent is salicylic acid; the mass concentration of the complexing agent is 0.1%;

[0060] The mass ratio of antimony trichloride to hydrochloric acid in the antimony trichloride solution is 1:2;

[0061] Step three, the antimony trichloride solution is added dropwise to the equilibrium agent solution and stirred for 3 hours to obtain a first mixed solution;

[0062] Step four, the first mixed solution is allowed to stand, so that the precipitate in the first mixed solution is settled to the bottom, the supernatant is clarified, and then the supernatant is poured out, and the bottom turbid liquid is filtered to obtain a first filter cake;

[0063] Step five, the first filter cake is dispersed in water to obtain a first turbid liquid, the first turbid liquid is neutralized by adding an alkaline solution to obtain a second turbid liquid, the second turbid liquid is filtered to obtain a second filter cake, the second filter cake is washed and dried to obtain a diantimony trioxide composite flame retardant as shown in Figure 1 .

[0064] The pH value of the second turbid liquid is 7; the alkaline solution is a saturated solution containing sodium hydroxide; and in this embodiment, the addition amount of the catalytic cracking equilibrium agent is 13% of the mass of the antimony trichloride

[0065] Example 2

[0066] The preparation method of the diantimony trioxide composite flame retardant is specifically implemented according to the following steps:

[0067] Step one, take catalytic cracking equilibrium agent, antimony trichloride, hydrochloric acid, water;

[0068] The mass concentration of hydrochloric acid is 15%;

[0069] Step two, after the catalytic cracking equilibrium agent is pretreated, an equilibrium agent solution is obtained, and antimony trichloride is added to hydrochloric acid to obtain an antimony trichloride solution;

[0070] The specific steps of the pre-treatment of the catalytic cracking equilibrium catalyst in step two are as follows: the catalytic cracking equilibrium catalyst is ground by a grinder, the ground catalytic cracking equilibrium catalyst is added into an activator for activation for 4 hours, a complexing agent is added to remove metal ions, and when the solution is colorless, the metal ions are removed completely, and the pre-treatment is completed.

[0071] The activator includes an acidic activator; the acidic activator is sulfuric acid, and the mass concentration of the acidic activator solution is 2.5%;

[0072] The complexing agent is citric acid, and the mass concentration of the complexing agent is 5%;

[0073] The mass ratio of antimony trichloride to hydrochloric acid in the antimony trichloride solution is 1:3;

[0074] Step three, the antimony trichloride solution is added dropwise into the equilibrium catalyst solution and stirred for 4 hours to obtain a first mixed solution;

[0075] Step four, the first mixed solution is allowed to stand, the precipitate in the first mixed solution is allowed to settle to the bottom, the supernatant is clarified, and then the supernatant is poured out, and the bottom turbid liquid is filtered to obtain a first filter cake;

[0076] Step five, the first filter cake is dispersed in water to obtain a first turbid liquid, the first turbid liquid is neutralized by adding an alkaline solution to obtain a second turbid liquid, the second turbid liquid is filtered to obtain a second filter cake, the second filter cake is washed and dried to obtain a diantimony trioxide composite flame retardant as shown in Figure 2 .

[0077] The pH value of the second turbid liquid is 8; the alkaline solution is a saturated solution containing potassium hydroxide, and the addition amount of the catalytic cracking equilibrium catalyst in this embodiment is 40% of the mass of the antimony trichloride.

[0078] Example 3

[0079] The preparation method of the diantimony trioxide composite flame retardant is specifically implemented according to the following steps:

[0080] Step one, catalytic cracking equilibrium catalyst, antimony trichloride, hydrochloric acid, and water are taken;

[0081] The mass concentration of the hydrochloric acid is 20%;

[0082] Step two, the catalytic cracking equilibrium catalyst is pre-treated to obtain an equilibrium catalyst solution, and the antimony trichloride is added into the hydrochloric acid to obtain an antimony trichloride solution;

[0083] The specific steps of the pre-treatment of the catalytic cracking equilibrium catalyst in step two are as follows: the catalytic cracking equilibrium catalyst is ground by a grinder, the ground catalytic cracking equilibrium catalyst is added into an activator for activation for 4 hours, a complexing agent is added to remove metal ions, and when the solution is colorless, the metal ions are removed completely, and the pre-treatment is completed.

[0084] The activator includes a basic activator, the basic activator is a mixture of sodium hydroxide and potassium hydroxide, and the mass concentration of the basic activator is 1%;

[0085] The complexing agent is ethylenediaminetetraacetic acid and its sodium salt, and the mass concentration of the complexing agent is 10%;

[0086] The mass ratio of antimony trichloride to hydrochloric acid in the antimony trichloride solution is 1:5;

[0087] Step three, drop the antimony trichloride solution into the equilibrium agent solution and stir for 5 hours to obtain a first mixed solution;

[0088] Step four, let the precipitate in the first mixed solution settle to the bottom, the upper clear liquid is clear, then pour out the upper clear liquid, and filter the bottom turbid liquid to obtain a first filter cake;

[0089] Step five, disperse the first filter cake with water to obtain a first turbid liquid, neutralize the first turbid liquid with an alkaline solution to obtain a second turbid liquid, filter the second turbid liquid to obtain a second filter cake, wash the second filter cake, and dry to obtain a Figure 3 diantimony trioxide composite flame retardant as shown.

[0090] The pH value of the second turbid liquid is 7; the alkaline solution is a saturated solution containing potassium carbonate and sodium carbonate, and the addition amount of the catalytic cracking equilibrium agent in this embodiment is 50% of the mass of the antimony trichloride.

[0091] Example 4

[0092] The preparation method of the diantimony trioxide composite flame retardant is specifically implemented according to the following steps:

[0093] Step one, take catalytic cracking equilibrium agent, antimony trichloride, hydrochloric acid, and water;

[0094] The mass concentration of the hydrochloric acid is 12.5%;

[0095] Step two, pretreat the catalytic cracking equilibrium agent to obtain an equilibrium agent solution, and add the antimony trichloride to the hydrochloric acid to obtain an antimony trichloride solution;

[0096] The specific steps of pretreating the catalytic cracking equilibrium agent in step two are as follows: grind the catalytic cracking equilibrium agent with a grinding machine, activate the ground catalytic cracking equilibrium agent in the activator for 5 hours, and then add a complexing agent to remove metal ions. When the solution color is colorless, the metal ions are removed, and the pretreatment is completed.

[0097] The activator includes electrochemical corrosion.

[0098] The complexing agent is thiocyanate, and the mass concentration of the complexing agent is 2.5%;

[0099] The mass ratio of antimony trichloride to hydrochloric acid in the antimony trichloride solution is 1:4;

[0100] Step three, drop the antimony trichloride solution into the equilibrium agent solution and stir for 3.5 hours to obtain a first mixed solution;

[0101] Step four, let the precipitate in the first mixed solution settle to the bottom, the supernatant is clear, then pour out the supernatant, and filter the bottom turbid liquid to obtain a first filter cake;

[0102] Step five, disperse the first filter cake with water to obtain a first turbid liquid, neutralize the first turbid liquid with an alkaline solution to obtain a second turbid liquid, filter the second turbid liquid to obtain a second filter cake, wash the second filter cake, and dry to obtain a diantimony trioxide composite flame retardant as shown in Figure 4 .

[0103] The pH value of the second turbid liquid is 7; the alkaline solution is a saturated solution containing ammonia water, and the addition amount of the catalytic cracking equilibrium agent in this embodiment is 100% of the mass of the antimony trichloride.

[0104] Example 5

[0105] The preparation method of the diantimony trioxide composite flame retardant is specifically implemented according to the following steps:

[0106] Step one, take catalytic cracking equilibrium agent, antimony trichloride, hydrochloric acid, and water;

[0107] The mass concentration of the hydrochloric acid is 17.5%;

[0108] Step two, pretreat the catalytic cracking equilibrium agent to obtain an equilibrium agent solution, and add the antimony trichloride to the hydrochloric acid to obtain an antimony trichloride solution;

[0109] The specific steps of pretreating the catalytic cracking equilibrium agent in step two are as follows: grind the catalytic cracking equilibrium agent with a grinder, activate the ground catalytic cracking equilibrium agent in an activator for 4.5 hours, and then add a complexing agent to remove metal ions. When the solution color is colorless, the metal ions are removed, and the pretreatment is completed.

[0110] The activator includes an alkaline activator, and the alkaline activator is a mixture of potassium hydroxide and sodium carbonate. The mass concentration of the alkaline activator is 3%;

[0111] The complexing agent is phenol, and the mass concentration of the complexing agent is 7.5%;

[0112] The mass ratio of antimony trichloride to hydrochloric acid in the antimony trichloride solution is 1:3.5;

[0113] Step three, drop the antimony trichloride solution into the equilibrium agent solution and stir for 4.5 hours to obtain a first mixed solution;

[0114] Step four, standing to make the precipitate in the first mixed solution to the bottom, the supernatant is clear, then pour out the supernatant, the bottom turbidity liquid filtration to obtain the first filter cake;

[0115] Step five, the first filter cake is dispersed in water to obtain a first turbid liquid, the first turbid liquid is neutralized by adding an alkaline solution to obtain a second turbid liquid, the second turbid liquid is filtered to obtain a second filter cake, the second filter cake is washed and dried to obtain a diantimony trioxide composite flame retardant as shown in Figure 5

[0116] The pH value of the second turbid liquid is 7; the alkaline solution is a saturated solution containing sodium hydroxide and potassium hydroxide.

[0117] Example 6

[0118] The preparation method of the diantimony trioxide composite flame retardant is specifically implemented according to the following steps:

[0119] Step one, taking catalytic cracking equilibrium agent, antimony trichloride, hydrochloric acid, and water;

[0120] The mass concentration of hydrochloric acid is 11%;

[0121] Step two, the catalytic cracking equilibrium agent is pretreated to obtain an equilibrium agent solution, and antimony trichloride is added to hydrochloric acid to obtain an antimony trichloride solution;

[0122] The specific steps of pretreating the catalytic cracking equilibrium agent in step two are as follows: the catalytic cracking equilibrium agent is ground by a grinding machine, the ground catalytic cracking equilibrium agent is activated in an activator for 5.5 hours, and a complexing agent is added to remove metal ions. When the solution color is colorless, the metal ions are removed, and the pretreatment is completed.

[0123] The activator includes an acidic activator, and the acidic activator is a mixture of hydrochloric acid and oxalic acid. The mass concentration of the acidic activator solution is 2.5%;

[0124] The complexing agent is salicylic acid, and the mass concentration of the complexing agent is 1%;

[0125] The mass ratio of antimony trichloride to hydrochloric acid in the antimony trichloride solution is 1:3;

[0126] Step three, adding the antimony trichloride solution dropwise to the equilibrium agent solution and stirring for 3 hours to obtain a first mixed solution;

[0127] Step four, standing to make the precipitate in the first mixed solution to the bottom, the supernatant is clear, then pour out the supernatant, the bottom turbidity liquid filtration to obtain the first filter cake;

[0128] ​Step five, the first filter cake is dispersed with water to obtain a first turbid liquid, the first turbid liquid is neutralized with an alkaline solution to obtain a second turbid liquid, the second turbid liquid is filtered to obtain a second filter cake, the second filter cake is washed and dried to obtain the antimony trioxide composite flame retardant as shown in Figure 6 .

[0129] The pH value of the second turbid liquid is 7; the alkaline solution is a saturated solution containing sodium hydroxide and potassium hydroxide.

[0130] Example 7

[0131] The preparation method of the antimony trioxide composite flame retardant is specifically implemented according to the following steps:

[0132] Step one, take catalytic cracking equilibrium agent, antimony trichloride, hydrochloric acid and water;

[0133] The mass concentration of the hydrochloric acid is 16%;

[0134] Step two, the catalytic cracking equilibrium agent is pretreated to obtain an equilibrium agent solution, and the antimony trichloride is added to the hydrochloric acid to obtain an antimony trichloride solution;

[0135] The specific steps of pretreating the catalytic cracking equilibrium agent in step two are as follows: the catalytic cracking equilibrium agent is ground by using a grinding machine, the ground catalytic cracking equilibrium agent is added to an activator and activated for 4.5 hours, and then a complexing agent is added to remove metal ions; when the solution color is colorless, the metal ions are removed, and the pretreatment is completed.

[0136] The activator includes a basic activator,

[0137] The basic activator is a mixture of sodium carbonate and potassium carbonate, and the mass concentration of the basic activator is 2%;

[0138] The complexing agent is ethylenediaminetetraacetic acid and its sodium salt, and the mass concentration of the complexing agent is 0.5%;

[0139] The mass ratio of antimony trichloride to hydrochloric acid in the antimony trichloride solution is 1:3;

[0140] Step three, the antimony trichloride solution is added dropwise to the equilibrium agent solution and stirred for 4 hours to obtain a first mixed solution;

[0141] Step four, the precipitate in the first mixed solution is allowed to settle to the bottom, the upper clear liquid is clarified, and then the upper clear liquid is poured out, and the bottom turbid liquid is filtered to obtain a first filter cake;

[0142] Step five, the first filter cake is dispersed with water to obtain a first turbid liquid, the first turbid liquid is neutralized with an alkaline solution to obtain a second turbid liquid, the second turbid liquid is filtered to obtain a second filter cake, the second filter cake is washed and dried to obtain the antimony trioxide composite flame retardant as shown in Figure 7 .

[0143] The pH value of the second turbid solution is 7; the alkaline solution is a saturated solution containing potassium carbonate and sodium carbonate.

[0144] Example 8

[0145] The preparation method of the antimony trioxide composite flame retardant is specifically implemented according to the following steps:

[0146] Step one, take the catalytic cracking equilibrium agent, antimony trichloride, hydrochloric acid, and water;

[0147] The mass concentration of hydrochloric acid is 15%;

[0148] Step two, the catalytic cracking equilibrium agent is pretreated to obtain an equilibrium agent solution, and antimony trichloride is added to hydrochloric acid to obtain an antimony trichloride solution;

[0149] The specific steps of pretreatment of the catalytic cracking equilibrium agent in step two are as follows: the catalytic cracking equilibrium agent is ground by a grinding machine, the ground catalytic cracking equilibrium agent is activated in an activator for 5 hours, and a complexing agent is added to remove metal ions. When the solution color is colorless, the metal ions are removed, and the pretreatment is completed.

[0150] The activator includes an acidic activator, and the acidic activator is sulfuric acid. The mass concentration of the acidic activator solution is 3%;

[0151] The complexing agent is salicylic acid, and the mass concentration of the complexing agent is 9%;

[0152] The mass ratio of antimony trichloride to hydrochloric acid in the antimony trichloride solution is 1:3;

[0153] Step three, the antimony trichloride solution is added dropwise to the equilibrium agent solution and stirred for 4 hours to obtain a first mixed solution;

[0154] Step four, the first mixed solution is allowed to stand, and the precipitate in the first mixed solution is allowed to settle to the bottom. The upper clear liquid is clear, and then the upper clear liquid is poured out. The bottom turbid liquid is filtered to obtain a first filter cake;

[0155] Step five, the first filter cake is dispersed in water to obtain a first turbid liquid. The first turbid liquid is neutralized by an alkaline solution to obtain a second turbid liquid. The second turbid liquid is filtered to obtain a second filter cake. After the second filter cake is washed and dried, an antimony trioxide composite flame retardant is obtained.

[0156] The pH value of the second turbid solution is 7; the alkaline solution is a saturated solution containing sodium hydroxide.

[0157] The performance of the antimony trioxide composite flame retardant is characterized as follows:

[0158] Morphology characterization: as Figures 1-8The scanning electron micrographs of the antimony trioxide composite flame retardant obtained in Examples 1-8 are shown in Figure 1. It can be seen that the morphology of the antimony trioxide composite flame retardant is dispersed distribution of parallelepiped or parallelepiped group and flower shape. When the addition amount of the catalytic cracking equilibrium agent is increased from 40% to 100%, the morphology of the product shows irregular block shape.

[0159] Structural characterization: As shown in Figure 2, the X-ray diffraction pattern of the antimony trioxide composite flame retardant shows that the X-ray diffraction phases of Examples 1-8 are the same. Figure 9 The X-ray diffraction pattern of the antimony trioxide composite flame retardant is shown in Figure 2. The results show that the X-ray diffraction phases of Examples 1-8 are the same.

Claims

1. A process for the preparation of a composite flame retardant of diantimony trioxide, characterized in that, The method is implemented according to the following steps: Step 1: Take catalytic cracking equilibrium agent, antimony trichloride, hydrochloric acid and water; Step 2: After pretreatment of the catalytic cracking equilibrium agent, a solution of the equilibrium agent is obtained, and antimony trichloride is added to hydrochloric acid to obtain a solution of antimony trichloride; Step 3: The solution of antimony trichloride is added dropwise to the solution of the equilibrium agent and stirred for 3-5 hours to obtain a first mixed solution; Step 4: The first mixed solution is allowed to stand, and the precipitate in the first mixed solution is allowed to settle at the bottom, the supernatant is clarified, and then the supernatant is poured out, and the turbid liquid at the bottom is filtered to obtain a first filter cake; Step 5: The first filter cake is dispersed in water to obtain a first turbid liquid, the first turbid liquid is neutralized with an alkaline solution to obtain a second turbid liquid, the second turbid liquid is filtered to obtain a second filter cake, the second filter cake is washed and dried to obtain a composite antimony trioxide flame retardant.

2. The preparation method of the antimony trioxide composite flame retardant according to claim 1, characterized in that, The catalytic cracking equilibrium agent comprises molecular sieve and a binder, and has a spherical or ellipsoidal micro-morphology and a particle size of 30-120 μm; The binder is one of kaolin, pseudo-boehmite, hydrochloric acid and aluminum glue, and the mass concentration of the hydrochloric acid is 10-20%.

3. The preparation method of the antimony trioxide composite flame retardant according to claim 2, characterized in that, The specific steps of pretreatment of the catalytic cracking equilibrium agent in Step 2 are as follows: the catalytic cracking equilibrium agent is ground by a grinder, the ground catalytic cracking equilibrium agent is added to an activator and activated for 3-6 hours, and a complexing agent is added to remove metal ions, and when the solution is colorless, the metal ions are removed, and the pretreatment is completed.

4. The preparation method of the antimony trioxide composite flame retardant according to claim 3, characterized in that, The particle size of the ground catalytic cracking equilibrium agent is D50=5-40 μm and D97=10-120 μm, and the activator comprises an acidic activator, an alkaline activator and electrochemical corrosion.

5. The process for the preparation of antimony trioxide complex flame retardant according to claim 4, characterized in that, The alkaline activator is one or a mixture of several of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium peroxide, and the mass concentration of the alkaline activator is 1-3%; The acidic activator is one or a mixture of several of hydrochloric acid, sulfuric acid and oxalic acid, and the mass concentration of the acidic activator solution is 1-5%; The complexing agent is one of salicylic acid, citric acid, ethylenediaminetetraacetic acid and its sodium salt, thiocyanate and phenol, and the mass concentration of the complexing agent is 0.1-10%.

6. The process for the preparation of antimony trioxide composite flame retardant according to claim 1, characterized in that, The mass ratio of antimony trichloride to hydrochloric acid in the solution of antimony trichloride is 1:(2-5).

7. The preparation method of the antimony trioxide composite flame retardant according to claim 1, characterized in that, The mass ratio of the solution of the equilibrium agent to the solution of antimony trichloride in the first mixed solution is 1:(1-7).

8. The process for the preparation of antimony trioxide complex flame retardant as claimed in claim 1, wherein, The pH value of the second turbid liquid is 7-8, and the alkaline solution is a saturated solution containing one or a mixture of several of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and ammonia.

9. The process for preparing antimony trioxide composite flame retardant according to claim 1, characterized in that, The particle size of the composite antimony trioxide flame retardant is 5-10 μm.

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