A supported catalyst for the production of high-whiteness decabromodiphenylethane and a preparation process of high-whiteness decabromodiphenylethane

Abstract

The invention discloses a supported catalyst for the production of high-whiteness decabromodiphenylethane and a preparation process of high-whiteness decabromodiphenylethane, and relates to the technical field of preparing supported catalysts by chemical methods, wherein the supported catalyst comprises a carrier and an active ingredient, wherein the carrier is a modified molecular sieve, the active ingredient comprises an active auxiliary agent, an aluminum salt or a zirconium salt, and the active auxiliary agent is at least one of phosphomolybdic acid or phosphotungstic acid, and the preparation method of the modified molecular sieve comprises the following steps: sintering the molecular sieve at a constant temperature under the condition of 350-450° C., cooling, dispersing in a solvent, adding aminosilane, condensing and refluxing under the condition of 50-70° C., cooling, solid-liquid separation, washing, and drying to obtain the modified molecular sieve. The supported catalyst of the invention has strong stability and long-lasting catalytic activity in the reaction system, is easy to recover and has a high reuse rate, and the decabromodiphenylethane prepared by the supported catalyst has a high yield and whiteness.

Description

Technical Field

[0001] The invention relates to the technical field of preparing supported catalysts by chemical methods, and in particular to a supported catalyst for producing high-whiteness decabromodiphenylethane and a preparation process of high-whiteness decabromodiphenylethane. Background Art

[0002] Decabromodiphenylethane is a flame retardant widely used in the new energy industry, especially in new energy vehicles and electronic equipment. This flame retardant has good thermal stability and UV resistance, so it is used as a high-end flame retardant material and is suitable for computers, telephones, home appliances, copiers and other electrical equipment. With the rapid development of the global new energy vehicle industry, the demand for engineering plastic flame retardants continues to increase, especially the fire protection and environmental protection safety requirements of various electrical components continue to increase, which has led to an increase in the demand for decabromodiphenylethane.

[0003] The patent application document with publication number CN114213210A discloses a method for preparing decabromodiphenylethane, in which a supported composite catalyst is added in the bromination stage. The supported composite catalyst is a mixture of iron salt and / or aluminum salt, antimony salt and organic nickel complex using cationic surfactant-modified montmorillonite as a carrier.

[0004] The supported catalyst in the patent application uses cationic surfactant-modified montmorillonite as a carrier. Montmorillonite is a layered silicate material with relatively large interlayer space, but this structural feature also means that it is more easily blocked by reactants. This blockage phenomenon will limit the diffusion of reactants and the release of products, thereby affecting the activity and selectivity of the catalyst. Summary of the invention

[0005] In order to reduce the blockage of supported catalyst pores and thus improve the yield and whiteness of decabromodiphenylethane, the present invention provides a supported catalyst for the production of high-whiteness decabromodiphenylethane and a preparation process of high-whiteness decabromodiphenylethane.

[0006] The present invention provides a supported catalyst for the production of high-whiteness decabromodiphenylethane, which adopts the following technical scheme:

[0007] A supported catalyst for the production of high-whiteness decabromodiphenylethane, the supported catalyst comprising a carrier and an active component, the carrier being a modified molecular sieve, the active component comprising an active promoter, an aluminum salt or a zirconium salt, and the active promoter being at least one of phosphomolybdic acid and phosphotungstic acid;

[0008] The preparation method of the modified molecular sieve comprises the following steps:

[0009] At 350-450°C, the molecular sieve is sintered at a constant temperature for 3-5 hours, cooled, dispersed in a solvent, and aminosilane is added and mixed evenly. At 50-70°C, the reaction is condensed and refluxed for 4-6 hours, cooled, solid-liquid separated, washed, and dried to obtain a modified molecular sieve.

[0010] By adopting the above technical scheme, first, after the molecular sieve is sintered at a constant temperature, the moisture and other impurities adsorbed in the molecular sieve pores can be removed, which helps to improve the adsorption performance and catalytic activity of the molecular sieve, and can also improve the dispersion and stability of the molecular sieve. On the one hand, the stability and mechanical strength of the modified molecular sieve can protect the active ingredients loaded thereon, reduce its loss during the reaction process, thereby maintaining the physical form of the catalyst stable, and can also be separated from the reaction system by simple filtering or centrifugation, which is convenient for the recycling of the catalyst. On the other hand, the active ingredient is effectively fixed on the modified molecular sieve, and the high specific surface area and uniform pore size distribution of the modified molecular sieve are conducive to the high dispersion of the active ingredient, thereby reducing the possibility of clogging while maintaining the activity and selectivity of the catalyst, and can also be more fully contacted with the reactant, thereby improving the yield and whiteness of decabromodiphenylethane.

[0011] Secondly, the active agent and aluminum salt or zirconium salt can be loaded on the molecular sieve at the same time to produce a synergistic effect and improve the performance of the loaded catalyst. The active agent and the active center of the aluminum salt or zirconium salt can form a more stable complex, which not only provides a large number of acid sites for the reaction, but also makes the loaded catalyst show stronger Lewis acidity, enhances the catalytic activity and stability of the loaded catalyst, and has a strong adsorption and activation effect on bromine molecules and diphenylethane, increases the local concentration of bromine molecules and diphenylethane in the reaction system, and makes bromine and diphenylethane have a higher collision probability, thereby increasing the yield of the finished decabromodiphenylethane. In addition, the active agent can also provide "quasi-liquid phase" behavior, so that bromine molecules and diphenylethane can enter its bulk phase and diffuse rapidly therein, increase the contact opportunities and reaction areas between the reactants and the catalytic active sites, make the reaction more sufficient and efficient, and further improve the yield of the finished decabromodiphenylethane.

[0012] Finally, the active auxiliary in the supported catalyst can, on the one hand, catalyze the oxidation or adsorb some impurities in the reaction system; on the other hand, the active auxiliary has a certain selectivity in the reaction of bromine and diphenylethane, and can preferentially catalyze the electrophilic substitution reaction of bromine and diphenylethane, while reducing other unnecessary reactions, reducing the generation of impurities, and improving the yield and purity of the finished decabromodiphenylethane, so that the synthesized decabromodiphenylethane has better quality and performance.

[0013] Preferably, the aminosilane is at least one of γ-aminopropyltrimethoxysilane and bis(ethylamino)dimethylsilane.

[0014] By adopting the above technical solution, firstly, the aminosilane used usually has one or more amino groups, which can interact with the active sites on the surface of the molecular sieve, and the other part of the aminosilane can react or adsorb with the surface of the active ingredient, thereby realizing the effective connection between the molecular sieve and the active ingredient. This connection not only enhances the interaction between the molecular sieve and the active ingredient, but also helps to improve the efficiency and selectivity of the catalytic reaction. In addition, the use of aminosilane not only increases the specific surface area of ​​the molecular sieve, but also helps to control the distribution of the active ingredient on the molecular sieve, reduce the agglomeration phenomenon between the active ingredient molecules, and further optimize the catalytic process.

[0015] Secondly, the amino group can interact with the active ingredients, increasing the electron cloud density of the active center of the supported catalyst, thereby enhancing the activation ability of the supported catalyst for bromine and diphenylethane, thereby improving the reaction activity, allowing the reaction to proceed under milder conditions, and also increasing the reaction rate and yield. At the same time, the amino group interacts with the active ingredients, which can better enhance the structural stability of the supported catalyst, reduce the loss of active ingredients during the reaction process, and thus increase the service life of the supported catalyst.

[0016] Preferably, the preparation method of the modified molecular sieve comprises the following steps:

[0017] At 350-450°C, the molecular sieve is sintered at a constant temperature for 3-5 hours, cooled, dispersed in a solvent, and aminosilane containing a carbon-carbon double bond is added and mixed evenly. At 50-70°C, the reaction is condensed and refluxed for 4-6 hours, cooled, solid-liquid separated, washed, dispersed in a solvent again, heated to 60-80°C, olefin sulfonic acid and an initiator are added, reacted for 2-4 hours, cooled, solid-liquid separated, washed, and dried to obtain a modified molecular sieve.

[0018] Preferably, the molar number of the olefin sulfonic acid is not greater than the molar number of the aminosilane containing a carbon-carbon double bond.

[0019] Preferably, the olefin sulfonic acid is vinyl sulfonic acid.

[0020] Preferably, the aminosilane is dimethyldimethylaminovinylsilane.

[0021] Preferably, the mass ratio of the vinyl sulfonic acid, dimethyldimethylaminovinylsilane and molecular sieve is 1-2:3:20.

[0022] Preferably, the molar number of the olefin sulfonic acid is not greater than the molar number of the aminosilane containing a carbon-carbon double bond.

[0023] By adopting the above technical scheme, after a small amount of polymer is grafted on the surface of the molecular sieve by monomer A, a polymer-coated molecular sieve microsphere structure is formed. On the one hand, the polymer coating layer can protect the internal molecular sieve from interference from the external environment, so that the active ingredient has long-term stability and catalytic activity, and the reuse rate of the supported catalyst is improved. On the other hand, after the molecular sieve is grafted with polyethylene sulfonic acid, the acid sites of the supported catalyst are increased and the reaction activity is enhanced, which not only stabilizes the reaction intermediates, but also enhances the adsorption performance of the supported catalyst, improves the contact probability of diphenylethane and bromine, and improves the reaction efficiency and rate. In addition, usually, the electrophilic substitution reaction on the benzene ring is more likely to occur in the para and ortho positions with higher electron cloud density, and a certain amount of polyethylene sulfonic acid is grafted on the molecular sieve, which will form a certain spatial structure in the pores or surfaces of the molecule, making the meta position relatively easy to be exposed to bromine to a certain extent, which helps the occurrence of the meta substitution reaction, thereby improving the yield and purity of the finished product decabromodiphenylethane.

[0024] Preferably, the method for preparing the supported catalyst comprises the following steps:

[0025] S1: Evenly mix the active agent, aluminum salt or zirconium salt and water, and adjust the pH to 4.0-6.0 to obtain an impregnation solution;

[0026] S2: Evenly mix the modified molecular sieve and the impregnation liquid, take out after impregnation for 12 to 24 hours, and dry to obtain a supported catalyst.

[0027] Preferably, the concentration of the active agent in the impregnation solution is 0.06-0.1 mol / L, the concentration of the aluminum salt or zirconium salt in the impregnation solution is 0.75-0.15 mol / L, and the ratio of the modified molecular sieve to the impregnation solution is 1 g: 0.8-1 ml.

[0028] By adopting the above technical solution, phosphomolybdic acid, aluminum salt or zirconium salt are evenly mixed, and the pH value is adjusted, so that the active additive and aluminum salt or zirconium salt in the impregnation solution can form a stable complex, which can enhance the stability and catalytic activity of the active ingredient. After mixed and impregnated with the modified molecular sieve, the components of the active ingredient can be loaded on the modified molecular sieve together, thereby improving the catalytic activity and selectivity of the loaded catalyst.

[0029] The present invention also provides a preparation process of high-whiteness decabromodiphenylethane, comprising the following steps:

[0030] S11 Bromination: Bromine and the above-mentioned supported catalyst are mixed evenly, molten diphenylethane is added and mixed evenly, the temperature is adjusted to 40-60°C, the temperature is kept for 3-5 hours, the temperature is lowered, and the solid-liquid separation is performed to obtain a pretreated brominated material;

[0031] S12 bromine distillation: the pretreated bromide material is mixed evenly with water, the temperature is raised to 80-100°C, the distilled bromine is recovered, the temperature is lowered, and the pretreated material is obtained;

[0032] S13 post-treatment: washing the pre-treated material, separating the solid and the liquid to obtain a crude product; mixing the crude product with an auxiliary agent, grinding, washing, drying, and air flow crushing to obtain high-whiteness decabromodiphenylethane;

[0033] The mass ratio of bromine to diphenylethane is 15-24:1;

[0034] The auxiliary agent is at least one of a sodium bicarbonate aqueous solution and a sodium sulfite aqueous solution.

[0035] Preferably, in step S12, in the bromine distillation, water and mixed acid are mixed evenly, the pH value is adjusted to 4-4.5, and then mixed evenly with the pretreated material, and the pH value is adjusted to 4-4.5, the temperature is raised to 80-100° C., the distilled bromine is recovered, and the temperature is lowered to obtain the pretreated material.

[0036] Preferably, the molar concentration of dilute hydrochloric acid in the mixed acid is 0.005-0.01 mol / L, and the molar concentration of tartaric acid is 0.01-0.03 mol / L.

[0037] In summary, the present invention includes at least one of the following beneficial technical effects:

[0038] 1. The supported catalyst of the present invention adopts a modified molecular sieve as a carrier, which not only improves the binding force and dispersion of the molecular sieve and the active ingredient, and reduces the dosage, but also provides an effective surface and a suitable pore structure, which can effectively carry the active component and enhance the mechanical strength of the catalyst. At the same time, its unique pore structure is conducive to the transmission of reactants and reduces the occurrence of blockage problems. Active additives and aluminum salts or zirconium salts are used to compound active ingredients. The active additives can enhance the Lewis acidity of aluminum salts or zirconium salts, making them more likely to accept electrons, thereby improving the electrophilicity of electrophilic reagents. At the same time, aluminum salts or zirconium salts can promote the dispersion and stability of active additives in the reaction system, so that the catalytic active center can be more effectively exerted. The effects of the two are mutually synergistic and complementary, and can more effectively catalyze the reaction of bromine and diphenylethane, significantly improve the reaction rate and conversion rate, and make the final decabromodiphenylethane higher in purity.

[0039] 2. The supported catalyst of the present invention adopts a modified molecular sieve as a carrier, and by introducing amino groups and polyolefin sulfonic acid into the modified molecular sieve, on the one hand, through its specific quasi-coating core-shell structure, the protective function of the catalytic active center core is given, the stability and catalytic activity of the supported catalyst are prolonged, and the reuse rate of the supported catalyst is improved. On the other hand, it can produce a strong adsorption and activation effect on bromine molecules and diphenylethane, enhance the local concentration of bromine molecular sieve in the reaction system, and increase the collision probability of bromine molecules and diphenylethane, thereby improving the reaction rate and yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 The XRD patterns of the modified molecular sieve in Preparation Example 1 and the supported catalyst in Example 1 are shown in FIG. DETAILED DESCRIPTION

[0041] The present invention is further described in detail below with reference to the embodiments.

[0042] In the following examples and preparations:

[0043] The main component of molecular sieve is porous aluminosilicate, which is composed of repeated SiO 4 and AlO 4 It is composed of tetrahedral units and was purchased from Zibo Yinghe Chemical Co., Ltd. It is spherical, with a particle size distribution of 1.5~1.7mm and a pore size of 2~50nm. The static adsorption accounts for about 20.5% of the molecular sieve mass.

[0044] γ-Aminopropyltrimethoxysilane was purchased from Henan Dazheng Chemical Products Co., Ltd.;

[0045] Bis(ethylamino)dimethylsilane was purchased from Zhengzhou Lingfang Chemical Co., Ltd.;

[0046] Dimethyldimethylaminovinylsilane was purchased from Shanghai Baishun Biotechnology Co., Ltd.;

[0047] Propyltrimethoxysilane was purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd.

[0048] Preparation Examples 1-5 Modification of Molecular Sieve

[0049] Preparation Example 1

[0050] 110g molecular sieve was placed in a muffle furnace and sintered at a constant temperature of 350°C for 5h. After cooling to room temperature, 100g molecular sieve was weighed and dispersed in 500ml toluene, and then added into 500ml γ-aminopropyltrimethoxysilane solution. A magnetic rod was used to stir and mix evenly. The stirring frequency was 300rpm. The reaction was condensed and refluxed at 70°C for 4h. The temperature was controlled by a constant temperature magnetic rod stirrer. After cooling, it was filtered with a suction filter and washed with anhydrous ethanol 3 times. The washed molecular sieve was dried in a vacuum drying oven at 100°C for 1h to obtain a modified molecular sieve.

[0051] The solvent used in the γ-aminopropyltrimethoxysilane solution is toluene, and the concentration of γ-aminopropyltrimethoxysilane is 10 g / 500 ml.

[0052] Preparation Example 2

[0053] 110g molecular sieve was placed in a muffle furnace and sintered at a constant temperature of 450°C for 3h. After cooling to room temperature, 100g molecular sieve was weighed and dispersed in 500ml toluene, and then added into 500ml bis(ethylamino)dimethylsilane solution. A magnetic rod was used to stir and mix evenly. The stirring frequency was 300rpm. The reaction was condensed and refluxed at 50°C for 6h. The temperature was controlled by a constant temperature magnetic rod stirrer. After cooling, it was filtered with a suction machine and washed with anhydrous ethanol 3 times. The washed molecular sieve was dried in a vacuum drying oven at 100°C for 1h to obtain a modified molecular sieve.

[0054] The solvent used in the bis(ethylamino)dimethylsilane solution is toluene, and the concentration of bis(ethylamino)dimethylsilane is 10 g / 500 ml.

[0055] Preparation Example 3

[0056] 110g molecular sieve was placed in a muffle furnace and sintered at a constant temperature of 350°C for 5h. After cooling to room temperature, 100g ZMS-5 molecular sieve was weighed and dispersed in 500ml toluene, and then added to 500ml dimethyldimethylaminovinylsilane solution. A magnetic bar was used to stir and mix evenly in the experiment. The stirring frequency was 300rpm. Condensation reflux reaction was carried out at 70°C for 5h. The temperature was controlled by a constant temperature magnetic bar stirrer in the experiment. After cooling, it was filtered with a suction filter and washed with anhydrous ethanol 3 times. The washed molecular sieve was dispersed in 100ml toluene, heated to 70°C, and 5.4g vinyl sulfonic acid was slowly added dropwise. The reaction temperature was controlled at 60°C, and then ammonium persulfate was added dropwise. The reaction was carried out for 4h. After cooling, it was filtered with a suction filter and washed with anhydrous ethanol 3 times. It was placed in a vacuum drying oven at 100°C for 1h to obtain a modified molecular sieve.

[0057] The amount of ammonium persulfate used is 0.5% of the total mass of dimethyldimethylaminovinylsilane and vinyl sulfonic acid; the solvent used in the dimethyldimethylaminovinylsilane solution is toluene, and the concentration of dimethyldimethylaminovinylsilane is 15g / 500ml.

[0058] Preparation Example 4

[0059] The difference between this Preparation Example and Preparation Example 3 is that the amount of vinyl sulfonic acid used is 8.1 g.

[0060] The rest is the same as Preparation Example 3.

[0061] Preparation Example 5

[0062] The difference between this Preparation Example and Preparation Example 3 is that the amount of vinyl sulfonic acid used is 10.8 g.

[0063] The rest is the same as Preparation Example 3.

[0064] Comparative Preparation Example 1

[0065] 110g of molecular sieve was placed in a muffle furnace and sintered at a constant temperature of 350°C for 5h. After cooling to room temperature, 100g of molecular sieve was weighed and dispersed in 500ml of toluene, and then added to 500ml of propyltrimethoxysilane solution. A magnetic rod was used to stir and mix evenly. The stirring frequency was 300rpm. The reaction was condensed and refluxed at 70°C for 4h. The temperature was controlled by a constant temperature magnetic rod stirrer in the experiment. After cooling, it was filtered with a suction machine and washed with anhydrous ethanol 3 times. The washed molecular sieve was dried in a vacuum drying oven at 100°C for 1h to obtain a modified molecular sieve.

[0066] The solvent used in the propyltrimethoxysilane solution is toluene, and the concentration of propyltrimethoxysilane is 10 g / 500 ml.

[0067] Comparative Preparation Example 2

[0068] 110 g of molecular sieve was placed in a muffle furnace and sintered at a constant temperature of 350° C. for 5 h. After cooling to room temperature, a modified molecular sieve was obtained.

[0069] The embodiments of the supported catalyst for producing high whiteness decabromodiphenylethane of the present invention are as follows:

[0070] Example 1

[0071] This embodiment provides a supported catalyst for the production of high-whiteness decabromodiphenylethane, comprising a carrier and an active component, wherein the carrier is a modified molecular sieve, and the active component comprises phosphomolybdic acid and aluminum chloride.

[0072] This embodiment also provides a method for preparing the above-mentioned supported catalyst, comprising the following steps:

[0073] S1: adding phosphomolybdic acid and aluminum chloride into deionized water to dissolve, and then dropping a 12% sodium bicarbonate aqueous solution to adjust the pH value to 4.0 to obtain an impregnation solution, wherein the concentration of phosphomolybdic acid is 0.06 mol / L, and the concentration of aluminum chloride is 0.75 mol / L;

[0074] S2: Weigh 100 ml of the impregnation solution, put it into an impregnation tank, heat it to 40°C, put 100 g of the modified molecular sieve into the impregnation tank, introduce appropriate air for bubbling, take it out after impregnation for 12 hours, and dry it in air at 110°C for 5 hours to obtain a supported catalyst.

[0075] The modified molecular sieve is the modified molecular sieve obtained in Preparation Example 1.

[0076] Depend on Figure 1 It can be seen that, first, after the modified molecular sieve is loaded with phosphomolybdic acid and aluminum chloride, the diffraction peak shows a phenomenon of shifting to a low angle direction. This is mainly attributed to the fact that phosphomolybdic acid and aluminum chloride have successfully entered the pores of the molecular sieve, or interacted with the surface of the molecular sieve. This interaction causes the lattice of the molecular sieve to expand to a certain extent, the interplanar spacing increases, and the diffraction angle decreases.

[0077] Second, it can be clearly seen from the figure that the intensity of the diffraction peak has increased. This is because phosphomolybdic acid forms a relatively uniform loading layer on the molecular sieve, and this uniform loading improves the overall crystallinity. When the crystallinity increases, the structure of the crystal is more regular, and the diffraction ability of X-rays is enhanced, so that the intensity of the corresponding diffraction peak is significantly enhanced. This change shows that during the loading process, a relatively stable and ordered structure is formed between phosphomolybdic acid and aluminum chloride and the modified molecular sieve.

[0078] This embodiment also provides a preparation process of high-whiteness decabromodiphenylethane, comprising the following steps:

[0079] S11 bromination: 50g of diphenylethane was placed in a dropping kettle, heated to 60°C, melted for later use, 750g of bromine and 20g of the above-mentioned supported catalyst were added to the reactor, and stirred and mixed evenly; while continuing to stir, diphenylethane was added dropwise to the reactor for 1h. During the dropping process, the temperature in the reactor was controlled at 18°C ​​and the pressure was controlled at -0.035MPa. After the dropping was completed, the temperature was raised to 40°C, kept warm for 5h, cooled to room temperature, and the supported catalyst was filtered out using a sieve to obtain a pretreated brominated material;

[0080] S12 bromine distillation: after transferring the pretreated brominated material to a distillation kettle, add deionized water twice the mass of the pretreated brominated material into the distillation kettle, start stirring, heat to 80°C, heat to recover evaporated bromine, and cool to room temperature to obtain a pretreated material;

[0081] S13 post-treatment: transfer the pretreated material to a rinsing tank, add 1 times the amount of water of the pretreated material, and while stirring, put the pretreated material into a filter press, wash with water until the material is neutral, and filter to obtain a crude product; transfer the crude product to a ball mill, add 0.5 times the amount of water of the crude product, stir and mix evenly, add 2% of the crude product mass of sodium bicarbonate aqueous solution and 1.5% of the crude product mass of sodium sulfite aqueous solution, ball mill for 5 hours at 40°C, transfer the ball-milled material to a storage tank, filter press again, put the filtered and dried material into a dryer for vacuum drying, and the dried decabromodiphenylethane is heated to 150 ℃ at an air flow rate of 15 m / s. 3 / min, the finished product of high-whiteness decabromodiphenylethane is crushed.

[0082] Among them, the mass fraction of sodium bicarbonate in the sodium bicarbonate aqueous solution is 12%, and the mass fraction of sodium sulfite in the sodium sulfite aqueous solution is 10%.

[0083] Example 2

[0084] The difference between this embodiment and embodiment 1 is that the modified molecular sieve used is the modified molecular sieve obtained in preparation example 2.

[0085] The rest is the same as in Example 1.

[0086] Example 3

[0087] The difference between this embodiment and embodiment 1 is that the modified molecular sieve used is the modified molecular sieve obtained in preparation example 3.

[0088] The rest is the same as in Example 1.

[0089] Example 4

[0090] The difference between this embodiment and embodiment 1 is that the modified molecular sieve used is the modified molecular sieve obtained in preparation example 4.

[0091] The rest is the same as in Example 1.

[0092] Example 5

[0093] The difference between this embodiment and embodiment 1 is that the modified molecular sieve used is the modified molecular sieve obtained in preparation example 5.

[0094] The rest is the same as in Example 1.

[0095] Example 6

[0096] This embodiment provides a supported catalyst for producing high-whiteness decabromodiphenylethane, comprising a carrier and an active component, wherein the carrier is a modified molecular sieve, and the active component comprises phosphomolybdic acid and zirconium chloride.

[0097] This embodiment also provides a method for preparing the above-mentioned supported catalyst, comprising the following steps:

[0098] S1: adding phosphomolybdic acid and zirconium chloride into deionized water to dissolve, and then dropping a 12% sodium bicarbonate aqueous solution to adjust the pH value to 4.0 to obtain an impregnation solution, wherein the concentration of phosphomolybdic acid is 0.06 mol / L, and the concentration of zirconium chloride is 0.1 mol / L;

[0099] S2: Weigh 100 ml of the impregnation solution, put it into an impregnation tank, heat it to 40°C, put 100 g of the modified molecular sieve into the impregnation tank, introduce appropriate air for bubbling, take it out after impregnation for 12 hours, and dry it in air at 110°C for 5 hours to obtain a supported catalyst.

[0100] The modified molecular sieve used is the modified molecular sieve obtained in Preparation Example 4.

[0101] This embodiment also provides a preparation process of high-whiteness decabromodiphenylethane, comprising the following steps:

[0102] S11 bromination: 50g of diphenylethane was placed in a dropping kettle, heated to 60°C, melted for later use, 750g of bromine and 20g of the above-mentioned supported catalyst were added to the reactor, and stirred and mixed evenly; while continuing to stir, diphenylethane was added dropwise to the reactor for 1h. During the dropping process, the temperature in the reactor was controlled at 40°C and the pressure was controlled at -0.035MPa. After the dropping was completed, the temperature was raised to 60°C, kept warm for 5h, cooled to room temperature, and the supported catalyst was filtered out using a sieve to obtain a pretreated brominated material;

[0103] S12 bromine distillation: after transferring the pretreated brominated material to a distillation kettle, add deionized water twice the mass of the pretreated brominated material into the distillation kettle, start stirring, heat to 90°C, heat to recover evaporated bromine, and cool to room temperature to obtain a pretreated material;

[0104] S13 post-treatment: transfer the pretreated material to a rinsing tank, add 1 times the amount of water of the pretreated material, and while stirring, put the pretreated material into a filter press, wash with water until the material is neutral, and filter to obtain a crude product; transfer the crude product to a ball mill, add 0.5 times the amount of water of the crude product, stir and mix evenly, add 2% of the crude product mass of sodium bicarbonate aqueous solution and 1.5% of the crude product mass of sodium sulfite aqueous solution, ball mill for 5 hours at 40°C, transfer the ball-milled material to a storage tank, filter press again, put the filtered and dried material into a dryer for vacuum drying, and the dried decabromodiphenylethane is heated to 150 ℃ at an air flow rate of 15 m / s. 3 / min, the finished product of high-whiteness decabromodiphenylethane is crushed.

[0105] Wherein, the mixed acid is an aqueous solution of dilute hydrochloric acid and tartaric acid, wherein the molar concentration of the dilute hydrochloric acid is 0.01 mol / L, and the molar concentration of the tartaric acid is 0.02 mol / L;

[0106] The mass fraction of sodium bicarbonate in the sodium bicarbonate aqueous solution is 12%, and the mass fraction of sodium sulfite in the sodium sulfite aqueous solution is 10%.

[0107] Example 7

[0108] This embodiment provides a supported catalyst for producing high-whiteness decabromodiphenylethane, comprising a carrier and an active component, wherein the carrier is a modified molecular sieve, and the active component comprises phosphotungstic acid and aluminum chloride.

[0109] This embodiment also provides a method for preparing the above-mentioned supported catalyst, comprising the following steps:

[0110] S1: adding phosphotungstic acid and aluminum chloride to deionized water to dissolve, then dropping a 12% sodium bicarbonate aqueous solution to adjust the pH value to 4.0 to obtain an impregnation solution, wherein the concentration of phosphotungstic acid is 0.08 mol / L, and the concentration of aluminum chloride is 0.75 mol / L;

[0111] S2: Weigh 100 ml of the impregnation liquid, put it into an impregnation tank, heat it to 40°C, put 100 g of the modified molecular sieve into the impregnation tank, introduce appropriate air for bubbling, take it out after impregnation for 24 hours, and dry it in air at 110°C for 5 hours to obtain a supported catalyst.

[0112] The modified molecular sieve used is the modified molecular sieve obtained in Preparation Example 4.

[0113] The rest is the same as Example 6.

[0114] Example 8

[0115] The difference between this embodiment and embodiment 7 is that:

[0116] This embodiment provides a supported catalyst for the production of high-whiteness decabromodiphenylethane, comprising a carrier and an active component, wherein the carrier is a modified molecular sieve, and the active component comprises phosphomolybdic acid, phosphotungstic acid, and aluminum chloride.

[0117] This embodiment also provides a method for preparing the above-mentioned supported catalyst, comprising the following steps:

[0118] S1: adding phosphomolybdic acid, phosphotungstic acid and aluminum chloride into deionized water to dissolve, then dropping a 12% sodium bicarbonate aqueous solution to adjust the pH value to 4.5 to obtain an impregnation solution, wherein the concentration of phosphomolybdic acid is 0.06 mol / L, the concentration of phosphotungstic acid is 0.02 mol / L, and the concentration of aluminum chloride is 0.75 mol / L;

[0119] S2: Weigh 100 ml of the impregnation liquid, put it into an impregnation tank, heat it to 40°C, put 100 g of the modified molecular sieve into the impregnation tank, introduce appropriate air for bubbling, take it out after impregnation for 24 hours, and dry it in air at 110°C for 5 hours to obtain a supported catalyst.

[0120] The modified molecular sieve used is the modified molecular sieve obtained in Preparation Example 4.

[0121] The rest is the same as Example 7.

[0122] Example 9

[0123] The difference between this embodiment and embodiment 7 is that:

[0124] This embodiment provides a supported catalyst for the production of high-whiteness decabromodiphenylethane, comprising a carrier and an active component, wherein the carrier is a modified molecular sieve, and the active component comprises phosphomolybdic acid, phosphotungstic acid, and aluminum chloride.

[0125] This embodiment also provides a method for preparing the above-mentioned supported catalyst, comprising the following steps:

[0126] S1: adding phosphomolybdic acid, phosphotungstic acid and aluminum chloride into deionized water to dissolve, then dropping a 12% sodium bicarbonate aqueous solution to adjust the pH value to 4.0, to obtain an impregnation solution, wherein the concentration of phosphomolybdic acid is 0.06 mol / L, the concentration of phosphotungstic acid is 0.04 mol / L, and the concentration of aluminum chloride is 1.5 mol / L;

[0127] S2: Weigh 80 ml of the impregnation solution, put it into an impregnation tank, heat it to 40°C, put 100 g of the modified molecular sieve into the impregnation tank, introduce appropriate air for bubbling, take it out after impregnation for 12 hours, and dry it in air at 110°C for 5 hours to obtain a supported catalyst.

[0128] The modified molecular sieve used is the modified molecular sieve obtained in Preparation Example 4.

[0129] The rest is the same as Example 8.

[0130] Example 10

[0131] This embodiment provides a supported catalyst for the production of high-whiteness decabromodiphenylethane, comprising a carrier and an active component, wherein the carrier is a modified molecular sieve, and the active component comprises phosphomolybdic acid, phosphotungstic acid, and aluminum chloride.

[0132] This embodiment also provides a method for preparing the above-mentioned supported catalyst, comprising the following steps:

[0133] S1: adding phosphomolybdic acid, phosphotungstic acid and aluminum chloride into deionized water to dissolve, then dropping a 12% sodium bicarbonate aqueous solution to adjust the pH value to 4.0, to obtain an impregnation solution, wherein the concentration of phosphomolybdic acid is 0.06 mol / L, the concentration of phosphotungstic acid is 0.04 mol / L, and the concentration of aluminum chloride is 1.5 mol / L;

[0134] S2: Weigh 90 ml of the impregnation solution, put it into an impregnation tank, heat it to 40°C, put 100 g of the modified molecular sieve into the impregnation tank, introduce appropriate air for bubbling, take it out after impregnation for 12 hours, and dry it in air at 110°C for 5 hours to obtain a supported catalyst.

[0135] The modified molecular sieve used is the modified molecular sieve obtained in Preparation Example 4.

[0136] This embodiment also provides a preparation process of high-whiteness decabromodiphenylethane, comprising the following steps:

[0137] S11 bromination: 50g of diphenylethane was placed in a dropping kettle, heated to 60°C, melted for later use, 1000g of bromine and 20g of the above-mentioned supported catalyst were added to the reactor, and stirred and mixed evenly; while continuing to stir, diphenylethane was added dropwise to the reactor for 1h. During the dropping process, the temperature in the reactor was controlled at 30°C and the pressure was controlled at -0.035MPa. After the dropping was completed, the temperature was raised to 50°C, kept warm for 3h, cooled to room temperature, and the supported catalyst was filtered out using a sieve to obtain a pretreated brominated material;

[0138] S12 bromine distillation: after the pre-treated brominated material is transferred to the distillation kettle, deionized water twice the mass of the pre-treated brominated material is added to the distillation kettle, stirring is started, the temperature is raised to 100°C, the evaporated bromine is recovered by heating, and the evaporated bromine is cooled to room temperature to obtain the pre-treated material;

[0139] S13 post-treatment: transfer the pretreated material to a rinsing tank, add 1 times the amount of water of the pretreated material, and while stirring, put the pretreated material into a filter press, wash with water until the material is neutral, filter, and obtain a crude product; transfer the crude product to a ball mill, add 0.5 times the amount of water of the crude product, stir and mix evenly, add 2.5% of the crude product mass of sodium bicarbonate aqueous solution and 2% of the crude product mass of sodium sulfite aqueous solution, ball mill for 5 hours at 40°C, transfer the ball-milled material to a storage tank, filter press again, put the filtered and dried material into a dryer for vacuum drying, and the dried decabromodiphenylethane is heated to 150 ℃ at an air flow rate of 15 m / s. 3 / min, the finished product of high-whiteness decabromodiphenylethane is crushed.

[0140] Among them, the mass fraction of sodium bicarbonate in the sodium bicarbonate aqueous solution is 12%, and the mass fraction of sodium sulfite in the sodium sulfite aqueous solution is 10%.

[0141] The rest is the same as Example 9.

[0142] Embodiment 11

[0143] The difference between this embodiment and embodiment 10 is that:

[0144] This embodiment provides a preparation process of high-whiteness decabromodiphenylethane, comprising the following steps:

[0145] S11 bromination: 50g of diphenylethane was placed in a dropping kettle, heated to 60°C, melted for later use, 1000g of bromine and 25g of the above-mentioned supported catalyst were added to the reactor, and stirred and mixed evenly; while continuing to stir, diphenylethane was added dropwise to the reactor for 1h. During the dropping process, the temperature in the reactor was controlled at 30°C and the pressure was controlled at -0.035MPa. After the dropping was completed, the temperature was raised to 50°C, kept warm for 3h, cooled to room temperature, and the supported catalyst was filtered out using a sieve to obtain a pretreated brominated material;

[0146] S12 bromine distillation: after the pre-treated brominated material is transferred to the distillation kettle, deionized water with a mass twice that of the pre-treated brominated material is mixed with the mixed acid to be evenly adjusted to a mixed solution with a pH value of about 4.5, and then added to the distillation kettle, stirring is started, and the mixed acid is slowly dripped again to adjust the pH value to about 4.5, the temperature is raised to 100°C, the evaporated bromine is recovered by heating, and the pre-treated material is obtained by cooling to room temperature;

[0147] S13 post-treatment: transfer the pretreated material to a rinsing tank, add 1 times the amount of water of the pretreated material, and while stirring, put the pretreated material into a filter press, wash with water until the material is neutral, filter, and obtain a crude product; transfer the crude product to a ball mill, add 0.5 times the amount of water of the crude product, stir and mix evenly, add 2.5% of the crude product mass of sodium bicarbonate aqueous solution and 2% of the crude product mass of sodium sulfite aqueous solution, ball mill for 5 hours at 40°C, transfer the ball-milled material to a storage tank, filter press again, put the filtered and dried material into a dryer for vacuum drying, and the dried decabromodiphenylethane is heated to 150 ℃ at an air flow rate of 15 m / s. 3 / min, the finished product of high-whiteness decabromodiphenylethane is crushed.

[0148] Wherein, the mixed acid is an aqueous solution of dilute hydrochloric acid and tartaric acid, wherein the molar concentration of the dilute hydrochloric acid is 0.005 mol / L, and the molar concentration of the tartaric acid is 0.01 mol / L;

[0149] The mass fraction of sodium bicarbonate in the sodium bicarbonate aqueous solution is 12%, and the mass fraction of sodium sulfite in the sodium sulfite aqueous solution is 10%.

[0150] The rest is the same as Example 10.

[0151] Example 12

[0152] The difference between this embodiment and embodiment 11 is that:

[0153] This embodiment provides a preparation process of high-whiteness decabromodiphenylethane, comprising the following steps:

[0154] S11 bromination: 50g of diphenylethane was placed in a dropping kettle, heated to 60°C, melted for later use, 1200g of bromine and 25g of the above-mentioned supported catalyst were added to the reactor, and stirred and mixed evenly; while continuing to stir, diphenylethane was added dropwise to the reactor for 1h. During the dropping process, the temperature in the reactor was controlled at 30°C and the pressure was controlled at -0.035MPa. After the dropping was completed, the temperature was raised to 50°C, kept warm for 3h, cooled to room temperature, and the supported catalyst was filtered out using a sieve to obtain a pretreated brominated material;

[0155] S12 bromine distillation: after the pre-treated bromine material is transferred to the distillation kettle, deionized water with a mass of 2 times the pre-treated bromine material is mixed with the mixed acid to be evenly adjusted to a mixed solution with a pH value of about 4, and then added to the distillation kettle, stirring is started, and the mixed acid is slowly dripped again to adjust the pH value to about 4, the temperature is raised to 100°C, the evaporated bromine is recovered by heating, and the pre-treated material is obtained;

[0156] S13 post-treatment: transfer the pretreated material to a rinsing tank, add 1 times the amount of water of the pretreated material, and while stirring, put the pretreated material into a filter press, wash with water until the material is neutral, filter, and obtain a crude product; transfer the crude product to a ball mill, add 0.5 times the amount of water of the crude product, stir and mix evenly, add 2.5% of the crude product mass of sodium bicarbonate aqueous solution and 2% of the crude product mass of sodium sulfite aqueous solution, ball mill for 5 hours at 40°C, transfer the ball-milled material to a storage tank, filter press again, put the filtered and dried material into a dryer for vacuum drying, and the dried decabromodiphenylethane is heated to 150 ℃ at an air flow rate of 15 m / s. 3 / min, the finished product of high-whiteness decabromodiphenylethane is crushed.

[0157] Wherein, the mixed acid is an aqueous solution of dilute hydrochloric acid and tartaric acid, wherein the molar concentration of the dilute hydrochloric acid is 0.01 mol / L, and the molar concentration of the tartaric acid is 0.03 mol / L.

[0158] The mass fraction of sodium bicarbonate in the sodium bicarbonate aqueous solution is 12%, and the mass fraction of sodium sulfite in the sodium sulfite aqueous solution is 10%.

[0159] The rest is the same as Example 11.

[0160] Comparative Example 1

[0161] The difference between this comparative example and Example 1 is:

[0162] This comparative example provides a supported catalyst for producing high-whiteness decabromodiphenylethane, comprising a carrier and an active component, wherein the carrier is a modified molecular sieve, and the active component comprises phosphomolybdic acid and aluminum chloride.

[0163] This comparative example also provides a method for preparing the above-mentioned supported catalyst, comprising the following steps:

[0164] S1: adding phosphomolybdic acid and aluminum chloride into deionized water to dissolve, and then dropping a 12% sodium bicarbonate aqueous solution to adjust the pH value to 4.0 to obtain an impregnation solution, wherein the concentration of phosphomolybdic acid is 0.06 mol / L, and the concentration of aluminum chloride is 0.75 mol / L;

[0165] S2: Weigh 100 ml of the impregnation solution, put it into an impregnation tank, heat it to 40°C, put 100 g of the modified molecular sieve into the impregnation tank, introduce appropriate air for bubbling, take it out after impregnation for 12 hours, and dry it in air at 110°C for 5 hours to obtain a supported catalyst.

[0166] The modified molecular sieve used is the modified molecular sieve obtained in Comparative Preparation Example 1.

[0167] The rest is the same as in Example 1.

[0168] Comparative Example 2

[0169] The difference between this comparative example and Example 1 is:

[0170] This comparative example provides a supported catalyst for producing high-whiteness decabromodiphenylethane, comprising a carrier and an active component, wherein the carrier is a modified molecular sieve, and the active component comprises phosphomolybdic acid and aluminum chloride.

[0171] This comparative example also provides a method for preparing the above-mentioned supported catalyst, comprising the following steps:

[0172] S1: adding phosphomolybdic acid and aluminum chloride into deionized water to dissolve, and then dropping a 12% sodium bicarbonate aqueous solution to adjust the pH value to 4.0 to obtain an impregnation solution, wherein the concentration of phosphomolybdic acid is 0.06 mol / L, and the concentration of aluminum chloride is 0.75 mol / L;

[0173] S2: Weigh 100 ml of the impregnation solution, put it into an impregnation tank, heat it to 40°C, put 100 g of the modified molecular sieve into the impregnation tank, introduce appropriate air for bubbling, take it out after impregnation for 12 hours, and dry it in air at 110°C for 5 hours to obtain a supported catalyst.

[0174] The modified molecular sieve used is the modified molecular sieve obtained in Comparative Preparation Example 2.

[0175] The rest is the same as in Example 1.

[0176] Comparative Example 3

[0177] The difference between this comparative example and Example 1 is:

[0178] This comparative example provides a supported catalyst for producing high-whiteness decabromodiphenylethane, comprising a carrier and an active component, wherein the carrier is a modified molecular sieve and the active component comprises aluminum chloride.

[0179] This comparative example also provides a method for preparing the above-mentioned supported catalyst, comprising the following steps:

[0180] S1: adding aluminum chloride to deionized water to dissolve, then dropping a 12% by mass sodium bicarbonate aqueous solution to adjust the pH value to 4.0 to obtain an impregnation solution, wherein the concentration of aluminum chloride is 1.5 mol / L;

[0181] S2: Weigh 100 ml of the impregnation solution, put it into an impregnation tank, heat it to 40°C, put 100 g of the modified molecular sieve into the impregnation tank, introduce appropriate air for bubbling, take it out after impregnation for 12 hours, and dry it in air at 110°C for 5 hours to obtain a supported catalyst.

[0182] The modified molecular sieve is the modified molecular sieve obtained in Preparation Example 1.

[0183] The rest is the same as in Example 1.

[0184] Performance Testing

[0185] Various parameters of the finished decabromodiphenylethane obtained in Examples 1 to 12 and Comparative Examples 1 to 3 were tested, and the results are shown in Table 1, wherein the whiteness stability is determined by treating the finished decabromodiphenylethane at 250° C. for 3 hours and then retesting the whiteness.

[0186] Table 1 Performance indicators of the finished decabromodiphenylethane obtained in Examples 1 to 12 and Comparative Examples 1 to 3

[0187]

[0188] Comprehensive analysis of the performance test data of the finished decabromodiphenylethane obtained in Examples 1 to 10 shows that the whiteness of the finished decabromodiphenylethane is not less than 95.6%, the thermal stability of the whiteness is not less than 91.0%, the 1% thermal weight loss is not less than 363°C, and the initial melting point is not less than 344°C.

[0189] Comparative analysis of the performance test data of the finished decabromodiphenylethane obtained in Example 1 and Comparative Examples 1 to 3 shows that:

[0190] The comprehensive performance of the finished decabromodiphenylethane obtained in Example 1 is improved to a certain extent compared with the finished decabromodiphenylethane obtained in Comparative Examples 1 to 3. This is because: by modifying the molecular sieve with aminosilane and introducing the active auxiliary agent phosphomolybdic acid, the supported catalyst can have a strong adsorption and activation effect on the bromine molecules and diphenylethane, and has more reaction paths and selectivity in the catalytic reaction of bromine and diphenylethane. It can also form a specific complex with the reaction intermediate, stabilize the transition state in the reaction process, guide the reaction in a specific direction, improve the selectivity of the reaction, and make the generated decabromodiphenylethane higher in purity and less in by-products.

[0191] In addition, phosphomolybdic acid and aluminum chloride are loaded on the molecular sieve together, which can improve the thermal stability of the catalyst on the one hand. During the reaction, the loaded catalyst can maintain good activity and stability, which is conducive to improving the reaction rate and the yield of decabromodiphenylethane. On the other hand, phosphomolybdic acid and aluminum chloride can form a relatively stable composite structure, which can also reduce the loss and deactivation of the catalyst, making the loaded catalyst more reusable and reducing the production cost.

[0192] Comparative analysis of the performance test data of the finished decabromodiphenylethane obtained in Examples 1 to 5 shows that: first, after the molecular sieve is modified by diaminosilane, it can form more interactions with the active ingredients and active additives, making the selectivity of the generated decabromodiphenylethane higher and reducing the generation of by-products, thereby further improving the purity of decabromodiphenylethane.

[0193] Secondly, after the molecular sieve is modified with vinyl sulfonic acid and aminosilane containing carbon-carbon double bonds, the activation energy of the reaction can be further reduced, and the molecular sieve can have a specific pore structure and surface properties, which makes the reaction more inclined to produce decabromodiphenylethane, reduces excessive bromination or insufficient bromination, thereby improving the purity of the product. At the same time, during the reaction process, the molecular sieve with this structure may also affect the molecular structure and aggregation state of decabromodiphenylethane, thereby improving its thermal stability.

[0194] Comparative analysis of the performance test data of the finished decabromodiphenylethane obtained in Example 4 and Examples 6 to 10 shows that the acid sites of the three substances cooperate with each other to produce a certain synergistic effect, which greatly improves the activity of the reaction system, thereby improving the reaction rate and yield.

[0195] After the three substances are compounded, compared with the compounding of phosphomolybdic acid and aluminum chloride alone, the catalyst has higher thermal stability, which enables it to maintain good catalytic activity during the reaction, improves the efficiency and yield of the reaction, extends the life of the catalyst, and reduces production costs. In addition, during the production process, it was also found that after the three substances are compounded, the particle size of the reaction product is more uniform and the shape is more regular. In the subsequent processing process, the product is easier to separate from impurities, which improves the purity and whiteness of the product.

[0196] Comparative analysis of the performance test data of the finished decabromodiphenylethane obtained in Examples 10 to 12 shows that the free bromine content of the finished decabromodiphenylethane obtained in Examples 11 to 12 is lower than that of the finished decabromodiphenylethane obtained in Example 10, and the yield and purity are improved to a certain extent. This is because the addition of a low concentration of mixed acid in the bromine distillation stage can more thoroughly recover bromine, reduce the residual bromine in decabromodiphenylethane, and remove some impurities that are more closely combined with decabromodiphenylethane, so that the loss of decabromodiphenylethane in the subsequent treatment is relatively small, and the purity and yield of bromodiphenylethane are improved to a certain extent.

[0197] At the same time, although the reaction proceeds relatively slowly in a weak acid environment, it will affect the molecular structure of decabromodiphenylethane to a certain extent, resulting in a decrease in the thermal stability and initial melting point of decabromodiphenylethane during thermal decomposition.

Claims

1. A supported catalyst for the production of high-whiteness decabromodiphenylethane, characterized in that: The supported catalyst comprises a carrier and an active component, wherein the carrier is a modified molecular sieve, the active component comprises an active promoter, an aluminum salt or a zirconium salt, and the active promoter is at least one of phosphomolybdic acid and phosphotungstic acid; The preparation method of the modified molecular sieve comprises the following steps: At 350-450°C, the molecular sieve is sintered at a constant temperature for 3-5 hours, cooled, dispersed in a solvent, and aminosilane is added and mixed evenly. At 50-70°C, the reaction is condensed and refluxed for 4-6 hours, cooled, solid-liquid separated, washed, and dried to obtain a modified molecular sieve.

2. The supported catalyst for producing high-whiteness decabromodiphenylethane according to claim 1, characterized in that: The aminosilane is at least one of γ-aminopropyltrimethoxysilane and bis(ethylamino)dimethylsilane.

3. The supported catalyst for producing high-whiteness decabromodiphenylethane according to claim 1, characterized in that: The preparation method of the modified molecular sieve also includes the following steps: At 350-450°C, the molecular sieve is sintered at a constant temperature for 3-5 hours, cooled, dispersed in a solvent, and aminosilane containing a carbon-carbon double bond is added and mixed evenly. At 50-70°C, the reaction is condensed and refluxed for 4-6 hours, cooled, solid-liquid separated, washed, dispersed in a solvent again, heated to 60-80°C, olefin sulfonic acid and an initiator are added, reacted for 2-4 hours, cooled, solid-liquid separated, washed, and dried to obtain a modified molecular sieve.

4. The supported catalyst for producing high-whiteness decabromodiphenylethane according to claim 3, characterized in that: The aminosilane is dimethyldimethylaminovinylsilane.

5. The supported catalyst for producing high-whiteness decabromodiphenylethane according to claim 4, characterized in that: The alkenyl sulfonic acid is vinyl sulfonic acid.

6. The supported catalyst for producing high-whiteness decabromodiphenylethane according to claim 2 or 5, characterized in that: The method for preparing the supported catalyst comprises the following steps: S1: Evenly mix phosphomolybdic acid, aluminum salt or zirconium salt with water, and adjust the pH to 4.0-4.5 to obtain an impregnation solution; S2: Evenly mix the modified molecular sieve and the impregnation liquid, take out after impregnation for 12 to 24 hours, and dry to obtain a supported catalyst.

7. The supported catalyst for producing high-whiteness decabromodiphenylethane according to claim 6, characterized in that: The concentration of the active agent in the impregnation solution is 0.06-0.1 mol / L, the concentration of the aluminum salt or zirconium salt in the impregnation solution is 0.75-0.15 mol / L, and the ratio of the modified molecular sieve to the impregnation solution is 1 g: 0.8-1 ml.

8. A process for preparing high whiteness decabromodiphenylethane, characterized in that: The steps include: S11 bromination: bromine and the supported catalyst according to any one of claims 1 to 7 are mixed evenly, molten diphenylethane is added and mixed evenly, the temperature is adjusted to 40 to 60° C., the temperature is kept for 3 to 5 hours, the temperature is lowered, and the solid-liquid separation is performed to obtain a pretreated brominated material; S12 bromine distillation: the pretreated bromination material and water are mixed evenly, the temperature is raised to 80-100°C, the distilled bromine is recovered, the temperature is lowered, and the pretreated material is obtained; S13 post-treatment: washing the pre-treated material, separating the solid and the liquid to obtain a crude product; mixing the crude product with an auxiliary agent, grinding, washing, drying, and air flow crushing to obtain high-whiteness decabromodiphenylethane; The mass ratio of bromine to diphenylethane is 15-24:1; The auxiliary agent is at least one of a sodium bicarbonate aqueous solution and a sodium sulfite aqueous solution.

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