Crystallization method for improving dissolving property of ethylene glycol antimony

Abstract

The invention relates to a crystallization method for improving dissolving property of ethylene glycol antimony, which comprises the following steps: preparing ethylene glycol, antimony oxide and modified activated carbon, reacting for 1-6 hours at 100-150 DEG C under the vacuum degree of 0.09-0.099 MPa, carrying out vacuum rectification separation on a reaction gas phase, and removing the activated carbon through a hyperfine filter; and cooling to 30-35 DEG C by using circulating cooling water, quenching for 3 hours by using cooling water of which the temperature is lower than 20 DEG C, crystallizing, centrifugally removing mother liquor, and drying by using a vacuum vibration bed to obtain an ethylene glycol antimony product. According to the preparation method disclosed by the invention, by accurately controlling reaction conditions and adopting a specific crystallization mode of first slow cooling and then rapid cooling, the crystal structure of the prepared ethylene glycol antimony is more regular, uniform and stable, and the dissolution speed and solubility of the ethylene glycol antimony in an ethylene glycol solution are greatly improved; and the functional effect of the product is optimized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical product preparation, in particular to a crystallization method for improving the solubility of ethylene glycol antimony. BACKGROUND

[0002] Ethylene glycol antimony is a very important catalyst in polyester polycondensation reaction, and its solubility in ethylene glycol solution has a crucial influence on the efficiency and quality of polyester production. Good solubility can ensure uniform dispersion of the catalyst in the reaction system, fully exert the catalytic activity, and thus improve the quality of the polyester product and the production capacity of the production device.

[0003] The existing ethylene glycol antimony is prone to reduce the solubility of the product in order to improve the dissolution speed, and has poor whiteness value and poor performance coordination of the product, which limits the use efficiency of the product. Based on this, the present application further improves it. SUMMARY

[0004] In view of the defects of the prior art, the purpose of the present application is to provide a crystallization method for improving the solubility of ethylene glycol antimony to solve the problems raised in the background art.

[0005] The technical problem solved by the present application adopts the following technical scheme:

[0006] The present application provides a crystallization method for improving the solubility of ethylene glycol antimony, comprising the following steps:

[0007] Prepare ethylene glycol, antimony oxide and modified activated carbon, and react at 100-150℃ under a vacuum degree of 0.09-0.099MPa for 1-6h. The reaction gas phase is separated by vacuum rectification, and the activated carbon is removed by an ultra-fine filter. Then, cool to 30-35℃ using circulating cooling water, and then quench using cooling water with a temperature lower than 20℃. The cooling time is 3 hours, and then crystallize. After centrifugal removal of the mother liquor, vacuum vibration bed drying is performed to obtain the ethylene glycol antimony product.

[0008] Preferably, the temperature of the vacuum vibration bed drying is 60-80℃, and the drying time is 1-2 hours.

[0009] The mass ratio of ethylene glycol, antimony oxide and modified activated carbon is (4-10):1:(0.01-0.02).

[0010] Preferably, the modification method of the modified activated carbon is:

[0011] Heat-treat the activated carbon at 220-230 DEG C for 1h, then cool the heat-treated activated carbon to 50 DEG C at a rate of 2-5 DEG C / min, and keep the temperature; stir the kept activated carbon in a modified liquid which is 3-5 times of the total amount of the activated carbon, after the stirring, filter and dry to obtain the modified activated carbon.

[0012] Preferably, the stirring speed of the stirring modification treatment is 350-400 r / min, and the stirring time is 1h.

[0013] Preferably, the preparation method of the modified liquid is as follows:

[0014] S01: add 3-5 parts of nano-alumina and 2-4 parts of sodium citrate into 5-8 parts of yttrium nitrate solution and stir to obtain a nano-alumina liquid;

[0015] S02: blend titanium dioxide, nano-cellulose and sodium silicate solution according to the weight ratio of (5-8):(3-5):5 to obtain a titanium dioxide modifier, and then add 4-7 parts of the titanium dioxide modifier into 5-8 parts of the nano-alumina liquid and stir to obtain the modified liquid.

[0016] Preferably, the mass fraction of the yttrium nitrate solution is 2-5%, and the mass fraction of the sodium silicate solution is 5-8%.

[0017] Preferably, the stirring speed of the stirring treatment is 350-400 r / min, and the stirring time is 1h.

[0018] Preferably, the antimony oxide is further pretreated, and the specific pretreatment method is as follows:

[0019] S11: add sodium lignosulfonate into deionized water, then add chitosan solution and silane coupling agent, and stir to obtain a modified sodium lignosulfonate liquid;

[0020] S12: preheat the antimony oxide at 55-60 DEG C for 1h, then add into the modified sodium lignosulfonate liquid which is 5-8 times of the total amount of the antimony oxide, and stir to obtain the modified antimony oxide.

[0021] Preferably, the mass fraction of the chitosan solution is 2-5%, and the silane coupling agent is silane coupling agent KH550.

[0022] Preferably, the mass ratio of the sodium lignosulfonate, deionized water, chitosan solution and silane coupling agent is (5-8):(11-13):(3-5):2.

[0023] Compared with the prior art, the present application has the following beneficial effects:

[0024] The application makes the prepared ethylene glycol antimony crystal structure more regular, uniform and stable by precisely controlling the reaction conditions and adopting the specific slow cooling and rapid cooling crystallization mode, greatly improves the dissolution speed and solubility of the ethylene glycol antimony in the ethylene glycol solution, and the modified activated carbon is treated by the activated carbon modification treatment, the functional effect of the product is optimized; the modified liquid is improved by the mutual cooperation of the nano-aluminum oxide liquid and the titanium white powder modifier, the raw materials are optimized by the mutual coordination, and the prepared antimony oxide further improves the solubility in the system, enhances the dissolution speed, solubility and whiteness value of the product, and the performance coordination effect of the product is remarkable. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the application will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all the other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0026] The crystallization method for improving the dissolution performance of ethylene glycol antimony in the embodiment comprises the following steps.

[0027] The ethylene glycol, antimony oxide and modified activated carbon are prepared, reacted at 100-150 DEG C and a vacuum degree of 0.09-0.099 MPa for 1-6 h, the reaction gas phase is separated by vacuum rectification, and the activated carbon is removed by an ultra-fine filter; then the reaction gas phase is cooled to 30-35 DEG C by circulating cooling water, and then rapidly cooled by cooling water with a temperature lower than 20 DEG C, the cooling time is 3 h, crystallization is performed, the mother liquor is removed by centrifugation, and the ethylene glycol antimony product is obtained by vacuum vibration bed drying.

[0028] The temperature of the vacuum vibration bed drying in the embodiment is 60-80 DEG C, and the drying time is 1-2 h.

[0029] The mass ratio of the ethylene glycol, antimony oxide and modified activated carbon is (4-10):1:(0.01-0.02).

[0030] The modification method of the modified activated carbon in the embodiment is as follows.

[0031] The activated carbon is heat treated at 220-230 DEG C for 1 h, then the heat-treated activated carbon is cooled to 50 DEG C at a rate of 2-5 DEG C / min, and is kept warm; the kept warm activated carbon is modified by stirring in a modified liquid with a total amount of 3-5 times of the activated carbon, after the stirring is completed, the modified activated carbon is obtained by suction filtration and drying.

[0032] The stirring speed of the stirring modification treatment in the embodiment is 350-400 r / min, and the stirring time is 1 h.

[0033] The preparation method of the modified liquid of the embodiment is as follows:

[0034] S01: 3-5 parts of nano-alumina, 2-4 parts of sodium citrate are added to 5-8 parts of yttrium nitrate solution to obtain a nano-alumina liquid by stirring;

[0035] S02: titanium white powder, nano-cellulose and sodium silicate solution are uniformly blended according to a weight ratio of (5-8):(3-5):5 to obtain a titanium white powder modifier, 4-7 parts of the titanium white powder modifier is added to 5-8 parts of the nano-alumina liquid for stirring treatment, and the stirring is stopped to obtain a modified liquid.

[0036] The mass fraction of the yttrium nitrate solution of the embodiment is 2-5%; and the mass fraction of the sodium silicate solution is 5-8%.

[0037] The stirring speed of the stirring treatment of the embodiment is 350-400 r / min, and the stirring time is 1 h.

[0038] The antimony oxide of the embodiment is also pretreated, and the specific pretreatment method is as follows:

[0039] S11: sodium lignosulfonate is added to deionized water, and then chitosan solution and silane coupling agent are added, and the mixture is stirred uniformly to obtain a modified sodium lignosulfonate liquid;

[0040] S12: The antimony oxide is preheated at 55-60℃ for 1 h, and then added to the modified sodium lignosulfonate liquid with 5-8 times the total amount of the antimony oxide, and stirred sufficiently, washed with water, filtered and dried.

[0041] The mass fraction of the chitosan solution of the embodiment is 2-5%; and the silane coupling agent is silane coupling agent KH550.

[0042] The mass ratio of sodium lignosulfonate, deionized water, chitosan solution and silane coupling agent of the embodiment is (5-8):(11-13):(3-5):2.

[0043] Embodiment 1.

[0044] The crystallization method for improving the solubility of antimony glycol is as follows:

[0045] Prepare ethylene glycol, antimony oxide and modified activated carbon, and react at 100℃ and a vacuum degree of 0.09 MPa for 1 h, the reaction gas phase is separated by vacuum rectification, and the activated carbon is removed by an ultra-fine filter; then cool to 30℃ by circulating cooling water, and then quench by cooling water with a temperature lower than 20℃, and the cooling time is 3 hours, and then crystallize, remove the mother liquor by centrifugation, and then dry by a vacuum vibrating bed to obtain antimony glycol product.

[0046] The temperature of the vacuum vibrating bed drying of the embodiment is 60℃, and the drying time is 1 hour.

[0047] The mass ratio of ethylene glycol, antimony oxide and modified activated carbon is 4:1:0.01.

[0048] The modification method of the modified activated carbon in this embodiment is as follows:

[0049] The activated carbon is heat treated at 220℃ for 1h, and then the heat treated activated carbon is cooled to 50℃ at a rate of 2℃ / min and kept for a certain time; the activated carbon kept for a certain time is modified by stirring in a modified liquid which is 3 times the total amount of the activated carbon, after stirring, it is filtered and dried to obtain the modified activated carbon.

[0050] The stirring speed of the stirring modification treatment in this embodiment is 350r / min, and the stirring time is 1h.

[0051] The preparation method of the modified liquid in this embodiment is as follows:

[0052] S01: 3 parts of nano-alumina, 2 parts of sodium citrate are added to 5 parts of yttrium nitrate solution to obtain a nano-alumina liquid by stirring;

[0053] S02: titanium white powder, nano-cellulose and sodium silicate solution are uniformly blended according to a weight ratio of 5:3:5 to obtain a titanium white powder modifier, 4 parts of the titanium white powder modifier are added to 5 parts of the nano-alumina liquid for stirring treatment, and the stirring is stopped to obtain the modified liquid.

[0054] The mass fraction of the yttrium nitrate solution in this embodiment is 2%; the mass fraction of the sodium silicate solution is 5%.

[0055] The stirring speed of the stirring treatment in this embodiment is 350r / min, and the stirring time is 1h.

[0056] The antimony oxide in this embodiment is also pretreated, and the specific pretreatment method is as follows:

[0057] S11: sodium lignosulfonate is added to deionized water, and then chitosan solution and silane coupling agent are added and stirred uniformly to obtain a modified sodium lignosulfonate liquid;

[0058] S12: the antimony oxide is preheated at 55℃ for 1h, and then added to 5 times the total amount of the antimony oxide in the modified sodium lignosulfonate liquid for stirring, and then washed with water, filtered and dried.

[0059] The mass fraction of the chitosan solution in this embodiment is 2%; the silane coupling agent is silane coupling agent KH550.

[0060] The mass ratio of sodium lignosulfonate, deionized water, chitosan solution and silane coupling agent in this embodiment is 5:11:3:2.

[0061] Example 2.

[0062] The crystallization method for improving the solubility of ethylene glycol antimony of the embodiment comprises the following steps:

[0063] The ethylene glycol, antimony oxide and modified activated carbon are prepared, and reacted at 150℃ under a vacuum degree of 0.099MPa for 6h. The reaction gas phase is separated by vacuum rectification, and the activated carbon is removed by ultra-fine filter. Then, the product is cooled to 35℃ by circulating cooling water, and then rapidly cooled by cooling water with a temperature lower than 20℃. The cooling time is 3h. Crystallization is carried out, and the mother liquor is removed by centrifugation. The product is dried in a vacuum vibrating bed to obtain the ethylene glycol antimony product.

[0064] The drying temperature of the vacuum vibrating bed of the embodiment is 80℃, and the drying time is 2h.

[0065] The mass ratio of ethylene glycol, antimony oxide and modified activated carbon is 10:1:0.02.

[0066] The modification method of the modified activated carbon of the embodiment is as follows:

[0067] The activated carbon is heat treated at 230℃ for 1h, and then cooled to 50℃ at a rate of 5℃ / min. The heat treated activated carbon is modified by stirring in a modified liquid with a volume of 5 times the total amount of activated carbon. After stirring, the modified activated carbon is obtained by suction filtration and drying.

[0068] The stirring speed of the stirring modification process of the embodiment is 400r / min, and the stirring time is 1h.

[0069] The preparation method of the modified liquid of the embodiment is as follows:

[0070] S01: 5 parts of nano-alumina, 4 parts of sodium citrate are added to 8 parts of yttrium nitrate solution to obtain a nano-alumina liquid by stirring;

[0071] S02: titanium white powder, nano-cellulose and sodium silicate solution are uniformly blended according to a weight ratio of 8:5:5 to obtain a titanium white powder modifier. 7 parts of the titanium white powder modifier are added to 8 parts of the nano-alumina liquid for stirring treatment. After stirring, the modified liquid is obtained.

[0072] The mass fraction of the yttrium nitrate solution of the embodiment is 5%, and the mass fraction of the sodium silicate solution is 8%.

[0073] The stirring speed of the stirring treatment of the embodiment is 400r / min, and the stirring time is 1h.

[0074] The antimony oxide of the embodiment is also pretreated. The specific pretreatment method is as follows:

[0075] S11: sodium lignosulfonate is added to deionized water, followed by the addition of chitosan solution and silane coupling agent, and stirred uniformly to obtain a modified sodium lignosulfonate liquid.

[0076] S12: The antimony oxide is preheated at 60℃ for 1h, and then added into the modified lignin sulfonate sodium solution with 8 times of the total amount of the antimony oxide, stirred fully, washed with water, filtered and dried.

[0077] The mass fraction of the chitosan solution in this embodiment is 5%; and the silane coupling agent is silane coupling agent KH550.

[0078] The mass ratio of the modified lignin sulfonate sodium, deionized water, chitosan solution and silane coupling agent in this embodiment is 8:13:5:2.

[0079] Example 3.

[0080] The crystallization method for improving the solubility of the ethylene glycol antimony in this embodiment comprises the following steps:

[0081] The ethylene glycol, antimony oxide and modified activated carbon are prepared, and reacted at 125℃ under a vacuum degree of 0.09MPa for 3h. The reaction gas phase is separated by vacuum rectification, and the activated carbon is removed by an ultra-fine filter. Then, the temperature is cooled to 32℃ by circulating cooling water, and then rapidly cooled by cooling water with a temperature lower than 20℃. The cooling time is 3h. Crystallization is performed, the mother liquor is removed by centrifugation, and the ethylene glycol antimony product is obtained by vacuum vibration bed drying.

[0082] The temperature of the vacuum vibration bed drying in this embodiment is 70℃, and the drying time is 1.5h.

[0083] The mass ratio of the ethylene glycol, antimony oxide and modified activated carbon is 7:1:0.015.

[0084] The modification method of the modified activated carbon in this embodiment is:

[0085] The activated carbon is heat treated at 225℃ for 1h, and then cooled to 50℃ at a rate of 3.5℃ / min. The heat treated activated carbon is modified by stirring in a modified solution with 4 times of the total amount of the activated carbon. After the stirring is completed, the modified activated carbon is obtained by filtering and drying.

[0086] The stirring speed of the stirring modification in this embodiment is 370r / min, and the stirring time is 1h.

[0087] The preparation method of the modified solution in this embodiment is:

[0088] S01: 4 parts of nano-alumina and 3 parts of sodium citrate are added into 6.5 parts of yttrium nitrate solution to obtain a nano-alumina solution by stirring fully;

[0089] S02: titanium dioxide, nanocellulose and sodium silicate solution were blended uniformly according to the weight ratio of 6.5:4:5 to obtain a titanium dioxide modifier, 5.5 parts of the titanium dioxide modifier was added into 6.5 parts of the nanometer alumina oxide solution for stirring treatment, and the modified solution was obtained after the stirring was completed.

[0090] The mass fraction of yttrium nitrate solution in the embodiment was 3.5%; and the mass fraction of sodium silicate solution was 6.5%.

[0091] The stirring speed of the stirring treatment in the embodiment was 375 r / min, and the stirring time was 1 h.

[0092] The antimony oxide in the embodiment was also pretreated, and the specific pretreatment method was as follows:

[0093] S11: sodium lignosulfonate was added into deionized water, and then chitosan solution and silane coupling agent were added, and stirring was uniformly performed to obtain a modified sodium lignosulfonate solution;

[0094] S12: the antimony oxide was preheated at 58℃ for 1 h, and then was added into the modified sodium lignosulfonate solution with 6.5 times the total amount of the antimony oxide for sufficient stirring, water washing, suction filtration and drying.

[0095] The mass fraction of the chitosan solution in the embodiment was 3.5%; and the silane coupling agent was silane coupling agent KH550.

[0096] The mass ratio of sodium lignosulfonate, deionized water, chitosan solution and silane coupling agent in the embodiment was 6.5:12:4:2.

[0097] Example 4.

[0098] The crystallization method for improving the solubility of ethylene glycol antimony in the embodiment included the following steps:

[0099] Ethylene glycol, antimony oxide and modified activated carbon were prepared, and were reacted at 110℃ and a vacuum degree of 0.09 MPa for 2 h, the reaction gas phase was separated by vacuum rectification, and the activated carbon was removed by an ultra-fine filter; then the reaction system was cooled to 32℃ by circulating cooling water, and was rapidly cooled by cooling water with a temperature lower than 20℃, and the cooling time was 3 h, and then crystallization was performed, the mother liquor was removed by centrifugation, and the product of ethylene glycol antimony was obtained by vacuum vibration bed drying.

[0100] The temperature of the vacuum vibration bed drying in the embodiment was 62℃, and the drying time was 1 h.

[0101] The mass ratio of ethylene glycol, antimony oxide and modified activated carbon was 5:1:0.012.

[0102] The modification method of the modified activated carbon in the embodiment was as follows:

[0103] The activated carbon is heat treated at 222℃ for 1h, then the heat treated activated carbon is cooled to 50℃ at a rate of 3℃ / min, and is kept for a certain time; the kept activated carbon is modified by stirring in a modified liquid which is 4 times the total amount of activated carbon, after stirring, it is filtered and dried to obtain the modified activated carbon.

[0104] The stirring speed of the stirring modification treatment in this example is 360r / min, and the stirring time is 1h.

[0105] The preparation method of the modified liquid in this example is as follows:

[0106] S01: 4 parts of nano-alumina, 3 parts of sodium citrate are added to 6 parts of yttrium nitrate solution to obtain a nano-alumina liquid by stirring;

[0107] S02: titanium white powder, nano-cellulose and sodium silicate solution are blended uniformly according to a weight ratio of 6:4:5 to obtain a titanium white powder modifier, and 5 parts of the titanium white powder modifier is added to 6 parts of the nano-alumina liquid for stirring treatment, and the stirring is stopped to obtain the modified liquid.

[0108] The mass fraction of the yttrium nitrate solution in this example is 3%, and the mass fraction of the sodium silicate solution is 6%.

[0109] The stirring speed of the stirring treatment in this example is 360r / min, and the stirring time is 1h.

[0110] The antimony oxide in this example is also pretreated, and the specific pretreatment method is as follows:

[0111] S11: sodium lignosulfonate is added to deionized water, and then chitosan solution and silane coupling agent are added and stirred uniformly to obtain a modified sodium lignosulfonate liquid;

[0112] S12: the antimony oxide is preheated at 57℃ for 1h, and then is added to the modified sodium lignosulfonate liquid which is 6 times the total amount of the antimony oxide for stirring, and is washed, filtered and dried.

[0113] The mass fraction of the chitosan solution in this example is 3%, and the silane coupling agent is silane coupling agent KH550.

[0114] The mass ratio of sodium lignosulfonate, deionized water, chitosan solution and silane coupling agent in this example is 6:11:4:2.

[0115] Example 5.

[0116] A crystallization method for improving the solubility of ethylene glycol antimony in this example includes the following steps:

[0117] Preparation of ethylene glycol, antimony oxide and modified activated carbon, reaction at 145℃, vacuum degree 0.099MPa for 5h, the reaction gas phase is separated by vacuum rectification, and the activated carbon is removed by superfine filter; then cooled to 32℃ by circulating cooling water, and then rapidly cooled by cooling water with a temperature lower than 20℃, cooling time 3h, crystallization, centrifugal removal of mother liquor, and vacuum vibration bed drying to obtain antimony ethylene glycol product.

[0118] The temperature of the vacuum vibration bed drying of the embodiment is 75℃, and the drying time is 2h;

[0119] The mass ratio of ethylene glycol, antimony oxide and modified activated carbon is 9:1:0.018.

[0120] The modification method of the modified activated carbon of the embodiment is:

[0121] Heat treatment of activated carbon at 228℃ for 1h, then cooling the heat-treated activated carbon to 50℃ at a rate of 4℃ / min, and holding; stirring the holding activated carbon in a modified liquid 4 times the total amount of activated carbon, after stirring, suction filtration and drying to obtain modified activated carbon.

[0122] The stirring speed of the stirring modification treatment of the embodiment is 370r / min, and the stirring time is 1h.

[0123] The preparation method of the modified liquid of the embodiment is:

[0124] S01: adding 4 parts of nano-alumina and 4 parts of sodium citrate to 7 parts of yttrium nitrate solution to obtain nano-alumina liquid by stirring;

[0125] S02: blending titanium dioxide, nano-cellulose and sodium silicate solution uniformly according to a weight ratio of 7:5:5 to obtain titanium dioxide modifier, and adding 6 parts of titanium dioxide modifier to 6 parts of nano-alumina liquid to obtain modified liquid by stirring.

[0126] The mass fraction of the yttrium nitrate solution of the embodiment is 4%, and the mass fraction of the sodium silicate solution is 7%.

[0127] The stirring speed of the stirring treatment of the embodiment is 380r / min, and the stirring time is 1h.

[0128] The antimony oxide of the embodiment is also pretreated, and the specific pretreatment method is:

[0129] S11: adding sodium lignosulfonate to deionized water, then adding chitosan solution and silane coupling agent, and stirring uniformly to obtain modified sodium lignosulfonate liquid;

[0130] S12: The antimony oxide is preheated at 55-60 DEG C for 1h, and then added into the modified lignin sulfonate sodium solution with 5-8 times of the total amount of the antimony oxide, stirred fully, washed with water, filtered and dried.

[0131] The mass fraction of the chitosan solution in this embodiment is 4%; the silane coupling agent is silane coupling agent KH550.

[0132] The mass ratio of the modified lignin sulfonate sodium, deionized water, chitosan solution and silane coupling agent in this embodiment is 7:12:4:2.

[0133] Comparative Example 1.

[0134] Different from Example 3 is that the modified activated carbon is directly replaced by activated carbon.

[0135] Comparative Example 2.

[0136] Different from Example 3 is that the modified liquid is not used in the preparation of the modified activated carbon.

[0137] Comparative Example 3.

[0138] Different from Example 3 is that the titanium white modifier is not added in the modified liquid.

[0139] Comparative Example 4.

[0140] Different from Example 3 is that the nano-alumina liquid is not added in the modified liquid.

[0141] Comparative Example 5.

[0142] Different from Example 3 is that the antimony oxide is not pretreated.

[0143] Performance test of Examples 1-5 and Comparative Examples 1-5, and the test results are as follows

[0144]

[0145] From Examples 1-5 and Comparative Examples 1-5, it can be seen that the product of the present application can realize the coordinated improvement of the solubility, the dissolution time and the whiteness value;

[0146] The performance of the product is significantly deteriorated when the modified activated carbon is directly replaced by activated carbon, the modified liquid is not used in the preparation of the modified activated carbon, the titanium white modifier is not added in the modified liquid, the nano-alumina liquid is not added in the modified liquid, and the antimony oxide is not pretreated. The performance of the product has a deteriorating trend. Only the product obtained by the process of the present application has the most significant performance effect.

[0147] It will be obvious to a person skilled in the art that the application is not limited to the details of the above-described exemplary embodiments, but that the application can be implemented in other embodiments without departing from the spirit or essential characteristics of the application. The embodiments should, therefore, be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the above description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

[0148] Furthermore, it should be understood that although the description is made on embodiments, not every embodiment contains only one independent technical solution, and the description is made in this way only for the sake of clarity, and a person skilled in the art should consider the description as a whole, and the technical solutions in each embodiment can also be combined appropriately to form other embodiments that can be understood by a person skilled in the art.

Claims

1. A crystallization process for improving the solubility of ethylene glycol antimony, characterized in that, It comprises the following steps: Preparation of ethylene glycol, antimony oxide and modified activated carbon, under the condition of 100-150℃, vacuum degree 0.09-0.099MPa, reaction for 1-6h, the reaction gas phase is separated by vacuum rectification, and the activated carbon is removed by ultra-fine filter; then cooled to 30-35℃ by circulating cooling water, and then rapidly cooled by cooling water with temperature lower than 20℃, cooling time 3h, crystallization, centrifugal removal of mother liquor, and vacuum vibration bed drying to obtain antimony ethylene glycol product.

2. The crystallization process for improving solubility of ethylene glycol antimony according to claim 1, characterized by, The temperature of the vacuum vibration bed drying is 60-80℃, and the drying time is 1-2h; The mass ratio of ethylene glycol, antimony oxide and modified activated carbon is (4-10):1:(0.01-0.02).

3. The crystallization process for improving solubility of ethylene glycol antimony according to claim 1, characterized by, The modification method of the modified activated carbon is: Heat treatment of activated carbon at 220-230℃ for 1h, then cooling the heat-treated activated carbon to 50℃ at a rate of 2-5℃ / min, and holding; Stirring modification treatment of the activated carbon in a modified liquid with 3-5 times the total amount of activated carbon, after stirring, suction filtration and drying to obtain modified activated carbon.

4. The crystallization process for improving solubility of ethylene glycol antimony according to claim 3, characterized by, The stirring speed of the stirring modification treatment is 350-400r / min, and the stirring time is 1h.

5. The crystallization process for improving solubility of ethylene glycol antimony according to claim 3, characterized by, The preparation method of the modified liquid is: S01: adding 3-5 parts of nano-alumina and 2-4 parts of sodium citrate to 5-8 parts of yttrium nitrate solution to obtain a nano-alumina liquid by stirring; S02: blending titanium white powder, nano-cellulose and sodium silicate solution according to the weight ratio (5-8):(3-5):5 to obtain a titanium white powder modifier, and adding 4-7 parts of the titanium white powder modifier to 5-8 parts of the nano-alumina liquid to obtain the modified liquid by stirring.

6. The crystallization process for improving solubility of ethylene glycol antimony according to claim 5, characterized by, The mass fraction of the yttrium nitrate solution is 2-5%, and the mass fraction of the sodium silicate solution is 5-8%.

7. The crystallization process for improving solubility of ethylene glycol antimony according to claim 6, characterized by, The stirring speed of the stirring treatment is 350-400r / min, and the stirring time is 1h.

8. The crystallization process for improving solubility of ethylene glycol antimony according to claim 1, characterized by, The antimony oxide is also pretreated, and the specific pretreatment method is: S11: adding sodium lignosulfonate to deionized water, then adding chitosan solution and silane coupling agent, and stirring uniformly to obtain a modified sodium lignosulfonate liquid; S12: preheating the antimony oxide at 55-60℃ for 1h, then adding to the modified sodium lignosulfonate liquid with 5-8 times the total amount of the antimony oxide, and stirring thoroughly, then washing with water, suction filtration and drying.

9. The crystallization process for improving solubility of ethylene glycol antimony according to claim 8, characterized by, The mass fraction of the chitosan solution is 2-5%, and the silane coupling agent is silane coupling agent KH550.

10. The crystallization process for improving solubility of ethylene glycol antimony according to claim 8, characterized by, The mass ratio of the sodium lignosulfonate, deionized water, chitosan solution and silane coupling agent is (5-8):(11-13):(3-5):2.

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