由硼砂和消石灰制备偏硼酸钙和过硼酸钠
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摘要
过硼酸钠(NaBO_3·H_2O或NaBO_3·4H_2O)是重要的硼化学品。在全世界,其产量仅次于硼砂、硼酸而居第三位。过硼酸钠是硼化合物的重要品种之一,又是一种用途广泛的无机过氧化物。可用作士林染料显色的氧化剂,活性染料沾色后的剥色剂,织物的漂白、脱色,医药上可作为消毒剂和杀菌剂等。近二十年来过硼酸钠在有机合成中的应用有了新的发现,它不仅能取代H_2O_2起到氧化作用,而且能克服H_2O_2稳定性差、易爆炸、毒性大、操作复杂、成本高等缺点。在有的氧化反应中,过硼酸钠比有机过氧酸的氧化效果还佳。因此,随着时间的推移,过硼酸钠在化工领域中的应用将不断扩大。
本文首先利用工业消石灰和工业硼砂反应合成六水偏硼酸钙(CaO·B_2O_3·6H_2O),然后以副产的偏硼酸钠母液为原料合成过硼酸钠。因此,研究内容包括两部分：
第一部分工艺路线是以工业硼砂和消石灰为原料经反应、过滤、洗涤及干燥制备出偏硼酸钙(CaO·B_2O_3·6H_2O)产品,母液中B_2O_3组分浓度在48-52g/L之间,Na_2O/B_2O_3摩尔比保持在1左右,基本不含镁和钙组分,可认为主要是偏硼酸钠的水溶液。物料配比、反应温度和反应时间是合成反应和产品质量的重要影响因素,液固比对合成反应影响较小。适宜的工艺条件为:配料硼钙比m(B_2O_3)/m(CaO)在2.2:1左右;液固比在2.76:1(mL/g)左右;反应温度35℃;反应时间8-10h。制得的偏硼酸钙产品组成为B_2O_329-31%,CaO 23-25%,Na_2O含量在0.5%之内,可以作为一般低碱和无碱玻璃纤维的含硼原料使用。
第二部分工艺路线是从第一部分合成产生的偏硼酸钠母液出发,经蒸发结晶后与30%的双氧水在稳定剂存在下经反应、过滤及干燥制备出四水过硼酸钠(NaBO_3·4H_2O)产品。最后将四水过硼酸钠经旋转蒸发脱水制得一水过硼酸钠(NaBO_3·H_2O)。实验考察了原料配比、反应温度、反应时间、液固比及稳定剂的种类等因素对合成反应和产品四水过硼酸钠质量的影响。根据产品产率最大原则确定适宜的工艺条件为:配料摩尔比n(NaBO_2·4H_2O):n(H_2O_2)在1:1:1左右:液固比在3.3:1(mL/g)左右;反应温度25℃;反应时间60-75min。在此条件下,制备的四水过硼酸钠的组成为:B_2O_3 22-24%,NaBO_3·4H_2O≥96%,其活性氧含量在10%以上,Fe≤0.004%。同时由脱水制得的一水过硼酸钠产品的活性氧在15%左右,符合工业过硼酸钠的要求。
Sodium perborate is an important boron product, whose yield ranks the world's third place next to borax and boric acid. It is one of the most versatile inorganic peroxide used as oxidant of indanthrene dye color development, stripping agent of reactive dyes staining, fabric bleaching and decoloration, disinfectant and fungicide in medicine and so on. There are some new discoveries of sodium perborate application in organic synthesis in the recent 20 years. It not only replaces hydrogen peroxide as oxidant, but also overcomes the disadvantages of the hydrogen peroxide, such as poor stability, explosiveness, high toxicity, complex operation and expensive cost. Its efficiency is better than organic peroxide acid in some oxidation reactions. Therefore, the application of sodium perborate in chemical industry will be extended in the future.
In this paper, sodium perborate product is prepared from mother liquor of sodium metaborate which is the by-product from the calcium metaborate hexahydrate production process, and calcium metaborate hexahydrate was prepared from borax and slaked lime. There are two projects in this study:
The first one is that borax was employed to react with slaked lime in water, and the resultant mixture was then filtrated to obtain calcium metaborate hexahydrate (CaO·B_2O_3·6H_2O). The contentration of B_2O_3 in mother liquor reaches 48-52g/L, Na_2O/B_2O_3 mol ratio is about 1, and there is no the composition of magnesium oxide and calcium oxide basically. Therefore, borate in the mother liquor exists in the form of sodium metaborate. Raw material ratio, reaction temperature and reaction time have a great effect on synthesis reaction and quality of the product. The little influence of liquid-to-solid ratio was found. Based on experiments, suitable processing parameters were obtained, i.e. m(B_2O_3)/m(CaO) of reactive raw materials, 2.2:1; liquid-to-solid ratio, 2.76:1(mL/g); reaction temperature and time, 35℃and 8-10h. The mass fractions of B_2O_3 and CaO in the product have reached 29-31%, 23-25% and that of Na_2O is less than 0.5% respectively. The calcium metaborate prepared by this process can be applied to low-alkali and alkali-free glass fiber industry as boron containing raw material.
The second one is that mother liquor is evaporated, concentrated and crystallized to obtain crystal of sodium metaborate, which was employed to react with 30% of hydrogen peroxide in the presence of stabilizer in water, and the resultant mixture was then filtrated and dried to obtain sodium perborate tetrahydrate (NaBO_3·4H_2O). Sodium perborate tetrahydrate was dehydrated to obtain sodium perborate monohydrate by rotary evaporator. The effect of raw material ratio, reaction temperature, reaction time, liquid-to-solid ratio and kinds of stabilizer on synthesis reaction and quality of the product was investigated. Based on experiments, suitable processing parameters were obtained according to the principle of maximum yield, i.e. n(NaBO_3·4H_2O)/n(H_2O_2) of reactive raw materials, 1:1.1; liquid-to-solid ratio, 3.3:1(mL/g); reaction temperature and time, 25℃, 60-75min. The mass fraction of B_2O_3 in the product has reached 22-24%, that of NaBO_3·4H_2O is more than 96%, the content of active oxygen is above 10wt% and that of Fe is less than 0.004wt% respectively. The content of active oxygen of sodium perborate monohydrate is about 15wt%.
本文首先利用工业消石灰和工业硼砂反应合成六水偏硼酸钙(CaO·B_2O_3·6H_2O),然后以副产的偏硼酸钠母液为原料合成过硼酸钠。因此,研究内容包括两部分：
第一部分工艺路线是以工业硼砂和消石灰为原料经反应、过滤、洗涤及干燥制备出偏硼酸钙(CaO·B_2O_3·6H_2O)产品,母液中B_2O_3组分浓度在48-52g/L之间,Na_2O/B_2O_3摩尔比保持在1左右,基本不含镁和钙组分,可认为主要是偏硼酸钠的水溶液。物料配比、反应温度和反应时间是合成反应和产品质量的重要影响因素,液固比对合成反应影响较小。适宜的工艺条件为:配料硼钙比m(B_2O_3)/m(CaO)在2.2:1左右;液固比在2.76:1(mL/g)左右;反应温度35℃;反应时间8-10h。制得的偏硼酸钙产品组成为B_2O_329-31%,CaO 23-25%,Na_2O含量在0.5%之内,可以作为一般低碱和无碱玻璃纤维的含硼原料使用。
第二部分工艺路线是从第一部分合成产生的偏硼酸钠母液出发,经蒸发结晶后与30%的双氧水在稳定剂存在下经反应、过滤及干燥制备出四水过硼酸钠(NaBO_3·4H_2O)产品。最后将四水过硼酸钠经旋转蒸发脱水制得一水过硼酸钠(NaBO_3·H_2O)。实验考察了原料配比、反应温度、反应时间、液固比及稳定剂的种类等因素对合成反应和产品四水过硼酸钠质量的影响。根据产品产率最大原则确定适宜的工艺条件为:配料摩尔比n(NaBO_2·4H_2O):n(H_2O_2)在1:1:1左右:液固比在3.3:1(mL/g)左右;反应温度25℃;反应时间60-75min。在此条件下,制备的四水过硼酸钠的组成为:B_2O_3 22-24%,NaBO_3·4H_2O≥96%,其活性氧含量在10%以上,Fe≤0.004%。同时由脱水制得的一水过硼酸钠产品的活性氧在15%左右,符合工业过硼酸钠的要求。
Sodium perborate is an important boron product, whose yield ranks the world's third place next to borax and boric acid. It is one of the most versatile inorganic peroxide used as oxidant of indanthrene dye color development, stripping agent of reactive dyes staining, fabric bleaching and decoloration, disinfectant and fungicide in medicine and so on. There are some new discoveries of sodium perborate application in organic synthesis in the recent 20 years. It not only replaces hydrogen peroxide as oxidant, but also overcomes the disadvantages of the hydrogen peroxide, such as poor stability, explosiveness, high toxicity, complex operation and expensive cost. Its efficiency is better than organic peroxide acid in some oxidation reactions. Therefore, the application of sodium perborate in chemical industry will be extended in the future.
In this paper, sodium perborate product is prepared from mother liquor of sodium metaborate which is the by-product from the calcium metaborate hexahydrate production process, and calcium metaborate hexahydrate was prepared from borax and slaked lime. There are two projects in this study:
The first one is that borax was employed to react with slaked lime in water, and the resultant mixture was then filtrated to obtain calcium metaborate hexahydrate (CaO·B_2O_3·6H_2O). The contentration of B_2O_3 in mother liquor reaches 48-52g/L, Na_2O/B_2O_3 mol ratio is about 1, and there is no the composition of magnesium oxide and calcium oxide basically. Therefore, borate in the mother liquor exists in the form of sodium metaborate. Raw material ratio, reaction temperature and reaction time have a great effect on synthesis reaction and quality of the product. The little influence of liquid-to-solid ratio was found. Based on experiments, suitable processing parameters were obtained, i.e. m(B_2O_3)/m(CaO) of reactive raw materials, 2.2:1; liquid-to-solid ratio, 2.76:1(mL/g); reaction temperature and time, 35℃and 8-10h. The mass fractions of B_2O_3 and CaO in the product have reached 29-31%, 23-25% and that of Na_2O is less than 0.5% respectively. The calcium metaborate prepared by this process can be applied to low-alkali and alkali-free glass fiber industry as boron containing raw material.
The second one is that mother liquor is evaporated, concentrated and crystallized to obtain crystal of sodium metaborate, which was employed to react with 30% of hydrogen peroxide in the presence of stabilizer in water, and the resultant mixture was then filtrated and dried to obtain sodium perborate tetrahydrate (NaBO_3·4H_2O). Sodium perborate tetrahydrate was dehydrated to obtain sodium perborate monohydrate by rotary evaporator. The effect of raw material ratio, reaction temperature, reaction time, liquid-to-solid ratio and kinds of stabilizer on synthesis reaction and quality of the product was investigated. Based on experiments, suitable processing parameters were obtained according to the principle of maximum yield, i.e. n(NaBO_3·4H_2O)/n(H_2O_2) of reactive raw materials, 1:1.1; liquid-to-solid ratio, 3.3:1(mL/g); reaction temperature and time, 25℃, 60-75min. The mass fraction of B_2O_3 in the product has reached 22-24%, that of NaBO_3·4H_2O is more than 96%, the content of active oxygen is above 10wt% and that of Fe is less than 0.004wt% respectively. The content of active oxygen of sodium perborate monohydrate is about 15wt%.
引文
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