技术领域Technical field
本发明及无机盐化工技术领域，尤其是涉及一种从盐湖提锂过程MVR硼浓缩液制取硼酸和硼砂的方法。The present invention and the technical field of inorganic salt chemical industry, in particular, relate to a method for preparing boric acid and borax from MVR boron concentrate during the lithium extraction process from salt lakes.
背景技术Background technique
硼酸，为白色粉末状结晶或三斜轴面鳞片状光泽结晶，有滑腻手感，水溶液呈弱酸性。用于玻璃、搪瓷、陶瓷、医药、冶金、皮革、染料、农药、肥料、纺织等工业。硼酸有防腐性，可作防腐剂，如木材防腐，用作pH调节剂、抑菌防腐剂。在金属焊接、皮革、照相等行业以及染料、耐热防火织物、人造宝石、电容器、化妆品的制造方面都用到它。还可作杀虫剂和催化剂用。农业上含硼微量元素肥料，对许多作物有肥效，能增进作物品质和提高产量。Boric acid is a white powdery crystal or a triclinic scale-like glossy crystal with a smooth feel, and its aqueous solution is weakly acidic. Used in glass, enamel, ceramics, medicine, metallurgy, leather, dyes, pesticides, fertilizers, textiles and other industries. Boric acid has antiseptic properties and can be used as a preservative, such as wood preservative, pH regulator, and antibacterial preservative. It is used in metal welding, leather, photography and other industries as well as in the manufacture of dyes, heat-resistant and fire-resistant fabrics, artificial gemstones, capacitors, and cosmetics. It can also be used as pesticide and catalyst. In agriculture, boron-containing trace element fertilizers are effective for many crops and can improve crop quality and yield.
西台吉乃尔盐湖卤水中除富含锂镁等元素外也含有大量的硼元素，现有的从原料卤水中提硼的方法有：酸化沉淀法、浮选法、离子交换法、溶剂萃取法等。酸化沉淀法提硼工艺具有工艺路线简单且设备投资小的优点，工业应用较为广泛，但该方法适用于含硼量较高的原料卤水。而在现有的盐湖卤水综合利用的工艺路线一般为传统的煅烧法等提锂工艺，在提锂前先将老卤直接酸化提取硼酸，但由于盐湖老卤中的硼浓度不高(B2O3含量介于3～35g/L)，导致此方法硼收率较低，同时因为在沉淀过程中，除了目标硼酸以外，可能还会有其他不需要的物质一同沉淀，影响硼酸的纯度，导致提取的硼酸产物中含有杂质。为此对硫酸镁亚型盐湖型盐湖卤水综合利用而言，一种低成本、稳定高效的提硼工艺显得尤为重要。In addition to being rich in elements such as lithium and magnesium, the brine of Xitaijinel Salt Lake also contains a large amount of boron. The existing methods for extracting boron from raw brine include: acidification precipitation method, flotation method, ion exchange method, solvent extraction method, etc. . The boron extraction process by acidification precipitation has the advantages of simple process route and low equipment investment, and is widely used in industry. However, this method is suitable for raw brine with high boron content. The existing process route for comprehensive utilization of salt lake brine is generally a lithium extraction process such as the traditional calcination method. Before extracting lithium, the old brine is directly acidified to extract boric acid. However, since the boron concentration in the old salt lake brine is not high (B2 The O3 content is between 3 and 35g/L), resulting in a low boron yield in this method. At the same time, during the precipitation process, in addition to the target boric acid, other unnecessary substances may precipitate together, affecting the purity of the boric acid. Resulting in the extracted boric acid product containing impurities. For this reason, a low-cost, stable and efficient boron extraction process is particularly important for the comprehensive utilization of magnesium sulfate subtype salt lake brine.
发明内容Contents of the invention
针对现有技术存在的不足，本发明提供了一种从盐湖提锂过程MVR硼浓缩液制取硼酸的方法，包括以下步骤：In view of the shortcomings of the existing technology, the present invention provides a method for preparing boric acid from the MVR boron concentrate in the salt lake lithium extraction process, which includes the following steps:
步骤1，以富硼溶液为原料，通过MVR蒸发器强制蒸发浓缩得到硼浓缩液，所述硼浓缩液的B2O3浓度为100～150g/L，其中，所述富硼溶液为盐湖老卤通过膜工艺锂镁分离后，经稀释后进反渗透膜将硼分离出来后再加入NaOH改变硼的形态后，继续用反渗透膜浓缩得到的B2O3浓度约为17g/L的浓缩液；Step 1: Use boron-rich solution as raw material, and obtain a boron concentrated solution through forced evaporation and concentration using an MVR evaporator. The B2 O3 concentration of the boron concentrated solution is 100 to 150 g/L, wherein the boron-rich solution is salt lake old After the halogen is separated from lithium and magnesium through the membrane process, it is diluted and then entered into the reverse osmosis membrane to separate the boron, and then NaOH is added to change the form of the boron, and then the reverse osmosis membrane is used to concentrate to obtain a concentrated solution with a B2 O3 concentration of approximately 17g/L. ;
步骤2，通过步骤1得到的硼浓缩液加酸调节pH值至1.5～4.5，然后将硼浓缩液温度降至常温，析出硼酸，分离固液相得到粗硼酸与硼酸母液，其中，每1L所述硼浓缩液的加酸量为205～292ml；Step 2: Add acid to the boron concentrate obtained in step 1 to adjust the pH value to 1.5-4.5, then lower the temperature of the boron concentrate to normal temperature, precipitate boric acid, and separate the solid and liquid phases to obtain crude boric acid and boric acid mother liquor. The amount of acid added to the boron concentrated solution is 205 to 292 ml;
步骤3，对通过步骤2得到粗硼酸进行一次洗涤和二次洗涤，得到湿硼酸。首先，将纯水按1:1～1:1.5的比例与粗硼酸混合，进行洗涤，洗涤时间约为0.5小时。然后，采用逆流洗涤，纯水与粗硼酸按1:1的比例混合，同样进行洗涤，洗涤时间为0.5小时，得到的二次洗液作为洗液进入一次洗涤；Step 3: Wash the crude boric acid obtained in step 2 once and twice to obtain wet boric acid. First, pure water is mixed with crude boric acid in a ratio of 1:1 to 1:1.5 and washed. The washing time is about 0.5 hours. Then, use countercurrent washing, mix pure water and crude boric acid in a ratio of 1:1, and wash in the same manner. The washing time is 0.5 hours. The obtained secondary washing liquid is used as the washing liquid to enter the primary washing;
步骤4，通过步骤3得到湿硼酸进行干燥处理，干燥温度85℃，干燥时间为2h～2.5h，得到精硼酸。Step 4: Obtain wet boric acid through step 3 and perform drying treatment at a drying temperature of 85°C and a drying time of 2h to 2.5h to obtain refined boric acid.
优选地，上述步骤1中的硼浓缩液的B2O3浓度为140～145g/L。Preferably, the B2 O3 concentration of the boron concentrated solution in step 1 above is 140 to 145 g/L.
优选地，上述步骤2中所加的酸为质量分数为37％的浓盐酸或将浓硫酸配制成1:1的硫酸溶液中的任意一种，加酸后调节硼浓缩液pH值1.5。Preferably, the acid added in step 2 above is either concentrated hydrochloric acid with a mass fraction of 37% or concentrated sulfuric acid prepared into a 1:1 sulfuric acid solution. After adding the acid, adjust the pH value of the boron concentrate to 1.5.
优选地，上述步骤3中的一次洗涤时纯水与粗硼酸的体积比为1:1。Preferably, the volume ratio of pure water to crude boric acid during one wash in step 3 above is 1:1.
另一方面，本发明还提供了一种从盐湖提锂过程MVR硼浓缩液制取硼砂的方法，包括以下步骤：On the other hand, the present invention also provides a method for preparing borax from the MVR boron concentrate in the salt lake lithium extraction process, which includes the following steps:
步骤1，以富硼溶液为原料，通过MVR强制蒸发浓缩得到硼浓缩液，其中，所述硼浓缩液的B2O3浓度为159g/L，所述富硼溶液为盐湖老卤通过膜工艺锂镁分离后，经稀释后进反渗透膜将硼分离出来后再加氢氧化钠改变硼的形态后，继续用反渗透膜浓缩得到的B2O3浓度不低于17g/L的浓缩液；Step 1: Use boron-rich solution as raw material, and obtain a boron concentrated solution through MVR forced evaporation and concentration, wherein the B2 O3 concentration of the boron concentrated solution is 159 g/L, and the boron-rich solution is old salt lake brine through a membrane process After lithium and magnesium are separated, dilute it and enter the reverse osmosis membrane to separate the boron, then add sodium hydroxide to change the form of boron, and continue to use the reverse osmosis membrane to concentrate to obtain a concentrated solution with a B2 O3 concentration of not less than 17g/L;
步骤2，通过步骤1得到的硼浓缩液加如浓盐酸调节pH值至9.45，然后将硼浓缩液温度降至常温，析出硼砂，分离固液相得到粗硼砂与硼砂母液；Step 2: Adjust the pH value to 9.45 by adding concentrated hydrochloric acid to the boron concentrate obtained in step 1, then lower the temperature of the boron concentrate to normal temperature, precipitate borax, and separate the solid and liquid phases to obtain crude borax and borax mother liquor;
步骤3，对通过步骤2得到的粗硼砂进行一次洗涤，得到硼砂，其中，所述一次洗涤为纯水与粗硼砂按1:1～1:2的比例加入，搅拌0.5h；Step 3: Wash the crude borax obtained in step 2 once to obtain borax, wherein the first washing is to add pure water and crude borax in a ratio of 1:1 to 1:2, and stir for 0.5h;
步骤4，通过步骤3得到的硼砂进行干燥处理，干燥温度50～80℃，干燥时间为0.5h～2h，得到干硼砂。Step 4: Dry the borax obtained in step 3 at a drying temperature of 50-80°C and a drying time of 0.5h-2h to obtain dry borax.
综上所述，本申请包括以下至少一种有益技术效果：To sum up, this application includes at least one of the following beneficial technical effects:
1.本发明提供了一种从盐湖提锂过程MVR硼浓缩液制取硼酸和硼砂的方法，该工艺方法通过引入MVR技术、二次逆流洗涤等多步骤的处理流程，综合、高效的从盐湖老卤中高效分离和浓缩硼元素，从而制取硼酸,且硼的回收率高，该工艺能够有效利用盐湖资源，具有广阔的市场前景；1. The present invention provides a method for preparing boric acid and borax from MVR boron concentrate during the lithium extraction process from salt lakes. The process method comprehensively and efficiently extracts boric acid and borax from salt lakes by introducing MVR technology, secondary countercurrent washing and other multi-step processing processes. The boron element is efficiently separated and concentrated in old brine to produce boric acid, and the boron recovery rate is high. This process can effectively utilize salt lake resources and has broad market prospects;
2.本发明通过采用膜工艺提锂过程中，镁锂分离得到的母液进行稀释后进入反渗透膜分离硼元素，并通过NaOH处理改变硼的形态，随后经过反渗透膜浓缩，获得富含硼的溶液为提硼原料，并通过MVR技术强制蒸发浓缩，提高硼浓缩液的硼含量，提高加酸结晶提硼的效率，硼回收率更高；2. In the process of extracting lithium by using membrane technology, the mother liquor obtained by separation of magnesium and lithium is diluted and then enters the reverse osmosis membrane to separate the boron element, and changes the form of boron through NaOH treatment, and then is concentrated through the reverse osmosis membrane to obtain boron-rich material. The solution is the raw material for boron extraction, and is forced evaporation and concentration through MVR technology to increase the boron content of the boron concentrate, improve the efficiency of boron extraction through acid crystallization, and achieve a higher boron recovery rate;
3.本发明通过采用二次逆流洗涤的洗涤方式，能够显著去除通过加酸结晶得到的粗硼酸中的氯酸盐、硫酸盐的含量，使得到的硼酸产品纯度更高；3. By adopting the washing method of secondary countercurrent washing, the present invention can significantly remove the chlorate and sulfate content in the crude boric acid obtained by adding acid crystallization, so that the purity of the obtained boric acid product is higher;
4.本发明还提供了一种从盐湖提锂过程MVR硼浓缩液制取硼砂的方法，采用制取硼酸同样的工艺方法，只需加酸将pH调节至约9.45后，冷却至常温后分离得到硼砂产品，粗硼砂经一次洗涤干燥后基本都能达到一等品标准。4. The present invention also provides a method for preparing borax from the MVR boron concentrate during the lithium extraction process from salt lakes. The same process is used to prepare boric acid. It only needs to add acid to adjust the pH to about 9.45, and then separate after cooling to normal temperature. The borax product is obtained, and the crude borax can basically reach the first-class standard after one washing and drying.
附图说明Description of drawings
图1是本发明提供的一种从盐湖提锂过程MVR硼浓缩液制取硼酸和硼砂的方法的流程示意图；Figure 1 is a schematic flow chart of a method for preparing boric acid and borax from MVR boron concentrate in the lithium extraction process from salt lakes provided by the present invention;
图2是本发明提供的一种MVR硼浓缩液制取硼砂的方法的流程示意图。Figure 2 is a schematic flow chart of a method for preparing borax from MVR boron concentrate provided by the present invention.
具体实施方式Detailed ways
以下，将结合本发明实施例中的附图，对本发明的实施例中的技术进行清楚、完整地描述；显然，所描述的实施例仅为本发明一部分实施例，而不是全部的实施例；基于本发明中的实施例，本领域内技术人员在没有做出创造性劳动前提下所获得的其它所有实施例，都应属于本发明的保护范围。Below, the technology in the embodiments of the present invention will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention; obviously, the described embodiments are only some of the embodiments of the present invention, not all of the embodiments; Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts should fall within the protection scope of the present invention.
实施例1：Example 1:
步骤1，取B2O3浓度为17.312g/L的富硼溶液，通过MVR蒸发器强制蒸发浓缩得到B2O3浓度为143.275g/L的硼浓缩液；Step 1: Take a boron-rich solution with a B2 O3 concentration of 17.312g/L, and use the MVR evaporator to force evaporate and concentrate to obtain a boron concentrated solution with a B2 O3 concentration of 143.275g/L;
步骤2，取1L硼浓缩液中加入质量分数为37％的浓盐酸292ml，调节硼浓缩液的pH值为1.5，冷却至常温，固液分离得到粗硼酸264.41g与硼酸母液1.098L。本实施例中各步骤物料化学组成等数据见表1。Step 2: Add 292 ml of concentrated hydrochloric acid with a mass fraction of 37% to 1 L of boron concentrate, adjust the pH value of the boron concentrate to 1.5, cool to room temperature, and perform solid-liquid separation to obtain 264.41 g of crude boric acid and 1.098 L of boric acid mother liquor. The chemical composition and other data of materials for each step in this example are shown in Table 1.
表1Table 1
在本实例中，粗硼酸的硼收率达到89.65％。In this example, the boron yield of crude boric acid reached 89.65%.
对比例1：Comparative example 1:
步骤1，取与实施例1中相同的富硼溶液，通过MVR蒸发器强制蒸发浓缩得到B2O3浓度为127.924g/L的硼浓缩液；Step 1: Take the same boron-rich solution as in Example 1 and concentrate it by forced evaporation using an MVR evaporator to obtain a boron concentrated solution with a B2 O3 concentration of 127.924 g/L;
步骤2，取1L硼浓缩液中加入质量分数为37％的浓盐酸240ml调节硼浓缩液的pH值为1.4，冷却至常温，固液分离得到粗硼酸227.42g与硼酸母液1.08L，本对比例中各步骤物料化学组成等数据见Step 2: Add 240 ml of concentrated hydrochloric acid with a mass fraction of 37% to 1 L of boron concentrated solution to adjust the pH value of the boron concentrated solution to 1.4, cool to normal temperature, and perform solid-liquid separation to obtain 227.42 g of crude boric acid and 1.08 L of boric acid mother liquor. This comparative example For data on the chemical composition of materials in each step, see
表2。Table 2.
表2Table 2
本对比例中，粗硼酸的硼收率达到86.38％。In this comparative example, the boron yield of crude boric acid reaches 86.38%.
对比例2：Comparative example 2:
步骤1，取与实施例1中相同的富硼溶液，通过MVR蒸发器强制蒸发浓缩得到B2O3浓度为104.116g/L的硼浓缩液；Step 1: Take the same boron-rich solution as in Example 1 and concentrate it by forced evaporation using an MVR evaporator to obtain a boron concentrated solution with a B2 O3 concentration of 104.116 g/L;
步骤2，取1.2L硼浓缩液中加入质量分数为37％的浓盐酸248ml调节硼浓缩液的pH值为2.5，冷却至常温，固液分离得到粗硼酸172.98g与硼酸母液1.34L，本对比例中各步骤物料化学组成等数据见Step 2: Take 1.2L boron concentrated solution and add 248ml of concentrated hydrochloric acid with a mass fraction of 37% to adjust the pH value of the boron concentrated solution to 2.5. Cool to normal temperature and perform solid-liquid separation to obtain 172.98g of crude boric acid and 1.34L of boric acid mother liquor. This pair For data on the chemical composition of materials in each step in the ratio, see
表3。table 3.
表3table 3
本对比例中，粗硼酸的硼收率达到70.12％。In this comparative example, the boron yield of crude boric acid reaches 70.12%.
对比例3：Comparative example 3:
步骤1，本对比例的步骤1与对比例2的步骤1相同；Step 1: Step 1 of this comparative example is the same as step 1 of comparative example 2;
步骤2，取1.2L硼浓缩液中加入质量分数为37％的浓盐酸247ml调节硼浓缩液的pH值为3.5，冷却至常温，固液分离得到粗硼酸168.46g与硼酸母液1.33L，本对比例中各步骤物料化学组成等数据见Step 2: Take 1.2L boron concentrated solution and add 247ml of concentrated hydrochloric acid with a mass fraction of 37% to adjust the pH value of the boron concentrated solution to 3.5. Cool to normal temperature and perform solid-liquid separation to obtain 168.46g of crude boric acid and 1.33L of boric acid mother liquor. This pair For data on the chemical composition of materials in each step in the ratio, see
表4。Table 4.
表4Table 4
本对比例中，粗硼酸的硼收率达到68.04％。In this comparative example, the boron yield of crude boric acid reaches 68.04%.
对比例4：Comparative example 4:
步骤1，本对比例的步骤1与对比例2的步骤1相同；Step 1: Step 1 of this comparative example is the same as step 1 of comparative example 2;
步骤2，取1.2L硼浓缩液中加入质量分数为37％的浓盐酸239ml调节硼浓缩液的pH值为4.5，冷却至常温，固液分离得到粗硼酸139.37g与硼酸母液1.35L，本对比例中各步骤物料化学组成等数据见Step 2: Take 1.2L boron concentrated solution and add 239ml of concentrated hydrochloric acid with a mass fraction of 37% to adjust the pH value of the boron concentrated solution to 4.5. Cool to normal temperature and perform solid-liquid separation to obtain 139.37g of crude boric acid and 1.35L of boric acid mother liquor. This pair For data on the chemical composition of materials in each step in the ratio, see
表5。table 5.
表5table 5
本对比例中，粗硼酸的硼收率达到56.75％。In this comparative example, the boron yield of crude boric acid reaches 56.75%.
实施例2：Example 2:
本实施例的实施过程与实施例1中的步骤1、2相同；The implementation process of this embodiment is the same as steps 1 and 2 in Embodiment 1;
步骤3，取100g粗硼酸，分别按1:1的比例加入纯水进行一次洗涤、二次逆流洗涤，洗涤时间均为0.5h，得到的二次洗液按1:1的比例返回用于一次洗涤，最终得到湿硼酸71.46g和母液0.108L。本实施例中各步骤物料化学组成等数据见表6。Step 3: Take 100g of crude boric acid and add pure water in a ratio of 1:1 for primary washing and secondary countercurrent washing. The washing time is both 0.5h. The obtained secondary washing liquid is returned for primary use in a ratio of 1:1. After washing, 71.46g of wet boric acid and 0.108L of mother liquor were finally obtained. The chemical composition and other data of the materials in each step in this example are shown in Table 6.
表6Table 6
本实施例中湿硼酸中的氯根含量小于0.050，达到工业硼酸一等品标准。In this embodiment, the chloride content in the wet boric acid is less than 0.050, which reaches the first-class industrial boric acid standard.
对比例5：Comparative example 5:
本对比例的实施过程与对比例1中的步骤1、2相同；The implementation process of this comparative example is the same as steps 1 and 2 in comparative example 1;
步骤3，取152g粗硼酸，按1:1的比例加入纯水进行一次洗涤，洗涤0.5h，得到湿硼酸131.33g和母液0.195L；Step 3: Take 152g of crude boric acid and add pure water in a ratio of 1:1 for one wash. Wash for 0.5h to obtain 131.33g of wet boric acid and 0.195L of mother liquor;
步骤4，对上述湿硼酸进行干燥处理，干燥温度85℃，干燥时间为2.5h，最终得到精硼酸120.01g。本对比例中各步骤物料化学组成等数据见表7。Step 4: Dry the above-mentioned wet boric acid at a drying temperature of 85°C and a drying time of 2.5 hours to finally obtain 120.01g of refined boric acid. The chemical composition and other data of materials in each step in this comparative example are shown in Table 7.
表7Table 7
本对比例中精硼酸中的氯根含量大于0.10，未达到工业硼酸合格品的标准。The chloride content in the refined boric acid in this comparative example is greater than 0.10, which does not meet the standards for industrial boric acid qualified products.
实施例3：Example 3:
步骤1，取B2O3浓度为17.312g/L的富硼溶液，通过MVR蒸发器强制蒸发浓缩得到B2O3浓度为177.685g/L的硼浓缩液；Step 1: Take a boron-rich solution with a B2 O3 concentration of 17.312g/L, and use the MVR evaporator to force evaporate and concentrate to obtain a boron concentrated solution with a B2 O3 concentration of 177.685g/L;
步骤2，取2L硼浓缩液中加入1:1硫酸329mg，调节硼浓缩液的pH值为1.5，冷却至常温，固液分离得到粗硼酸470.87g与硼酸母液2L；Step 2: Add 329 mg of 1:1 sulfuric acid to 2L of boron concentrated solution, adjust the pH value of the boron concentrated solution to 1.5, cool to room temperature, and perform solid-liquid separation to obtain 470.87g of crude boric acid and 2L of boric acid mother liquor;
步骤3与实施例2中的步骤3相同，最终得到湿硼酸78.41g和母液0.091L。本实施例中各步骤物料化学组成等数据见表8。Step 3 is the same as step 3 in Example 2, and finally 78.41g of wet boric acid and 0.091L of mother liquor are obtained. The chemical composition and other data of materials for each step in this example are shown in Table 8.
表8Table 8
本实施例中，湿硼酸的硼收率达到93.93％，同时湿硼酸中的氯根含量小于0.050，硫酸根含量小于0.60，达到工业硼酸合格品标准。In this embodiment, the boron yield of wet boric acid reaches 93.93%. At the same time, the chloride content in wet boric acid is less than 0.050, and the sulfate content is less than 0.60, which meets the standard of industrial boric acid qualified products.
对比例6：Comparative example 6:
本对比例的的实施过程与实施例3中的步骤1、2相同；The implementation process of this comparative example is the same as steps 1 and 2 in Example 3;
步骤3，取200g粗硼酸，分别按1:1的比例加入纯水进行一次洗涤、二次洗涤，洗涤时间均为0.5h，最终得到湿硼酸152.55g和母液0.19L。本实施例中各步骤物料化学组成等数据见表9。Step 3: Take 200g of crude boric acid and add pure water in a ratio of 1:1 for primary washing and secondary washing. The washing time is 0.5h. Finally, 152.55g of wet boric acid and 0.19L of mother liquor are obtained. The chemical composition and other data of materials for each step in this example are shown in Table 9.
表9Table 9
本对比例中，湿硼酸的硼收率达到94.20％，同时湿硼酸中的氯根含量小于0.050，但硫酸根含量大于0.60，未达到工业硼酸合格品标准。In this comparative example, the boron yield of wet boric acid reaches 94.20%. At the same time, the chloride content in wet boric acid is less than 0.050, but the sulfate content is more than 0.60, which does not meet the standard of industrial boric acid qualified products.
实施例4：Example 4:
步骤1，取B2O3浓度为23.490g/L的富硼溶液，通过MVR蒸发器强制蒸发浓缩得到B2O3浓度为159.010g/L的硼浓缩液；Step 1: Take a boron-rich solution with a B2 O3 concentration of 23.490g/L, and use the MVR evaporator to force evaporate and concentrate to obtain a boron concentrated solution with a B2 O3 concentration of 159.010g/L;
步骤2，取2.85L硼浓缩液中加入质量分数为37％的浓盐酸175mg，调节硼浓缩液的pH值为9.45，冷却至常温，固液分离得到粗硼砂1136.1g与硼砂母液2.18L；Step 2: Take 2.85L boron concentrated solution and add 175mg concentrated hydrochloric acid with a mass fraction of 37%, adjust the pH value of the boron concentrated solution to 9.45, cool to normal temperature, and separate the solid and liquid to obtain 1136.1g of crude borax and 2.18L of borax mother liquor;
步骤3，取100g粗硼砂，按1:1的比例加入纯水进行一次洗涤，洗涤时间均为0.5h，得到湿硼砂68.38g和母液0.107L；Step 3: Take 100g of crude borax and add pure water in a ratio of 1:1 for one wash. The washing time is 0.5h to obtain 68.38g of wet borax and 0.107L of mother liquor;
步骤4，对上述湿硼砂进行干燥处理，干燥温度80℃，干燥时间为2h，最终得到干硼砂68.38g。本对比例中各步骤物料化学组成等数据见表10。Step 4: Dry the above-mentioned wet borax at a drying temperature of 80°C and a drying time of 2 hours to finally obtain 68.38g of dry borax. The chemical composition and other data of materials in each step in this comparative example are shown in Table 10.
表10Table 10
本实施例的硼收率达到80.63％，同时达到了工业十水四硼酸钠标准。The boron yield in this embodiment reaches 80.63%, and simultaneously reaches the industrial standard of sodium tetraborate decahydrate.
结合实施例1～4，对比例1～6，可以看出一下几点：Combining Examples 1 to 4 and Comparative Examples 1 to 6, the following points can be seen:
(1)结合实施例1～3，本发明提供的MVR硼浓缩液制取硼酸的工艺，通过先将富硼溶液通过MVR蒸发器强制蒸发得到硼浓缩液，在通过加酸结晶、逆流洗涤、分离干燥工艺得到的精硼酸，硼收率到达80％以上，并且品质能够符合国家规定的工业硼酸标准，提高了硫酸镁亚型盐湖卤水中的提硼效率。(1) Combined with Examples 1 to 3, the process for producing boric acid from the MVR boron concentrate provided by the present invention is to first forcefully evaporate the boron-rich solution through the MVR evaporator to obtain the boron concentrate, and then crystallize by adding acid, countercurrent washing, The purified boric acid obtained by the separation and drying process has a boron yield of more than 80%, and its quality can meet the national industrial boric acid standards, which improves the efficiency of boron extraction from magnesium sulfate subtype salt lake brine.
(2)通过实施例1与对比例1对比，通过MVR蒸发器强制蒸发得到的硼浓缩液中，实施例1的硼浓缩液中B2O3浓度控制在140～145g/L时，加酸结晶得到的粗硼酸硼收率最高；而对比例1硼浓缩液中B2O3浓度为127.924g/L，硼收率相对较低，由此说明，通过强制蒸发得到不同浓度的浓缩液，浓度越高，收率、产量越高。(2) By comparing Example 1 with Comparative Example 1, in the boron concentrated liquid obtained by forced evaporation with the MVR evaporator, when the concentration of B2 O3 in the boron concentrated liquid of Example 1 is controlled at 140 to 145 g/L, add acid The crude borate boron yield obtained by crystallization is the highest; while the B2 O3 concentration in the boron concentrated solution in Comparative Example 1 is 127.924g/L, and the boron yield is relatively low. This shows that concentrated solutions of different concentrations are obtained through forced evaporation. The higher the concentration, the higher the yield and output.
(3)通过实施例1与对比例2～4对比，加酸调节硼浓缩液的pH值分别为1.5、2.5、3.5、4.5，而pH值越低，加酸结晶得到的粗硼酸硼收率越高。(3) Comparing Example 1 with Comparative Examples 2 to 4, the pH values of the boron concentrated solution adjusted by adding acid are 1.5, 2.5, 3.5, and 4.5 respectively. The lower the pH value, the lower the yield of crude boron borate obtained by adding acid to crystallize. The higher.
(4)通过实施例2与对比例5对比，粗硼酸只经过一次洗涤后硼酸中的氯根超标达不到合格品标准；对粗硼酸进行二次逆流洗涤时，硼酸氯根合格能达到一等品标准。(4) Comparing Example 2 with Comparative Example 5, after only one washing of the crude boric acid, the chlorine in the boric acid exceeded the standard and failed to meet the standard of qualified products; when the crude boric acid was washed twice with countercurrent, the qualified chlorine of borate could reach a level of Equivalent standard.
(5)通过实施例3与对比例6对比，加硫酸生产硼酸时，粗硼酸中氯根能达到合格品标准，但硫酸根超标；对加硫酸生产出的粗硼酸使用纯水分二次洗涤后，得到的湿硼酸中硫酸根变化不大，为不合格品、氯根达到一等品；使用纯水进行逆流二次洗涤时，硫酸根能达到合格品、氯根达到一等品。(5) Comparing Example 3 with Comparative Example 6, when adding sulfuric acid to produce boric acid, the chlorine radical in the crude boric acid can meet the standard of qualified products, but the sulfate radical exceeds the standard; the crude boric acid produced by adding sulfuric acid is washed twice with pure water. Afterwards, the sulfate radical in the wet boric acid obtained has little change, and it is a substandard product, and the chlorine radical reaches the first-class product. When pure water is used for countercurrent washing for the second time, the sulfate radical reaches the qualified product, and the chlorine radical reaches the first-class product.
(6)通过实施例4可以看出，本发明提供的MVR硼浓缩液制取硼砂的工艺，通过先将富硼溶液通过MVR蒸发器强制蒸发得到硼浓缩液，用盐酸调节PH约9.45后，冷却至常温后分离得到硼砂产品，硼收率到达80％以上，提高了硫酸镁亚型盐湖卤水中的提硼效率；粗硼砂经一次洗涤干燥后基本都能达到国家规定的工业十水四硼酸钠一等品的标准。(6) It can be seen from Example 4 that the process for preparing borax from the MVR boron concentrate provided by the present invention is to first forcefully evaporate the boron-rich solution through an MVR evaporator to obtain the boron concentrate, and then adjust the pH to about 9.45 with hydrochloric acid. After cooling to normal temperature, the borax product is separated, and the boron yield reaches more than 80%, which improves the efficiency of boron extraction in magnesium sulfate subtype salt lake brine; after being washed and dried once, crude borax can basically reach the industrial tetraborate decahydrate required by the state. Standard for first-class sodium.
以上均为本申请的较佳实施例，并非依此限制本申请的保护范围，故：凡依本申请的结构、形状、原理所做的等效变化，均应涵盖于本申请的保护范围之内。The above are all preferred embodiments of the present application, and are not intended to limit the scope of protection of the present application. Therefore, any equivalent changes made based on the structure, shape, and principle of the present application shall be covered by the scope of protection of the present application. Inside.
| Application Number | Priority Date | Filing Date | Title |
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| CN202311168278.5ACN117163968A (en) | 2023-09-12 | 2023-09-12 | Method for preparing boric acid and borax from MVR boron concentrate in lithium extraction process of salt lake |
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| CN202311168278.5ACN117163968A (en) | 2023-09-12 | 2023-09-12 | Method for preparing boric acid and borax from MVR boron concentrate in lithium extraction process of salt lake |
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| CN202311168278.5APendingCN117163968A (en) | 2023-09-12 | 2023-09-12 | Method for preparing boric acid and borax from MVR boron concentrate in lithium extraction process of salt lake |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917600A (en)* | 2022-06-01 | 2022-08-19 | 启东神农机械有限公司 | Evaporative crystallization process and device for producing borax from lithium extraction liquid from salt lake |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5676916A (en)* | 1995-05-12 | 1997-10-14 | Sociedad Minera Salar De Atacama S.A. | Process for extracting the boron content in the brine of natural or industrial salt mines |
| CN1850605A (en)* | 2006-05-22 | 2006-10-25 | 大连理工大学 | Manufacture of boron-containing compound using cotton balls hydrothermal method and its comprehensive utilization |
| CN101659418A (en)* | 2009-09-02 | 2010-03-03 | 达州市恒成能源（集团）有限责任公司 | Method for preparing boric acid in boracic sodium chloride and potassium chloride saturated bittern solution containing boron |
| CN102602953A (en)* | 2012-04-12 | 2012-07-25 | 青海锂业有限公司 | Method for preparing high borosilicate glass industry-level boric acid by utilizing salt lake lithium-extracting mother solution |
| CN116177557A (en)* | 2023-01-13 | 2023-05-30 | 格尔木藏格锂业有限公司 | A method for preparing borax by discharging boron-containing wastewater from the electrodialysis process section |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5676916A (en)* | 1995-05-12 | 1997-10-14 | Sociedad Minera Salar De Atacama S.A. | Process for extracting the boron content in the brine of natural or industrial salt mines |
| CN1850605A (en)* | 2006-05-22 | 2006-10-25 | 大连理工大学 | Manufacture of boron-containing compound using cotton balls hydrothermal method and its comprehensive utilization |
| CN101659418A (en)* | 2009-09-02 | 2010-03-03 | 达州市恒成能源（集团）有限责任公司 | Method for preparing boric acid in boracic sodium chloride and potassium chloride saturated bittern solution containing boron |
| CN102602953A (en)* | 2012-04-12 | 2012-07-25 | 青海锂业有限公司 | Method for preparing high borosilicate glass industry-level boric acid by utilizing salt lake lithium-extracting mother solution |
| CN116177557A (en)* | 2023-01-13 | 2023-05-30 | 格尔木藏格锂业有限公司 | A method for preparing borax by discharging boron-containing wastewater from the electrodialysis process section |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917600A (en)* | 2022-06-01 | 2022-08-19 | 启东神农机械有限公司 | Evaporative crystallization process and device for producing borax from lithium extraction liquid from salt lake |
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