CN115676854A - A kind of method that soda ash industry jointly prepares battery-grade sodium carbonate and basic magnesium carbonate - Google Patents
A kind of method that soda ash industry jointly prepares battery-grade sodium carbonate and basic magnesium carbonate Download PDFInfo
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- magnesium carbonate
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 259
- 235000017550 sodium carbonate Nutrition 0.000 title claims abstract description 128
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 128
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 title claims abstract description 122
- 239000001095 magnesium carbonate Substances 0.000 title claims abstract description 122
- 229910000021 magnesium carbonate Inorganic materials 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000012452 mother liquor Substances 0.000 claims abstract description 50
- 239000000047 product Substances 0.000 claims abstract description 39
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- 239000000460 chlorine Substances 0.000 claims abstract description 25
- 239000012065 filter cake Substances 0.000 claims abstract description 25
- 239000011268 mixed slurry Substances 0.000 claims abstract description 23
- 238000000967 suction filtration Methods 0.000 claims abstract description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 235000002639 sodium chloride Nutrition 0.000 claims description 25
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 23
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 238000005189 flocculation Methods 0.000 claims description 7
- 230000016615 flocculation Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 239000004760 aramid Substances 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000004685 tetrahydrates Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 239000002244 precipitate Substances 0.000 abstract description 4
- 239000011777 magnesium Substances 0.000 description 11
- 230000006872 improvement Effects 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- AYEFNFKJWNTFNX-UHFFFAOYSA-L magnesium carbonate tetrahydrate Chemical compound O.O.O.[OH-].C([O-])(O)=O.[Mg+2] AYEFNFKJWNTFNX-UHFFFAOYSA-L 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 238000005119 centrifugation Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
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- 230000015271 coagulation Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明公开了一种纯碱工业联合制备电池级碳酸钠和碱式碳酸镁的方法，包括：将低盐纯碱与水混合，获得NaCO3溶液，调节至碱性，过滤获得清液A；降温冷却结晶并抽滤分离，获得滤饼和母液Ⅰ；将滤饼处理后得到电池级高纯碳酸钠产品；将盐泥进行酸化处理形成混合浆液B，絮凝沉淀、抽滤分离获得粗钙滤饼和MgSO4滤液；将母液Ⅰ与MgSO4滤液混合加热生成碳酸镁，升温使碳酸镁转化成碱式碳酸镁形成混合浆液C，经过滤、洗涤得到碱式碳酸镁固体及母液Ⅱ。本发明可在不破坏原有制碱系统平衡的条件下，可使得最终制得的碳酸钠中的氯含量在极低水平，达到电池级别产品。
The invention discloses a method for jointly preparing battery - grade sodium carbonate and basic magnesium carbonate in the soda ash industry. Crystallize and separate by suction filtration to obtain filter cake and mother liquor I; process the filter cake to obtain battery-grade high-purity sodium carbonate product; acidify the salt mud to form mixed slurry B, flocculate and precipitate, and separate by suction filtration to obtain coarse calcium filter cake and MgSO 4 filtrate; mix and heat mother liquor I and MgSO 4 filtrate to generate magnesium carbonate, heat up to convert magnesium carbonate into basic magnesium carbonate to form mixed slurry C, filter and wash to obtain basic magnesium carbonate solid and mother liquor II. The present invention can make the chlorine content in the finally prepared sodium carbonate at an extremely low level without destroying the balance of the original alkali-making system, reaching battery level products.
Description
技术领域technical field
本发明属于固废资源化技术领域，特别涉及一种纯碱工业联合制备电池级碳酸钠和碱式碳酸镁的方法。The invention belongs to the technical field of solid waste recycling, in particular to a method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda ash industry.
背景技术Background technique
锂离子电池的综合性能优异，但锂在地壳中仅0.0065％，资源分布不均，供给矛盾日益凸显，多国已将其列为战略性矿产资源。钠元素资源丰富、分布广、成本低，且钠离子电池具有高低温性能佳、快充能力强、安全性高等独优势，因而可作为锂电池的重要补充和替代，经济价值和战略意义重大。目前钠离子电池在技术开发和产品生产上已初具规模，逾二十家企业已开展产业化布局。The comprehensive performance of lithium-ion batteries is excellent, but lithium only accounts for 0.0065% of the earth's crust, the distribution of resources is uneven, and the supply contradiction is becoming increasingly prominent. Many countries have listed it as a strategic mineral resource. Sodium is rich in resources, widely distributed, and low in cost, and sodium-ion batteries have unique advantages such as good high and low temperature performance, strong fast charging capability, and high safety. Therefore, they can be used as an important supplement and replacement for lithium batteries, with great economic value and strategic significance. At present, sodium-ion batteries have begun to take shape in technology development and product production, and more than 20 companies have launched industrialization layout.
电池级碳酸钠是钠离子电池正极材料制备的关键原料，为保障电池综合性能，对质量指标要求苛刻(关键杂质指标如Cl—≤0.01％)。目前工业级低盐重质纯碱约含Cl—0.2％，受制碱过程母液平衡等因素限制，不能采用增加滤过洗水量控制重碱盐分直接获得高纯产品；采用一水碱洗涤，则会产生相当数量无法消化的含盐母液，同时增加纯碱消耗；采用纯碱碳化-小苏打充分洗涤-煅烧分解路线能耗高，亦会进一步加剧过剩母液的体积膨胀；公开的沉淀结晶、化学络合、离子吸附等提纯技术则流程繁琐、成本较高，不适于产业化生产和未来钠离子电池产业的规模化需求。Battery-grade sodium carbonate is the key raw material for the preparation of anode materials for sodium-ion batteries. In order to ensure the overall performance of the battery, there are strict requirements on quality indicators (key impurity indicators such as Cl − ≤0.01%). At present, industrial-grade low-salt heavy soda ash contains about Cl — 0.2%. Limited by factors such as the balance of the mother liquor in the soda-making process, it is impossible to directly obtain high-purity products by increasing the amount of filtered washing water to control the salt content of heavy alkali; A considerable amount of indigestible salt-containing mother liquor increases the consumption of soda ash at the same time; the use of soda ash carbonization-baking soda full washing-calcination decomposition route has high energy consumption and will further aggravate the volume expansion of excess mother liquor; open precipitation crystallization, chemical complexation, ion Purification technologies such as adsorption are cumbersome and costly, and are not suitable for industrial production and the large-scale demand of the future sodium-ion battery industry.
发明内容Contents of the invention
本发明的目的在于提供一种纯碱工业联合制备电池级碳酸钠和碱式碳酸镁的方法，以解决上述存在的一个或多个技术问题。本发明提供的制备方法耦合已有工业制碱工艺，在不破坏原有制碱系统平衡的条件下，可使得最终制得的碳酸钠中的氯含量在极低水平，达到电池级别产品。The object of the present invention is to provide a kind of method that soda ash industry jointly prepares battery-grade sodium carbonate and basic magnesium carbonate, to solve one or more technical problems of above-mentioned existence. The preparation method provided by the invention is coupled with the existing industrial soda-making process, and the chlorine content in the finally prepared sodium carbonate can be kept at an extremely low level without destroying the balance of the original soda-making system, reaching battery-level products.
为达到上述目的，本发明采用以下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
本发明提供的一种纯碱工业联合制备电池级碳酸钠和碱式碳酸镁的方法，包括以下步骤：A kind of soda ash industry provided by the invention jointly prepares the method for battery grade sodium carbonate and basic magnesium carbonate, comprises the following steps:
将纯碱工业生产的低盐纯碱与水混合，获得预设浓度的NaCO3溶液；采用预设浓度的 NaOH溶液调节所述NaCO3溶液的pH至碱性，获得混合液；对所述混合液进行过滤以除去不溶性杂质，获得富含Na+和CO3 2-的清液A；将所述清液A进行降温冷却结晶，结晶预设时间后抽滤分离，获得滤饼和母液Ⅰ；将所述滤饼洗涤干燥处理后得到电池级高纯碳酸钠产品；Mix the low-salt soda ash produced by the soda ash industry with water to obtain a preset concentration of NaCO solution; use the preset concentration of NaOH solution to adjust the pH of the NaCO solution to alkaline to obtain a mixed solution; Filtration to remove insoluble impurities to obtain Na + and CO 3 2- rich clear liquid A; cooling and crystallizing the clear liquid A, and suction filtration separation after crystallization for a preset time to obtain filter cake and mother liquor I; Obtain the battery-grade high-purity sodium carbonate product after the filter cake is washed and dried;
将纯碱工业产生的盐泥进行酸化处理，形成MgSO4溶液与二水硫酸钙沉淀的混合浆液B；将所述混合浆液B进行絮凝沉淀和抽滤分离，获得粗钙滤饼和MgSO4滤液；Acidifying the salt mud produced in the soda ash industry to form a mixed slurry B of MgSO4 solution and calcium sulfate dihydrate precipitation; subjecting the mixed slurry B to flocculation precipitation and suction filtration separation to obtain coarse calcium filter cake and MgSO4 filtrate;
将所述母液Ⅰ与所述MgSO4滤液混合加热生成碳酸镁，加热预设时长后升温使碳酸镁转化成碱式碳酸镁，形成含碱式碳酸镁结晶的混合浆液C；Mixing and heating the mother liquor I and the MgSO4 filtrate to generate magnesium carbonate, heating for a preset period of time and raising the temperature to convert the magnesium carbonate into basic magnesium carbonate to form a mixed slurry C containing basic magnesium carbonate crystals;
所述混合浆液C经过滤、洗涤得到碱式碳酸镁固体及含硫酸钠、硫酸镁、碳酸钠、氯化钠的母液Ⅱ；所述碱式碳酸镁固体经干燥得到碱式碳酸镁产品。The mixed slurry C is filtered and washed to obtain basic magnesium carbonate solid and mother liquor II containing sodium sulfate, magnesium sulfate, sodium carbonate and sodium chloride; the basic magnesium carbonate solid is dried to obtain basic magnesium carbonate product.
本发明的进一步改进在于，所述将纯碱工业生产的低盐纯碱与水混合，获得预设浓度的 NaCO3溶液的步骤包括：A further improvement of the present invention is that the low-salt soda ash produced by the soda ash industry is mixed with water to obtain a preset concentration of NaCO The step of the solution includes:
在35℃～70℃条件下，选用去离子水进行低盐纯碱的溶解并加以搅拌，获得NaCO3溶液；其中，低盐纯碱与去离子水的固液质量比为1：(2～4)。Under the condition of 35℃～70℃, choose deionized water to dissolve low-salt soda ash and stir it to obtain NaCO 3 solution; the solid-liquid mass ratio of low-salt soda ash to deionized water is 1: (2～4) .
本发明的进一步改进在于，所述将所述清液A进行降温冷却结晶，结晶预设时间后抽滤分离，获得滤饼和母液Ⅰ的步骤中，The further improvement of the present invention lies in that in the step of cooling and crystallizing the clear liquid A, suction filtration and separation after crystallization for a preset time, and obtaining the filter cake and mother liquor I,
降温冷却结晶的终点温度设置为15℃～30℃；The end point temperature of cooling and crystallization is set at 15°C to 30°C;
抽滤分离时，选用芳香族聚酰胺材质的分离膜。When separating by suction filtration, the separation membrane made of aromatic polyamide is selected.
本发明的进一步改进在于，以Cl—计，制备获得的所述电池级高纯碳酸钠产品的含氯量小于0.005％。A further improvement of the present invention is that, in terms of Cl , the chlorine content of the battery-grade high-purity sodium carbonate product prepared is less than 0.005%.
本发明的进一步改进在于，所述将所述母液Ⅰ与所述MgSO4滤液混合加热生成碳酸镁，加热预设时长后升温使碳酸镁转化成碱式碳酸镁，形成含碱式碳酸镁结晶的混合浆液C的步骤中，A further improvement of the present invention is that the mother liquor I and the MgSO4 filtrate are mixed and heated to generate magnesium carbonate, and the temperature is raised after heating for a preset period of time to convert magnesium carbonate into basic magnesium carbonate to form a crystal containing basic magnesium carbonate. In the step of mixing slurry C,
母液Ⅰ与MgSO4滤液的混合体积比为1：(8～10)。The mixing volume ratio of mother liquor I and MgSO 4 filtrate is 1: (8-10).
本发明的进一步改进在于，所述将所述母液Ⅰ与所述MgSO4滤液混合加热生成碳酸镁，加热预设时长后升温使碳酸镁转化成碱式碳酸镁，形成含碱式碳酸镁结晶的混合浆液C的步骤中，A further improvement of the present invention is that the mother liquor I and the MgSO4 filtrate are mixed and heated to generate magnesium carbonate, and the temperature is raised after heating for a preset period of time to convert magnesium carbonate into basic magnesium carbonate to form a crystal containing basic magnesium carbonate. In the step of mixing slurry C,
加热生成碳酸镁时，温度控制在50℃～80℃。When heating to generate magnesium carbonate, the temperature is controlled at 50°C to 80°C.
本发明的进一步改进在于，所述将所述母液Ⅰ与所述MgSO4滤液混合加热生成碳酸镁，加热预设时长后升温使碳酸镁转化成碱式碳酸镁，形成含碱式碳酸镁结晶的混合浆液C的步骤中，A further improvement of the present invention is that the mother liquor I and the MgSO4 filtrate are mixed and heated to generate magnesium carbonate, and the temperature is raised after heating for a preset period of time to convert magnesium carbonate into basic magnesium carbonate to form a crystal containing basic magnesium carbonate. In the step of mixing slurry C,
加热预设时长后升温使碳酸镁转化成碱式碳酸镁时，预设时长为20min～60min；升温后的温度控制在80℃～120℃。When heating for a preset time and then raising the temperature to convert magnesium carbonate into basic magnesium carbonate, the preset time is 20 minutes to 60 minutes; the temperature after heating is controlled at 80°C to 120°C.
本发明的进一步改进在于，制备获得的碱式碳酸镁产品为四水合碱式碳酸镁；以Cl—计，含氯量为0.03％～0.05％。The further improvement of the present invention is that the basic magnesium carbonate product obtained is basic magnesium carbonate tetrahydrate; calculated as Cl, the chlorine content is 0.03% to 0.05%.
本发明的进一步改进在于，制备获得的母液Ⅱ用于纯碱生产。A further improvement of the present invention is that the prepared mother liquor II is used for the production of soda ash.
本发明的进一步改进在于，制备获得的粗钙滤饼用于制取半水石膏。A further improvement of the present invention lies in that the prepared coarse calcium filter cake is used to produce hemihydrate gypsum.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供的制备方法中，耦合已有工业制碱工艺，在不破坏原有制碱系统平衡的条件下，工业化制取高纯碳酸钠，助力钠资源优势向产能优势转变，破解锂资源困局；在碳酸钠除杂的同时，促进了原有纯碱产品的同步脱氯，使得最终制得碳酸钠中的氯含量在极低水平，达到电池级别产品；结晶后的碳酸钠母液，恰好可以直接与酸浸后的镁浸提液充分反应制备碱式碳酸镁，无需额外浓缩或稀释等附加操作。In the preparation method provided by the present invention, the existing industrial soda-making process is coupled, and high-purity sodium carbonate is industrially produced without destroying the balance of the original soda-making system, which helps to transform the advantage of sodium resources into the advantage of production capacity, and solves the problem of lithium resources. bureau; while removing impurities in sodium carbonate, it promotes the synchronous dechlorination of the original soda ash product, so that the chlorine content in the final sodium carbonate is at an extremely low level, reaching a battery-level product; the crystallized sodium carbonate mother liquor can just The basic magnesium carbonate is prepared by fully reacting with the magnesium extract solution after acid leaching directly, without additional operations such as additional concentration or dilution.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面对实施例或现有技术描述中所需要使用的附图做简单的介绍；显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来说，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art; obviously, the accompanying drawings in the following description are For some embodiments of the present invention, those skilled in the art can also obtain other drawings based on these drawings without creative effort.
图1是本发明实施例的一种纯碱工业联合制备电池级碳酸钠和碱式碳酸镁的方法的流程示意图；Fig. 1 is a kind of soda ash industry joint preparation process schematic diagram of the method for battery grade sodium carbonate and basic magnesium carbonate of the embodiment of the present invention;
图2是本发明实施例中，产出的电子级碳酸钠产品示意图；Fig. 2 is in the embodiment of the present invention, the electronic grade sodium carbonate product schematic diagram of output;
图3是本发明实施例中，产出的碱式碳酸镁产品示意图。Fig. 3 is in the embodiment of the present invention, the basic magnesium carbonate product schematic diagram of output.
具体实施方式Detailed ways
下面结合具体实施例进一步阐述本发明，应理解，这些实施例仅用于说明本发明而不用于限制本发明的保护范围。The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the protection scope of the present invention.
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。Embodiments of the present invention are described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation modes, and various modifications or changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of the present invention.
须知，下列实施例中未具体注明的工艺设备或装置均采用本领域内的常规设备或装置。It should be noted that the process equipment or devices not specifically indicated in the following examples all adopt conventional equipment or devices in the art.
此外应理解，本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤，除非另有说明；还应理解，本发明中提到的一个或多个设备/装置之间的组合连接关系并不排斥在所述组合设备/装置前后还可以存在其他设备/装置或在这些明确提到的两个设备/装置之间还可以插入其他设备 /装置，除非另有说明。而且，除非另有说明，各方法步骤的编号仅为鉴别各方法步骤的便利工具，而非为限制各方法步骤的排列次序或限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容的情况下，当亦视为本发明可实施的范畴。In addition, it should be understood that one or more method steps mentioned in the present invention do not exclude that there may be other method steps before and after the combined steps or other method steps may be inserted between these explicitly mentioned steps, unless otherwise It should also be understood that the combined connection relationship between one or more devices/devices mentioned in the present invention does not exclude that there may be other devices/devices before and after the combined device/devices or those explicitly mentioned Other devices/apparatus can also be interposed between the two devices/apparatus, unless otherwise stated. Moreover, unless otherwise stated, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the sequence of each method step or limit the scope of the present invention. The change or adjustment of its relative relationship is in In the case of no substantive change in the technical content, it shall also be regarded as the applicable scope of the present invention.
请参阅图1，本发明实施例提供的一种纯碱工业联合制备电池级碳酸钠和碱式碳酸镁的方法，具体步骤如下：Please refer to Fig. 1, a kind of soda ash industry joint preparation method for battery grade sodium carbonate and basic magnesium carbonate that the embodiment of the present invention provides, concrete steps are as follows:
步骤1，将纯碱工业生产的低盐纯碱与水混合，得到高浓度NaCO3溶液；Step 1, mixing the low-salt soda ash produced by the soda ash industry with water to obtain high-concentration NaCO solution;
步骤2，向NaCO3溶液中加入一定量的NaOH调节pH为碱性，促进溶液中Ca2+、Mg2+转化为沉淀；Step 2, adding a certain amount of NaOH to the NaCO 3 solution to adjust the pH to be alkaline, and promote the conversion of Ca 2+ and Mg 2+ in the solution into precipitates;
步骤3，对步骤2得到混合液进行过滤，去除CaCO3、Mg(OH)2和其他不溶性的杂质，得到富含Na+和CO3 2-的清液A；Step 3, filtering the mixed solution obtained in step 2 to remove CaCO 3 , Mg(OH) 2 and other insoluble impurities to obtain a clear liquid A rich in Na + and CO 3 2- ;
步骤4，将清液A进行降温冷却结晶，结晶一段时间后抽滤，分离得到的清液为含氯化钠和碳酸钠的母液Ⅰ；滤饼经过洗涤后，置于105℃～125℃环境下中干燥得到电池级高纯碳酸钠产品；Step 4, cooling and crystallizing the supernatant liquid A, suction filtration after crystallization for a period of time, the separated supernatant liquid is the mother liquor I containing sodium chloride and sodium carbonate; after the filter cake is washed, place it in an environment of 105°C to 125°C Dried down to obtain battery grade high-purity sodium carbonate product;
步骤5，将纯碱工业产生的盐泥进行酸化处理，将浆液中的Ca2+沉淀出来，形成MgSO4溶液及二水硫酸钙沉淀的混合浆液B；而后，进行絮凝沉淀和抽滤分离，粗钙滤饼送至制钙工序制取半水石膏，MgSO4滤液送至制镁环节；Step 5, carry out acidification treatment to the salt mud produced by the soda ash industry, and precipitate Ca in the slurry to form a mixed slurry B of MgSO solution and calcium sulfate dihydrate precipitation; then, carry out flocculation precipitation and suction filtration separation, crude The calcium filter cake is sent to the calcium production process to produce hemihydrate gypsum, and the MgSO4 filtrate is sent to the magnesium production link;
步骤6，将步骤4得到的母液Ⅰ与步骤5得到的MgSO4滤液混合加热生成碳酸镁，一段时间后升高加热温度促进碳酸镁转化成碱式碳酸镁，形成含碱式碳酸镁结晶的混合浆液C；Step 6, the mother liquor I obtained in step 4 and the MgSO4 filtrate obtained in step 5 are mixed and heated to generate magnesium carbonate, and after a period of time, the heating temperature is increased to promote the transformation of magnesium carbonate into basic magnesium carbonate, forming a mixture containing basic magnesium carbonate crystals slurry C;
步骤7，浆液C经过滤、洗涤得到碱式碳酸镁固体及含硫酸钠、硫酸镁、碳酸钠、氯化钠的母液Ⅱ，母液Ⅱ送入盐水精制单元用于纯碱生产；经干燥得到碱式碳酸镁产品。Step 7, the slurry C is filtered and washed to obtain the basic magnesium carbonate solid and the mother liquor II containing sodium sulfate, magnesium sulfate, sodium carbonate and sodium chloride, and the mother liquor II is sent to the brine refining unit for soda ash production; after drying, the basic magnesium carbonate is obtained. Magnesium carbonate products.
本发明实施例中，步骤1具体是在35～70℃条件下，选用去离子水进行低盐纯碱的溶解，并加以搅拌，低盐纯碱与水的固液质量比为1：(2～4)。In the embodiment of the present invention, step 1 is specifically to use deionized water to dissolve low-salt soda ash under the condition of 35-70°C, and stir it. The solid-liquid mass ratio of low-salt soda ash to water is 1:(2-4 ).
本发明实施例示例性可选的，步骤2中采用的NaOH溶液的浓度为0.2～5g/L，温度和搅拌条件维持步骤1不变。Optionally, as an example of the embodiment of the present invention, the concentration of the NaOH solution used in step 2 is 0.2-5 g/L, and the temperature and stirring conditions are kept unchanged in step 1.
本发明实施例具体示例性的，步骤3的过滤采用离心分离技术，可在2000r/min～5000r/min 的转速条件下，离心时间为4～5min，有效分离碳酸钠混合液中残渣与清液，上清液浊度为0.2 NTU。The embodiment of the present invention is specifically exemplary. The filtration in step 3 adopts centrifugal separation technology, which can effectively separate the residue and clear liquid in the sodium carbonate mixture under the condition of a rotating speed of 2000r/min to 5000r/min and a centrifugation time of 4 to 5min. , the turbidity of the supernatant was 0.2 NTU.
本发明实施例进一步优选的，步骤4中清液A降温结晶的终点温度设置为15℃～30℃，既可保证碳酸钠的结晶产量，亦可控制碳酸钠结晶产品的氯含量维持在较低水平。In the embodiment of the present invention, it is further preferred that in step 4, the end point temperature of the cooling crystallization of the clear liquid A is set at 15°C to 30°C, which can ensure the crystallization yield of sodium carbonate, and can also control the chlorine content of the sodium carbonate crystallization product to be maintained at a low level level.
本发明实施例中，步骤4进行抽滤分离时采用的抽滤单元选用芳香族聚酰胺材质的分离膜，膜孔径为1nm，采用一级两段式设计(6芯膜壳)，一段与二段膜壳数量比为2:1；上述方案可截留分子量范围在200～1000道尔顿，并且其表面带有负电荷，可高效拦截二价或高价离子特别是阴离子，对氯化钠的截留率到达95％。In the embodiment of the present invention, the suction filtration unit used in the suction filtration separation in step 4 is a separation membrane made of aromatic polyamide, with a membrane pore size of 1 nm, and a one-stage two-stage design (6-core membrane shell), one stage and two stages. The number ratio of segmented membrane shells is 2:1; the above scheme can cut off molecular weights ranging from 200 to 1000 Daltons, and its surface has a negative charge, which can efficiently intercept divalent or high-valent ions, especially anions, and the interception of sodium chloride The rate reaches 95%.
本发明实施例中，步骤4中得到的碳酸钠产品采用无水乙醇洗涤，无水乙醇已用于去除碳酸钠纳米棒中的残余的氯化钠等杂质，最终获的碳酸钠产品纯度在99％以上，含氯量(以Cl —计)小于0.005％。In the embodiment of the present invention, the sodium carbonate product obtained in step 4 is washed with absolute ethanol, and absolute alcohol has been used to remove impurities such as residual sodium chloride in the sodium carbonate nanorods, and the sodium carbonate product finally obtained has a purity of 99% More than %, the chlorine content (calculated as Cl- ) is less than 0.005%.
本发明实施例的步骤5中，盐泥与自来水混合制备盐泥浆液；混凝环节可选用阴离子型聚丙烯酰胺(PAM)或聚合氯化铝(PAC)作为混凝剂。In step 5 of the embodiment of the present invention, salt mud is mixed with tap water to prepare salt mud slurry; in the coagulation process, anionic polyacrylamide (PAM) or polyaluminum chloride (PAC) can be used as a coagulant.
本发明实施例的步骤6中，母液Ⅰ与MgSO4滤液的混合体积比为1：(8～10)，混合后的水热温度控制在50℃～80℃，采用搅拌速率为50～300r/min的旋桨搅拌促进水热反应进行。水热反应阶段持续20～60min后，温度升高至80℃～120℃，进行碳酸镁热解反应，同时继续维持搅拌速率为50～300r/min的旋桨搅拌促进热解反应进行。In step 6 of the embodiment of the present invention, the mixing volume ratio of mother liquor I and MgSO4 filtrate is 1: (8-10), the hydrothermal temperature after mixing is controlled at 50°C-80°C, and the stirring rate is 50-300r/ Min propeller stirring promotes the hydrothermal reaction. After the hydrothermal reaction stage lasted for 20-60 minutes, the temperature was raised to 80°C-120°C to carry out the pyrolysis reaction of magnesium carbonate, while continuing to maintain the propeller stirring at a stirring rate of 50-300r/min to promote the pyrolysis reaction.
本发明实施例的步骤7中，采用抽滤设备经孔径为0.45μm的滤膜可实现固液快速分离，得到的碱式碳酸镁产品为四水合碱式碳酸镁，纯度在99％以上，含氯量(以Cl—计)为0.03～0.05％。In step 7 of the embodiment of the present invention, the fast separation of solid and liquid can be realized through a filter membrane with a pore size of 0.45 μm using suction filtration equipment, and the basic magnesium carbonate product obtained is basic magnesium carbonate tetrahydrate with a purity of more than 99%, containing Chlorine content (calculated as Cl- ) is 0.03～0.05%.
本发明上述实施例的方法耦合已有工业制碱工艺，在不破坏原有制碱系统平衡的条件下，工业化制取高纯碳酸钠，助力钠资源优势向产能优势转变，破解锂资源困局。在碳酸钠钙镁除杂的同时，促进了原有纯碱产品的同步脱氯，使得最终制得碳酸钠中的氯含量在极低水平，达到电池级别产品。结晶后的碳酸钠母液，恰好可以直接与酸浸后的镁浸提液充分反应制备碱式碳酸镁，无需额外浓缩或稀释等附加操作。电池级高纯碳酸钠经二次碳化、脱水干燥，获得注射级小苏打产品，母液回用于制碱系统。The method of the above-mentioned embodiment of the present invention is coupled with the existing industrial soda production process. Under the condition of not destroying the balance of the original soda production system, high-purity sodium carbonate can be industrially produced, which will help the transformation of sodium resource advantages to production capacity advantages, and solve the dilemma of lithium resources. . While removing impurities from sodium carbonate, calcium and magnesium, it promotes the synchronous dechlorination of the original soda ash product, so that the chlorine content in the final sodium carbonate is extremely low, reaching battery-level products. The crystallized sodium carbonate mother liquor can just fully react with the magnesium extract solution after acid leaching to prepare basic magnesium carbonate without additional operations such as additional concentration or dilution. Battery-grade high-purity sodium carbonate undergoes secondary carbonization, dehydration and drying to obtain injection-grade baking soda products, and the mother liquor is reused in the alkali-making system.
本发明实施例提供的方法所述技术路线规避了原料或产品端直接洗涤降盐导致的母液膨胀技术难题，弥补了已有提纯工艺流程繁琐、成本高、产业化困难的技术缺陷，并将制碱-提纯过程外排的盐泥、母液等耦合盐水精制形成高附加值的碱式碳酸镁、半水石膏等系列产品，实现副产物的全部资源化回收利用，实现工艺流程零废物排放，提升纯碱行业产品盈利空间。初步核算，每处理1吨盐泥的净收益约270元。根据盐泥产量，每天的净利润约27万元，年利润超过9000万元，具有突出的经济效益、环境效益与社会效益。The technical route of the method provided by the embodiment of the present invention avoids the technical problem of mother liquor expansion caused by direct washing of raw materials or product ends to reduce salt, and makes up for the technical defects of the existing purification process, which are cumbersome, high cost, and difficult to industrialize, and will Alkali-salt mud, mother liquor and other coupled brine are refined during the alkali-purification process to form a series of products such as basic magnesium carbonate and hemihydrate gypsum with high added value, to realize the recycling and utilization of all by-products, to realize zero waste discharge in the process, and to improve Profitability of products in the soda ash industry. According to preliminary calculations, the net income of processing 1 ton of salt mud is about 270 yuan. According to the output of salt mud, the daily net profit is about 270,000 yuan, and the annual profit exceeds 90 million yuan, which has outstanding economic, environmental and social benefits.
实施例1Example 1
请参阅图1至图3，本发明实施例提供的一种纯碱工业联合制备电池级碳酸钠和碱式碳酸镁的新方法，首先将纯碱工业生产的低盐纯碱与水混合得到高浓度NaCO3溶液，再加入一定量的NaOH溶液调节pH，以促进溶液中Ca2+、Mg2+转化为沉淀；对过滤后富含NaCO3的清液 A进行降温冷却结晶，抽滤分离得到母液Ⅰ送至后续制镁环节，滤饼经过洗涤、干燥得到电池级高纯碳酸钠产品；将纯碱工业盐泥与硫酸混合，进行酸化处理；然后进行絮凝沉淀和抽滤分离，粗钙滤饼送至制钙工序制取半水石膏，MgSO4滤液送至制镁环节；而后，将母液Ⅰ与MgSO4滤液混合加热生成碳酸镁，一段时间后升温促进碳酸镁转化成碱式碳酸镁，形成含碱式碳酸镁结晶的混合浆液C；最后，将浆液C经过滤、洗涤得到碱式碳酸镁滤饼及含硫酸钠、硫酸镁、碳酸钠、氯化钠的母液Ⅱ，母液Ⅱ送入盐水精制单元用于纯碱生产；滤饼经干燥得到碱式碳酸镁产品，碱式碳酸镁经加工可制取其他镁系产品。Please refer to Fig. 1 to Fig. 3, a kind of new method that soda ash industry jointly prepares battery-grade sodium carbonate and basic magnesium carbonate provided by the embodiment of the present invention, first mix the low-salt soda ash produced by soda ash industry with water to obtain high-concentration NaCO 3 solution, and then add a certain amount of NaOH solution to adjust the pH, so as to promote the conversion of Ca 2+ and Mg 2+ in the solution into precipitates; cool and crystallize the clear liquid A rich in NaCO 3 after filtration, and separate by suction filtration to obtain the mother liquor I. In the subsequent magnesium production process, the filter cake is washed and dried to obtain battery-grade high-purity sodium carbonate; the soda ash industrial salt mud is mixed with sulfuric acid for acidification; then flocculation and precipitation and suction filtration are carried out, and the coarse calcium filter cake is sent to the production The calcium process produces hemihydrate gypsum, and the MgSO 4 filtrate is sent to the magnesium production link; then, the mother liquor I and the MgSO 4 filtrate are mixed and heated to generate magnesium carbonate, and after a period of time, the temperature is raised to promote the conversion of magnesium carbonate into basic magnesium carbonate, forming a basic magnesium carbonate. The mixed slurry C of magnesium carbonate crystallization; finally, the slurry C is filtered and washed to obtain the basic magnesium carbonate filter cake and the mother liquor II containing sodium sulfate, magnesium sulfate, sodium carbonate, and sodium chloride, and the mother liquor II is sent to the brine refining unit for use It is produced in soda ash; the filter cake is dried to obtain basic magnesium carbonate products, and basic magnesium carbonate can be processed to produce other magnesium-based products.
在本发明的一个具体实施例中，实验所选盐泥来自河北唐山某化工企业所产盐泥，已知其含水率为40％～48％，盐泥的主要元素如表1所示，处理步骤如下。In a specific embodiment of the present invention, the salt mud selected for the experiment comes from a salt mud produced by a chemical enterprise in Tangshan, Hebei. It is known that its moisture content is 40% to 48%. The main elements of the salt mud are shown in Table 1. Proceed as follows.
表1：盐泥的全岩指标性元素分析Table 1: Whole-rock index element analysis of salt mud
(1)取40.00g碳酸钠固体(食品级)溶于100mL去离子水，于35℃水浴、100r/min 搅拌条件下中充分溶解；(1) Dissolve 40.00g of sodium carbonate solid (food grade) in 100mL of deionized water, and fully dissolve in a 35°C water bath with 100r/min stirring;
(2)加入NaOH溶液(0.25g/L)1mL，于35℃水浴条件下，以100r/min搅拌充分反应30min；在3000r/min的转速条件下，离心4min，有效分离碳酸钠混合液中残渣与清液，上清液浊度为0.2NTU；(2) Add 1mL of NaOH solution (0.25g/L), and fully react at 100r/min for 30min in a water bath at 35°C; centrifuge for 4min at a speed of 3000r/min to effectively separate the residue in the sodium carbonate mixture With the supernatant, the turbidity of the supernatant is 0.2NTU;
(3)过滤后的清液A于25℃条件下进行降温冷却结晶，60min后抽滤，采用无水乙醇洗涤，放入120℃鼓风干燥箱中烘干得到碳酸钠产品，产品纯度高达到99.5％，含氯量(以Cl—计)为0.0043％，母液Ⅰ用于后续制镁环节；(3) Clear liquid A after filtration is cooled and crystallized under the condition of 25° C., suction filtered after 60 minutes, washed with absolute ethanol, put into 120° C. blast drying oven and dried to obtain sodium carbonate product, the product purity is as high as 99.5%, chlorine content ( calculated as Cl) is 0.0043%, and mother liquor I is used for follow-up magnesium production link;
(4)取100.0g湿基纯碱盐泥并加入820mL去离子水制浆，加入20mL浓硫酸进行酸化，待充分反应、不再有气泡产生(60min)，酸化结束，控制反应温度在50℃；(4) Take 100.0g of wet-base soda ash salt mud and add 820mL of deionized water to make slurry, add 20mL of concentrated sulfuric acid for acidification, wait for full reaction, no bubbles will be generated (60min), the acidification is completed, and the reaction temperature is controlled at 50°C;
(5)向步骤(4)所得的混合浆液B中加入PAM溶液是清液A中PAM含量达到3mg/L，整个絮凝沉淀过程在常温常压条件下进行。控制快搅阶段控制搅拌速度在200r/min，时间为1min；慢搅阶段控制搅拌速度在60r/min范围内，时间为3min。待搅拌结束静置10min完成絮凝沉淀操作，经砂滤分离后获得富含Mg2+、SO42-、Na+和Cl-的清液B；(5) Add the PAM solution to the mixed slurry B obtained in step (4) so that the PAM content in the supernatant liquid A reaches 3 mg/L, and the whole flocculation and sedimentation process is carried out under normal temperature and pressure conditions. In the fast stirring stage, the stirring speed is controlled at 200r/min, and the time is 1min; in the slow stirring stage, the stirring speed is controlled within the range of 60r/min, and the time is 3min. After the stirring is finished, let it stand for 10 minutes to complete the flocculation and precipitation operation, and obtain the supernatant B rich in Mg 2+ , SO4 2- , Na + and Cl - after separation by sand filtration;
(6)将100mL母液Ⅰ与1000mL清液B混合，控制水热温度为50℃，在120r/min搅拌条件下反应30min，而后将温度提高至85℃，在120r/min搅拌条件下反应60min并继续陈化一段时间，经洗涤、过滤、干燥后即为最终产物-碱式碳酸镁，其纯度高达99.3％，含氯量(以Cl—计)为0.03～0.05％。而余下的过滤清液即为副产物—Na2SO4和NaCl混合液，可送入盐水精制模块用于纯碱生产。(6) Mix 100mL mother liquor I with 1000mL clear solution B, control the hydrothermal temperature to 50°C, react for 30min under 120r/min stirring condition, then raise the temperature to 85°C, react under 120r/min stirring condition for 60min and Continue to age for a period of time, after washing, filtering and drying, the final product - basic magnesium carbonate, with a purity of up to 99.3% and a chlorine content (calculated as Cl ) of 0.03 to 0.05%. The remaining filtered clear liquid is the by-product— Na 2 SO 4 and NaCl mixture, which can be sent to the brine refining module for soda ash production.
实施例2Example 2
本发明实施例提供的一种纯碱工业联合制备电池级碳酸钠和碱式碳酸镁的方法，包括以下步骤：A kind of soda ash industry joint preparation method for battery grade sodium carbonate and basic magnesium carbonate provided by the embodiment of the present invention comprises the following steps:
将纯碱工业生产的低盐纯碱与水混合，获得预设浓度的NaCO3溶液；采用预设浓度的 NaOH溶液调节所述NaCO3溶液的pH至碱性，获得混合液；对所述混合液进行过滤以除去不溶性杂质，获得富含Na+和CO3 2-的清液A；将所述清液A进行降温冷却结晶，结晶预设时间后抽滤分离，获得滤饼和母液Ⅰ；将所述滤饼洗涤干燥处理后得到电池级高纯碳酸钠产品；Mix the low-salt soda ash produced by the soda ash industry with water to obtain a preset concentration of NaCO solution; use the preset concentration of NaOH solution to adjust the pH of the NaCO solution to alkaline to obtain a mixed solution; Filtration to remove insoluble impurities to obtain Na + and CO 3 2- rich clear liquid A; cooling and crystallizing the clear liquid A, and suction filtration separation after crystallization for a preset time to obtain filter cake and mother liquor I; Obtain the battery-grade high-purity sodium carbonate product after the filter cake is washed and dried;
将纯碱工业产生的盐泥进行酸化处理，形成MgSO4溶液与二水硫酸钙沉淀的混合浆液B；将所述混合浆液B进行絮凝沉淀和抽滤分离，获得粗钙滤饼和MgSO4滤液；Acidifying the salt mud produced in the soda ash industry to form a mixed slurry B of MgSO4 solution and calcium sulfate dihydrate precipitation; subjecting the mixed slurry B to flocculation precipitation and suction filtration separation to obtain coarse calcium filter cake and MgSO4 filtrate;
将所述母液Ⅰ与所述MgSO4滤液混合加热生成碳酸镁，加热预设时长后升温使碳酸镁转化成碱式碳酸镁，形成含碱式碳酸镁结晶的混合浆液C；Mixing and heating the mother liquor I and the MgSO4 filtrate to generate magnesium carbonate, heating for a preset period of time and raising the temperature to convert the magnesium carbonate into basic magnesium carbonate to form a mixed slurry C containing basic magnesium carbonate crystals;
所述混合浆液C经过滤、洗涤得到碱式碳酸镁固体及含硫酸钠、硫酸镁、碳酸钠、氯化钠的母液Ⅱ；所述碱式碳酸镁固体经干燥得到碱式碳酸镁产品；The mixed slurry C is filtered and washed to obtain a basic magnesium carbonate solid and mother liquor II containing sodium sulfate, magnesium sulfate, sodium carbonate, and sodium chloride; the basic magnesium carbonate solid is dried to obtain a basic magnesium carbonate product;
其中，所述将纯碱工业生产的低盐纯碱与水混合，获得预设浓度的NaCO3溶液的步骤包括：在35℃条件下，选用去离子水进行低盐纯碱的溶解并加以搅拌，获得NaCO3溶液；其中，低盐纯碱与去离子水的固液质量比为1：2；Wherein, the step of mixing low-salt soda ash produced by the soda ash industry with water to obtain a preset concentration of NaCO solution includes: under the condition of 35°C, select deionized water to dissolve low-salt soda ash and stir to obtain NaCO 3 solution; wherein, the solid-liquid mass ratio of low-salt soda ash to deionized water is 1:2;
其中，所述将所述清液A进行降温冷却结晶，结晶预设时间后抽滤分离，获得滤饼和母液Ⅰ的步骤中，降温冷却结晶的终点温度设置为15℃；抽滤分离时，选用芳香族聚酰胺材质的分离膜；Wherein, in the step of cooling and crystallizing the clear liquid A, and separating by suction filtration after crystallization for a preset time, in the step of obtaining the filter cake and mother liquor I, the end point temperature of cooling and crystallization is set at 15°C; during the separation by suction filtration, The separation membrane made of aromatic polyamide is selected;
其中，所述将所述母液Ⅰ与所述MgSO4滤液混合加热生成碳酸镁，加热预设时长后升温使碳酸镁转化成碱式碳酸镁，形成含碱式碳酸镁结晶的混合浆液C的步骤中，母液Ⅰ与MgSO4滤液的混合体积比为1：8；加热生成碳酸镁时，温度控制在50℃；加热预设时长后升温使碳酸镁转化成碱式碳酸镁时，预设时长为20min；升温后的温度控制在80℃。Wherein, the step of mixing and heating the mother liquor I and the MgSO4 filtrate to generate magnesium carbonate, heating for a preset period of time and raising the temperature to convert magnesium carbonate into basic magnesium carbonate, forming a mixed slurry C containing basic magnesium carbonate crystals In this method, the mixing volume ratio of mother liquor Ⅰ and MgSO 4 filtrate is 1:8; when heating to generate magnesium carbonate, the temperature is controlled at 50°C; 20min; the temperature after heating is controlled at 80°C.
本发明实施例中，制备获得的碱式碳酸镁产品为四水合碱式碳酸镁；以Cl—计，含氯量在 0.03％～0.05％范围内；以Cl—计，制备获得的所述电池级高纯碳酸钠产品的含氯量小于0.005％。In the embodiment of the present invention, the basic magnesium carbonate product prepared is basic magnesium carbonate tetrahydrate; calculated as Cl- , the chlorine content is in the range of 0.03% to 0.05%; calculated as Cl- , the prepared battery The chlorine content of high-grade high-purity sodium carbonate products is less than 0.005%.
实施例3Example 3
本发明实施例提供的一种纯碱工业联合制备电池级碳酸钠和碱式碳酸镁的方法，与实施例 2的区别仅在于，所述将纯碱工业生产的低盐纯碱与水混合，获得预设浓度的NaCO3溶液的步骤包括：在50℃条件下，选用去离子水进行低盐纯碱的溶解并加以搅拌，获得NaCO3溶液；其中，低盐纯碱与去离子水的固液质量比为1：3；所述将所述清液A进行降温冷却结晶，结晶预设时间后抽滤分离，获得滤饼和母液Ⅰ的步骤中，降温冷却结晶的终点温度设置为20℃；所述将所述母液Ⅰ与所述MgSO4滤液混合加热生成碳酸镁，加热预设时长后升温使碳酸镁转化成碱式碳酸镁，形成含碱式碳酸镁结晶的混合浆液C的步骤中，母液Ⅰ与MgSO4滤液的混合体积比为1：9；加热生成碳酸镁时，温度控制在60℃；加热预设时长后升温使碳酸镁转化成碱式碳酸镁时，预设时长为40min；升温后的温度控制在100℃。A method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate provided by the soda ash industry in the embodiment of the present invention is only different from Example 2 in that the low-salt soda ash produced by the soda ash industry is mixed with water to obtain a preset The steps of the NaCO3 solution include: under the condition of 50 ℃, select deionized water to dissolve the low-salt soda ash and stir it to obtain the NaCO3 solution; wherein, the solid-to-liquid mass ratio of the low-salt soda ash to the deionized water is 1 : 3; in the step of cooling and crystallizing the clear liquid A, suction filtration and separation after crystallization for a preset time, and obtaining the filter cake and mother liquor I, the end temperature of cooling and crystallization is set at 20° C.; The mother liquor I and the MgSO4 filtrate are mixed and heated to generate magnesium carbonate, and the temperature is raised after heating for a preset period of time to convert the magnesium carbonate into basic magnesium carbonate to form a mixed slurry C containing basic magnesium carbonate crystals. 4 The mixing volume ratio of the filtrate is 1:9; when heating to generate magnesium carbonate, the temperature is controlled at 60°C; when the temperature is raised after heating for a preset time to convert magnesium carbonate into basic magnesium carbonate, the preset time is 40 minutes; the temperature after heating Controlled at 100°C.
本发明实施例中，制备获得的碱式碳酸镁产品为四水合碱式碳酸镁；以Cl—计，含氯量在 0.03％～0.05％范围内；以Cl—计，制备获得的所述电池级高纯碳酸钠产品的含氯量小于0.005％。In the embodiment of the present invention, the basic magnesium carbonate product prepared is basic magnesium carbonate tetrahydrate; calculated as Cl- , the chlorine content is in the range of 0.03% to 0.05%; calculated as Cl- , the prepared battery The chlorine content of high-grade high-purity sodium carbonate products is less than 0.005%.
实施例4Example 4
本发明实施例提供的一种纯碱工业联合制备电池级碳酸钠和碱式碳酸镁的方法，与实施例 2的区别仅在于，所述将纯碱工业生产的低盐纯碱与水混合，获得预设浓度的NaCO3溶液的步骤包括：在70℃条件下，选用去离子水进行低盐纯碱的溶解并加以搅拌，获得NaCO3溶液；其中，低盐纯碱与去离子水的固液质量比为1：4；所述将所述清液A进行降温冷却结晶，结晶预设时间后抽滤分离，获得滤饼和母液Ⅰ的步骤中，降温冷却结晶的终点温度设置为30℃；所述将所述母液Ⅰ与所述MgSO4滤液混合加热生成碳酸镁，加热预设时长后升温使碳酸镁转化成碱式碳酸镁，形成含碱式碳酸镁结晶的混合浆液C的步骤中，母液Ⅰ与MgSO4滤液的混合体积比为1：10；加热生成碳酸镁时，温度控制在80℃；加热预设时长后升温使碳酸镁转化成碱式碳酸镁时，预设时长为60min；升温后的温度控制在120℃。A method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate provided by the soda ash industry in the embodiment of the present invention is only different from Example 2 in that the low-salt soda ash produced by the soda ash industry is mixed with water to obtain a preset The steps of the NaCO 3 solution include: under the condition of 70°C, select deionized water to dissolve the low-salt soda ash and stir it to obtain the NaCO 3 solution; wherein, the solid-liquid mass ratio of the low-salt soda ash to the deionized water is 1 : 4; the clear liquid A is subjected to cooling and crystallization, and the crystallization is separated by suction filtration after a preset time, and in the step of obtaining the filter cake and mother liquor I, the end temperature of cooling and crystallization is set to 30° C.; The mother liquor I and the MgSO4 filtrate are mixed and heated to generate magnesium carbonate, and the temperature is raised after heating for a preset period of time to convert the magnesium carbonate into basic magnesium carbonate to form a mixed slurry C containing basic magnesium carbonate crystals. 4 The mixing volume ratio of the filtrate is 1:10; when heating to generate magnesium carbonate, the temperature is controlled at 80°C; when the temperature is raised after heating for a preset time to convert magnesium carbonate into basic magnesium carbonate, the preset time is 60 minutes; the temperature after heating Controlled at 120°C.
最后应当说明的是：以上实施例仅用以说明本发明的技术方案而非对其限制，尽管参照上述实施例对本发明进行了详细的说明，所属领域的普通技术人员应当理解：依然可以对本发明的具体实施方式进行修改或者等同替换，而未脱离本发明精神和范围的任何修改或者等同替换，其均应涵盖在本发明的权利要求保护范围之内。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: the present invention can still be Any modifications or equivalent replacements that do not depart from the spirit and scope of the present invention shall fall within the protection scope of the claims of the present invention.
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