WO2014026402A2 - Secondary salt-water refining method for producing caustic soda by means of ion exchange membrane - Google Patents
Secondary salt-water refining method for producing caustic soda by means of ion exchange membrane Download PDFInfo
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- WO2014026402A2 WO2014026402A2 PCT/CN2012/080636 CN2012080636W WO2014026402A2 WO 2014026402 A2 WO2014026402 A2 WO 2014026402A2 CN 2012080636 W CN2012080636 W CN 2012080636W WO 2014026402 A2 WO2014026402 A2 WO 2014026402A2
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- brine
- ion
- exchange membrane
- refining method
- ion exchange
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/04—Hypochlorous acid
- C01B11/06—Hypochlorites
Definitions
- the invention relates to a method for preparing an alkali secondary brine by an ion membrane method.
- the key to the operation of the ion-exchange membrane electrolyzer is to enable the ion membrane to maintain high current efficiency and low cell voltage for a long period of time, thereby stabilizing, reducing DC power consumption and prolonging the service life of the ion membrane.
- the key to this technology is the quality of the brine entering the cell.
- the salt of Ca 2+ and Mg 2+ in the chelate resin column is ⁇ 20.0 ppm, and the regeneration time of the chelate resin column is 24 to 48 hours. Therefore, there is still an opportunity to further improve the purification and prolongation of the brine solution. Integrate the resin regeneration cycle.
- the raw salt brine is the main chemical raw material of the chlor-alkali industry. The impurities are brought into the solution. The known primary brine refining will reach the following quality.
- the object of the present invention is to provide an ion-exchange membrane alkali secondary brine refining method which is effective for improving the purification of a brine solution and prolonging the regeneration cycle of the integrated resin.
- the technical solution of the present invention is: An ion-exchange membrane method for preparing alkali secondary brine refining method, characterized in that:
- the first brine solution of C10-ion is input into the first graphite reactor, and phosphoric acid and/or phosphorous acid is input into the first graphite reactor, and then flows into the backstage graphite reactor in series, and the 5% mass concentration is input into the background reactor.
- the sodium acid aqueous solution is treated to obtain secondary purified brine; the reaction formula is as follows:
- the primary salt solution for removing the CIO-ion is an aqueous solution containing Na 2 S0 4 and C1 - formed by removing the C10-ion from the primary brine after adding sodium sulfite.
- Sodium polyphosphate aka trisodium metaphosphate
- the treated brine of the invention is adsorbed by a conventional filtration and chelating resin column, and the total content of Ca 2+ and Mg 2+ in the secondary purified brine solution is about 2PPb, and S0 4 2 - can be reduced to 2g/L, the chelating resin
- the tower can be regenerated from 24 hours to 240 hours.
- the refined brine treated by the above purification enters the ion membrane of the electrolytic cell, and contains a small amount of Ca 2+ , Mg 2+ , and S0 4 2 - ions, which reduces the precipitation scale on the ionic membrane and further reduces the existing groove.
- the voltage increases the current efficiency, greatly reduces the energy consumption of the production, and prolongs the life of the ionic membrane.
- An ionic membrane method for preparing a secondary secondary brine refining method wherein a primary brine solution from which C10-ion is removed is input into a first graphite reactor, and phosphoric acid and/or phosphorous acid is input into the first graphite reactor, and then flows into a series of backstage graphite.
- the reactor is treated by inputting a 5% mass concentration of sodium polyphosphate aqueous solution into a background reactor to obtain a secondary purified brine;
- the primary salt solution for removing the CIO-ion is an aqueous solution containing Na 2 SO 4 and C ⁇ formed by subjecting the primary brine to a conventional addition of sodium sulfite to remove C10- ions.
- the concentration of C10- in the known primary brine is ⁇ 101112/1
- the total content of Ca 2+ and Mg 2+ in the secondary purified brine solution is about 2PPb
- S0 4 2 - can be reduced to 2g / L
- the chelate resin tower can reach from 24 hours. Extended to 240 hours of regeneration.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
离子膜法制碱二次盐水精制方法 Method for preparing alkali secondary brine by ion membrane method
技术领域 Technical field
本发明涉及一种离子膜法制碱二次盐水精制方法。 The invention relates to a method for preparing an alkali secondary brine by an ion membrane method.
背景技术 Background technique
离子膜电解槽的操作关键是使离子膜能够长期稳定地保持较高 的电流效率和较低的槽电压， 进而稳定、 并降低直流电耗， 延长离子 膜的使用寿命。 这项技术的关键是进入电解槽的盐水质量。 The key to the operation of the ion-exchange membrane electrolyzer is to enable the ion membrane to maintain high current efficiency and low cell voltage for a long period of time, thereby stabilizing, reducing DC power consumption and prolonging the service life of the ion membrane. The key to this technology is the quality of the brine entering the cell.
盐水中的主要杂质含量及其对离子膜的影响 The main impurity content in brine and its effect on ionic membrane
表 1 Table 1
经对盐水中 Ca、 Mg、 Fe、、 Al、 Sr、 I、 Si02等的检测分析， 对 膜的影响最为明显的还是 Ca2+， Mg2+， S04 2 , 它们的微量存在， 就 会使电流效率下降， 使槽电压上升。 Through the detection and analysis of Ca, Mg, Fe, Al, Sr, I, Si0 2 in brine, the most obvious effect on the membrane is Ca 2+ , Mg 2+ , S0 4 2 , and their trace presence, This will reduce the current efficiency and increase the cell voltage.
当前， 国内外离子膜制碱盐水二次精制工艺流程大致相同为： 将 一次盐水除 C10—离子，然后经过滤、调节 pH值， 并经螯合树脂吸附。 At present, the secondary refining process of ion-exchange membrane alkaline brine at home and abroad is roughly the same as follows: C10-ion is removed once, then filtered, adjusted to pH value, and adsorbed by chelating resin.
其精制后出螯合树脂塔的盐水 Ca2+,Mg2+总含量 <20.0PPb,螯合树 脂塔的再生时间为 24〜48小时， 因此， 仍然存在的机会是进一步改 善盐水水溶液纯化， 延长整合树脂再生周期。
原盐成卤水是氯碱工业的主要化学原料， 其中的杂质带入溶液之 中， 已知的一次盐水精制将会达到如下质量 After purification, the salt of Ca 2+ and Mg 2+ in the chelate resin column is <20.0 ppm, and the regeneration time of the chelate resin column is 24 to 48 hours. Therefore, there is still an opportunity to further improve the purification and prolongation of the brine solution. Integrate the resin regeneration cycle. The raw salt brine is the main chemical raw material of the chlor-alkali industry. The impurities are brought into the solution. The known primary brine refining will reach the following quality.
发明内容 Summary of the invention
本发明的目的在于提供一种有效改善盐水溶液纯化，延长整合树 脂再生周期的离子膜法制碱二次盐水精制方法。 SUMMARY OF THE INVENTION The object of the present invention is to provide an ion-exchange membrane alkali secondary brine refining method which is effective for improving the purification of a brine solution and prolonging the regeneration cycle of the integrated resin.
本发明的技术解决方案是：
一种离子膜法制碱二次盐水精制方法， 其特征是： 将来自除去 The technical solution of the present invention is: An ion-exchange membrane method for preparing alkali secondary brine refining method, characterized in that:
C10—离子的一次盐水溶液输入首台石墨反应器，向首台石墨反应器内 输入磷酸和 /或亚磷酸， 再流入串联的后台石墨反应器， 向后台反应 器内输入 5%质量浓度的聚酸钠水溶液处理， 得到二次精制盐水； 反应式如下： The first brine solution of C10-ion is input into the first graphite reactor, and phosphoric acid and/or phosphorous acid is input into the first graphite reactor, and then flows into the backstage graphite reactor in series, and the 5% mass concentration is input into the background reactor. The sodium acid aqueous solution is treated to obtain secondary purified brine; the reaction formula is as follows:
(1) C1" + Na2C2P209 NaCl + H3 P04 + (1) C1" + Na 2 C 2 P 2 0 9 NaCl + H 3 P0 4 +
(2) SO — + Na2C2P209 Na2S04 + H3 PO4 + (2) SO — + Na 2 C 2 P 2 0 9 Na 2 S0 4 + H 3 PO4 +
(3) Ca/+ + Η3 ΡΟ' Ca3 (P04) 2 (3) Ca /+ + Η 3 ΡΟ' Ca 3 (P0 4 ) 2
(4) Mg/+ + H3 P04 Mg3 (P04) 2 (4) Mg /+ + H 3 P0 4 Mg 3 (P0 4 ) 2
所述除去 CIO—离子的一次盐水溶液， 是将一次盐水经过添加亚 硫酸钠后， 去除 C10— 离子， 形成的含 Na2S04和 C1—的水溶液。 聚酸钠： 又名三偏酸钠 The primary salt solution for removing the CIO-ion is an aqueous solution containing Na 2 S0 4 and C1 - formed by removing the C10-ion from the primary brine after adding sodium sulfite. Sodium polyphosphate: aka trisodium metaphosphate
分子式： Na2C2P20; Molecular formula: Na 2 C 2 P 2 0 ;
( Q/320691NGA01-2011, 201 1-3-28 发布， 江苏省南通质量技术监督 局标准备案， 通质技监标备第 63号 2011-G)。 (Q/320691NGA01-2011, 201 1-3-28 Released, Jiangsu Nantong Quality and Technical Supervision Bureau Standard Record, Tongji Technology Supervision Standard No. 63 2011-G).
本发明处理后的盐水经常规的过滤及螯合树脂塔吸附， 二次精 制盐水水溶液中 Ca2+、 Mg2+总含量在 2PPb左右， S04 2—可降至 2g/L, 螯合树脂塔可达从 24小时延长到 240小时再生。 The treated brine of the invention is adsorbed by a conventional filtration and chelating resin column, and the total content of Ca 2+ and Mg 2+ in the secondary purified brine solution is about 2PPb, and S0 4 2 - can be reduced to 2g/L, the chelating resin The tower can be regenerated from 24 hours to 240 hours.
经过以上纯化处理的精制盐水， 进入电解槽离子膜， 极少含量 的 Ca2+、 Mg2+、 S04 2—离子， 减少了在离子膜上的沉淀结垢， 进一步 降低了现有的槽电压， 提高了电流效率， 大量降低了生产能耗， 延长 了离子膜寿命。 The refined brine treated by the above purification enters the ion membrane of the electrolytic cell, and contains a small amount of Ca 2+ , Mg 2+ , and S0 4 2 - ions, which reduces the precipitation scale on the ionic membrane and further reduces the existing groove. The voltage increases the current efficiency, greatly reduces the energy consumption of the production, and prolongs the life of the ionic membrane.
下面结合实施例对本发明作进一步说明。 The invention is further illustrated by the following examples.
具体实施方式 detailed description
一种离子膜法制碱二次盐水精制方法， 将来自除去 C10—离子的 一次盐水溶液输入首台石墨反应器，向首台石墨反应器内输入磷酸和 /或亚磷酸， 再流入串联的后台石墨反应器， 向后台反应器内输入 5% 质量浓度的聚酸钠水溶液处理， 得到二次精制盐水； An ionic membrane method for preparing a secondary secondary brine refining method, wherein a primary brine solution from which C10-ion is removed is input into a first graphite reactor, and phosphoric acid and/or phosphorous acid is input into the first graphite reactor, and then flows into a series of backstage graphite. The reactor is treated by inputting a 5% mass concentration of sodium polyphosphate aqueous solution into a background reactor to obtain a secondary purified brine;
反应式如下： The reaction formula is as follows:
(1) C1" + Na2C2P209 ► NaCl + H3 P04 + … (1) C1" + Na 2 C 2 P 2 0 9 ► NaCl + H 3 P0 4 + ...
(2) S04 2"+ Na2C2P209 ^ Na2S04 + H3 P04+ - (2) S0 4 2 "+ Na 2 C 2 P 2 0 9 ^ Na 2 S0 4 + H 3 P0 4 + -
(3) Ca2+ + H3 P04 ► Ca3 (P04) 2 (3) Ca 2+ + H 3 P0 4 ► Ca 3 (P0 4 ) 2
(4) Mg2+ + H3 P04 ► Mg3 (P04) 2 °
所述除去 CIO—离子的一次盐水溶液， 是将一次盐水经过常规的 添加亚硫酸钠后， 去除 C10— 离子， 形成的含 Na2S04和CΓ的水溶液。 (4) Mg 2+ + H 3 P0 4 ► Mg 3 (P0 4 ) 2 ° The primary salt solution for removing the CIO-ion is an aqueous solution containing Na 2 SO 4 and C 形成 formed by subjecting the primary brine to a conventional addition of sodium sulfite to remove C10- ions.
输入 5%质量浓度的的聚酸钠， 其中用量计算为： Enter 5% mass concentration of sodium polyphosphate, the amount of which is calculated as:
已知的一次盐水中 C10—的浓度为< 101112/1 The concentration of C10- in the known primary brine is <101112/1
1 m3盐水 C10—的最大摩尔量 10 _ 0.194mol 1 m 3 brine C10 - maximum molar amount 10 _ 0 .194mol
35. 5+16 — 35. 5+16 —
1 m3盐水中 C10—与 Na2S04反应需要 Na2S04， 0. 194* ( 23*2+32+48 ) =24. 4g 1 m 3 C10- brine and Na 2 S0 4 required for the reaction Na 2 S0 4, 0. 194 * (23 * 2 + 32 + 48) = 24. 4g
产生 CF 0. 194*35. 5=6. 887 g Generate CF 0. 194*35. 5=6. 887 g
每日盐水用量 24t* 11 m3/t=264m3 Daily salt consumption 24t* 11 m 3 /t=264m 3
每日生成的 C1— 264 m *6.887 g/ m3=1818.2 g =1.818Kg 故根据方程 (1) 可计算出 Na2C2P209的用量， 及产生的 H3 P04的 根据方程 (2) 可计算出 Na2C2P209的用量， 及产生的 H3 P04的 根据方程 (1)、 （2)， 计算出的 Na2C2P209的用量相加， 即为投入 反应的 Na2C2P209的用量； The daily generated C1 - 264 m *6.887 g / m 3 =1818.2 g = 1.818Kg Therefore, according to equation (1), the amount of Na 2 C 2 P 2 0 9 can be calculated, and the generated H 3 P0 4 according to the equation (2) Calculate the amount of Na 2 C 2 P 2 0 9 and the amount of Na 2 C 2 P 2 0 9 calculated according to equations (1) and (2) for H 3 P0 4 produced. , that is, the amount of Na 2 C 2 P 2 0 9 put into the reaction;
根据一次精制盐水中 Ca2+,Mg2+的已知检测量； According to the known detection amount of Ca 2+ and Mg 2+ in one refined brine;
根据方程 (3X4) 可计算出所需要的 H3 P04用量， 减去所反应产 生的 H3 P04数量， 即为所需的投入量。 Calculated according to equation (3X4) required amount of H 3 P0 4, by subtracting the amount of H 3 P0 4 produced by the reaction, is the desired inputs.
经过公知的过滤及螯合树脂塔吸附， 二次精制盐水水溶液中 Ca2+、 Mg2+总含量在 2PPb左右， S04 2—可降至 2g/L,螯合树脂塔可达从 24小 时延长到 240小时再生。
Through the well-known filtration and chelation resin column adsorption, the total content of Ca 2+ and Mg 2+ in the secondary purified brine solution is about 2PPb, S0 4 2 - can be reduced to 2g / L, and the chelate resin tower can reach from 24 hours. Extended to 240 hours of regeneration.
Claims
1. 一种离子膜法制碱二次盐水精制方法， 其特征是： 将来自除去 C10—离子的一次盐水溶液输入首台石墨反应器，向首台石墨反应器内 输入磷酸和 /或亚磷酸， 再流入串联的后台石墨反应器， 向后台反应 器内输入 5%质量浓度的聚酸钠水溶液处理， 得到二次精制盐水。 An ion membrane method for preparing a secondary secondary brine refining method, characterized in that: a primary brine solution from which C10 ions are removed is introduced into a first graphite reactor, and phosphoric acid and/or phosphorous acid is input into the first graphite reactor. Then, it flows into a backstage graphite reactor in series, and is treated with a sodium 5% aqueous solution of sodium 5% in a background reactor to obtain secondary purified brine.
2. 根据权利要求 1 所述的离子膜法制碱二次盐水精制方法， 其 特征是： 所述除去 C10—离子的一次盐水溶液， 是将一次盐水经过添 加亚硫酸钠后， 去除 C10— 离子， 形成的含 Na2SO^P Cr的水溶液
The method for purifying an alkali secondary brine by an ion-exchange membrane method according to claim 1, wherein the primary salt solution for removing C10-ion is formed by removing C10-ion by adding sodium sulfite to the primary brine. An aqueous solution containing Na 2 SO ^ P Cr
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| CN201210291536.4 | 2012-08-15 | ||
| CN 201210291536 CN102774859A (en) | 2012-08-15 | 2012-08-15 | Ionic membrane method for preparing alkali secondary refining salt water |
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| CN105126937A (en) * | 2015-08-14 | 2015-12-09 | 芜湖融汇化工有限公司 | Chelate resin tower regeneration prolongation process method |
| CN105347363A (en) * | 2015-11-26 | 2016-02-24 | 山东潍坊润丰化工股份有限公司 | Process for treating byproduct industrial salt by water-washing adsorption method |
| CN113401924B (en) * | 2021-07-27 | 2023-02-03 | 恒信润丰科技开发（北京）有限公司 | Brine refining method |
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