CN112939295A - Method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis - Google Patents
Method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis Download PDFInfo
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- CN112939295A CN112939295A CN202110319539.3A CN202110319539A CN112939295A CN 112939295 A CN112939295 A CN 112939295A CN 202110319539 A CN202110319539 A CN 202110319539A CN 112939295 A CN112939295 A CN 112939295A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/745—Preparation from sulfates
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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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/28—Purification; Separation
- C01D1/38—Purification; Separation by dialysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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Abstract
The invention discloses a method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis, belongs to the technical field of acid and alkali preparation, and aims to solve the problems of complex process and high production cost of the existing acid and alkali preparation. Which comprises the following steps: (1) dissolving the sodium sulfate decahydrate solid to form a sodium sulfate solution; (2) adding sodium carbonate and sodium hydroxide into the sodium sulfate solution, reacting to form solid precipitate, and adjusting the pH value of the solution to 8-10; (3) filtering the solution, and performing advanced oxidation to remove solid impurities and organic impurities; (4) filtering the solution for the second time, adsorbing impurities by active carbon, and adsorbing calcium and magnesium ions by resin; (5) filtering the solution by a precision filter to ensure that the contents of various ions and impurities in the filtrate meet the design requirements of entering bipolar membrane electrodialysis; (6) and treating the filtrate by a bipolar membrane electrodialysis process to obtain a sodium hydroxide solution and a sulfuric acid solution, and recycling the low-concentration sodium sulfate solution. The method is suitable for preparing acid and alkali by electrodialysis of the sodium sulfate bipolar membrane.
Description
Technical Field
The invention belongs to the technical field of acid and alkali preparation, and particularly relates to a method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis.
Background
China is a big agricultural country, the huge demand of agricultural production on chemical fertilizers directly leads to the vigorous development of the sulfuric acid industry in China, and meanwhile, sulfuric acid is widely applied to the chemical industry. The sulfuric acid yield of China increases year by year in the last decade, and important raw material guarantee is provided for the development of national economy. However, many problems exist behind the rapid development, serious environmental problems are caused by the discharge of acid waste water and harmful waste residues for many years, the solution is urgently needed, and the sulfuric acid production is gradually shifted to the direction of low pollution and high efficiency.
Sulfuric acid is an important industrial raw material, the production process of the sulfuric acid mainly comprises the steps of preparing acid by using sulfur, preparing acid by using pyrite, preparing acid by using smelting flue gas, preparing acid by using waste sulfuric acid through cracking, and the like, the processes generate flue gas containing SO2 by using methods of combustion and the like, and the flue gas is purified, converted and absorbed to prepare the finished product sulfuric acid. However, these conventional sulfuric acid-to-acid processes are complicated in flow, low in heat recovery rate, and can generate a large amount of waste liquid and cause serious environmental pollution. With the increasing emphasis on environmental protection in China, enterprises often need to adopt more complex processes to purify pollutants in the production process, so that the whole preparation process is more complex and the production cost is higher.
Disclosure of Invention
The invention aims to: provides a method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis, which solves the problems of complex process and high production cost of the existing acid and alkali preparation process.
The technical scheme adopted by the invention is as follows:
a method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis comprises the following steps:
(1) dissolving sodium sulfate decahydrate solid by pure water to form a sodium sulfate solution;
(2) adding sodium carbonate and sodium hydroxide into the sodium sulfate solution, reacting the sodium carbonate and the sodium hydroxide with metal ions in the sodium sulfate solution to form solid precipitates, and adjusting the pH value of the solution after reaction to be 8-10;
(3) the adjusted solution is filtered for one time to remove solid impurities in the solution, and the filtrate is treated by an advanced oxidation process to remove organic impurities in the filtrate;
(4) the solution treated by the advanced oxidation process is subjected to secondary filtration, impurities in the solution are adsorbed by active carbon, and calcium and magnesium ions in the solution are adsorbed by resin;
(5) filtering the adsorbed solution by a precision filter to enable the content of various ions and impurities in the filtrate to meet the design requirement of bipolar membrane electrodialysis;
(6) and (3) performing bipolar membrane electrodialysis process treatment on the filtrate reaching the standard, obtaining sodium hydroxide and sulfuric acid solution through bipolar membrane electrodialysis, and adding the low-concentration sodium sulfate solution into the sodium sulfate solution obtained in the step (1) for recycling.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. in the invention, after dissolving, pH adjusting, filtering and impurity removing, the formed solution is filtered by a precision filter according to production requirements and then is treated by a bipolar membrane electrodialysis process to obtain sodium hydroxide and sulfuric acid, the generated low-concentration sodium sulfate solution can be reused, the whole treatment process has high conversion utilization rate of the sodium sulfate decahydrate, low production cost and high economic benefit, no by-product is generated in the preparation process, no environmental protection problem is generated, and the problems of complexity and high production cost of the existing acid and alkali preparation process are solved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and that for those skilled in the art, other relevant drawings can be obtained according to the drawings without inventive effort, wherein:
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a flow diagram of a bipolar membrane electrodialysis process of the present invention;
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: reference numerals and letters designate similar items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings or the orientations or positional relationships that the products of the present invention usually place when in use, and are simply used for simplifying the description of the present invention, but do not indicate or imply that the devices or elements indicated must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
Furthermore, the terms "horizontal", "vertical" and the like do not imply that the components are required to be absolutely horizontal or pendant, but rather may be slightly inclined. For example, "horizontal" merely means that the direction is more horizontal than "vertical" and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the present invention, it should also be noted that, unless otherwise explicitly specified or limited, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; mechanical connection or electrical connection can be realized; the two original pieces can be directly connected or indirectly connected through an intermediate medium, or the two original pieces can be communicated with each other. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
A method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis comprises the following steps:
(1) dissolving sodium sulfate decahydrate solid by pure water to form a sodium sulfate solution;
(2) adding sodium carbonate and sodium hydroxide into the sodium sulfate solution, reacting the sodium carbonate and the sodium hydroxide with metal ions in the sodium sulfate solution to form solid precipitates, and adjusting the pH value of the solution after reaction to be 8-10;
(3) the adjusted solution is filtered for one time to remove solid impurities in the solution, and the filtrate is treated by an advanced oxidation process to remove organic impurities in the filtrate;
(4) the solution treated by the advanced oxidation process is subjected to secondary filtration, impurities in the solution are adsorbed by active carbon, and calcium and magnesium ions in the solution are adsorbed by resin;
(5) filtering the adsorbed solution by a precision filter to enable the content of various ions and impurities in the filtrate to meet the design requirement of bipolar membrane electrodialysis;
(6) and (3) performing bipolar membrane electrodialysis process treatment on the filtrate reaching the standard, obtaining sodium hydroxide and sulfuric acid solution through bipolar membrane electrodialysis, and adding the low-concentration sodium sulfate solution into the sodium sulfate solution obtained in the step (1) for recycling.
Among them, the bipolar membrane is a novel ion exchange composite membrane, which is usually composed of a cation exchange layer (N-type membrane), an interfacial hydrophilic layer (catalyst layer) and an anion exchange layer (P-type membrane), and is a reaction membrane in the true sense. Under the action of a direct current electric field, the bipolar membrane can dissociate water to obtain hydrogen ions and hydroxyl ions on two sides of the membrane respectively. By utilizing the characteristic, the bipolar membrane electrodialysis system combining the bipolar membrane and other anion-cation exchange membranes can convert the salt in the aqueous solution into corresponding acid and alkali without introducing new components.
When sodium sulfate enters the salt chamber, sulfate ions migrate to the acid chamber through the cathode membrane under the action of a direct current electric field and encounter the anode membrane surface of the bipolar membrane, and because the anode membrane surface is negatively charged, the sulfate ions cannot continuously migrate and are left in the acid chamber to combine with hydrogen ions decomposed from the anode membrane surface of the bipolar membrane to generate sulfuric acid. Under the action of DC electric field, the negative film surface of the bipolar membrane continuously decomposes out hydroxide ions which are combined with sodium ions in an alkaline chamber to produce sodium hydroxide. The sodium sulfate is converted to sulfuric acid and sodium hydroxide by bipolar membrane electrodialysis.
The process design comprises the following steps:
1) treatment capacity: 330t/a (sodium sulfate book Baiji)
2) The main components are as follows:
the filter liquor water quality after the precision filtration is designed, and the water inlet water quality of the bipolar membrane system is designed as follows:
(1)Na2SO4≥150g/L
(2) the water temperature is 5-40 DEG C
(3) Does not contain macromolecular organic matters such as phenol, fatty acid, aromatic hydrocarbon and the like
(4)SS＜1mg/L
(5) Iron is less than 0.3mg/L
(6) Manganese is less than 0.1mg/L
(7) Turbidity < 1NTU
(8)Mg\Ca＜1mg/L
(9) Other divalent heavy metals are less than 0.1mg/L
(10) Oil content is less than 0.1mg/L
(11) Silicon dioxide is less than 1mg/L
(12) Surfactant less than 0.1mg/L
According to the water inlet requirement of the bipolar membrane, the sodium sulfate solution is pretreated to remove heavy metal ions and other impurities in the solution.
3) Quality of effluent water
Side of alkaline water: NaOH 40g/L
Acid water side: h2SO4 40g/L
The above description is an embodiment of the present invention. The foregoing is a preferred embodiment of the present invention, and the preferred embodiments in the preferred embodiments can be combined and used in any combination if not obviously contradictory or prerequisite to a certain preferred embodiment, and the specific parameters in the embodiments and examples are only for the purpose of clearly illustrating the verification process of the invention and are not intended to limit the patent protection scope of the present invention, which is subject to the claims and all the equivalent structural changes made by the content of the description and the drawings of the present invention are also included in the protection scope of the present invention.
Claims (1)
1. A method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis is characterized by comprising the following steps:
(1) dissolving sodium sulfate decahydrate solid by pure water to form a sodium sulfate solution;
(2) adding sodium carbonate and sodium hydroxide into the sodium sulfate solution, reacting the sodium carbonate and the sodium hydroxide with metal ions in the sodium sulfate solution to form solid precipitates, and adjusting the pH value of the solution after reaction to be 8-10;
(3) the adjusted solution is filtered for one time to remove solid impurities in the solution, and the filtrate is treated by an advanced oxidation process to remove organic impurities in the filtrate;
(4) the solution treated by the advanced oxidation process is subjected to secondary filtration, impurities in the solution are adsorbed by active carbon, and calcium and magnesium ions in the solution are adsorbed by resin;
(5) filtering the adsorbed solution by a precision filter to enable the content of various ions and impurities in the filtrate to meet the design requirement of bipolar membrane electrodialysis;
(6) and (3) performing bipolar membrane electrodialysis process treatment on the filtrate reaching the standard, obtaining sodium hydroxide and sulfuric acid solution through bipolar membrane electrodialysis, and adding the low-concentration sodium sulfate solution into the sodium sulfate solution obtained in the step (1) for recycling.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110319539.3A CN112939295A (en) | 2021-03-25 | 2021-03-25 | Method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis |
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| CN202110319539.3A CN112939295A (en) | 2021-03-25 | 2021-03-25 | Method for preparing acid and alkali by sodium sulfate bipolar membrane electrodialysis |
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| CN112939295A true CN112939295A (en) | 2021-06-11 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113830740A (en) * | 2021-10-11 | 2021-12-24 | 浙江志澄环境资源科技有限公司 | Method for preparing acid and base by bipolar membrane based on electrodialysis technology |
| CN115555054A (en) * | 2022-10-18 | 2023-01-03 | 西安西热水务环保有限公司 | System for industrial salt electricity regeneration ion exchange resin |
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| CN111003854A (en) * | 2019-12-23 | 2020-04-14 | 新疆中泰创新技术研究院有限责任公司 | Device and method for electrolyzing mirabilite by using bipolar membrane electrodialysis equipment |
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| CN113830740A (en) * | 2021-10-11 | 2021-12-24 | 浙江志澄环境资源科技有限公司 | Method for preparing acid and base by bipolar membrane based on electrodialysis technology |
| CN113830740B (en) * | 2021-10-11 | 2023-06-02 | 浙江志澄环境资源科技有限公司 | Method for preparing acid and alkali by bipolar membrane based on electrodialysis technology |
| CN115555054A (en) * | 2022-10-18 | 2023-01-03 | 西安西热水务环保有限公司 | System for industrial salt electricity regeneration ion exchange resin |
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