CN111607802A - Method for preparing acid and alkali from by-product sodium sulfate - Google Patents
Method for preparing acid and alkali from by-product sodium sulfate Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/006—Recovery of sodium sulfate from coagulation baths for the spinning of viscose
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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Abstract
The invention discloses a method for preparing acid and alkali by using a by-product sodium sulfate, belonging to the technical field of by-product sodium sulfate treatment, and the method for preparing acid and alkali by using the by-product sodium sulfate comprises the following steps: s1, removing redundant metal ions in the sodium sulfate solution, and S2: and S3, feeding the sodium sulfate decahydrate obtained by crystallization in the step S2 into an electrolytic cell as anode feed of the electrolytic cell, electrolyzing the electrolytic cell, continuously preparing alkali liquor at a cathode, preparing acid liquor at an anode, and performing diffusion dialysis separation on the acid liquor prepared at the anode to separate the acid liquor and the sodium sulfate liquor, recovering the sulfuric acid liquor, and recycling the separated sodium sulfate liquor to an anode chamber of the electrolytic cell for recycling. The method for preparing acid and alkali by using the byproduct sodium sulfate has high acid-alkali concentration, effectively separates the sulfuric acid and the sodium sulfate in the anolyte, and can recycle the sodium sulfate.
Description
Technical Field
The invention belongs to the technical field of treatment of by-product sodium sulfate, and particularly relates to a method for preparing acid and alkali from by-product sodium sulfate.
Background
Viscose fiber is a globally important basic chemical industry, and is prepared by using wood, cotton linter and the like as raw materials, impregnating the raw materials with a dilute sodium hydroxide solution, reacting the raw materials with carbon disulfide to form sodium cellulose xanthate, dissolving the sodium xanthate in the sodium hydroxide solution to obtain a viscose solution, then entering a coagulation bath consisting of sulfuric acid, sodium sulfate, zinc sulfate and the like through fine holes of a spinning nozzle to form fiber, and then carrying out washing, desulfurization, bleaching, drying and other processes to prepare a finished product. A large amount of sodium sulfate is produced as a byproduct in the whole reaction process, excessive sodium sulfate is accumulated in the system and is easy to crystallize and separate out, and the excessive sodium sulfate concentration in the coagulating bath leads the fiber to be too fast to solidify, so that a fine structure is difficult to form and the quality of a fiber product is influenced. In order to ensure the balance of salinity of the system, in the prior art, sodium sulfate is separated from acid bath liquid mainly in an evaporation and freezing crystallization mode, then impurities in sodium sulfate crystals are removed through processes of recrystallization, dehydration and the like, and the obtained sodium sulfate product is not easy to sell, becomes an industry bottleneck problem of solid waste treatment in the fiber industry, and even forms a valuable and non-marketable situation.
How to solve the problem of byproduct mirabilite in the fiber industry can greatly promote the environmental protection and green sustainable development of the whole fiber industry. On the basis of the related work of the predecessors, the invention develops a set of technology for preparing acid and alkali by efficiently electrolyzing a byproduct sodium sulfate ion membrane in the viscose fiber industry, and the generated acid and alkali can be directly recycled to an on-site working section, so that the problem of balancing sodium sulfate in the viscose fiber industry is solved from the source.
The ion exchange membrane is a selective separation and extraction technology developed in recent decades and matured gradually, is a film made of a high polymer material with selective permeability to ions, and has been widely applied to the preparation of sodium hydroxide and chlorine gas by the electrolysis of a modern sodium chloride membrane in chlor-alkali chemical industry. Recently, research on the preparation of acid and alkali by electrolyzing sodium sulfate by ion exchange membrane technology has been advanced to some extent by related scientific research institutes at home and abroad, but the research is terminated because related technical and economic indexes have no industrial feasibility. The patent: a treatment process (CN201611078301.1) of sodium sulfate wastewater discloses a method for heating, evaporating and concentrating sodium sulfate by adopting a falling film evaporator, and cannot fundamentally solve the problem of high value of sodium sulfate. The patent: a method for preparing acid and alkali from viscose sodium sulfate waste liquid by a bipolar membrane electrodialysis method (CN201310311739.X) discloses a method for treating by-product sodium sulfate in viscose industry by a bipolar membrane electrodialysis technology, the method has low production efficiency of preparing acid and alkali, low concentration of obtained alkali (less than 10%), and high content of sodium sulfate in alkali (5-10 g/L); especially residual hemicellulosic material in sodium sulphate, can cause fatal irreversible damage to the negative membrane in the electrodialysis equipment if not treated thoroughly. The patent: the method for comprehensively utilizing the sodium sulfate wastewater (CN201010612329.5) discloses a method for preparing acid and alkali by electrolyzing sodium sulfate through an ionic membrane for recycling, and an organic medicament Polyacrylamide (PAM) used for pretreatment is unreasonable and can increase the damage to the ionic membrane; meanwhile, in the process, the mixture of sulfuric acid and sodium sulfate is finally obtained in the anolyte, and the problem of separation of sulfuric acid and sodium sulfate in the anolyte is not solved, so that the decomposition efficiency of sodium sulfate is low, the energy consumption is high, the current efficiency is low, and the problem is the biggest bottleneck problem of the process technology.
Disclosure of Invention
The invention aims to provide a method for preparing acid and alkali by using sodium sulfate as a byproduct, which has high concentration of prepared acid and alkali, can effectively separate sulfuric acid and sodium sulfate in anolyte, can recycle the sodium sulfate, has high decomposition efficiency of the sodium sulfate, low energy consumption and reduced cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing acid and alkali by-product sodium sulfate, which comprises the following steps: s1, removing redundant metal ions in the sodium sulfate solution, and S2: and S3, feeding the sodium sulfate decahydrate obtained by crystallization in the step S2 into an electrolytic cell as anode feed of the electrolytic cell, electrolyzing the electrolytic cell, continuously preparing alkali liquor at a cathode, collecting or recycling the alkali liquor to other sections on site, preparing acid liquor at the anode, and S4, performing diffusion dialysis separation treatment on the acid liquor prepared at the anode, separating to obtain sulfuric acid solution and sodium sulfate solution, recovering the sulfuric acid solution, collecting or recycling the sulfuric acid solution to other sections on site, and recycling the separated sodium sulfate solution to the anode chamber of the electrolytic cell for recycling.
Preferably, the mass concentration of the sodium sulfate in the anode liquid in the electrolytic cell is 150-350 g/L.
Preferably, the sodium sulfate solution in step S1 is prepared by using sodium sulfate decahydrate precipitated from the byproduct crystals as a feed material and water, or the sodium sulfate solution is prepared by using the byproduct sodium sulfate solution, wherein the temperature of the sodium sulfate solution is 35-60 ℃, and the mass concentration of the sodium sulfate solution is 150-.
Preferably, the specific steps of step S1 include the following: s11: adding sodium hydroxide and sodium carbonate into the sodium sulfate solution to primarily remove calcium and magnesium ions in the sodium sulfate solution, and S12: and (2) carrying out microfiltration on the sodium sulfate solution, carrying out cation exchange after microfiltration, and carrying out deep adsorption treatment on calcium, magnesium and other metal ions, S13: and performing secondary microfiltration on the sodium sulfate solution subjected to the deep adsorption treatment.
Preferably, ceramic membrane filtration equipment, PVDF (polyvinylidene fluoride) ultrafiltration membrane filtration equipment or disc tube membrane filtration equipment is adopted as precise filtration equipment, the diameter of the micro pores is 0.1-0.5 mu m, cation exchange is carried out by adopting cation chelating resin, the adsorption retention time is 0.5-2.5h, the mass concentration of calcium ions in the sodium sulfate solution after adsorption is less than 0.05mg/L, and the mass concentration of magnesium ions is less than 0.01 mg/L.
Preferably, the electrolytic cell is a diaphragm electrolytic cell, the diaphragm is a perfluorosulfonic acid type cation exchange membrane, the negative and positive electrolytes in the electrolytic cell adopt a forced circulation or elevated tank self-flow circulation mode, the anode material of the electrolytic cell is a titanium-based anode, the oxygen evolution active substance is a graphene, platinum, iridium and tantalum composite coating, the coating thickness is 5.0-15 μm, and the mass percentages are respectively: graphene: 5-15%, platinum: 5-10% of iridium, 40-60% of iridium and 15-50% of tantalum, wherein the cathode material of the electrolytic cell is a nickel-based cathode, the hydrogen evolution active substance is a platinum, ruthenium and titanium suboxide composite coating, the thickness of the coating is 5.0-15 μm, and the mass percentages are respectively as follows: platinum: 10-20%, ruthenium: 65-75% of iron oxide and 5-25% of ferric oxide.
Preferably, the initial catholyte in the cathode chamber is ultrapure water or sodium hydroxide solution, when the feed is ultrapure water, the discharge is sodium hydroxide solution with the mass concentration of 50-250g/L, and the cathode liquid level is 0.5-5cm higher than the anode liquid level.
Preferably, the electrolysis working current density of the electrolytic cell is 200-2The temperature of the electrolyte is 45-70 ℃;
preferably, the electrolytic cell is connected with a diffusion dialysis device to recover the sulfuric acid solution and the sodium sulfate solution on line for recycling, specifically, the anode feeding liquid adopts an internal circulation mode connected with an external storage tank, a diffusion dialysis membrane assembly is installed in the external storage tank on line, and the sulfuric acid in the anode liquid is recovered on line.
Preferably, the diffusion dialysis device adopts an aromatic polyether anion membrane to carry out diffusion dialysis separation, the recovery rate of the sulfuric acid is 85-90%, and the mass solubility of the sulfuric acid solution is 90-120 g/L.
The invention has the beneficial effects that:
1. the acid and alkali are prepared by membrane electrolysis, and the prepared acid and alkali have high concentration and can be reused in other working sections on site, so that resource recycling is realized.
2. Sulfuric acid and sodium sulfate in the anolyte are effectively separated, the sodium sulfate can be recycled, the utilization rate is improved, and the decomposition rate of the sodium sulfate is high.
3. High recovery rate of sulfuric acid and high purity of alkali.
3. The method has strong applicability, is more environment-friendly, has low investment and energy consumption, and is more environment-friendly.
4. Low pretreatment requirement and long service life of the membrane.
Drawings
Fig. 1 is a process flow diagram of a first embodiment and a second embodiment of the invention.
FIG. 2 is a process flow diagram of a third embodiment of the present invention.
FIG. 3 is a schematic diagram of the electrolysis of the electrolytic cell of the present invention.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and detailed description.
The first embodiment is as follows:
as shown in figures 1 and 3, a chemical fiber production enterprise adopts a freeze crystallization method to open mirabilite, and prepares a sodium sulfate solution with the mass concentration of 250-300g/L by taking precipitated sodium sulfate decahydrate as a feed at the temperature of 40-45 ℃. Because the zinc ion content in the solution is high, the crystallized sodium sulfate decahydrate contains 300mg/L of 250-fold zinc, firstly, the zinc is recovered by adopting a conventional chemical precipitation method, then sodium hydroxide and sodium carbonate are added into the sodium sulfate solution to primarily remove calcium and magnesium ions in the sodium sulfate solution, the sodium sulfate solution is subjected to precise filtration, the precise filtration equipment is ceramic membrane filtration equipment, the filtrate enters a cation chelating resin exchange system for deep adsorption and purification, the deep adsorption treatment of calcium, magnesium and trace zinc is carried out, the adsorption retention time is controlled for 0.5-2.5h, and the concentration of the calcium ions in the purified liquid is ensured to be less than 0.05mg/L and the concentration of the magnesium ions is ensured to be less than 0.01 mg/L. After the adsorbed solution is subjected to precise filtration, sodium sulfate solution is subjected to freezing crystallization, crystallized sodium sulfate decahydrate is fed into an electrolytic cell as anode feed of the electrolytic cell, and mother liquor is returned to the front end for blending and then is recycled. The working current density of the electrolysis of the electrolytic cell is 2500A/m2The temperature of the electrolyte is 45-50 ℃, the cathode continuously prepares sodium hydroxide solution, the alkali concentration is controllable to be 150g/L, the anode is a mixture of sulfuric acid solution and sodium sulfate solution, a diffusion dialysis membrane is adopted to carry out online recovery of sulfuric acid in anode mixed solution, and the recovered sulfuric acidThe mass concentration is 110g/L, the sodium sulfate decahydrate obtained by freezing crystallization is added into the anolyte, and the circulation of the sodium sulfate concentration of 250-300g/L is ensured for electrolysis. The direct ton alkali energy consumption of the whole operation process is 2200 plus 2300 kW.h. The prepared acid and alkali can be collected and stored or can be applied to each required section by concentration adjustment in the modes of dilution, evaporation concentration, addition of solid alkali or pure sulfuric acid and the like. Such as: the sodium hydroxide solution generated by electrolysis can be recycled to the impregnation section. The sulfuric acid solution generated by electrolysis can be recycled to the coagulation bath section.
Example two:
as shown in the figure 1 and the figure 3, a certain fiber company Limited produces about 5 ten thousand tons of mirabilite annually, sodium sulfate decahydrate separated out by secondary crystallization is used as a feed, and a sodium sulfate solution with the mass concentration of 300-350g/L is prepared under the condition of 55-60 ℃. Firstly, recovering zinc by adopting a conventional chemical precipitation method, then adding sodium hydroxide and sodium carbonate into a sodium sulfate solution to primarily remove calcium and magnesium ions in the sodium sulfate solution, carrying out precision filtration on the sodium sulfate solution, wherein the precision filtration equipment is PVDF (polyvinylidene fluoride) ultrafiltration membrane filtration equipment, the filtrate enters a cation chelating resin exchange system to carry out deep adsorption purification, carrying out deep adsorption treatment on calcium, magnesium and trace zinc, and controlling the adsorption retention time to be 0.5-2.5h to ensure that the concentration of the calcium ions in the purified liquid is less than 0.05mg/L and the concentration of the magnesium ions is less than 0.01 mg/L. After the adsorbed solution is subjected to precise filtration, sodium sulfate solution is subjected to freezing crystallization, crystallized sodium sulfate decahydrate is fed into an electrolytic cell as anode feed of the electrolytic cell, and mother liquor is returned to the front end for blending and then is recycled. The electrolytic bath electrolyzes with working current density of 3500A/m2And the temperature of the electrolyte is 55-60 ℃, the cathode continuously prepares a sodium hydroxide solution, the alkali concentration is controllable to be 200g/L, the anode is a mixture of a sulfuric acid solution and a sodium sulfate solution, a diffusion dialysis membrane is adopted to carry out online recovery of sulfuric acid in the anode mixed solution, the mass concentration of the recovered sulfuric acid is 120g/L, the sodium sulfate decahydrate obtained by freezing crystallization is supplemented into the anode solution, and the circulation of the sodium sulfate concentration of 300-350g/L is ensured for electrolysis. The direct ton alkali energy consumption of the whole operation process is 2600-2700 kW.h. The prepared acid and alkali can be collected and stored or concentrated by diluting, evaporating and concentrating, adding solid alkali or pure sulfuric acid, and the likeAnd (4) adjusting the degree and applying to each required section. Such as: the sodium hydroxide solution generated by electrolysis can be recycled to the impregnation section. The sulfuric acid solution generated by electrolysis can be recycled to the coagulation bath section.
Example three:
as shown in figures 2 and 3, the gold ore of a certain mine is subjected to desulfurization and gold extraction by adopting sodium hydroxide, the pH of ore pulp after cyanidation is adjusted to 4-5 by using sulfuric acid, gold concentrate is obtained by flotation, the gold is efficiently recovered, and the demand of acid and alkali on site is large. After the raw ore is subjected to sodium hydroxide pre-oxidation desulfurization, the solution is mainly a sodium sulfate solution with the concentration of about 150-200 g/L; adjusting the pH value of the prepared sodium sulfate solution to 8.5-9.0 by adopting sodium carbonate and sodium hydroxide, preliminarily removing calcium and magnesium ions in the sodium sulfate solution, carrying out precise filtration on the sodium sulfate solution, wherein the precise filtration equipment is disc-tube membrane filtration equipment, the filtrate enters a cation chelating resin exchange system for deep adsorption and purification, carrying out deep adsorption treatment on calcium and magnesium, controlling the adsorption retention time for 0.5-2.5h, and ensuring that the concentration of calcium ions in the purified liquid is less than 0.05mg/L and the concentration of magnesium ions is less than 0.01 mg/L. After the adsorbed solution is subjected to precise filtration, sodium sulfate solution is subjected to freezing crystallization, crystallized sodium sulfate decahydrate is fed into an electrolytic cell as anode feed of the electrolytic cell, and mother liquor is returned to the front end for blending and then is recycled. The working current density of the electrolysis of the electrolytic cell is 1500A/m2And the temperature of the electrolyte is 45-50 ℃, the cathode continuously prepares a sodium hydroxide solution, the alkali concentration can be controlled to be 100g/L, the anode is a mixture of a sulfuric acid solution and a sodium sulfate solution, a diffusion dialysis membrane is adopted to carry out online recovery of sulfuric acid in the anode mixed solution, the mass concentration of the recovered sulfuric acid is 90g/L, the sodium sulfate decahydrate obtained by freezing crystallization is supplemented into the anode solution, and the circulation of the sodium sulfate concentration of 150-200g/L is ensured for electrolysis. The direct ton alkali energy consumption of the whole operation process is 2100-plus 2200 kW-h. The prepared acid and alkali can be directly applied to the working sections of ore pretreatment and flotation operation after being blended in the modes of dilution, evaporation concentration, addition of solid alkali or pure sulfuric acid and the like.
Compared with the prior art, the invention has the following advantages: the index pair of the method for comprehensively utilizing sodium sulfate wastewater (application No. CN201010612329.5) is shown in Table 1:
TABLE 1
The comparison result shows that compared with the traditional membrane electrode technology, the optimized membrane electrolysis sodium sulfate technology disclosed by the invention has strong advantages in the aspects of energy consumption, product purity, efficiency and equipment stability. Especially, the purity of the cathode alkali directly determines the quality of the viscose fiber, especially in the viscose fiber industry, and has remarkable economic and social benefits.
Compared with the existing bipolar membrane treatment technology, the bipolar membrane treatment technology has the technical and economic advantages of low pretreatment requirement, long membrane service life, simple equipment structure, low investment, high concentration of generated acid and alkali, strong applicability, environment friendliness, high cost performance and the like, and realizes the purpose of changing waste into valuable.
Besides the adhesive fiber industry and the mine industry, the invention has good applicability to other industries producing sodium sulfate byproducts, such as chemical industry, lithium battery, hydrometallurgy and the like, through adjustment and optimization of related processes.
Those not described in detail in this specification are within the skill of the art. The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art; the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing acid and alkali by-product sodium sulfate is characterized by comprising the following steps:
s1, removing redundant metal ions in the sodium sulfate solution;
s2: freezing and crystallizing the sodium sulfate solution treated in the step S1, wherein a crystal is sodium sulfate decahydrate, and the crystallization mother liquor is recycled to prepare the sodium sulfate solution;
s3, feeding the sodium sulfate decahydrate obtained by crystallization in the step S2 into an electrolytic cell as anode feed of the electrolytic cell, electrolyzing the electrolytic cell, continuously preparing alkali liquor at the cathode, and preparing acid liquor at the anode;
s4, carrying out diffusion dialysis separation treatment on the acid solution prepared by the anode, separating to obtain a sulfuric acid solution and a sodium sulfate solution, recovering the sulfuric acid solution, and recycling the separated sodium sulfate solution to the anode chamber of the electrolytic cell for recycling.
2. The method for producing an acid or base with by-produced sodium sulfate according to claim 1,
the mass concentration of the sodium sulfate in the anode liquid in the electrolytic cell is 150-350 g/L.
3. The method for producing an acid or base with by-produced sodium sulfate according to claim 1,
in the step S1, the sodium sulfate solution is prepared by taking the sodium sulfate decahydrate precipitated from the byproduct crystals as a raw material and water, or the sodium sulfate solution is a byproduct, and the temperature of the sodium sulfate solution is 35-60 ℃ and the mass concentration of the sodium sulfate solution is 150-350 g/L.
4. The method for producing an acid or base with by-produced sodium sulfate according to claim 1,
the specific steps of step S1 include the following:
s11: adding sodium hydroxide and sodium carbonate into the sodium sulfate solution to primarily remove calcium and magnesium ions in the sodium sulfate solution;
s12: carrying out precise filtration on the sodium sulfate solution, carrying out cation exchange after the precise filtration, and carrying out deep adsorption treatment on calcium, magnesium and other metal ions;
s13: and performing secondary microfiltration on the sodium sulfate solution subjected to the deep adsorption treatment.
5. The method for producing an acid or base with by-produced sodium sulfate according to claim 4,
adopting ceramic membrane filtration equipment, PVDF ultrafiltration membrane filtration equipment or disc tube membrane filtration equipment as precise filtration equipment, wherein the micro-pore diameter is 0.1-0.5 mu m;
cation exchange is carried out by adopting cation chelating resin, the adsorption retention time is 0.5-2.5h, the mass concentration of calcium ions in the sodium sulfate solution after adsorption is less than 0.05mg/L, and the mass concentration of magnesium ions is less than 0.01 mg/L.
6. The method for producing an acid or base with by-produced sodium sulfate according to claim 1,
the electrolytic cell is a diaphragm electrolytic cell, and the diaphragm is a perfluorosulfonic acid type cation exchange membrane;
the cathode electrolyte and the anode electrolyte in the electrolytic cell adopt a forced circulation or elevated tank self-flow circulation mode;
the anode material of the electrolytic cell is a titanium-based anode, wherein the oxygen evolution active substance is a graphene, platinum, iridium and tantalum composite coating, the thickness of the coating is 5.0-15 mu m, and the mass percentages are respectively as follows:
graphene: 5-15%, platinum: 5-10% of iridium, 40-60% of iridium and 15-50% of tantalum;
the cathode material of the electrolytic cell is a nickel-based cathode, wherein the hydrogen evolution active substance is a platinum, ruthenium and titanium suboxide composite coating, the thickness of the coating is 5.0-15 mu m, and the mass percentages are respectively as follows:
platinum: 10-20%, ruthenium: 65-75% of iron oxide and 5-25% of ferric oxide.
7. The method for producing an acid or base with by-produced sodium sulfate according to claim 1,
the initial catholyte of the cathode chamber is ultrapure water or sodium hydroxide solution, and when the feed is ultrapure water, the discharge is sodium hydroxide solution with the mass concentration of 50-250 g/L;
the liquid level of the cathode is 0.5-5cm higher than that of the anode.
8. The method for producing an acid or base with by-produced sodium sulfate according to claim 7,
the electrolysis working current density of the electrolytic cell is 200-2And the temperature of the electrolyte is 45-70 ℃.
9. The method for producing an acid or base with by-produced sodium sulfate according to claim 1,
the electrolytic cell is connected with a diffusion dialysis device to carry out on-line recovery of sulfuric acid solution and sodium sulfate solution for recycling.
10. The method for producing an acid or base with by-produced sodium sulfate according to claim 9,
the diffusion dialysis device adopts an aromatic polyether anion membrane to carry out diffusion dialysis separation.
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