CN108623197A - The conversion reuse method of sodium sulphate in ardealite conversion recycling - Google Patents

The conversion reuse method of sodium sulphate in ardealite conversion recycling Download PDF

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CN108623197A
CN108623197A CN201710181477.8A CN201710181477A CN108623197A CN 108623197 A CN108623197 A CN 108623197A CN 201710181477 A CN201710181477 A CN 201710181477A CN 108623197 A CN108623197 A CN 108623197A
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耿兆翔
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    • 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
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    • C01B17/88—Concentration of sulfuric acid
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    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid
    • C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
    • C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
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    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
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    • C—CHEMISTRY; METALLURGY
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    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/06—Preparation of sulfates by double decomposition
    • C01D5/08—Preparation of sulfates by double decomposition with each other or with ammonium sulfate
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    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/466—Conversion of one form of calcium sulfate to another
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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    • C04B11/02—Methods and apparatus for dehydrating gypsum
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    • C04B11/00—Calcium sulfate cements
    • C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract

The conversion reuse method of sodium sulphate in ardealite conversion recycling, be related to inorganic chemical technology field, aqueous sodium persulfate solution electrolysis, sodium hydrate aqueous solution recycle react with calcium bisulfate, sulfuric acid recycles react to produce phosphoric acid and react with gypsum calcium sulfate with apatite and produces calcium bisulfate.Apply to ardealite conversion recycling.

Description

The conversion reuse method of sodium sulphate in ardealite conversion recycling
Technical field：
The present invention relates to the conversion of sodium sulphate in inorganic chemical technology field, especially ardealite conversion recycling is sharp again Use method.
Background technology：
Chinese invention patent, application number：201410430521.0 the applying date：2014.08.23
Applicant：Geng Zhaoxiang, invention and created name：The resource utilization of industrial phosphogypsum waste residue utilizes method, application public Cloth CN104211099A, data of publication of application：2014.12.17 this application Ca (HSO4)2+ 4NaOH=2Na2SO4+Ca(OH)2↓+ 2H2O；Due to sodium sulphate Na2SO4The market price is too low, and the sodium hydroxide NaOH market prices are relatively too high, lead to manufacturing enterprise Profit is meagre, in some instances it may even be possible to lose.The annual phosphogypsum slag output in China is huge, up to 50,000,000 tons, also inventory in history 300,000,000 tons of accumulation need the phosphogypsum slag yield for handling recycling huge.Due to the shortage of China's potassium resource, by hydrogen Potassium oxide KOH converts ardealite, just very unrealistic due to being limited by raw material；And rely on sodium hydroxide NaOH conversions Ardealite, downstream product sodium sulphate Na2SO4Price is low, and market demand is again very limited；So can not be huge by China's yield Phosphogypsum slag have the conversion of distinct economic to recycle.Feasible and necessary method is only by sodium sulphate Na2SO4 Further conversion reduces cost to carry out resource reclaim and cycling and reutilization, only in this way, China's ardealite recycling production Industry could sustainably develop.
But by sodium sulphate Na2SO4With hydrogen H2Catalysis reduction, in 550~600 DEG C of pyrolytic conversions at vulcanized sodium Na2S, turn Rate is only 90% or so, such sodium sulphate Na2SO4With vulcanized sodium Na2The mixture of S also greatly reduces vulcanized sodium Na2S Use value；Vulcanized sodium Na2The market demand of S is very limited, far can not be adapted with the conversion of ardealite；High-temperature catalytic Reaction, energy-output ratio are huge；Since its reaction has water generation, so gas pressure is too big in reactor, equipment investment is big, Production capacity is small, can technically realize industrialized production not yet.Hydrogen H simultaneously2Source be also huge technological challenge；Electrolysis Water hydrogen manufacturing production efficiency is too low, and cost is too high；Preferable hydrogen source is methanol high temperature (at 220~280 DEG C) catalytic pyrolysis： CH3OH+H2O=CO2+3H2, hydrogen manufacturing and carbon dioxide, but the discharge capacity of its GHG carbon dioxide is too big.
Sodium sulphate Na2SO4It is reduced into vulcanized sodium with carbon C or carbon monoxide CO, production technology is immature, and there are no can Realize industrialized production；The discharge capacity of its GHG carbon dioxide is too big simultaneously；Its technical solution is undesirable.
And vulcanized sodium Na2S adds water electrolysis further to convert recycling sulphur, hydrogen and sodium hydroxide, anode electrolytic cell easily by Sulphur S coverings, and the anode of electrolysis is made to be passivated, restrict and influence vulcanized sodium Na2S adds the industrialization production feasibility of water electrolysis And production efficiency；1 vulcanized sodium Na2S molecules add water electrolysis that can only generate 1 hydrogen molecule, and a sodium sulphate Na2SO4Molecule with Hydrogen H2Catalysis reduction need 4 hydrogen molecules；Hydrogen H2Source be huge technological challenge.
So far, ardealite conversion recycles and has the resource recycling for capableing of sustainable development of distinct economic to recycle Seem to be faced with impasse.
Therefore, it is necessary to creatively to sodium sulphate Na2SO4Further transformation technology carry out it is substantive it is whole again Design recycles recycling and reuse industry for ardealite and provides strong feasible technical support；It is energy saving, environmental protection, And have larger significantly stable economic benefit；To push ardealite conversion recycling industry sustainably to develop.
Invention content：
Inventive principle：
(1)《Kunming University of Science and Technology's journal》(science and engineering version) in June, 2006, the phase of volume 31 the 3rd,《Film electrolytic sulfite regenerates The research of acid》-- Zhu Yun, Guo Shuxian, Kunming University of Science and Technology's material and metallurgical engineering institute；Reaction equation：Na2SO4+H2O electrolysis → H2SO4+NaOH+O2+H2。
Sodium sulphate is decomposed with the method that film is electrolysed, experiment has carried out the cathode of electrolytic sulfite, anode material selection, research The influence of sodium sulfate concentration and naoh concentration to electrolysis determines the tank voltage composition of electrolytic sulfite, finds preferably Electrolytic condition.In [Na2SO4]=1.5mol/L, [NaOH]=0.5mol/L, under conditions of alloy lead anode, nickel cathode, film The decomposition voltage of electrolytic sulfite is 3.4V.
Middle figure classification number：TF111.52, Document code：A, article number：1007-855X(2006)03-0009-03
It is ripe in view of chlorine industry film electrolysis tech, the film electrolysis of chlor-alkali industry is applied to sodium sulphate and is decomposed, is carried Go out and obtains sodium hydroxide and sulfuric acid using cation-exchange membrane electrolytic sulfite solution.The rule of film electrolytic sulfite are studied herein Rule.
Its experimental method and principle：Electrolytic cell is divided into cathode chamber and anode chamber with cationic membrane, is each fitted with anode plate And cathode plate, metabisulfite solution is full of in anode chamber, is full of water or NaOH solution in cathode chamber, under DC electric field effect sodium from Son enters cathode chamber through cationic membrane, and as a result the NaOH concentration of cathode chamber constantly increases, the H of anode chamber2SO4Concentration constantly increases It is high.Finally obtain a small amount of sodium sulphate and a large amount of H2SO4Solution.
Cationic membrane electrolysis basic principle be：Fixing base band due to membrane body has negatively charged ions, cationic membrane may be selected Property through cation.The reaction occurred on the electrode is as follows：Anode reaction：2OH-- 2e=H2O+1/2O2；Cathode reaction：2H+ + 2e=H2；Na++OH-=NaOH；Constantly decline to the PH of anode chamber, the NaOH of cathode chamber is constantly enriched with.Have in a cell It acts below：1. being electrolysed：H+、OH-Ion discharges on cathode-anode plate respectively；2. counter ion migrates：Na+The migration of ion, ion The direction of migration is opposite with concentration gradient direction；3. the migration of ion of the same name：OH-The migration of ion, migration direction with it is dense Degree gradient direction is identical, since Donnan equilibrium makes the selective penetrated property of ion exchange that can not possibly reach 100%；4. electric osmose dehydration： The migration of ion is actually the migration of hydrated ion, therefore the inevitable loss for causing water simultaneously when ion is migrated through film； 5. dialysis：Electrolyte ion is because of the phenomenon that concentration difference penetrates film；6. permeating：Water penetrates the phenomenon that film；7. leaking：Solution penetrates Film；8. the first two processes in sodium sulphate electrolytic process that polarize are main process.
Experiment and as a result, the used film of this experiment is perfluorinated sulfonic acid-Carboxylic Acid Ions exchange membrane that DuPont Corporation produces, The trade mark is N-900-TX.In order to enable ionic membrane to keep electric under higher current efficiency and lower tank voltage steadily in the long term Solution has carried out the experiment of electrode material, concentration of electrolyte, tank voltage composition, fixed current density 500A/m2。
Electrode material has a significant impact to the tank voltage of electrolysis.For sulfuric acid system, can be met the requirements with metal, and It is cheap, therefore test using calcium strontium argentalium alloy sheets as anode.Influence of the cathode material to electrode overpotential is also very big.
Film electrolytic process is with the extension of electrolysis time, tank voltage increase；There are one inflection points when 2min, this is film electrodeposition body System does not set up balance；8min caudacoria electrodeposition Establishings balance, tank voltage tend to be steady.The tank voltage of nickel alloy cathode is also very It is low, it is 3.38V, it is close with platinum, palladium composite material, but price is very low, is good cathode material.
The tank voltage that the concentration of electrolyte is electrolysed sodium sulphate film has an impact, experimental study anode chamber sodium sulfate concentration, The tank voltage of cathode chamber naoh concentration and anode chamber's acid adding.Tank voltage is 3.3~3.5V.
Electrolysis under different temperatures, temperature increase, and ion diffusion is accelerated, and the polarization of sodium sulphate film electrolysis reduces, tank voltage Stablize.Influence of the temperature to sodium sulphate membrane electrolysis cells voltage, initial sodium sulfate concentration are 1.5mol/L, initial naoh concentration For 0.5mol/L, naoh concentration increment is 0.058mol/L.As it can be seen that the inflection point that temperature increases when film electrolysis starts tends to be flat Slow, film electrodeposition system establishes balance quickly, and tank voltage reduces, but temperature is to the influence very little of sodium sulphate membrane electrolysis cells voltage.One Aspect, temperature increase the solubility for increasing sodium sulphate, and can stablize the tank voltage of electrolysis.At 50~100 DEG C, the slot of beginning Voltage fluctuation slows down.On the other hand, temperature is high, and the service life of film reduces, and temperature cannot be excessively high.Chlorine industry is electric at 80 DEG C Solution is electrolysed for sodium sulphate film and refers to.
The tank voltage of electrolysis is constituted：The tank voltage drop of sodium sulphate film electrolysis is by sodium sulphate decomposition voltage (including theoretical decomposition Voltage and ultra-voltage), membrane voltage drop, electrolyte voltage drop and contact drop composition.The pressure drop of each section is found out to reducing slot Voltage is of great significance.It is 500A/m that experiment, which is determined in current density,2Under conditions of sodium sulphate decomposition voltage be 1.58V drops in 1.48V, membrane voltage, and 0.11V (catholyte voltage drop 0.05V, anode fluid pressure drop 0.06V), contact drop in electrolyte voltage Voltage drop 0.05V, tank voltage are reduced to 3.22V (overall presure drop).It follows that membrane voltage drop accounts for the significant portion of total voltage drop, It is the main path for reducing sodium sulphate film electrolysis energy consumption to find the film that voltage reduces.
Conclusion：Experiment shows that sodium sulphate progress film electrolysis process is feasible, is 500A/m in current density2Under conditions of electricity The tank voltage of solution is reduced to 3.3~3.4V, and tank voltage drop is close with chlorine industry, but current density is low more than chloric alkali electrolysis.It can Happiness be sodium sulphate film electrolysis pole plate and anti-corrosion all than the easy solution of chlorine industry, have good industrial prospect.Selection is suitable When sodium sulfate concentration (1.5mol/L), catholyte sodium hydroxide concentration (0.5mol/L) and plate material (alloy lead anode, Plating nickel cathode) tank voltage can be reduced, stablize electrolysis.
The optium concentration of anode chamber aqueous sodium persulfate solution electrolysis is 1.5 mol/Ls, cathode chamber sodium hydroxide it is a concentration of 0.5 mol/L, 50~80 DEG C of electrolysis temperature, temperature is increased at 80 DEG C or less can accelerate diffusion and the electrolytic speed of ion.Electrolysis Temperature is proportional with electrolytic speed.Electrolysis direct current electric current and voltage and electrode material are with reference to the above-mentioned prior art.
(2) for according to the prior art, ion-exchange membrane electrolysis is also known as film electricity slot electrolysis, and being will be single using cation-exchange membrane First electrolytic cell is divided into anode chamber and cathode chamber, the method for making electrolytic production separate.
Ion-exchange membrane electrolysis is the new technology to grow up on the basis of ion exchange resin.Utilize ion exchange Film has zwitterion a characteristic that selection penetrates, a kind of ion of charge of allowed band by by limit opposite charges ion it is logical It crosses, to achieve the purpose that concentration, desalination, purification, purification and electrification synthesize.
This technology has been used to the production of chlor-alkali, the desalination of seawater and bitter, the preparation of industrial water and ultra-pure water, Refined, the recycling of electroplating effluent of the drugs such as enzyme, vitamin and amino acid, processing of radioactive wastewater etc., wherein applying Most extensively, effect most significantly chlorine industry.In chlorine industry, cation-exchange membrane electrolytic tank electrolysis salt or chlorine are utilized Change aqueous solutions of potassium to manufacture chlorine, hydrogen and the sodium hydroxide of high-purity.Perfluor is made in industrial group of Japanese Asahi Chemical Industry within 1975 Carboxylic acid type amberplex realizes electrolysis with ion-exchange film legal system caustic soda first, and the same year, Japan realized industrialized production.
Sodium ion under electric field action through cation-exchange membrane to cathode chamber move, into catholyte sodium ion together with Electrolysis water on cathode and the hydroxyl ion that generates generates sodium hydroxide, while hydrogen is released on cathode.In common salt aqueous solution Chlorion is limited by film, substantially chlorine cannot be oxidized on anode into cathode chamber.Partial oxidation sodium electricity Xie Hou, remaining light salt brine outflow electrolytic cell dissolve chlorine solid salt is saturated and is refined again after through removing and return to anode chamber, structure At the brine loop similar with mercury process.A sodium hydroxide solution part for cathode chamber is left as product, a part is added pure Cathode chamber is returned after water.The cycle of lye helps to accurately control the water of addition, and energy band walks the heat of electrolyte bath generation Amount.
The amberplex of ion-exchange membrane electrolysis：It can be rolled into a ball with anion palaces such as sulfonic group and (or) carboxylic acid groups on side chain Film made of (per) fluoropolymer.Requirement to ionic membrane：1. cation selective permeability is good；2. electrolyte diffusion rate is low；③ Higher chemical stability and thermal stability；4. high mechanical strength is unlikely to deform；5. resistance is small.Modern cation-exchange membrane is big Perfluorinated sulfonic acid-perfluorocarboxylic acid composite membrane of mostly poly- fluorohydrocarbon fabric enhancing.Side towards anode is the smaller sulfonic group of resistance； Side towards cathode is the low carboxylic acid group of water content, and hydroxyl ion can be inhibited mobile to anode chamber and improve current efficiency, had Be also treated as coarse surface, or have micropore shape inorganic matter film, to increase the hydrophily of perfluorocarboxylic acid film, reduce hydrogen The delay of bubble on the surface of the film.The ion that this film is suitable for minimum so-called " zero " pole span or " film " gap of the two poles of the earth spacing is handed over Change membrane electrolysis cells.The characteristics of ion-exchange membrane electrolysis, 1. total energy consumption was minimum, in 4000A/m2Under current density, the direct current of caustic soda per ton Power consumption is 7.56~7.92GJ (2100~2200kWh)；2. caustic soda purity is high, 50% sodium hydroxide lye, sodium chloride-containing 50 ~60ppm；3. without mercury or the problem of asbestos pollution environment；4. operation, control are all easier；5. adapting to the energy of load variations Power is larger；6. it is required that with the brine of high quality；7. the price of ionic membrane is more expensive.
(3) formation basic theory of 50%~70% sulfuric acid of mass contents：In aqueous sodium persulfate solution electrolysis, 1 numerator sulphuric acid companion It is generated with 1 molecular water, at this moment the mass fraction of sulfuric acid is 84.4% (concentration principle of electrolysis), this is electrolytically generated sulfuric acid The theoretical Up limit of mass content.
It is placed in the anode plane electrode of electrolysis, and in the side of netted discharge and the anode planes electrode of collection sulfuric acid The sieve of 200~500 acidproof mesh/square centimeter terylene material, sieve are close to the anode planes of netted discharge and collection sulfuric acid The one side of electrode, mesh (mesh) number on sieve unit area (square centimeter) increase with the vertical depth of sodium sulphate water electrolysis liquid Add and increases；The plane electrode thickness of anode is 2~5mm.This design method can be effectively reduced free water and flow out netted sun The speed of pole, the excessive free water reduced in anode chamber enter sulfuric acid；Make a water under the horizontal pressure force of aqueous sodium persulfate solution One numerator sulphuric acid carries a molecular water again when flowing out anode, and a numerator sulphuric acid of outflow anode so only carries two molecules Water, aqueous sulfuric acid mass percent at this moment is 73.1%.One sulfuric acid molecule can be with two hydrone knots by hydrogen bond It closes, so aqueous sulfuric acid mass percent is no more than 73.1% in aqueous sodium persulfate solution electrolysis.
The sieve of terylene material can also be replaced with acidproof evanohm stainless steel mesh.Resistance to 120 DEG C of the sieve of terylene material with Under temperature and resistance to 70% mass percentage concentration aqueous sulfuric acid below.
Thus principle is it is found that the aqueous sulfuric acid of 50%~70% mass percentage concentration of production is feasible；It is higher than The sulfuric acid of 73.1% mass percentage concentration is difficult to obtain, and the sulfuric acid less than 73.1% mass percentage concentration is easy to get.Pass through Mesh (mesh) in selection and adjustable screen unit area (square centimeter) counts to improve the mass percentage concentration of aqueous sulfuric acid Reach 50%~70%.
Since dilute sulfuric acid dehydration concentration is relatively difficult, need to consume the energy；So the mass percent for improving sulfuric acid be for It is anti-for 98% concentrated sulfuric acid and gypsum calcium sulfate it to be condensed into 98% concentrated sulfuric acid circulating in the dehydration of aqueous sulfuric acid heating, vacuum When phosphoric acid and gypsum should be reacted into floats at calcium bisulfate and 98% concentrated sulfuric acid (add water and dilute heat release), to reduce The usage amount of sulfur trioxide and energy saving reduces during above-mentioned cycle is used and generates excessive surplus sulfuric acid, also reduces ammonium sulfate Or the yield of potassium sulfate；The dehydration of aqueous sulfuric acid heating, vacuum is also reduced simultaneously is condensed into generated heat when 98% concentrated sulfuric acid Water reduces thermal water pollutilon.
(4) sulfur trioxide is a kind of sulfur oxide, molecular formula SO3, have the smell of similar sulfur dioxide, be dissolved in water Middle reaction is at sulfuric acid.16.8 DEG C of fusing point, 44.8 DEG C of boiling point, soluble easily in water, strong oxidizer.It is dissolved in water, is reacted with water, water reaction is met Acutely.Strong oxidizer, the dehydration compared with sulfuric acid, oleum are stronger.
The chemical property of sulfur trioxide, SO3Middle S atom is in highest oxidation state+6, so SO3It is a kind of strong oxidizer； SO3Moisture is easily absorbed, is smoldered strongly in air, water is dissolved in and generates sulfuric acid and release big calorimetric.
(5) bassanite, English name：Bassanite. ingredient Ca [SO4]·0.5H2O.Chemical formula CaSO4·0.5H2O。
Calcium sulfate, chemical formula CaSO4.White solid.1450 DEG C of fusing point.It is called gypsum or life with two molecular crystalline water Gypsum (CaSO4·2H2O).When gypsum is heated to 150-170 DEG C, most of crystallization water loses, and becomes the plaster of paris (CaSO4· 1/2H2O)。
Dihydrate gypsum CaSO4·2H2O is also known as gypsum, by calcining, levigate obtains beta-type semi-hydrated gypsum CaSO4·1/ 2H2O.If calcination temperature, which is 190 DEG C, can obtain model plaster.If being calcined gypsum to get calcium sulfate at 400-500 DEG C.
(6) sulfuric acid
Sulfuric acid (chemical formula：H2SO4), the most important oxyacid of sulphur.It is produced with tower process and contact method.The former is at gained Crude dilute sulfuric acid, mass fraction is generally 75% or so；The pure concentrated sulfuric acid of the latter Ke get mass fractions 98.3%.
Bright sulfur acid is generally colourless oil liquid, density 1.84g/cm3, 337 DEG C of boiling point can be mutual with arbitrary proportion with water It is molten, while a large amount of heat is released, make boiling water.Be heated to start to release sulfur trioxide at 290 DEG C, ultimately become for 98.54% aqueous solution boils at 317 DEG C and becomes azeotropic mixture.The boiling point and viscosity of sulfuric acid are higher, are because of its point The stronger reason of hydrogen bond inside son.
Bright sulfur acid is heated to 290 DEG C and decomposes to give off part sulfur trioxide, until the concentration of acid drops to 98.3%, at this moment Sulfuric acid is constant boiling solution, and boiling point is 338 DEG C.
(7) standard GB/T/T50815-2013--《Dilute sulfuric acid is concentrated in vacuo treatment technology specification》(May 01 in 2013 It rises day and implements).
Technical solution of the present invention：
(1) mono-, of are by Ca (HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓ reaction in temperature be 80~100 DEG C sodium sulphate hydrothermal solution is not required to dehydrate, and is cooled to after 50~80 DEG C and directly continuously inputs electrolytic cell or electrolysis with pipeline The anode chamber of slot；The anode chamber of electrolytic cell is previously added deionized water or edible soft water；Or the anode chamber of electrolytic cell is previously added The aqueous sodium persulfate solution of a concentration of 1.4~1.5 mol/L of sodium sulfate quality；The cathode chamber of electrolytic cell is previously added 0.5 and rubs simultaneously You/liter deionized water or edible soft water sodium hydrate aqueous solution；And above-mentioned sodium sulphate hot water is adjusted according to the speed of electrolysis The input speed of solution, it is the sodium sulphate water of 1.4~1.5 mol/Ls to keep sodium sulfate quality content in the anode chamber of electrolytic cell Solution；
The sodium sulfate quality content of above-mentioned (one) is the aqueous sodium persulfate solution perfluor sulphur of 1.4~1.5 mol/Ls by two, Acid-carboxylic acid cation-exchange membrane carries out film direct current electrolysis；Generate the sodium hydroxide water that mass percentage concentration is 30%~40% The aqueous sulfuric acid and hydrogen and oxygen that solution and mass percentage concentration are 50%~70%；In the anode plane electricity of electrolysis Pole, and it is netted discharge and collection aqueous sulfuric acid anode planes electrode side place 200~500 acidproof mesh/square The sieve or acidproof evanohm stainless steel mesh of centimetre terylene material, sieve are close to the anode planes of netted discharge and collection sulfuric acid The one side of electrode, mesh mesh number on sieve unit area square centimeter increase with the vertical depth of sodium sulphate water electrolysis liquid and Increase；The plane electrode thickness of anode is 2~5mm；Mass percentage to improve the aqueous sulfuric acid of outflow anode reaches 50%~70%；
The sodium hydrate aqueous solution recycling of above-mentioned (two) is applied to calcium bisulfate and reacts generation sulphur with sodium hydroxide by three, The reaction of sour sodium and calcium hydroxide and water；
Reaction equation：Ca(HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓；
Four, recycle the hydrogen partial of above-mentioned (two) as clean energy resource, are heated for phosphogypsum slag, heating temperature 180~200 DEG C of degree makes dihydrate gypsum dehydration generate semi-hydrated gypsum；Or phosphogypsum slag is heated under the conditions of 400~500 DEG C, make Dihydrate gypsum dehydration generates calcium sulfate；
It is 100% that five, which regard the aqueous sulfuric acid that the mass percentage of above-mentioned (two) is 50%~70% as gross mass, Entirety, it is 45%, 30% and 25% three parts to be divided into quality, this ratio cut partition is not necessarily to stringent boundary, can be according to production Actual needs make adjustment appropriate；45% part of sulfuric acid aqueous solution of above-mentioned wherein gross mass is used for floats and sulphur In the reaction of acid reaction generation phosphoric acid and gypsum or directly as commodity selling；By 25% part sulphur of above-mentioned wherein gross mass Aqueous acid produces ammonium sulfate or potassium sulfate for the reactant aqueous solution with ammonia or potassium hydroxide；
Six, are by 30% part of sulfuric acid aqueous solution of the wherein gross mass of above-mentioned (five) in 100~190 DEG C, air pressure 100pa Under conditions of~20Kpa, it is water-soluble to obtain the sulfuric acid that sulfuric acid mass percentage is 84%~98% for heating decompression spraying dehydration Liquid；Mass percentage of the sulfuric acid less than 98% just uses sulfur trioxide SO3Moisture therein is absorbed, generating mass percentage is 98% concentrated sulfuric acid；The concentrated sulfuric acid that this mass percentage is 98% is used for the semi-hydrated gypsum or calcium sulfate with above-mentioned (four) again Reaction generates calcium bisulfate；
Reaction equation, CaSO4+ dense H2SO4=Ca (HSO4)2；
(2) mono-, of are by Ca (HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓ reaction in temperature be 80~100 DEG C sodium sulphate hydrothermal solution is not required to dehydrate, and is cooled to after 50~80 DEG C and directly continuously inputs electrolytic cell or electrolysis with pipeline The anode chamber of slot；The anode chamber of electrolytic cell is previously added deionized water or edible soft water；Or the anode chamber of electrolytic cell is previously added Sodium sulfate quality content is the aqueous sodium persulfate solution of 1.4~1.5 mol/Ls；The cathode chamber of electrolytic cell is previously added 0.5 and rubs simultaneously You/liter deionized water or edible soft water sodium hydrate aqueous solution；And above-mentioned sodium sulphate hot water is adjusted according to the speed of electrolysis The input speed of solution, it is the sodium sulphate water of 1.4~1.5 mol/Ls to keep sodium sulfate quality content in the anode chamber of electrolytic cell Solution；
The sodium sulfate quality content of above-mentioned (one) is the aqueous sodium persulfate solution perfluor sulphur of 1.4~1.5 mol/Ls by two, Acid-carboxylic acid cation-exchange membrane carries out film direct current electrolysis；Generate the sodium hydroxide water that mass percentage concentration is 30%~40% The aqueous sulfuric acid and hydrogen and oxygen that solution and mass percentage concentration are 50%~70%；In the anode plane electricity of electrolysis Pole, and it is netted discharge and collection aqueous sulfuric acid anode planes electrode side place 200~500 acidproof mesh/square The sieve or acidproof evanohm stainless steel mesh of centimetre terylene material, sieve are close to the anode planes of netted discharge and collection sulfuric acid The one side of electrode, mesh mesh number on sieve unit area square centimeter increase with the vertical depth of sodium sulphate water electrolysis liquid and Increase；The plane electrode thickness of anode is 2~5mm；Mass percentage to improve the aqueous sulfuric acid of outflow anode reaches 50%~70%；
The sodium hydrate aqueous solution recycling of above-mentioned (two) is applied to calcium bisulfate and reacts generation sulphur with sodium hydroxide by three, The reaction of sour sodium and calcium hydroxide and water；
Reaction equation：Ca(HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓；
Four, recycle the hydrogen partial of above-mentioned (two) as clean energy resource, are heated for phosphogypsum slag, heating temperature 180~200 DEG C of degree makes dihydrate gypsum dehydration generate semi-hydrated gypsum；Or phosphogypsum slag is heated under the conditions of 400~500 DEG C, make Dihydrate gypsum dehydration generates calcium sulfate；
It is 100% that five, which regard the aqueous sulfuric acid that the mass percentage of above-mentioned (two) is 50%~70% as gross mass, Entirety, be divided into quality be its 45% and 55% two parts, this ratio cut partition be not necessarily to stringent boundary, can be according to the reality of production It needs to make adjustment appropriate；45% part of sulfuric acid aqueous solution of above-mentioned wherein gross mass is used for floats and sulfuric acid reaction It generates in the reaction of phosphoric acid and gypsum or directly as commodity selling；
Six, are by 55% part of sulfuric acid aqueous solution of the wherein gross mass of above-mentioned (five) in 100~190 DEG C, air pressure 100pa Under conditions of~20Kpa, heating decompression spraying dehydration obtains the concentrated sulfuric acid that sulfuric acid mass percentage is 98%；Again by this matter The concentrated sulfuric acid that amount percentage composition is 98% generates calcium bisulfate for being reacted with the semi-hydrated gypsum of above-mentioned (four) or calcium sulfate；
Reaction equation, CaSO4+ dense H2SO4=Ca (HSO4)2；
Thoroughly recycle the Sulphur ressource and sodium hydroxide of sulfuric acid.
Hydrogen output of the present invention is big, hydrogen can be used for phosphogypsum slag heating slough the crystallization water, aqueous sulfuric acid decompression plus Heat dehydration concentrates and synthesis ammonia, avoids CO2 emission and the production cost of synthesis ammonia is greatly lowered.
The calcium ion of micro water-soluble calcium hydroxide is reacted with hydrofluoric acid HF in aqueous sodium persulfate solution, generates the extremely difficult water that is dissolved in Calcirm-fluoride removes the calcium ion in aqueous sodium persulfate solution；So that aqueous sodium persulfate solution electrolysis is smoothed out.
Hydrogen produced by the invention is the aqueous sulfuric acid heating thickening that mass percentage is 50%~70%, The concentrated sulfuric acid of production 98%.
In production with hydrogen be heated to be gypsum dehydration and for 50%~70% aqueous sulfuric acid dehydration concentration generate more than Heat is absorbed with water, and hot water reacts production sodium sulphate/potassium sulfate and hydrogen-oxygen with sodium hydroxide or potassium hydroxide for calcium bisulfate Change calcium or/and in floats and sulfuric acid reaction generation phosphoric acid and the reacting of gypsum.
The aqueous sulfuric acid hydrogen that mass percentage is 50%~70% heats thickening, produces 98% dense sulphur Acid；It is generated in the reacting of phosphoric acid for apatite and sulfuric acid reaction.
Advantageous effect：
1. the present invention has greatly saved the energy.
2. this invention greatly reduces the production cost that sodium sulphate converts recycling cycling and reutilization, have larger significant Economic benefit.
3. the present invention is discharged without GHG carbon dioxide, environment is effectively protected.
4. the present invention has simply and efficiently recycled Sulphur ressource and calcium resource, the production cost of enterprise is significantly reduced, is The large-scale recovery recycling of industrial phosphogypsum waste residue opens extremely vast potential for future development.
5. the present invention phosphogypsum slag is also produced into ammonium sulfate and potassium sulfate, for China's agricultural development provide it is abundant Quick-acting sulfur fertilizers, nitrogenous fertilizer and potash fertilizer.
6. sodium sulphate Na2SO4Hydrogen (the H that water-soluble liquid film is electrolysed2) and oxygen (O2) income from sales can offset or cut The electric cost of powered down solution；Hydrogen (H2) it also can be used as the raw material for synthesizing ammonia；Or by hydrogen (H2) it is used as clean energy resource, it reduces The energy consumption of enterprise.
7. the present invention directly considerably reduces the production cost of phosphoric acid and ammonium dihydrogen phosphate (or diammonium hydrogen phosphate).
8. the present invention has greatly saved non-renewable Sulphur ressource, the huge waste of Sulphur ressource is avoided, especially to me The sustainable development of state's agricultural is of great immediate significance.
The preferred embodiment of technical solution of the present invention：
(1) mono-, of are by Ca (HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓ reaction in temperature be 80~100 DEG C sodium sulphate hydrothermal solution is not required to dehydrate, and is cooled to and directly continuously inputs electrolytic cell or electrolytic cell after 80 DEG C with pipeline Anode chamber；The anode chamber of electrolytic cell is previously added deionized water or edible soft water；Or the anode chamber of electrolytic cell is previously added sulfuric acid Sodium mass concentration is the aqueous sodium persulfate solution of 1.5 mol/Ls；The cathode chamber of electrolytic cell is previously added going for 0.5 mol/L simultaneously The sodium hydrate aqueous solution of ionized water or edible soft water；And the input of above-mentioned sodium sulphate hydrothermal solution is adjusted according to the speed of electrolysis Speed, it is the aqueous sodium persulfate solution of 1.5 mol/Ls to keep sodium sulfate quality content in the anode chamber of electrolytic cell；
The sodium sulfate quality content of above-mentioned (one) is aqueous sodium persulfate solution perfluorinated sulfonic acid-carboxylic of 1.5 mol/Ls by two, Sour cation-exchange membrane carries out film direct current electrolysis；Generate sodium hydrate aqueous solution and the quality hundred that mass percentage concentration is 40% Point a concentration of 70% aqueous sulfuric acid and hydrogen and oxygen；In the anode plane electrode of electrolysis, and in netted discharge and receipts Place the acidproof evanohm stainless steel of 200~500 acidproof mesh/square centimeter in the side for collecting the anode planes electrode of aqueous sulfuric acid Sieve, sieve is close to the one side of the anode planes electrode of netted discharge and collection sulfuric acid, on sieve unit area square centimeter Mesh mesh number with sodium sulphate water electrolysis liquid depth increase and increase；The plane electrode thickness of anode is 5mm；To improve outflow The mass percentage of the aqueous sulfuric acid of anode reaches 70%；
The sodium hydrate aqueous solution recycling of above-mentioned (two) is applied to calcium bisulfate and reacts generation sulphur with sodium hydroxide by three, The reaction of sour sodium and calcium hydroxide and water；
Reaction equation：Ca(HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓；
Four, recycle the hydrogen partial of above-mentioned (two) as clean energy resource, are heated for phosphogypsum slag, 400 Phosphogypsum slag is heated under the conditions of~500 DEG C, dihydrate gypsum dehydration is made to generate calcium sulfate；
The aqueous sulfuric acid that the mass percentage of above-mentioned (two) is 70% by five, is divided into quality for 45%, 30% and 25% three parts, this ratio cut partition are not necessarily to stringent boundary, can make adjustment appropriate according to the actual needs of production；By it is above-mentioned its The part of sulfuric acid aqueous solution of the 45% of middle gross mass in the reacting of apatite and sulfuric acid reaction generation phosphoric acid or directly as Commodity selling；25% part of sulfuric acid aqueous solution of above-mentioned wherein gross mass is used for anti-with the aqueous solution of ammonia or potassium hydroxide It answers, produces ammonium sulfate or potassium sulfate；
Six, are by 30% part of sulfuric acid aqueous solution of the wherein gross mass of above-mentioned (five) in 100~190 DEG C, air pressure 100pa Under conditions of~20Kpa, heating decompression spraying dehydration obtains the aqueous sulfuric acid that sulfuric acid mass percentage is 98%；Again will The concentrated sulfuric acid that this mass percentage is 98% generates calcium bisulfate for being reacted with the calcium sulfate of above-mentioned (four)；
Reaction equation, CaSO4+ dense H2SO4=Ca (HSO4)2；
(2) mono-, of are by Ca (HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓ reaction in temperature be 80~100 DEG C sodium sulphate hydrothermal solution is not required to dehydrate, and is cooled to and directly continuously inputs electrolytic cell or electrolytic cell after 80 DEG C with pipeline Anode chamber；The anode chamber of electrolytic cell is previously added deionized water or edible soft water；Or the anode chamber of electrolytic cell is previously added sulfuric acid Sodium mass content is the aqueous sodium persulfate solution of 1.5 mol/Ls；The cathode chamber of electrolytic cell is previously added going for 0.5 mol/L simultaneously The sodium hydrate aqueous solution of ionized water or edible soft water；And the input of above-mentioned sodium sulphate hydrothermal solution is adjusted according to the speed of electrolysis Speed, it is the aqueous sodium persulfate solution of 1.5 mol/Ls to keep sodium sulfate quality content in the anode chamber of electrolytic cell；
The sodium sulfate quality content of above-mentioned (one) is aqueous sodium persulfate solution perfluorinated sulfonic acid-carboxylic of 1.5 mol/Ls by two, Sour cation-exchange membrane carries out film direct current electrolysis；Generate sodium hydrate aqueous solution and the quality hundred that mass percentage concentration is 40% Point a concentration of 70% aqueous sulfuric acid and hydrogen and oxygen；In the anode plane electrode of electrolysis, and in netted discharge and receipts Place the acidproof evanohm stainless steel of 200~500 acidproof mesh/square centimeter in the side for collecting the anode planes electrode of aqueous sulfuric acid Sieve, sieve is close to the one side of the anode planes electrode of netted discharge and collection sulfuric acid, on sieve unit area square centimeter Mesh mesh number with sodium sulphate water electrolysis liquid depth increase and increase；The plane electrode thickness of anode is 5mm；To improve outflow The mass percentage of the aqueous sulfuric acid of anode reaches 70%；
The sodium hydrate aqueous solution recycling of above-mentioned (two) is applied to calcium bisulfate and reacts generation sulphur with sodium hydroxide by three, The reaction of sour sodium and calcium hydroxide and water；
Reaction equation：Ca(HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓；
Four, recycle the hydrogen partial of above-mentioned (two) as clean energy resource, are heated for phosphogypsum slag, 400 Phosphogypsum slag is heated under the conditions of~500 DEG C, dihydrate gypsum dehydration is made to generate calcium sulfate；
Five, by the mass percentage of above-mentioned (two) be 70% aqueous sulfuric acid, be divided into quality be its 45% and 55% Two parts, this ratio cut partition are not necessarily to stringent boundary, can make adjustment appropriate according to the actual needs of production；It will be above-mentioned wherein total The part of sulfuric acid aqueous solution of the 45% of quality is in the reacting of apatite and sulfuric acid reaction generation phosphoric acid or directly as commodity It sells；
Six, are by 55% part of sulfuric acid aqueous solution of the wherein gross mass of above-mentioned (five) in 100~190 DEG C, air pressure 100pa Under conditions of~20Kpa, heating decompression spraying dehydration obtains the concentrated sulfuric acid that sulfuric acid mass percentage is 98%；Again by this matter The concentrated sulfuric acid that amount percentage composition is 98% generates calcium bisulfate for being reacted with the calcium sulfate of above-mentioned (four)；
Reaction equation, CaSO4+ dense H2SO4=Ca (HSO4)2；Thoroughly recycle the Sulphur ressource and sodium hydroxide of sulfuric acid.
Specific implementation mode：
Embodiment：
(1) mono-, of are by Ca (HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓ reaction in temperature be 80~100 DEG C sodium sulphate hydrothermal solution is not required to dehydrate, and is cooled to after 50~80 DEG C and directly continuously inputs electrolytic cell or electrolysis with pipeline The anode chamber of slot；The anode chamber of electrolytic cell is previously added deionized water or edible soft water；Or the anode chamber of electrolytic cell is previously added The aqueous sodium persulfate solution of a concentration of 1.5 mol/L of sodium sulfate quality；The cathode chamber of electrolytic cell is previously added 0.5 mol/L simultaneously Deionized water or edible soft water sodium hydrate aqueous solution；And above-mentioned sodium sulphate hydrothermal solution is adjusted according to the speed of electrolysis Input speed, it is the aqueous sodium persulfate solution of 1.5 mol/Ls to keep sodium sulfate quality content in the anode chamber of electrolytic cell；
The sodium sulfate quality content of above-mentioned (one) is aqueous sodium persulfate solution perfluorinated sulfonic acid-carboxylic of 1.5 mol/Ls by two, Sour cation-exchange membrane carries out film direct current electrolysis；Generate sodium hydrate aqueous solution and the quality hundred that mass percentage concentration is 30% Point a concentration of 50% aqueous sulfuric acid and hydrogen and oxygen；In the anode plane electrode of electrolysis, and in netted discharge and receipts The sieve of 200~500 acidproof mesh/square centimeter terylene material is placed in the side for collecting the anode planes electrode of aqueous sulfuric acid, Sieve is close to the one side of the anode planes electrode of netted discharge and collection sulfuric acid, the mesh on sieve unit area square centimeter Mesh number increases with the depth of sodium sulphate water electrolysis liquid and is increased；The plane electrode thickness of anode is 2mm；To improve outflow anode The mass percentage of aqueous sulfuric acid reaches 50%；
The sodium hydrate aqueous solution recycling of above-mentioned (two) is applied to calcium bisulfate and reacts generation sulphur with sodium hydroxide by three, The reaction of sour sodium and calcium hydroxide and water；
Reaction equation：Ca(HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓；
Four, recycle the hydrogen partial of above-mentioned (two) as clean energy resource, are heated for phosphogypsum slag, heating temperature 180~200 DEG C of degree makes dihydrate gypsum dehydration generate semi-hydrated gypsum；
The aqueous sulfuric acid that the mass percentage of above-mentioned (two) is 50% by five, is divided into quality for 45%, 30% and 25% three parts, this ratio cut partition are not necessarily to stringent boundary, can make adjustment appropriate according to the actual needs of production；By it is above-mentioned its The part of sulfuric acid aqueous solution of the 45% of middle gross mass in the reacting of apatite and sulfuric acid reaction generation phosphoric acid or directly as Commodity selling；25% part of sulfuric acid aqueous solution of above-mentioned wherein gross mass is used for anti-with the aqueous solution of ammonia or potassium hydroxide It answers, produces ammonium sulfate or potassium sulfate；
Six, are by 30% part of sulfuric acid aqueous solution of the wherein gross mass of above-mentioned (five) in 100~190 DEG C, air pressure 100pa Under conditions of~20Kpa, heating decompression spraying dehydration obtains the aqueous sulfuric acid that sulfuric acid mass percentage is 84%；With three Absorption of sulfur oxides moisture therein generates the concentrated sulfuric acid that mass percentage is 98%；It is again 98% by this mass percentage The concentrated sulfuric acid for react with the semi-hydrated gypsum of above-mentioned (four), generation calcium bisulfate；
Reaction equation, CaSO4+ dense H2SO4=Ca (HSO4)2；
(2) mono-, of are by Ca (HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓ reaction in temperature be 80~100 DEG C sodium sulphate hydrothermal solution is not required to dehydrate, and is cooled to after 50~80 DEG C and directly continuously inputs electrolytic cell or electrolysis with pipeline The anode chamber of slot；The anode chamber of electrolytic cell is previously added deionized water or edible soft water；Or the anode chamber of electrolytic cell is previously added Sodium sulfate quality content is the aqueous sodium persulfate solution of 1.5 mol/Ls；The cathode chamber of electrolytic cell is previously added 0.5 mol/L simultaneously Deionized water or edible soft water sodium hydrate aqueous solution；And above-mentioned sodium sulphate hydrothermal solution is adjusted according to the speed of electrolysis Input speed, it is the aqueous sodium persulfate solution of 1.5 mol/Ls to keep sodium sulfate quality content in the anode chamber of electrolytic cell；50~ In the range of 80 DEG C, the temperature of aqueous sodium persulfate solution and the velocity efficiency of electrolysis are proportional.
The sodium sulfate quality content of above-mentioned (one) is aqueous sodium persulfate solution perfluorinated sulfonic acid-carboxylic of 1.5 mol/Ls by two, Sour cation-exchange membrane carries out film direct current electrolysis；Generate sodium hydrate aqueous solution and the quality hundred that mass percentage concentration is 30% Point a concentration of 50% aqueous sulfuric acid and hydrogen and oxygen；In the anode plane electrode of electrolysis, and in netted discharge and receipts The sieve of 200~500 acidproof mesh/square centimeter terylene material is placed in the side for collecting the anode planes electrode of sulfuric acid, and sieve is tight The one side for pasting the anode planes electrode of netted discharge and collection sulfuric acid, mesh mesh number on sieve unit area square centimeter with The depth of sodium sulphate water electrolysis liquid increases and increases；The plane electrode thickness of anode is 2mm；To improve the sulfuric acid water of outflow anode The mass percentage of solution reaches 50%；
The sodium hydrate aqueous solution recycling of above-mentioned (two) is applied to calcium bisulfate and reacts generation sulphur with sodium hydroxide by three, The reaction of sour sodium and calcium hydroxide and water；
Reaction equation：Ca(HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓；
Four, recycle the hydrogen partial of above-mentioned (two) as clean energy resource, are heated for phosphogypsum slag, heating temperature 180~200 DEG C of degree makes dihydrate gypsum dehydration generate semi-hydrated gypsum；
Five, by the mass percentage of above-mentioned (two) be 50% aqueous sulfuric acid, be divided into quality be its 45% and 55% Two parts, this ratio cut partition are not necessarily to stringent boundary, can make adjustment appropriate according to the actual needs of production；It will be above-mentioned wherein total The part of sulfuric acid aqueous solution of the 45% of quality is in the reacting of apatite and sulfuric acid reaction generation phosphoric acid or directly as commodity It sells；
Six, are by 55% part of sulfuric acid aqueous solution of the wherein gross mass of above-mentioned (five) in 100~190 DEG C, air pressure 100pa Under conditions of~20Kpa, heating decompression spraying dehydration obtains the concentrated sulfuric acid that sulfuric acid mass percentage is 98%；Again by this matter The concentrated sulfuric acid that amount percentage composition is 98% generates calcium bisulfate for being reacted with the semi-hydrated gypsum of above-mentioned (four)；
Reaction equation, CaSO4+ dense H2SO4=Ca (HSO4)2；Thoroughly recycle the Sulphur ressource and sodium hydroxide of sulfuric acid.
About the data area of the present invention, principle and the prior art knowledge according to the present invention includes not only data area The data at both ends further include the data between two end datas.To save the length of specification, the present invention is not between two end datas Data make simple unnecessary repetition and repeat, independently selected by the data between two end data of those skilled in the art couple It realizes.

Claims (5)

1. the conversion reuse method of sodium sulphate in ardealite conversion recycling, it is characterised in that：
(1) mono-, of are by Ca (HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓ reaction in temperature be 80~100 DEG C of sulphur Sour sodium hydrothermal solution is not required to dehydrate, and is cooled to and directly continuously inputs electrolytic cell or electrolytic cell after 50~80 DEG C with pipeline Anode chamber；The anode chamber of electrolytic cell is previously added deionized water or edible soft water；Or the anode chamber of electrolytic cell is previously added sulfuric acid Sodium mass concentration is the aqueous sodium persulfate solution of 1.4~1.5 mol/Ls；Simultaneously electrolytic cell cathode chamber be previously added 0.5 mole/ The sodium hydrate aqueous solution of the deionized water or edible soft water that rise；And above-mentioned sodium sulphate hydrothermal solution is adjusted according to the speed of electrolysis Input speed, it is the aqueous sodium persulfate solution of 1.4~1.5 mol/Ls to keep sodium sulfate quality content in the anode chamber of electrolytic cell；
The sodium sulfate quality content of above-mentioned (one) is aqueous sodium persulfate solution perfluorinated sulfonic acid-carboxylic of 1.4~1.5 mol/Ls by two, Sour cation-exchange membrane carries out film direct current electrolysis；Generate mass percentage concentration be 30%~40% sodium hydrate aqueous solution and The aqueous sulfuric acid and hydrogen and oxygen that mass percentage concentration is 50%~70%；In the anode plane electrode of electrolysis, and Place 200~500 acidproof mesh/square centimeter terylene in the side of the anode planes electrode of netted discharge and collection aqueous sulfuric acid The sieve of material or acidproof evanohm stainless steel mesh, sieve are close to the one of the anode planes electrode of netted discharge and collection sulfuric acid Side, the mesh mesh number on sieve unit area square centimeter increase with the vertical depth of sodium sulphate water electrolysis liquid and are increased；Sun The plane electrode thickness of pole is 2~5mm；Mass percentage to improve the aqueous sulfuric acid of outflow anode reaches 50%~ 70%；
The sodium hydrate aqueous solution recycling of above-mentioned (two) is applied to calcium bisulfate and reacts generation sodium sulphate with sodium hydroxide by three, With the reaction of calcium hydroxide and water；
Reaction equation：Ca(HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓；
Four, recycle the hydrogen partial of above-mentioned (two) as clean energy resource, are heated for phosphogypsum slag, heating temperature 180~200 DEG C, dihydrate gypsum dehydration is made to generate semi-hydrated gypsum；Or phosphogypsum slag is heated under the conditions of 400~500 DEG C, make two Water gypsum dehydration generates calcium sulfate；
Five, by the aqueous sulfuric acid that the mass percentage of above-mentioned (two) is 50%~70% regard as gross mass be 100% it is whole Body is divided into quality for 45%, 30% and 25% three parts, this ratio cut partition is not necessarily to stringent boundary, according to the reality of production It needs to make adjustment appropriate；45% part of sulfuric acid aqueous solution of above-mentioned wherein gross mass is used for floats and sulfuric acid reaction It generates in the reaction of phosphoric acid and gypsum or directly as commodity selling；25% part of sulfuric acid of above-mentioned wherein gross mass is water-soluble Liquid produces ammonium sulfate or potassium sulfate for the reactant aqueous solution with ammonia or potassium hydroxide；
Six, by 30% part of sulfuric acid aqueous solution of the wherein gross mass of above-mentioned (five) 100~190 DEG C, air pressure 100pa~ Under conditions of 20Kpa, heating decompression spraying dehydration obtains the aqueous sulfuric acid that sulfuric acid mass percentage is 84%~98%； Mass percentage of the sulfuric acid less than 98% just uses sulfur trioxide absorption moisture therein, and it is 98% to generate mass percentage The concentrated sulfuric acid；Again the concentrated sulfuric acid that this mass percentage is 98% is used to react with the semi-hydrated gypsum of above-mentioned (four) or calcium sulfate, Generate calcium bisulfate；
Reaction equation, CaSO4+ dense H2SO4=Ca (HSO4)2；
(2) mono-, of are by Ca (HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓ reaction in temperature be 80~100 DEG C of sulphur Sour sodium hydrothermal solution is not required to dehydrate, and is cooled to and directly continuously inputs electrolytic cell or electrolytic cell after 50~80 DEG C with pipeline Anode chamber；The anode chamber of electrolytic cell is previously added deionized water or edible soft water；Or the anode chamber of electrolytic cell is previously added sulfuric acid Sodium mass content is the aqueous sodium persulfate solution of 1.4~1.5 mol/Ls；Simultaneously electrolytic cell cathode chamber be previously added 0.5 mole/ The sodium hydrate aqueous solution of the deionized water or edible soft water that rise；And above-mentioned sodium sulphate hydrothermal solution is adjusted according to the speed of electrolysis Input speed, it is the aqueous sodium persulfate solution of 1.4~1.5 mol/Ls to keep sodium sulfate quality content in the anode chamber of electrolytic cell；
The sodium sulfate quality content of above-mentioned (one) is the aqueous sodium persulfate solution perfluorinated sulfonic acid one of 1.4~1.5 mol/Ls by two, Carboxylic acid cation-exchange membrane carries out film direct current electrolysis；Generate the sodium hydrate aqueous solution that mass percentage concentration is 30%~40% The aqueous sulfuric acid and hydrogen and oxygen that are 50%~70% with mass percentage concentration；In the anode plane electrode of electrolysis, and 200~500 acidproof mesh/square centimeter is placed in the side of netted discharge and the anode planes electrode of collection aqueous sulfuric acid to wash The sieve of synthetic fibre material or acidproof evanohm stainless steel mesh, sieve are close to the anode planes electrode of netted discharge and collection sulfuric acid One side, the mesh mesh number on sieve unit area square centimeter increase with the vertical depth of sodium sulphate water electrolysis liquid and are increased； The plane electrode thickness of anode is 2~5mm；Mass percentage to improve the aqueous sulfuric acid of outflow anode reaches 50%~ 70%；
The sodium hydrate aqueous solution recycling of above-mentioned (two) is applied to calcium bisulfate and reacts generation sodium sulphate with sodium hydroxide by three, With the reaction of calcium hydroxide and water；
Reaction equation：Ca(HSO4)2+ 4NaOH=2Na2SO4+2H2O+Ca(OH)2↓；
Four, recycle the hydrogen partial of above-mentioned (two) as clean energy resource, are heated for phosphogypsum slag, heating temperature 180~200 DEG C, dihydrate gypsum dehydration is made to generate semi-hydrated gypsum；Or phosphogypsum slag is heated under the conditions of 400~500 DEG C, make two Water gypsum dehydration generates calcium sulfate；
Five, by the aqueous sulfuric acid that the mass percentage of above-mentioned (two) is 50%~70% regard as gross mass be 100% it is whole Body, it is its 45% and 55% two parts to be divided into quality, this ratio cut partition is not necessarily to stringent boundary, is made according to the actual needs of production Adjustment appropriate；45% part of sulfuric acid aqueous solution of above-mentioned wherein gross mass is generated into phosphorus for floats and sulfuric acid reaction In the reaction of acid and gypsum or directly as commodity selling；
Six, by 55% part of sulfuric acid aqueous solution of the wherein gross mass of above-mentioned (five) 100~190 DEG C, air pressure 100pa~ Under conditions of 20Kpa, heating decompression spraying dehydration obtains the concentrated sulfuric acid that sulfuric acid mass percentage is 98%；Again by this quality The concentrated sulfuric acid that percentage composition is 98% generates calcium bisulfate for being reacted with the semi-hydrated gypsum of above-mentioned (four) or calcium sulfate；
Reaction equation, CaSO4+ dense H2SO4=Ca (HSO4)2；Thoroughly recycle the Sulphur ressource and sodium hydroxide of sulfuric acid.
The conversion reuse method of sodium sulphate during 2. according to claim 1, ardealite conversion is recycled, it is characterised in that：Sulphur The calcium ion of micro water solubility calcium hydroxide is reacted with hydrofluoric acid HF in acid sodium aqueous solution, generates the extremely difficult calcirm-fluoride for being dissolved in water, Remove the calcium ion in aqueous sodium persulfate solution；So that aqueous sodium persulfate solution electrolysis is smoothed out.
The conversion reuse method of sodium sulphate during 3. according to claim 1, ardealite conversion is recycled, it is characterised in that：With Hydrogen produced by the invention is the aqueous sulfuric acid heating thickening that mass percentage is 50%~70%, produces 98% The concentrated sulfuric acid.
The conversion reuse method of sodium sulphate during 4. according to claim 1, ardealite conversion is recycled, it is characterised in that：It is raw It is heated to be gypsum dehydration with hydrogen in production and is absorbed with water for the waste heat of 50%~70% aqueous sulfuric acid dehydration concentration generation, Its hot water reacts production sodium sulphate/potassium sulfate and calcium hydroxide or/and use with sodium hydroxide or potassium hydroxide for calcium bisulfate In floats and sulfuric acid reaction generate the reacting of phosphoric acid and gypsum.
The conversion reuse method of sodium sulphate during 5. according to claim 1, ardealite conversion is recycled, it is characterised in that：Matter It measures the aqueous sulfuric acid hydrogen that percentage composition is 50%~70% and heats thickening, produce 98% concentrated sulfuric acid；For phosphorus Limestone flour and sulfuric acid reaction generate in the reacting of phosphoric acid and gypsum.
CN201710181477.8A 2017-03-18 2017-03-18 The conversion reuse method of sodium sulphate in ardealite conversion recycling Pending CN108623197A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111206258A (en) * 2020-01-17 2020-05-29 厦门欣亿凯科技有限公司 Resource recycling method for byproduct mirabilite
CN111364055A (en) * 2020-01-17 2020-07-03 华中科技大学 Phosphogypsum treatment device and method based on sodium sulfate electrolysis

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111206258A (en) * 2020-01-17 2020-05-29 厦门欣亿凯科技有限公司 Resource recycling method for byproduct mirabilite
CN111364055A (en) * 2020-01-17 2020-07-03 华中科技大学 Phosphogypsum treatment device and method based on sodium sulfate electrolysis
CN111364055B (en) * 2020-01-17 2021-04-20 华中科技大学 Phosphogypsum treatment device and method based on sodium sulfate electrolysis

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