CN1880223A - Saltcake-ammonia circulation method for combined production of barium chloride, potassium sulfate, sodium carbonate - Google Patents

Abstract

The invention refers to a co-production technique of three inorganic chemicals, that is co-production technique of barium chloride, potassium sulfate, sodium carbonate in sodium sulfate-ammonia circulating method in detail, including: (1)mixing the witherite and ammonium chloride and pumping into evaporation tower to get ammonia, CO2 gas, and barium chloride; (2)getting the ammonia, CO2 gas evaporated from the tower react with sodium sulfate to get ammonia sulfate and sodium acid carbonate that is burnt to sodium carbonate; (3) getting the ammonia sulfate react with potassium chloride for potassium sulfate, the byproduct of which is ammonium chloride that returns to (1) step to react with barium carbonate, and so on in cycles.

Description

Co-production technology of barium chloride, potassium sulfate and sodium carbonate by mirabilite-ammonia circulation method

One, the technical field

The invention relates to a coproduction technology of three inorganic chemicals, in particular to a coproduction technology of barium chloride, potassium sulfate and sodium carbonate by a mirabilite-ammonia circulation method.

Second, State of the Art

The invention relates to a technology for producing soda ash and coproducing ammonium sulfate from mirabilite, in particular to a technology of producing sodium carbonate and coproducing ammonium sulfate from Prosoviz Bellopersiki, which cuts off the first half part of the sodium sulfate, removes the ammonium sulfate concentration and crystallization parts, and simplifies and optimizes the process. In addition, mirabilite is used as raw material, and the preparation of alkali by the Loulan method is too late, causes great pollution and waste, and is not advisable (please refer to the book 76-84 pages of the book "alkali-preparing technology"). Preparing potassium sulfate by an ammonium sulfate method; barium chloride is prepared by ammonium chloride method. The application of the method is not repeated at home and in many plants. The invention has no precedent for connecting the three products into a combined production method, and has qualitative change just like the combined alkali method formed by the solveline alkali preparation and the ammonium chloride preparation by Mr. Chengdannan, thereby generating great benefit.

Third, technical content

The invention simultaneously solves the problems of large investment, high cost and low profit caused by the fact that expensive hydrochloric acid and sulfuric acid can not be separated and the existing process equipment with huge investment is used for preparing barium chloride by barium carbonate ore and potassium sulfate by potassium chloride.

The process of the invention is as follows: (1) adding 270g/l NH₄Cl liquid and BaCO₃Mixing mineral powder with half mole number of carbonate containing Ba, Sr and Mg, x 1.05 and NH to obtain slurry after 200 days₄Cl is preferably equal in molar number, CaCO₃Not counting, preheating to 85-95 deg.C to obtain ammonia smell, pumping into ammonia still at a temperature of not less than 104 deg.C, and reacting Distilling off NH₃、CO₂Reacting until the slag contains BaCO₃Filtering to remove residue until the concentration is less than or equal to 1%, washing with water, and making into building material to obtain filtrate, purifying, concentrating, crystallizing to obtain barium chloride product, and treating mother liquor with the old process; (2) distilling off NH₃、CO₂Introducing into 330g/l mirabilite mineral liquid, and distilling off NH from 1.4 tons of barium chloride per yield₃·CO₂And 3m³Absorbing ammonia and CO from mirabilite liquid with the concentration of 330g/l₂Heating to 45 deg.C, controlling the temperature, and adjusting P_HThe value is 7 + -0.5, Ca, Mg, Fe, Mn, etc. in the solution are precipitated by carbonate, and heavy metal and Na with corresponding arsenic content can be added simultaneously₂The amount of S is added to 8g/m³Movable partPurifying with gelatin, clarifying, and filtering to obtain purified Na₂SO₄+(NH₄)CO₃Measure Na thereof₂SO₄、(NH₄)CO₃Adding ammonium bicarbonate to make Na⁺∶NH₃1: 1.1, pumping into carbonating tower drum CO₂Gas, controlling the temperature at the bottom of the tower to be 25-26 ℃, controlling the temperature in the tower to be 55-60 ℃ and reacting Proceeding to measure the content of (NH)₄)₂SO₄More than or equal to 200g/l, filtering out NaHCl after the discharge is stood still₃Crystals, isosmotic washing to SO₄ ^-2Until the crystal content is less than or equal to 0.3 percent, cleaning the crystal and putting the crystal into a calcining furnace Get out of the furnace Na₂CO₃I.e. soda ash product, recovery of CO₂For carbonation, the mother liquor is cooled to a temperature of-5 deg.C to-10 deg.C, and unreacted Na is present in the mother liquor₂SO₄+NH₄HCO₃Separating out by crystallization, recovering the crystal, adding into mirabilite solution in a lower tank for utilization, adding sulfuric acid into cold mother liquor to neutralize excessive ammonium bicarbonate to heat ③ mother liquor to 85-100 ℃, and measuring SO content₄ ^-2The amount of the ammonium sulfate solution is equal to that of KCl, and the reaction is carried out Stirring for 2.5-3 h at 85-100 ℃, cooling the slurry to room temperature K after the reaction is finished₂SO₄Most of the crystal is separated out by crystallization, and wet crystal is put into a drying furnace for hot air drying at the temperature of more than or equal to 350 ℃ after separation, and the crystal contains NH₄Fully gasifying and separating Cl mother liquor, and leaching NH from furnace gas water₄Cl, discharging dry materials, namely potassium sulfate products, and if mother liquor contains K₂SO₄Not less than 3 percent, can be concentrated and then cooled and crystallized to recover K₂SO₄Crystal, obtaining mother liquor for ④ to measure SO₄ ^-2Amount of BaCl added in an equivalent amount₂To BaSO₄Removing SO ↓₄ ^-2The filtrate is SO-free₄ ^-2NH of₄And (4) Cl liquid for circulation in step ①.

Fourthly, the attached drawings are as follows:

process flow chart for combined production of barium chloride, potassium sulfate and sodium carbonate by mirabilite-ammonia circulation method "

Fifth, technical implementation example

1. Mixing BaCO₃Mixing 200 mesh ore powder with 270g/l ammonium chloride solution to obtain ore pulp, preheating to 85-95 deg.C to smell ammonia smell, wherein the amount of ore powder added is half of total mole number of Ba, Sr and Mg carbonates, x 1.05 and NH₄Cl molar number is equal, which should be noted: CaCO with maximum impurities in ore₃Hardly participates in the reaction, does not waste Cl^-The preheated ore pulp enters an ammonia still for reaction The carbonates of Sr, Mg, Ca, etc. in the ore react similarly until the slag contains BaCO₃Less than 1% of ore pulp can be discharged, the residue is filtered, cleaned and can be used as building material, the filtrate is conventionally purified, concentrated and crystallized to obtain barium chloride product, and NH is evaporated₃·CO₂Gas supply (2) introducing mirabilite liquid to absorb NH₃、CO₂Directly using mirabilite liquid ore containing NaSO₄Absorption of 330g/l concentration to distill off NH₃、CO₂At the same time, the temperature is increased to 45 ℃, the temperature is controlled to be not more than 45 ℃ by cooling, and NH is produced when 1.4 tons of barium chloride are produced₃、CO₂Air pressure can make 3m³Ammoniating and carbonizing Natrii sulfas with concentration of 330g/l, adding carbonic acid to Natrii sulfas containing calcium, magnesium, ferrum, etc., stirring, adding sodium sulfide according to heavy metal and arsenic content to precipitate in sulfide state, and adding animal glue (hide glue, bone glue, etc.)Glue, fish glue) silicic acid, Al⁺³Filtering out the flocculated precipitate to obtain Na₂SO₄Purified liquid, Na of which can be measured⁺、NH₃ ⁺Adding sodium bicarbonate to make Na⁺∶NH₄ ⁺Pumping into a carbonization tower and blowing CO into the carbonization tower at a ratio of 1: 1.1₂Reaction of The temperature of the tower bottom is controlled between 25 ℃ and 26 ℃, and the temperature of the tower bottom is controlled between 55 ℃ and 60 ℃ to measure (NH)₄)₂SO₄Discharging when the content is more than 200g/l, standing, and filtering NaHCO₃Crystals, isotonic washing to SO₄ ^-2Less than or equal to 0.3 percent, and calcining in a furnace Obtaining Na₂CO₃The product is soda ash. Recovery of CO₂The gas is used for carbonizing mirabilite. Filtering the mother liquor, cooling to-5 to-10 deg.C to obtain unreacted Na₂SO₄And NH₂HCO₃May precipitate as crystals. Separating the crystal and adding into mirabilite in the lower tank for utilization. Adding sulfuric acid into the cold mother water obtained by filtering to neutralize excessive ammonium bicarbonate for (3) heating to 85-95 ℃ first, and measuring the content of (NH)₄)SO₄Calculating the equivalent weight of KCl to be added, adding KCl, stirring and reacting for 2.5-3 h Stopping stirring, standing and cooling to room temperature, and separating out K₂SO₄Wet crystal, drying in a drying furnace at 350 deg.C or higher, discharging the dried product, recovering NH₄Cl, filtering mother liquor and adding NH₄Cl washing gas and water integrated supply (4) measuring residual SO in ammonium chloride mother liquor₄ ^-2Amount of BaCl added in an equivalent amount₂Residual SO₄ ^-2Will be mixed with BaCO₄↓ofsolid is filtered out as precipitate BaSO₄And (5) paying a product. Removal of SO₄ ^-2NH of₄BaCO can be added into Cl liquid₃And (3) repeating the reaction in the step (1) by using the mineral powder and ammonia distillation … … in cycles. (5) In the whole process, for example, the precipitated mud washing water, the slag washing water and the light ammonia water have too low concentration, the pollution and the waste are caused by abandoning, and the utilization can damage the water balance of the system. Can be additionally provided with a Nanofiltration (NF) membrane system for dehydration and thickening, and can achieve material recovery with low cost and energy consumption and clean production.

The crossing of Chuan, Shanan and Yu has the only super-huge type of BaCO available for industrial use in the world₃The invention and another invention 'gypsum-ammonia circulation method barium chloride and potassium sulfate co-production technology' can utilize mirabilite and gypsum resources which are very rich and cheap at the periphery of the mining area to solve the problem of unique BaCO at the day₃The development problem of low cost of ore is that every 1 ten thousand tons of pure thenardite is about 3 thousand meters³About 200 ten thousand yuan of 330g/l mirabilite mineral liquid mining area, 1.3 ten thousand tons of barium chloride dihydrate can be produced by utilizing the method, and 1.1 ten thousand tons of potassium sulfate can be co-produced; 0.65 million tons of soda ash, the output value is more than or equal to 0.6 million yuan, the profit and tax is more than or equal to 0.3 million yuan, which means that 98 percent of sulfuric acid and 31 percent of hydrochloric acid are saved by 0.7 million tons, and only mirabilite, sulfuric acid and ammonium chloride are not concentrated and are directly used in liquid state, so that the coal-saving and electric equipment becomes … … million yuan, which is particularly suitable for the national conditions, especially for the development of poor western resources.

And (4) conclusion: the invention is novel, has no precedent in overall view and has novelty; the innovation is not much and wonderful; the 'ammonia-ammonium' salt circulation reaction is unique and innovative; after application, the efficiency is greatly increased, the investment is greatly reduced, the clean production is pollution-free, and the method has practicability. The patent rights of the invention should be granted to the country for patent protection.

Claims (1)

1. The combined production technology of barium chloride, potassium sulfate and sodium carbonate by the Miscanthus sinensis-ammonia circulation method is characterized in that: (1)270g/l ammonium chloride solution is added into barium carbonate mineral powder to lead the mineral to contain BaCO₃、SrCO₃、MgCO₃Half of the total mole number multiplied by 1.05 is equal to the mole number of ammonium chloride to form ammonium chloride solution BaCO₃Preheating the ore pulp to 85-95 deg.C, pumping into ammonia still, and evaporating ammonia and CO at not less than 104 deg.C₂Reaction of Similar reactions occur with carbonates of Sr, Mg, Ca, etc. but only after the above carbonates of Ba, Mg, Ca have reacted, CaCO₃The reaction is started and NH is added₄Cl not counting CaCO₃Namely to reduce CaCl production₂Waste of Cl^-Is one of the improvements of the method; after the reaction is finished, slag is filtered out and washed by water to be used as building materials, filtrate is obtained, and BaCl is produced through purification, concentration and crystallization₂·2H₂And O. (2) The above-mentioned ammonia and CO generation₂Introducing gas into 330g/l mirabilite mineral liquid to ammoniate and carbonize the mirabilite mineral liquid, and producing NH as a by-product of 1.4 tons of barium chloride per product₃、CO₂Qi can harmonize with 3m³The treatment is carried out under the action ratio of 330g/l mirabilite liquid. When the temperature of mirabilite is raised to 45 deg.C, it is kept at 45 deg.C, and cooled to control temperature, at this moment, the metal ions of Ca, Mg and Fe, etc. in mirabilite are all precipitated in carbonate state, the contents of heavy metal and arsenic can be measured, sodium sulfide is added, and P is regulated_HThe value is 7 ± 0.5. Adding animal glue (bone glue, skin glue) 8g/m³Precipitating heavy metal and arsenic as sulfide, and adding silicic acid and Al⁺³Flocculating, settling, clarifying, filtering to obtain clear solution of Natrii sulfas and ammonium carbonate, and measuring Na content₂SO₄And (NH)₄)₂CO₃Adding ammonium bicarbonate. Make Na in the liquid⁺∶NH₃Pumping into carbonating tower and drum CO at ratio of 1: 1.1₂The temperature of the bottom of the tower is controlled to be 25-26 ℃, the temperature in the tower is controlled to be 55-60 ℃, and the reaction is carried out Detecting it (NH)₄)₂SO₄Discharging the feed liquid when the concentration is more than or equal to 200g/l, standing, and filtering NaHCO₃The crystals are washed by isotonic liquid until the crystals contain SO₄ ^-2Until the content is less than or equal to 0.3 percent, washing with NaHCO₃Calcining the crystal into Na at 200 ℃ in a calcining furnace₂CO₃(soda) product, reaction 2NaHCO₃ ^≥200℃Na₂CO₃+CO₂↑+H₂O, recovery of CO₂Carbonizing Natrii sulfas, filtering to obtain mother liquor, cooling to-5 deg.C to-10 deg.C, and allowing unreacted Na₂SO₄And NH₄HCO₃Separating out by crystallization, filtering out the crystallization, adding mirabilite solution in a lower tank for utilization, filtering to obtain mother liquor so that (3) the ammonium sulfate mother liquor contains a small amount of ammonium bicarbonate and alkali, adding sulfuric acid to neutralize ammonium bicarbonate to form ammonium sulfate, and adding sulfuric acid to neutralize ammonium bicarbonate to obtain P_HHeating to 85-100 deg.C for 6-7 deg.C, and measuring SO₄ ^-2Adding KCl with equivalent weight in the total amount, stirring and reacting for 2.5-3 h The reaction solution is cooled to room temperature, mostlyDivide K₂SO₄Precipitated as crystals. Separating out wet crystals. Measuring residual K of mother liquor₂SO₄More than or equal to 3 percent of K can be concentrated, cooled and crystallized, and the K is recovered₂SO₄Wet crystal, no need of washing crystal, hot-air drying at temp. greater than 350 deg.C in drying furnace, and the crystal contains NH₄Cl mother water is gasified and separated together, and NH is recovered by spraying furnace gas water₄Cl, discharging the dried crystal from the furnace to obtain a potassium sulfate product; the mother liquor and the washing gas water are mixed and mainly contain NH₄Cl for obtaining NH from (4)₄Cl liquid, according to the measurement of residual SO₄ ^-2Adding barium chloride in an equivalent amount to make SO₄ ^-2All with BaSO₄↓recoveredsediment BaSO₄By-product, SO removal₄ ^-2NH of₄Adding BaCO into Cl liquid₃And (3) repeating the reaction and cyclic production of the mineral powder in the step (1). The barium mother liquor treatment is the same as the old process and is not repeated.

   It can be seen that ① directly uses liquid mirabilite, saving concentration and crystallization, saving energy in mining area, reducing equipment, and making liquid state good for pipeline transportation, ② uses mirabilite to prepare soda ash, and the by-product ammonium sulfate liquid can directly react with KCl double decomposition reaction without concentration to obtain potassium sulfate product, and the by-product ammonium sulfate liquid isProduction of NH₄Cl, no need of concentration, saving equipment and steam, ③ obtaining ammonium chloride solution, BaCl must be added₂Can remove residual SO₄ ^-2Recovering the precipitated BaSO₄By-products, ammonium chloride solution can replace hydrochloric acid and BaCO₃Reacting to obtain BaCl₂·2H₂O product, low cost, distilling off NH₃Gas, CO₂④ reaction with mirabilite to prepare ammonium sulfate and ammonium chloride, which can be reused only to supplement loss and make up for consumption of 1/10, ⑤ to prepare agricultural fertilizer, SO and SO₄ ^-2、Cl^-No charge, this method uses SO₄ ^-2Substituted sulfuric acid with Cl^-The cost of the substituted hydrochloric acid is greatly reduced, the ammoniais used as a medium to ensure that the reaction is completely carried out in a water phase, the reaction is mild, high temperature and high pressure do not exist, strong acid and strong alkali are used, the reaction is flammable and explosive, the equipment is simple, the mechanization is high, the investment is less, and the device is large. Consume 3 kilometers per year³330g/l liquid mirabilite ore containing pure Na₂SO₄1 ten thousand tons, the invention can co-produce more than or equal to 1.3 ten thousand tons of barium chloride dihydrate, more than or equal to 1.1 ten thousand tons of potassium sulfate, more than or equal to 0.65 ten thousand tons of sodium carbonate, more than or equal to 6 million/year of output value, more than or equal to 3 million yuan of profit and tax reduction equal to 3 ten thousand meters³The mirabilite is added with ammonium sulfate and ammonium chloride, which are not concentrated and not crystallized, and coal power is saved by tens of millions of yuan, so that the dream of producing barium chloride without using hydrochloric acid and producing potassium sulfate without using sulfuric acid is realized.

   The invention has the advantages of little innovation, great benefit, novelty and practicability, and patent protection.