WO2009124493A1 - 一种将表面工程技术应用于天然碱生产领域的联合制碱法 - Google Patents

一种将表面工程技术应用于天然碱生产领域的联合制碱法 Download PDF

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Publication number
WO2009124493A1
WO2009124493A1 PCT/CN2009/071178 CN2009071178W WO2009124493A1 WO 2009124493 A1 WO2009124493 A1 WO 2009124493A1 CN 2009071178 W CN2009071178 W CN 2009071178W WO 2009124493 A1 WO2009124493 A1 WO 2009124493A1
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Prior art keywords
soda ash
crystal
sodium carbonate
salt
solution
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PCT/CN2009/071178
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English (en)
French (fr)
Inventor
崔怀奇
Original Assignee
Cui Huaiqi
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Application filed by Cui Huaiqi filed Critical Cui Huaiqi
Priority to CN200980112153.2A priority Critical patent/CN102036914B/zh
Publication of WO2009124493A1 publication Critical patent/WO2009124493A1/zh
Priority to US12/898,222 priority patent/US8470055B2/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/22—Purification
    • C01D7/24—Crystallisation

Definitions

  • the sodium carbonate decahydrate crystal obtained in the step (b) is subjected to hot steam autolysis at a temperature of 34.5 ° C to 109 ° C, preferably 50 to 100 ° C. Recrystallization gives crystals of sodium carbonate monohydrate and separates them, or obtains soda ash by natural weathering at a temperature of 0 to 34 ° C, preferably 10 to 32 ° C.
  • the solution obtained by separating the sodium carbonate decahydrate crystals in the step (b) is returned to the trona solution to carry out the attached crystals again.
  • the anhydrous sodium carbonate crystals, the sodium carbonate monohydrate crystals and the sodium hydrogencarbonate crystals obtained above are calcined to obtain a soda ash; the sodium hydrogencarbonate crystal slurry is wet-decomposed by high pressure atomization and Drying to obtain soda ash.
  • the concentration is 6% ⁇ 32.9%.
  • the temperature of the trona solution is preferably -2.1 ° C to 32 ° C, preferably -2.rC to 20 ° C, and the concentration is 5.9% to 31.3%.
  • Figure 1 is a schematic process flow diagram of a combined alkali process in accordance with one embodiment of the present invention.
  • FIG 3 is a schematic view of a brushed air sent to burn tube in accordance with an embodiment of the present invention.
  • Figure 4 is a schematic process flow diagram of a combined alkali process in accordance with another embodiment of the present invention.
  • Figure 7 is a schematic illustration of a forced evaporation, cryogenic crystallizer in accordance with one embodiment of the present invention.
  • Figure 8 is a schematic illustration of a dual energy dual effect drying decomposition column in accordance with one embodiment of the present invention. Mode for carrying out the invention
  • the caustic soda is prepared by dissolving and clarifying to obtain a lye solution having a concentration of about 30% by a conventional method.
  • the trona mother liquor is injected into an underground condensing tank with a depth of about 1 m (the specification of the chilling tank is determined according to the production demand, and the purpose of the underground chilling tank is to reduce the influence of the ambient temperature on the liquid, which is easy to operate).
  • the lye level rises slowly from bottom to top in the chiller.
  • the lye concentration may be 6% to 32.9%, and the temperature may be from 0 ° C to 35 ° C.
  • the lye concentration may be 5.9% to 31.3%, and the temperature may be -2.rC to 32 °C.
  • the slowly rising lye is in contact with the fiber rope on the crystallizer in the pool, and the sodium carbonate solution with the least solubility is first attached to the rope body and becomes a seed crystal.
  • the seed crystal continuously attracts the same medium to attach it to the crystal on the crystal rope.
  • Growing up At the same time of crystallization, since the crystallization pond is a subterranean pool, the temperature of the liquid in the crystallization tank will continuously decrease, and the solubility of the solute in the solution also decreases as the temperature of the liquid decreases, which is more convenient for crystal precipitation.
  • the solution is quickly discharged, and the discharged solution is converted into sodium hydrogencarbonate by an atomization converter.
  • the sodium carbonate crystal crystallized on the crystallizer is sodium carbonate decahydrate.
  • the sodium carbonate decahydrate crystal is dissolved in its own water to a solution containing about 37% sodium carbonate at an ambient temperature of more than 34 ° C, and the sodium carbonate solution is atomized.
  • the concentrated crystallizer was heated and boiled at a temperature of 109 ° C to precipitate anhydrous sodium carbonate crystals.
  • the anhydrous sodium carbonate crystals are sent to a brushing air and sent to a calcining tube for calcination, and the water is evaporated to obtain a heavy particle soda ash.
  • the sodium bicarbonate prepared from the atomization converter is not subjected to a centrifugal dehydration process, and is formed into a slurry in a high-speed agitator and then driven into a high-pressure atomization drying tower by a high-pressure slurry pump to be pulverized and calcined to form a spherical shape. Soda ash.
  • the separated sodium chloride solution is subjected to high-pressure atomization technology to absorb ammonia and carbonation, and is converted into sodium hydrogencarbonate, and calcined to obtain a light soda ash.
  • the soda ash and the Yuanming powder are obtained by weathering and drying the crystal on the crystallizer by natural weathering method; by improving the conventional ammonia-base method, the atomization technology is applied to steaming ammonia, ammonia absorption, and carbonation to obtain soda ash.
  • the above embodiment of the present invention dissolves a trona containing a mixture of a salt, a base and a nitrate in water (alkaloid), clarifies to prepare a certain concentration of an aqueous solution, and performs at a certain temperature.
  • sodium carbonate decahydrate crystals were separated. Then, the obtained sodium carbonate decahydrate crystal is subjected to hot-distillation auto-dissolution boiling recrystallization, centrifugal dehydration to obtain anhydrous sodium carbonate crystals, and calcined to obtain a soda ash finished product.
  • the remaining sodium carbonate is converted into lower solubility sodium hydrogencarbonate by high pressure atomization evaporation and carbonation, and then cooled and crystallized by centrifugal dehydration separation, or obtained by high speed stirring.
  • the crystal slurry is then calcined and decomposed to obtain a soda ash.
  • the dehydrated supernatant is concentrated and subjected to crystallization to separate sodium sulfate decahydrate crystals, which are naturally weathered to obtain Yuanming powder.
  • the trona solution is separated from the sodium carbonate decahydrate crystal by the attached crystal.
  • the solution is quickly discharged, and then the new one is removed.
  • the concentrated solution is introduced and the above steps are repeated until the crystal is attached. Seek the degree.
  • the discharged low concentration solution is returned to the trona mother liquor to further extract the residual base therein.
  • the sodium carbonate decahydrate crystal separated by the attached crystal may be directly obtained by natural weathering at 0 ° C or more and 34 ° C or less, preferably 10 to 32 ° C, or may be at 35.4 ° C to 109 ° C, preferably 50 ° C. Hot-steam auto-dissolution recrystallization at a temperature of ⁇ 100 °C.
  • the sodium carbonate decahydrate crystal changes its hydration characteristics in the environment of 35.4 ° C ⁇ 109 ° C to produce a change in the lattice structure order. When the solution concentration is greater than 30.8%, it will precipitate in the form of sodium carbonate monohydrate. Quickly obtain sodium carbonate monohydrate crystals. After the crystal is dehydrated by Wanxin, the crystal is decomposed by calcination to obtain a soda ash.
  • FIG. 6 is a phase diagram of the Na 2 C0 3 -Na 2 S0 4 -H 2 0 system. As shown in the figure, the range of 35.4 ° C ⁇ 50 ° C is the region where the difference in solubility between sodium carbonate and sodium sulfate is the largest, so the crystal separation of sodium carbonate monohydrate is selected in this temperature range.
  • the sodium sulfate decahydrate is separated according to the above method, and the natural gas is obtained by natural weathering.
  • the sodium chloride in the remaining solution is converted into sodium hydrogencarbonate, and then calcined and decomposed to obtain a soda ash.
  • the method of the present invention is used for the combined production of alkali to realize the saline-alkali nitrate.
  • the separation of simple substances according to the different needs of the market, has produced light powdered soda ash, light spherical granule soda ash, heavy granule soda ash and yuan Ming powder.
  • the product variety is high, the purity is high, and the whole production process can realize cyclical chain utilization. Smoke-free, dust-free, no waste liquid discharge and other environmental pollution problems.
  • Example 1 The method of the present invention will be illustrated in more detail by the following examples. However, the examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention.
  • Example 1 The method of the present invention will be illustrated in more detail by the following examples. However, the examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention.
  • Example 1
  • the cold separation separation treatment of salt, alkali and nitrate is carried out by the attached crystallization method.
  • the trona base is dissolved and clarified by a conventional method to prepare an aqueous solution having a concentration of about 30%.
  • the crystallization treatment device is as follows: 1.
  • the attached crystallizer is about lmxlmx2.7m angle steel frame, the upper and bottom of the frame is welded with 1 fine steel bar every 1cm interval, the upper and lower steel bars are parallel to each other, corresponding to Each piece of steel in the upper part is connected by 1cm of fine fiber rope at intervals of 1cm.
  • the total length of the fiber strands of each crystallizer is about 25,000 meters, thereby expanding the surface area of the attached crystal.
  • Each crystallizer can reach more than 1000kg of crystal in 8-12 hours.
  • the crystallizers are arranged in a ratio. 3.
  • the sliding sky hoist is an electric hoist that can slide back and forth on the top of the crystallization tank to complete the feeding and sending operation of the crystallizer. According to the daily production of more than 100 tons of heavy soda ash, 10 crystallizing tanks and 200 crystallizers are required. The total length of the fiber ropes is more than 5 million meters.
  • the treatment process is: injecting the alkali solution into the cold precipitation tank, so that the liquid level of the alkali liquid rises slowly from bottom to top in the pool, and the rising alkali liquid contacts the fiber rope of the crystallizer, and the sodium carbonate solutes with the least solubility are quickly attached thereto.
  • the rope becomes a seed crystal, and the seed crystal is continuously absorbed into the same medium to attach it, so that the crystal on the crystal rope grows continuously.
  • the crystal grows to a certain extent, the liquid in the pool is released, and the crystallizer is suspended by sliding the crane. Out, send to the next process.
  • This crystal is mainly sodium carbonate decahydrate).
  • the auto-dissolver is a device used according to the characteristics that sodium carbonate decahydrate dissolves in its own water at an ambient temperature of more than 34 ° C. The specification of the device depends on the size of the crystallizer. To seal the hot steam chamber, dissolve it with hot air.
  • Atomization and concentration crystallizer (as shown in Fig. 2): The atomization and concentration crystallizer is an erected tower tank, and the outer surface of the tank is insulated.
  • the upper part and the middle part are forced evaporation areas, and two annular air inlets are provided;
  • the lower part is a boiling crystallization area, and an air inlet is provided to provide heat source for the heat transfer tube in the crystallization area (the bottom heating tube total)
  • the cross-sectional area is larger than the cross-sectional area of the air duct of the hot blast stove.
  • the specific processing process is as follows: the heat of the first hot blast stove is introduced into the upper first annular air inlet 201 through the heat transfer tube at the bottom of the crystallizer, and the heat of the second hot blast stove is directly sent into the second annular inlet.
  • the tuyere 202 the hot air of the two annular air inlets, is heated by the blowing force of the hot air blower and the gravitational force of the top air blower of the crystallizer, and the rising hot air flow and the mist of the sodium carbonate solution atomized by the top high pressure spray gun 203
  • the droplets show a convective trend, produce heat exchange, and the water evaporates rapidly, so that the solution is quickly concentrated.
  • the concentrated solution is stored in the boiling crystallization zone during the heat exchange process, and the temperature is rapidly increased due to the heating of the three rows of heating tubes in the crystallization zone. When it reaches 109 ° C or higher, anhydrous sodium carbonate crystals are precipitated.
  • the high-pressure atomization carbonizer is a vertical tower with a diameter of 1.5 meters and a height of 15 meters, and a carbon dioxide gas inlet is arranged at the bottom.
  • the treatment process is as follows: The carbon dioxide gas of the tail gas decomposing sodium bicarbonate (see the fourth process) is sent to the inlet of the bottom of the carbonizer by the induced draft fan. Since the diameter of the carbonizer is larger than the diameter of the air inlet duct, the flow rate of the carbon dioxide gas is slowed down slowly. Upward trend.
  • the sodium carbonate solution reacts with carbon dioxide gas in an atomized state, on the one hand, the gas-liquid contact area is enlarged, and on the other hand, the atomic droplets have a reduced resistance to the ascending air flow, which is advantageous for the rapid absorption and conversion of the two, and from the bottom.
  • the rising carbon dioxide gas continuously flows upward during the reaction, so the exotherm does not affect the dissolution of carbon dioxide by the sodium carbonate droplets.
  • the sodium bicarbonate-containing solution falls into the cone at the lower part of the converter, is discharged through the discharge port, and is cooled by the cooling bath. Since the solubility of sodium hydrogencarbonate is extremely small, it rapidly crystallizes and is separated from other media.
  • the air is sent to calcination with anhydrous sodium carbonate and the air is sent to calcination decomposition of sodium bicarbonate.
  • the treatment device is a brushed air-driven calcining tube (as shown in Figure 3).
  • the brushing air sending and forging pipe is composed of a high temperature blower 301, a high speed stirring brush 302, a vertical screw feeder 303, a material temporary storage bin 304, a bottom trough 305, an accumulation bin 306 and a cyclone dust collector.
  • the specific processing process is as follows:
  • the hot air supplies hot air with a wind pressure of 5000 Pa and a temperature of 200 ° C or higher to the calcining tube under the action of the high temperature blower, and the material is supplied from the hopper from the vertical screw conveyor to the calcining tube at a constant speed.
  • the material of the calcining tube is brushed by high-speed stirring to expand the heated area.
  • the material to be brushed is blown forward and released by the wind. Some materials with high moisture content and large grain size are accumulated in the temporary storage due to the wind load.
  • the warehouse is slid into the trough through the chute, and then sent to the calcining tube through the second group of screw conveyors. After the second brush is heated, the moisture of the material evaporates continuously.
  • the sodium bicarbonate separated by the process of the three crystals is obtained by high-speed stirring to obtain a sodium hydrogencarbonate crystal slurry, and the following steps are substituted for the fourth step of the high-pressure atomization calcination decomposition and carbonation of the sodium hydrogencarbonate crystal slurry.
  • the processing unit is an upright drying tower for heat exchange.
  • the height is higher. According to the scale of more than 100 tons per day, the general height is 25 ⁇ 30m, the straight is 5 ⁇ 7m, and the insulation layer is added.
  • the device can be used in two ways.
  • the high-pressure atomization method can be used to atomize the thick sodium bicarbonate crystal slurry through the high-pressure spray gun, and the crystal solid can be dried by the brush diffusion method.
  • the specific treatment process is as follows: 1. Stirring by a high-speed mixer The sodium bicarbonate crystal slurry is sprayed into the drying tower through a high-pressure spray gun and is atomized. It is pushed down by the pressure of the discharge pressure and the self-weight, and is subjected to the hot air flow running from the bottom to the top to generate heat exchange, sodium hydrogencarbonate.
  • the water evaporates rapidly, and the sodium carbonate is thermally expanded and dried to form hollow particles falling into the bottom pollination funnel to form a shaped product.
  • the carbon dioxide and the water vapor are extracted into the cyclone by the induced draft fan to separate the alkali dust, and then introduced into the high-pressure atomization carbonation process.
  • the anhydrous sodium carbonate and sodium bicarbonate are centrifugally dehydrated and transported by the bucket elevator to the top of the drying tower.
  • the material distributor distributes the material to the brushing tray at a constant speed.
  • the brushing disc is a circular sieve tray with a diameter of 2 meters or more.
  • the material is evenly sprinkled by the high-speed stirring brush in the brushing disc, and the sprinkled material exchanges heat with the high-heat airflow running from the bottom.
  • the moisture evaporates quickly, the material quickly decomposes and decomposes, and falls into the bottom pollination.
  • the funnel becomes a shaped product.
  • the carbon dioxide gas and water vapor are pumped into the cyclone through the induced draft fan and then introduced into another process.
  • the treatment device is the same as the above-described atomization concentration crystallizer.
  • the residual halogen is heat exchanged by atomization and hot gas flow, and the water is quickly evaporated.
  • the concentrated saturated solution is then precipitated by the crystal separation method, and the sodium sulfate decahydrate crystals deposited on the crystallizer are placed in a ventilated and dry state.
  • the natural drying is achieved by weathering, and the finished product is anhydrous sodium sulfate (ie, Yuanming powder).
  • the last remaining liquid is a solution based on sodium chloride.
  • the natural weathering workshop is an open space that can be built in an open space.
  • Semi-open workshop for rapid circulation of dry air.
  • the weathering workshop is surrounded by a metal mesh as an air filter wall.
  • the top of the workshop uses sunlight.
  • the plate is closed and provided with a drafting device sufficient to direct the amount of flowing air.
  • the crystal net is arranged on the crystal frame in the workshop and suspended and suspended. The distance between the crystal net and the crystal net should be greater than 400mm.
  • the middle air supply passage is designed, and the top of the air supply passage can be made into a sealed curved glass shed, and the roof is installed with a plurality of air blowing devices according to the required air volume.
  • the sodium carbonate decahydrate or sodium decanoate added to the crystal network is weathered and converted into anhydrous sodium carbonate or anhydrous sodium sulfate, which is shaken off by shaking and sieved.
  • the treatment device has a high pressure atomization ammonia absorber and a high pressure atomization carbonizer. According to the reaction principle of the reaction formula NaCl + NH 3 + C0 2 + H 2 0 ⁇ NaHC0 3
  • the sodium chloride solution is allowed to absorb ammonia and carbon dioxide to form sodium bicarbonate. Since the process of ammonia absorption and carbonization cannot be carried out at the same time, it is necessary to absorb carbon dioxide and then absorb carbon dioxide, so it needs to be treated by two devices.
  • the high pressure atomizing ammonia aspirator is the same as the high pressure atomizing carbonizer described above.
  • the carbonization of the ammonia brine should be carried out at normal temperature.
  • the specific treatment process is as follows: the brine is atomized and sent to the rising ammonia gas at the bottom annular air outlet to generate ammonia brine, and then the ammonia brine is atomized inside the carbonizer to send the ascending carbon dioxide gas to the bottom air inlet.
  • the reaction produces sodium hydrogencarbonate, and the solution after the reaction is cooled to precipitate sodium hydrogencarbonate crystals, and the crystals are decomposed into light sodium carbonate by calcination at a temperature of more than 160 °C.
  • the above sodium bicarbonate crystal or crystal slurry is treated in the fourth or fifth process.
  • a trona solution was prepared in the same manner as in Example 1, and sodium carbonate decahydrate was separated by adhering crystallization.
  • the difference from Example 1 is that the attached crystallizer is a 100 cm x 300 cm mesh fiber rope structure, and the equipment used also includes a pair of roller mills.
  • the pair of rolling mill is a A device in which the group rolling width is equal to the width of the crystal mesh and is rotated by the opposite direction to achieve crushing of the crystal. The rolling of the crystal on the crystallized web is carried out into a subsequent process by using a rolling mill.
  • the processing device is a hot steam auto-dissolver, which is a device selected according to the characteristics that sodium carbonate decahydrate dissolves in its own water at an ambient temperature of more than 32 ° C (as shown in FIG. 5 ). ), the process is as follows.
  • the crushed material is sent to the feed port 502 via the belt conveyor 501, and the material is evenly spread by the umbrella screen 503 on the first sieve tray 504 (the mesh diameter is 10 mm), and the material on the sieve tray is sent by the annular air inlet 508.
  • the solution starts to dissolve and is sprayed by the homogenizing brush 505 to the second sieve tray 507 (the mesh diameter is 5 mm), and the small crystals falling on the second sieve tray are in the homogenizing brush 506.
  • the homogenizing brush 505 Under the action of brushing and rubbing, it is uniformly dissolved by heat, and the alkali liquid falls into the crystallization zone 509 at the bottom of the hot-dip autoclave.
  • the temperature in the hot-dip autoclave is controlled to be 35.4 °C ⁇ 109 °C, and the lye after autolysis is at In an extremely supersaturated state, sodium carbonate monohydrate is rapidly precipitated in the crystallization zone, and the crystallized sodium carbonate monohydrate is continuously grown under the action of the agitator 510.
  • the crystal reserve of sodium carbonate monohydrate in the crystallization zone reaches a certain level It is discharged from the discharge port 511, and is subjected to centrifugal dehydration to enter a subsequent process.
  • the solution separated by the centrifugal dehydration step is subjected to forced evaporation and low-temperature crystallization to separate the sodium carbonate monohydrate from the sodium sulphate.
  • the sodium sulfate content of the solution separated by the second process is continuously increased, and when the sodium sulfate content exceeds 3%, it is difficult to separate it by a conventional evaporation method.
  • the solubility curve of Na 2 C0 3 and Na 2 S0 4 in the phase diagram of Na 2 C0 3 , Na 2 S0 4 and H 2 0 Fig. 6
  • the preferred method is to select the interval with the greatest difference in solubility between the two to crystallize one of the solutes for separation purposes.
  • solubility curve analysis shown in Figure 6 When the solution temperature is maintained between 35.4 °C ⁇ 50 °C, the solubility of sodium carbonate is 33.2% ⁇ 30.8%, crystallized in the form of sodium carbonate monohydrate.
  • the solubility of sodium sulfate is 55% ⁇ 50%, and it crystallizes in the form of anhydrous sodium sulfate. The difference in solubility between the two is 20%. Therefore, forced evaporation and low temperature crystallization are used in this interval. Extraction of sodium carbonate into monohydrate.
  • the processing device is a forced evaporation, low temperature crystallizer (as shown in Figure 7).
  • the treatment process is as follows: the hot air enters the device through the annular air inlet 702 under the pumping force of the air guiding duct 701, and the alkali liquid is atomized by the high pressure spray gun 703 to contact the rising hot air flow to generate a strong evaporation effect, and the moisture is in the mist.
  • the evaporation zone 704 is rapidly evaporated, and the concentrated alkali liquid is collected in the crystallization zone 705.
  • the sodium carbonate monohydrate is precipitated in a temperature range of 35.4 ° C to 50 ° C, and the fresh liquid is filled and then discharged through the overflow port 706 for recycling.
  • the crystal slurry is intermittently withdrawn through the discharge port 707.
  • the obtained sodium carbonate monohydrate crystal slurry is subjected to centrifugal dehydration to obtain sodium carbonate monohydrate crystals and a salt nitrate solution.
  • the salt-nitrogen solution separated by forced evaporation and low-temperature crystallization is further subjected to sodium sulfate extraction by an attached crystal separation method.
  • the salt nitrate solution separated by forced evaporation and low-temperature crystallization is concentrated to a concentration of sodium sulphate of 8% to 56.7%, and then the same crystallization process as in Process 1 is used at a temperature of 0 to 32.4 ° C to precipitate sulfuric acid decahydrate.
  • Sodium crystals, separation of salt and nitrate is used at a temperature of 0 to 32.4 ° C to precipitate sulfuric acid decahydrate.
  • the sodium carbonate decahydrate obtained in the above first embodiment can also be naturally weathered under the same conditions to directly obtain the finished product of soda ash.
  • the remaining solution after separation of sodium depotassate is mainly sodium chloride, which is subjected to high-pressure atomization, ammonia absorption, atomization and carbonation, and sodium chloride in the solution is converted into sodium hydrogencarbonate.
  • the method comprises the steps of: expanding the surface area of the aqueous solution of the refined salt, causing the aqueous solution of the fine salt to be in an atomized state to form an aerosol convective contact with the ammonia gas in the atomization state, and the refined brine rapidly dissolves the ammonia gas to form the ammonia salt water, and the ammonia salt water is in the same manner as above.
  • the sodium hydrogencarbonate crystals are obtained by centrifugal dehydration, or the sodium hydrogencarbonate crystal slurry is obtained by high-speed stirring.
  • the dual-energy double-effect drying decomposition tower is used to calcine sodium carbonate monohydrate, and the sodium bicarbonate is decomposed by the atomization wet decomposition method or the brushing granulation technique.
  • the dual energy double effect drying decomposition tower is an upright tower tank (As shown in Figure 8), the height is determined according to different production requirements.
  • the bottom is a cone-shaped discharge funnel 801, the upper part of the funnel is an annular air inlet 802, the top is a tower cap 803, and an air-inducing duct 804 is provided to extract the tower.
  • the inner gas is provided with a high pressure spray gun 805 and a material scraping distribution plate 806 at the top of the tower.
  • the dual energy means that it can produce liquid raw materials by high pressure atomization wet decomposition method, and can also produce solid raw materials by brushing granulation technology.
  • Double effect means that it can calcine dry sodium carbonate and calcined to decompose sodium bicarbonate.
  • the working principle is as follows: 1.
  • the liquid raw material, that is, the sodium bicarbonate slurry is sprayed into the top of the tower by a high pressure pump, which is caused by pressure.
  • the mist gradually descends from the top of the tower from top to bottom, and heat exchange occurs in contact with the hot airflow from the bottom up during the landing process.
  • the moisture of the misty material evaporates rapidly into a finished product, and the material is puffed due to high pressure.
  • the finer material rolls down and collides with each other under the brushing action of the separating brush, and becomes a granular product when falling into the pollination funnel.
  • the exhaust gas for treating sodium carbonate crystals is taken out through the top air inlet duct and is introduced into the hot steam autocluster by cyclone dust removal and bag dust removal to provide a heat source for the hot air.
  • the tail gas of the sodium bicarbonate crystal or the crystal slurry is extracted through the top draft duct and It is supplied to the high pressure atomization carbonation process after cyclone dust removal and bag dust removal.
  • the combined alkali process achieved by the present invention reduces the requirements on raw materials and is suitable for treating most trona minerals.
  • the actual production comparison not only reduces the investment in production facilities (equipment investment is 1% of the investment in conventional production methods), but also greatly reduces energy consumption, shortens the production process, shortens the production cycle, and makes full use of natural energy.
  • the production cost is greatly reduced, and the number of workers is only one tenth of the conventional production method, and can meet the requirements of environmental protection production.

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Description

一种将表面工程技术应用于天然碱生产领域的联合制碱法 技术领域
本发明涉及从天然碱中制取纯碱的联合制碱法， 特别涉及应用表面 工程技术，使用依附结晶分离法、 高压雾化浓缩法、 高压雾化碳酸化法、 高压雾化吸氨法对盐、 碱、 硝混合溶液进行分步分离； 使用刷撒风送锻 烧管对碳酸钠、 碳酸氢钠半成品进行锻烧分解等为主体的联合制碱法。 背景技术
纯碱生产， 目前采用的是常规氨碱法和多效蒸发浓缩法。 氨碱法使 用精制盐为原料， 经氨化、 碳酸化制得碳酸氢钠， 再经锻烧制得纯碱。 多效蒸发浓缩法是使用含碳酸钠纯度极高的天然碱原料经常规蒸发浓 缩析出无水碳酸钠， 再经锻烧制得纯碱。 这两种方法生产纯碱设备投资 高、 能耗大、 程序多、 技术要求繁杂， 而且用人多、 劳动强度大、 生产 周期长， 废水、 废气对环境的污染也极其严重， 更重要的是对原料的选 择性强。 如果要生产高纯度纯碱必须选用精制盐水或含碳酸钠单一成份 较高的原料。 这种选择性决定了其生产的局限性。 从全世界天然碱储藏 的状况来看， 大部分天然碱为伴生矿物质， 盐、 碱、 硝混合并存， 以原 有的生产方法提纯分离难度很大， 致使天然碱原料的利用价值大大降 低。 盐、 碱、 硝的分离至今仍是天然碱领域的一大难题， 以致影响到全 世界天然碱加工工业的发展。 发明内容
本发明的方案在于对传统生产工艺进行改进，通过依附结晶分离法、 高压雾化浓缩法、 高压雾化碳酸化法、 高压雾化吸氨法对天然碱伴生矿 物中的盐、 碱、 硝进行分离、 提纯和转化。 依此可达到如下目的： 扩大 了纯碱生产中原料的选择性， 实现了伴生矿物的分离、 提纯， 提高了资 源的利用价值； 将表面工程技术引入纯碱的生产， 加快了物质物理转化 和化学转化的速度，提高了转化率； 筒化了生产工艺， 缩短了生产流程， 降低了生产成本， 节约了能源和人力， 并充分利用了自然能源， 使高污 染的生产环境变为环保生产环境。
为此本发明提供一种从含有盐、 碱、 硝混合物的天然碱中制取纯碱 的联合制碱法， 该方法包括： （a)将天然碱制成水溶液； （b)使用依附 结晶分离法从天然碱溶液中分离得到十水碳酸钠晶体； 和（c)对所得的 十水碳酸钠晶体进行处理得到纯碱。
根据本发明的一种实施方式， 在步骤（c) 中将步骤（b)所得的十 水碳酸钠晶体在》 109 °C的温度下进行热蒸自溶沸腾结晶并分离以制得 无水碳酸钠晶体。 对步骤（b)中分离出十水碳酸钠晶体后的溶液进行高 压雾化， 并通入 C02使其中的碳酸钠转化为碳酸氢钠并结晶分萬得到碳 酸氢钠晶体和剩余溶液或搅拌得到晶浆。 将分离出碳酸氢钠晶体后的溶 液浓缩， 进行依附结晶并分离制得十水硫酸钠晶体。 将分离出十水硫酸 钠晶体后的溶液经高压雾化吸氨、 高压雾化碳酸化将其中的氯化钠转化 为碳酸氢钠晶体或晶浆。
根据本发明的一种实施方式， 在步骤（c) 中将步骤（b)所得的十 水碳酸钠晶体在 34.5°C ~109°C,优选 50~100°C的温度下进行热蒸自溶 重结晶得到一水碳酸钠晶体并分离， 或者在 0~34°C, 优选 10~32°C的 温度下经过自然风化制得纯碱。 对步骤（b) 中分离出十水碳酸钠晶体 后的溶液返还到所述天然碱溶液中再次进行依附结晶。
该实施方式进一步包括通过在 35.4°C ~50°C的温度下进行强制蒸 发、 低温结晶将分离出一水碳酸钠晶体后的溶液中残余的碳酸钠以一水 碳酸钠晶体的形式结晶并与仍保留在溶液中的硫酸钠分离得到一水碳 酸钠晶体和剩余溶液。 对分离所述一水碳酸钠晶体后剩余的溶液进一步 进行浓缩、 依附结晶并分离制得十水硫酸钠晶体。 将分离出十水硫酸钠 晶体后的溶液经高压雾化吸氨、 高压雾化碳酸化将其中的氯化钠转化为 碳酸氢钠晶体或晶浆。
根据本发明的一种实施方式， 以上制得的无水碳酸钠晶体、 一水碳 酸钠晶体和碳酸氢钠晶体采用煅烧处理制得纯碱； 所述碳酸氢钠晶浆经 高压雾化湿分解并干燥处理制得纯碱。
根据本发明的一种实施方式， 优选所述十水硫酸钠晶体的依附结晶 在 8 ~ 56.7%的溶液浓度及 0°C ~ 32.4°C的温度下进行。 并优选所述十水 硫酸钠晶体在 0 ~ 34°C , 更优选在 10 ~ 32°C的温度下经过自然风化制得 元明粉。
根据本发明的一种实施方式， 优选上述高压雾化、 高压雾化浓缩、 高压雾化吸氨、 高压雾化碳酸化、 高压雾化湿分解和高压雾化干燥中进 行高压雾化所需的喷枪压力为 20kg/cm2 ~ 60kg/cm2。
根据本发明的一种实施方式， 优选所述依附结晶所用的依附结晶器 为网状纤维结构。
根据本发明的一种实施方式， 其中所述煅烧处理优选在刷撒风送煅 烧管中进行， 包括： 为所述煅烧管内提供风压为 5000Pa、 温度为 200°C 以上的热风； 将物料送入所述煅烧管； 物料在所述煅烧管内经刷撒、 煅 烧和吹送后快速干燥和 /或分解； 水分含量高、 粒度大的物料被再次送 入煅烧管内进行刷撒、 煅烧和吹送； 干燥后得到的重质纯碱被吹送到积 料仓； 粉尘状物料经旋风分离后得到轻质纯碱。
根据本发明的另一种实施方式， 其中所述煅烧处理和所述高压雾化 干燥处理分别在双能双效干燥塔中进行。 根据本发明的一种实施方式， 优选所述天然碱溶液的温度为 o°c ~
35 °C , 浓度为 6% ~ 32.9%。
根据本发明的另一种实施方式， 优选所述天然碱溶液的温度为 -2.1 °C ~ 32°C , 优选 -2.rC ~ 20°C , 浓度为 5.9% ~ 31.3%。
附图简要说明
图 1 是根据本发明一种实施方式的联合制碱法的示意性工艺流程 图。
图 2是根据本发明一种实施方式的雾化浓缩结晶器的示意图。
图 3是根据本发明一种实施方式的刷撒风送锻烧管的示意图。
图 4是根据本发明另一种实施方式的联合制碱法的示意性工艺流程 图。
图 5是根据本发明一种实施方式的热蒸自溶器的示意图。
图 6是 Na2C03-Na2S04-H20体系相图。
图 7是根据本发明一种实施方式的强制蒸发、低温结晶器的示意图。 图 8是根据本发明一种实施方式的双能双效干燥分解塔的示意图。 实施本发明的方式
根据本发明的一个实施方式， 本发明目的的实现通过下述方法来完 成：
原碱通过溶解、 澄清制得浓度为 30%左右的清碱液， 其方法采用常 规法。
将天然碱母液注入深度为 1米左右的地下冷析池（冷析池的规格根 据生产需求量而定， 地下冷析池的目的是为了减小环境温度对液体的影 响， 便于操作）， 使碱液液面在冷析池内由下而上緩慢上升。 根据一种 实施方式， 碱液浓度可为 6% ~ 32.9% , 温度可为 0°C ~ 35 °C。 根据另一 实施方式， 碱液浓度可为 5.9% ~ 31.3% , 温度可为 -2.rC ~ 32°C。 緩慢 上升的碱液与池内结晶器上的纤维绳接触， 溶解度最小的碳酸钠溶液首 先迅速着附于绳体， 成为晶种， 晶种不断吸引同类介质向其着附， 使结 晶绳上的晶体不断长大。 在结晶的同时， 由于结晶池为地下池， 结晶池 内液体的温度会不断下降， 溶液中溶质的溶解度也随着液体温度的降低 而降低， 更加便于晶体析出。 为了控制不让其它溶质结晶， 当溶液中碳 酸钠含量降低到一定程度时即需迅速将溶液排出， 排出的溶液再经雾化 转化器将残留的碳酸钠转化为碳酸氢钠。
在结晶器上结晶的碳酸钠晶体为十水碳酸钠， 十水碳酸钠晶体在环 境温度大于 34 °C时会溶解于自身水中成为含碳酸钠 37%左右的溶液，将 碳酸钠溶液经雾化浓缩结晶器在》 109°C的温度下加温沸腾结晶， 析出 无水碳酸钠晶体。
将无水碳酸钠晶体送入刷撒风送锻烧管锻烧， 蒸发掉水分， 制得重 质颗粒纯碱。
从冷析池排出的低浓度溶液由于碳酸钠含量降低， 不便于用冷析分 离法和浓缩分离法精确分离， 则采用化学转化法， 利用高压雾化碳酸化 法将剩余碳酸钠转化为碳酸氢钠。 由于碳酸氢钠溶解度偏低，极易与硝、 盐分离， 由此实现碱与其它介质的分离。
从雾化转化器转化而制得的碳酸氢钠， 经刷撒风送锻烧管的锻烧分 解， 便制得轻质纯碱。
从雾化转化器制得的碳酸氢钠不经过离心脱水工序， 将其在高速搅 拌器内制成料浆再经高压泥浆泵打入高压雾化干燥塔经对流干燥锻烧 分解后制成球形颗粒纯碱。
与碳酸氢钠分离后的盐硝溶液经雾化蒸发器快速浓缩后， 在 0°C ~ 32.4°C的温度下， 溶液浓度为 8% ~ 56.7%时， 再经依附结晶分离法将硝 提出， 完成盐硝分离。
由于硝的价值关系不适于耗能生产， 可将结晶器上的晶体硝置于环 境温度大于 0°C小于 34°C , 优选大于 10°C到 32°C的空间使其自然风化 干燥制得成品元明粉。
经分离后的氯化钠溶液采用高压雾化技术使其吸氨、 碳酸化， 转化 为碳酸氢钠， 经锻烧制得轻质纯碱。
通过自然风化法对结晶器上的晶体进行风化干燥制得纯碱、元明粉； 通过对常规氨碱法的改进， 将雾化技术应用于蒸氨、 吸氨、 碳酸化， 制 得纯碱。
概括地说， 如附图 1所示， 本发明上述实施方式是将含有盐、 碱、 硝混合物的天然碱溶于水（化碱）， 经澄清制成一定浓度的水溶液， 在 一定温度下进行依附结晶， 分离出十水碳酸钠晶体。 然后对所得十水碳 酸钠晶体进行热蒸自溶沸腾重结晶， 离心脱水得到无水碳酸钠晶体， 经 煅烧后制得纯碱成品。
对于提取了十水碳酸钠晶体后的剩余清液， 利用高压雾化蒸发浓缩 并碳酸化将其中剩余的碳酸钠转化为溶解度较低的碳酸氢钠后冷却结 晶离心脱水分离， 或经高速搅拌得到晶浆， 再经煅烧分解制得纯碱。 离 心脱水的清液经浓缩后进行依附结晶分离出十水硫酸钠晶体， 自然风化 制得元明粉。
剩余溶液中主要含有氯化钠， 通过高压雾化吸氨和雾化碳酸化将其 转化为碳酸氢钠制得晶体或晶浆， 再经煅烧制得纯碱。
根据本发明的另一个实施方式， 如图 4所示， 天然碱溶液经过依附 结晶分离出十水碳酸钠晶体， 当溶液中碳酸钠含量低于一定程度时， 迅 速将溶液排出， 再将新的浓溶液导入重复上述步骤直到附着晶体达到要 求程度为止。 排出的低浓度溶液返回天然碱母液， 以进一步提取其中残 余的碱。
对依附结晶分离出的十水碳酸钠晶体可在 0°C以上 34°C以下， 优选 10 ~ 32°C经自然风化直接得到纯碱， 或者可在 35.4°C ~ 109°C , 优选 50 °C ~ 100°C的温度下进行热蒸自溶重结晶。 十水碳酸钠晶体在 35.4°C ~ 109 °C的环境中改变其水合特性而产生晶格结构排列顺序的变化， 当溶 液浓度大于 30.8%时便会以一水碳酸钠的形态析出， 由此快速得到一水 碳酸钠晶体。 经萬心脱水得到晶体后经煅烧分解制得纯碱。
上述依附结晶分离出的十水碳酸钠晶体中有少量的硫酸钠和氯化钠 同时结晶出来。 因此， 热蒸自溶重结晶分离出的溶液中含有硫酸钠， 当 硫酸钠含量超过 3%时会形成复盐 (2Na2S04.Na2C03)从溶液中结晶出来， 常规蒸发法难以完成碱硝分离， 因此采用强制蒸发、 低温结晶的方法选 择二者溶解度差异最大的温度区间促使一水碳酸钠结晶， 实现与硫酸钠 的分离。 图 6为 Na2C03-Na2S04-H20体系相图。 如图所示， 35.4°C ~ 50 °C的区间是碳酸钠和硫酸钠溶解度差异最大的区域， 因此选择在该温度 区间内进行一水碳酸钠的结晶分离。
与一水碳酸钠分离后的含盐硝的溶液经蒸发浓缩后， 依照上述方法 进行依附结晶分离出十水硫酸钠， 并自然风化制得元明粉。
最后将剩余溶液中的氯化钠转化为碳酸氢钠分离后再经过煅烧分解 制得纯碱。
概括地说， 本发明上述实施方式对依附结晶法分离出十水碳酸钠晶 体进行热蒸自溶重结晶， 得到一水碳酸钠结晶， 再将热蒸自溶重结晶分 离出来的溶液经强制蒸发在碱硝溶解度差异最大的 35.4°C ~ 50 °C的区间 结晶析出一水碳酸钠晶体， 实现碱硝分离。 从而得到纯度更高的成品。
综合上述说明可知， 以本发明的方法进行联合制碱， 实现了盐碱硝 的单质分离， 根据市场的不同需求同时制得了轻质粉状纯碱、 轻质球形 颗粒纯碱、 重质颗粒纯碱和元明粉， 产品品种全， 纯度高， 而且整个生 产过程可实现循环连锁利用， 无烟、 无尘、 无废液排放等污染环境的问 题。
通过以下实施例将更详细地说明本发明的方法。 但是， 这些实施例 仅用于说明的目的， 而不应理解为对本发明范围的限制。 实施例 1
一、 通过依附结晶法进行盐、 碱、 硝的冷析分离处理。 用常规方法 将天然碱原碱通过溶解、 澄清制得浓度为 30%左右的水溶液。 依附结晶 处理装置为： 1、 地下冷析池： 所述地下冷析池深度 1 米左右 （因为结 晶过程受液体压力的影响故不宜过深）， 宽 3米左右， 长 20米左右， 便 于操作，也能扩大容量； 2、依附结晶器：所述依附结晶器为 lmxlmx2.7m 左右的角钢框架， 框架的上部和底部每间隔 lcm焊接 1条细钢筋， 上下 的钢筋互相平行、 ——对应， 上部每条钢筋每间隔 lcm系 1条细纤维绳 与底部相对应的钢筋连接。 每一个结晶器所系纤维线的总长度约 2.5万 米， 依此扩大依附结晶的表面积。 每一个结晶器在 8 ~ 12个小时内能结 到晶体的重量大于 1000kg。 结晶器栉比排列。 3、 滑动天吊 （电葫芦） 所述滑动天吊为结晶池顶部固定跑道可来回滑动的电葫芦， 以此完成结 晶器的送进送出作业。 按日产重质纯碱 100吨以上计算， 需 10个结晶 池， 200个结晶器， 纤维绳的总长度达到 500万米以上。 其处理过程是： 将清碱液注入冷析池， 使碱液液面在池内由下而上緩慢上升， 上升的碱 液与结晶器的纤维绳接触， 溶解度最小的碳酸钠溶质迅速着附于绳体成 为晶种， 晶种不断吸收到同类介质向其着附， 使结晶绳上的晶体不断长 大。 晶体长到一定程度时， 放出池内的液体， 利用滑动天吊将结晶器吊 出， 送入下一道工序。 （此晶体主要为十水碳酸钠）。
二、 进行十水碳酸钠的自溶与重结晶 （沸腾结晶）。 其处理装置为：
1、 自溶器： 所述自溶器是根据十水碳酸钠在环境温度大于 34°C时会溶 解于自身水中的特性而采用的一种装置， 此装置的规格根据结晶器的大 小而定， 为密封热蒸室， 以通入的热气将其溶解。 2、 雾化浓缩结晶器 (如图 2所示）： 所述雾化浓缩结晶器为一个竖立的塔罐， 罐体外表加 保温层。 根据功能的不同分为两个区域： 上部、 中部为强制蒸发区， 设 两个环形进风口； 下部为沸腾结晶区， 设一个进风口， 为结晶区内的导 热管提供热源 （底部加热管总截面积大于热风炉送风管截面积）。 其具 体处理的过程是： 第一热风炉的热量经过结晶器底部的导热管对溶液加 温后的余热导入上部的第一环形进风口 201 , 第二热风炉的热量直接送 入第二环形进风口 202, 两个环形进风口的热风在热风炉送风机的吹力 作用和结晶器顶部引风机的引力作用下成上升热气流， 上升的热气流与 顶部高压喷枪 203雾化下落的碳酸钠溶液雾滴呈对流趋势，产生热交换， 水分迅速蒸发， 使溶液快速浓缩， 浓缩的溶液在热交换过程中温度升高 蓄于沸腾结晶区， 在结晶区内由于三排加热管的加热作用， 温度迅速升 高， 达到 109°C以上时无水碳酸钠晶体析出。 析出的无水碳酸钠沉积于 底部锥形体 204经出料口 205放出。 当雾化浓缩结晶器内溶液的液面超 出溢流管 206的位置时， 溶液通过溢流管自行流入高位储料罐 207。
三、 利用高压雾化碳酸化进行盐、 碱、 硝混合溶液中碳酸钠的化学 转化。 其处理装置为高压雾化碳化器。 所述高压雾化碳化器为一个直径 1.5米、 高 15米的竖塔， 底部设二氧化碳气体进气口。 其处理过程是： 分解碳酸氢钠的尾气二氧化碳气体（见实施过程四）经引风机送入碳化 器底部进气口， 由于碳化器的直径大于引风管道的直径， 二氧化碳气体 流速减慢呈緩慢上升趋势。 竖塔内部从上至下每隔 3米安装一个高压雾 化喷枪， 碱液经喷枪雾化后呈雾状下落， 与上升的二氧化碳气体接触， 二氧化碳迅速溶解于碳酸钠溶液， 产生如下反应：
Na2C03 + C02+ H20→ 2NaHC03 + 59.789kj/mol 。
由于碳酸钠溶液是在雾化状态下与二氧化碳气体反应， 所以一方面气液 接触面积扩大， 另一方面雾态液滴对上升气流阻力减小， 极利于二者的 迅速吸收转化， 而且从底部上升的二氧化碳气体在反应过程中不停地向 上流动， 所以放热不会影响碳酸钠液滴溶解二氧化碳。 最后这种含碳酸 氢钠的溶液落入转化器下部的锥形体，通过出料口放出，经冷却槽冷却， 因碳酸氢钠溶解度极小， 所以迅速结晶， 与其它介质分离。
四、 进行无水碳酸钠的风送锻烧与碳酸氢钠的风送锻烧分解。 其处 理装置为一个刷撒风送式锻烧管 （如图 3 所示）。 所述刷撒风送锻烧管 是由高温送风机 301、 高速搅拌刷 302、 立式螺旋送料机 303、 物料暂存 仓 304、 底料槽 305、 积料仓 306和旋风除尘器组成。 其具体处理的过 程是： 热风在高温送风机的作用下给锻烧管提供风压为 5000Pa、 温度为 200 °C以上的热风， 物料从料斗由立式螺旋输送机向锻烧管匀速提供， 进入锻烧管的物料经高速搅拌刷刷撒以扩大受热面积， 刷撒的物料在风 力的作用下向前吹送并释放水分， 部分水分含量高、 粒度大的物料因风 力无法负重而积于暂存仓， 并经斜槽滑向料槽， 再经第二组螺旋输送机 送入锻烧管， 经过次第的刷撒受热， 物料的水分不断蒸发， 当积存于积 料仓时物料己达到成品要求， 而且积存的物料均为比重大的颗粒重质纯 碱， 比重小的粉尘体经旋风分离器分离后包装。 此锻烧法同样适用碳酸 氢钠的锻烧分解， 分解后排出的二氧化碳气体可为上述高压雾化碳化器 提供， 实现循环利用。
五、将过程三结晶分离出的碳酸氢钠经高速搅拌制得碳酸氢钠晶浆， 由以下步骤代替过程四进行碳酸氢钠晶浆的高压雾化锻烧分解及碳酸 钠晶体、 碳酸氢钠晶体在干燥塔内的锻烧、 分解。 其处理装置是一个进 行热交换的竖立的干燥塔。 为达到充分锻烧干燥， 高度要高一些， 按日 产 100吨以上的规模考虑一般高度在 25 ~ 30m 、 直经为 5 ~ 7m , 外加 保温层。 此种装置可一式二用， 既可用高压雾化法经高压喷枪雾化浓稠 状碳酸氢钠晶浆，又可用刷撒扩散法干燥晶体固体，其具体处理过程是： 1、 经高速搅拌机搅拌成的碳酸氢钠晶浆经高压喷枪喷入干燥塔呈雾化 状态， 受喷出压力推动和自重作用向下降落， 同时受到自下而向上运行 的热气流作用， 产生热交换， 碳酸氢钠受热分解成碳酸钠、 二氧化碳和 水 （2NaHC03 →Na2C03 + C02 + H20 ), 水分迅速蒸发， 碳酸钠受热膨胀 干燥成空心颗粒落入底部授粉漏斗成为定型产品。 二氧化碳与水蒸气经 引风机抽入旋风分离器分离出碱尘后导入高压雾化碳酸化工序。 2、 无 水碳酸钠、 碳酸氢钠离心脱水后由斗式提升机输送至干燥塔顶， 经物料 分配器向刷撒盘匀速供料， 刷撒盘为直径 2米以上的圆形筛底盘， 物料 在刷撒盘中经高速搅拌刷的作用均匀刷撒向下洒漏， 洒漏的物料与自底 而上运行的高热气流产生热交换， 水分迅速蒸发， 物料快速干燥分解， 落入底部授粉漏斗成为定型产品。 二氧化碳气体及水蒸气经引风机抽入 旋风分离器后导入另一道工序。
六、 进行残面的浓缩与利用。 其处理装置与上述雾化浓缩结晶器相 同。 残卤经雾化与热气流产生热交换， 水分快速蒸发， 浓缩后的饱和溶 液再经依附结晶分离法将十水硫酸钠晶体析出， 在结晶器上析出的十水 硫酸钠晶体置于通风干燥处通过风化作用实现自然干燥， 成品为无水硫 酸钠 （即元明粉）。 最后剩下的液体为以氯化钠为主的溶液。
根据十水碳酸钠或十水硫酸钠晶体在环境温度小于 32°C的通风干 燥空间会迅速自然风化的化学性质， 将其置于环境温度大于 0°C小于 32 °0的自然风化车间。 所述自然风化车间， 是一种建于空旷开阔场所能使 干燥空气快速循环流通的半开放车间。 为避免自然风夹带的沙粒等杂质 进入产品， 风化车间四周用金属筛网围封做为空气过滤墙， 为了保持风 化车间内较好的温度和避免杂质从顶部间入， 车间的顶部用阳光板封闭 并设有足以导出流动空气量的引风装置。 晶网在车间内晶架上栉比排列 并悬空搭挂， 晶网与晶网的间距应大于 400mm。根据风化车间的面积设 计中间送风通道， 可将送风通道顶部做成密封式弧形玻璃棚， 棚顶根据 所需风量安装若干送风装置。 着附于结晶网上的十水碳酸钠或十水^ L酸 钠经风化后转变为无水碳酸钠或无水硫酸钠， 经震动脱落， 筛分包装。
七、 利用高压吸氨和氨水碳酸化进行氯化钠溶液的转化： 其处理装 置有一个高压雾化吸氨器和一个高压雾化碳化器。 根据反应式 NaCl + NH3 + C02 + H20→NaHC03| + NH4C1 的反应原理。 使氯化钠溶液 吸收氨和二氧化碳生成碳酸氢钠。 由于吸氨和碳化的过程不能同时 进行， 必须先吸氨后吸二氧化碳， 因此需通过两个装置处理。 所述高 压雾化吸氨器与上述的高压雾化碳化器相同。 但是由于氨盐水受热会分 解的原故， 因此氨盐水的碳化应在常温下进行。 其具体处理过程是： 精 盐水经雾化与底部环形风口送入上升的氨气产生反应生成氨盐水， 再将 氨盐水在碳化器内部雾化使之与底部进风口送入上升的二氧化碳气体 产生反应生成碳酸氢钠， 反应后的溶液经冷却析出碳酸氢钠晶体， 晶体 经大于 160°C温度的锻烧分解为轻质碳酸钠。 以上碳酸氢钠晶体或晶浆 的处理采用过程四或五。 实施例 1
一、 按照实施例 1相同的方法制备天然碱溶液， 并通过依附结晶分 离出十水碳酸钠。与实施例 1不同的是所用依附结晶器为 100cmx300cm 的网状纤维绳结构， 所用设备还包括对滚碾料机。 所述对滚碾料机是一 组碾滚宽度与结晶网宽度相等并通过相向旋转来实现碾碎晶体的装置。 利用对滚碾料机将结晶网上的晶体碾落后送入后续工序。
二、 对十水碳酸钠晶体进行热蒸自溶、 重结晶。 其处理装置为热蒸 自溶器，所述热蒸自溶器是根据十水碳酸钠在环境温度大于 32°C时会溶 解于自身水中的特性而选用的一种装置 （如图 5 所示）， 其处理过程如 下。 碾碎的物料经皮带输送机 501送至进料口 502, 物料经伞筛 503均 匀抛撒于第一层筛盘 504 (筛眼直径为 10mm ), 筛盘上的物料在受到环 形进风口 508送入热风的热力作用下开始溶解并经均料刷 505刷撒落至 第二层筛盘 507 (筛眼直径为 5mm ), 落入第二层筛盘上的碎小晶体在 均料刷 506的刷撒磨擦作用下均匀受热快速溶解， 碱液落入热蒸自溶器 底部的结晶区 509, 控制热蒸自溶器内的温度为 35.4 °C ~ 109°C , 自溶后 的碱液处于极度过饱和状态， 在结晶区内一水碳酸钠迅速析出， 结晶后 的一水碳酸钠在搅拌器 510的作用下晶粒不断生长， 当结晶区内的一水 碳酸钠晶体储量达到一定程度时从放料口 511放出， 经离心脱水后进入 后续工序。
三、 对离心脱水工序分离出的溶液进行强制蒸发、 低温结晶， 实现 一水碳酸钠与石 υ酸钠的分离。 经过程二分离出的溶液中的硫酸钠含量不 断增加， 当硫酸钠含量超过 3%时采用常规蒸发法则难以将其分离。 根 据 Na2C03、 Na2S04、 H20三元体系相图 （图 6 ) 中 Na2C03、 Na2S04溶 解度曲线走向分析， 在液相中使两种溶质得以分离的最佳方法是选择二 者溶解度差异最大的区间来使其中一种溶质结晶以达到分离目的。 根据 图 6所示的二者溶解度曲线分析： 当溶液温度保持在 35.4 °C ~ 50°C之间 的区间时，碳酸钠的溶解度为 33.2% ~ 30.8% ,以一水碳酸钠的形态结晶， 而硫酸钠的溶解度则为 55% ~ 50%, 以无水硫酸钠的形态结晶， 二者溶 解度的差异达到 20%, 因此在该区间内采用强制蒸发、 低温结晶法来完 成一水碳酸钠的提取。 其处理装置为强制蒸发、 低温结晶器（如图 7所 示）。 其处理过程是： 热风在引风管道 701 的抽力作用下经环形进风口 702进入装置， 碱液经高压喷枪 703雾化后在装置内与上升的热气流接 触产生强烈蒸发效果， 水分在雾化蒸发区 704迅速蒸发， 浓缩后的碱液 集于结晶区 705 , 在 35.4°C ~ 50°C的温度区间内析出一水碳酸钠， 淡液 蓄满后经溢流口 706流出循环使用， 晶浆经出料口 707间断抽出。 将所 得一水碳酸钠晶浆经过离心脱水得到一水碳酸钠晶体和盐硝溶液。
四、 强制蒸发、 低温结晶分离出的盐硝溶液通过依附结晶分离法进 一步提取硫酸钠。 将强制蒸发、 低温结晶分离出的盐硝溶液经浓缩至硫 酸钠浓度为 8% ~ 56.7%后， 在 0 ~ 32.4°C的温度下， 采用与过程一相同 的依附结晶过程， 析出十水硫酸钠晶体， 实现盐硝分离。
五、对依附结晶器上的十水硫酸钠按照实施例 1中相同的方法在 0 ~ 32°C进行自然风化， 制得元明粉。
上述实施过程一中得到的十水碳酸钠也可在同样条件下进行自然风 化， 直接得到纯碱成品。
六、 十水石 酸钠分离后的剩余溶液中以氯化钠为主， 对其进行高压 雾化吸氨、 雾化碳酸化， 将溶液中的氯化钠转化为碳酸氢钠。 其方法是 采取扩大精盐水溶液的表面积， 使精盐水溶液在氨化器内以雾化状态与 氨气产生气雾混合式对流接触， 精盐水迅速溶解氨气生成氨盐水， 氨盐 水以上述同样方法在碳化器内以雾化状态与二氧化碳气体接触快速溶 解二氧化碳， 发生以下化学反应： NaCl + NH3 + C02 + H20 = NaHC03 + NH4C1, 从而使氯化钠转化为碳酸氢钠。 将生成碳酸氢钠的溶液稠厚后， 经离心脱水制得碳酸氢钠晶体， 或经高速搅拌制得碳酸氢钠晶浆。
七、 采用双能双效干燥分解塔锻烧一水碳酸钠， 采用雾化湿分解法 或刷撒造粒技术分解碳酸氢钠。 双能双效干燥分解塔是一个竖立的塔罐 (如图 8 所示）， 根据不同的生产要求来确定其高度， 底部为锥形出料 漏斗 801 , 漏斗上部为环形进风口 802, 顶部为塔帽 803 , 配有引风管道 804 以抽出塔内气体， 塔内顶部装有高压喷枪 805 及物料刷撒分配盘 806。 所述的双能是指它即可用高压雾化湿分解法生产液体原料， 又可 用刷撒造粒技术生产固体原料。 双效是指它即可煅烧干燥碳酸钠， 又可 煅烧分解碳酸氢钠， 工作原理是： 1、 液体原料， 即碳酸氢钠料浆经高 压泵打入塔顶的喷枪， 由于压力作用使之成为雾状物从塔内顶部由上而 下徐徐降落， 在降落过程中与由下而上的热气流接触产生热交换， 雾状 物料的水份迅速蒸发变为成品， 由于高压作用使物料膨化成空心体， 制 成空心超轻质纯碱。 2、 固体原料， 如一水碳酸钠或碳酸氢钠晶体经斗 式提升机提至塔顶， 再经滑槽投入塔内顶部的物料分配盘， 经分配后抛 撒至塔顶筛盘， 筛盘上的物料经分料刷的刷散经过筛眼向下洒落， 在洒 落的过程中与上升热气流接触产生热交换， 较细物料迅速干燥或分解成 为成品， 较粗的物料经滚筛分选出再经输送设施送至进料线粉碎后返入 进料， 重复煅烧。 较细的物料在分料刷的刷撒作用下向下滚落碰撞互相 粘合， 当落入授粉漏斗时成为颗粒产品。 处理碳酸钠晶体的废气经塔顶 引风管道抽出并经旋风除尘和布袋除尘后导入热蒸自溶器作为热风提 供热源， 处理碳酸氢钠晶体或晶浆的尾气经塔顶引风管道抽出并经旋风 除尘和布袋除尘后提供给高压雾化碳酸化过程使用。
以本发明实现的联合制碱工艺， 降低了对原料的要求， 适于处理多 数天然碱矿物。 经实际生产对比不但降低了生产设施的投资（设备投资 为常规生产法投资的 1 % ) , 而且大大降低了能耗， 筒化了生产工艺， 缩短了生产周期， 并充分利用了自然能源， 使生产成本大幅度降低， 用 工人数仅为常规生产法的十分之一， 且能达到环保生产要求。

Claims

权利要求书
1、一种从含有盐、碱、硝混合物的天然碱中制取纯碱的联合制碱法， 该方法包括：
(a) 将所述天然碱制成水溶液；
(b)使用依附结晶分离法从所述天然碱溶液中分离得到十水碳酸钠 晶体； 和
(c)对所得的十水碳酸钠晶体进行处理得到纯碱。
2、 如权利要求 1所述的从含有盐、碱、硝混合物的天然碱中制取纯 碱的联合制碱法，其中在步骤 (c)中将步骤 (b)所得的十水碳酸钠晶体在》 109 °C的温度下进行热蒸自溶沸腾结晶并分离以制得无水碳酸钠晶体， 随后将所述无水碳酸钠晶体采用煅烧处理制得纯碱。
3、如权利要求 1所述的从含有盐、碱、硝混合物的天然碱中制取纯 碱的联合制碱法， 其中进一步包括：
将步骤 (b)中分离出十水碳酸钠晶体后的溶液进行高压雾化， 并通入 co2使其中的碳酸钠转化为碳酸氢钠并结晶， 分离得到碳酸氢钠晶体和 剩余溶液， 或搅拌得到晶浆； 和
将所得碳酸氢钠晶体采用煅烧处理制得纯碱， 所得碳酸氢钠晶浆采 用高压雾化干燥处理制得纯碱。
4、 如权利要求 1所述的从含有盐、碱、硝混合物的天然碱中制取纯 碱的联合制碱法， 其中在步骤 (c)中将步骤 (b)所得的十水碳酸钠晶体在 34.5 °C ~ 109 °C的温度下进行热蒸自溶重结晶并分离得到一水碳酸钠晶 体后采用煅烧处理制得纯碱； 或者在 0 ~ 34°C的温度下经过自然风化制 得纯碱； 且
将步骤 (b)中分离出十水碳酸钠晶体后的溶液返还到所述天然碱溶 液中。
5、如权利要求 4所述的从含有盐、碱、硝混合物的天然碱中制取纯 碱的联合制碱法， 其中所述十水硫酸钠晶体优选在 50°C ~ 100°C的温度 下进行热蒸自溶重结晶。
6、如权利要求 4所述的从含有盐、碱、硝混合物的天然碱中制取纯 碱的联合制碱法， 其中进一步包括：
通过在 35.4 °C ~ 50°C的温度下进行强制蒸发、 低温结晶将分离出一 水碳酸钠晶体后的溶液中残余的碳酸钠以一水碳酸钠晶体的形式结晶 并分离得到一水碳酸钠晶体和剩余溶液； 和
将所述一水碳酸钠晶体采用煅烧处理后制得纯碱。
7、 如权利要求 3或 6所述的从含有盐、碱、硝混合物的天然碱中制 取纯碱的联合制碱法， 其中对分离所述碳酸氢钠晶体或所述一水碳酸钠 晶体后的剩余溶液进行进一步处理包括：
将所述剩余溶液浓缩， 进行依附结晶并分萬制得十水硫酸钠晶体； 将分离出十水硫酸钠晶体后的溶液经高压雾化吸氨、 高压雾化碳酸 化将其中的氯化钠转化为碳酸氢钠并结晶， 分离得到碳酸氢钠晶体或搅 拌得到晶浆； 和
将所述碳酸氢钠晶体采用煅烧处理制得纯碱， 或将所述碳酸氢钠晶 浆采用高压雾化湿分解并干燥处理制得纯碱。
8、如权利要求 7所述的从含有盐、碱、硝混合物的天然碱中制取纯 碱的联合制碱法，其中所述十水硫酸钠晶体的依附结晶在 8 ~ 56.7%的溶 液浓度及 0°C ~ 32.4 °C的温度下进行。
9、如权利要求 7所述的从含有盐、碱、硝混合物的天然碱中制取纯 碱的联合制碱法， 其中所述十水硫酸钠晶体进一步在 0 ~ 34°C的温度下 经过自然风化制得元明粉。
10、 如权利要求 3或 7所述的从含有盐、 碱、 硝混合物的天然碱中 制取纯碱的联合制碱法， 其中所述高压雾化所需喷枪压力为 20kg/cm2 ~ 60kg/cm2。
11、 如权利要求 1或 7所述的从含有盐、 碱、 硝混合物的天然碱中 制取纯碱的联合制碱法， 其中所述依附结晶采用网状纤维结构的依附结 晶器。
12、 如权利要求 2或 3或 7所述的从含有盐、 碱、 硝混合物的天然 碱中制取纯碱的联合制碱法， 其中所述煅烧处理在刷撒风送煅烧管中进 行， 包括：
为所述煅烧管内提供风压为 5000Pa、 温度为 200°C以上的热风； 将物料送入所述煅烧管；
物料在所述煅烧管内经刷撒、 煅烧和吹送后快速干燥和 /或分解； 水分含量高、 粒度大的物料被再次送入煅烧管内进行刷撒、 煅烧和 吹送；
干燥后得到的重质纯碱被吹送到积料仓；
粉尘状物料经旋风分离后得到轻质纯碱。
13、 如权利要求 4、 6或 7所述的从含有盐、 碱、 硝混合物的天然碱 中制取纯碱的联合制碱法， 其中所述煅烧处理在双能双效干燥塔中进 行。
14、 如权利要求 7所述的从含有盐、 碱、 硝混合物的天然碱中制取 纯碱的联合制碱法， 其中所述高压雾化湿分解干燥处理在双能双效干燥 塔中进行。
15、 如权利要求 1所述的从含有盐、 碱、 硝混合物的天然碱中制取 纯碱的联合制碱法， 其中所述天然碱溶液的浓度为 6% ~ 32.9% , 温度为 0°C ~ 35 °C。
16、 如权利要求 1所述的从含有盐、 碱、 硝混合物的天然碱中制取 纯碱的联合制碱法， 其中所述天然碱溶液的浓度为 5.9% ~ 31.3%, 温度 为 -2.1°C ~32°C。
17、 如权利要求 16所述的从含有盐、碱、硝混合物的天然碱中制取 纯碱的联合制碱法， 其中所述天然碱溶液的温度优选为 -2.1°C ~32°C。
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