WO2016086734A1 - 烟气脱硫生产硫酸镁的装置与方法 - Google Patents

烟气脱硫生产硫酸镁的装置与方法 Download PDF

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Publication number
WO2016086734A1
WO2016086734A1 PCT/CN2015/092540 CN2015092540W WO2016086734A1 WO 2016086734 A1 WO2016086734 A1 WO 2016086734A1 CN 2015092540 W CN2015092540 W CN 2015092540W WO 2016086734 A1 WO2016086734 A1 WO 2016086734A1
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flue gas
magnesium sulfate
slurry
product
sulfur dioxide
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PCT/CN2015/092540
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English (en)
French (fr)
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童裳慧
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童裳慧
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/40—Magnesium sulfates

Definitions

  • the invention relates to a device and a method for producing magnesium sulfate by flue gas desulfurization, in particular to a device and a method for directly crystallizing magnesium sulfate in a magnesium oxide desulfurization waste liquid column.
  • the apparatus and method of the present invention are particularly suitable for preparing magnesium sulfate by using a waste slurry after flue gas desulfurization such as a sintering machine, a pellet, or a rotary kiln.
  • Magnesium oxide flue gas desulfurization technology has been gradually promoted and applied. The market share has been less than 1% since 2005, and currently exceeds 6%. The wet magnesia desulfurization technology has been recognized by more and more people.
  • the magnesium oxide desulfurization process is adopted and the desulfurization waste liquid is prepared to form a magnesium sulfate by-product, which not only solves the problem of desulfurization gypsum treatment caused by the conventional calcium desulfurization, but also can offset the operation and maintenance cost of the partial desulfurization device through the sales of the magnesium sulfate by-product. Both technical and economic perspectives have greater market application advantages than traditional calcium methods.
  • the method for producing magnesium sulfate by using the desulfurization waste liquid requires a large amount of steam, which directly increases the desulfurization operation cost.
  • the Chinese invention patent application with the publication number CN1733656A provides a "method for preparing magnesium sulfate heptahydrate by using boiler flue gas", wherein the magnesium sulfate solution is concentrated and crystallized, and the method uses magnesium sulfate at a temperature exceeding Crystallization is carried out at a characteristic of a decrease in solubility at 60 ° C.
  • This high-temperature crystallization method requires consumption of more high-quality steam and causes frequent clogging of the slurry transport line, making it difficult to achieve continuous and stable production of by-products.
  • Another example is the Chinese invention patent No. 201210100244.8, which provides a method for producing magnesium sulfate heptahydrate by using desulfurization waste liquid.
  • the crystallization method used is: “The liquid obtained is sent to an evaporator, and the slurry is discharged after concentration. The evaporation temperature was 100 to 130 ° C, and the discharged slurry was cooled and crystallized at a temperature of 30 to 45 ° C to obtain magnesium sulfate heptahydrate.
  • This evaporation and crystallization method requires high steam quality, and consumption is increased if low-grade steam is used.
  • the present invention provides an apparatus and method for producing magnesium sulfate by flue gas desulfurization, and more particularly to an apparatus and method for directly crystallizing magnesium sulfate in a magnesium oxide desulfurization waste liquid column.
  • the invention provides a device for producing magnesium sulfate by flue gas desulfurization, comprising:
  • a flue gas desulfurization device which is internally provided with a sulfur dioxide absorption spray zone for removing sulfur dioxide in the flue gas by using magnesium oxide method, and forming a slurry containing magnesium sulfate;
  • a slurry circulation tank for receiving the magnesium sulfate-containing slurry from the flue gas desulfurization apparatus, and circulating the magnesium sulfate-containing slurry to the sulfur dioxide absorption spray zone and the evaporation concentration zone;
  • a circulating sedimentation device for receiving concentrated product from the evaporation concentration zone and sedimenting the concentrated product to form a sedimentation product
  • the evaporation concentration zone, the circulating sedimentation device and the slurry circulation tank are all disposed inside the flue gas desulfurization device.
  • the sulfur dioxide absorption shower zone comprises two or more sulfur dioxide absorption spray layers; the evaporation concentration zone is located at a lower portion of the sulfur dioxide absorption shower zone.
  • the apparatus further includes a sump for separating the slurry produced by the sulphur dioxide absorption spray zone from the evaporation concentration zone.
  • the circulation settling apparatus is located at a lower portion of the evaporation concentration zone; and the slurry circulation tank includes a slurry circulation tank disposed at a bottom of the flue gas desulfurization apparatus.
  • the device further comprises:
  • a crystallization apparatus for crystallizing a sedimentation product from a circulating settling apparatus to form a crystalline product
  • a centrifugation apparatus for centrifuging the crystalline product from the crystallization apparatus to form a mother liquor and a magnesium sulfate product
  • a drying apparatus for drying the magnesium sulfate product from the centrifugation apparatus for drying the magnesium sulfate product from the centrifugation apparatus.
  • the flue gas satisfies one of the following conditions:
  • the flue gas is smoke from a sintering machine, a pellet, or a kiln;
  • sulfur dioxide content of the flue gas is 300mg / Nm 3 ⁇ 20000mg / Nm 3, and the oxygen content of 8 ⁇ 20vt%.
  • the present invention also provides a method of producing magnesium sulfate using the above apparatus, comprising the steps of:
  • Flue gas desulfurization step removing sulfur dioxide in the flue gas by using magnesium oxide in a flue gas desulfurization device, and forming a slurry containing magnesium sulfate;
  • a slurry circulation step receiving the magnesium sulfate-containing slurry from a flue gas desulfurization apparatus in a slurry circulation tank, and circulating the magnesium sulfate-containing slurry into a sulfur dioxide absorption spray zone and an evaporation concentration zone;
  • Evaporation concentration step evaporating and concentrating the magnesium sulfate-containing slurry in an evaporation concentration zone to form a concentrated product
  • Circulating settling step receiving concentrated product from the evaporation concentration zone in a circulating settling device and sedimenting the concentrated product to form a settling product.
  • the method further comprises
  • the magnesium sulfate product from the centrifugation apparatus is dried in a drying apparatus.
  • the slurry overflowed from the circulating settling device in the cycle settling step is filtered and recycled to the evaporation concentration zone; and/or
  • the mother liquor separated in the centrifugation step is recycled to the evaporation concentration zone.
  • the magnesium sulfate grains in the sedimentation product are larger than 0.1 mm; and the magnesium sulfate grains in the crystallized product are more than 0.15 mm.
  • the invention provides a device and a production process for directly producing the magnesium sulfate by using magnesium oxide as an absorbent, capable of removing sulfur dioxide in the flue gas, and generating the slurry by concentration, crystallization, discharge and the like, especially providing a device.
  • the invention adopts a combination of multi-stage absorption and circulating evaporation concentration, can ensure desulfurization efficiency and by-product quality under the condition of greatly reducing steam consumption, and more reduces the operation cost of the by-product production system and reduces the desulfurization operation cost.
  • FIG. 1 is a schematic view of an apparatus according to an embodiment of the present invention.
  • Fig. 1 1 is a desulfurization tower, 2 is a circulating settling tank, 3 is an evaporative concentrated spray layer, 4 is a liquid accumulator, 5 is an overflow port, 6 is a circulating settling tank discharge port, and 7 is a secondary sulfur dioxide absorption spray.
  • Leaching layer, 8 is a three-stage sulfur dioxide absorption spray layer, 9 is a mist eliminator, 10 is a flue gas outlet, 11 is a slurry circulation tank, 12 is an evaporation concentration circulating pump, and 13 is a secondary sulfur dioxide absorption spray layer circulating pump, 14 is a three-stage sulfur dioxide absorption spray layer circulating pump, 15 is an over-temperature emergency cooling device circulating pump, 16 is a crystallization tank, 17 is a centrifuge, 18 is a dryer, 19 is a packaging machine, and 20 is a mother liquid back evaporation concentrated spray
  • the layer circulation pump, 21 is the slurry pool discharge pump, 22 is the filter, 23 is the flue gas inlet, and 24 is the over-temperature emergency cooling device.
  • the “%” described in the present invention is a volume percentage unless otherwise specified.
  • the “vt%” described in the present invention means a volume percentage.
  • the “device” of the present invention is a product, that is, a system of each device. Unified collection.
  • the inlet has the same meaning as the inlet, and the two can be replaced.
  • the flue gas of the present invention may be flue gas from a sintering machine, pellets, or kiln. Due to the presence of a certain amount of oxygen in the flue gas and moderate sulfur dioxide content, the purity of the magnesium sulfate product can be increased.
  • the flue gas may be 300mg / Nm 3 ⁇ 20000mg / 3 between the oxygen content in the flue gas between 8 ⁇ 20vt% of the sulfur dioxide content in any Nm.
  • the sulfur dioxide content in the flue gas is preferably from 500 mg/Nm 3 to 10000 mg/Nm 3 , more preferably from 1000 mg/Nm 3 to 5000 mg/Nm 3 .
  • the oxygen content in the flue gas is preferably from 9 to 20 vt%, more preferably from 15 to 19 vt%. This can increase the purity of the magnesium sulfate product.
  • the magnesium oxide flue gas desulfurization of the present invention refers to a flue gas desulfurization process in which magnesium oxide is used as a main component of a desulfurizing agent, but is not limited to the addition of any other component (for example, calcium oxide, quicklime, etc.).
  • the structure and composition of the desulfurizing agent may vary, and formulations or variations thereof are well known to the skilled person.
  • the apparatus for producing magnesium sulfate by flue gas desulfurization of the present invention comprises the following equipment: flue gas desulfurization equipment, slurry circulation tank, evaporation concentration zone, and circulating sedimentation equipment.
  • the device further comprises a crystallization device, a centrifugation device, a drying device.
  • the device of the invention further comprises a packaging device.
  • the evaporation concentration zone, the slurry circulation tank, and the circulation settling apparatus are both disposed inside the flue gas desulfurization apparatus.
  • the flue gas desulfurization device of the invention has a sulfur dioxide absorption spray zone on the upper part thereof for removing sulfur dioxide in the flue gas by using magnesium oxide method, and forming a slurry containing magnesium sulfate.
  • the flue gas desulfurization equipment may be a flue gas desulfurizer or a flue gas desulfurization tower. From the viewpoint of industrial application, a flue gas desulfurization tower is preferred.
  • the sulfur dioxide absorption shower zone comprises at least one sulfur dioxide absorption spray layer; preferably comprises two or more sulfur dioxide absorption spray layers, more preferably two or three sulfur dioxide absorption spray layers.
  • the evaporation concentration zone of the present invention is used for concentrating and concentrating a magnesium sulfate-containing slurry formed in a flue gas desulfurization apparatus to form a concentrated product.
  • the evaporation concentration zone is disposed inside the flue gas desulfurization apparatus and disposed at a lower portion of the sulfur dioxide absorption shower zone.
  • the evaporation concentration zone is an evaporation concentrated spray layer; according to still another embodiment of the present invention, the evaporation concentrated spray layer and the sulfur dioxide absorption spray zone pass through the liquid accumulation Isolation.
  • the material of the liquid eliminator may be a fiber reinforced composite plastic FRP, and preferably has a temperature resistance ranging from 50 to 95 degrees Celsius; but is not limited to the above materials.
  • the flue gas enters the interior of the device from the flue gas inlet of the lower part of the flue gas desulfurization equipment, passes through the evaporation concentration zone during the ascending process, and after entering the temperature and preliminary absorption, enters the sulfur dioxide absorption spray zone for desulfurization absorption reaction, in the flue gas
  • the sulphur dioxide is absorbed and the purified flue gas is discharged from the top of the flue gas desulfurization equipment.
  • the flue gas desulfurization device of the present invention may further be provided with a mist eliminator, and the flue gas after desulfurization may be directly discharged after dehydration and defogging.
  • the preparation used for the desulfurization of the present invention may be those used for the removal of flue gas by the magnesium oxide method commonly used in the art, for example, a magnesium hydroxide slurry prepared by adding magnesium oxide powder to industrial tap water.
  • the desulfurizing agent of the present invention may use those disclosed in CN102745726 A, CN102745725A, CN102836636A.
  • those disclosed in Example 1 or 2 of CN 102745726 A are desulfurizing agents.
  • the entire contents of the above-identified patent application are incorporated herein by reference. Disperse these desulfurizers evenly in water to get off Sulfur agent slurry.
  • the cyclic sedimentation apparatus of the present invention is for receiving a concentrated product from an evaporation concentration zone and allowing the concentrated product to settle to form a sedimentation product (including a preliminary crystallization process).
  • the circulating settling device is disposed inside the flue gas desulfurization device and is located at a lower portion of the evaporation concentration zone.
  • the circulating settling device may be a circulating settling tank, and may be set to a single layer settlement or a double layer settlement or a multilayer settlement according to working conditions.
  • the material can be made of FRP or special steel, or ordinary steel material with anti-corrosion treatment.
  • the circulating settling tank is arranged below the flue gas inlet, and an overflow port is arranged in the middle of the circulating settling tank, and the overflow port is connected with the filter through the slurry tank discharge pump; and a circulating settling tank discharge port is arranged at the lower part of the circulating settling tank.
  • the slurry circulation tank of the present invention is for receiving the magnesium sulfate-containing slurry formed in a flue gas desulfurization apparatus, and circulating the magnesium sulfate-containing slurry into a sulfur dioxide absorption spray zone and an evaporation concentration zone.
  • the magnesium sulfate-containing slurry is filtered and recycled to the sulfur dioxide absorption spray zone and the evaporation concentration zone. More preferably, the magnesium sulfate-containing slurry is filtered and recycled to the evaporation concentration zone.
  • the slurry circulation tank comprises a slurry circulation tank disposed at the bottom of the flue gas desulfurization apparatus, and the slurry is separately circulated to the sulfur dioxide absorption spray zone and the evaporation concentration zone by a circulation pump.
  • the magnesium sulfate-containing slurry is sent from a slurry circulation tank to a filtration device by a discharge pump, filtered, and then passed through a circulation pump into an evaporation concentration zone for evaporation concentration.
  • the filter device may be a plate filter or a vacuum belt filter, preferably a plate filter.
  • the slurry recycled to the evaporation concentration zone preferably accounts for 40 to 55 vt%, preferably 45 to 50 vt% of the output (ie, the total amount of circulating output of the slurry circulation tank); is circulated from the slurry circulation tank to the sulfur dioxide absorption spray.
  • the slurry of the leaching zone can be separately fed into the two or more sulphur dioxide absorption spray layers by two or more circulation pumps, and circulated to the sulphur dioxide absorption spray.
  • the slurry in the zone preferably comprises from 45 to 60 vt%, preferably from 45 to 50 vt%, of the output.
  • the crystallization apparatus of the present invention is for receiving a sedimentation product in a circulating sedimentation apparatus (a mixture of crystal and slurry discharged after preliminary crystallization) and further crystallization thereof to obtain a crystal slurry; a sedimentation product entering the crystallization apparatus, which is cooled in the crystallization apparatus
  • the method further forms a crystal slurry in which the magnesium sulfate grains are larger than 0.15 mm, preferably larger than 0.3 mm.
  • a stirring device may be disposed in the crystallization apparatus, and the stirring device may be an air stirring device or an electric stirring device.
  • the crystallization apparatus of the present invention may be a crystallization tank, preferably having an automatic cooling system with a water-cooling ring device.
  • the cold source may be normal temperature water or chilled water. Cooling devices such as cooling towers can also be installed separately.
  • the crystallization apparatus of the present invention may be a continuous cooling crystallizer, more preferably a DTB continuous cooling crystallizer.
  • the DTB crystallizer consists of a crystallization tank, a condenser, a forced circulation pump, a discharge pump, a vacuum pump, and the like.
  • the DTB (Drabt Tube Babbled) type crystallizer that is, the draft tube and the baffle type crystallizer, is a fine crystal slurry circulating crystallizer.
  • the crystallizer is provided with a draft tube and a cylindrical baffle, and a propulsion stirring system is arranged.
  • the hot saturated liquid is continuously added to the lower part of the circulation pipe, mixed with the mother liquid with small crystals in the circulation pipe, and pumped to the heater.
  • the heated solution flows into the crystallizer near the bottom of the draft tube and is sent to the liquid level along the draft tube by a slowly rotating propeller.
  • the solution is evaporatively cooled on the liquid surface to reach a supersaturated state, in which part of the solute is deposited on the surface of the suspended particles to grow the crystal.
  • a settling zone is also provided at the periphery of the annular baffle. Large particles settle in the settling zone, while small particles enter the circulation pipe with the mother liquor and are dissolved by heat. The crystals settled into the elutriation column at the bottom of the crystallizer.
  • the cooling crystallization temperature is generally controlled at 25 to 35 ° C, preferably 28 to 30 ° C.
  • the centrifugation apparatus of the present invention is for receiving a crystal slurry (crystalline product) discharged from a crystallization apparatus, and centrifuging it to form a magnesium sulfate product.
  • Centrifugal devices can use those well known in the art.
  • the drying apparatus of the present invention is for receiving a magnesium sulfate product (preliminary product magnesium sulfate crystal) discharged from a centrifugal device and drying it to a finished product.
  • the drying device of the present invention is preferably a vibrating fluidized bed drying device which is particularly suitable for the drying process of magnesium sulfate crystals.
  • the present invention preferably employs a vibrating fluidized bed drying apparatus equipped with a hot air device. The blower sends the filtered air to the air heater, and the heated hot air enters the lower tank of the main machine, and then blows the dried material vertically from the bottom to the top through the air distribution plate of the fluidized bed, so that the material is in a boiling state.
  • the material enters from the feeding port, and the main machine generates symmetrical vibration under the excitation force of the vibration motor, so that the material is thrown horizontally, and the dried material forms a fluidized state under the combined action of the above-mentioned hot air flow and machine vibration.
  • This allows the material to be in contact with hot air for a long time and has a large area, thereby obtaining a highly efficient drying effect.
  • the device of the invention can use the lower calorific value of 120-133 ° C and the pressure of 0.2-0.3 MPa saturated steam to heat the air into the vibrating fluidized bed and fully dry the magnesium sulfate crystal under the action of mechanical vibration. Magnesium sulfate material.
  • the steam output from the fluidized bed can be used in the evaporation concentration zone, which not only saves energy but also reduces operating costs.
  • the packaging apparatus of the present invention is used to package the dried product.
  • Packaging equipment can use those well known in the art.
  • the "discharge” described in the present invention (for example, discharging a mixture of crystals and slurry from a circulating sedimentation apparatus, discharging a crystal slurry from a crystallization apparatus, discharging magnesium sulfate crystals from a centrifugal apparatus, etc.) can be obtained by using a discharge apparatus.
  • the discharge device is a discharge pump.
  • the invention can also set an over-temperature emergency cooling device at the flue gas inlet position of the flue gas desulfurization device to solve the occurrence of the flue gas temperature over-temperature condition after the bypass flue is cancelled.
  • an over-temperature emergency cooling device at the flue gas inlet position of the flue gas desulfurization device to solve the occurrence of the flue gas temperature over-temperature condition after the bypass flue is cancelled.
  • the temperature exceeds the limit temperature
  • the slurry in the upper part of the slurry circulation tank is sent to the accident area determined by the over-temperature emergency cooling device through the circulation pump, and is used for the emergency cooling of the flue gas desulfurization equipment.
  • the above defined temperature may be 160 to 200 ° C, preferably 180 ° C or more.
  • the magnesium sulfate can be produced by the above apparatus of the present invention, comprising the steps of a flue gas desulfurization step, a slurry circulation step, an evaporation concentration step, and a cyclic sedimentation step.
  • the method further comprises a crystallization step, a centrifugation step, and a drying step, and optionally, a packaging step.
  • the flue gas desulfurization step of the present invention is to remove sulfur dioxide from the flue gas by using a magnesium oxide method in a flue gas desulfurization apparatus, and form a slurry containing magnesium sulfate.
  • the upper portion of the flue gas desulfurization device is provided with a sulfur dioxide absorption shower zone.
  • the flue gas enters the interior of the equipment from the flue gas inlet of the flue gas desulfurization equipment, and undergoes the desulfurization absorption reaction through the sulfur dioxide absorption spray zone during the ascending process, the sulfur dioxide in the flue gas is absorbed, and the purified flue gas is from the top of the flue gas desulfurization equipment. discharge.
  • the formulations used in the desulfurization of the present invention are as described above.
  • the flow rate of the flue gas at the flue gas inlet of the flue gas desulfurization equipment is 2.5 to 4.5 m/s, preferably 3 to 4 m/s, and the inlet flue gas temperature is 110 to 180 ° C, preferably 110 to 150 ° C.
  • the slurry circulation step of the present invention is to recycle the slurry received in the slurry circulation tank to the sulfur dioxide absorption spray zone and the evaporation concentration zone in the flue gas desulfurization apparatus.
  • the cycle can be carried out by a circulation pump.
  • the magnesium sulfate-containing slurry is filtered and recycled to the sulfur dioxide absorption spray zone and the evaporation concentration zone. More preferably, the magnesium sulfate-containing slurry is filtered and recycled to the evaporation concentration zone.
  • the slurry circulation tank comprises a flue gas desulfurization device The slurry circulation tank at the inner bottom is circulated to the sulphur dioxide absorption spray zone and the evaporation concentration zone by a circulation pump.
  • the magnesium sulfate-containing slurry is sent from a slurry circulation tank to a filtration device by a discharge pump, filtered, and then passed through a circulation pump into an evaporation concentration zone for evaporation concentration.
  • the filtration device is as described above.
  • the slurry recycled to the evaporation concentration zone preferably accounts for 40 to 55 vt%, preferably 45 to 50 vt% of the output (ie, the total circulation output of the slurry circulation tank); the slurry recycled to the sulfur dioxide absorption shower zone can pass two or more A circulating pump is separately fed into each of the sulfur dioxide absorption spray layers, and the slurry recycled to the sulfur dioxide absorption shower zone preferably accounts for 45 to 60 vt%, preferably 45 to 50 vt% of the output.
  • the pH in the slurry circulation tank is preferably controlled between 5 and 7.
  • the evaporation concentration step of the present invention is to circulate and evaporate the magnesium sulfate-containing slurry formed in the flue gas desulfurization apparatus to form a concentrated product.
  • the evaporation concentration zone is disposed inside the flue gas desulfurization apparatus and disposed at a lower portion of the sulfur dioxide absorption shower zone.
  • the flue gas of the invention first passes through the evaporation concentration zone in the rising process, and after cooling and preliminary absorption, the sulfur dioxide absorption spray zone is subjected to the desulfurization absorption reaction.
  • the flue gas after desulfurization can be further discharged by defogging and defogging through a mist eliminator.
  • the cyclic settling step of the present invention receives the concentrated product from the evaporation concentration zone in a circulating settling apparatus and sediments the concentrated product to form a settled product (a mixture of crystals and slurry discharged after preliminary crystallization).
  • the magnesium sulfate grains in the sedimentation product are larger than 0.1 mm; preferably, the solid content of the sedimentation product (mixture of crystals and slurry) discharged from the cycle sedimentation step is more than 30% by weight.
  • the temperature of the circulating settling apparatus is generally controlled at 55 to 70 ° C, preferably 60 to 65 ° C.
  • the crystal grains discharged by the cyclic sedimentation step are larger than 0.1 mm, and the sedimentation product (mixture of crystal and slurry) having a solid content of more than 30% by weight enters into the crystallization apparatus via the discharge port located at the bottom.
  • the slurry overflowing from the circulating settling device can be recycled to the evaporation concentration zone for cyclic evaporation and concentration, preferably after being filtered by a filtering device, and then recycled to the evaporation concentrated spray layer through a circulation pump; the filtering device is as described above.
  • the crystallization step of the present invention is used to further crystallize the sedimentation product (mixture of crystal and slurry) discharged in the cycle sedimentation step in a crystallization apparatus to obtain a crystal slurry; the sedimentation product entering the crystallization apparatus is cooled by means in the crystallization apparatus.
  • Magnesium sulfate is cooled and crystallized in a supersaturated state to further form a crystal slurry, and the crystallization temperature is generally controlled at 20 to 30 ° C, preferably 20 to 25 ° C; the crystal grains formed in the crystallization step are more than 0.15 mm, more preferably more than 0.2 mm, and the particle size of the present invention It is determined by sieving method (see GB/T21524-2008); in order to prevent grain sedimentation, a stirring device is arranged in the crystallization equipment, and the magnesium sulphate crystal gradually grows out in the crystallization equipment and is separated from the stirrer to settle at the bottom of the crystallization equipment.
  • the discharge pump discharges the crystal slurry and feeds it into the centrifugal device.
  • the discharged crystal slurry has a solid content of more than 40% by weight.
  • the centrifugation step of the present invention is used for centrifuging the crystal slurry discharged from the crystallization step into a mother liquor and a magnesium sulfate product (preliminary product magnesium sulfate crystal) in a centrifugation apparatus; in order to ensure sufficient centrifugation, the centrifugal speed is controlled at 1,500 to 2,000 rpm, preferably 1600. ⁇ 1800rpm.
  • the centrifugation time of each batch of material is controlled to 5 to 30 minutes, preferably 5 to 10 minutes.
  • the centrifugation time of each batch of material is controlled to be from 10 to 30 minutes, preferably from 10 to 15 minutes.
  • the magnesium sulfate product (preliminary product magnesium sulfate crystals) obtained in the centrifugation step has a water content of less than 2% by weight.
  • the mother liquor separated in the centrifugation step can be recycled to the evaporation concentration zone, for example, can be recycled to the evaporation concentration zone by a circulation pump.
  • the drying step of the present invention is used to dry the magnesium sulfate product to the finished product in a drying apparatus.
  • the drying step of the present invention can be carried out by vacuum drying or by passing heated air. Drying temperature It is 90 to 150 ° C, preferably 100 to 130 ° C, more preferably 110 to 120 ° C; and the drying pressure is 0.01 to 0.5 MPa, preferably 0.05 to 0.2 MPa.
  • the moisture content of the precipitate after drying is less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight.
  • the air is heated to a vibrating fluidized bed by a saturated steam having a temperature of 120 ° C and a pressure of 0.2 MPa, and the magnesium sulfate crystals are sufficiently dried to form a magnesium sulfate product under the action of mechanical vibration.
  • the magnesium sulfate according to the present invention is not limited to magnesium sulfate heptahydrate, and also includes magnesium sulfate monohydrate, magnesium sulfate trihydrate, magnesium sulfate pentahydrate, and anhydrous magnesium sulfate.
  • a different type of magnesium sulphate product can be obtained by using a conventional extended drying time or extending the size and size of the process equipment in the drying stage so that the material stays longer or shorter in the dryer.
  • the invention can also be applied to the traditional wet calcium method, the magnesium method and the ammonia method modification, as long as the traditional calcium method, the structure and process of the ammonia method are modified according to the structure and process method provided by the invention, and the original structure and process can be all Modifications to the original calcium method, magnesium method, and ammonia method which are consistent with the method of the present invention fall within the scope of protection of the present invention.
  • FIG. 1 is a schematic view of the apparatus of the first embodiment, which apparatus includes a desulfurization tower 1.
  • the middle and lower part of the desulfurization tower 1 is provided with a flue gas inlet 23, and the top is provided with a flue gas outlet 10.
  • An over-temperature emergency cooling device 24 is arranged above the flue gas inlet 23 to solve the occurrence of overheating of the flue gas temperature after the bypass flue is cancelled.
  • the slurry in the upper portion of the slurry circulation tank 11 is sent to the accident zone determined by the over-temperature emergency cooling device 24 through the over-temperature emergency cooling device circulation pump 15 for desulfurization.
  • Tower 1's emergency cooling is arranged emergency cooling.
  • An evaporation concentrated spray layer 3 is arranged above the over-temperature emergency cooling device 24, and an accumulator 4 is arranged above the evaporative concentration spray layer; a secondary sulfur dioxide absorption spray layer 7 and a tertiary sulfur dioxide absorption are arranged above the liquid accumulator 4 a spray layer 8; a demister 9 is disposed above the third-stage sulphur dioxide absorption spray layer 8; a circulation settling tank 2 is disposed below the flue gas inlet 23, and an overflow port 5 is disposed at a middle portion of the circulation settling tank 2, overflowing
  • the mouth 5 is connected to the filter 22 via the slurry pool discharge pump 21; the lower part of the circulation settling tank 2 is provided with a circulating settling tank discharge port 6; the slurry circulation tank 11 is arranged at the bottom of the desulfurization tower 1, and the outlet line is divided into four paths, one way
  • the filter unit 22 is connected to the filter 22 from the lower portion of the slurry circulation tank 11 via the slurry tank discharge
  • the pump 12 is sent to the evaporation concentrated spray layer 3 for concentrated crystallization; the other two channels are respectively passed from the upper part of the slurry circulation tank 11 through the secondary sulfur dioxide absorption spray layer circulation pump 13 and the third-stage sulfur dioxide absorption spray layer circulation pump 14 and the second stage.
  • the absorption spray layer 7 is connected with the third-stage sulfur dioxide absorption spray layer 8; the fourth road is connected from the upper portion of the slurry circulation tank 11 to the accident area determined by the over-temperature emergency cooling device 24 through the over-temperature emergency cooling device circulation pump 15
  • the slurry in the upper part of the slurry circulating tank 11 is sent to the accident zone determined by the over-temperature emergency cooling device 24 through the over-temperature emergency cooling device circulating pump 15; the circulating settling tank discharge port 6, the crystallization tank 16, the centrifuge 17, the dryer 18,
  • the packaging machine 19 is connected in series; and the centrifuge 17 is further connected to the evaporation concentration circulation pump 12 via the mother liquid back evaporation concentration layer circulation pump 20 to send the centrifugally generated mother liquid to the evaporation concentrated spray layer 3 for cyclic crystallization.
  • the flue gas enters the desulfurization tower 1 from the flue gas inlet 23 of the desulfurization tower 1, and is cooled by the over temperature emergency
  • the device 24 enters the evaporative concentration spray layer 3, after cooling and preliminary absorption, it enters the second-stage sulfur dioxide absorption spray layer 7 and the third-stage sulfur dioxide absorption spray layer 8 for desulfurization absorption reaction, and finally enters the mist eliminator 9 for dehydration and defogging.
  • the second sulfur dioxide absorption spray layer 7 and the tertiary sulfur dioxide absorption spray layer 8 absorb the sulfur dioxide-containing slurry formed by the sulfur dioxide into the slurry circulation tank 11;
  • the slurry in the lower part of the slurry circulation tank 11 is discharged through the slurry tank discharge pump 21, and then filtered through the filter 22 and sent to the evaporation concentrated spray layer 3 for evaporation concentration, the circulation amount of which accounts for 50 vt% of the total output of the slurry circulation tank slurry;
  • the slurry in the upper part of the slurry circulation tank 11 is sent to the second-stage sulfur dioxide absorption spray layer 7 and the third-stage sulfur dioxide absorption spray layer 8 through the secondary sulfur dioxide absorption spray layer circulation pump 13 and the third-stage sulfur dioxide absorption spray layer circulation pump 14 respectively.
  • the circulation amount of the two accounts for 50vt% of the total output, and the volume ratio of the two is 1:1;
  • the slurry overflowing from the overflow port 5 of the circulating settling tank 2 enters the filter 22 through the slurry tank discharge pump 21, is filtered, and is sent to the evaporation concentrated spray layer 3 for recycling crystallization;
  • the sedimentation product (mixture of magnesium sulfate crystal and slurry) with crystal grains larger than 0.1 mm discharged from the circulating sedimentation tank discharge port 6 at the bottom of the circulating settling tank 2 has a solid content of more than 30% by weight, enters the crystallization tank 16, and is in the crystallization tank.
  • a stirring device is arranged in the crystallization tank, and the stirring device is an electric stirring device;
  • the sedimentation product entering the crystallization tank 16 from the circulating settling tank 2 is further crystallized in the crystallization tank 16, and a crystal slurry having a solid content of more than 40% by weight is sent to the centrifuge 17 for separation, and the mother liquid separated by the centrifuge 17 is sent to the evaporation.
  • the concentrated spray layer 3 is concentrated by circulating evaporation, and the obtained magnesium sulfate product having a water content of less than 2% by weight is sent to the dryer 18 for further drying to the finished product, and sent to the packaging machine. 19 for packaging.
  • the flue gas (oxygen content of 16 vt%) generated by the sintering machine enters the desulfurization tower 1 from the flue gas inlet 23 of the desulfurization tower 1, and is discharged from the flue gas outlet 10.
  • the pH of the slurry circulation tank 11 at the bottom of the desulfurization tower 1 is controlled to be between 5 and 7.
  • the temperature of the circulating settling tank 2 is controlled at 60 degrees Celsius, and the sedimentation product having a solid content of more than 30% by weight enters the crystallization tank 16 through the discharge port 6 of the circulating settling tank 2, and is further cooled and crystallized;
  • Serial number project Quantity unit 1 Main content (calculated as MgSO 4 ⁇ 7H 2 O) 98.5 % mass percentage 2 Iron (in terms of Fe) content 0.005 % mass percentage 3 Chloride (as Cl) content 0.30 % mass percentage 4 Heavy metal content 0.0005 % mass percentage 5 Water insoluble content 0.08 % mass percentage
  • the measurement method of magnesium sulfate quality adopts "Chemical Industry Standard of the People's Republic of China HG/T 2680-2009”.

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Abstract

提供一种烟气脱硫生产硫酸镁的装置和方法，适用于在氧化镁法脱硫废液塔内直接结晶生产硫酸镁。该装置包括烟气脱硫设备（1）、浆液循环槽（11）、蒸发浓缩区（3）和循环沉降设备（2），其中浆液循环槽（11）、蒸发浓缩区（3）和循环沉降设备（2）均设置在烟气脱硫设备内。该装置和方法能够解决目前镁法脱硫后废液生产硫酸镁消耗蒸汽较多、吨矿生产成本较高和增加脱硫运行费用较多的问题。

Description

烟气脱硫生产硫酸镁的装置与方法 技术领域
本发明涉及一种烟气脱硫生产硫酸镁的装置与方法，尤其涉及一种氧化镁法脱硫废液塔内直接结晶生产硫酸镁的装置及方法。本发明的装置及方法尤其适用于利用烧结机、球团、回转窑等烟气脱硫后的废浆液制备硫酸镁。
背景技术
氧化镁法烟气脱硫技术逐步得到推广应用，市场份额从2005年不到1％，至目前超过6％，湿式氧化镁法脱硫技术得到了越来越多人的认可。采用氧化镁法脱硫工艺并将脱硫废液制备生成硫酸镁副产品，不仅解决了传统钙法脱硫产生的脱硫石膏处理问题，而且还可以通过硫酸镁副产品的销售冲抵部分脱硫装置的运行维护费用，从技术及经济角度都比传统钙法具有较大的市场应用优势。
由于传统的氧化镁法脱硫废液生产硫酸镁技术使用蒸汽作为蒸发、结晶、干燥的介质，所以造成采用脱硫废液生产硫酸镁的方法需要消耗较多的蒸汽，直接增加了脱硫运行费用。如公开号为CN1733656A的中国发明专利申请提供了一种“利用锅炉烟气制取七水硫酸镁肥料的方法”，其中硫酸镁溶液采用浓缩结晶的方式，这种方式是利用硫酸镁在温度超过60℃溶解度降低的特性进行结晶的，这种高温结晶方式需要消耗更多的高品质蒸汽而且会造成晶浆输送管路频繁堵塞，很难实现副产品的连续稳定生产。 又如申请号为201210100244.8的中国发明专利提供了一种“利用脱硫废液生产七水硫酸镁的方法”，所采用的结晶方法为“将所得液体送入蒸发器，浓缩后将浆料排出，蒸发温度为100～130℃，排出的浆料进行冷却结晶，温度为30～45℃，获得七水硫酸镁”。这种蒸发、结晶方法需要蒸汽品质较高，如果使用低品位蒸汽则消耗量增加。
综上所述，不论采用上述二种方法的任何一种，生产一吨硫酸镁都需要耗费1.2～2吨左右的蒸汽，蒸汽价格以80元/吨计算，一吨硫酸镁的蒸汽消耗成本在160元左右。因此，尽管镁法脱硫综合成本比钙法要低，但目前镁法脱硫塔外利用三效蒸发等工艺生产硫酸镁的方式仍然存在浪费蒸汽资源，脱硫运行费用仍然较高。
发明内容
为了克服现有技术的上述缺陷，本发明提供一种烟气脱硫生产硫酸镁的装置与方法，尤其提供一种氧化镁法脱硫废液塔内直接结晶生产硫酸镁的装置及方法。采用本发明提供的装置和方法，能够解决目前镁法脱硫后废液生产硫酸镁消耗蒸汽较多、吨矿生产成本较高和增加脱硫运行费用较多的问题。
本发明提供一种烟气脱硫生产硫酸镁的装置，包括：
烟气脱硫设备，其内部设有二氧化硫吸收喷淋区，用于采用氧化镁法脱除烟气中的二氧化硫，并形成含硫酸镁的浆液；
浆液循环槽，用于接收来自烟气脱硫设备的所述含硫酸镁的浆液，并将所述含硫酸镁的浆液循环至二氧化硫吸收喷淋区和蒸发浓缩区中；
蒸发浓缩区，用于将所述含硫酸镁的浆液蒸发浓缩，以形成浓缩产物；和
循环沉降设备，用于接收来自蒸发浓缩区中的浓缩产物，并将浓缩产物进行沉降，以形成沉降产物；
其中，所述蒸发浓缩区、循环沉降设备和浆液循环槽均设置在烟气脱硫设备内部。
根据本发明的的装置，优选地，所述二氧化硫吸收喷淋区包括两个或更多个二氧化硫吸收喷淋层；所述蒸发浓缩区位于二氧化硫吸收喷淋区的下部。
根据本发明的的装置，优选地，所述装置还包括积液器，该积液器用于将所述二氧化硫吸收喷淋区产生的浆液与蒸发浓缩区隔开。
根据本发明的的装置，优选地，所述循环沉降设备位于所述蒸发浓缩区的下部；所述浆液循环槽包括设置在烟气脱硫设备底部的浆液循环池。
根据本发明的的装置，优选地，所述装置进一步包括：
结晶设备，用于将来自循环沉降设备的沉降产物结晶，以形成结晶产物；
离心设备，用于将来自结晶设备的结晶产物离心分离，以形成母液和硫酸镁产物；和
干燥设备，用于将来自离心设备的硫酸镁产物干燥。
根据本发明的的装置，优选地，所述的烟气满足如下条件之一：
1)所述的烟气为来自烧结机、球团、或窑炉的烟气；
2)所述烟气的二氧化硫含量为300mg/Nm3～20000mg/Nm3、并且氧 气含量为8～20vt％。
本发明还提供一种利用上述装置生产硫酸镁的方法，包括如下步骤：
烟气脱硫步骤：在烟气脱硫设备中采用氧化镁法脱除烟气中的二氧化硫，并形成含硫酸镁的浆液；
浆液循环步骤：在浆液循环槽中接收来自烟气脱硫设备的所述含硫酸镁的浆液，并将所述含硫酸镁的浆液循环至二氧化硫吸收喷淋区和蒸发浓缩区中；
蒸发浓缩步骤：在蒸发浓缩区中将所述含硫酸镁的浆液蒸发浓缩，以形成浓缩产物；
循环沉降步骤：在循环沉降设备中接收来自蒸发浓缩区中的浓缩产物，并将浓缩产物进行沉降，以形成沉降产物。
根据本发明的方法，优选地，所述方法进一步包括
结晶步骤，在结晶设备中将来自循环沉降设备的沉降产物结晶，以形成结晶产物；
离心步骤，在离心设备中将来自结晶设备的结晶产物离心分离，以形成母液和硫酸镁产物；和
干燥步骤，在干燥设备中将来自离心设备的硫酸镁产物干燥。
根据本发明的方法，优选地，在所述循环沉降步骤中由循环沉降设备中溢出的浆液经过滤后循环至蒸发浓缩区中；和/或
在所述离心步骤中分离出的母液循环至蒸发浓缩区中。
根据本发明的方法，优选地，沉降产物中的硫酸镁晶粒大于0.1mm；结晶产物中的硫酸镁晶粒大于0.15mm。
本发明提供了一种以氧化镁作吸收剂，能够将烟气中的二氧化硫脱除，产生的浆液经浓缩、结晶、排出等功能直接结晶生产硫酸镁的装置和生产工艺，尤其是提供了一种集脱硫、浓缩、结晶、排出等功能于一体的塔内脱硫过程直接结晶生产硫酸镁的装置和工艺方法。
本发明采用多级吸收和循环蒸发浓缩相结合的方式，可在大量减少蒸汽消耗的条件下，保证脱硫效率和副产品质量，并且较多地降低副产品生产系统的运行成本，减小脱硫运行费用。
附图说明
图1是本发明实施例的装置示意图。
图1中：1为脱硫塔，2为循环沉降槽，3为蒸发浓缩喷淋层，4为积液器，5为溢流口，6为循环沉降槽排出口，7为二级二氧化硫吸收喷淋层，8为三级二氧化硫吸收喷淋层，9为除雾器，10为烟气出口，11为浆液循环池，12为蒸发浓缩循环泵，13为二级二氧化硫吸收喷淋层循环泵，14为三级二氧化硫吸收喷淋层循环泵，15为超温应急降温装置循环泵，16为结晶槽，17为离心机，18为干燥器，19为包装机，20为母液回蒸发浓缩喷淋层循环泵，21为浆液池排出泵，22为过滤器，23为烟气进口，24为超温应急降温装置。
具体实施方式
本发明所述的“％”，如无特殊说明，均为体积百分比。本发明所述的“vt％”表示体积百分比。本发明所述的“装置”为一种产品，即各装置的系 统集合。在本发明中，入口与进口具有相同的含义，二者可以替换。
根据本发明的一个实施方式，本发明的烟气可以为来自烧结机、球团、窑炉的烟气。由于上述烟气中存在一定量的氧气以及二氧化硫含量适中，可以提高硫酸镁产物的纯度。根据本发明的另一个实施方式，所述烟气也可以为任何二氧化硫含量在300mg/Nm3～20000mg/Nm3之间，氧气含量在8～20vt％之间的烟气。烟气中的二氧化硫含量优选为500mg/Nm3～10000mg/Nm3，更优选为1000mg/Nm3～5000mg/Nm3。烟气中的氧气含量优选为9～20vt％，更优选为15～19vt％。这样可以提高硫酸镁产物的纯度。
本发明的氧化镁法烟气脱硫是指以氧化镁为脱硫剂主要成份，但不限于添加其它任一成份(例如氧化钙、生石灰等)的烟气脱硫工艺。在氧化镁法脱硫工艺中，脱硫剂的结构和组成成份可能会有所变化，其配方或变化对于技术人员来说是熟知的。
<烟气脱硫生产硫酸镁的装置>
本发明的烟气脱硫生产硫酸镁的装置包括如下设备：烟气脱硫设备，浆液循环槽，蒸发浓缩区，循环沉降设备。优选地，所述装置进一步包括结晶设备、离心设备、干燥设备。任选地，本发明的装置还包括包装设备。根据本发明的装置，所述蒸发浓缩区、浆液循环槽、和循环沉降设备均设置在烟气脱硫设备内部。
本发明的烟气脱硫设备，其内部的上部设有二氧化硫吸收喷淋区，用于采用氧化镁法脱除烟气中的二氧化硫，并形成含硫酸镁的浆液。本发明 的烟气脱硫设备可以为烟气脱硫器或者烟气脱硫塔。从工业应用的角度讲，优选为烟气脱硫塔。所述的二氧化硫吸收喷淋区包括至少一个二氧化硫吸收喷淋层；优选包括两个或更多个二氧化硫吸收喷淋层，更优选为两个或三个二氧化硫吸收喷淋层。
本发明的蒸发浓缩区，用于将烟气脱硫设备中形成的含硫酸镁的浆液进行循环蒸发浓缩并形成浓缩产物。根据本发明的一个具体实施方式，所述蒸发浓缩区设置在烟气脱硫设备内部，并设置在二氧化硫吸收喷淋区的下部。根据本发明的另一个具体实施方式，所述蒸发浓缩区为蒸发浓缩喷淋层；根据本发明的再一个具体实施方式，所述蒸发浓缩喷淋层和所述二氧化硫吸收喷淋区通过积液器隔离。所述积液器的材质可以为纤维增强复合塑料FRP，优选其耐温范围在50-95摄氏度；但不限于上述材质。
本发明中，烟气从烟气脱硫设备下部的烟气进口进入设备内部，在上升过程中经过蒸发浓缩区，经降温及初步吸收后，进入二氧化硫吸收喷淋区进行脱硫吸收反应，烟气中的二氧化硫被吸收，净化后的烟气从烟气脱硫设备的顶部排出。本发明的烟气脱硫设备中还可以设置有除雾器，脱硫后的烟气可进行脱水除雾后再直接排放。
本发明脱硫所使用的制剂可以为本领域常用的氧化镁法脱除烟气所使用的那些脱硫剂浆液，例如将氧化镁粉中加入工业自来水制成的氢氧化镁浆液。优选地，本发明的脱硫剂可以使用CN102745726 A、CN102745725A、CN102836636A中所公开的那些脱硫剂。例如，CN102745726 A的实施例1或2公开的那些脱硫剂。在此，将上述专利申请的全部内容引入本文作为参考。将这些脱硫剂均匀分散在水中即得到脱 硫剂浆液。
本发明的循环沉降设备，用于接收来自蒸发浓缩区中的浓缩产物，并使浓缩产物沉降形成沉降产物(其中包括初步结晶过程)。优选地，所述循环沉降设备设置在烟气脱硫设备内部，并位于蒸发浓缩区的下部。所述循环沉降设备可以为循环沉降槽，根据工况可设置成单层沉降或双层沉降或多层沉降。其材质可以是玻璃钢，也可以是特种钢，或普通钢材料加防腐处理。循环沉降槽设置在烟气进口下方，循环沉降槽的中上部设置有溢流口，溢流口经浆液池排出泵与过滤器连接；循环沉降槽下部设置有循环沉降槽排出口。
本发明的浆液循环槽，用于接收烟气脱硫设备中形成的所述含硫酸镁的浆液，并将所述含硫酸镁的浆液循环至二氧化硫吸收喷淋区和蒸发浓缩区中。作为优选，将所述含硫酸镁的浆液经过过滤后循环至二氧化硫吸收喷淋区和蒸发浓缩区中。作为更优选，将所述含硫酸镁的浆液经过过滤后循环至蒸发浓缩区中。优选地，所述浆液循环槽包括设置在烟气脱硫设备内底部的浆液循环池，并通过循环泵将浆液分别循环至二氧化硫吸收喷淋区和蒸发浓缩区中。更优选地，将所述含硫酸镁的浆液从浆液循环池由排出泵送入过滤设备，过滤后再通过循环泵进入蒸发浓缩区中进行蒸发浓缩。所述过滤设备可以为板式过滤机或真空皮带过滤机，优选为板式过滤机。在一个具体实施方式中，循环至蒸发浓缩区的浆液优选占输出量(即浆液循环槽的循环输出总量)的40～55vt％，优选45～50vt％；由浆液循环池循环至二氧化硫吸收喷淋区的浆液可以通过两个或更多个循环泵分别送入所述的两个或更多个二氧化硫吸收喷淋层，循环至二氧化硫吸收喷淋 区的浆液优选占输出量的45～60vt％，优选45～50vt％。
本发明的结晶设备用于接收循环沉降设备中的沉降产物(初步结晶后排出的晶体与浆液的混合物)并将其进一步结晶得到晶浆；进入结晶设备的沉降产物，在结晶设备内通过降温的方式进一步形成晶浆，晶浆中硫酸镁晶粒大于0.15mm，优选大于0.3mm。为防晶粒沉降，在结晶设备内可以设置有搅拌装置，搅拌装置可以采用空气搅拌装置或电动搅拌装置等。在一个具体实施方式中，本发明的结晶设备可以为结晶槽，优选地，所述结晶槽具有带水冷环装置的自动降温系统。其冷源可以是常温水也可是冷冻水。也可单独设置涼水塔等降温装置。在一个具体实施方式中，本发明的结晶设备可以为连续冷却结晶器，更优选DTB连续冷却结晶器。该DTB结晶器由结晶罐、冷凝器、强制循环泵、出料泵、真空泵等组成。DTB(Drabt Tube Babbled)型结晶器即导流筒加档板型结晶器是一种细晶浆循环式结晶器。结晶器内设有导流筒和筒形挡板，配置推进式搅拌系统，操作时热饱和料液连续加到循环管下部，与循环管内夹带有小晶体的母液混合后泵送至加热器。加热后的溶液在导流筒底部附近流入结晶器，并由缓慢转动的螺旋桨沿导流筒送至液面。溶液在液面蒸发冷却，达到过饱和状态，其中部分溶质在悬浮的颗粒表面沉积，使晶体长大。在环形挡板外围还设有一个沉降区。在沉降区内大颗粒沉降，而小颗粒则随母液进入循环管并受热溶解。晶体于结晶器底部沉入淘析柱。为使结晶产品的粒度尽量均匀，将沉降区来的部分母液加到淘析柱底部，利用水力分级的作用，使小颗粒随溶液流回结晶器，结晶产品从淘析腿下部排出。冷却结晶温度一般控制在25～35℃，优选28～30℃。
本发明的离心设备用于接收结晶设备排出的晶浆(结晶产物)，并将其离心分离形成硫酸镁产物。离心设备可以使用本领域所熟知的那些。
本发明的干燥设备用于接收离心设备排出的硫酸镁产物(初步产品硫酸镁晶体)，并将其干燥至成品。本发明的干燥装置优选为振动流化床干燥装置，该装置特别适合硫酸镁晶体的干燥过程。本发明优选采用配置热风装置的振动流化床干燥装置。送风机将过滤后的空气输入空气加热器，经过加热的热空气，进入主机的下箱体内，然后通过流化床的空气分布板由下向上垂直吹入被干燥的物料，使物料呈沸腾状态。物料自进料口进入，主机在振动电机的激振力作用下产生匀称振动，使物料沿水平抛掷，被干燥的物料在上述的热气流和机器振动的综合作用下，形成流态化状态，这样就使物料与热空气接触时间长，面积大，因而获得高效率的干燥效果。本发明的装置可以利用热值较低的温度为120～133℃、压力为0.2～0.3MPa饱和蒸汽将空气加热送入振动流化床在并机械振动的作用下实现硫酸镁晶体充分烘干成硫酸镁物料。从流化床输出的蒸汽可以用于蒸发浓缩区，其不但节约能源，还降低了运营成本。
本发明的包装设备用于将干燥后的成品包装。包装设备可以使用本领域所熟知的那些。
本发明中所述的“排出”(例如从循环沉降设备中排出晶体与浆液的混合物，从结晶设备中排出晶浆，从离心设备中排出硫酸镁晶体等)可以使用排出设备，在一个具体得到实施方式中，所述排出设备为排出泵。
本发明还可以在烟气脱硫设备的烟气进口位置设置超温应急降温装置，以解决旁通烟道取消后烟气温度超温情况的出现。当温度超过限定温 度时，浆液循环池上部的浆液经循环泵送入超温应急降温装置确定的事故区，用于烟气脱硫设备的应急降温。上述限定温度可以为160～200℃，优选大于等于180℃。
<烟气脱硫生产硫酸镁的方法>
利用本发明的上述装置可以生产硫酸镁，包括如下步骤：烟气脱硫步骤，浆液循环步骤，蒸发浓缩步骤，循环沉降步骤。优选地，本方法进一步包括结晶步骤、离心步骤、和干燥步骤，任选地，还可以包括包装步骤。
本发明的烟气脱硫步骤为在烟气脱硫设备中采用氧化镁法脱除烟气中的二氧化硫，并形成含硫酸镁的浆液。在本发明的一个具体实施方案中，所述的烟气脱硫设备内部的上部设有二氧化硫吸收喷淋区。烟气从烟气脱硫设备的烟气进口进入设备内部，在上升过程中经过二氧化硫吸收喷淋区进行脱硫吸收反应，烟气中的二氧化硫被吸收，净化后的烟气从烟气脱硫设备的顶部排出。本发明脱硫所使用的制剂如前所述。烟气在烟气脱硫设备的烟气进口处的流速为2.5～4.5m/s，优选3～4m/s，进口烟气温度为110～180℃，优选110～150℃。
本发明的浆液循环步骤为将浆液循环槽中接收的浆液循环至烟气脱硫设备中的二氧化硫吸收喷淋区和蒸发浓缩区中。所述循环可以通过循环泵进行。作为优选，将所述含硫酸镁的浆液经过过滤后循环至二氧化硫吸收喷淋区和蒸发浓缩区中。作为更优选，将所述含硫酸镁的浆液经过过滤后循环至蒸发浓缩区中。优选地，所述浆液循环槽包括设置在烟气脱硫设备 内底部的浆液循环池，并通过循环泵将浆液分别循环至二氧化硫吸收喷淋区和蒸发浓缩区中。更优选地，将所述含硫酸镁的浆液从浆液循环池由排出泵送入过滤设备，过滤后再通过循环泵进入蒸发浓缩区中进行蒸发浓缩。所述过滤设备如上文所述。循环至蒸发浓缩区的浆液优选占输出量(即浆液循环槽的循环输出总量)的40～55vt％，优选45～50vt％；循环至二氧化硫吸收喷淋区的浆液可以通过两个或更多个循环泵分别送入各个二氧化硫吸收喷淋层，循环至二氧化硫吸收喷淋区的浆液优选占输出量的45～60vt％，优选45～50vt％。浆液循环槽内的pH值优选控制在5～7之间。
本发明的蒸发浓缩步骤为将烟气脱硫设备中形成的含硫酸镁的浆液进行循环蒸发浓缩并形成浓缩产物。根据本发明的一个具体实施方式，所述蒸发浓缩区设置在烟气脱硫设备内部，并设置在二氧化硫吸收喷淋区的下部。本发明的烟气在上升过程中先经过蒸发浓缩区，经降温及初步吸收后，再经过二氧化硫吸收喷淋区进行脱硫吸收反应。脱硫后的烟气可进一步通过除雾器进行脱水除雾后再直接排放。
本发明的循环沉降步骤为在循环沉降设备中接收来自蒸发浓缩区中的浓缩产物，并将浓缩产物进行沉降，以形成沉降产物(初步结晶后排出的晶体与浆液的混合物)。沉降产物中的硫酸镁晶粒大于0.1mm；优选地，循环沉降步骤排出的沉降产物(晶体与浆液的混合物)中固含量大于30wt％。循环沉降设备的温度一般控制在55～70℃，优选60-65℃。优选地，循环沉降步骤排出的晶粒大于0.1mm，并且固含量大于30wt％的沉降产物(晶体与浆液的混合物)经由位于底部的排出口进入到结晶设备中进 一步结晶。由循环沉降设备溢出的浆液可循环至蒸发浓缩区中进行循环蒸发浓缩，优选先经过滤设备过滤后，再经循环泵进入蒸发浓缩喷淋层进行再循环；所述过滤设备如上文所述。
本发明所述结晶步骤用于在结晶设备中将循环沉降步骤中排出的沉降产物(晶体与浆液的混合物)进一步结晶得到晶浆；进入结晶设备的沉降产物，在结晶设备内通过冷却的方式实现硫酸镁过饱和状态降温结晶，进一步形成晶浆，结晶温度一般控制在20～30℃，优选20-25℃；结晶步骤中形成的晶粒大于0.15mm，更优选大于0.2mm，本发明的粒度采用筛分法测定(参见GB/T21524-2008)；为防晶粒沉降，在结晶设备内设置有搅拌装置，硫酸镁晶体在结晶设备内逐渐长大脱离搅拌器扰动沉降在结晶设备底部，通过排出泵将晶浆排出，并送入离心设备中。排出的晶浆的固含量大于40wt％。
本发明的离心步骤用于在离心设备中将结晶步骤排出的晶浆离心分离形成母液和硫酸镁产物(初步产品硫酸镁晶体)；为了保证离心充分，离心速度控制在1500～2000rpm，优选为1600～1800rpm。对于间歇式操作，每批物料的离心时间控制在5～30分钟，优选为5～10分钟。对于连续式操作，每批物料的离心时间控制在10～30分钟，优选为10～15分钟。离心步骤中得到的硫酸镁产物(初步产品硫酸镁晶体)的含水量小于2wt％。离心步骤中分离出的母液可循环至蒸发浓缩区中，例如可以通过循环泵循环至蒸发浓缩区中
本发明的干燥步骤用于在干燥设备中将硫酸镁产物干燥至成品。本发明的干燥步骤可以通过真空干燥或者通入加热空气的方式进行。干燥温度 为90～150℃，优选为100～130℃，更优选为110～120℃；干燥压力为0.01～0.5MPa，优选为0.05～0.2MPa。通过干燥步骤，干燥后的沉淀的水分含量小于1wt％，优选小于0.5wt％，更优选小于0.1wt％。在一个具体实施方式中，通过温度为120℃压力为0.2MPa的饱和蒸汽将空气加热送入振动流化床在并机械振动的作用下实现硫酸镁晶体充分烘干成硫酸镁成品。
本发明所述的硫酸镁，不限定为七水硫酸镁，也包括一水硫酸镁、三水硫酸镁、五水硫酸镁及无水硫酸镁。对于技术人员来说，在干燥阶段采用普通的延长干燥时间或延伸工艺设备的尺寸、大小以使物料在干燥器中停留时间更长或更短即可得到不同品类的硫酸镁产品。
本发明也可适用于传统湿式钙法、镁法、氨法改造，只要将传统钙法、氨法塔内结构、工艺按照本发明提供的结构、工艺方法改造原有结构、工艺即可，所有采用本发明方法一致的、对原有钙法、镁法、氨法的改造均落入本发明的保护范围。
以下结合附图对本发明进行更详细的说明。
<实施例1>
图1是本实施例1的装置示意图，该装置包括一个脱硫塔1。脱硫塔1的中下部设有烟气进口23、顶部设有烟气出口10。烟气进口23上方设置有超温应急降温装置24，以解决旁通烟道取消后烟气温度超温情况的出现。在温度超过限定温度180时，浆液循环池11上部的浆液经超温应急降温装置循环泵15送至由超温应急降温装置24确定的事故区，用于脱硫 塔1的应急降温。在超温应急降温装置24上方设置有蒸发浓缩喷淋层3，蒸发浓缩喷淋层上方设置有积液器4；积液器4上方设置有二级二氧化硫吸收喷淋层7和三级二氧化硫吸收喷淋层8；三级二氧化硫吸收喷淋层8上方设置有除雾器9；在烟气进口23下方设置有循环沉降槽2，循环沉降槽2的中上部设置有溢流口5，溢流口5经浆液池排出泵21与过滤器22连接；循环沉降槽2下部设置有循环沉降槽排出口6；浆液循环池11设置在脱硫塔1的底部，其出口管路分为四路，一路从浆液循环池11的下部经由浆液池排出泵21与过滤器22连接，过滤器22经蒸发浓缩循环泵12连接至蒸发浓缩喷淋层3，使过滤器22过滤得到的清液经由蒸发浓缩循环泵12送至蒸发浓缩喷淋层3进行浓缩结晶；另两路从浆液循环池11的上部分别经二级二氧化硫吸收喷淋层循环泵13和三级二氧化硫吸收喷淋层循环泵14与二级二氧化硫吸收喷淋层7和三级二氧化硫吸收喷淋层8连接；第四路从浆液循环池11的上部经超温应急降温装置循环泵15与超温应急降温装置24所确定的事故区连接，以将浆液循环池11上部的浆液经超温应急降温装置循环泵15送至由超温应急降温装置24确定的事故区；循环沉降槽排出口6、结晶槽16、离心机17、干燥器18、和包装机19依次连接；并且离心机17还经由母液回蒸发浓缩层循环泵20与蒸发浓缩循环泵12连接，以将离心产生的母液送至蒸发浓缩喷淋层3进行循环结晶。
本实施例的工艺流程如下：
a.烟气从脱硫塔1的烟气进口23进入到脱硫塔1，经过超温应急降温 装置24后进入蒸发浓缩喷淋层3，降温及初步吸收后依次进入二级二氧化硫吸收喷淋层7和三级二氧化硫吸收喷淋层8进行脱硫吸收反应，最后进入除雾器9进行脱水除雾后经顶部烟囱的烟气出口10中直接排放；
b.二级二氧化硫吸收喷淋层7及三级二氧化硫吸收喷淋层8吸收二氧化硫形成的含硫酸镁的浆液进入浆液循环池11；
c.浆液循环池11下部的浆液经浆液池排出泵21排出，然后经过滤器22过滤后送至蒸发浓缩喷淋层3进行蒸发浓缩，其循环量占浆液循环池浆液输出总量的50vt％；浆液循环池11上部的浆液通过二级二氧化硫吸收喷淋层循环泵13、三级二氧化硫吸收喷淋层循环泵14分别送至二级二氧化硫吸收喷淋层7及三级二氧化硫吸收喷淋层8，二者的循环量占输出总量的50vt％，二者体积比例为1∶1；
d.由循环沉降槽2的溢流口5溢出的浆液经浆液池排出泵21进入过滤器22，经过滤后送至蒸发浓缩喷淋层3进行再循环结晶；
e.循环沉降槽2底部的循环沉降槽排出口6排出的晶粒大于0.1mm的沉降产物(硫酸镁晶体与浆液的混合物)，其固含量大于30wt％，进入结晶槽16，在结晶槽内经降温，进一步形成晶粒大于0.15mm的硫酸镁晶体，为防晶体沉降，在结晶槽内设置有搅拌装置，搅拌装置为电动搅拌装置；
f.由循环沉降槽2进入结晶槽16的沉降产物在结晶槽16中进一步结晶后，得到固含量大于40wt％的晶浆送入离心机17进行分离，离心机17分离得到的母液送至蒸发浓缩喷淋层3进行循环蒸发浓缩，得到的含水量小于2wt％的硫酸镁产物送至干燥器18进一步干燥至成品，并送至包装机 19进行包装。
在本实施例的工艺流程中：
1)：将氧化镁粉中加入工业自来水制成氢氧化镁浆液，泵送至脱硫塔1作为脱硫剂；
2)：烧结机产生的烟气(氧气含量为16vt％)从脱硫塔1的烟气进口23进入到脱硫塔1，由烟气出口10排放。脱硫塔1底部的浆池循环池11的pH值控制在5～7之间。
3)：循环沉降槽2的温度控制在60摄氏度，固含量超过30wt％的沉降产物经由循环沉降槽2的排出口6进入结晶槽16，进行进一步降温结晶；
4)：通过温度稳定在20～30℃循环冷却水给结晶槽16内的硫酸镁溶液降温实现硫酸镁过饱和状态降温结晶；
5)：通过温度为120℃、压力为0.2MPa的饱和蒸汽将空气加热送入干燥器18(即振动流化床)在并机械振动的作用下实现硫酸镁晶体充分烘干成硫酸镁成品并输送至自动包装机包装。最终得到质量为工业合格品以上的硫酸镁产品；
6)：上述工艺的其它参数详见表1，本实施例烟气排放状况以及所得硫酸镁的状况参见表2和表3。
表1烧结机烟气脱硫项目工况参数
Figure PCTCN2015092540-appb-000001
Figure PCTCN2015092540-appb-000002
表2脱硫项目排放情况
序号 项目 数量 单位
1 脱硫塔出口烟气量(工况) 176117 Nm3/h
2 排烟温度 50 ℃
3 SO2排放浓度 ＜50 mg/Nm3
4 硫酸镁产出量 1.1 t/h
5 硫酸镁品质 ＞98 ％质量百分比
表3脱硫项目产出硫酸镁品质
序号 项目 数量 单位
1 主含量(以MgSO4·7H2O计) 98.5 ％质量百分比
2 铁(以Fe计)含量 0.005 ％质量百分比
3 氯化物(以Cl计)含量 0.30 ％质量百分比
4 重金属含量 0.0005 ％质量百分比
5 水不溶物含量 0.08 ％质量百分比
硫酸镁品质的测量方法采用《中华人民共和国化工行业标准HG/T 2680-2009》。
本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。

Claims (10)

  1. 一种烟气脱硫生产硫酸镁的装置，其特征在于，包括：
    烟气脱硫设备，其内部设有二氧化硫吸收喷淋区，用于采用氧化镁法脱除烟气中的二氧化硫，并形成含硫酸镁的浆液；
    浆液循环槽，用于接收来自烟气脱硫设备的所述含硫酸镁的浆液，并将所述含硫酸镁的浆液循环至二氧化硫吸收喷淋区和蒸发浓缩区中；
    蒸发浓缩区，用于将所述含硫酸镁的浆液蒸发浓缩，以形成浓缩产物；和
    循环沉降设备，用于接收来自蒸发浓缩区中的浓缩产物，并将浓缩产物进行沉降，以形成沉降产物；
    其中，所述浆液循环槽、蒸发浓缩区、和循环沉降设备均设置在烟气脱硫设备内部。
  2. 根据权利要求1所述的烟气脱硫生产硫酸镁的装置，其特征在于，所述二氧化硫吸收喷淋区包括两个或更多个二氧化硫吸收喷淋层；所述蒸发浓缩区位于二氧化硫吸收喷淋区的下部。
  3. 根据权利要求1或2所述的烟气脱硫生产硫酸镁的装置，其特征在于，所述装置还包括积液器，该积液器用于将所述二氧化硫吸收喷淋区产生的浆液与蒸发浓缩区隔开。
  4. 根据权利要求1或2所述的烟气脱硫生产硫酸镁的装置，其特征在于，所述循环沉降设备位于所述蒸发浓缩区的下部；所述浆液循环槽包括设置在烟气脱硫设备底部的浆液循环池。
  5. 根据权利要求1或2所述的烟气脱硫生产硫酸镁的装置，其特征 在于，所述装置进一步包括：
    结晶设备，用于将来自循环沉降设备的沉降产物结晶，以形成结晶产物；
    离心设备，用于将来自结晶设备的结晶产物离心分离，以形成母液和硫酸镁产物；和
    干燥设备，用于将来自离心设备的硫酸镁产物干燥。
  6. 根据权利要求1或2所述的烟气脱硫生产硫酸镁的装置，其特征在于，所述的烟气满足如下条件之一：
    1)所述的烟气为来自烧结机、球团、或窑炉的烟气；
    2)所述烟气的二氧化硫含量为300mg/Nm3～20000mg/Nm3、并且氧气含量为8～20vt％。
  7. 一种利用权利要求1-6任一项所述的装置生产硫酸镁的方法，其特征在于，包括如下步骤：
    烟气脱硫步骤：在烟气脱硫设备中采用氧化镁法脱除烟气中的二氧化硫，并形成含硫酸镁的浆液；
    浆液循环步骤：在浆液循环槽中接收来自烟气脱硫设备的所述含硫酸镁的浆液，并将所述含硫酸镁的浆液循环至二氧化硫吸收喷淋区和蒸发浓缩区中；
    蒸发浓缩步骤：在蒸发浓缩区中将所述含硫酸镁的浆液蒸发浓缩，以形成浓缩产物；和
    循环沉降步骤：在循环沉降设备中接收来自蒸发浓缩区中的浓缩产物，并将浓缩产物进行沉降，以形成沉降产物。
  8. 根据权利要求7所述的方法，其特征在于，所述方法进一步包括：
    结晶步骤，在结晶设备中将来自循环沉降设备的沉降产物结晶，以形成结晶产物；
    离心步骤，在离心设备中将来自结晶设备的结晶产物离心分离，以形成母液和硫酸镁产物；和
    干燥步骤，在干燥设备中将来自离心设备的硫酸镁产物干燥。
  9. 根据权利要求8所述的方法，其特征在于，在所述循环沉降步骤中由循环沉降设备中溢出的浆液经过滤后循环至蒸发浓缩区中；和/或
    在所述离心步骤中分离出的母液循环至蒸发浓缩区中。
  10. 根据权利要求7或8所述的方法，其特征在于，沉降产物中的硫酸镁晶粒大于0.1mm；结晶产物中的硫酸镁晶粒大于0.15mm。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106395951A (zh) * 2016-11-15 2017-02-15 青岛达能环保设备股份有限公司 低温喷淋蒸发脱硫废水处理系统

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104556157B (zh) * 2014-12-03 2016-04-20 北京中晶佳镁环境科技股份有限公司 烟气脱硫生产硫酸镁的装置与方法
CN104556159B (zh) * 2014-12-15 2016-10-12 北京中晶环境科技股份有限公司 烟气脱硫生产亚硫酸镁的装置和方法
CN104843749A (zh) * 2015-05-19 2015-08-19 金小弟 一种利用氧化镁脱硫废液、废渣制备胶凝材料原料的方法
CN104959010A (zh) * 2015-06-05 2015-10-07 北京中晶佳镁环境科技股份有限公司 基于臭氧的脱硫脱硝装置及方法
CN104959013B (zh) * 2015-06-05 2017-07-25 中晶环境科技股份有限公司 可除尘的烟气处理装置及方法
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CN104923044B (zh) * 2015-06-05 2017-06-09 中晶环境科技股份有限公司 基于臭氧的烟气治理系统及方法
CN105032138B (zh) * 2015-06-05 2017-07-04 中晶环境科技股份有限公司 烟气治理装置和方法
CN106698486B (zh) * 2015-08-19 2017-12-08 中晶环境科技股份有限公司 一种生产硫酸镁的装置和方法
CN106467313B (zh) * 2015-08-19 2017-12-08 中晶环境科技股份有限公司 一种燃煤锅炉烟气脱硫生产硫酸镁的装置及工艺
CN106467387B (zh) * 2015-08-19 2018-12-21 中晶环境科技股份有限公司 一种镁法脱硫生产的硫酸镁发泡制品
CN105797581A (zh) * 2016-06-03 2016-07-27 中冶京诚工程技术有限公司 焦炉烟气脱硫脱硝余热利用工艺及系统
CN107827130B (zh) * 2017-12-13 2024-04-02 青岛锐丰源化工有限公司 利用烷基化废酸制备硫酸镁的生产线
CN115353132A (zh) * 2022-09-23 2022-11-18 西安交通大学 一种基于氯碱盐泥的七水硫酸镁制备方法及系统

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1481926A (zh) * 2003-04-11 2004-03-17 清华大学 一种氧化镁湿法烟气脱硫及产物回收新工艺
CN101085411A (zh) * 2007-07-16 2007-12-12 娄爱娟 一种烟气净化装置和方法
CN102806004A (zh) * 2011-05-30 2012-12-05 中国石油化工股份有限公司 镁法脱硫副产物回收工艺
CN103990360A (zh) * 2014-03-06 2014-08-20 华东理工大学 一种脱硫副产物硫酸镁溶液连续浓缩纯化的方法
CN104556157A (zh) * 2014-12-03 2015-04-29 北京中晶佳镁环境科技股份有限公司 烟气脱硫生产硫酸镁的装置与方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10109013A (ja) * 1996-10-04 1998-04-28 Hisaji Koyama 酸化マグネシウム再生硫酸回収型排煙脱硫装置
JP3573950B2 (ja) * 1997-06-24 2004-10-06 東洋エンジニアリング株式会社 排ガスの脱硫方法
CN201235279Y (zh) * 2008-07-07 2009-05-13 中国石化集团宁波工程有限公司 带有搅拌器的镁法喷淋式脱硫吸收塔

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1481926A (zh) * 2003-04-11 2004-03-17 清华大学 一种氧化镁湿法烟气脱硫及产物回收新工艺
CN101085411A (zh) * 2007-07-16 2007-12-12 娄爱娟 一种烟气净化装置和方法
CN102806004A (zh) * 2011-05-30 2012-12-05 中国石油化工股份有限公司 镁法脱硫副产物回收工艺
CN103990360A (zh) * 2014-03-06 2014-08-20 华东理工大学 一种脱硫副产物硫酸镁溶液连续浓缩纯化的方法
CN104556157A (zh) * 2014-12-03 2015-04-29 北京中晶佳镁环境科技股份有限公司 烟气脱硫生产硫酸镁的装置与方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106395951A (zh) * 2016-11-15 2017-02-15 青岛达能环保设备股份有限公司 低温喷淋蒸发脱硫废水处理系统

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