WO2010025620A1 - 一种用立式密闭隔烟窑炉生产黄磷或磷酸的方法及设备 - Google Patents

一种用立式密闭隔烟窑炉生产黄磷或磷酸的方法及设备 Download PDF

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Publication number
WO2010025620A1
WO2010025620A1 PCT/CN2009/000985 CN2009000985W WO2010025620A1 WO 2010025620 A1 WO2010025620 A1 WO 2010025620A1 CN 2009000985 W CN2009000985 W CN 2009000985W WO 2010025620 A1 WO2010025620 A1 WO 2010025620A1
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Prior art keywords
kiln
phosphorus
phosphoric acid
vertical
yellow phosphorus
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PCT/CN2009/000985
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English (en)
French (fr)
Inventor
张定斌
汤才洲
曾富强
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湖北三新磷酸有限公司
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Publication of WO2010025620A1 publication Critical patent/WO2010025620A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/02—Preparation of phosphorus
    • C01B25/027—Preparation of phosphorus of yellow phosphorus
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid

Definitions

  • the invention relates to a method for producing yellow phosphorus or phosphoric acid by using a vertical sealed kiln furnace; the invention also relates to a vertical sealed kiln furnace used in the process of producing yellow phosphorus or phosphoric acid by using a vertical sealed kiln furnace .
  • This method requires a large amount of electric energy (production of 15,000-16,000 kwh per ton of yellow phosphorus) and medium-high grade phosphate ore, and the environmental pollution is serious, which is almost at present.
  • the kiln method phosphoric acid is the third method which is different from the wet method and the thermal method.
  • the reaction principle is similar to that of the thermal method phosphoric acid, but the mixture is subjected to a solid phase reaction, and the reduction and oxidation process of the phosphorus element is placed in a device.
  • the heat released by the combustion of phosphorus and by-product carbon monoxide can be used to provide the heat required for the reduction of phosphorus, which can save energy.
  • the P 2 0 5 > 10% medium and low grade phosphate rock can be used to greatly broaden the phosphorus.
  • the mine is a range of grades that are directly utilized. However, this process has not been successfully applied in large-scale industrial production.
  • the kiln method phosphoric acid has two research routes for a long time: one is the rotary kiln method phosphoric acid, and the other is the tunnel kiln method phosphoric acid, which is mainly distinguished by the difference of the main reactor in which the phosphorus reduction and oxidation process is located.
  • Rotary kiln It is a heavy-duty, high-torque, multi-point, cylindrical hollow furnace operating system; the spherical material moves in the kiln with the rotation of the kiln, and the reduction of phosphorus takes place in the reduction zone, phosphorus Oxidation is carried out in the oxidation zone, both the reduction zone and the oxidation zone are in the kiln; the fuel is directly burned in the kiln;
  • Tunnel kiln generally a long linear tunnel with fixed walls on both sides and at the top The vault, the kiln car is running on the track laid on the bottom, and the combustion equipment is located on the central side of the tunnel kiln; it is fired by flame or flame, and the material is placed on the kiln car, passing the pre-tropical zone, high temperature zone and cooling zone. .
  • the main difficulty of the rotary kiln is that the kiln head is crusted, the outlet temperature is too high, the dust is large and the chemical protection cost is high; the main problem of the tunnel kiln is the high temperature and corrosion resistance requirements of the green body protection material and the low thermal efficiency of the tunnel kiln.
  • the object of the present invention is to provide a method for producing yellow phosphorus or phosphoric acid in a vertical sealed kiln furnace capable of better realizing the industrial production of kiln method phosphoric acid by overcoming the defects of rotary kiln and tunnel kiln;
  • the purpose is to provide a vertical closed-air kiln for use in the production process.
  • the object of the present invention is achieved by: a method for producing yellow phosphorus or phosphoric acid by using a vertical sealed kiln furnace, which comprises a phosphate ore, a carbonaceous reducing agent and other ingredients into a spherical material; the spherical material is sealed from the vertical The upper part of the smoke-free kiln is added, and the gravity is operated downward, and the reaction is carried out in a solid phase state. The material in the vertical sealed kiln is heated and reduced to phosphorus vapor, and the phosphorus vapor is cooled to obtain yellow phosphorus or introduce phosphorus vapor. The phosphorus combustion passage in the vertical sealed kiln is oxidized into phosphorus pentoxide and then hydrated to form phosphoric acid; the solid residue after the reaction is cooled by heat exchange Unloaded from the lower part of the kiln.
  • the material is subjected to a reduction reaction of phosphorus under solid phase conditions, and the molten portion of the material is 0-30% of the total amount of the material.
  • the selected phosphate rock is P 2 0 5 > 6%
  • the carbonaceous reducing agent is coke, coal or coal stone
  • the other ingredients are silica or lime or limestone, and the molar ratio of calcium to silicon in the spherical material is Ca: S i ⁇ 0.4 or > 3. 5.
  • the binder is made up of water and phosphoric acid at a concentration of 10 - 30% dilute phosphoric acid, and the binder is added in an amount of 0. 1-3%.
  • a vertical sealed smoke-free kiln comprising a kiln body, the kiln body is mounted on the support, a hopper is arranged on the upper part of the kiln body, a cooling hopper is arranged on the lower part, a burner for refueling is inserted into the kiln body, and the vertical sealing is arranged
  • the kiln body of the kiln is divided into two types of channels: material passage and fuel passage.
  • the furnace is divided into three types: material passage, fuel passage and phosphorus combustion passage.
  • the heat refractory material is hermetically sealed.
  • the vertical closed-air kiln used in the preparation of phosphoric acid is a kiln group consisting of a single kiln or a plurality of kiln, and the vertical closed kiln furnace group is connected with a plurality of interconnected vertical closed kiln furnaces. Based on the basic composition, each vertical sealed kiln is connected by a passage for mass transfer heat transfer.
  • One end of the passage is connected to the exhaust port of the material passage of the previous kiln, and the other end is connected to the inlet of the fuel passage of the next kiln.
  • the invention provides a method for producing yellow phosphorus or phosphoric acid by using a vertical sealed kiln, wherein the mixture is added from the top or the upper part of the vertical sealed kiln, and the material runs downward by gravity, and reacts in a solid phase state. After the reaction, the solid material residue is discharged from the bottom or the lower part of the kiln by heat exchange cooling.
  • This method is the third feasible route in addition to the tunnel kiln method phosphoric acid and rotary kiln method phosphoric acid, and can flexibly produce yellow phosphorus. Or adjust the phosphoric acid.
  • the heat generated by the combustion of phosphorus and carbon monoxide is transmitted to the ball in the material passage through the partition wall to supply the heat energy required for the reduction reaction, thereby realizing the core idea of the kiln phosphoric acid, and greatly saving energy consumption.
  • the outer surface does not need to add a wrapping agent, which simplifies the process, reduces the cost, and completely removes the mass of the ball material occupied by the wrapping agent, so that the phosphorus yield per unit mass of the ball material is higher.
  • the combustion and heating of the smoke separation effectively separates the reducing atmosphere and the oxidizing atmosphere in the vertical sealed kiln, which fundamentally solves the problem that the carbonaceous material is oxidized in advance during the heating process, reducing the composite pellets.
  • the amount of carbonaceous reducing agent When the material is reduced to produce phosphorus, the phosphorus is not oxidized immediately, but is burned and oxidized in the phosphorus combustion channel, thereby solving the problem of phosphorus oxidation back-feeding on the surface of the ball.
  • the combustion of phosphorus is carried out in a controlled and ordered state.
  • the upper and lower hoppers of the vertical sealed kiln and the ball column of several meters high in the cooling hopper can effectively ensure the sealing inside the vertical sealed kiln and prevent external gas from entering the kiln. Really guarantees the reducing atmosphere and reduces the absorption of kiln gas.
  • the exhaust gas produced by fuel combustion does not contain toxic and corrosive gases such as phosphorus and fluorine, and is easy to be used for heat recovery. Moreover, the kiln gas has no gas to be added, and the gas volume is reduced, which reduces the processing capacity of the hydration system, saving Investment and production of electricity consumption.
  • the quality of phosphoric acid is not affected by the type of fuel, so that the kiln process phosphoric acid is no longer limited to natural gas, and ordinary coal powder can also be used, thereby reducing energy costs again, thereby greatly reduce manufacturing cost.
  • the present invention can also be carried out in the form of a vertical closed kiln furnace group in the preparation of phosphoric acid.
  • the vertical closed-air kiln furnace group is composed of a plurality of interconnected vertical closed-air kiln furnaces.
  • the production method of the furnace group is used to expand the idea of producing phosphoric acid in a single vertical sealed kiln, and a single kiln.
  • the idea of using phosphorus vapor and carbon monoxide to self-supple part of the heat is broadened to a furnace group consisting of a plurality of vertical closed-air kiln furnaces, and the process of achieving heat transfer by mass transfer (phosphorus vapor and carbon monoxide) between the kiln is completed.
  • the kiln structure is simplified, the control is facilitated, the safety is improved, and the heat of combustion of phosphorus vapor and carbon monoxide is more fully utilized, thereby improving the comprehensive utilization level of heat.
  • the reduction and oxidation of phosphorus are carried out in an ordered state under controlled conditions.
  • Fig. 1 is a schematic flow chart showing the yellow phosphorus produced by the present invention.
  • FIG. 2 is a schematic flow chart of the phosphoric acid of the present invention.
  • Fig. 3 is a schematic view showing the structure of a kiln in the production of yellow phosphorus of the present invention.
  • Fig. 4 is a schematic view showing the structure of a kiln in the production of phosphoric acid according to the present invention.
  • Fig. 5 is a schematic view showing the connection of the furnace group when the phosphoric acid is produced by the furnace group in the present invention.
  • the structure of the vertical sealed kiln of the present invention is as follows: comprising a kiln body 1, the kiln body 1 is mounted on the support 2, the upper part of the kiln body 1 is provided with a hopper 3, and the lower part is provided with a cooling hopper 6, a burner for refueling 7 extends into the kiln body 1 internal closed sealed kiln kiln body 1
  • the furnace is divided into two types of channels: material passage 4 and fuel passage 5.
  • the furnace is divided into material passages 4 and fuel.
  • Channel 5 and phosphorus combustion channel 8 are three types of channels; the channels are sealed by heat transfer refractories.
  • the invention can also be carried out in the form of a vertical closed kiln furnace group in the preparation of phosphoric acid.
  • the vertical closed-air kiln is a kiln group composed of a plurality of kiln furnaces
  • the vertical sealed kiln furnace group is composed of a plurality of interconnected vertical sealed kiln furnaces, each of which is composed of
  • the vertical sealed kiln is connected by a passage 9 for mass transfer heat transfer.
  • One end of the passage 9 is connected to the exhaust port of the material passage 4 of the previous kiln, and the other end is connected to the combustion passage 5 of the next kiln.
  • the invention adopts a vertical sealed kiln as the main reaction equipment to complete the reduction process of the phosphate rock or the reduction and oxidation process of the phosphate rock, and the yellow phosphorus can be obtained by spraying the phosphorus vapor with water spray, or the phosphorus vapor and the carbon monoxide can be obtained.
  • the phosphoric acid is oxidized and then absorbed by circulating acid spray to obtain phosphoric acid.
  • the embodiment of the invention is: firstly, the unloading device of the lower part of the vertical sealed kiln is closed, and the material passages in the kiln are all filled with waste slag to form a solid material column. Then the kiln is heated to reach the required temperature, and the mixed ball hopper at the top of the kiln and the lower unloading device are opened. As the lower part is slowly discharged, the ball in the upper hopper gradually enters automatically under the action of gravity. The material channel is heated and reacted to complete the production process.
  • the production process of the invention is as follows: the phosphate ore, the carbonaceous reducing agent is mixed with other ingredients into a spherical material and ground to -100 mesh > 80%, and the selected phosphate rock is P 2 0 5 > 6 ° /.
  • the other ingredients are silica or lime or limestone, and the molar ratio of calcium to silicon in the mixture is Ca: S i ⁇ 0.4 or > 3. 5.
  • a 030 mm ball is formed.
  • the ball material is dried in a roller kiln to a moisture content of less than 2% and then sent to the upper conical hopper 3 of the vertical closed kiln, with the lower hopper of the vertical sealed kiln, the upper hopper
  • the ball inside gradually enters the material passage 4 of the vertical closed kiln, and the temperature is raised to 1300 ° C.
  • the ball is reduced to produce elemental phosphorus vapor and carbon monoxide.
  • the cooling hopper 6 is placed in the lower part of the vertical sealed kiln, and the cooled ball is discharged by the reverse flow heat exchange of the cold gas and the hot ball.
  • phosphoric acid When producing phosphoric acid, it can be oxidized into phosphorus pentoxide and carbon dioxide by adding an appropriate amount of combustion air into the phosphorus combustion passage 8 of the vertical sealed kiln, and then extracted and absorbed by circulating acid spray. Concentration of phosphoric acid, the heat released by oxidation is conducted to the material through the refractory partition to support the heat required for the reduction of phosphorus in some of the furnaces.
  • the produced elemental phosphorus vapor and carbon monoxide are returned to the kiln, and an appropriate amount of air is introduced to oxidize it into phosphorus pentoxide and carbon dioxide, and the released heat is used to supplement the heat required for the reduction reaction, and then the pentoxide is included.
  • the kiln gas of phosphorus is extracted and absorbed by circulating acid spray to obtain a high concentration of phosphoric acid.
  • Figure 3 is a schematic diagram of a vertical sealed smoke-free kiln made of yellow phosphorus.
  • the kiln body is seated on the support 2, and the ball falls into the hopper 3.
  • the ball in the whole kiln is slowly downward. The state of motion.
  • the ball After the ball enters the material passage 4 in the kiln, it exchanges heat with the rising phosphorus vapor and carbon monoxide and replenishes it with fuel heating, and gradually heats up to 1320. C, thereby reacting and generating phosphorus vapor and carbon monoxide.
  • the ball material enters the cooling hopper 6 by its own weight, exchanges heat with the charged cold gas, and is cooled and discharged.
  • the phosphorus vapor and carbon monoxide after heat exchange are extracted from the upper end of the kiln, and then cooled with water to obtain yellow. Phosphorus, recovered carbon monoxide can be used as a fuel.
  • the replenished fuel is injected from the burner 7 and burned in the fuel combustion chamber 5 in the kiln, and the flue gas is withdrawn from the upper portion of the combustion chamber for drying the pellet.
  • Figure 4 is a schematic diagram of a vertical sealed smoke-free kiln of phosphoric acid. Different from yellow phosphorus, the phosphorus vapor and carbon monoxide after heat exchange are extracted from the upper end of the kiln and then filled into a separate phosphorus combustion passage 8 in the kiln to supplement the appropriate amount of air. It is burned to produce the same flame temperature as the fuel combustion to supply heat for the reduction reaction, and then the kiln gas containing phosphorus pentoxide is extracted and circulated by the acid leaching acid spray to obtain a high concentration of phosphoric acid.
  • Figure 5 is a schematic view of the kiln connection when the phosphoric acid is produced by the furnace group method, and the phosphorus vapor and carbon monoxide generated in the material passage in the vertical sealed kiln are taken out, and enter the other kiln through the passage between the kiln, as Fuel burning.
  • the preparation and reaction process of this kiln is the same as above.
  • the phosphorus vapor and carbon monoxide generated in the vertical sealed kiln are sent to another kiln through the passage or partially supplied to the kiln, and partially supplied to other kiln, thereby completing the joint production of the vertical sealed kiln furnace group.
  • phosphoric acid is obtained by concentrating and absorbing the phosphorus pentoxide produced by combustion in all vertical muffle furnaces.
  • the phosphorus vapor and carbon monoxide generated by the external fuel heating are taken out from the exhaust port 10 at the upper portion of the material passage 4, and sent to the combustion passage 5 of the other vertical sealed kiln furnace through the passage 9 for combustion heating, and the kiln is produced.
  • the phosphorus vapor and carbon monoxide are sent to the next vertical closed kiln. This completes the joint production of the entire kiln group.
  • the amount of gas is completely under control.
  • the length of the material is 1. 4m, the length of the material is 1. 4m, the width is 0. 35m, the height is 4. 9m; the phosphorus combustion channel and the fuel channel are 1. 4m, Width of 0. 24m, height of 4. 9m, heat transfer between the channels refractory material is 80mm thick, made of electricity Melted corundum bricks; 3 material channels, 2 phosphorus combustion channels and 2 fuel channels.
  • the 035 surface having a moisture content of not more than 2% after drying is prepared.
  • the ball material is transported to the top hopper of the kiln body, and the unloading device is opened. After continuous discharge, the ball material enters the material passage under the action of natural gravity, and is heated to the reaction temperature to generate phosphorus vapor and carbon monoxide. After the ball material is completely reacted, it enters the cooling hopper from the material passage, exchanges heat with 98% nitrogen shielding gas charged from the lower part of the cooling hopper, and then is discharged from the discharge facility. The nitrogen gas exchanges with the ball material and flows back to the high temperature reaction zone to protect the generated phosphorus and C0.
  • the cold ball material is heated upwards in the countercurrent flow, and is discharged from the upper part of the material passage at about 400 , and then sent to the phosphorus combustion passage to supplement the proper amount of combustion air. It is oxidized by combustion, and the heat released is used to supplement the heat of the reduction reaction.
  • the kiln gas containing phosphorus pentoxide is extracted from the upper part of the phosphorus combustion passage into the hydration tower for cyclic spray absorption to obtain phosphoric acid.
  • the natural gas and the combustion air and the collected CO mixed gas are introduced into the fuel combustion kiln, and the combustion exhaust gas is discharged in the kiln and then discharged for use as a material ball to be dried.

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Description

一种用立式密闭隔烟窑炉
生产黄磷或磷酸的方法及设备 技术领域
本发明涉及一种用立式密闭隔烟窑炉生产黄磷或磷酸的方 法； 本发明还涉及用立式密闭隔烟窑炉生产黄磷或磷酸过程中所 使用的立式密闭隔烟窑炉。
背景技术
磷酸制取工艺发展至今， 其主要工艺有两种： （1 )湿法： 用 硫酸分解中高品位磷矿石制取磷酸， 该方法需要大量优质磷矿石 和硫酸， 同时产生大量磷石膏废渣难以利用， 湿法磷酸杂质含量 高， 净化工艺复杂， 成本高， 而且目前国内疏磺价格持续居于高 位， 导致湿法磷酸成本也大幅上涨； （2 )热法： 用电炉法还原磷 矿石以生产单质黄磷， 然后在燃烧塔内燃烧吸收制取磷酸， 该方 法需要大量电能 （生产每吨黄磷耗电 15000— 16000 kwh ) 和中高 品位磷矿块矿， 且环境污染严重， 这也几乎是目前全世界生产黄 磷的唯一方法， 但许多发达国家限制使用热法生产黄磷。
窑法磷酸是区别于湿法和热法的第三种方法， 其反应原理与 热法磷酸相似， 但混合料进行固相反应， 且将磷单质的还原与氧 化过程置于一个设备中， 这样磷单质与副产的一氧化碳燃烧释放 的热量可以用来提供磷单质还原所需的热量， 大大节省能耗， 同 时可利用 P205 > 10%的中低品位磷矿石， 大大拓宽了磷矿是直接利 用的品位范围。 然而此工艺还未能十分成功应用在规模化工业生 产中。
窑法磷酸的思路于 20世纪 30年代就已被提出， 美国的西方 石油公司曾投入大量的精力进行研究， 但由于工程化难度太大而 最终放弃。
窑法磷酸长时间以来有两条研究路线： 一是回转窑法磷酸， 二是隧道窑法磷酸， 主要是以磷还原与氧化过程所在的主反应器 的不同来区分的。 （1 ) 回转窑： 是一种重载、 大扭矩、 多支点、 筒状中空窑炉运行系统；球状物料在窑内随着窑体的旋转而运动， 磷的还原在还原区进行， 磷的氧化在氧化区进行， 还原区和氧化 区都在窑体内； 燃料在窑内燃烧直接供热； （2 )隧道窑： 一般是 一条长的直线型隧道， 其两侧及顶部有固定的墙壁及拱顶， 底部 铺设的轨道上运行着窑车， 燃烧设备设在隧道窑的中部两侧； 采 用隔烟或明焰烧成， 物料放在窑车上， 经过预热带、 高温带和冷 却带。
回转窑的主要困难是窑头结圏， 出气温度过高， 粉尘大以及 化学保护代价大； 隧道窑的主要难题是坯体保护材料的耐温防腐 要求高、 隧道窑热效率较低等。
发明内容
本发明的目的是提供一种能够克服回转窑和隧道窑的缺陷， 能够较好地实现窑法磷酸工业化生产的用立式密闭隔烟窑炉生产 黄磷或磷酸的方法； 本发明的另一个目的是提供生产过程中所使 用的立式密闭隔烟窑炉。
本发明的目的是这样实现的: 一种用立式密闭隔烟窑炉生产 黄磷或磷酸的方法， 将磷矿石、 碳质还原剂与其他配料制成球形 物料； 球形物料从立式密闭隔烟窑炉上部加入， 依靠重力向下运 行， 反应在固相状态下进行， 在立式密闭隔烟窑炉内物料被加热 还原成磷蒸气， 将磷蒸气冷却得到黄磷或将磷蒸气引入立式密闭 隔烟窑炉内的磷燃烧通道， 被充入的空气氧化成为五氧化二磷， 然后水合吸收制成磷酸； 反应后的固体物料残渣经过换热冷却后 从窑炉下部卸出。
物料在固相条件下完成磷的还原反应， 物料的熔融部分为物 料总量的 0-30%。
选用的磷矿中 P205 > 6%, 碳质还原剂为焦碳、 煤或煤 石， 磷矿石与碳质还原剂按照有效成分摩尔比为： P205 : C=l : 5-10。
其他配料为硅石或石灰或石灰石， 球形物料中钙硅摩尔比为 Ca: S i < 0. 4或 > 3. 5。
在制备成球形物料过程中粘接剂， 粘接剂为水和磷酸配制成 的浓度为 10 - 30%稀磷酸， 粘接剂的加入量为制成球形物料中 用干基物料重量的 0. 1— 3%。
一种立式密闭隔烟窑炉， 包括窑体， 窑体安装在支撑上， 窑 体上部设有料斗， 下部设有冷却料斗， 用于补充燃料的烧嘴伸入 到窑体内， 立式密闭隔烟窑炉窑体在制黄磷时炉内分为物料通道 和燃料通道两类通道； 制磷酸时炉内分为物料通道、 燃料通道和 磷燃烧通道三类通道； 各种通道间用传热耐火材料密闭隔开 。
在制备磷酸时所用立式密闭隔烟窑炉是由单个窑炉组成或多 个窑炉构成的窑炉群， 立式密闭隔烟窑炉群以多个相互联系的立 式密闭隔烟窑炉为基础组成， 各个立式密闭隔烟窑炉之间通过用 于传质传热的通道连接。
通道一端与上一窑炉的物料通道的排气口连接， 另一端与下 一窑炉的燃料通道进口连接。
本发明所提供的用立式密闭隔烟窑炉生产黄磷或磷酸的方 法， 混合料从立式密闭隔烟窑炉顶部或上部加入， 物料依靠重力 向下运行， 在固相状态下发生反应， 反应后的固体物料残渣经过 换热冷却后从窑炉底部或下部卸出。 这种方法是除隧道窑法磷酸 和回转窑法磷酸外的第三条可行路线， 并可以灵活地对生产黄磷 或是磷酸进行调整。 生产磷酸时磷单质与一氧化碳燃烧产生的热 量通过隔墙传导给物料通道中的球料，以供应还原反应所需热能， 从而实现了窑法磷酸的核心思想， 大量节省了能源消耗。
本发明和隧道窑法磷酸与回转窑法磷酸的对比：
1、 外表面不需要加包裹剂， 简化了工艺， 降低了成本， 且完 全去除了包裹剂所占球料的质量，使单位质量球料的产磷率更高。
2、隔烟燃烧加热有效区分开了立式密闭隔烟窑炉内的还原气 氛与氧化气氛， 根本解决了混合球料在升温的过程中碳质被提前 氧化的问题， 减少了复合球团中碳质还原剂的用量； 物料发生还 原反应产生磷单质时， 磷不会马上氧化， 而是在磷燃烧通道内燃 烧氧化， 从而解决了磷在料球表面氧化反吸的问题。 磷的燃烧在 可控有序状态下进行。
3、 大量减少了球料间的摩擦， 极大地减少了粉尘的产生， 从 而提高磷酸盾量。
4、相比于隧道窑不需要窑车，从而大大减少了窑具带出热耗， 降低了能耗； 相比于回转窑， 除了单位质量产磷率更高外， 减少 了回转窑旋转的能耗。
5、立式密闭隔烟窑炉上部和下部的料斗与冷却料斗内数米高 的球料料柱能有效地保证立式密闭隔烟窑炉内的密封， 防止外部 气体进入窑炉内， 从而真正保证还原气氛， 并减少吸收窑气处理 量。
6、燃料燃烧产生的尾气不含磷、 氟等毒性和腐蚀性较强的气 体， 易于热量回收综合利用， 而且窑气由于没有尾气的加入， 气 量减少， 降低了水合系统的处理量， 节省了投资和生产电能消耗。
7、磷酸质量不受燃料种类影响，使窑法磷酸不再局限于天然 气， 还可以使用一般的煤粉， 从而再次降低能源费用， 从而大大 降低生产成本。
本发明在制备磷酸时还可采用立式密闭隔烟窑炉群的方式进 行。 立式密闭隔烟窑炉群以多个相互联系的立式密闭隔烟窑炉为 基础组成， 采用炉群的生产方式拓展了单个立式密闭隔烟窑炉生 产磷酸的思想， 将单个窑炉使用磷蒸气与一氧化碳自供部分热量 的思路拓宽到由多个立式密闭隔烟窑炉组成的窑炉群， 在窑炉之 间完成通过传质 （磷蒸气与一氧化碳） 达到传热的目的的过程， 简化了窑炉结构， 方便了控制， 提高了安全性， 同时便于更加充 分地利用磷蒸气与一氧化碳燃烧的热量， 提高了热量的综合利用 水平。 使磷的还原和氧化在受控状态下有序进行。
附图说明
图 1是本发明制黄磷的流程方框示意图。
图 2是本发明制磷酸的流程方框示意图。
图 3是本发明生产黄磷时的窑炉结构示意图。
图 4是本发明生产磷酸时的窑炉结构示意图。
图 5是本发明以炉群方式生产磷酸时炉群连接示意图。
具体实施方式
本发明的立式密闭隔烟窑炉结构如下： 包括窑体 1， 窑体 1 安装在支撑 2上， 窑体 1上部设有料斗 3， 下部设有冷却料斗 6， 用于补充燃料的烧嘴 7伸入到窑体 1 内立式密闭隔烟窑炉窑体 1 在制黄磷时炉内分为物料通道 4和燃料通道 5两类通道； 制磷酸 时炉内分为物料通道 4、 燃料通道 5和磷燃烧通道 8三类通道； 各种通道间用传热耐火材料密闭隔开 。
本发明在制备磷酸时还可采用立式密闭隔烟窑炉群的方式进 行。 立式密闭隔烟窑炉是由多个窑炉构成的窑炉群， 立式密闭隔 烟窑炉群以多个相互联系的立式密闭隔烟窑炉为基础组成， 各个 立式密闭隔烟窑炉之间通过用于传质传热的通道 9连接。 通道 9 一端与上一窑炉的物料通道 4的排气口连接， 另一端与下一窑炉 的燃烧通道 5进品连接。
本发明的工作原理叙述如下：
本发明是以立式密闭隔烟窑炉为主要反应设备来完成磷矿的 还原过程或磷矿的还原与氧化过程， 通过用水喷淋冷却磷蒸气可 制得黄磷， 或将磷蒸气与一氧化碳返回立式密闭隔烟窑炉中的磷 燃烧通道氧化后再通过循环酸喷淋吸收可制得磷酸。
本发明的实施方式为： 先将立式密闭隔烟窑炉下部的卸料装 置关闭，将窑炉内物料通道全部用废渣料填满，形成充实的料柱。 然后窑炉进行升温， 达到要求的温度后， 将窑炉顶部的混合球料 料斗和下部的卸料装置打开， 随着下部緩慢地卸料， 上部料斗内 的球料在重力作用下逐渐自动进入物料通道， 经过升温、 反应， 完成生产过程。
本发明的生产工艺为： 将磷矿石、 碳质还原剂与其他配料制 成球形物料混合后磨细至 -100目 > 80%, 选用的磷矿中 P205 > 6°/。， 碳质还原剂为焦碳、 煤或煤矸石， 磷矿石与碳质还原剂按照有效 成分摩尔比为： P205: C=l : 5-10。 其他配料为硅石或石灰或石灰 石， 混合物中钙硅摩尔比为 Ca: S i < 0. 4或> 3. 5。
在成球盘成球的过程中喷入浓度为 10% - 30%稀磷酸作为粘 接剂， 粘接剂的加入量为制成球形物料中所用干基物料重量的 0. 1— 3%, 以加强球料的强度， 形成 030mm的球料。 球料在辊道 烘干窑内烘干至水分含量低于 2%后被送入立式密闭隔烟窑炉上 部锥形料斗 3， 随着立式密闭隔烟窑炉下部排料， 上部料斗内的 球料逐渐进入立式密闭隔烟窑炉物料通道 4内， 升温至 1300°C， 球料发生还原反应生成单质磷蒸气和一氧化碳。球料反应完全后， 进入立式密闭隔烟窑炉下部冷却料斗 6， 通过充入冷气体与热球 料逆流换热， 冷却后的球料排出。
生产黄磷时， 产生的磷蒸气和一氧化碳直接抽出， 使用水进 行喷淋冷却后即可得到黄磷，一氧化碳经过收集可作为燃料使用。
生产磷酸时， 通过补入适量的助燃空气进立式密闭隔烟窑炉 磷燃烧通道 8内， 使磷和一氧化碳氧化成为五氧化二磷和二氧化 碳， 然后抽出使用循环酸喷淋吸收即可得到高浓度磷酸， 氧化释 放的热量通过耐火隔墙传导给物料， 用以支持部分窑炉内磷的还 原所需的热量。
制黄磷时， 磷矿石、 焦炭、 硅石或石灰或石灰石按比例混合 后粉磨成细粉，在成球过程中加入粘接剂，原料比例和生产磷酸时 相同， 再将得到的球料烘干， 送入立式密闭隔烟窑炉上部料斗。 在重力作用下球料緩慢进入窑炉内， 升温至 1250— 1500 发生反 应，产生单质磷蒸气和一氧化碳，将其引出用水冷却即得到黄磷， 收集一氧化碳作为燃料使用。
制磷酸时， 将产生的单质磷蒸气与一氧化碳返回窑炉内， 通 入适量空气使其氧化成五氧化二磷和二氧化碳， 释放的热量用以 补充还原反应所需热量， 再将含五氧化二磷的窑气抽出， 用循环 酸喷淋吸收即得到高浓度的磷酸。
图 3是制黄磷立式密闭隔烟窑炉示意图， 窑体 1座在支撑 2 上， 球料落入料斗 3内， 在匀速下料的情况下， 整个窑内的球料 呈緩慢向下运动的状态。 球料进入窑内物料通道 4后， 与上升的 磷蒸气和一氧化碳换热并补充以燃料加热， 逐渐升温至 1320。C , 从而发生反应并生成磷蒸气和一氧化碳， 反应完全后， 球料依靠 自重向下进入冷却料斗 6， 与充入的冷气体换热， 冷却后排出。 换热后的磷蒸气与一氧化碳从窑上端抽出， 用水冷却后即得到黄 磷， 回收的一氧化碳可作为燃料使用。补充的燃料从烧嘴 7喷入， 在窑内燃料燃烧室 5内燃烧， 烟气从燃烧室上部抽出， 用于烘干 球料。
图 4是制磷酸立式密闭隔烟窑炉示意图， 与制黄磷不同的是 换热后的磷蒸气与一氧化碳从窑上端抽出后再充入窑内单独的磷 燃烧通道 8， 补充适量的空气使其燃烧， 产生与燃料燃烧相同的 火焰温度为还原反应供热， 然后将含五氧化二磷的窑气抽出经水 合塔循环酸喷淋吸收即可制得高浓度磷酸。
图 5是采用炉群方式生产磷酸时的窑炉连接示意图， 立式密 闭隔烟窑炉内物料通道内生成的磷蒸气和一氧化碳被引出， 通过 窑炉间的通道进入另一窑炉， 做为燃料燃烧。 此窑炉升温前准备 和反应过程都同上。 再将此立式密闭隔烟窑炉内产生的磷蒸气和 一氧化碳通过通道全部送往另一窑炉或部分供给自身， 部分供给 其他窑炉， 从而完成立式密闭隔烟窑炉群的联合生产。 最终将所 有立式隔焰窑炉内经燃烧生成的五氧化二磷集中水合吸收即可得 到磷酸。
使用外部燃料供热产生的磷蒸气和一氧化碳从物料通道 4上 部的排气口 10抽出，经通道 9送往另一立式密闭隔烟窑炉的燃烧 通道 5进行燃烧供热， 此窑炉产生的磷蒸气与一氧化碳再送往下 一立式密闭隔烟窑炉。 这样完成整个窑炉群的联合生产。 气体量 的大小完全在受控状态。
实例：
一条生产 3000吨 85%磷酸 /年的立式密闭隔烟窑炉中试生产 线。 立式密闭隔烟窑炉总长 4. 5m， 宽 3. 9m， 高 20. 0m; 物料通道 长 1. 4m， 宽 0. 35m， 高 4. 9m; 磷燃烧通道与燃料通道长 1. 4m， 宽 0. 24m, 高 4. 9m， 各通道之间的传热耐火材料厚 80mm， 材质为电 熔刚玉砖； 共设 3个物料通道， 2个磷燃烧通道， 2个燃料通道。 升温前先将卸料装置关闭， 用废渣将窑炉内冷却料斗和物料通道 充满， 然后点火升温， 待达到要求的温度后， 将制好经烘干后水 分含量不超过 2%的 035麵的球料输送至窑体顶部料斗，打开卸料 装置， 经过不断地排料使球料在自然重力作用下进入物料通道， 升温至反应温度， 产生磷蒸气和一氧化碳。 球料反应完全后从物 料通道进入冷却料斗， 与从冷却料斗下部充入的 98%氮气保护气 进行换热， 然后从排料设施排出。 氮气与球料换热并逆流至高温 反应带保护生成的磷和 C0， 再逆流向上加热冷球料， 约于 400 Ό 时从物料通道上部排出， 再输送入磷燃烧通道， 补充适量的助燃 风使其燃烧氧化， 释放的热量用以补充还原反应需热， 含五氧化 二磷的窑气从磷燃烧通道上部抽出进入水合塔进行循环喷淋吸 收，制取磷酸。将天然气与助燃空气和收集到的 CO混合气通入燃 料燃烧窑， 燃烧尾气在窑内折流换热后排出用作料球烘干。
利用立式密闭隔烟窑作为主反应器制磷酸， 与电炉制黄磷相 比， 由于充分利用了磷与一氧化碳燃烧释放的热量， 使得窑炉能 耗降低了 60%以上， 磷酸质量和电炉法黄磷制酸基本持平， 磷酸 产品成本降低了约 40%。

Claims

1、 一种用立式密闭隔烟窑炉生产黄磷或磷酸的方法， 其特征 在于： 将磷矿石、 碳质还原剂与其他配料制成球形物料； 球形物 料从立式密闭隔烟窑炉上部加入， 依靠重力向下运行， 反应在固 相状态下进行，在立式密闭隔烟窑炉内物料被加热还原成磷蒸气， 将磷蒸气冷却得到黄磷或将磷蒸气引入立式密闭隔烟窑炉内的磷 燃烧通道， 被充入的空气氧化成为五氧化二磷， 然后水合吸收制 成磷酸；反应后的固体物料残渣经过换热冷却后从窑炉下部卸出。
2、 根据权利要求 1所述的用立式密闭隔烟窑炉生产黄磷或磷 酸的方法， 其特征在于： 物料在固相条件下完成磷的还原反应， 物料的熔融部分为物料总量的 0-30%。
3、 根据权利要求 1所述的用立式密闭隔烟窑炉生产黄磷或磷 酸的方法， 其特征在于： 选用的磷矿中 P205 > 6%， 碳质还原剂为 焦碳、煤或煤矸石，磷矿石与碳质还原剂按照有效成分摩尔比为： P205: C=l : 5-10。
4、 根据权利要求 1所述的用立式密闭隔烟窑炉生产黄磷或磷 酸的方法， 其特征在于： 其他配料为硅石或石灰或石灰石， 球形 物料中钙硅摩尔比为 Ca: S i < 0. 4或> 3. 5。
5、 根据权利要求 1所述的用立式密闭隔烟窑炉生产黄磷或磷 酸的方法， 其特征在于： 在制备成球形物料过程中粘接剂， 粘接 剂为水和磷酸配制成的浓度为 1 0 - 30%稀磷酸, 粘接剂的加入量 为制成球形物料中所用干基物料重量的 0. 1— 3%。
6、 一种立式密闭隔烟窑炉， 包括窑体（1 ) ， 窑体（1 ) 安装 在支撑 （2 )上，
其特征在于： 窑体（1 )上部设有料斗 （3 ) ， 下部设有冷却 料斗（6) ， 用于补充燃料的烧嘴（7)伸入到窑体（1) 内， 立式 密闭隔烟窑炉窑体（1)在制黄磷时炉内分为物料通道（4) 和燃 料通道（5) 两类通道； 制磷酸时炉内分为物料通道（4) 、 燃料 通道（5) 和磷燃烧通道（8) 三类通道； 各种通道间用传热耐火 材料密闭隔开 。
7、 根据权利要求 1所述的用立式密闭隔烟窑炉生产黄磷或磷 酸的方法， 其特征在于： 在制备磷酸时所用立式密闭隔烟窑炉是 由单个窑炉组成或多个窑炉构成的窑炉群， 立式密闭隔烟窑炉群 以多个相互联系的立式密闭隔烟窑炉为基础组成， 各个立式密闭 隔烟窑炉之间通过用于传质传热的通道（9)连接。
8、 根据权利要求 7所述的用立式密闭隔烟窑炉生产黄磷或磷 酸的方法，其特征在于：通道（9)一端与上一窑炉的物料通道（4) 的排气口连接， 另一端与下一窑炉的燃料通道（5) 进口连接。
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CN107816887A (zh) * 2016-09-14 2018-03-20 马松怀 一种新型生物质化铁炉
CN112624069A (zh) * 2019-10-09 2021-04-09 车建青 基于氧热法的黄磷制备工艺
CN113336207A (zh) * 2021-06-30 2021-09-03 昆明理工大学 黄磷与合成气的联合生产系统
CN114485172A (zh) * 2022-01-20 2022-05-13 陆彦霖 一种黄磷气化燃烧炉

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