WO2010075670A1 - 用于在高炉中生产磷酸的方法及用于焙烧泥磷并回收热量的装置 - Google Patents

用于在高炉中生产磷酸的方法及用于焙烧泥磷并回收热量的装置 Download PDF

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WO2010075670A1
WO2010075670A1 PCT/CN2009/001533 CN2009001533W WO2010075670A1 WO 2010075670 A1 WO2010075670 A1 WO 2010075670A1 CN 2009001533 W CN2009001533 W CN 2009001533W WO 2010075670 A1 WO2010075670 A1 WO 2010075670A1
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phosphorus
blast furnace
mud
phosphoric acid
roasting
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PCT/CN2009/001533
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French (fr)
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马叔骥
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贵州众一联创科技开发有限责任公司
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Publication of WO2010075670A1 publication Critical patent/WO2010075670A1/zh

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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27BFURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B15/00Fluidised-bed furnaces; Other furnaces using or treating finely-divided materials in dispersion
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/12Oxides of phosphorus
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/16Oxyacids of phosphorus; Salts thereof
    • C01B25/18Phosphoric acid
    • C01B25/185Preparation neither from elemental phosphorus or phosphoric anhydride nor by reacting phosphate-containing material with an acid, e.g. by reacting phosphate-containing material with an ion-exchange resin or an acid salt used alone
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

Definitions

  • the present invention relates to the field of phosphoric acid technology, and more particularly to a method and apparatus for producing phosphoric acid using a blast furnace.
  • the grade of phosphate rock resources is high, and the content of various metal oxides and non-metal oxides is low, so that the high-grade phosphate rock with limited reserves can only be used through certain beneficiation processes; and accounting for more than 90%.
  • Medium and low grade phosphate rock is simply not directly usable. As a result, the supply of phosphorus resources has become increasingly tight.
  • the large amount of heat required in the smelting process of the blast furnace is generated by the high-temperature hot air blown into the furnace to burn coke and coal. Therefore, not only the phosphorus vapor but also a large amount of dust is contained in the produced blast furnace gas, and the test is carried out.
  • the amount of dust is about 10 times that of the electric furnace smelting furnace gas.
  • the blast furnace smelting is a highly reinforced smelting device, and its production intensity is higher than that of the electric furnace. More than one order of magnitude, although it is very favorable for future industrialization, it is very unfavorable for the recovery rate of the regenerated phosphorus, resulting in a low recovery rate of reduced phosphorus.
  • Phosphorus smelting is a new process with high energy consumption. Therefore, how to save energy and reduce consumption is also an important part of the invention.
  • the "prioritized oxidation" of the original invention is not only dangerous in the production process (although it can also be controlled: ), and phosphorus is produced during preferential oxidation Heat is difficult to recycle.
  • the technical problem to be solved by the present invention is to solve the deficiencies of the prior art and provide a new method for producing blast furnace phosphoric acid, which can solve the problem that the existing blast furnace phosphoric acid is easy to generate explosion when "prioritized oxidation", and the total amount of phosphoric acid produced in the blast furnace is The phosphorus recovery rate is increased to more than 80%. At the same time, the existing equipment is improved to better recover the heat generated by the oxidative combustion of the mud phosphorus.
  • the present invention adopts the following technical solutions:
  • the invention uses the blast furnace to produce phosphoric acid: the phosphate ore is subjected to blast furnace smelting and batching, blast furnace smelting, blast furnace gas recovery of mud phosphorus, phosphorus phosphorus oxidation combustion and cyclic absorption of P 2 0 5 to prepare phosphoric acid.
  • the temperature at which the phosphorus phosphorus is oxidized and burned is controlled at 800 to 1000 ° C, and the amount of air required is 1.5 to 2 times the amount of air required for oxidation of the phosphorus contained in the mud phosphorus.
  • a three-stage recovery method for recovering mud phosphorus from a blast furnace gas
  • the first stage is a wet water bath dust collection and recovery
  • the second stage is jet recovery
  • the third stage is a venturi tube recovery. More than 98% of phosphorus-containing dust can be recovered through three-stage recovery.
  • Mud phosphorus produces a large amount of heat during oxidative combustion, and the calorific value can be as high as 6100 kcal/kgp 2 . (Corresponding to 25.5 X 10 3 kJ / kgP 2), in order to better take advantage of this part of the heat, the oxide of phosphorus sludge combustion furnace gases generated by natural circulation heat recovery boiler and recycled P 2 absorbed by a plurality of vertical flue 0 5 Preparation of phosphoric acid.
  • the present invention also provides a mud-phosphorus boiling roasting and heat recovery device, which is a mud-boil boiling roaster 1 and
  • the vertical multi-flue natural circulation boiler 2 is composed of a feed port 3 and an overflow ash discharge port 6 on one side of the mud-phosphorus boiling roaster 1 , and the hood layer 5 is located at the feed port 3 and the overflow ash discharge port 6 Below, the air inlet 4 is provided at the bottom of the mud-phosphorus boiling roaster 1, and below the vertical multi-flue circulating boiler 2 is an ash discharge hopper 8 to which the steam pipe 7 is connected.
  • the vertical multi-flue circulating boiler 2 may be connected to the dust deposition chamber 9, and one side of the dust deposition chamber 9 is provided with a furnace gas discharge P10.
  • the invention adopts the method of first recovering mud phosphorus and then oxidizing and burning the mud phosphorus, not only can utilize the low-grade phosphate rock to produce blast furnace phosphoric acid, but also completely solves the problem that the blast furnace produces an explosion when the phosphoric acid is preferentially oxidized.
  • the problem is to increase the recovery rate of reducing phosphorus in the phosphating process of phosphoric acid to 98%, and combine the mud-phosphorus boiling roaster and the vertical multi-flue natural circulation boiler to recover the heat generated by the mud-phosphorus combustion, which is a high-energy blast furnace.
  • the phosphoric acid process has great practical significance in terms of energy saving, consumption reduction and comprehensive development and utilization.
  • FIG. 1 is a schematic view showing the structure of a mud-phosphor boiling roasting and heat recovery apparatus according to the present invention.
  • the weight ratio of 0.15-0.5 is sent to the blast furnace for smelting.
  • the blast furnace gas smelted by the blast furnace is firstly subjected to the first stage mud phosphorus recovery by the wet water bath dust collector, and the high level after the first stage mud phosphorus recovery.
  • the phosphorus-containing dust that has not been removed from the furnace gas is then injected into the second-stage mud-phosphorus recovery device to spray the dust collector.
  • the jet dust collector can further reduce the temperature of the blast furnace gas, and at the same time, the mud-phosphorus dust is recovered and recovered.
  • the fine mud phosphorus is then passed through the third-stage mud-phosphorus tube recovery device, so that the recovery effect can reach more than 98%.
  • All the recovered mud phosphorus is collected, sent from the feed port 3 to the mud phosphorus boiling roaster and the heat recovery device, and the mud phosphorus is oxidized and burned in the mud phosphorus boiling roaster 1 , and the air is blown in from the air inlet 4 and enters through the hood 5 5 ⁇ 2 ⁇ ,
  • the amount of air required for the oxidation of phosphorus in the phosphorus phosphorus is 1. 5 ⁇ 2 times
  • the temperature of the phosphorus in the mud phosphorus boiling roaster 1 is controlled at 800-1000 °C
  • the dust deposited during the mud-phosphorus boiling roasting process is discharged from the overflow ash discharge pipe 6.
  • the furnace gas of the mud-phosphorus boiling roasting contains a relatively large amount of heat, so the vertical multi-flue natural circulation boiler 2 is used to recover the heat, and the dust deposited in the process of recovering heat enters the ash discharge hopper 8, and the generated steam pressure is about 2.45 MPa.
  • the medium temperature medium pressure steam is recovered by the steam pipe 7.
  • the roasting furnace gas from the vertical multi-flue natural circulation boiler 2 is subjected to a settling dust in the dust deposition chamber 9, and then discharged from the furnace gas outlet 10, and the discharged roasting furnace gas is cyclically absorbed by a conventional method to prepare phosphoric acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Description

用于在高炉中生产磷酸的方法及用于焙烧泥
磷并回收热量的装置 技术领域
本发明涉及磷酸技术领域,特别是涉及一种使用高炉生产磷酸的 方法及所用设备。
背景技术
作为与世界各国农业发展紧密相关的化肥工业已完成了从无到 有, 从小到大, 从单一低效到高效复合肥产品的三大歩发展, 而当今 世界各国的高效复肥工业又无一不是建立在以优质硫、 磷资源和石 油、天然气能源的基础上, 因为, 当今世界 70%的合成氨是以天然气 为原料生产的,而合成氨是生产占当今世界高效复肥 70%的主导产品 ——磷铵的二大主要原料之一, 作为另一更为重要原料的 "湿法"磷 酸又是建立在优质硫、磷资源的基础上, 尤其目前作为优质硫资源的 硫磺, 90%以上来源于对含硫石油、 天然气的提取。 所以, 支撑当今 世界各国农业发展的化肥工业, 完全可以毫不夸张地说是建立在石 油、 天然气能源的基础上, 但石油、 天然气是不可再生的有限资源; 所以, 虽然 "湿法"磷酸具有工艺成熟, 能大规模生产的优点, 但这 种传统生产工艺发展到今天,已逐渐突显其结构上种种难于克服的如 下严重弊端。
1、 石油、 天然气等不可再生有限资源的短缺, 世界迟早会面临 严重的能源危机; 同样, 也将面临优质硫磺资源的稳定供应问题。 2、 量大且集中的白色磷石膏所造成的严重污染。
3、 磷矿资源品位要求高, 而且各种金属氧化物和非金属氧化物 的含量要低,致使目前储量有限的高品位磷矿也要通过一定的选矿工 艺才能使用; 而占 90%以上的中、低品位磷矿, 更是根本无法直接利 用。 从而造成磷资源的供应越来越紧张。
4、 "湿法"磷酸工艺冗长、 复杂, 基建投入巨大, 生产过程腐蚀 严重、维护工作量大, 产品质量离现在大力倡导的绿色农产品的要求 还有相当的差距, 生产成本偏高。
本发明申请人于 1998年 7月 20日提出的"高炉磷酸的生产方法 及所用设备"提出了一种建立在煤、磷资源基础上的非硫工艺来生产 磷酸的热法新工艺, 并获得了授权。经过进一歩的研究发现, 该发明 专利还存在一些不足:
1、 在高炉冶炼过程中需要的大量热量是由鼓入炉内的高温热风 燃烧焦、 煤所产生的, 所以, 在产生的高炉煤气中不仅有磷蒸汽, 还 含有大量的粉尘, 经过试验实测, 其粉尘量是电炉炼磷炉气中粉尘量 的 10倍左右, 虽然原工艺有除尘装置, 但由于高炉炼磷是一种高强 化的冶炼装置,其生产强度较电炉黄磷生产强度可提高一个数量级以 上, 这虽然对今后的产业化非常有利, 但对己炼出磷的回收率却非常 不利, 致使还原磷的回收率很低。
2、 高炉炼磷是高能耗的新工艺, 所以, 如何节能降耗也是本发 明需要考虑的重要内容, 原发明的 "优先氧化"不仅在生产过程中存 在相当的危险性 (虽然也可以控制:), 而且磷在优先氧化过程中产生的 热量难以回收利用。
发明内容
本发明所要解决的技术问题是解决现有技术的不足,提供一种新 的高炉磷酸的生产方法, 可以解决现有高炉磷酸在"优先氧化"时易 产生爆炸的问题, 将高炉生产磷酸的总磷回收率提高到 80 %以上, 同时, 对现有设备进行了改进以更好的回收泥磷氧化燃烧产生的热 为了解决上述技术问题, 本发明采用如下的技术方案:
本发明使用高炉生产磷酸的方法: 将磷矿石进行高炉冶炼配料、 高炉冶炼, 高炉气回收泥磷, 将泥磷氧化燃烧后循环吸收 P205制备 磷酸。
上述方法中, 泥磷氧化燃烧时的温度控制在 800〜1000°C, 所需 的空气量为泥磷中所含磷量氧化时所需空气量的 1.5— 2倍。
前述使用高炉生产磷酸的方法,高炉气回收泥磷时采用三级回收 方式, 第一级为湿式水浴除尘回收, 第二级为喷射回收, 第三级为文 氏管回收。 通过三级回收, 可回收 98 %以上的含磷粉尘。
按照重量份计算, 前述方法中高炉冶炼配料的配比为焦或煤: 磷 矿: 石灰石: 硅石 =1 : 1— 1.8: 0.05—0.25: 0.15〜0.5。
泥磷在氧化燃烧时产生大量的热量,热值可高达 6100大卡 /kgp2。 (相当于 25.5 X 103千焦 /kgP2), 为了更好的利用此部分热量, 将泥磷 氧化燃烧所产生的炉气通过立式多烟道自然循环锅炉热量回收后再 循环吸收 P205制备磷酸。 为了使泥磷能很好地氧化生成 P205, 同时回收泥磷燃烧产生的 热量, 本发明还提供了一种泥磷沸腾焙烧及热量回收设备, 它是由泥 磷沸腾焙烧炉 1和立式多烟道自然循环锅炉 2组成,在泥磷沸腾焙烧 炉 1的一侧设有进料口 3和溢流排灰口 6, 风帽层 5位于进料口 3和 溢流排灰口 6的下面,空气入口 4设在泥磷沸腾焙烧炉 1的底部, 立 式多烟道循环锅炉 2的下面有排灰斗 8, 上面连接蒸汽管 7。
为了对泥磷沸腾焙烧炉出来的炉气更好的除尘,还可以将立式多 烟道循环锅炉 2连接灰尘沉降室 9, 灰尘沉降室 9的一侧设有炉气出 P 10。
与现有技术相比, 本发明采用先回收泥磷, 再将泥磷氧化燃烧的 方法, 不仅可以利用中低品位磷矿来生产高炉磷酸, 而且还完全解决 了高炉生产磷酸优先氧化时产生爆炸的问题,并将高炉生产磷酸工艺 中还原磷的回收率提高到 98 %, 联合泥磷沸腾焙烧炉和立式多烟道 自然循环锅炉来回收泥磷燃烧产生的热量,这对高能耗的高炉磷酸工 艺在节能降耗、 进一歩综合开发利用方面, 具有重大的现实意义。
附图说明
图 1为本发明泥磷沸腾焙烧及热量回收设备结构示意图。
具体实施方式
下面结合附图来说明本发明的实施方式: 将磷矿石初歩破碎, 筛 除粉矿, 按照焦或煤: 磷矿: 石灰石: 硅石 =1 : 1-1.8: 0.05-0.25:
0.15-0.5的重量比配料, 送入高炉进行冶炼, 高炉冶炼出来的高炉气 先经湿式水浴除尘器进行第一级泥磷回收,经第一级泥磷回收后的高 炉气中未除去的含磷粉尘, 再进入第二级泥磷回收装置喷射除尘器, 喷射除尘器可以进一歩降低高炉气的温度,同时对泥磷粉尘作进一歩 回收, 还未除去的很细的泥磷再经第三级泥磷文氏管回收装置, 使其 回收效果最终可达 98 %以上。 收集回收的所有泥磷, 从进料口 3送 入泥磷沸腾焙烧炉及热量回收设备, 在泥磷沸腾焙烧炉 1中进行泥磷 氧化燃烧,空气从空气入口 4鼓入,经风帽 5进入泥磷沸腾焙烧炉 1, 泥磷沸腾焙烧炉 1的温度控制在 800— 1000 °C, 所需的空气量为泥磷 中所含磷量氧化时所需空气量的 1 . 5〜2倍, 泥磷沸腾焙烧过程中沉 降的灰尘从溢流排灰管 6排出。泥磷沸腾焙烧的炉气含有较大量的热 量, 所以采用立式多烟道自然循环锅炉 2来回收热量, 回收热量过程 中沉降的灰尘进入排灰斗 8排出,产生的汽包压力约 2.45MPa的中温 中压蒸汽经蒸汽管 7回收。从立式多烟道自然循环锅炉 2出来的焙烧 炉气在灰尘沉降室 9中进一歩沉降灰尘, 然后从炉气出口 10排出, 排出的焙烧炉气采用常规方法循环吸收, 制备磷酸。

Claims

权利要求
1、 一种使用高炉生产磷酸的方法, 其特征在于: 将磷矿石进行 高炉冶炼配料、 高炉冶炼, 高炉煤气回收泥磷, 将泥磷氧化燃烧后循 环吸收 P205制备磷酸。
2、按照权利要求 1所述使用高炉生产磷酸的方法, 其特征在于: 泥磷氧化燃烧时的温度控制在 800~1000°C, 所需的空气量为泥磷中 所含磷量氧化时所需空气量的 1.5~2倍。
3、按照权利要求 1所述使用高炉生产磷酸的方法, 其特征在于: 高炉煤气回收泥磷时采用三级回收方式, 第一级为湿式水浴除尘回 收, 第二级为喷射回收, 第三级为文氏管回收。
4、按照权利要求 1所述使用高炉生产磷酸的方法, 其特征在于: 按照重量份计算, 高炉冶炼配料的配比为焦或煤: 磷矿: 石灰石: 硅 石 =1 : 1.0-1.8: 0.05-0.25: 0· 15~0·5。
5、按照权利要求 1所述使用高炉生产磷酸的方法, 其特征在于: 泥磷氧化燃烧所产生的炉气通过立式多烟道自然循环锅炉回收热量 后再循环吸收 Ρ205制备磷酸。
6、 一种泥磷沸腾焙烧及热量回收设备, 其特征在于: 它是由泥 磷沸腾焙烧炉 (1 )和立式多烟道自然循环锅炉 (2)组成, 在泥磷沸 腾焙烧炉(1 )的一侧设有进料口(3 )和溢流排灰口(6), 风帽层(5 ) 位于进料口 (3 ) 和溢流排灰口 (6) 的下面, 空气入口 (4) 设在泥 磷沸腾焙烧炉 (1 ) 的底部, 立式多烟道循环锅炉 (2) 的下面有排灰 斗 (8), 上面连接蒸汽管 (7)。
7、 按照权利要求 6所述泥磷沸腾焙烧及热量回收设备, 其特征 在于: 立式多烟道循环锅炉 (2) 连有灰尘沉降室 (9), 灰尘沉降室 (9) 的一侧设有炉气出口 (10)。
PCT/CN2009/001533 2009-01-04 2009-12-22 用于在高炉中生产磷酸的方法及用于焙烧泥磷并回收热量的装置 WO2010075670A1 (zh)

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CN110615415A (zh) * 2019-09-27 2019-12-27 成都易态科技有限公司 泥磷处理系统及工艺
CN112506158A (zh) * 2020-12-14 2021-03-16 云南煜锜环保科技有限公司 泥磷蒸馏温度自动化控制系统

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