CN113336207A - 黄磷与合成气的联合生产系统 - Google Patents
黄磷与合成气的联合生产系统 Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 43
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 43
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000003245 coal Substances 0.000 claims abstract description 149
- 238000002309 gasification Methods 0.000 claims abstract description 90
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 76
- 239000011574 phosphorus Substances 0.000 claims abstract description 76
- 239000000843 powder Substances 0.000 claims abstract description 54
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 20
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- 229910019142 PO4 Inorganic materials 0.000 claims description 12
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
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- 239000007787 solid Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
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- 229910052799 carbon Inorganic materials 0.000 claims description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
本发明公开了一种黄磷与合成气的联合生产系统，包括磷煤气化炉，煤粉制备单元的出料口与所述磷煤气化炉的煤粉进入口连接，分单元的出气口与所述磷煤气化炉底部的进气口连接，矿料成型单元与磷煤气化炉顶部的进料口连接，所述磷煤气化炉的炉气出口与分离洗涤单元的进气口连接，所述分离洗涤单元的一个输出口为黄磷产品输出口，所述分离洗涤单元的另一个输出端为粗合成气输出口，所述粗合成气输出口与净化单元的输入口连接，所述净化单元的输出口输出精制合成气，所述磷煤气化炉底部的排渣口与所述炉渣冷萃单元的输入口连接。所述系统能够提高黄磷生产的㶲效能以及黄磷生产能力与合成气产量，减少CO2排放。
Description
技术领域
本发明涉及磷、煤化工技术领域，尤其涉及一种煤气化与磷矿还原反应耦合生产黄磷和合成气的方法。
背景技术
黄磷是一种重要的化工原料，是医药、农药、电子化学品、表面活性剂的基础产品。目前工业上生产黄磷的方法为电炉法，即焦炭在1350-1450℃高温电炉中将磷矿石还原为单质磷，磷矿石还原所需热量均来自电能，每生产1吨黄磷的电耗高达1.38-1.45万度，使用高品位的电能为黄磷生产供热，导致系统㶲效能低，受电炉、电极及导电体的制约，单台磷电炉产量仅为13kt/a，副产的炉气量仅为5000-5500Nm3，难于实现规模化利用。煤气化是煤化工行业中运用最广泛、最成熟的技术之一，是煤基化工品合成的重要环节；在煤气化过程内，煤与纯氧的燃烧区温度高达1800-2000℃，需要利用大量的冷却介质将热量排出以维持系统的热平衡；因此，原有的两个独立系统存在以下问题：①黄磷还原需要电能供给热量；②煤气化过程中产生大量的热需要排出；③碳还原磷矿所产生的CO总量少，难于规模化利用。
发明内容
本发明所要解决的技术问题是如何提供一种能够提高黄磷生产的㶲效能以及黄磷生产能力与合成气产量，减少CO2排放的黄磷与合成气的联合生产系统。
为解决上述技术问题，本发明所采取的技术方案是：一种黄磷与合成气的联合生产系统，其特征在于：包括磷煤气化炉，煤粉制备单元的出料口与所述磷煤气化炉的煤粉进入口连接，用于向磷煤气化炉中输入煤粉，空分单元的出气口与所述磷煤气化炉底部的进气口连接，用于向所述磷煤气化炉内输入氧气，矿料成型单元与磷煤气化炉顶部的进料口连接，用于向所述磷煤气化炉内输送生产用原料，所述磷煤气化炉的炉气出口与分离洗涤单元的进气口连接，所述分离洗涤单元的一个输出口为黄磷产品输出口，所述分离洗涤单元的另一个输出端为粗合成气输出口，所述粗合成气输出口与净化单元的输入口连接，所述净化单元的输出口输出精制合成气，所述磷煤气化炉底部的排渣口与所述炉渣冷萃单元的输入口连接，所述炉渣冷萃单元的输出口输出炉渣。
进一步的技术方案在于：所述磷煤气化炉为固定床反应器，其下部通过烧嘴燃烧空分单元喷入的纯氧和煤粉制备单元输入的煤粉，形成超过1600℃以上的高温煤气化燃烧区，以此燃烧区为界，上部为矿料成型单元输入的块状磷矿石、焦炭、硅石或三者的球状混合物，下部是磷矿还原的熔融区，在高温下发生还原反应生成黄磷，煤气化的CO+H2以及磷蒸气从磷煤气化炉底部逐渐上升到顶部，从导气管送入分离洗涤单元，炉气温度300-700℃，操作压力1.5-3.5MPa。
进一步的技术方案在于：来自空分单元的纯氧与来自煤粉制备单元的干燥煤粉通过烧嘴以80-120m/s的速度进入磷煤气化炉下部，发生煤气化反应，其高速的氧化气流区与上段固定床形成拱形界面以托住上端的固体矿料，煤气化形成的高温使来自上部的磷矿与硅石在氧化气流区内形成低共熔物。
进一步的技术方案在于：所述矿料成型单元中的生产用原料是磷矿、焦炭、硅石以块矿的形式加入，或采用磷矿粉、焦炭粉、硅石粉的两种或三种成球加入，经干燥后通过料仓进入磷煤气化炉上段的固定床。
进一步的技术方案在于：从磷煤气化炉顶部导气管导出的工艺气体，顺序进入分离洗涤单元分离磷与CO、H2粗合成气，含有CO、H2粗合成气进入净化单元得到精制的合格合成气。
进一步的技术方案在于：通过烧嘴燃烧纯氧和煤粉，形成超过1600℃ 以上的高温煤气化燃烧区，或者通过烧嘴通纯氧，纯氧与来自矿料成型单元的过量碳反应，形成超过1600℃ 以上的高温煤气化燃烧区。
进一步的技术方案在于：所述熔融区采用高温烟气进行液封，液相排渣，渣料水淬。
进一步的技术方案在于：所述分离洗涤单元包括除尘系统和黄磷冷凝系统，炉气首先进入除尘系统，保持炉气温度高于黄磷露点温度，实现气固分离，然后进入黄磷冷凝系统，得到黄磷产品，含有CO、H2的粗合成气进入净化工段，脱除含硫化合物和微量磷化合物，得到满足下游产品加工的合成气原料。
进一步的技术方案在于：所述煤粉制备单元的工作流程为：原料煤由磨辊在磨煤机内碾磨达到目标粒径，来自惰性气体发生器的热烟气对湿煤粉进行干燥，干燥后的煤粉被热惰性气体带入旋转分离器，粗颗粒被分离下来后返回磨煤机，惰性气流夹带着细颗粒粉煤进入煤粉袋式除尘器，煤粉和惰性气体在袋式除尘器中进行气固分离，合格的粉煤输送至磷煤气化炉。
进一步的技术方案在于：所述空分单元用于产生O2和N2，并将O2输送至磷煤气化炉为烧嘴提供纯氧。
采用上述技术方案所产生的有益效果在于：所述系统与传统的磷电炉相比，使用了一次能源，热能利用效率高，大幅降低黄磷生产的能源成本。采用加压反应，不仅提高了黄磷单系列产能，联产的合成气总量大幅上升，有利于形成产业规模效应，如磷煤气化炉为30万吨/年合成氨提供合成气的同时，同时联产2万吨/年黄磷。托举烟气的液相排渣水淬技术，改善了生产与操作环境。经干法除尘，炉气中的粉尘含量大大降低，杜绝黄磷冷凝过程中泥磷的生成，直接获得高纯度黄磷产品。
附图说明
下面结合附图和具体实施方式对本发明作进一步详细的说明。
图1是本发明实施例所述系统的原理框图。
具体实施方式
下面结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在下面的描述中阐述了很多具体细节以便于充分理解本发明，但是本发明还可以采用其他不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似推广，因此本发明不受下面公开的具体实施例的限制。
如图1所示，本发明实施例公开了一种黄磷与合成气的联合生产系统，包括磷煤气化炉，煤粉制备单元的出料口与所述磷煤气化炉的煤粉进入口连接，用于向磷煤气化炉中输入煤粉，空分单元的出气口与所述磷煤气化炉底部的进气口连接，用于向所述磷煤气化炉内输入氧气，矿料成型单元与磷煤气化炉顶部的进料口连接，用于向所述磷煤气化炉内输送生产用原料，所述磷煤气化炉的炉气出口与分离洗涤单元的进气口连接，所述分离洗涤单元的一个输出口为黄磷产品输出口，所述分离洗涤单元的另一个输出端为粗合成气输出口，所述粗合成气输出口与净化单元的输入口连接，所述净化单元的输出口输出精制合成气，所述磷煤气化炉底部的排渣口与所述炉渣冷萃单元的输入口连接，所述炉渣冷萃单元的输出口输出炉渣。
进一步的，所述磷煤气化炉为固定床反应器，其下部通过烧嘴燃烧空分单元喷入的纯氧和煤粉制备单元输入的煤粉，形成超过1600℃以上的高温煤气化燃烧区，以此燃烧区为界，上部为矿料成型单元输入的块状磷矿石、焦炭、硅石或三者的球状混合物，下部是磷矿还原的熔融区，在高温下发生还原反应生成黄磷，煤气化的CO+H2以及磷蒸气从磷煤气化炉底部逐渐上升到顶部，从导气管送入分离洗涤单元，炉气温度300-700℃，操作压力1.5-3.5MPa。
所述磷煤气化炉内发生磷矿的还原与煤气化的耦合反应采用加压固定床，磷矿、焦炭（煤炭）、硅石从顶部进入，随着物料的下降，温度逐渐上升直至处于熔融状态，炉顶炉气的气体温度约500℃ 。
所述煤粉制备单元的工作流程为：原料煤由磨辊在磨煤机内碾磨达到目标粒径，来自惰性气体发生器的热烟气对湿煤粉进行干燥，干燥后的煤粉被热惰性气体带入旋转分离器，粗颗粒被分离下来后返回磨煤机，惰性气流夹带着细颗粒粉煤进入煤粉袋式除尘器，煤粉和惰性气体在袋式除尘器中进行气固分离，合格的粉煤输送至磷煤气化炉。
来自空分单元的纯氧与来自煤粉制备单元的干燥煤粉通过烧嘴以80-120m/s的速度进入磷煤气化炉下部，发生煤气化反应，其高速的氧化气流区与上段固定床形成拱形界面以托住上端的固体矿料，煤气化形成的高温使来自上部的磷矿与硅石在氧化气流区内形成低共熔物。
所述矿料成型单元中的生产用原料是磷矿、焦炭（煤炭）、硅石以块矿的形式加入，或采用磷矿粉、焦炭粉（煤炭粉）、硅石粉的两种或三种成球加入，经干燥后通过料仓进入磷煤气化炉上段的固定床。
通过烧嘴燃烧纯氧和煤粉，形成超过1600℃以上的高温煤气化燃烧区，或者通过烧嘴通纯氧，纯氧与来自矿料成型单元的过量碳反应，形成超过1600℃以上的高温煤气化燃烧区。
从磷煤气化炉顶部导气管导出的工艺气体，顺序进入分离洗涤单元分离磷与CO、H2粗合成气，含有CO、H2粗合成气进入净化单元得到精制的合格合成气。
所述熔融区采用高温烟气进行液封，液相排渣，渣料水淬。渣池接纳来自固定床底部的液态炉渣，熔融的炉渣经磷矿还原熔融池进入磷煤气化炉底部的锥型渣池，间歇液相排渣，排出的矿渣进入炉渣冷淬池，经水淬后排出；
所述分离洗涤单元包括除尘系统和黄磷冷凝系统，炉气首先进入除尘系统，保持炉气温度高于黄磷露点温度，实现气固分离，然后进入黄磷冷凝系统，得到黄磷产品，含有CO、H2的粗合成气进入净化工段，脱除含硫化合物和微量磷化合物，得到满足下游产品加工的合成气原料。
本发明所述系统将磷矿的还原反应体系引入到煤气化过程中，将煤气化与磷矿还原反应耦合在一台气化设备内，利用煤气化过程中产生的热量供给磷矿还原热，并利用煤灰分中含有的硅、铝元素减少硅石等助溶剂用量，提高磷蒸汽的产出率。通过分离磷蒸气与CO+ H2，获得黄磷产品，粗合成气进一步净化得到精制合成气。综上，所述系统能够提高黄磷生产的㶲效能；通过加压转化，能够提高单系列黄磷生产能力与合成气产量；将煤气化先进技术引入到黄磷生产过程中；经成型处理，该磷煤气化炉可以接纳不同品质的磷矿石；并能够减少CO2排放。
Claims (10)
1.一种黄磷与合成气的联合生产系统，其特征在于：包括磷煤气化炉，煤粉制备单元的出料口与所述磷煤气化炉的煤粉进入口连接，用于向磷煤气化炉中输入煤粉，空分单元的出气口与所述磷煤气化炉底部的进气口连接，用于向所述磷煤气化炉内输入氧气，矿料成型单元与磷煤气化炉顶部的进料口连接，用于向所述磷煤气化炉内输送生产用原料，所述磷煤气化炉的炉气出口与分离洗涤单元的进气口连接，所述分离洗涤单元的一个输出口为黄磷产品输出口，所述分离洗涤单元的另一个输出端为粗合成气输出口，所述粗合成气输出口与净化单元的输入口连接，所述净化单元的输出口输出精制合成气，所述磷煤气化炉底部的排渣口与所述炉渣冷萃单元的输入口连接，所述炉渣冷萃单元的输出口输出炉渣。
2.如权利要求1所述的黄磷与合成气的联合生产系统，其特征在于：所述磷煤气化炉为固定床反应器，其下部通过烧嘴燃烧空分单元喷入的纯氧和煤粉制备单元输入的煤粉，形成超过1600℃以上的高温煤气化燃烧区，以此燃烧区为界，上部为矿料成型单元输入的块状磷矿石、焦炭、硅石或三者的球状混合物，下部是磷矿还原的熔融区，在高温下发生还原反应生成黄磷，煤气化的CO+H2以及磷蒸气从磷煤气化炉底部逐渐上升到顶部，从导气管送入分离洗涤单元，炉气温度300-700℃，操作压力1.5-3.5MPa。
3.如权利要求1所述的黄磷与合成气的联合生产系统，其特征在于：来自空分单元的纯氧与来自煤粉制备单元的干燥煤粉通过烧嘴以80-120m/s的速度进入磷煤气化炉下部，发生煤气化反应，其高速的氧化气流区与上段固定床形成拱形界面以托住上端的固体矿料，煤气化形成的高温使来自上部的磷矿与硅石在氧化气流区内形成低共熔物。
4.如权利要求1所述的黄磷与合成气的联合生产系统，其特征在于：所述矿料成型单元中的生产用原料是磷矿、焦炭、硅石以块矿的形式加入，或采用磷矿粉、焦炭粉、硅石粉的两种或三种成球加入，经干燥后通过料仓进入磷煤气化炉上段的固定床。
5.如权利要求1所述的黄磷与合成气的联合生产系统，其特征在于：从磷煤气化炉顶部导气管导出的工艺气体，顺序进入分离洗涤单元分离磷与CO、H2粗合成气，含有CO、H2粗合成气进入净化单元得到精制的合格合成气。
6.如权利要求1所述的黄磷与合成气的联合生产系统，其特征在于：通过烧嘴燃烧纯氧和煤粉，形成超过1600℃ 以上的高温煤气化燃烧区，或者通过烧嘴通纯氧，纯氧与来自矿料成型单元的过量碳反应，形成超过1600℃ 以上的高温煤气化燃烧区。
7.如权利要求2所述的黄磷与合成气的联合生产系统，其特征在于：所述熔融区采用高温烟气进行液封，液相排渣，渣料水淬。
8.如权利要求1所述的黄磷与合成气的联合生产系统，其特征在于：所述分离洗涤单元包括除尘系统和黄磷冷凝系统，炉气首先进入除尘系统，保持炉气温度高于黄磷露点温度，实现气固分离，然后进入黄磷冷凝系统，得到黄磷产品，含有CO、H2的粗合成气进入净化工段，脱除含硫化合物和微量磷化合物，得到满足下游产品加工的合成气原料。
9.如权利要求1所述的黄磷与合成气的联合生产系统，其特征在于：所述煤粉制备单元的工作流程为：原料煤由磨辊在磨煤机内碾磨达到目标粒径，来自惰性气体发生器的热烟气对湿煤粉进行干燥，干燥后的煤粉被热惰性气体带入旋转分离器，粗颗粒被分离下来后返回磨煤机，惰性气流夹带着细颗粒粉煤进入煤粉袋式除尘器，煤粉和惰性气体在袋式除尘器中进行气固分离，合格的粉煤输送至磷煤气化炉。
10.如权利要求1所述的黄磷与合成气的联合生产系统，其特征在于：所述空分单元用于产生O2和N2，并将O2输送至磷煤气化炉为烧嘴提供纯氧。
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| EP4112538A1 (en) | 2023-01-04 |
| US20230002692A1 (en) | 2023-01-05 |
| EP4112538B1 (en) | 2023-10-11 |
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