CN1093338A - 烟灰/煤灰泥浆水的过滤以及改进的碳氢化合物原料的部分氧化工艺 - Google Patents

烟灰/煤灰泥浆水的过滤以及改进的碳氢化合物原料的部分氧化工艺 Download PDF

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CN1093338A
CN1093338A CN93121333A CN93121333A CN1093338A CN 1093338 A CN1093338 A CN 1093338A CN 93121333 A CN93121333 A CN 93121333A CN 93121333 A CN93121333 A CN 93121333A CN 1093338 A CN1093338 A CN 1093338A
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W·科瓦力克
H·J·马茨
T·施米茨
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment
    • C10J2300/1628—Ash post-treatment
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Abstract

本发明涉及改进的部分氧化、汽化工艺。过程中 所生成的烟灰泥浆含有未燃烧的碳和煤灰。过滤得 到碳和煤灰的滤饼，除去滤饼，由此建立了一种直接 一次化部分氧化工艺。本发明还涉及对烟灰/煤灰 泥浆的过滤方法。这种泥浆被冷却到低于80℃，装 入可移动的靠近的滤带之间进行过滤，使滤带中的碳 /煤灰颗粒维持在恒定的压力下，直到含水量降低到 重量的80％以下，在过滤之前，向泥浆中加入絮凝 剂，得到一种饼状的或颗粒状的适合进一步加工处理 的滤饼。

Description

本发明涉及对烟灰/煤灰泥浆水的过滤，这些泥浆水是在一些化学工艺中得到的，如以重碳氢化合物类为原料的化学气化工艺，本发明尤其涉及一种改进的部分氧化、气化工艺;其中使生成的烟灰/煤灰泥浆经过这一工艺的除碳步骤后，进行过滤并直接处置。
碳氢化合物类原料的部分氧化工艺早在本世纪五十年代就已经发展起来了，并且已经商业化了，众所周知的工艺如Shell气化工艺和Texaco气化工艺已经在一些工业化装置上使用了。
这种利用碳氢化合物原料的气化工艺包括三个主要步骤：
-气化，在有氧气和水蒸汽存在的情况下，原料被转化成原合成气体;
-回收废热，从离开反应器的热气体中得到高压蒸汽;以及
-去除碳，采用多级水洗除去反应器出流气体中的剩余的碳。
由此，气化器中未被燃烧的碳将形成一种碳的泥浆，一种含有烟灰和大量煤灰的悬浮水溶液，这取决于所用的原料，这种碳的泥浆需要经过进一步加工和回收。
这种工艺存在一个严重的缺陷，就是一定百分数量的原料没有被汽化，它们以烟灰的形式存在，与相当量的来自重碳氢化合物原料的煤灰混合在一起。
传统的烟灰回收过程有两种可供选择的方法：
1、用造粒的方法来回收碳，其中用一种蒸馏物或一种剩余的燃烧油与碳颗粒形成附聚物，这些颗粒很容易从水中分离，被循环回到反应器中和/或在碳油焚烧炉中烧掉。
2、另外一种是使含碳泥浆与挥发油在一分离器中相接触，使之形成挥发油烟灰附聚物，随后用沉淀法取出或过滤出这些附聚物，并将其与原料一起转化为可用泵抽取的混合物，并且循环到反应器中。
然而，由于烟灰对煤灰的严重污染，对于这种气化工艺来说，烟灰/煤灰混合物的处置已经逐渐成为最严重的问题。
用过滤法分离烟灰/煤灰混合物并直接处置的可能性被认为是一个有吸引力的解决方案，但是还未被大规模使用。
更具体地说，过滤法已经在特殊的场合用来回收烟灰，如吸附的碳。传导性碳和碳墨。然而，这种应用还没有解决在大型气化装置中的处置问题。
从碳分离步骤得到的烟灰/煤灰泥浆通常含有0.5-3%的未燃烧碳和0.1-2%的烟灰。烟灰中含有大量的Ni、Fe和V。这种泥浆的过滤是非常困难的。当水被除去时，泥浆逐渐地转变成一种像肥皂的糊，而这种像肥皂样的糊用常规的过滤方法是非常难处理的，滤饼的最终含水量是85%或更高些，这种滤饼的糊稠粘性使它不适合被进一步处理。
随后的燃烧将产生过量的结块并需要很高的燃烧温度，以烧掉这些烟灰，这将产生严重的环境问题和腐蚀问题。
为了克服这些棘手问题，曾建议向这种泥浆中加入其它固体物质。因此，根据DE-A-4003242，使一种烟灰水泥浆与泥浆混合在一起（Klaorschlamm），随后，过量的水很容易从这种混合物中除去。之后剩余固态的泥浆能够被处置，但是重金属和其它污染物质不能被清除和处置的问题还是没有被解决。
本发明的主要目的是提供一种烟灰/煤灰泥浆水的过滤方法，该方法使生成的滤饼适合进行随后的处理和加工。
本发明的另一个目的是实现一种过滤方法，该方法使得到的滤饼具有非常低的含水量，是颗粒状或者饼状，而不是糊状。
本发明的再一个目的是使用这种过滤方法以提供一种改进的部分氧化气化工艺，以一种完全连续的工艺形式得到一种适合进一步处理的滤饼。
本发明的再一个目的是提供一种部分氧化工艺，它没有煤灰和未燃烧的碳的回流，以改进气化过程的所有效率。
本发明的这些目的和其他的目的通过在低于80℃的低温度下实施过滤来达到，将烟灰水泥浆限制在可移动的过滤器滤带之间，施加一恒定的线性压力，直到滤饼的含水量小于80%，最好小于75%，并且它不再是像肥皂样的或糊状的，而是转变成饼状或结块，这种东西容易分离，并且非常适合随后的运输和用干燥和/或燃烧过程处理。
为进一步改进过滤效率，可以将烟灰泥浆与两种不同的聚合电解质絮凝剂混合在一起，即一种阳离子的和另一种阴离子的。
本发明的其它基体特征如所附的权利要求1-5中所限定的，通过下面对本发明的详细描述也会清楚的。
图1是过滤过程的流程图。
图2是在不同的烟灰泥浆温度下，滤饼的干物质的含量曲线。
最初的在实验室中的过滤试验揭示，当滤饼的干物质含量增加到20%或更高时，所生成的干燥滤饼或块状物适合进一步的处理。然而，对传统的过滤法，尽管仔细选择最佳参数、使用助滤剂、优化过滤速度、在现场装置试验中都没有得到满意的结果，含水量仍然大于85%，生成的滤饼不适合进一步的处理。
然后，又开始了一组新的试验，在过滤阶段前并入冷却单元，并使用两种聚合电解质絮凝剂，一种带负电荷，一种带正电荷。烟灰泥浆从95-90℃冷却到60℃，50℃等等，然后测量滤饼中干物质含量。
测试结果见下表1：
泥浆    泥浆    烟灰    絮凝剂1    絮凝剂2    絮凝剂总量    干物质
oC m3/h kg/m3l/h l/h ppm %
35    8.0    4.40    140    90    71.9    32.6
40    8.0    3.55    140    90    71.9    28.9
60    8.0    3.43    140    90    71.9    26.7
53    8.0    3.30    140    90    71.9    25.0
令人惊奇地发现低温能够增加过滤效率，图2中也表示出了当泥浆的温度＞80℃时，即使其他的过滤参数最佳也不能得到令人满意的稠度的滤饼，干物质的含量会低于20%。
运用最初的试验结果，研制出了一个全等级的过滤方法，并对其进行了成功地试验，图1所示的流程图中，表示了一个完全整体化的气化工艺，其中重的剩余油在传统的气化单元中与烟灰单独反应。
根据本发明的最佳实施例，如图1所示，进料管12连接着气化单元13，含有烟灰/煤灰的气体在烟灰分离区1被清洗。于是原气11被净化。从烟灰分离区1流出的烟灰/煤灰泥浆水先通过一个冷却器2，从大约95℃冷却到20-60℃，并使泥浆进入贮槽3，然后使泥浆通过一个混合器4，从源5向混合器4中加入絮凝剂，使用两种絮凝剂，一种商标为Praestol    611BC（阳离子的）带正电荷的聚电解质和一种商标为Praestol    2440（阴离子的）带负电荷的聚电解质，两者可以是白色聚丙烯酰胺颗粒。加入到混合槽4的泥浆中的絮凝剂是0.1-0.3%的水溶液，所加入的絮凝剂的总量被调整到60-100ppm，阳离子与阴离子聚电解质的比为1.5∶1。
随后使泥浆进入沉淀池6，在沉淀池6中，沉淀物质从底部排走，过量的水从顶部排出，并通过管线10循环回到烟灰分离区1中。
在沉淀或沉降单元6后，安装着一个整体化的过滤单元7，然而，沉淀过程是可选择的，也可以使泥浆从混合池4直接进入过滤单元。
进到可移动的过滤器7中的泥浆被脱水，过滤器7有一个水平可移动的滤带，后面有两个垂直移动的过滤带，借助于滚筒的挤压使这些滤带挤压在一起，经历一个恒定的压力，直到滤饼中的含水量小于80%。然后将滤饼放在一个可移动的传送带上，以平均厚度大约为2mm的干燥的饼或片，送入燃烧单元8。其产物9可以毫无问题地进行处理和进一步的加工。滤液可以用来清洗滤饼，滤饼是连续产生的，滤液可以回到烟灰分离区，而不会影响过滤过程的效果。

Claims (4)

1、一种改进的部分氧化、气化工艺，使用低级碳氢化合物原料，包括气化、废热回收和除碳步骤，在所生成的烟灰泥浆中含有未燃烧的碳和煤灰，其特征在于对烟灰泥浆进行过滤，以形成一种碳和煤灰的滤饼，从该过程中除去滤饼，由此建立了一个直接一次化的部分氧化工艺，避免了未燃烧碳和煤灰的回流。
2、一种对烟灰/煤灰泥浆的过滤方法，这种泥浆是在如权利要求1所述的部分氧化工艺中在分离出碳后得到的，其中这种泥浆中含有0.5-3%的未燃烧碳和0.1-2%的煤灰，及大量的Fe、Ni和V，其特征在于将泥浆冷却到温度低于80℃、将以一种阳离子絮凝剂和一种阴离子絮凝剂形式的絮凝剂加入泥浆悬浮液中，然后将泥浆置于可移动的靠近的滤带之间进行过滤，使带中的碳/煤灰缩块保持在一恒定的压力下，使含水量降低到占重量的80%以下，得到一种饼状的，或颗粒状的适合进一步加工的滤饼。
3、如权利要求2所述的过滤方法，其特征在于泥浆被冷却到60-20℃温度之间，然后进行过滤，直到含水量降低到低于重量的80%。
4、如权利要求2所述的过滤方法，其特征在于絮凝剂的加入总量为60-100ppm，阳离子聚电解质与阴离子聚电解质的比大约为1.5∶1。
CN93121333A 1992-11-11 1993-11-11 一种处理烟灰/煤灰水泥浆的方法 Expired - Lifetime CN1035306C (zh)

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BR9307427A (pt) 1999-08-31
PL308909A1 (en) 1995-09-04
CN1035306C (zh) 1997-07-02
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EP0670748A1 (en) 1995-09-13
US5628911A (en) 1997-05-13
WO1994011085A1 (en) 1994-05-26
NO924338D0 (no) 1992-11-11
EP0670748B1 (en) 1997-01-15
NO176650B (no) 1995-01-30
NO176650C (no) 1995-05-10
KR100278394B1 (ko) 2001-02-01
JPH08505313A (ja) 1996-06-11
DE69307545T2 (de) 1997-06-12
CZ286278B6 (cs) 2000-03-15
CZ121995A3 (en) 1996-01-17
ES2102182T3 (es) 1997-07-16
KR950704021A (ko) 1995-11-17
NO924338L (zh) 1994-05-13

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