CN103237868A - 一种由含碳原料获得石化产品的工艺 - Google Patents

一种由含碳原料获得石化产品的工艺 Download PDF

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CN103237868A
CN103237868A CN2011800522576A CN201180052257A CN103237868A CN 103237868 A CN103237868 A CN 103237868A CN 2011800522576 A CN2011800522576 A CN 2011800522576A CN 201180052257 A CN201180052257 A CN 201180052257A CN 103237868 A CN103237868 A CN 103237868A
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凯基·霍尔穆斯吉·格哈达
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Abstract

本发明公开了一种从含碳原料中，例如从煤炭、焦炭、褐煤、生物质、沥青等中，获得石化产品的工艺。把含碳原料粉碎并加入到一台热解反应器中。在其中，原料在700-1000℃和2-25巴压力下反应2-10秒。其中，在热解过程，原料夹带在高温合成气中。

Description

一种由含碳原料获得石化产品的工艺
发明领域
本公开涉及一种由含碳原料获得有价值产品的工艺。
发明背景
由于石油资源日渐减少，近年来，一直存在着一种不断增长的需求，即，作为一种获得石油化工化合物的替代方法，从非挥发性的含碳物质中，例如从煤炭、生物质、褐煤、城市固体废物及其它的含碳废物中回收烃类化合物。常用的方法是热解或热处理，通过这种方式把含碳物质分解成烃类产物。当煤在高温下热解时，它经历破坏性的热解，并转化成液态的和气态的轻烃流体和焦炭。伴随该工艺的一个关键问题是效率低。此外，难以操控热解区内的接触时间/停留时间，而这是决定工艺效率的一个重要因素。另外，热解工艺需要非常短的反应时间；因此，非常需要在反应期间，提供贯穿整个含碳原料的均匀热分布，以便得到最优的产率。
在过去已经进行了若干尝试，以便提供由含碳原料获得烃类产物的各种工艺。在以下的现有技术中，列出了一些公开资料：
US3855070公开了一种用于加氢热解固态或液态烃类燃料的一种工艺，其中包括把燃料加入到一个流化床中。该流化床具有一个用含氢气体流化的焦炭颗粒床。该流化床在温度1100-1800°F和大于20atm下操作；其中，在焦炭颗粒上生成加氢热解的固态产物，在流化床上方的空间内收集气态产物。该工艺的目的是提供一种改进的方法，用于向热解煤炭或油类的流化床区域进行供热（或移走热量）。
US4210492公开了一种煤的热解工艺，其特征在于高效率的脱水和传热，其中，粉碎的煤被预热、热解、并且在热解后回收热量；通过把两段预热区中第一段内的、作为稀相流化床的粉碎煤炭，接触第一微粒热载体，并接触第二预热段中密相流化床内的第二微粒热载体，随后在密相流化床的热解区内热解，从而影响传热。
在上述现有技术中，所公开的热解含碳原料工艺比较复杂，具有多个反应段，并且在非常高的压力下操作，并且不能解决上面所列的、热解工艺的全部缺点。因此，感觉到需要一种改进的含碳材料热解工艺，它应该简单、仅需要单段，并且解决了已知工艺的缺点。
发明目的
本发明的目的是提供一种高效的热解工艺，用于由含碳原料获得石化产品。
本发明的另一个目的是提供一种简单和易于操作的热解工艺，用于由含碳原料获得石化产品。
本发明的另一个目的是提供一种热解工艺，用于由含碳原料获得石化产品，其中，该工艺在热解期间，整个含碳原料具有均匀的热分布。
本发明的再一个目的是提供一种热解工艺，用于由含碳原料获得石化产品，其中，该工艺是单段的，并且不要求非常高的操作压力。
本发明还有一个目的是提供一种热解工艺，用于由含碳原料获得石化产品，其中，热解产物易于加工，从而获得有价值的产品。
发明概述
根据本发明，它公开了一种由含碳原料获得石化产品的工艺。所述的工艺包括下列步骤：
■粉碎含碳原料，得到粉碎的原料，其目数为50-300，首选100-200；并且
■在热解反应器中，在700-1000℃温度范围内，在2-25巴压力范围内，并且在2-10秒范围内，使用合成气热解粉碎的原料。得到热解产物，其中含有焦炭、液态石化产品，以及至少一部分合成气。
通常，根据本发明，该工艺包括选择含碳原料的步骤，该原料来自于由煤炭、褐煤、生物质、焦炭、沥青、有机废物等等组成的至少一种材料。
根据本发明，该工艺首选包括处理热解产物的步骤，以便分离焦炭、液态石化产品和合成气。
通常，根据本发明，该工艺包括热解液态石化产品的步骤，以便从乙烯、丙烯、苯、甲苯、二甲苯、甲烷和乙烷中获得至少一种烃。
根据本发明，该工艺首选包括在热解期间，把粉碎的原料夹带到合成气中的步骤。
通常，根据本发明，该工艺包括温度在1200-1700℃时，在高于热解压力的压力下，用氧气气化焦炭的步骤，以便获得具有20-30%（摩尔）之间氢含量的合成气。
根据本发明，该热解反应器首选是一种衬砖的立式反应器。
作为替代，根据本发明，该工艺包括一个使用裂化催化剂的步骤，通过把干燥的煤粉，与由精细赤泥和含氧化钼的氧化铝合成的至少一种化合物相混合，得到这种催化剂。
发明详述
本发明设计了一种工艺，从含碳原料中，例如从煤炭、焦炭、褐煤、沥青、生物质、有机废物及其它的含碳废物中，获得有价值产物，尤其是石化产品。本发明的工艺包括粉碎步骤，粉碎含碳原料到目数为50-300，首选100-200。然后，在热解反应器中，在700-1000℃之间的温度，首选800℃，在2-25巴之间的压力下，在2-10秒之间，首选2-5秒可控地热解粉碎的原料；其中，在热解反应器中，通过反应器的活动底部接收高温合成气，以便在热解工艺期间，夹带粉碎的含碳原料。在热解反应器内这样得到的热解产物含有焦炭、液态石化产品，以及至少一部分合成气。
可以干燥粉碎的原料，以便在热解工艺之前脱除水分。在本发明的工艺中，在热解反应器的反应期间，粉碎的含碳原料必须夹带在合成气中。根据所用含碳材料的类型，可以操控热解反应器内的压力，以便使原料保持在夹带状态。热解反应器通常是一种衬砖的立式反应器，以便在热解期间，允许短的停留时间和均匀的热分布。热解工艺首选使用夹带床反应器。作为替代，也可以使用流化床反应器、沸腾床反应器或固-气接触床反应器，用于进行本发明的热解工艺。
通过以1200-1700℃之间的温度，以高于热解反应器的压力，使用氧气和水蒸汽气化焦炭，从而制取热解工艺期间所用的合成气。气化可以在热解反应器的最下方区域内或在单独的气化炉中完成，在此，把合成气输送到热解反应器，从而，使高温合成气在热解反应器中向上流动。在热解工艺中所用的高温合成气主要含有一氧化碳、二氧化碳和氢气，其中氢含量首选在20-30%（摩尔）之间。
从热解反应器的活动顶部排出热解产物。趁热分离出焦炭，然后，冷却石化产品。这样得到的焦炭应用在气化工艺中，与氧气和水蒸汽一起制取合成气。焦炭还可用作燃料、作为含碳物质或用在任何其它的化学工艺中。热解产物中的合成气在高压下分离和净化，并且可进一步应用于化工合成。液态石化产品可控制热解，以便得到许多产物，包括乙烯、丙烯、苯、甲苯、二甲苯、甲烷和乙烷。在裂化过程中，除了焦炭，还可选使用裂化催化剂。通过把干燥的煤粉，与由精细赤泥和含氧化钼的氧化铝合成的至少一种化合物相混合，得到这种催化剂。
试验结果
现在，结合下列实施例对本专利进行说明。这些实施例绝不限定本发明的范围和界限，并且仅用于说明本发明。
实施例1：
使用一种原产于印度尼西亚的低阶烟煤；煤的性质如下表1中所示。磨碎煤样，在干燥器中干燥，得到具有最终含水量1.2%的干煤样。在冲击式粉碎机内粉碎干燥后的煤样，并且在原位筛分到100微米以下。把粉碎后的煤粉放入到加料斗中，外部加热到150℃。通过螺旋输送机，把加料斗连接到热解炉。热解炉是一台钢制的高温高压管式反应器，内径40mm，高10m。气化炉连接到热解炉的活动底部。
表1
Figure BDA00003116901400051
在气化炉中，由焦炭（3kg/hr）、氧气（3kg/hr）和过热水蒸汽（3kg/hr），通过在1300℃的反应，制备高温合成气。用一台联机气相色谱仪，分析合成气的成分。合成气主要含有H2和CO，还有一些少量的CO2、CH4和水蒸汽。通过螺旋输送机，把粉碎的煤粉以30kg/hr的速度，加入到热解炉，被夹带微粒的合成气闪速加热。在2巴的绝对压力下，在平均热解温度800℃下，进行热解过程，气体停留时间为5秒。在热解条件下，由多个旋风分离器从热解产物中分离出焦炭。热解的气态产物穿过多个冷凝器。通过联机的气相色谱仪分析气态产物。气态热解产物除了含有合成气和少量其它轻烃之外，还含有大量的乙烯和丙烯。分离液态热解产物和水层，并且分析苯、甲苯、二甲苯和其它芳烃的产率。对热解得到的焦炭进行工业分析，分析结果与气化炉中使用的焦炭具有良好的一致性，具有1.2%的挥发分含量。
实施例2：
把烟煤（具有类似于表1中列出的特性），加入到60mm内径（ID）和6m高的IN519型转化炉式的钢制热解炉。该热解炉连接到一台单独的气化炉。在气化炉内，把含有5kg/hr碳的5.75kg/hr焦炭，与4.2kg/hr氧气和5kg/hr水蒸汽共同燃烧。在气化炉中，在1600℃和2巴压力下制备高温合成气。合成气中主要含有CO and H2。热解炉的加料条件保持在：60kg/hr，2巴的压力和900℃的温度。在热解和裂化期间，热解炉的平均温度保持在940℃，停留时间为3.5秒。热解产物的气体穿过多个冷凝器并且分离。在预处理之后，包括净化和冷却之后，使用气相色谱仪分析液态和气态产物。液态和气态产物表现为大量的CO、H2、CO2、烯烃（乙烯和丙烯）、苯、甲苯，二甲苯，以及少量的甲烷、丙烷、乙烷等等。焦炭在旋风分离器内分离，然后冷却和分析。分析表明焦炭含有仅1%的挥发物。
实施例3：
在转化炉式的钢制反应器中，把烟煤（具有类似于表1中列出的特性），在10巴压力下进行热解。在气化炉中，通过把焦炭与预热的O2和水蒸汽，在600℃共同燃烧，制备高温合成气。高温合成气含有CO-52％，H2-21％，二氧化碳-9.6％，H2O-16％（摩尔）。在热解炉的高温区，用1600℃合成气闪速加热预热的煤炭。在850℃平均热解温度和停留时间3秒的条件下，进行热解。通过多个旋风分离器，从热解产物中分离出焦炭。气态的石化产品在一系列冷凝器中冷却。收集、纯化液态石化产品，并分析苯、甲苯、二甲苯及其它的芳烃。已经发现，液态石化产品的收率是反应器煤炭总进料的15%，其中发现，焦炭收率为52%。通过联机的气相色谱仪，分析气态产物中的烯烃、CO、CO2及其它轻烃。在惰性气氛中冷却焦炭，并分析其挥发物含量。焦炭含有1.4％的挥发物。
实施例4：
在转化炉式的钢制反应器中，把烟煤（具有类似于表1中列出的特性），在20巴压力下进行热解。在气化炉中，通过把焦炭与预热的O2和水蒸汽，在600℃共同燃烧，制备高温合成气。高温合成气含有CO-45％，H2-21％，以及CO2、CH4和H2O。在热解炉的高温区，用1600℃合成气闪速加热预热的煤炭。在800℃平均热解温度和停留时间2秒的条件下，进行热解。通过多个旋风分离器，从热解产物中分离出焦炭。气态的石化产品在一系列冷凝器中冷却。收集、纯化液态石化产品，并分析苯、甲苯、二甲苯及其它的芳烃。已经发现，液态石化产品的收率是反应器煤炭总进料的18%，其中发现，焦炭收率为49%。通过联机的气相色谱仪，分析气态产物中的烯烃、CO、CO2及其它轻烃。在惰性气氛中冷却焦炭，并进行分析。焦炭含有2％的挥发物。
技术优势
一种由含碳原料获得石化产品的工艺；正如本发明中所述，它具有若干技术优势，包括但不限于实现：
●本发明的工艺高效、简单并且易于操作；
●本发明的工艺在热解期间，提供含碳原料内的均匀热分布；
●本发明的工艺是单段的、不需要非常高的操作压力；并且
●在本发明的工艺中，可以方便地加工热解产物，以便获得多种有价值产物。
各种物理参数、尺寸或数量的所述数值仅是近似值。高于或低于指定给参数、尺寸或数量的数值，应该被视为属于本发明的范围内。除非在说明书中具有相反的说明。无论在哪里规定了数值范围，分别超过规定范围最高数值和低于最低数值直至10%的数值，也包括在本发明的范围中。
鉴于本发明的原理可以适用于许许多多的实施例，因此，举出的实施例应该被视为仅用于说明。虽然这里对本发明的特点已经给予了大量的强调，应该理解为，在不违背本发明原理条件下，可以在首选的实施例中，进行各种改进，进行各种多种改变。具有本发明或首选实施例性质的这些和其它改进，在此，对所公开领域内的技术人员都是显而易见的，因此，应该清楚地理解为，上述说明事项被视为仅作为本发明的说明，而不是作为限制。

Claims (8)

1.一种由含碳原料获得石化产品的工艺，所述的工艺包括下列步骤：
■粉碎含碳原料，得到粉碎的原料，其目数为50-300，首选100-200；并且
■在热解反应器中，在700-1000℃温度范围内，在2-25巴压力范围内，并且在2-10秒范围内，使用合成气热解粉碎的原料，得到热解产物，其中含有焦炭、液态石化产品，以及至少一部分合成气。
2.根据权利要求1所述的工艺，其中包括选择含碳原料的步骤，该原料来自于由煤炭、褐煤、生物质、焦炭、沥青、有机废物等等组成的至少一种材料。
3.根据权利要求1所述的工艺，该工艺包括处理热解产物的步骤，以便分离焦炭、液态石化产品和合成气。
4.根据权利要求1所述的工艺，该工艺包括热解液态石化产品的步骤，以便从乙烯、丙烯、苯、甲苯、二甲苯、甲烷和乙烷中获得至少一种烃。
5.根据权利要求1所述的工艺，该工艺包括在热解期间，把粉碎的原料夹带到合成气中的步骤。
6.根据权利要求1所述的工艺，该工艺包括温度在1200-1700℃时，在高于热解压力的压力下，用氧气气化焦炭的步骤，以便获得具有20-30%（摩尔）之间氢含量的合成气。
7.根据权利要求1所述的工艺，该热解反应器是一种衬砖的立式反应器。
8.根据权利要求4所述的工艺，该工艺包括一个使用裂化催化剂的步骤，通过把干燥的煤粉，与由精细赤泥和含氧化钼的氧化铝合成的至少一种化合物相混合，得到这种催化剂。
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