由塑料废物快速热解获得的热解油蒸馏

抽象
在 500-800℃的温度下，塑料废物的快速热解作为主要产品，产生深棕色液体（汽油
柴油和重油的混合物）。分馏通常用于分离石油。然而，关于从塑料废物的快速热解获得
的热解油蒸馏的信息很少。我们研究了由聚乙烯和混合塑料废物的快速热解衍生的两种热
解油样品的蒸馏。前者在 180℃的温度下蒸馏 60 分钟，后者在 150℃和 180℃的温度下蒸
馏 90 分钟。我们观察到馏出物的颜色比热解油样品浅。馏出物在 180℃时为浅黄色，在
150℃时为无色。在蒸馏的早期阶段，蒸馏速率随着时间的推移而增加，并在约 25-
35mL / min 时达到最大值，然后逐渐下降。馏分油的密度和粘度均低于热解油，两种馏分
油性质都与汽油相似，即密度为 706-728kg / m3，粘度为 0.39-0.43×10-6m2s-1。
1.介绍
由市政塑料废物商业回转窑热解获得的原料热解油含有 a
C5 以及 C25 等多种化合物[1]。这种热解油表示可再生
能源。例如，从废高密度聚乙烯（HDPE）催化裂解的'塑料'油混合物，柴油在压缩点
火（CI）发动机[2]中进行了测试。结果显示制动器具体的油耗
（BSFC）随着废塑料油混合比的增加而增加并且随着发动机负荷的增加而减小。
在所有混合比下，机械效率随制动功率增加而增加另外，一氧化碳（CO）
几乎所有负载和所有混合物的排放都低于柴油。
从快速热解获得的热解油已经用各种蒸馏方法分离和改进，
催化和分子蒸馏和真空分馏。 Wang 等人[3]采用了甲醇水
方法通过分子蒸馏富集生物油重质馏分中的热解木质素。汽油和柴油
使用催化蒸馏法生产来自废轮胎油（WTO）的类似燃料[4]。 WTO 生产燃料
分别为轻质燃料，重质燃料和其他产品的重量百分比分别为 18％，70％和 12％。
Choi 等人[5]，
从褐藻（Saccharina japonica）中提取粗制生物油，并在真空分馏中将其分成四个部分
蒸馏塔。根据控制的馏出物温度，三馏分作为馏出物冷凝
底部部分是固体残留物。然而，研究快速热解得到的热解油的蒸馏
塑料废物很少。因此，我们的目标是研究从聚乙烯和聚乙烯热解油获得的产品
混合塑料废物

2.方法
2.1 原材料
汽油和柴油从泰国的普通商用 PTT 加油站购买。热解油
是从聚乙烯和混合塑料废物的快速热解过程中收集的。快速热解在 a
加热速度 10o
C / min 高达 420o
C 在实验室规模的反应器。
2.2 汽油和柴油混合物的蒸馏
K 型热电偶安装在 6 个位置：再沸器，冷却水进出口，外部立柱
环境，气相和馏分。将 5 升 1：1 体积比的汽油和柴油混合物倒入
重新煮沸，然后在 70-200℃的温度下加热
C，即组分的沸点范围
汽油和柴油。冷却水流量设定为每分钟 20 升。蒸馏塔是 10 个盘子
分馏柱。每分钟记录 1 小时的温度。从第一滴馏分油开始的时间
然后每 500 毫升蒸馏 1 小时并记录馏出物体积。馏出物保持在 a
玻璃瓶在黑暗的地方。第一滴馏分油，最高蒸汽温度和再沸器中的混合物
如图 1 所示为稳定状态下的温度。
2.3 蒸馏从塑料废物快速热解中获得的热解油
在本节中，我们进行了两套实验以蒸馏从（a）聚乙烯废物中获得的热解油
（不透明塑料瓶）和（b）混合塑料废物。蒸馏过程与 2.2 节中的相似：我们
只将再沸器的温度改为 180o
C 用于聚乙烯和 150-180°的 1 小时的操作
C
用混合塑料 1.5 小时。
2.4 馏出物产品性能的测定
蒸馏产物的热值用炸弹量热计（Gallenkamp 模型绝热）测试。
粘度通过定时油流量通过粘度计数量 50 来测量并计算
粘度=校准常数 x 时间校准常数为 0.004484，时间和粘度分钟和 mm2
/ s（或 cSt）。质量
用余量（Ohuas 型号 EP413，精度 0.001g）测量容量瓶中的 20ml 并用于
计算密度。每个属性测量一式三份
3.1 蒸馏汽油和柴油的混合物
图 2 显示了在蒸馏 1 小时期间蒸汽，馏出物和再沸器中的混合物的温度。汽
 温度和再沸器温度的混合物随时间逐渐增加。蒸气温度达到了
最大值与再沸器中稳定状态（接近设定温度）时的混合物温度一致。后
那蒸气温度就降到了 34o 左右
C，因为再沸器中混合物的体积减少。馏出物和
在 1 小时蒸馏期间，周围温度几乎不变。之间的温差
冷却水入口和出口约为 3-4o
C（数据未显示）。
在蒸馏温度为 70℃时，蒸气在塔顶不冷凝
因为加热再沸器在
这个温度不能产生足够的压力来克服整个长度上的压降
蒸馏塔。然而，在 80-200℃的温度下蒸馏
C 导致第一滴水蒸气出现在水中
5 分钟后塔顶。稳态时再沸器的最高蒸汽温度和混合物温度
由于蒸馏温度的升高而被移动。
馏出物体积和冷凝速率在早期阶段增加并且随后减少。整体
蒸馏速率随蒸馏温度升高而增加（图 3）。每个蒸馏温度下的馏出物都是清澈的
均匀无杂质，放置 3 天后无变化。
3.2 蒸馏从塑料废物的快速热解中获得的热解油
再沸器中蒸气，馏出物和混合物的温度变化与蒸馏的变化类似
汽油和柴油的混合物 - 见图 2.第一滴聚乙烯和混合塑料的馏分油
由于热解油中有几种组分，废物出现后（约 14-15 分钟）。而且，最大
稳定状态下的再沸器中的蒸气温度和混合物温度出现较晚（约 30 分钟）
与蒸馏汽油和柴油混合物相比。
来自聚乙烯废蒸馏的馏出物在 180℃的冷凝速率
C 在 1 小时内增加了 1 个小时
以 25 毫升/分钟 15-25 分钟，然后以 4 毫升/分钟在 25-45 分钟后降低。没有出现进一
步的馏出物
45 分钟后直至蒸馏 1 小时。整体蒸馏速度约为 5.5 毫升/分钟。用于蒸馏
从 150o 的混合废塑料中提取
C，馏分仅在 31 毫升/分钟的前 14-25 分钟出现。同时，
蒸馏的冷凝速率在 180°
C 在第一个 15-35 分钟内增加了 35 毫升/分钟，然后下降了
 此后 35 分钟，以 9.3 毫升/分钟。
馏出物从聚乙烯和混合塑料废物中获得的 180°
C 淡黄色，清澈
均匀无杂质，2 周后呈现深黄色。但是，来自聚乙烯的馏分
废物比混合塑料废物的废物更黑（图 4）。然而，从混合塑料馏出热解油
在 150o
C 在 2 周后没有改变。
各种塑料废物在 150℃以上馏出热解油
C 具有性质（密度，
粘度和热值）类似于汽油（表 1）。另外，在剩下的混合物中
蒸馏结束后的再沸器具有比柴油更低的密度和粘度但更高的热值
4。结论
蒸馏可以将轻质产品与热解油中的重质残渣分离。更轻的产品
（馏出物）从混合塑料废物的热解油得到的在 150℃下是无色的
C，黄色为 180 度
C.
操作过程中蒸馏速率不是恒定的;它在早期增加并逐渐下降。该
混合废塑料的总体蒸馏率高于聚乙烯废料。增加蒸馏
温度导致馏出物体积增加。两种塑料废物的馏出物密度和粘度均为
低于蒸馏前的热解油。馏出物的密度和粘度都与
汽油，除热值外。来自塑料废物的热解油蒸馏产品有潜力
用作汽油替代燃料。
致谢
我们感谢工程学院的财务支持和设施。
参考
[1] Lee K. Thermal and catalytic degradation of pyrolytic oil from pyrolysis of municipal
waste。 J. Anal。申请 Pyrolysis 2009; 85：第 372-379 页。
[2] Kumar S，Prakash R，Murgan S，Singh R.K.催化裂解制取废塑料油共混物的性能
和排放分析
在 CI 发动机中使用柴油的废 HDPE。 2013 年能源转换管理; 74：p。 323-331。
[3]王，，王，，冷峰，陈俭，朱莉，罗。。生物油重馏分中热解木质素的分离与表征
分子蒸馏。分离和纯化技术 2015; 152：p。 123-132。
 [4] Ayanoglu A，Yumrutas R.使用催化热解法从废轮胎油生产汽油和柴油类燃料。能源
2016; 103：p。
456-468。
[5]来自热解大藻（Saccharina japonica）生物油的真空分馏的特征。工业与工程
工程化学 2016;新闻报道，http://dx.doi.org/10.1016/j.jiec.2017.03.002。

Distillation of Pyrolytic Oil Obtained from Fast Pyrolysis of Plastic Wastes

Abstract
Fast pyrolysis of plastic wastes, at temperatures from 500-800°C, gives as a main product, a
dark brown liquid (a mixture of gasoline, diesel and heavy oils). Fractional distillation is
commonly used to separate petroleum oils. However, information on the distillation of the
pyrolytic oil obtained from fast pyrolysis of plastic wastes is scarce. We studied the distillation of
two pyrolytic oil samples derived from fast pyrolysis of polyethylene and mixed plastic wastes.
The former was distilled at the temperature of 180°C for 60 minutes and the latter was distilled at
the temperature of 150°C and 180°C for 90 minutes. We observed that the distillates had a lighter
color than the pyrolytic oil samples. The distillates were light yellowish at 180°C and colorless at
150°C. In the early stage of distillation, distillation rates increased with elapsed time and reached
a maximum at approximately 25-35 mL/min and then gradually dropped. The distillates had
lower densities and viscosities than the pyrolytic oils and both distillate properties were similar
to those of gasoline, i.e. densities of 706-728 kg/m3and viscosities of 0.39-0.43 ×10-6m2s-1.

Keywords: Alternative energy; distillate; gasoline; plastic waste; fast pyrolysis

Introduction

The raw pyrolytic oil obtained from commercial rotary kiln pyrolysis for municipal plastic
waste contained a wide range from compounds from C5 about C25 as well as other products [1].
This pyrolytic oil represents renewable energy. For example, blends of ‘plastic’ oil from catalytic
pyrolysis of waste high density polyethylene (HDPE) with diesel was tested in a compression
ignition (CI) engine [2]. The result showed brake specific fuel consumption (BSFC) increases
with increase in waste plastic oil blend ratio and decreases with increase in engine load.
Mechanical efficiency increases with brake power at all blend ratios. In addition, the carbon
monoxide (CO) emission for almost all loads and all blends was lower than for diesel. The
pyrolytic oil obtained from fast pyrolysis has been separated and improved with various
distillation methods, catalytic and molecular distillations and vacuum fractional distillation.
Wang et al. [3] adopted the methanol-water method to enrich pyrolytic lignins in the heavy
fraction of bio-oil by molecular distillation. The gasoline and diesel like fuels from waste tire oil
(WTO) was produced by using catalytic distillation [4]. The WTO in produced fuels was 18%,
70%, and 12% by weight for the light fuel, heavy fuel, and other product, respectively. Choi et
al. [5], took crude bio-oil from brown algae (Saccharina japonica) and separated it into four
fractions in a vacuum fractional distillation column. Three fractions condensed as distillate
according to the controlled distillate temperature and bottom fraction was solid residue.
However, study of distillation of the pyrolytic oil obtained from fast pyrolysis of plastic wastes is
scant. Therefore, we aimed to study the product obtained from pyrolytic oil from polyethylene
and mixed plastic wastes.
2. Methods 2.1 Raw materials Gasoline and diesel oil were purchased from common
commercial PTT oil stations in Thailand. The pyrolytic oil was collected from fast pyrolysis
process of polyethylene and mixed plastic wastes. The fast pyrolysis operates at a heating rate of
10o C/min up to 420o C in a laboratory scale reactor. 2.2 Distillation of mixture of gasoline and
diesel oil Type K thermocouples were installed in 6 positions: re-boiler, cooling water inlet and
outlet, outside column environment, vapor phase and distillate. 5 liters of 1:1 by volume gasoline
and diesel oil mixture was poured into the re-boiler and then heated at temperatures between 70-
200o C, i.e. the range of boiling points of the components of gasoline and diesel oil. Cooling
water flow rate was set at 20 liters per minute. The distillation column is a 10 tray fractionation
column. The temperature was recorded every minute for 1 hour. Time from the first drop of
distillate and then for every 500 ml of distillate for an hour and distillate volume were recorded.
The distillate was kept in a glass bottle in a dark place. The first drop of distillate, maximum
vapor temperature and mixture in reboiler temperature at steady state was illustrated as Fig. 1.
2.3 Distillation of pyrolytic oil obtained from fast pyrolysis of plastic waste In this section, we
ran two sets of experiments to distill pyrolytic oil obtained from (a) polyethylene waste (opaque
plastic bottles) and (b) mixed plastic waste. The distillation procedure was similar to that in
Section 2.2: we only changed the temperature at the re-boiler to 180o C with 1 hour of operation
for polyethylene and 150-180o C with 1.5 hours for mixed plastic. 2.4 Determination of
properties of distillate product The calorific value of the distillate product was tested using a
bomb calorimeter (Gallenkamp model adiabatic). The viscosity was measured by timing oil flow
through viscometer number 50 and calculated from Viscosity = calibration constant x time
where the calibration constant is 0.004484, time and and viscosity are in minute and mm2 /s
(or cSt). The mass of 20ml in a volumetric flask was measured with a balance (Ohuas model
EP413 with accuracy of 0.001 g) and used to calculate density. Each property was measured in
triplicate.
3. Results and Discussion 3.1 Distillation of mixture of gasoline and diesel oil Fig. 2 shows
the temperatures of vapor, distillate and mixture in reboiler during 1 hour of distillation. Vapor
temperature and mixture in reboiler temperature gradually increased with time. The vapor
temperature reached a maximum coinciding with the mixture temperature in the reboiler at
steady state (close to set temperature). After that, vapor temperature fell to around 34o C because
the volume of mixture in the reboiler decreased. Distillate and surrounding temperatures were
nearly constantly during 1 hour distillation. The temperature difference between cooling water
inlet and outlet was approximate 3-4o C (data not shown). Vapor did not condense at the top of
tower for a distillation temperature of 70o C because heating the reboiler at this temperature
could not generate sufficient pressure to overcome the pressure drop over the length of the
distillation tower. However, distillation at temperatures of 80-200o C led to the first drop of
vapor appearing at the top of tower after 5 minutes. The maximum vapor temperature and
mixture temperature in reboiler at steady state have been moved due to increasing of distillation
temperature.
3.2 Distillation of pyrolytic oil obtained from fast pyrolysis of plastic waste Temperature
changes of vapor, distillate, and mixture in reboiler were similar to changes for distillation of
mixtures of gasoline and diesel oil - see Fig. 2. The first drops of distillates from polyethylene
and mixed plastic wastes appeared later (about 14-15 minutes) due to several components in the
pyrolytic oil. Moreover, maximum vapor temperature and mixture temperature in the reboiler at
steady state appeared later (about 30 minutes) compared with the distillation of the gasoline and
diesel oil mixture. The condensation rate of distillate from polyethylene waste distillation at 180o
C for 1 hour increased in the first 15-25 minutes at 25 ml/min and then decreased after 25-45
minutes at 4 ml/min. Further distillate did not appear after 45 minutes until 1 hour of distillation.
Overall distillation rate was approximate 5.5 ml/min. For distillation from mixed plastic waste at
150o C, distillate only appeared in the first 14-25 minutes at 31 ml/min. Whilst, condensation
rate of distillation at 180o C increased in the first 15-35 minutes at 35 ml/min and then decreased
in the 35 minutes thereafter at 9.3 ml/min. Distillate obtained from polyethylene and mixed
plastic wastes at 180o C was light yellow, clear and homogeneous without impurities and
showed a darker yellow after 2 weeks. However, distillate from polyethylene waste was darker
than that from mixed plastic waste (Fig. 4). However, distillate of pyrolytic oil from mixed
plastic at 150o C was not changed after 2 weeks.
4. Conclusion The distillation can separate the lighter product from heavy residue in
pyrolytic oil as well. The lighter products (distillate) obtained from pyrolytic oil of mixed plastic
waste were colorless at 150o C and yellowish at 180o C. The distillation rate was not constant
during operation; it increased in the early period and gradually dropped. The overall distillation
rate for mixed plastic waste was higher than that for polyethylene waste. Increased distillation
temperature led to increased distillate volume. The densities and viscosities of distillate for both
plastic wastes were lower than the pyrolytic oils before distillation. Both of density and viscosity
of distillate were similar to those of gasoline, except the calorific value. The distilled product
from pyrolytic oil from plastic waste has potential to be used as gasoline replacement fuel.
Acknowledgements We thank the Faculty of Engineering for financial support and facilities.
References [1] Lee K. Thermal and catalytic degradation of pyrolytic oil from pyrolysis of
municipal wastes. J. Anal. Appl. Pyrolysis 2009; 85: p.372-379. [2] Kumar S, Prakash R, Murgan
S, Singh R.K. Performance and emission analysis of blends of waste plastic oil obtained by
catalytic pyrolysis of waste HDPE with diesel in CI engine. Energy conversion Management
2013; 74: p. 323-331. [3] Wang Y, Wang S, Leng F, Chen J, Zhu L, Luo Z. Separation and
characterization of pyrolytic lignin from the heavy fraction of bio-oil by molecular distillation.
Separation and purification Technology 2015; 152: p. 123-132. [4] Ayanoglu A, Yumrutas R.
Production of gasoline and diesel like fuels from waste tire oil by using catalytic pyrolysis.
Energy 2016; 103: p. 456-468. [5] Characteristics of vacuum fractional distillation from
pyrolytic macroalgae (Saccharina japonica) bio-oil. Journal of Industrial and Engineering
Chemistry 2016; Article in press, http://dx.doi.org/10.1016/j.jiec.2017.03.002.