生活垃圾热解半焦-热解油重整过程中水分的消耗与转移

doi:10.11949/0438-1157.20190663

摘要/Abstract

摘要：

热解炭原位重整城市固体废物的挥发分是改善热解产物的良好方法。在这个过程中，水蒸气在产品转化中起着重要作用。为了了解水分在重整过程中的作用，本研究中将热解液中的油相和水相分离，然后用D₂O代替重整过程中的水相，以跟踪液体、气体和固体之间的氢转移。热解油/焦炭重整过程在600、700和800℃下进行。用GC-MS（气相色谱质谱法）分析重整后液体中的油相；IR-MS（同位素比质谱法）分析重整后液体和固体中的氘浓度。研究发现，在实验温度范围内，水蒸气对焦炭的气化作用非常弱，当D₂O/焦炭的比例为2/1时，D₂O中2％（质量）的氘在反应后残留在炭中;但水蒸气与热解油的气化反应很强烈，在800℃时，78.68％（质量）的热解液（水油混合物）被气化,且热解油中脂肪烃被大量分解，重整液的油相组分中芳香烃占到96.17%；同时，当D₂O/油的比例为2/3时，D₂O中59％的氘转移到合成气中。研究结果将为生活垃圾热解处理控制最终产物提供理论指导。

关键词: 热解半焦, 热解油, 同位素, 氘, 氢转移

Abstract:

The in situ reforming of volatiles from municipal solid waste by pyrolytic carbon is a good method for improving pyrolysis products. In this process water vapor plays an important role on product conversion. In order to understand the role of water vapor during the reforming process, oil phase and aqueous phase in the pyrolysis liquid are separated and then D₂O was used to replace the aqueous phase to mix with oil so that hydrogen transfer between liquid, gas and solid can be tracked in the reforming process. The vaporized oil/char reforming process was performed at 600℃, 700℃ and 800℃, respectively. The oil phase and deuterium concentration in the liquid (oil and aqueous phase together) after reforming were measured with help of GC-MS and IR-MS(isotope ratio mass spectrometry); at the same time deuterium concentration in the solid phase was also checked. It has been found that char gasification by water vapor at all testing temperature ranges is very weak, at 700℃ 2% of deuterium in D₂O was remained in the char when the ratio of D₂O/char was 2/1. While oil gasification by water vapor during char-catalytic reforming process is very intense: at 800℃ 78.68% of total oil-water mixture is gasified, and the aliphatic hydrocarbons in the oil are decomposed to a large extent, but the aromatic hydrocarbons are found to account for 96.17% of the oil phase after reforming. Simultaneously 59% of deuterium in D₂O was found to transfer into syngas when the ratio of D₂O/oil was 2/3. The research results obtained here will provide guide for improving the final products of MSW pyrolysis.

Key words: pyrolysis char, pyrolysis oil, isotope, deuterium, hydrogen transfer

中图分类号:

X 705

雷开元, 陈德珍. 生活垃圾热解半焦-热解油重整过程中水分的消耗与转移[J]. 化工学报, 2019, 70(12): 4795-4803.

Kaiyuan LEI, Dezhen CHEN. Water consumption and transfer during MSW pyrolysis char-vaporized pyrolysis oil reforming process[J]. CIESC Journal, 2019, 70(12): 4795-4803.

图/表 14

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Composition/%(mass)					Residue	HHV/(MJ/kg)
Kitchen wastes	Paper	Cloth and fiber	Plastics	Wood	Residue	HHV/(MJ/kg)
14.23±0.88	6.32±0.27	27.54±1.14	22.44±0.98	3.42±0.41	26.05±1.03	15.77±0.21

Composition/%(mass)					Residue	HHV/(MJ/kg)
Kitchen wastes	Paper	Cloth and fiber	Plastics	Wood	Residue	HHV/(MJ/kg)
14.23±0.88	6.32±0.27	27.54±1.14	22.44±0.98	3.42±0.41	26.05±1.03	15.77±0.21

Proximate analysis			Ultimate analysis
A	V	FC	C	H	S	N
41.74±1.01	11.05±0.77	47.21±1.23	41.39±1.12	1.19±0.12	0.71±0.09	1.07±0.11

Proximate analysis			Ultimate analysis
A	V	FC	C	H	S	N
41.74±1.01	11.05±0.77	47.21±1.23	41.39±1.12	1.19±0.12	0.71±0.09	1.07±0.11

Experiment scenario	Reactant	Temperature/℃	Liquid product	Gas product	Residue char
1	water	600	RL1	RG1	RC1
2	water	700	RL2	RG2	RC2
3	water	800	RL3	RG3	RC3
4	water +oil	600	RL4	RG4	RC4
5	water +oil	700	RL5	RG5	RC5
6	water +oil	800	RL6	RG6	RC6
7	water +oil	800	RL7	RG7	—