High-efficiency catalytic synthesis of polyoxymethoxy dimethylether from sulfolane-treated sulfonic acid resin

Yan WANG; Lei SHI; Jiaqi FAN; Fei CHEN; Jie YAO; Guangwen XU

doi:10.11949/j.issn.0438-1157.20180925

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High-efficiency catalytic synthesis of polyoxymethoxy dimethylether from sulfolane-treated sulfonic acid resin

Catalysis, kinetics and reactors | 更新时间：2020-06-24

- High-efficiency catalytic synthesis of polyoxymethoxy dimethylether from sulfolane-treated sulfonic acid resin
- CIESC Journal Vol. 70, Issue 1, Pages: 116-127(2019)
- 作者机构：
  
  1.沈阳化工大学能源与化工产业技术研究院，辽宁沈阳 110142
  2.沈阳化工大学应用化学学院，辽宁沈阳 110142
- 作者简介：
- 基金信息：
- DOI：10.11949/j.issn.0438-1157.20180925
  CLC： O 643.32
- Received：14 August 2018，
  
  Revised：2018-11-01，
  
  Published：05 January 2019
- 稿件说明：
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王岩, 石磊, 范家麒, 陈飞, 姚杰, 许光文. 环丁砜处理磺酸树脂高效催化聚甲氧基二甲醚合成[J]. 化工学报, 2019, 70(1): 116-127

WANG Yan, SHI Lei, FAN Jiaqi, CHEN Fei, YAO Jie, XU Guangwen. High-efficiency catalytic synthesis of polyoxymethoxy dimethylether from sulfolane-treated sulfonic acid resin[J]. CIESC Journal, 2019, 70(1): 116-127
王岩, 石磊, 范家麒, 陈飞, 姚杰, 许光文. 环丁砜处理磺酸树脂高效催化聚甲氧基二甲醚合成[J]. 化工学报, 2019, 70(1): 116-127 DOI： 10.11949/j.issn.0438-1157.20180925.

WANG Yan, SHI Lei, FAN Jiaqi, CHEN Fei, YAO Jie, XU Guangwen. High-efficiency catalytic synthesis of polyoxymethoxy dimethylether from sulfolane-treated sulfonic acid resin[J]. CIESC Journal, 2019, 70(1): 116-127 DOI： 10.11949/j.issn.0438-1157.20180925.

摘要

聚甲氧基二甲醚（DMM

3～7

）作为柴油添加剂可提高柴油十六烷值和燃料利用率，具有广阔应用前景。以环丁砜处理后的磺酸树脂为催化剂，用于甲缩醛（DMM）和三聚甲醛（TOX）合成DMM

3~7

反应，系统地研究了不同条件因素对反应过程中原料转化率和产物选择性的影响，并推断了反应机理。发现：反应体系中含有不同微量（mg/kg级）H

O对原料转化率和产物选择性影响较大；当H

O含量超过一定值时，有白色沉淀多聚甲醛（PF）生成，PF选择性随H

O含量增加而增大，同时生成大量甲醇，导致目标产物DMM

3~7

选择性降低。创新地采用环丁砜对酸性磺酸树脂NKC-9进行脱水处理，使固体催化剂表面及孔道吸附H

O含量从2154 mg/kg显著降至198 mg/kg；同时使用13X分子筛对原料DMM进行吸附脱水处理，使DMM中H

O含量从710 mg/kg明显降至54 mg/kg。当反应温度313 K（40℃）、反应2 h、压力1.0 MPa、DMM与TOX质量比2/1时，DMM和TOX转化率以及DMM

3～7

质量选择性分别从48.27%、88.41%以及45.27%显著提升至52.91%、93.34%和61.58%。与文献报道的数据相比，改性后的磺酸树脂在低温下即表现出极佳的催化效果，DMM

3～7

质量选择性突破60%。

Abstract

Polymethoxy dimethylether (DMM

3—7

) as a diesel additive can improve diesel cetane number and fuel utilization rate

and has broad application prospects. For the synthesis of DMM

3—7

from dimethoxymethane (DMM) and trioxymethylene(TOX)

this work systematically studied the effects of different conditional parameters on the conversions and products selectivity with the sulfolane-treated sulfonic acid as the catalyst and the reaction routes were proposed according to the results of products analysis by GC-MS. It was observed that trace amounts (mg/kg level) of H

O left in the reaction system significantly influenced the reactants conversions and products selectivity. With raising H

O content

more white precipitation paraformaldehyde (PF) was gradually produced

while methanol was substantially generated to lower the selectivity of DMM

3—7

. The sulfolane-treated method was first proposed and sulfolane solvent was acted as dehydration and pore-forming reagent

that resulted in the absorbed H

O in the surface/pores of NKC-9

sulfolane

obvious decrease from 2154 mg/kg to 198 mg/kg. Meanwhile

13X molecular sieve was applied to significantly reduce H

O content of DMM from 710 mg/kg to 54 mg/kg. When the reaction temperature is 313 K (40℃)

the reaction is 2 h

the pressure is 1.0 MPa

and the mass ratio of DMM to TOX is 2/1

the DMM and TOX conversion rates and the DMM

3-7

mass selectivity increase from 48.27%

88.41% and 45.27% to 52.91%

93.34% and 61.58%

respectively. Comparing to literatures reports

the mass selectivity to DMM

3-7

was higher than 60% that makes it promising for industrial applications.

关键词

Keywords

references

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