Addition methods of sulfur and sulfur/phosphorus-based compounds on coking behavior during thermal cracking of naphtha

WANG Zhiyuan; DING Xudong; WANG Boyan; XING Zhihong

doi:10.11949/0438-1157.20200332

您当前的位置：

首页 >

文章列表页 >

Addition methods of sulfur and sulfur/phosphorus-based compounds on coking behavior during thermal cracking of naphtha

Energy and environmental engineering | 更新时间：2026-07-24

- Addition methods of sulfur and sulfur/phosphorus-based compounds on coking behavior during thermal cracking of naphtha
- CIESC Journal Vol. 71, Issue 11, Pages: 5320-5336(2020)
- 作者机构：
  
  上海理工大学能源与动力工程学院，上海市动力工程多相流动与传热重点实验室，上海 200093
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20200332
  CLC： TE 624;TK 227.2
- Received：30 March 2020，
  
  Revised：2020-06-10，
  
  Online First：03 November 2020，
  
  Published：05 November 2020
- 稿件说明：
移动端阅览
王志远, 丁旭东, 王博研, 邢志宏. 硫化物和硫/磷化合物的添加方式对石脑油热裂解结焦影响的研究[J]. 化工学报, 2020, 71(11): 5320-5336

WANG Zhiyuan, DING Xudong, WANG Boyan, XING Zhihong. Addition methods of sulfur and sulfur/phosphorus-based compounds on coking behavior during thermal cracking of naphtha[J]. CIESC Journal, 2020, 71(11): 5320-5336
王志远, 丁旭东, 王博研, 邢志宏. 硫化物和硫/磷化合物的添加方式对石脑油热裂解结焦影响的研究[J]. 化工学报, 2020, 71(11): 5320-5336 DOI： 10.11949/0438-1157.20200332.

WANG Zhiyuan, DING Xudong, WANG Boyan, XING Zhihong. Addition methods of sulfur and sulfur/phosphorus-based compounds on coking behavior during thermal cracking of naphtha[J]. CIESC Journal, 2020, 71(11): 5320-5336 DOI： 10.11949/0438-1157.20200332.

摘要

以石脑油为裂解原料，考察了硫化物和硫/磷化合物的添加方式对热裂解结焦行为的影响。采用Raman光谱、XRD、SEM和XPS等检测手段表征了HP40试样的氧化层和焦炭的形貌与结构。结果表明，原料连续注入硫化物条件下，磷化物的加入使得焦炭结构改变，显示出优异的抗结焦效果。硫化物和硫/磷化合物预处理导致氧化层中Fe含量升高，抑制结焦效果有限。硫/磷预处理与原料连续注入硫/磷化合物联合方式与原料连续注入硫/磷化合物方式的抗结焦效果接近，但前者在初期的抑制效果更明显。所有添加方式都会引起结焦层中无定形焦炭含量升高，焦炭的石墨化程度降低。热裂解焦炭缩合程度较高，硫化物和硫/磷化合物减少了催化结焦的生成，在一定程度上提高了焦层中氢含量。

Abstract

Using naphtha as raw material for cracking

the effects of adding sulfides and sulfur/phosphorus compounds on the coking behavior of thermal cracking were investigated. The morphologies and structures of the pretreated HP40 alloy specimen and coke deposits were characterized by Raman spectroscopy

XRD

SEM and XPS. The results showed that the addition of phosphide into the sulfide additives led to the change in the structure of coke deposits under the condition of continuous addition of additives into the feed. The method with continuous addition of sulfur/phosphorus-based compounds showed excellent anti-coking properties. The surface pretreatment with sulfur or sulfur/phosphorus-based compounds made the increase of Fe content in the oxide film on the specimen. So anti-coking effect was limited when the pretreatment method was applied. The coking inhibition property of the application of surface pretreatment with sulfide/phosphide followed by continuous addition of sulfur/phosphorus-based compounds were similar to that of the application of continuous addition of sulfur/phosphorus-based compounds in the feed. However

the combination method showed the better anti-coking effect during the initial cracking process. All the addition methods led to the increased amounts of amorphous coke in the coke layer and the decreased graphitization degree of cokes. The results of the low H/C ratios showed the highly condensed structure of the coke deposits during thermal cracking process. The addition of sulfur and sulfur/phosphorus-based compounds could influence the dehydrogenation reaction to some extent during the coke formation by reducing catalytic coking.

关键词

Keywords

references

Sarris S A , Olahova N , Verbeken K , et al . Optimization of the in-situ pretreatment of high temperature Ni-Cr alloys for ethane steam cracking [J ] . Industrial & Engineering Chemistry Research , 2017 , 56 ( 6 ): 1424 - 1438 .

Reyniers M F , Froment G F . Influence of metal surface and sulfur addition on coke deposition in the thermal cracking of hydrocarbons [J ] . Industrial & Engineering Chemistry Research , 1995 , 34 ( 3 ): 773 - 785 .

Singh A , Paulson S , Farag H , et al . Role of presulfidation and H 2 S cofeeding on carbon formation on SS304 alloy during the ethane-steam cracking process at 700℃ [J ] . Industrial & Engineering Chemistry Research , 2018 , 57 ( 4 ): 1146 - 1158 .

Wang J , Reyniers M F , Van Geem K M , et al . Influence of silicon and silicon/sulfur-containing additives on coke formation during steam cracking of hydrocarbons [J ] . Industrial & Engineering Chemistry Research , 2008 , 47 ( 5 ): 1468 - 1482 .

Kumar S . Triethyl phosphite additive-based fouling inhibition studies [J ] . Industrial & Engineering Chemistry Research , 1999 , 38 ( 4 ): 1364 - 1368 .

Wang J D , Reyniers M F , Martin G B . The influence of phosphorous containing compounds on steam cracking of n -hexane [J ] . Journal of Analytical and Applied Pyrolysis , 2006 , 77 ( 2 ): 133 - 148 .

Bao B B , Liu J L , Xu H , et al . Effect of selective oxidation and sulphur/phosphorus-containing compounds on coking behaviour during light naphtha thermal cracking [J ] . The Canadian Journal of Chemical Engineering , 2017 , 95 ( 8 ): 1480 - 1488 .

屈笑雨 , 刘京雷 , 徐宏 , 等 . 25Cr35NiNb 合金表面Al-Si-Cr 涂层抑制结焦性能 [J ] . 化工学报 , 2015 , 66 ( 3 ): 1059 - 1065 .

Qu X Y , Liu J L , Xu H , et al . Anti-coking characteristics of Al-Si-Cr coating on 25Cr35NiNb alloy [J ] . CIESC Journal , 2015 , 66 ( 3 ): 1059 - 1065 .

Bao B B , Liu J L , Xu H , et al . Inhibitory effect of MnCr 2 O 4 spinel coating on coke formation during light naphtha thermal cracking [J ] . RSC Advances , 2016 , 6 ( 73 ): 68934 - 68941 .

Yan N , Luo J L , Chuang K T . Improved coking resistance of direct ethanol solid oxide fuel cells with a Ni-S x anode [J ] . Journal of Power Sources , 2014 , 250 ( 15 ): 212 - 219 .

Sanchez-Tovar R , Leiva-Garcia R , Garcia-Anton J . Characterization of thermal oxide films formed on a duplex stainless steel by means of confocal-Raman microscopy and electrochemical techniques [J ] . Thin Solid Films , 2015 , 576 ( 2 ): 1 - 10 .

Ramya S , Anita T , Shaikh H , et al . Laser Raman microscopic studies of passive films formed on type 316LN stainless steels during pitting in chloride solution [J ] . Corrosion Science , 2010 , 52 ( 6 ): 2114 - 2121 .

Oblonsky L J , Devine T M . A Surface enhanced Raman spectroscopic study of the passive films formed in borate buffer on iron, nickel, chromium and stainless steel [J ] . Corrosion Science , 1995 , 37 ( 11 ): 17 - 41 .

Olahova N , Sarris S A , Reyniers M F , et al . Coking tendency of 25Cr-35Ni alloys: influence of temperature, sulfur addition, and cyclic aging [J ] . Industrial & Engineering Chemistry Research , 2018 , 57 ( 9 ): 3138 - 3148 .

Wang B , Wang S X , Liu B , et al . Oxide film prepared by selective oxidation of stainless steel and anti-coking behavior during n -hexane thermal cracking [J ] . Surface & Coating Technology , 2019 , 378 ( 25 ): 12492 - 12499 .

Boehm H P . Carbon from carbon monoxide disproportionation on nickel and iron catalysts: morphological studies and possible growth mechanisms [J ] . Carbon , 1973 , 11 ( 6 ): 583 - 595 .

Bennett M J , Chaffey G H , Myatt B L , et al . Inhibition by sulfur poisoning of the heterogeous decomposition of acetone [C ] // Lyle F A, Baker R T K. Coke Formation on Metal Surfaces . Washington D C, America : America Chemical Society , 1982 : 223 - 238 .

Salaha M B , Sabot R , Refait P , et al . Passivation behaviour of stainless steel (UNS N-08028) in industrial or simplified phosphoric acid solutions at different temperatures [J ] . Corrosion Science , 2015 , 99 : 320 - 332 .

Zhou J X , Xu H , Luan X J , et al . Influence of the SiO 2 /S coating and sulfur/phosphorus-containing coking inhibitor on coke formation during thermal cracking of light naphtha [J ] . Fuel Processing Technology , 2012 , 104 : 198 - 203 .

Reshetenko T V , Avdeeva L B , Ismagilov Z R , et al . Catalytic filamentous carbon: structure and textural properties [J ] . Carbon , 2003 , 41 ( 8 ): 1605 - 1615 .

Sadezkv A , Muckernhuber H , Grothe H , et al . Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information [J ] . Carbon , 2005 , 43 ( 8 ): 1731 - 1742 .

Sheng C D . Char structure characterised by Raman spectroscopy and its correlations with combustion reactivity [J ] . Fuel , 2007 , 86 ( 15 ): 2316 - 2324 .

Qian Z H , Zhang H F , Dai D J , et al . Study on occurrence of sulfur in different group components of Xinyu clean coking coal [J ] . Journal of Fuel Chemistry and Technology , 2014 , 42 ( 11 ): 1286 - 1294 .

Kicinski W , Szala M , Bystrzejewski M . Sulfur-doped porous carbon: synthesis and application [J ] . Carbon , 2014 , 68 : 1 - 32 .

Bu J , Loh G , Gwie C G , DeWiyanti S , et al . Desulfurization of diesel fuels by selective adsorption on activated carbons: competitive adsorption of polycyclic aromatic sulfur heterocycles and polycyclic aromatic Hydrocarbons [J ] . Chemical Engineering Journal , 2011 , 166 ( 1 ): 207 - 217 .

Timko M T , Wang J A , Burgess J , et al . Roles of surface chemistry and structural defects of activated carbons in the oxidative desulfurization of benzothiophenes [J ] . Fuel , 2016 , 163 ( 1 ): 223 - 231 .

Niakolas D K . Sulfur poisoning of Ni-based anodes for solid oxide fuel cells in H/C-based fuels [J ] . Applied Catalysis A: General , 2014 , 486 ( 22 ): 123 - 142 .

Yang Y , Zhang H P , Yan Y . Synthesis of CNTs on stainless steel microfibrous composite by CVD: effect of synthesis condition on carbon nanotube growth and structure [J ] . Composites Part B , 2019 , 160 ( 1 ): 369 - 383 .

Yu X , Kang Y , Park H S . Sulfur and phosphorus co-doping of hierarchically porous graphene aerogels for enhancing supercapacitor performance [J ] . Carbon , 2016 , 101 : 49 - 56 .

Cui S H , Li J H , Jayakumar A , et al . Effects of H 2 S and H 2 O on carbon deposition over La 0.4 Sr 0.5 Ba 0.1 TiO 3 /YSZ perovskite anodes in methane fueled SOFCs [J ] . Journal of Power Source , 2014 , 250 ( 15 ): 134 - 142 .

刘玉新 , 许志明 , 赵锁奇 , 等 . 哈萨克斯坦及俄罗斯渣油馏分中的硫化物裂解色谱分析 [J ] . 燃料化学学报 , 2008 , 36 ( 6 ): 712 - 719 .

Liu Y X , Xu Z M , Zhao S Q , et al . Analysis of sulfur species in the residue fractions of Kazakhstan and Russia crude oils pyrolysis-gas chromatography [J ] . Journal of Fuel Chemistry and Technology , 2008 , 36 ( 6 ): 712 - 719 .

Ren Y , Mahinpey N , Feeitag N . Kinetic model for the combustion of coke derived at different coking temperatures [J ] . Energy and Fuels , 2007 , 21 ( 1 ): 82 - 87 .

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Research on the characterization of the molecular weight and its distribution of perfluoropolyether

Study on dissolution kinetics of erythromycin thiocyanate

Thermodynamic study of germanium-impurity competitive deposition in GeCl4-MxCly-H2 system

Oxygen mass transfer performance of hollow fiber non-bubble aeration membrane based on gas/liquid-phase measurement method

Physics-informed spatio-temporal graph convolutional network for fermentation processes

Related Author

No data

Related Institution

No data

⁰