S Zorb™ 吸附脱硫技术: 能同时解决 FCC 汽油脱硫和辛烷值增加的先进技术 Dayong Dong Technology Licensing Director Ricky Snelling, PhD Product Director

演讲内容提要 S Zorb 的基本化学反应 S Zorb 的基础工艺流程 工业化使用的经验 近期的发展

解决硫再次反应的问题 Hydrotreating + 3H2 H2S + S Zorb SRT Treatment Catalyst S + 2H2 + Sorbent Sorbent-S + S

S Zorb SRT 工艺流程概观

S Zorb SRT 工艺的长处 反应活性自始至终持久不衰 极低的生焦反应 高度的工艺弹性/适应性 流动床操作温度分布均匀 可以轻易的调整工艺操作条件来适应进料组成的变化 可进行在线的吸附剂替换 氢气纯度对操作性能影响不大

S Zorb SRT 工艺的特别效应 以低成本脱硫至10ppm以下 维持最低限度的成品汽油辛烷值的损失 极低限度的氢耗 极低限度（接近于零）的液流损失 除脱硫外，对进料的其他组成几乎完全没有影响 操作周期可完全 配合FCC 装置

已经在运行的工业装置 康菲公司的 Borger 炼厂 - 6,000 bbl/d (0.3 MM MTY) - 2001年4月开工 康菲公司的 Ferndale 炼厂 - 20,000 bbl/d (0.9 MM MTY) - 2003年11月开工 康菲公司 Lake Charles 炼厂 - 38,500 bbl/d, (1.7 MM MTY) - 2005年10月开工

康菲公司的工业装置 Borger 炼厂

康菲公司的工业装置 Ferndale 炼厂

Ferndale 工业装置的实际效应

正在进行中的工业装置 燕山石化 (中国北京) 29,000 BPD (1.2 MM MTY) 预计2006年8月开工 PRSI (美国休斯顿), 40,000 BPD (1.8 MM MTY) 预计2007年初开工 康菲公司 Wood River 炼厂 32,000 bbl/d (1.3 MM MTY) 预计2007年初开工 Unannounced, North America 30,000 bbl/day ( 1.3 MM MTY) 预计2007年12月开工

汽油脱硫过程中保持辛烷值 传统加氢脱硫技术都避免不了相当程度的成品油辛烷值损失 用S Zorb技术脱硫几乎能完全避免成品油辛烷值的损失 烯烃加氢饱和是辛烷值损失的主要原因 用加氢脱硫技术脱硫到95%时，成品汽油的RON值就会降低至少2个单位 用S Zorb技术脱硫几乎能完全避免成品油辛烷值的损失 S Zorb能在烯烃饱和活性极低的条件下有效地脱硫 少量的烯烃饱和反应还是难免的 在S Zorb工艺上使用适量的辛烷值增效添加剂能达到使成品油辛烷值不变甚至辛烷值增加的效用 此添加剂的应用使S Zorb工艺的经济性更高 此反应的副产品还能用来做烷基油的原料

一般辛烷值增效的手段 加氢异构 加氢裂化 烷烃异构 把烯烃先分离后再加氢脱硫* * 需要添加设备，操作费用也可能提高

调配选择性异构和裂化反应 n-decane 2,2,3,3 tetramethylhexane 异构 (R+M)/2 = -20 Propylene (R+M)/2 = 83.7 无反应 分子太大 (R+M)/2 = 93.4 异构 裂化 2,4 dimethylpentane

工业化经验 催化剂已成功应用于工业装置操作 试验数据得到验证: (Borger and Ferndale) 辛烷值改进性良好 – 增加0.5～1.0 (R+M)/2 C4- 略有增加 –损失 <0.2 vol% (低辛烷值组分) 催化剂与过程及吸附剂有量好的兼容性 吸附剂磨损速率无增加 催化剂寿命长 具有维持和恢复催化剂活性能力 操作性能可靠 ConocoPhillips experience with process enhancing catalysts has not been limited to the laboratory and pilot scale. Third party commercial zeolite catalysts have been used in the S Zorb unit located in Borger, Texas, USA for the past two years. Likewise, the S Zorb unit located in Ferndale, Washington, USA has been using an octane enhancing zeolite catalyst for the last nine months. Experience to date has been very positive and has demonstrated a good octane boost with only a slight decrease in gasoline yield. Depending on feedstock properties, anywhere from 0.5 to 1.0 (R+M)/2 increases have been achieved relative to baseline operation without the catalyst. The resulting gasoline volume loss is typically less than 0.2 vol%. In addition, the zeolite catalysts have shown excellent compatibility with the S Zorb sorbent and process. No effect on sorbent attrition has been observed. The catalyst is continuously regenerated along with the sorbent and shows no evidence of activity degradation over time. This is not surprising since the S Zorb reaction and regeneration conditions are much less severe than in typical FCC conditions where these kind of zeolite catalysts can deactivate rather quickly. The S Zorb regeneration conditions have proven more than adequate to remove any coke which may be deposited on the catalyst in the reactor and, thus, full catalyst activity is retained.

Octane Change vs. wt% Octane-Enhancing Catalyst Borger 炼厂催化剂操作性能 Octane Change vs. wt% Octane-Enhancing Catalyst 0.5 0.4 0.3 0.2 RON Octane Change (Product - Feed) 0.1 MON (R+M)/2 -0.1 This slide shows the C5+ FCC gasoline octane enhancement vs catalyst concentration experienced during initial trials in the S Zorb unit in Borger, Texas. Again this confirm a positive boost in both gasoline RON and MON with relatively small amounts of catalyst addition. Most of the benefit of the catalyst, in terms of octane enhancement, can seen within the first 0 to 10wt% of addition. Beyond that, we see diminishing benefits to gasoline octane. -0.2 -0.3 2 4 6 8 Octane-Enhancing Catalyst Concentration, wt%

工业化数据 平均脱硫率 = 99.0% At Ferndale, the value created by these incremental octane barrels has been significant. This figure illustrates the average RON and MON loss experienced before and after the addition of the octane enhancing catalyst. The average increase in RON and MON was 0.8 and 0.5 respectively. The S Zorb unit operating with catalyst enhancement not only allows the refinery to comply with US EPA Tier II gasoline sulfur specifications and beyond, but puts additional octane barrels in the pool and has allowed for significant reductions in the severity of their reformer operations. This is just one of many ways a refiner can realize value from the increased flexibility that this development offers. The most attractive feature of this technology is that the benefits can be achieved with no incremental investment cost and minimal incremental operating costs. For example, the incremental catalyst costs at Ferndale equates to <0.3 US cents/barrel.

辛烷值增效催化剂 为什么应该用在S Zorb SRT 而不是用在FCC装置? 磨损率非常低 不影响 FCC 处理量 (比如湿气压缩机WGC的限制) 使炼厂在汽油辛烷值调配的选择上有更大的灵活性 经济效应更好 The specialized zeolite catalyst technology that is being used with S Zorb SRT was actually developed for use in FCC units and has been used successfully in that application for many years. This raises the natural question of: “Why would one wish to use these catalysts in an S Zorb unit rather than the FCC unit?” There are a number of good reasons. As was discussed previously, the lower reaction temperatures used for S Zorb SRT allow for much more selective octane enhancement than is achievable using a similar zeolite catalyst in the FCC. If the goal is to increase the FCC naphtha octane value without sacrificing yield or creating additional LPG and light gases to deal with, then using this catalyst in an S Zorb may be the preferred option. Our experience has shown that S Zorb SRT is at least eight times more selective than the FCC in this regard. Another factor to consider when comparing the two applications is the cost of zeolite catalyst replacement. Relatively harsh FCC regeneration conditions along with the high levels of contaminants (like vanadium) in FCC feed mean that the special zeolite catalysts added to the FCC will deactivate rather quickly. This creates a need for high FCC catalyst turnover rates, and subsequently high catalyst costs are associated with octane enhancement in the FCC. In contrast, the feed to the S Zorb unit is relatively free of these contaminants and process conditions are relatively mild leading to much longer catalysts life. Since both the sorbent and catalyst attrition rates are very low, the resulting zeolite catalyst make up costs are extremely low relative to those of the FCC application. Perhaps the most important advantage of applying process enhancing zeolite catalysts to the S Zorb unit rather than the FCC is the simple fact that doing so will have no impact on the existing FCC operations. FCC wet gas compressor limits or catalyst circulation limits can sometimes restrict a refinery’s ability to take advantage of zeolite catalyst addition due to the increased gas make and/or coke make associated with using them. These constraints can ultimately limit or reduce FCC throughput making the use of special zeolite catalysts uneconomical. Having the ability to use the enhancement catalysts in an S Zorb unit avoids any negative impacts on FCC operations. For all of these reasons, octane enhancement via S Zorb SRT will have stronger economics than the traditional FCC application. The next slides gives an example of what we mean here.

Refinery Flexibility Sulfur Removal Alkylation Feed Blending Options One Reactor One Step Economical 10-ppm Solution Alkylation Feed Selective C4 olefin make Selective C3 olefin make Blending Options High Octane Retention No need for Blend stocks Reformer Runs Reformer Severity Reformer Off Load Feed Freedom Feed Upset Tolerant Opportunity Feed Pool Octane Increased Blending Octane No Removal Sulfur Penalty Coker Naphtha Free reformer Free HDS capacity FCC Operations FCC Throughput Stability Reduced Additive Cost Hydrogen Options Once Through Low Purity / Sweetening Splitter Operations Optimize for Profits Lights ends / Heavy ends

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