SSHT PROCESS A LOW COST SOLUTION FOR LOW SULFUR AND LOW AROMATIC DIESEL

Gao Xiao-dong; Nie Hong; Shi Yu-lin; Shi Ya-hua; Li Da-dong Research Institute of Petroleum Processing (RIPP), SINOPEC, China

Abstract
The need for cleaner fuels has resulted in a continuing worldwide trend to reduce diesel sulfur and aromatics. There are many approaches for reducing sulfur and aromatics in diesel. Major of them have a common drawback of expensive cost because of adopting two stages of hydrotreating and using noble-metal catalyst, especially for reducing aromatics. Which has led to the recent development of the SSHT process by Research Institute of Petroleum Processing (RIPP), SINOPEC. The SSHT process is a single-stage hydrotreating technology for producing low sulfur and low aromatics diesel. The process uses one or two unnoble-metal catalysts system and operates at moderate pressure. When revamping an existing unit to meet low aromatics diesel specification, the only thing need to do is adding a reactor or replacing the existing reactor. In pilot plant tests, SSHT technology has successfully treated SRGO, LCO and it's blends. It is shown, by using SSHT process, product diesel with sulfur of 30wppm and aromatics of 15wt% can be obtained from Middle-East SRGO (Straight Run Gas Oil), and product diesel with aromatics content of 25wt% from cracked feed, such as FCC-LCO. High diesel yields and cetane gain (from cracked feed stocks) gives SSHT technology a performance advantage compared to conventional hydrocracking and hydrotreating approachesrespectively. The lower cost for both investment and operating is anther the SSHT's advantage. The first commercial application of SSHT technology has been in operation in September of 2001.

1 Introduction
The SSHT process is a single-stage hydrotreating technology for producing ultra low sulfur and low aromatics diesel. It employs new Ni-W type catalysts, which are loaded in two reactors in series. The catalysts in the two reactors can be the same or difference. The reaction conditions in the two reactors are different. Today, many technologies of producing LSLA diesel adopt noble-metal catalyst. So these kinds of technologies have to adopt two-stage process to prevent noble-metal catalysts from poisoning by contaminants like sulfur or nitrogen compounds. But the catalysts used in SSHT process are unnoble-metal catalysts. So, both unit investment and operation cost are lower than two-stage process.

2 Performance of SSHT process 2.1 The pilot plant results

Table 1 illustrates the performance of SSHT process. From table 1 we can see that for the feed of LCO, which has aromatics content of more than 50wt%, LSLA diesel can be obtained. Under hydrogen partial pressure of 6.7MPa, aromatic content of product can meet the specification of diesel of category 2 of WWFC (World-Wide Fuel Chart); Additional, cetane number gain can be reach more than 14 units. So, the higher cetane gain is another advantage of SSHT process compared to conventional hydrotreating process. Nowadays, exception of two-stage process, which uses noble-metal catalyst, hydrocracking process, like MHUG process[1,2] developed by RIPP, can also produce LSLA diesel. But the two processes also have drawbacks. Two-stage process needs expensive cost on construction and operation, and hydrocracking process has lower diesel yield compared to conventional hydrotreating. From table 1 and table 2 we can see the diesel yield from SSHT process is more than 99%, it is almost the same as hydrotreating process. So, SSHT process is the best selection for production of LSLA diesel. Comparing table 2 with table 1, we can see that if the feed is SRGO, the operation condition is relative moderate compared to LCO. For the feed of SRGO with aromatics content of less than 30wt%, under hydrogen partial pressure of 6.4MPa, both category 2 and category 3 diesel of WWFC can be produced. Table 1 The performance of SSHT process (Pilot plant) Catalyst RN-10 PH2, MPa 6.7 Feedstock (LCO) LCO Properties: Product 876.1 Density (200C), kg/m3 839.0 Sulfur, wtppm 1518 26 Nitrogen, wtppm 959 <1.0 Total Aromatics, %m/m 53.4 23.1 Polyaromatics (di+tri+), %m/m 35.3 4.2 Cetane number 34.2 48.3 Distillation (D86), 0C TBP/50%/FBP 191/282/365 178/265/365 Cetane number gain 14.1 Diesel yield, %m/m Table 2 Catalyst Product Diesel PH2, MPa >99.0 Production of LSLA diesel from SRGO (Pilot plant) RN-10 Category 2 of Category 3 of WWFC WWFC 6.4 6.4 Feedstock (Arabian SRGO) 2Base Base 846.2 1.28 30.0 11.5 +5 825.1 0.017 17.0 1.1 +30 >99.0% 811.7 <0.003 9.0 0.5 +20 >99.0%

LHSV, h-1 Density (200C), kg/m3 Sulfur, %m/m Total Aromatics, %m/m Polyaromatics, %m/m Color (Saybolt) Diesel yield, %m/m

2.2 Commercial application results

The first commercial application of SSHT process was in September 2001 in refinery A of China. Table 3 shows the result of commercial application. From table 3 we can see that in commercial application SSHT technology acquits the same HDS and HDA performance as in pilot plant. Viz., under the hydrogen partial pressure of 6.1MPa, both sulfur and aromatic content of diesel product can meet the specification of diesel of category 2 of WWFC. The cetane number gain reaches 13.3 unit and diesel yield is more than 99wt%. Table 3 Commercial application result of SSHT process (Refinery A) Catalyst RN-10 PH2 of reactor inlet, MPa 6.10 Properties: Feedstock Diesel product Density(20)kg/m3 880.4 835.0 Sulfurwtppm 1400 0.6 Nitrogenwtppm 1121 0.6 Color (D1500) 3.0 0.5 Total Aromatics, %m/m 58.2 23.2 Polyaromatics, %m/m 35.2 4.9 Cetane number 31.5 44.8 Distillation(D-86) IBP/50%/90%/FBP 188/263/340/371 173/238/319/363 Diesel yield, %m/m 99.31

3 Conclusion
SSHT process is a low cost solution for producing low sulfur and low aromatics diesel, because of adopting unnoble-metal catalyst and single-stage process. It is shown, by using SSHT process, the category 3 diesel of WWFC can be obtained from Middle-East SRGO (Straight Run Gas Oil), and the category 2 diesel of WWFC from cracked feed, such as FCC-LCO. Compared to conventional hydrotreating process, SSHT has higher cetane number gain, normally more than 10 units. And compared to hydrocracking process, which is a method of production of LSLA diesel, SSHT process has higher diesel yield, normally higher than 99.0%.

Reference
1 NPRA, AM-93-56, 1993. 2 NPRA, AM-96-65, 1996.