Project Description

MS Gasoline Sulfur Reducing Additive FCC addtive

Applicable Scope

MS012 is an additive for reducing sulfur content in gasoline during FCC process.

Characteristics

MS012 is developed for reducing sulfur content in gasoline during FCC process. The physicochemical property of the additive is similar to cracking catalyst. It has fairly good fluidization property and appropriate cracking activity, so it can be directly blended with cracking catalyst and has no obvious negative influences on FCC operation, catalyst activity and selectivity, as well as product distribution and properties.

Design Philosophy

According to absorption and chemical reaction of sulfur compound on the additive, MS012 sulfur reduction additive performs hydrogen transfer reaction with alkenes via the Brönsted acid sites of the molecular sieve, to form the intermediate compounds like thioether or mercaptan. Then these intermediates are finally cracked to hydrogen sulphide and di-olefin, and the sulfur content in gasoline is effectively decreased.

Property

The main specification of MS012 were shown in Table 1.

Table 1 Main Specification of MS012

Item MS012
Attrition Index, %/h ≤3.5
Apparent Bulk Density, g/ml ≥0.66
Pore volume, ml/g 0.2
Surface area, m2/g ≥100
Average Particle size, μm 65-8.0
LOI, m% ≤13.0

Commercial Reference

The commercial trial of MS012 additive was carried out in refineries of SINOPEC Jingmen Petrochemical and Shijiazhuang Petrochemical. The feedstocks were both unhydrotreated and their properties during the commercial trial were shown in Table 2 and Table 3. In Jingmen Petrochemical, MS012 additive was about 10.6 wt% of the catalyst inventory after 4 months addition. Figure 1 showed that, with the addition of MS012, the S/S0 (sulfur in gasoline/sulfur in feedstock) gradually decreased by ~33 %. The end point of the naphtha was 190℃. The most challenging conditions for the application of gasoline sulfur reduction additive is encountering an E-cat with high levels of contaminating metals. In the commercial trial of Shijiazhuang Petrochemical, MS012 additive was added steadily into FCCU with 7382ppm of V and 4091ppm of Ni on the E-cat. In this trial, MS012 was added to a level of 10 wt% of the inventory. Figure 2 showed the additive achieved at least 16% reduction in naphtha sulfur corrected by the changing of feed sulfur.In addition, coke yield decreased slightly and the naphtha yield increased when compared to base case (Tables 4 and 5), negative influences on product yields were not observed.

Table 2 Feedstock Properties of Jingmen Commercial Trial

Items Base MS012
Residue blending ratio 37.89 37.44
Density (20℃ ), g/cm3 0.9356 0.9430
Carbon residue, % 4.89 5.01
Freezing point, ℃ 30 35
Total sulfur, % 0.5833 0.5850
C, % 88.07 88.29
H, % 12.93 12.61
Ni, μg/g 8.6 9.4
V, μg/g 0.83 1.24
Na, μg/g 3.6 3.2
Distillation range, ℃
IBP 205 215
10 % 360 370
30 % 409 414
50 % 453 465
<500 ℃ fraction, v% 59 57

Table 3 Feedstock Properties of Shijiazhuang Commercial Trial

Items Base MS012
Density (20 ℃), g/cm3 0.9031 0.8970
Carbon residue, % 4.86 4.40
Total sulfur, % 0.73 0.66
Ni, μg/g 7.4 2.9
V, μg/g 5.1 3.4
Fe, μg/g 3.9 6.9
Na, μg/g 0.5 2.1
Distillation range, ℃
IBP 251 238
50% 413 432

Table 4 Products Distribution of Jingmen Commercial Trial

Product distribution, wt% Base MS012
Dry gas 5.19 6.19
LPG 16.40 18.08
Naphtha 43.93 45.78
LCO 22.40 18.66
Slurry 3.75 3.30
Coke 8.33 7.99
Light ends yield 82.73 82.52

Table 5 Products Distribution of Shijiazhuang Commercial Trial

Product distribution, wt% Base MS012
Dry gas 3.93 4.29
LPG 14.37 14.55
Naphtha 39.57 41.62
LCO 27.75 26.57
Slurry 6.22 4.90
Coke 8.16 8.08
Light ends yield 81.69 82.74

image001

Figure 1 Sulfur reduction in naphtha in Jingmen commercial trial

(S/S0 is sulfur in gasoline/sulfur in feedstock)

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Figure 2 Sulfur reduction in naphtha in Shijiazhuang commercial trial

Commercial Application

SINOPEC Jingmen Petrochemical, SINOPEC Shijiazhuang Petrochemical

Products/Grades

MS011 and MS012

 

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