“I was reminded that when we lose and I strike out, a billion people in China don't care.” -- Reggie Jackson (African-American baseball player, b.1933)
Patents constitute a unique source of technical literature. In many cases, the information you find in a patent is available nowhere else.
If you are an expert in a specific field, you will want to search the patent database to keep up with new developments in the field.
Patents are also a great way for the novice to get up to speed on an unfamiliar topic.
Google®, through a partnership with the U.S. Patent & Trademark Office, has made it so easy to search for patents there is no excuse not to do so.
Suppose you want to see how nanotech is impacting desulfurization. Suppose, further, that you are only interested in the most recent technical literature. One way to approach the task …
- Go to Google® (www.google.com) in your browser
- Click on “more” in the Google® Web ribbon at the top of the Google search page … then click on “even more” [see screen shot]
- Scroll down and click on “Patent Search”
- Click on “Advanced Patent Search” [see second screen shot]
- Type nano desulfurization in the “With All The Words” box
- Type 2010 and 2011 in the “Return patents between” boxes [see third screen shot]
- Click Google Search and browse results (one of which appears below the screen shots)
One of the results is …
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Method For Hydro-Upgrading Inferior Gasoline Via Ultra Deep Desulfurization And Octane Number Recovery
Inventors: Yu FAN, Xiaojun BAO, Gang SHI, Haiyan LIU
Assignee: China University Of Petroleum - Beijing (Cupb)
Application number: 12/725,939
Publication number: US 2010/0236978 A1
Filing date: Mar 17, 2010
TECHNICAL FIELD
[0001] The invention relates to a hydro-upgrading method for inferior gasoline, especially to a hydro-upgrading method by ultra-deep desulfurization and octane number preservation for inferior gasoline, in particular for poor fluid catalytic cracking (FCC) gasoline with ultra-high sulfur compounds and high olefins in the field of petroleum refining.
RELATED ART
[0002] Currently, the high sulfur and olefin content of FCC gasoline have become a main source of trouble in the production of clean gasoline worldwide. In the case of deficient reformed gasoline and alkylated gasoline with high octane number, the hydro-upgrading of FCC gasoline becomes one of the key technologies for the production of clean fuels for vehicles in order to meet increasingly strict standards required for clean gasoline.
[0003] U.S. Pat. No. 5,770,047, U.S. Pat. No. 5,413,697, U.S. Pat. No.5,411,658, and U.S. Pat. No. 5,308,471 have disclosed a desulfurization and olefin-reducing process primarily based on hydro fining and cracking/single-branchedchain hydroisomerization. This process includes cutting fullrange FCC gasoline into the light and heavy fractions, deeply desulfurizing the heavy fraction of FCC gasoline by using conventional hydrofining catalysts to convert olefin into alkane completely, then carrying out alkane cracking and hydroisomerization reaction over the highly acidic HZSM-5 zeolite-based catalyst, and finally obtaining the full-range upgraded gasoline by blending the light and heavy fractions. According to the description of the above patents, the liquid yield of the final blended product is 94 wt % by weight, and the loss of research octane number (RON) in gasoline is about 2.0 units.
[0004] US2008116112A1 has disclosed a method for upgrading gasoline with high aromatics and sulfur contents. The procedures of such upgrading method disclosed by this patent are as follows: firstly the gasoline is cut into the light and heavy fractions; then the light fraction undergoes a alkylation reaction in a fixed-bed reactor followed by a desulfurization process without hydrogen and the heavy fraction is subjected to an alkylation reaction between olefins and sulfur compounds to make the boiling point of the sulfur compounds therein higher than the end boiling point of the heavy gasoline and the sulfur compounds with the higher boiling point removed by cutting. This method cannot remove the sulfur compounds in gasoline, but only excludes the obtained sulfur compounds with the higher boiling point from gasoline by cutting and fractionating.
[0005] US2005092655A1 has disclosed a desulfurization method for gasoline including the following steps: firstly cutting gasoline into the light and heavy fractions to allow the light thiophene and methylthiophene to remain in the light fraction and the heavy aromatic sulfur compounds to remain in the heavy fraction, then subjecting the heavy fraction to hydrodesulfurization and desulfurizing the light fraction in contact with solid adsorbents. Since the feedstock used in this method is a model gasoline composed of a mixture of mono
mer sulfur compounds and monomer hydrocarbons, it is difficult to predict the upgrading effect of the method on real FCC gasoline.
[0006] Although desulfurization and olefin reduction could be achieved by the above-mentioned gasoline hydro-upgrading methods, the targeted feedstock generally has an olefin content of20-30 v % by volume and a high aromatics content (about 25 v % by volume). For the gasoline with high olefin and sulfur contents but low aromatics content (about 15 v % by volume), such as Chinese FCC gasoline in which the olefin content is up to 40 v % by volume or more, the above hydroupgrading process can lead to the great saturation of olefins via hydrogenation, substantially increasing the loss in gasoline octane number. Therefore, these upgrading technologies reported publicly are clearly not applicable to the above case. In view of this, aiming at the particularity of Asian (especially Chinese) FCC gasoline, a more scientifically rational method for upgrading more inferior gasoline has always been a research focus in the petroleum refining industry. [0007] CN1465666A (Chinese Patent Application No. 02121595.2) and CN1488722A (Chinese Patent Application No. 02133111.1) have provided a method for deep desulfurization and olefin reduction of gasoline. According to the above-mentioned characteristics of Chinese FCC gasoline, the method involves subjecting the heavy gasoline fraction to hydrodesulfurization, hydrodenitrogenation and complete olefin saturation over a hydrofining catalyst, then cracking and hydroisomerizing of the formed alkanes with low octane number to recover the product octane number over a catalyst with sufficiently acidic function, and finally mixing the light and heavy fractions to obtain the final upgraded product. According to the description of the above patent, olefins are completely saturated by hydrogenation in the first reaction stage, so it is required to increase the cracking ability of the second-stage catalyst to recover the product octane number, which results in a significant reduction in the product liquid yield (only 86%) and greatly increases the processing cost. [0008] CN1743425A (Chinese Patent Application No. 200410074058.7) has disclosed a hydro-upgrading process for Chinese FCC gasoline with high olefin content. Wherein, after the full-range FCC gasoline undergoes the three reactions of diene removal, olefin aromatization and supplemental olefin reduction, the full-range product is obtained with a desulfurization ratio at 78%, the content of olefins at 30 v % by volume, the RON loss at 1.0 unit, and the liquid yield at about 98.5 wt % by weight. However, this method is only suitable for the FCC gasoline with the low sulfur content, and has a low desulfurization ratio and a poor olefin reduction, leading to worse product quality than that regulated by European III and IV standard for clean gasoline. Thereby, this method is obviously not suitable for FCC gasoline feedstock with the medium and high sulfur content. [0009] CN1718688A (Chinese Patent Application No. 200410020932.9) has disclosed a hydro-upgrading method for inferior FCC gasoline. This method includes removing dienes in full-range FCC gasoline at high feeding space velocity (6 h-1) over a conventional hydrofining catalyst, followed by olefin aromatization at high temperature (415° C.) using a nano-zeolite catalyst and by selective desulfurization at high temperature (415° C.) and higher space velocity (40 h"1) using a Co—Mo—K—P/A1203 catalyst. The resulting product has low olefin and sulfur contents, while the RON loss of the product is about 3.0 units and the product liquid yield is only about 94 wt % by weight. The nano-zeolite with complicated preparation is prone to be deactivated at high temperature and has a poor regeneration performance. In addition, the desulfurization catalyst in the third stage also tends to be deactivated at very high space velocity and very high temperature. Thus, the reaction stability of the whole process is undesirable.
[0010] In summary, for inferior fuels such as FCC gasoline with high sulfur and olefin contents, it has been attempted in different ways to achieve desulfurization and olefin reduction while maintaining and improving the product octane number as much as possible, and the effect of single-branched-chain hydroisomerization of hydrogenated product on the octane number recovery is also mentioned. However, the disclosed methods have their own advantages and disadvantages, especially lacking of a further concern about the importance of eco-friendly multi-branched-chain hydroisomerization of hydrocarbons in increasing the octane number of FCC gasoline. Thus, it is always the object sought in the petroleum refining field to probe for a more reasonable upgrading process and select the catalysts with suitable functions and activities, in order to achieve deep desulfurization and olefin reduction while maintaining octane number, and to solve problems such as undesirable catalyst stability and high processing cost.
SUMMARY
[0011] To solve the above technical problems, an object of the invention is to provide a method for hydro-upgrading inferior gasoline by a combined process, which includes prefractionating inferior full-range gasoline into the light and heavy fractions, then treating the light fraction and the heavy fraction respectively, and finally obtaining the ultra-clean gasoline product with the ultra-low sulfur content, the ultralow olefin content and the high octane number by blending the respectively upgraded light and heavy fraction gasolines. This method is particularly suitable for upgrading inferior FCC gasoline with high olefin content and ultra-high sulfur content, and can achieve the effects of ultra-deep desulfurization, great olefin reduction and octane number recovery. [0012] To accomplish the above objects, the invention provides a method of hydro-upgrading inferior gasoline through ultra-deep desulfurization and octane number recovery, comprising ... [ et cetera ]
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