Super deep desulfurization combined method for FCC (fluid catalytic cracking) gasoline

A combined method and deep desulfurization technology, which is applied in the petroleum industry, hydrocarbon oil treatment, hydrotreating process, etc., can solve the problems of long hydrodesulfurization process route, low sulfur capacity of adsorbent, frequent regeneration of adsorbent, etc., to achieve guaranteed Long-term stable operation, high activity, high adsorption selectivity and high adsorption capacity

Active Publication Date: 2014-03-26
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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Problems solved by technology

This shows that the adsorption sulfur capacity of the adsorbent still cannot meet the requirements of industrial applications; greatly limit its industrial application
[0009] To sum up, in the existing literature or patents, there are still some shortcomings in the ultra-deep desulfurization (sulfur content below 10ppmw) technology of gasoline: 1. The choice of hydrodesulfurization process is long, energy consumption is high, octane 2. In the process of selective hydrodesulfurization, the process of alkali washing to remove mercaptans also produces a large amount of alkali residue and other environmental problems; 3. The adsorption selectivity and adsorption of su

Method used

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  • Super deep desulfurization combined method for FCC (fluid catalytic cracking) gasoline
  • Super deep desulfurization combined method for FCC (fluid catalytic cracking) gasoline
  • Super deep desulfurization combined method for FCC (fluid catalytic cracking) gasoline

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preparation example Construction

[0054] 1. Preparation of protective agent 1: impregnate 100 grams of alumina carrier with 116 ml of a solution containing 0.44 grams of potassium hydroxide, dry at 120 degrees and roast at 450 degrees, then impregnate 5.95 grams of nickel nitrate and 3.72 grams of ammonium molybdate 85 milliliters of co-impregnation solution, after drying at 120 degrees and roasting at 450 degrees, the protective agent 1 is obtained, and its composition is 1.43wt%NiO-2.86wt%-0.30wt% / Al 2 o 3 . The preparation method of the protective agent 1 used in the following examples 1-8 is exactly the same, except that the content of each component is different.

[0055] 2. Preparation of protective agent 2: impregnate 100 grams of alumina carrier with 100 ml of a solution containing 0.92 grams of potassium hydroxide, dry at 120 degrees and roast at 450 degrees, then impregnate 11.90 grams of nickel nitrate and 7.44 grams of ammonium molybdate 70 milliliters of the co-impregnation solution, after dryin...

Embodiment 1

[0075] The full-cut FCC gasoline with the properties described in Table 1 is mixed with hydrogen and then enters the de-diene reactor after heat exchange through a heat exchanger. The de-diene reactor is filled with protective agent 1 (1.2%NiO-2.4%MoO 3 -0.28%K 2 O / Al 2 o 3 ) 2.5mL, protective agent 2 (2.8%NiO-5.2%MoO 3 -0.8%K 2 O / Al 2 o 3 ) 2.5mL, de-diene catalyst (16.2%NiO-18.2%ZnO-10.4%MoO 3 -13.5% WO 3 -5.2%Al 2 o 3 -2.4%TiO 2 -3.2%K 2 O / 30.9%SiO 2 -Al 2 o 3 ) 10mL, before the oil and hydrogen enter the diene reactor, the protective agent and the diene catalyst should be pre-sulfurized in the reactor. The vulcanization condition is to use straight-run gasoline containing 2wt% carbon disulfide to presulfurize the catalyst. The specific vulcanization conditions are hydrogen partial pressure 1.6MPa, temperature 290°C, liquid hourly space velocity 2.0h -1 , the volume ratio of hydrogen to oil is 300, and the vulcanization time is 9 hours. After the sulfidation...

Embodiment 2

[0077] The protective agent, diene removal catalyst, selective hydrodesulfurization catalyst and adsorbent used are the same as in Example 1, except that the diene removal process conditions become 100°C of reaction temperature, hydrogen partial pressure of 1.4MPa, and hydrogen-to-oil volume ratio of 80NL / L , night time space speed 3.0h -1 . Sampling analysis after reacting 500 hours, finds diene value from 1.1gI 2 / 100g oil drops below 0.1. The selected hydrodesulfurization process conditions become reaction temperature 280°C, hydrogen partial pressure 1.2MPa, hydrogen-oil volume ratio 100NL / L, night time space velocity 2.5h -1 . Adsorption desulfurization process conditions become adsorption temperature 300°C, hydrogen partial pressure 1.4MPa, hydrogen-oil volume ratio 50NL / L, night time space velocity 3.0h -1 . Sampling and analysis after 500 hours of reaction revealed that the total sulfur content had dropped from 268.6ppmw of the feedstock to 7.6ppmw, while the octan...

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Abstract

The invention relates to a super deep desulfurization combined method for FCC (fluid catalytic cracking) gasoline. The method comprises the steps of (1) with full fraction FCC gasoline and hydrogen as raw materials, enabling the raw materials to contact with protective agents 1 and 2 and a catalyst selectively removing alkadiene in a reactor removing alkadiene under proper conditions so as to remove most alkadiene in full fraction FCC gasoline raw material; (2) after the full fraction FCC gasoline with alkadiene removed in step (1) passes through a gas-liquid separator, dividing the liquid entering a fractionating tower into a light gasoline fraction and a heavy gasoline fraction; (3) enabling the heavy gasoline fraction obtained in step (2) to contact with the catalyst in a selective hydrogen desulfurization reactor under proper operation condition; (4) mixing the light gasoline fraction obtained in step (2) with the heavy gasoline fraction subjected to selective hydrogen desulfurization in step (3), then mixing with new hydrogen, and enabling the mixture to contact with an adsorbent in an adsorbing super deep desulfurization reactor under proper condition so as to remove most sulphur in the gasoline to obtain the ultra low sulphur gasoline product with content of sulphur less than 10ppmw.

Description

technical field [0001] The invention relates to a combined method for ultra-deep desulfurization of FCC gasoline, in particular to a combined method for ultra-deep desulfurization of FCC gasoline with a sulfur content of 200-1000 ppmw. The combined process can desulfurize FCC gasoline with a sulfur content of 200-1000 ppmw to below 10 ppm , while the octane loss is less than 1.5 units, and the liquid yield is greater than 99.8%. Background technique [0002] The SOx produced by the combustion of organic sulfur compounds in gasoline has many hazards to the environment, mainly including: acid rain, irreversible poisoning of the noble metal "three-way catalyst" in the engine exhaust gas purification system, and the main contributor to particulate matter in the atmosphere , corrosion of metal equipment, etc. For this reason, the United States promulgated a new Clean Air Act Amendment (CAAA) in the early 1990s, formulated more stringent environmental regulations, and imposed str...

Claims

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Application Information

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IPC IPC(8): C10G67/06
Inventor 李灿蒋宗轩刘铁峰杨民
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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