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Ultra-deep combined desulphurization method for full-fraction FCC gasoline

A technology of deep desulfurization and combination method, which is applied in the petroleum industry, hydrocarbon oil treatment, hydrotreating process, etc., can solve the problems of low sulfide adsorption selectivity and adsorption capacity, limited industrial application, and prone to disproportionation reaction.

Active Publication Date: 2013-01-30
陕西延长石油(集团)有限责任公司炼化公司 +1
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AI Technical Summary

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 sulfide by the adsorbent used in selective adsorption desulfurization The capacity is low, and it is difficult to achieve industrialization; 4. In the fluidized bed hydrogenation reaction-adsorption desulfurization, the operating conditions are harsh, the energy consumption is high, the loss of the adsorbent is serious, and the operating cost is high
Especially when the olefin content is high, the resulting octane loss exceeds 2 units; 5. In the fluidized bed hydrogenation reaction-adsorption desulfurization, the sulfur capacity of the adsorbent is low, the regeneration of the adsorbent is frequent, the energy consumption is high, and the operating cost is high. high

Method used

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  • Ultra-deep combined desulphurization method for full-fraction FCC gasoline
  • Ultra-deep combined desulphurization method for full-fraction FCC gasoline

Examples

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preparation example Construction

[0077] 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.

[0078] 2. Preparation of protective agent 2: impregnate 100 grams of alumina carrier with 100 ml of 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 drying ...

Embodiment 1

[0092] Example 1 (According to the present invention): Combination method of whole-distillation FCC gasoline de-diolefins and selective hydrodesulfurization and adsorption desulfurization

[0093] 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 (1 cm inner diameter) 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 deolefinization reactor, the protective agent and the deolefination catalyst must 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...

Embodiment 2

[0095] Example 2 (According to the present invention): Combination method of whole-fraction FCC gasoline de-diolefins, selective hydrodesulfurization and adsorption desulfurization

[0096] The protective agent used, the diene removal catalyst, the selective hydrodesulfurization catalyst and the adsorbent are the same as in Example 1, and the difference from Example 1 is that only the diene removal process conditions become 100 ° C of reaction temperature, and the hydrogen partial pressure is 1.4 MPa, hydrogen oil volume ratio 80NL / L, night hourly space velocity 3.0h -1 . Sampling analysis after reacting 500 hours, finds diene value from 1.2gI 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 1.4M...

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Abstract

The invention relates to an ultra-deep combined desulphurization method for full-fraction FCC gasoline. The method comprises the following steps: (1) with full-fraction FCC gasoline and hydrogen as raw materials, successively contacting the raw materials with a protective agent 1, a protective agent 2 and a selective dialkene removing catalyst in a dialkene removing reactor under proper operation conditions to remove the most of dialkene in the full-fraction FCC gasoline raw material; (2) contacting the full-fraction FCC gasoline having undergone dialkene removal in step (1) with a catalyst in a selective hydrodesulfurization reactor under proper operation conditions so as to remove 40 to 60% of sulfur in the full-fraction FCC gasoline; and (3) subjecting the full-fraction FCC gasoline having undergone selective hydrodesulfurization in step (2) to separation in a gas-liquid separator and gas stripping to remove hydrogen sulfide dissolved in the full-fraction FCC gasoline, then mixing the full-fraction FCC gasoline with fresh hydrogen and contacting the full-fraction FCC gasoline with a catalyst in an adsorption ultra-deep desulphurization reactor under proper operation conditions so as to remove the most of sulfur in the gasoline, thereby obtaining a gasoline product with ultra low content of sulfur. The method has the advantages of low loss of an octane value, high liquid yield, high adsorptive selectivity of an adsorbent, great sulfur capacity and the like while carrying out ultra-deep desulphurization.

Description

technical field [0001] The invention relates to a combined method for ultra-deep desulfurization of full-fraction FCC gasoline, in particular to a combined method for de-diene, selective hydrodesulfurization and adsorption ultra-deep desulfurization of full-fraction FCC gasoline with a sulfur content of 100-200 ppmw. The combined method can desulfurize sulfur The sulfur in the full-cut FCC gasoline with a content of 100-200ppmw is removed to less than 10ppm, while the octane number loss is less than 1.5 units, and the liquid yield is greater than 99.8%. Background technique [0002] SO produced by the combustion of organic sulfur compounds in gasoline 2 There are many harms to the environment, mainly including: acid rain, irreversible poisoning of the precious metal "three-way catalyst" in the engine exhaust gas purification system, the main contributor to particulate matter in the atmosphere, and corrosion of metal equipment. For this reason, the United States promulgated ...

Claims

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Application Information

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IPC IPC(8): C10G65/06
Inventor 沈浩李灿袁定雄罗万明刘宏伟王军峰李铖李达蒋宗轩刘铁峰杨民张荣
Owner 陕西延长石油(集团)有限责任公司炼化公司
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