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Method of diesel oil oxidation extraction and desulfurization

A diesel oil and extraction technology, which is applied in the direction of multi-stage serial refining process, can solve the problems of difficult removal of thiophene sulfides, high processing costs, and large investment, so as to prevent the quality of oil products from being affected and reduce operating costs , the effect of reducing production costs

Inactive Publication Date: 2006-11-29
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the traditional hydrofining process is effective, there are still many problems as follows: 1. Large investment; in addition to building high-temperature and high-pressure treatment equipment, hydrogen production equipment (if there is no hydrogen reforming), sulfur recovery equipment, etc.
2. Due to the high temperature and high pressure hydrogen consumption involved in the processing process, the processing cost is relatively high; 3. Due to the generation of highly toxic hydrogen sulfide during the processing process, it will inevitably cause environmental pollution
4. Hydrofining can effectively remove non-thiophene sulfides in diesel oil, but it is very difficult to remove thiophene sulfides, especially benzothiophene, dibenzothiophene and their derivatives
Since the catalyst can only handle low-concentration (sulfur content ≤ 1000ppm) pre-hydrogenated diesel, it is difficult to remove a large amount of sulfur in high-concentration pre-hydrogenated diesel and non-hydrogenated diesel, so there are great defects. to be further improved

Method used

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Embodiment 1: the preparation of catalyst

[0039] The expression of the phase transfer catalyst of the present invention is Q 3 [XM n o q ], where: 1≤n≤11;

[0040] Q is a quaternary ammonium salt cation (C x h 2x+1 ) 4 N + ), the carbon chain length of at least one group in the quaternary ammonium salt cation is greater than or equal to 8 carbon atoms. It is not difficult to understand that the quaternary ammonium salt ion in the phase transfer catalyst of the present invention can be one of the following:

[0041] (C 8 h 17 ) 4 N + , (C 12 h 25 ) 4 N + , (C 16 h 33 ) 4 N + , (π-C 5 h 5 N + C 16 h 33 ), [(C 18 h 37 )(75%)+(C 16 h 33 )(25%)] 2 N + (CH 3 ) 2 , (C 18 h 37 ) 2 N + (CH 3 ) 2 .

[0042] X is phosphorus, silicon or arsenic, preferably phosphorus or arsenic is selected for effect, and phosphorus is the best effect.

[0043] M is molybdenum or tungsten, the most effective is tungsten.

[0044] It should be noted that as...

Embodiment 2

[0047] (1) Take 25ml of hydrogenated refined diesel oil with a sulfur content of 340ppm in a conical flask, add 0.02248g of catalyst A (after grinding) at room temperature, then add 0.11ml of hydrogen peroxide, stir vigorously for 30min, (2) put the above treatment Catalyst is recovered by centrifugal separation of diesel oil. (3) Add 13ml of 5% sodium thiosulfate solution to the diesel oil treated in the above step (2), stir for 30min, remove the lower aqueous solution with a separatory funnel, wash with water three times (25ml each time), and use 10g of water and sodium sulfate to dry. (4) Extract the dry diesel oil with 25ml of composite extractant ([N-methylpyrrolidone: (N-methylpyrrolidone+water)]=75-95%), separate the lower composite extractant, and repeat the extraction twice. The sulfur content of the obtained diesel oil was determined by microcoulomb titration, and the results are listed in Table 1.

Embodiment 3

[0049] The temperature of step 1 is 30 ℃, all the other operating conditions are the same as embodiment 2.

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PUM

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Abstract

The invention relates to diesel oil oxidation extraction desulphurization method. It includes the following steps: mixing the hydro-fining or non diesel oil with phase-transfer catalyst; adding hydrogen peroxide to react for 30-300min to transform organic sulfide to sulfone or sulfoxide; cooling the oxidation diesel oil to room temperature to separate out the phase-trasnfer catalyst; processing by reducer aqueous solution with 5-20% density to remove un-reacted hydrogen peroxide; and processing by extracting agent to remove sulfone or sulfoxide to gain low sulfur diesel oil with less than 350ppm sulfur content.

Description

technical field [0001] The invention relates to a method for oxidative desulfurization, in particular to a method for oxidative extraction desulfurization of diesel oil. Background technique [0002] SO produced by the combustion of organic sulfur compounds in fuel oil x Not only can it cause acid rain, but it can also cause irreversible poisoning of the three-way catalyst of the automobile engine exhaust gas purification system, so it has attracted widespread attention. The refining of distillate oil is an essential and important process in petrochemical industry, which is to remove organic sulfides and organic nitrogen compounds in fuel oil to meet the needs of environmental protection. The traditional refining process is hydrofining, which converts organic sulfides and organic nitrogen compounds into hydrogen sulfide and ammonia through hydrogenation, so as to achieve the purpose of removing sulfur and nitrogen. Although the traditional hydrofining process is effective,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G53/14
Inventor 李灿吕宏缨高金波
Owner CHINA PETROLEUM & CHEM CORP
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