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Method for extraction-oxidation ultra-deep desulfurization of diesel in microreactor system

A micro-reactor, deep desulfurization technology, applied in chemical instruments and methods, chemical/physical processes, chemical/physical/physical-chemical processes, etc. The problem of poor mixing effect of phase materials can shorten the mixing time of materials, improve the efficiency of single-pass desulfurization, and increase energy consumption.

Active Publication Date: 2018-01-09
YANTAI UNIV
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Problems solved by technology

These systems more or less have problems such as low single-pass desulfurization rate, long reaction time, large amount of ionic liquid and oxidant, and high cost.
[0006] All of the above reaction systems adopt batch stirred tank reactor technology, which has disadvantages such as poor mixing effect of multiphase materials, poor mass transfer performance, discontinuous process, and low safety.
The ionic liquid-based extraction-oxidative desulfurization process involves complex multiphase processes such as diesel-ionic liquid phase dispersion, sulfide transfer from oil phase to ionic liquid phase, ionic liquid-oxidant mixing, sulfide-oxidant reaction, and corresponding heat transfer. Controlled by liquid-liquid mass transfer, the existing stirred tank reactor process can reduce the sulfur content of diesel from hundreds of μg / g to tens of μg / g, but if the sulfur content is reduced to below 10 μg / g, it will take several hours (more than 3 hours, CN104593056A), or increase the multi-stage desulfurization process (CN104673370A), which also leads to an increase in the amount of ionic liquid (the molar ratio of ionic liquid to sulfur is higher than 500)
[0007] In addition, in the current public reports on the diesel oil extraction-oxidative desulfurization process based on ionic liquids, peroxides such as hydrogen peroxide (CN102408915A, CN101220293B, CN105176570A, CN103509590A) are used as oxidants, and these peroxides are unstable. Decomposition easily occurs in the interior, resulting in weakened oxidation, so the existing batch stirred tank reactor process usually adds an excess of oxidant (the molar ratio of oxidant to sulfur is higher than 50) to ensure that the sulfide is completely oxidized
[0008] In addition, the process of batch stirred tank reactor is complex in operation, high in energy consumption, and there are safety hazards in the operation and storage of a large amount of oxidant, which is not conducive to industrial production

Method used

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  • Method for extraction-oxidation ultra-deep desulfurization of diesel in microreactor system

Examples

Experimental program
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Effect test

Embodiment 1

[0024] For verifying the effect of the present invention, be the model diesel oil (the mixture of dibenzothiophene and n-octane) of 500ppm with sulfur content as research object, adopt ionic liquid BmimPF 6 as extractant, containing 30wt% hydrogen peroxide (H 2 o 2 ) of hydrogen peroxide as oxidant, ammonium heptamolybdate [(NH 4 ) 6 Mo 7 o 24 4H 2 O] as a catalyst, using figure 1 As shown in the process flow, the desulfurization experiment is carried out on the model diesel. Among them, the two micro-mixers adopt the T-shaped mixing method, the diameter of the micro-mixing channel is 0.5 mm, and the length is 100 mm; the diameter of the micro-reaction channel is 0.5 mm, and the length is 5000 mm.

[0025] Before carrying out the desulfurization experiment, first prepare [(NH 4 ) 6 Mo 7 o 24 4H 2 O] BmimPF at a concentration of 4 g / L 6 -[(NH 4 ) 6 Mo 7 o 24 4H 2 O] mixture, and vibrated with ultrasonic waves, to get dispersed with [(NH 4 ) 6 Mo 7 o 24 4H ...

Embodiment 2

[0052] The reaction process is described with reference to Example 1. Set the reaction temperature to 60°C, the outlet pressure of the microchannel reactor to 275kPa, and BmimPF 6 The molar ratio to sulfur is 100, H 2 o 2 The molar ratio to sulfur is 18, the diesel flow rate is adjusted to 13.83μL / min, BmimPF 6 The flow rate of the suspension is 2.77 μL / min, and the flow rate of hydrogen peroxide is 0.28 μL / min, so that the diesel-BmimPF 6-The residence time of the hydrogen peroxide three-phase material in the micro-reaction channel is 60min, and the model diesel oil is desulfurized in the same micro-reactor system as in Example 1. The results show that the sulfur content of desulfurized diesel oil is 3.8ppm, and the desulfurization rate is 99.24%, which meets the requirements of ultra-deep desulfurization of diesel oil; the pressure drop of the microchannel reactor is 0.7kPa, which meets the process design requirements.

Embodiment 3

[0060] The reaction process is described with reference to Example 1. Set the reaction temperature to 60°C, the outlet pressure of the microchannel reactor to 275kPa, and BmimPF 6 The molar ratio to sulfur is 250, H 2 o 2 The molar ratio to sulfur is 45, the diesel flow rate is adjusted to 21.78μL / min, BmimPF 6 The flow rate of the suspension is 10.89 μL / min, and the flow rate of hydrogen peroxide is 1.09 μL / min, so that the diesel-BmimPF 6 -The residence time of the hydrogen peroxide three-phase material in the micro-reaction channel is 30min, and the desulfurization experiment is carried out on the model diesel in the same micro-reactor system as in Example 1. The results show that the sulfur content of desulfurized diesel oil is 6.2ppm, and the desulfurization rate is 98.76%, meeting the requirements of ultra-deep desulfurization of diesel oil; the pressure drop of the microchannel reactor is 0.7kPa, which meets the process design requirements.

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Abstract

The invention provides a method for extraction-oxidation ultra-deep desulfurization of diesel in a microreactor system. The method is characterized by improving an existing extraction-oxidation ultra-deep desulfurization technology based on ionic liquid by utilizing the microreactor system. The method comprises the following steps: enabling the diesel and an extracting agent-ionic liquid to be subjected to contact and mixing in a first micromixer; extracting most of sulfide from the diesel to the ionic liquid in a micromixing channel; then enabling a diesel-ionic liquid two-phase mixed material and an oxidant to be subjected to contact and mixing in a second micromixer, and completing oxidation and removing of the sulfide in a microchannel reactor connected with an outlet of the second micromixer, thus realizing ultra-deep desulfurization of the diesel, wherein the retention time of reaction materials in the microchannel reactor is 10 to 90 minutes. Compared with the prior art, the method has the advantage that efficient desulfurization and equipment miniaturization are realized through intensification on a desulfurization process; the technology is simple, continuous production can be realized, and a wide practical industrial application prospect is obtained.

Description

technical field [0001] The invention relates to a method for diesel oil extraction-oxidation ultra-deep desulfurization in a microreactor system, belonging to the field of desulfurization of petroleum products. Background technique [0002] The proportion of diesel oil in vehicle fuel is increasing, and the sulfur compounds contained in it will generate SO X It will cause irreversible poisoning of the three-way catalyst in the automobile exhaust purifier, increase of sulfate content on solid particles in the atmosphere, corrosion of engine parts and other hazards, and eventually lead to NO X , CO and volatile CH X The increase in emissions has intensified acid rain and smog. For this reason, countries all over the world have imposed strict restrictions on the sulfur content of diesel oil. The United States has been supplying diesel with a sulfur content of less than 15 μg / g since 2006, while Japan and the European Union have also implemented diesel standards with a sulfur...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G53/14B01J19/00
Inventor 赵玉潮金楠吕宏缨马海云张鹏
Owner YANTAI UNIV
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