Method and apparatus for continuous oil product hydrodesulphurization by using microwaves

A hydrodesulfurization and microwave technology, applied in the chemical/physical/physicochemical process of energy application, refining to remove heteroatoms, etc., can solve the problems of low desulfurization rate, easy to block pipelines, cumbersome operation, etc., to improve oil quality Effect of desulfurization rate and economic improvement

Inactive Publication Date: 2013-01-02
北京众诚汇微能源科技有限公司 +1
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Problems solved by technology

These two types of technologies have their own advantages and disadvantages: FCC gasoline selective hydrodesulfurization technology can achieve deep desulfurization effect, and the yield is high. Although the reduction of olefins is limited, hydrogenation saturation is inevitable during the hydrodesulfurization process, resulting in product The octane number is lost compared with the raw material, and the higher the olefin saturation, the greater the octane loss of the product; the combined technology of hydrodesulfurization and octane number recovery can greatly reduce the sulfur content and olefin content, and can also be adjusted by adjusting The severity of the reaction is used to recover the octane number of the product through reactions such as isomerization and aromatization. The octane number of the product is even higher than that of the raw material, but this type of technology inevitably produces a certain amount of dry gas and liquefied gas due to cracking reactions, resulting in gasoline Yield reduction
However, this technology has the following problems: It is recorded that crude oil and catalyst are mixed by stirring, but in fact, due to the large cavity, there will be certain problems in the mixing uniformity of oil, gas, and catalyst. It is also easy to block the pipeline during the actual operation; in this method, after the hydrodesulfurization reaction is completed, the catalyst and the crude oil need to be separated, and the operation is cumbersome by gravity sedimentation or filtration; all the embodiments of the method are carried out under batch conditions It does not explain how to achieve continuous. CEM’s microwave device is a batch reactor, hydrogen is pre-filled into it and does not flow, or a hydrogen supplier is used. The supplier has many restrictions and cannot be effectively used for HDS; in addition , In terms of desulfurization effect, the desulfurization rate of the raw material oil used by this technology is very low, and the desulfurization rate recorded in the examples is all below 40%, and some even only have 1% to 5%
Among them, the purpose of avoiding the leakage of combustible gas is achieved by opening holes on the safety isolator (actually, the leaked gas is emitted through these holes), however, how to prevent hydrogen or combustible fuel gas from entering, this document does not make a clear description, The leakage of hydrogen is absolutely prohibited for the oil hydrogenation reaction, and there are potential safety hazards
[0007] The technology reported in the above prior art about the use of microwaves for hydrodesulfurization of oil products is difficult to implement in actual production

Method used

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  • Method and apparatus for continuous oil product hydrodesulphurization by using microwaves
  • Method and apparatus for continuous oil product hydrodesulphurization by using microwaves
  • Method and apparatus for continuous oil product hydrodesulphurization by using microwaves

Examples

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Effect test

Embodiment 1

[0047] Choose Co-Mo / γ-Al 2 o 3 Catalyst and FCC gasoline from a refinery, the total sulfur content is 340ppm, and the sulfide types are mainly: thiophene, C1 thiophene, C2 thiophene, and C3 thiophene. At heavy hourly space velocity 2h -1 , reaction pressure 2MPa, reaction temperature 250°C, hydrogen-oil ratio 200:1. The conditions of HDS with microwave action (1.2kW) and without microwave action were investigated respectively. It was found that the desulfurization rate was 78.2% with microwave and 52.6% without microwave. It can be seen that under the same operating conditions, the presence of microwave field can significantly improve the hydrodesulfurization rate of FCC gasoline. Further research on the hydrodesulfurization of FCC gasoline shows that the degree of olefin hydrogenation is low in the presence of microwaves, which is the effect of selective heating by microwaves. decreased, but increased by one unit (the octane value of the hydrodesulfurization process witho...

Embodiment 2

[0049] Select microwave high temperature and high pressure reactor and Ni-Mo / γ-Al 2 o 3 Catalyst, catalyst loading is 25mL catalyzer, and wherein catalyst grain number is 60~80 orders, prepares gasoline model compound, the thiophene of 200ppm is matched in 70% n-heptane, 20% hexanaphthene, 5% toluene and 5% benzene In ethylene, the model compound was subjected to hydrodesulfurization reaction, the specific operating conditions: catalyst loading 20ml, reaction temperature 280°C, reaction pressure 2MPa, weight hourly space velocity (WHSV) 2.5h -1 , Hydrogen oil volume ratio 150:1, microwave power 2kW. After the microwave reaction, the sulfur content of the gasoline model product is less than 5ppm, the hydrodesulfurization rate is 98%, and the liquid yield is more than 98%.

Embodiment 3

[0051] Ni-Mo / γ-Al is selected in this reaction system 2 o 3 The catalyst is tested on FCC gasoline with a sulfur content of 450ppm. The reaction conditions are: reaction temperature 240 degrees, pressure 2.5MPa, space velocity 2h -1 , Hydrogen oil ratio 200:1, microwave power 2.0KW, the sulfide removal rate in FCC is 98%.

[0052] image 3 Co-Mo / γ-Al is shown 2 o 3 The electric field distribution diagram of the catalyst bed in the device when the catalyst is used (the electric field distribution forms of the three embodiments are basically the same). Picture A is the overall picture, and pictures B, C, and D are cross-sectional views in the X, Y, and Z directions, respectively. It can also be seen from the figure that the microwave distribution is uniform, and there is no microwave leakage, and the operation is safe and reliable.

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Abstract

The invention provides a method and an apparatus for continuous oil product hydrodesulphurization by using microwaves. The method comprises the steps that: a fixed bed reactor is adopted; a hydrodesulphurization catalyst is filled in a middle part in the rector; with a microwave generation and transmission apparatus, microwaves are generated and are fed into the reactor; an oil raw material is mixed with hydrogen gas, and the mixture is continuously delivered into the fixed bed reactor, such that the oil raw material and the hydrogen gas contact the hydrodesulphurization catalyst and are subjected to a hydrodesulphurization reaction under the effect of microwaves; and a product of the hydrodesulphurization reaction is fetched from the reactor, and is subjected to post-treatment. According to the invention, a microwave technology is practically applied in the oil product continuous hydrodesulphurization process, such that process conditions are moderated, oil product desulphurization efficiency can be effectively improved, and oil refining can be more economical.

Description

technical field [0001] The invention relates to a continuous method and device for hydrodesulfurization of oil by using microwaves. Background technique [0002] At present, all countries in the world are devoting themselves to the research and development of FCC gasoline desulfurization technology, and have made great progress. The existing FCC gasoline desulfurization technologies mainly include hydrodesulfurization (HDS) technology and non-hydrogenation desulfurization technology. Among them, HDS technology is an effective method for large-scale production of clean oil products. Traditional HDS technology requires high temperature and pressure to achieve the corresponding sulfur content, but high temperature will cause side reactions such as cracking, resulting in gasoline octane and diesel oil. There is a loss of cetane number and its yield. With the current heavy and inferior quality of FCC raw materials, the sulfur content in FCC gasoline is increasing, and the corre...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G45/02B01J19/12
Inventor 商辉赵金岷刘植昌白冰张海超
Owner 北京众诚汇微能源科技有限公司
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