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Method for selective hydrogenation of reforming generated oil

A technology of reforming to generate oil and selectivity, which is applied in the direction of selective hydrofining, petroleum industry, and hydrocarbon oil treatment. It can solve the problems of reactor overheating, prolonging the start-up time, and processing difficulties, and achieve the reduction of sulfide Effects of pollution, shortened start-up time, and cost reduction

Active Publication Date: 2015-02-11
PETROCHINA CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] For a newly started reformed oil selective hydrogenation unit, it is necessary to purchase a large amount of solvent oil with low aromatics and low olefins as the carrier oil of the passivation agent. This passivation method is complicated to operate and prolongs the start-up time, and these carriers Solvent oil contains sulfide after use, which pollutes the environment and is difficult to handle
If the catalyst is not deactivated, the reaction temperature cannot be controlled due to the heat generated by the hydrogenation of aromatics, which may cause the reactor to overheat
In industrial installations, pipelines, pumps and valves specially installed for passivation are added, which increases investment

Method used

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  • Method for selective hydrogenation of reforming generated oil
  • Method for selective hydrogenation of reforming generated oil
  • Method for selective hydrogenation of reforming generated oil

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] It can be seen from Table 1 that the unpassivated fresh catalyst has high activity for the hydrogenation of aromatics and olefins, and the loss of aromatics is serious. For the start-up of fresh catalysts, catalyst deactivation must be carried out.

[0019] Table 1. Unpassivated hydrogenation results after fresh catalyst reduction

[0020] Reaction conditions: 170°C, 1.6MPa, 4h -1 , hydrogen / oil (V) 200

[0021]

Embodiment 2

[0023] The amount of dry passivation has a great influence on the passivation effect. Table 2 is a comparison of different dimethyl disulfide additions. The passivation conditions are 170° C., normal pressure, 50 milliliters of catalyst loading, and 20 liters / hour of hydrogen flow.

[0024] Table 2

[0025]

[0026]

[0027] As can be seen from Table 2, when the palladium-sulfur molar ratio is lower than 3, the product aromatics have no loss compared with the raw material, and when the palladium-sulfur molar ratio is 3.5, the aromatics are slightly lost. After the palladium-sulfur molar ratio is operated in this range for 16 hours, the bromine index can reach the requirement below 1000. That is to say, if the molar ratio of palladium to sulfur is lower than 3, the requirement that the loss of aromatics is less than 0.5 (weight) % and the bromine index is lower than 100 mgBr / 100 g oil can be achieved.

Embodiment 3

[0029] When the molar ratio of palladium to sulfur is 3, dimethyl disulfide, methyl sulfide, hydrogen sulfide, and butyl mercaptan are used to dry passivate the palladium catalyst respectively. The passivation conditions are 170 ° C, normal pressure, catalyst The filling volume is 50 ml, and the hydrogen flow rate is 20 liters / hour.

[0030] The effect is shown in Table 3.

[0031] table 3

[0032]

[0033]

[0034] Table 3 shows that the passivation of the palladium catalyst using the above sulfides can meet the requirements for the bromine index of the product and the loss of aromatics.

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Abstract

The invention relates to a method for selective hydrogenation of reforming generated oil. According to the reforming generated oil, the bromine index is 7270mgBr / 100g oil, and the weight of arene is 66.83%; the reaction conditions are as follows: the reaction temperature is 170 DEG C, the hydrogen partial pressure is 1.6MPa, the speed of liquid is 4h<-1> and the volume ratio between hydrogen and oil is 200. The method is characterized in that the used catalyst is Pd / gamma-Al2O3 containing 0.3wt% of palladium, and is passivated by a dry method with sulfur-containing compounds such as dimethyl disulfide, methyl thioether, butyl mercaptan or hydrogen sulfide before being filled; the added amount of the sulfide for passivation is as follows: the molar ratio of the palladium and the sulfur is 1-3.5; and the passivation temperature ranges from normal temperature to 230 DEG C. The method has the advantages that the pollution can be reduced, the investment can be reduced, convenience is brought for starting operation; after the palladium catalyst is passivated by the sulfide, the loss of arene of a hydrorefined product is lower than 0.5% (weight); after short-time reaction, the bromine index of the product is lower than 100 and the requirement of arene extraction for the raw materials can be met.

Description

Technical field: [0001] The invention relates to a method for selective hydrogenation of reformed oil. Background technique: [0002] Palladium-based catalysts are often used in the catalytic hydrogenation of unsaturated hydrocarbons. The authorized invention patents CN86108622 and CN97118845.9 are Pd / γ-Al 2 o 3 It is used in the selective hydrogenation process of reforming oil, which requires deep removal of olefins, and the hydrogenation loss of aromatics is less than 0.5%. [0003] Reformed oil is the product of naphtha reacting with Pt-based catalysts at high temperature to generate aromatics, which contains a large amount of aromatics and a small amount of alkanes and alkenes. Due to differences in raw materials or production processes, the composition of reformed oil is generally: aromatics content 50-85%, alkanes 20-50%, olefins 3-15%. In order to produce high-purity aromatics, the selective hydrogenation of reformed oil requires the removal of olefins by hydrogena...

Claims

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Application Information

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IPC IPC(8): C10G45/40
CPCC10G45/40C10G2300/4006C10G2300/4012C10G2300/705C10G2400/30
Inventor 邵文李学宽栗雪云吕占军任建生杜明仙刘传强周立功杨英朱颖黄丙耀李小平
Owner PETROCHINA CO LTD
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