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A two-stage reaction process for hydrogen aromatization of C4 liquefied petroleum gas

A technology of liquefied gas and aromatization, which is applied in hydrotreating process, petroleum industry, production of liquid hydrocarbon mixture, etc., can solve the problems of low positive-to-isolation ratio, lack of attractiveness, low ethylene propylene yield, etc., to ensure quality , increase flexibility, optimize the effect of gasoline quality

Active Publication Date: 2016-08-10
PETROCHINA CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In the process of steam cracking to ethylene and propylene, the yield of n-butane to ethylene propylene is high, but the yield of isobutane to ethylene propylene is very low
Therefore, the remaining butane from the low-temperature aromatization reaction is directly used as a raw material for steam cracking, which is unattractive due to the low positive-to-isotropic ratio.

Method used

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  • A two-stage reaction process for hydrogen aromatization of C4 liquefied petroleum gas

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Using the C4 liquefied gas produced by the catalytic cracking unit as the raw material, its composition is: isobutane: 26.24%, n-butane: 11.53%, n-isobutene: 29.54%, trans-butene-2: 18.60%, cis- Butene-2: 13.86%, carbon five (C 5 ): 0.23%. The positive-to-isotropic ratio of C4-alkanes in this feedstock is about 0.44. Load the aromatization catalyst SIHZSM-5(A)-12 prepared according to Example 10 of CN1586721A in the upstream butene low-temperature aromatization reactor, named DS-1, and select a temperature of 380°C and a reaction pressure of 3.0MPa , feed space velocity 2.0h -1 , the reaction condition of hydrogen oil ratio 500 (v / v). The output of the reactor is analyzed for mass balance, and the liquefied gas fractions (isobutane, n-butane and a small amount of unconverted butene, propane and a small amount of propylene produced by the reaction) are sent to the downstream isobutane selection Aromatization reactor, the aromatization catalyst SIHZSM-5(A)-07 prepared...

Embodiment 2

[0036] Repeat Example 1, but change the operating conditions of the upstream butene low-temperature aromatization reactor to a reaction temperature of 360°C, a reaction pressure of 2.0MPa, and a feed space velocity of 1.0h -1 , Hydrogen oil ratio 50 (v / v). Then the dry gas yield (methane, ethane, ethylene) of the upstream reactor is 1.2%, the liquefied gas yield is 58.2%, and C 5 The above liquid hydrocarbon yield is 40.6%. Among them, C 5 The content of aromatics in the above liquid hydrocarbons is 35.4%, the content of benzene is 0.7%, the content of olefins is 9.2%, and the rest are alkanes and naphthenes; the composition of isobutane-rich liquefied gas is propane 18.3%, isobutane 62.8%, n-butane 21.7%, total butene 5.19%, and the isotropic ratio of carbon tetraalkanes is about 0.35. The above-mentioned isobutane-rich liquefied gas is sent as a raw material to the downstream isobutane selective aromatization reactor. The operating conditions are: reaction temperature 460...

Embodiment 3

[0038] Repeat Example 1, but change the operating temperature of downstream isobutane selective aromatization reactor to 480°C, reaction pressure 1.0MPa, feed space velocity 4.0h -1 , Hydrogen oil ratio 200 (v / v). Then the product distribution of the isobutane-rich liquefied gas in the upstream reactor reacted in the downstream reactor is: dry gas 6.1%, propane 31.0%, propylene 0.1%, isobutane 15.9%, n-butane 21.5%, total butane ene 0.2%, C 5 The above liquid hydrocarbon yield is 25.2%. Among them, C 5 The content of aromatics in the above liquid hydrocarbons is 92.6%, and the positive-to-isotropic ratio of C4-alkanes in the isobutane-depleted liquefied gas rises to about 1.35. It can be seen that the operating temperature of the downstream reactor is an effective means to adjust the positive and negative ratio of C4 alkanes.

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Abstract

The invention belongs to the field of petroleum chemistry, and relates to a two-stage reaction process of hydro-aromatization of C4 liquefied gas in a fixed bed reactor. The reaction process is mainly formed by a butene low-temperature aromatization reactor and an iso-butane selective aromatization reactor, so that the C4 liquefied gas can be processed into gasoline fraction with high octane value and a steam cracking material. The operation flexibility can be improved due to two-stage reactors, the quality of the gasoline product with high octane value and the steam cracking material can be guaranteed, and dry gas, coke and other side products can be reduced; the two reactors are under a hydrogenating condition, so that the one-way operation cycle and total service life of the catalyst can be prolonged.

Description

technical field [0001] The invention belongs to the field of petrochemical industry. The invention relates to a two-stage reaction process of hydrogen aromatization of C4 liquefied gas in a fixed-bed reactor. Background technique [0002] A large amount of C4 liquefied gas is by-produced in the steam cracking unit and various catalytic cracking units of the refinery. Converting various olefins in C4 liquefied gas into liquid fuels such as aromatics or gasoline through aromatization is a method of liquefied gas utilization that has attracted much attention. [0003] In the open literature and patent literature, there have been a large number of reports on the aromatization of liquefied gas and other low-carbon hydrocarbons. E.g: [0004] US4150062 (1979) discloses a zeolite catalyst capable of producing high-octane aromatic gasoline with carbon two to carbon four olefins, which is metal ion modified ZSM-5, ZSM-11, ZSM-12, ZSM-35 or ZSM-38 zeolite. The examples describe i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G65/04C10G45/68C10G50/00
Inventor 刘飞郭洪臣李吉春刘国东马安李长明马应海黄剑锋程亮亮
Owner PETROCHINA CO LTD
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