Method for removing alkine and dialkene from pyrolysis gas through selective hydrogenation

A technology for selective hydrogenation and cracking of gas, applied in chemical instruments and methods, processing of gas mixtures, treatment of hydrocarbon oil, etc., can solve problems such as the influence of catalyst hydrogenation performance

Active Publication Date: 2012-04-11
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0015] In order to satisfy the adaptability of the catalyst performance to the raw material containing water or the fluctuation of water content in the cracking gas selective hydrogenation reaction process and the two requirements for the suppression of carbon deposition, the present invention proposes a method that can effectively solve the problem of water content in the cracking gas raw material. Or the problem that the fluctuation of water content affects the hydrogenation performance of the catalyst, and the method of the present invention can also suppress the generation of carbon deposits on the catalyst

Method used

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  • Method for removing alkine and dialkene from pyrolysis gas through selective hydrogenation
  • Method for removing alkine and dialkene from pyrolysis gas through selective hydrogenation
  • Method for removing alkine and dialkene from pyrolysis gas through selective hydrogenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0062] Take a toothed spherical Pd-Au-Ca / Al with a diameter of 2.0mm 2 o 3 Catalyst 15 grams (produced by Beijing Research Institute of Chemical Industry, volume 35ml, the mass percentage content of Pd, Au, Ca is respectively 0.1%, 0.1%, 0.5%, and the balance is Al 2 o 3 , the catalyst loses 1.2wt% when the temperature rises to 500° C. on the thermogravimetric analyzer), and the catalyst is loaded into a fixed-bed reactor (diameter 15 mm, length 400 mm, with two temperature display control points). After the reactor temperature is stabilized at 110°C, nitrogen containing 2vol% trimethylmethoxysilane is passed into the reactor, the flow rate is controlled at 150ml / min, and the temperature is raised to 150°C after maintaining 110°C for 1 hour, and the temperature is stable After keeping for 0.5 hours, the nitrogen gas containing trimethylmethoxysilane was stopped, and argon gas was added to lower the temperature to obtain the catalyst Cat-1.

[0063] Comparison of Pd-Au-Ca / Al...

Embodiment 2

[0068] Take a spherical Pd-F-Cu-K / SiO with a diameter of 3mm 2 Catalyst 25 grams (produced by Beijing Research Institute of Chemical Industry, volume 53ml, the mass percentage content of Pd, F, Cu and K is respectively 0.08%, 0.4%, 1.0% and 0.5%, the balance is SiO 2, weight loss 1.1wt% when the temperature rose to 500°C on the thermogravimetric analyzer), the catalyst was packed into a 500ml three-necked bottle, the three-necked bottle was placed in the oil bath, one of the three-necked bottles was connected to the cooling coil, one was connected to the thermometer, and Connect to the feed port. First, 150ml of p-xylene was poured into the three-necked flask, and after the temperature of the reactor was stabilized at 110°C, 8ml of trimethylchlorosilane was passed into the reactor. After maintaining 110°C for 1 hour, the temperature was raised to 140°C. After the temperature was stabilized, the temperature was maintained for 1 hour and then lowered. The catalyst was taken out...

Embodiment 3

[0074] The catalysts of Example 1 and Comparative Example 1 were respectively applied to the mixed-phase hydrogenation reaction of cracked gas. The raw cracked gas came from Sinopec Yanshan Petrochemical Company and was taken from the outlet of the fifth-stage compressor. The composition is shown in Table 1.

[0075] Table 1 cracked gas composition (mol%)

[0076]

[0077] The mixed-phase hydrogenation reactor uses pyrolysis gasoline as the flushing phase, and the liquid space velocity is 5h -1 , wherein pyrolysis gasoline is hydrogenated and saturated, with a boiling point of 82°C to 178°C and a water content of 500ppm (mol).

[0078] The hydrogenation reactor is a 15ml isothermal fixed bed, and the catalyst is 5.0g. The process conditions of the hydrogenation reaction are shown in Table 2. In the hydrogenation reaction, 1ml of water vapor was pulsed in at 100h to investigate the water fluctuation resistance of the catalyst. After 700 h of reaction, the amount of carbon...

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Abstract

The invention discloses a method for removing dialkene and alkine from pyrolysis gas through selective hydrogenation, belonging to the hydrogenation field. In order to satisfy the adaptability of catalyst performance to small water content or fluctuant water content in raw material in the selective hydrogenation reaction process of the pyrolysis gas and the inhibition on the generation of carbon deposition, the invention is characterized in that the pyrolysis gas used as the raw material is in contact with a hydrogenation catalyst under the conditions that the temperature is 15-150 DEG C, the pressure is 0.1-5.0 Mpa and the gas hourly space velocity of the pyrolysis gas is 500-20000h<-1>; and alkine and dialkene are changed into alkene through selective hydrogenation, wherein the hydrogenation catalyst contains a carrier, a metal active component palladium and a silane group, and the silane group is subjected to silylation and grafting and has a content of 0.05-25wt%. Compared with the existing method, the method disclosed by the invention ensures that the reaction performance can not be changed obviously when the hydrogenated raw material contains small water content and the reaction performance can be kept basically stable when the hydrogenated raw material contains fluctuant water content; and meanwhile, only a small amount of carbon deposition is generated on the catalyst, thereby ensuring that the catalyst has a longer service life.

Description

technical field [0001] The invention relates to a hydrogenation method, in particular to a method for selectively hydrogenating cracked gas to remove alkynes and dienes. Background technique [0002] Monoolefins are important raw materials in industry, among which ethylene, propylene, butene and styrene are extremely important chemical intermediates. The current commercial production methods of olefins include steam cracking, catalytic cracking, thermal cracking, alcohol dehydration, methanol cracking reaction and syngas synthesis of olefins, among which steam cracking is the main way of monoolefin production. The ethylene, propylene, butene and other products produced in the above-mentioned industrial processes contain a small amount of alkynes or dienes. Since alkynes and dienes affect the subsequent polymerization effect and product quality, the removal of alkynes and dienes is an important part of mono-olefin production technology. [0003] The industry usually adopts ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G70/02B01J31/28
Inventor 黄龙田保亮戴伟唐国旗彭晖李宝芹
Owner CHINA PETROLEUM & CHEM CORP
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