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Modified molecular sieve for hydro-desulfurization as well as preparation and application thereof

A molecular sieve and modification technology, which is applied in molecular sieve catalysts, refined hydrocarbon oils, chemical instruments and methods, etc., can solve the problems of octane number loss, affecting the desulfurization effect of sulfur-containing hydrocarbons, and high deactivation rate of adsorbents

Pending Publication Date: 2020-05-01
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Hydrodesulfurization reacts sulfur-containing hydrocarbons such as gasoline with hydrogen in the presence of a hydrogenation catalyst. With the increasingly stringent fuel standards, this requires more severe hydrogenation reaction conditions such as higher reaction pressure or temperature to make sulfur Lower levels, but due to the large amount of olefins in gasoline, increasing the hydrogenation severity will result in higher octane loss
Adsorption desulfurization is usually carried out by contacting the adsorbent with sulfur-containing hydrocarbons under the condition of hydrogen. First, the sulfur-containing hydrocarbons in the oil are captured on the adsorbent, hydrogenated to generate hydrogen sulfide, and then combined with zinc oxide to form sulfur-zinc compounds. , will also lead to a decrease in the octane number of gasoline products; in addition, when the sulfur bound on the zinc oxide reaches saturation, it will lead to a decrease in desulfurization activity, and the sulfur must be removed through oxidation regeneration. In the frequent oxidation regeneration-reduction process, the adsorbent The deactivation rate is high, which affects the implementation effect of sulfur-containing hydrocarbon desulfurization

Method used

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  • Modified molecular sieve for hydro-desulfurization as well as preparation and application thereof
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  • Modified molecular sieve for hydro-desulfurization as well as preparation and application thereof

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preparation example Construction

[0045] The preparation method of the modified molecular sieve provided by the invention comprises the steps of preparing a suspension and mixing the suspension with molecular sieve raw materials. The preparation method of the suspension includes: forming a mixture of metal powder, a hydroxyl-containing solvent and a surfactant, and treating it under ultrasonic waves to obtain a mixed liquid after ultrasonic treatment; wherein, during the ultrasonic treatment process, the fine particles are peeled off from the metal powder The metal particles are suspended in the solvent; the ultrasonically mixed solution separates the larger particles to obtain a suspension, which contains fine particles containing modified metals. The metal powder (metal powder) can be pure metal powder (when the metal film only contains modified metal and the modified metal is one kind), alloy powder containing modified metal and boron, containing multiple Alloy powders of modified metals. When the prepared...

specific Embodiment approach

[0057] The present invention provides a specific implementation of the preparation method of the modified molecular sieve, which includes the following steps: uniformly mixing the metal powder and the hydroxyl-containing solvent, and then using a specific ultrasonic power of 50-250W / (100g hydroxyl-containing solvent), preferably 100-150W / (100g hydroxyl-containing solvent) under the power of ultrasonic treatment for 4 to 10 hours, such as 5 to 8 hours, and then the ultrasonic mixture is centrifuged at 1200 to 3000 rpm, preferably 1500 to 2500 rpm, and the suspension is obtained after separation liquid; then put the molecular sieve solid powder or the molecular sieve slurry containing the molecular sieve solid powder into the obtained suspension, disperse evenly, and freeze-dry to prepare the modified molecular sieve. The average particle diameter of the metal fine powder is less than 20 microns, preferably 1-15 microns or 3-18 microns; the D of the molecular sieve solid powder...

Embodiment 1

[0070] This example is used to illustrate the modified molecular sieve of the present invention and its preparation method.

[0071] First, add 10g of nickel powder (average particle size of nickel powder is 10 microns, source: Sinopharm Group) and 100ml of ethylene glycol (Sinopharm Group, purity AR) to a 200ml jar, mix well, then add 60mg of surfactant Gandan Na2SO4 (purity AR, source: Nanjing Pars Biotechnology Co., Ltd.); then, the reaction vessel (jar) was placed in an ultrasonic cleaning machine, and was ultrasonically treated with 160W power for 6h (frequency 40KHz); the ultrasonically The liquid is centrifuged at 1500r / min for 20min in a centrifuge, and the supernatant (i.e. suspension) is taken out with a straw. The concentration of metallic nickel in the suspension is 15g / Kg, D 90 is 5nm;

[0072] 14.5 grams (on a dry basis) of SAPO-11 molecular sieve powder (Si: Al: P molar ratio = 1: 9: 10, D 90 =14 microns, relative crystallinity 91%, industrial grade, product o...

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Abstract

The invention discloses a modified molecular sieve for hydro-desulfurization as well as preparation and application thereof. The modified molecular sieve comprises a molecular sieve and a modifying metal film positioned on the outer surface of molecular sieve particles, wherein the modifying metal film contains one or more first modifying metals selected from Fe, Co, Ni and Mn and optional B. Thepreparation method of the modified molecular sieve comprises the following steps: forming a mixture from metal powder, a hydroxyl-containing solvent and a surfactant, then treating the mixture under ultrasonic waves to obtain a mixed solution after the ultrasonic treatment; separating the mixed solution after the ultrasonic treatment to obtain suspension, mixing the suspension with a molecular sieve, and carrying out freeze-drying to obtain the modified molecular sieve. The modified molecular weight is used for hydro-desulfurization of sulfur-containing hydrocarbons, has high activity and stability, can obviously reduce the olefin content, increase the iso-hydrocarbon content and increase the octane number of gasoline when used for gasoline desulfurization, and has a high gasoline yield.

Description

technical field [0001] The invention relates to a modified molecular sieve used for hydrogen desulfurization, a preparation method and an application method thereof. Background technique [0002] Sulfur in hydrocarbon fuels burns to produce sulfur oxides. The sulfur oxides produced by vehicle fuels will inhibit the activity of noble metal catalysts in automobile exhaust converters and cause irreversible poisoning, and catalytic conversion of toxic gases in automobile exhaust cannot be achieved. The role of gas, so that the exhaust of vehicles contains unburned non-methane hydrocarbons, nitrogen oxides and carbon monoxide. These toxic gases are easily catalyzed by sunlight to form photochemical smog, causing acid rain, and sulfur oxide itself is also the main cause of acid rain. one. [0003] Reducing the sulfur content in gasoline and diesel is considered one of the most important measures to improve air quality. As people pay more and more attention to environmental prote...

Claims

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Application Information

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IPC IPC(8): B01J29/85C10G45/12
CPCB01J29/85C10G45/12C10G2300/1037C10G2300/104C10G2300/1044C10G2300/70C10G2300/202C10G2400/02
Inventor 王鹏田辉平林伟孙言宋海涛姜秋桥严加松龙军
Owner CHINA PETROLEUM & CHEM CORP
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