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Good-hydrothermal-stability hydrodeoxygenation catalyst, and preparation and application thereof

A deoxidation catalyst and stability technology, applied in the preparation of liquid hydrocarbon mixtures, physical/chemical process catalysts, chemical instruments and methods, etc., to achieve good hydrothermal stability and high catalytic activity

Inactive Publication Date: 2013-11-06
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The catalyst meets the general fixed-bed hydrodeoxygenation continuous reaction process

Method used

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  • Good-hydrothermal-stability hydrodeoxygenation catalyst, and preparation and application thereof
  • Good-hydrothermal-stability hydrodeoxygenation catalyst, and preparation and application thereof
  • Good-hydrothermal-stability hydrodeoxygenation catalyst, and preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Choose a specific surface area of ​​230m 2 / g, 0.5ml / g pore volume, pseudo-boehmite powder with an average pore diameter of 6nm, and a surface area of ​​150m2 prepared in a membrane dispersion reactor at a mass ratio of 1-25:1 2 / g, pore volume 0..8ml / g, magnesium aluminum spinel with an average pore diameter of 20.4nm, mixed with turnip powder, methyl cellulose and citric acid mixed evenly. Add molybdenum trioxide at a ratio of 15-25% by mass, and after fully mixing, add 2-3mol / L nitric acid at a mass ratio of 0.8-1.2 water, knead, and put it into an extruder for forming. Dry the formed molybdenum oxide-containing carrier in an oven at 80°C for 8h-12h, then place it in a muffle furnace for 200-280min at 550-650°C, and obtain a pretreated magnesia-aluminum spinel modified catalyst carrier after cooling . Measure the water absorption of the formed carrier obtained, and prepare a nickel nitrate solution with a concentration of 0.1-1mol / L according to the pore saturated ...

Embodiment 2

[0032] Take 15ml of catalyst in oxidation state, place it in the middle of the tube of the fixed-bed reactor, and plug it with certain mesh of quartz sand on both sides. Set the furnace temperature of the reactor to 300°C, adjust the system pressure to 2.5MPa, set the hydrogen flow rate to 100ml / min, adjust the feeding rate of the advection pump to 0.5ml / min, and stabilize the system temperature, pressure, and gas flow rate to react The device delivers 3% CS 2 After 4 hours, the liquid feed was stopped, the system pressure was removed after the hydrogen flow was stopped, the pipeline was purged with nitrogen gas and the temperature was lowered.

[0033]The TEM photograph of gained sulfide state catalyst is attached image 3 shown

Embodiment 3

[0035] Take 5ml of the sulfided catalyst in Example 2, place it in the middle of the tube of the fixed-bed reactor, and plug it with a certain number of quartz sands on both sides. Set the furnace temperature of the reactor to 300°C, adjust the system pressure to 4MPa, and adjust the feeding rate of the advection pump to 0.2ml / min. After the system temperature, pressure, and gas flow are stable, deionized water is sent to the reactor, and the liquid is stopped after 4 hours. Feeding, stop the hydrogen flow, release the system pressure, blow the nitrogen to purge the pipeline and cool down.

[0036] Take 5ml of shaped γ-alumina, place it in the middle of the tube of the fixed bed reactor, and plug it with certain mesh of quartz sand on both sides. Set the furnace temperature of the reactor to 300°C, adjust the system pressure to 4MPa, and adjust the feeding rate of the advection pump to 0.2ml / min. After the system temperature, pressure, and gas flow are stable, deionized water ...

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Abstract

The invention relates to a good-hydrothermal-stability hydrodeoxygenation catalyst, and preparation and applications thereof. The preparation method of the catalyst comprises: mixing alumina and magnesium aluminate spinel according to a mass ratio of 1-25:1, adding molybdenum trioxide accounting for 5-50% by mass of the mixed powder and kneading to prepare a support containing molybdenum trioxide; drying the support, roasting and cooling to obtain a magnesium-aluminate-spinel-modified catalyst support; immersing the support in a nickel nitrate solution, and roasting to obtain an oxidation-state catalyst; performing precuring on the oxidation-state catalyst to obtain an activated hydrodeoxygenation catalyst used to prepare biodiesel by hydrodeoxygenation of animal and vegetable oil; and wherein the operation temperature is 350-380 DEG C, the liquid hourly space velocity is 4-6 h<-1>, the hydrogen partial pressure is 3.5-5.5 MPa, and the hydrogen-oil ratio is 200-600. The alkane yield is 81.8%, the deoxidation rate is 99.8%, and the ratio of a hydrogenation decarboxylation / decarbonylation reaction and a dehydration reaction is 1-1.5:2; and the hydrodeoxygenation catalyst has higher hydrodeoxygenation activity, stability and good hydrothermal stability.

Description

technical field [0001] The invention relates to a hydrodeoxygenation catalyst with good hydrothermal stability and its preparation and application. The catalyst is suitable for the process of preparing biodiesel by hydrogenation and deoxygenation of animal and vegetable oils. Background technique [0002] With the continuous development of human society, our demand for energy is increasing, but fossil energy is being exhausted, and the development of renewable energy has become an important research topic. Converting biomass into biodiesel is considered to be an important way to solve the problem of energy shortage. [0003] Among them, the method of transesterification of animal and vegetable oils to prepare biodiesel has been used in industry, but there are problems such as high oxygen content, low calorific value, poor stability and low temperature performance of the product, so it can only be mixed with petrochemical diesel at a relatively low ratio. , thereby limiting...

Claims

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Application Information

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IPC IPC(8): B01J23/883B01J35/10C10G3/00
CPCY02P30/20
Inventor 赵光辉王玉军齐泮仑李建忠王桂芝董平何玉莲马建英崔锡红佟华芳何皓秦丽华孙洪磊王树植邵伟王智勇贾云刚马克存孟锐刘剑
Owner PETROCHINA CO LTD
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