Hydrogenation deoxidation catalyst for producing biological diesel oil

A technology of deoxygenation catalyst and hydrogenation catalyst, which is applied in the preparation of biological raw materials, biofuels, and liquid hydrocarbon mixtures, etc. It can solve the problems of poor hydrogenation activity of animal and vegetable oils, difficult recovery of esterification products, and complicated processes.

Active Publication Date: 2008-09-24
PETROCHINA CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The chemical synthesis of biodiesel has the following disadvantages: the process is complicated, the alcohol must be excessive, and the subsequent process must have a corresponding alcohol recovery device; the unsaturated fatty acids in the fat are easy to deteriorate at high temperatures, resulting in dark color; Waste lye discharge, etc.
However, these methods are complicated in technology, and the preparation and application of catalysts are immature, and they have poor hydrogenation activity for animal and vegetable oils, poor stability, and are easy to deactivate.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Embodiment 1: 1. Weigh and contain 2wt% TiO 2 Active Al 2 o 3 25g, 6.5g and 10.8g of molybdenum-containing compound and 10.8g of nickel-containing compound, respectively, to prepare 0.15g / mL and 0.30g / mL solutions, shake well and set aside for later use. ② Use a certain concentration of NH 4 F impregnate the carrier and dry at 120°C for 5 hours. ③Impregnate molybdenum-containing solution by incipient wetness impregnation method, let it stand at room temperature for 1 hour, then dry it in a water bath at 60°C for 3 hours, dry it in an oven at 120°C for 10 hours, and then bake it in a muffle furnace at 500°C for 4 hours. hours, get MoO 3 / Al 2 o 3 catalyst. ④ The catalyst prepared in ③ was also impregnated with the nickel-containing solution by the incipient wetness impregnation method, and stood at room temperature for 1 hour. After each impregnation, it was dried in a water bath at 60°C for 3 hours, and then placed in an oven at 120°C overnight. Baked in a muff...

Embodiment 2

[0022] Embodiment 2: 1. take by weighing containing 2wt% TiO 2 Active Al 2 o 3 30g, 8.0g and 15.8g of the molybdenum-containing compound and 15.8g of the cobalt-containing compound, respectively, were made into 0.1g / mL and 0.20g / mL solutions, shake well and set aside for later use. ② With a certain concentration of H 3 PO 4 The carrier is impregnated and dried at 120° C. for 5 hours. ③Impregnate the solution containing molybdenum by equal volume impregnation, let it stand at room temperature for 1 hour, then dry it in a water bath at 60°C for 3 hours, dry it in an oven at 120°C for 10 hours, and then bake it in a muffle furnace at 500°C 4 hours, get MoO 3 / Al 2 o 3 . ④ The catalyst prepared in ③ was also impregnated with the cobalt-containing solution by the incipient wetness impregnation method, and stood at room temperature for 1 hour. After each impregnation, it was dried in a 60°C water bath for 3 hours, and overnight in an oven at 120°C. Baked in a muffle furnac...

Embodiment 3

[0023] Embodiment 3: self-made NiMo / Al on miniature fixed-bed reactor 2 o 3 was evaluated to palm oil (with the addition of CS 2 , so that the sulfur content is 500 μg / g) as the raw material, and the catalyst composition is 14% MoO 3 , 5% NiO, 1% TiO 2 , the remaining components are Al 2 o 3 and phosphorus oxides. Load 30ml of the catalyst into the reactor, 120°C N 2 Purging for 1 hour, and then pre-reduction, the conditions are pressure 1MPa, hydrogen space velocity 300 hours -1, the temperature of the reduction process was stabilized for 6 hours when the temperature was raised to 360 °C by program. At a reaction pressure of 3MPa, a reaction temperature of 390°C, a volume ratio of hydrogen to oil of 700, and a space velocity of 0.7 hours -1 Under the conditions, using this catalyst for reaction, the generated liquid products account for 96% of diesel oil, 3% of gasoline, 1% of unconverted heavy components, 73% of the total gaseous hydrocarbons in gaseous products, and...

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Abstract

The invention provides a hydrodeoxidation catalyzer used exclusively in producing biologic diesel oil, which is primarily used in the process of the production of the novel super-clean alternative fuel of diesel motors. The catalyzer has high hydrodeoxidation activity and high selectivity of diesel oil. By the catalyzer, animal and vegetable oil or the mixture of animal and vegetable oil and fossil fuel oil are hydrodeoxidated to produce biologic diesel oil. The hydrogenation catalyzer can be kept stable by adding sulfur-supplementing reagents in right amount in the reaction raw materials.

Description

technical field [0001] The invention relates to a hydrodeoxygenation catalyst used for producing biodiesel and precautions for use. It is mainly used for the preparation and use of a new generation of ultra-clean alternative fuels for diesel engines and supporting catalysts in its production process. A catalyst with higher hydrodeoxygenation activity and higher diesel selectivity is prepared. Special technical means are adopted to enable the catalyst or other hydrogenation catalysts to catalyze the reaction of hydrodeoxygenation to produce biodiesel with high stability. Background technique [0002] At present, the most commonly used biodiesel production method is the transesterification method, including chemical method, enzymatic synthesis method, and supercritical methanol method. Chemical methods are widely used in industry, and enzymatic synthesis and supercritical methanol methods are in the stage of laboratory development. The chemical method is to use animal and v...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G45/08C10G3/00
CPCY02E50/13Y02E50/10Y02P30/20
Inventor 李春义宋晨曦杨朝合山红红
Owner PETROCHINA CO LTD
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