Preparation of hydrodeoxygenation isomerization catalyst and application thereof in preparation of diesel oil from illegal cooking oil

A deoxygenation catalyst, hydrodeoxygenation technology, applied in physical/chemical process catalysts, molecular sieve catalysts, preparation of liquid hydrocarbon mixtures, etc. Catalyst deactivation, etc.

Active Publication Date: 2015-12-09
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] In view of the shortcomings of existing catalysts, such as the reaction activity still can not meet the requirements of industrial production, underdeveloped mesoporous channels are easy to cause carbon deposition and catalyst deactivation, and the proportion of isomerized alkanes in the obtained product is small, etc.

Method used

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  • Preparation of hydrodeoxygenation isomerization catalyst and application thereof in preparation of diesel oil from illegal cooking oil
  • Preparation of hydrodeoxygenation isomerization catalyst and application thereof in preparation of diesel oil from illegal cooking oil
  • Preparation of hydrodeoxygenation isomerization catalyst and application thereof in preparation of diesel oil from illegal cooking oil

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0061]Example 1 Preparation of HUSY-1 molecular sieve by hydrothermal aging treatment of Y molecular sieve

[0062] Air was introduced at a flow rate of 2L / min, and 2gY molecular sieve was raised from room temperature to 750°C in the quartz tube, and then 20mL / min water vapor was introduced, and after 4 hours of treatment, it was cooled to room temperature; the parent Y molecular sieve and hydrothermal aging (HUSY-1 ) specific surface and pore volume data (see Table 1), adsorption-desorption isotherm (see figure 1 ). From the data in Table 1, it can be seen that the carrier after steam aging treatment has a higher outer surface (from 17 to 45m 2 g -1 ) and larger mesopore volume (from 0.07 to 0.11cm 3 g -1 ). figure 1 It is also shown that water vapor treatment will make molecular sieve materials have more mesopore specific surface area and volume.

[0063] In this embodiment, when the reaction temperature is 350-850°C, the reaction time is 0.5-6h, and the water vapor fl...

Embodiment 2

[0064] Example 2 Acid dealumination of HUSY-1 molecular sieve to prepare HUSY-2 molecular sieve

[0065] Feed 2g of HUSY-1 molecular sieve and nitric acid solution at a ratio of 2 / 70g / mL, heat in an oil bath at 90°C for 6 hours, and after a full reaction, filter, wash, dry, and roast to obtain acid dealuminated molecular sieve HUSY-2; The specific surface and pore volume data of the obtained HUSY-2 molecular sieve and the HUSY-1 obtained by hydrothermal aging are shown in Table 1, and the outer surface (from 45 to 105m 2 g -1 ) and larger mesopore volume (from 0.11 to 0.29cm 3 g -1 ); see the pore size distribution of HUSY-1 and HUSY-2 figure 2 . figure 2 It shows that the molecular sieve after acid dealumination has a larger mesopore diameter, and Table 1 shows that the treated carrier has a higher external surface area and a larger mesopore volume.

[0066] In this embodiment, when the acid is hydrochloric acid, the acid concentration is 0.1-2mol / L, the pickling time ...

Embodiment 3

[0069] Example 3 Alkali desiliconization treatment of HUSY-2 molecular sieve to prepare HUSY-3 molecular sieve

[0070] Feed the mixed solution of HUSY-2 molecular sieve, sodium hydroxide and tetraethylammonium hydroxide at a ratio of 3 / 100g / mL, the total alkali concentration is 0.6mol / L, and the molar ratio of alkali to protective agent is 1.2:1, 90 Heating in an oil bath at ℃ for 3 hours, after fully reacting, filtering, washing, drying, roasting and three times ammonia exchange to obtain alkali desiliconization molecular sieve HUSY-3; HUSY-3 molecular sieve obtained by alkali desiliconization and acid dealumination The specific surface and pore volume data of HUSY-2 are shown in Table 1, the outer surface (increased from 105 to 150m 2 g -1 ) and larger mesopore volume (from 0.29 to 0.42cm 3 g -1 ); see the pore size distribution of HUSY-2 and HUSY-3 figure 2 . figure 2 It shows that the molecular sieve after alkali desilication has mesopores with narrower pore size d...

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Abstract

The invention discloses a hydrodeoxygenation isomerization catalyst, which includes a hydrodeoxygenation catalyst of an ultrastable Y molecular sieve loaded metal and a hydroisomerization catalyst of a molecular sieve loaded noble metal. The ultrastable Y molecular sieve has a microporous-mesoporous composite pore system, and the metal selected from Zn, Ni and Cu is loaded by means of deposition precipitation so as to obtain the hydrodeoxygenation catalyst. The hydroisomerization catalyst adopts the microporous molecular sieve SAOP-11, SAPO-31, SAPO-34, HZSM-5, HZSM-22 or HBEA as the carrier, and the noble metal selected from Pt, Pd and Ru are loaded on the molecular sieve through impregnation method, thus obtaining the hydroisomerization catalyst. The invention also puts forward application of the hydrodeoxygenation isomerization catalyst in preparation of high cetane number diesel oil from illegal cooking oil. The mixed catalyst has high activity and anti-carbon deposition capacity, and the obtained diesel oil product has the advantages of high cetane number and low freezing point.

Description

technical field [0001] The invention relates to the field of catalysts and their application and transformation, in particular to the preparation of hydrodeoxygenation isomerization catalysts and their application in waste oil to prepare diesel. Background technique [0002] With the deepening of the energy crisis and the increasing demand for it, it is imminent to find new renewable energy to replace fossil fuels. Grease is a very important green and renewable energy carrier, and is considered to be one of the most promising biomass resources, among which waste oil occupies a large proportion, especially in China, where the annual output of waste oil is tens of millions of tons. How to make effective use of these waste oils, rather than letting waste oil flow back to the dining table is particularly important. [0003] The current application of gutter oil is mainly to transesterify it with methanol in the presence of an acid-base catalyst to generate fatty acid methyl est...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/12B01J29/14B01J29/85B01J29/44B01J29/67B01J29/74C10G3/00
CPCY02P30/20
Inventor 赵晨马冰
Owner EAST CHINA NORMAL UNIV
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