Hydrodeoxygenation catalyst for Fischer Tropsch synthesis oil and preparation method and application of hydrodeoxygenation catalyst

A deoxidation catalyst and Fischer-Tropsch synthesis technology, applied in organic compound/hydride/coordination complex catalysts, metal/metal oxide/metal hydroxide catalysts, molecular sieve catalysts, etc., can solve the problem of increasing equipment investment and operating costs , single carrier and other issues

Active Publication Date: 2012-11-28
SYNFUELS CHINA TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] Chinese patent ZL200410012436.9 discloses a catalyst for Fischer-Tropsch synthetic oil hydrodeoxygenation and olefin saturation. The catalyst carrier is alumina, silicon oxide or activated carbon. The carrier needs high-temperature steam treatment before impregnating the active components of the catalyst. Increased equipment investment and operating costs to a certain extent
[0006] It can be seen from the above that there is still little research on hydrodeoxygenation catalysts, and the existing patents use a single carrier, and some require pretreatment, etc.

Method used

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  • Hydrodeoxygenation catalyst for Fischer Tropsch synthesis oil and preparation method and application of hydrodeoxygenation catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Weigh 100.0g of pseudo-boehmite (dry basis weight) and 3.0g of scallop powder and mix evenly, add 60ml of 4% dilute nitric acid, mix and shape in an extruder, dry at 110°C, and roast at 550°C After 8 hours, the alumina carrier was prepared; then the alumina carrier was impregnated with 1mol / L phosphoric acid solution, dried at 120°C, and calcined at 500°C for 8 hours to obtain the phosphoric acid-modified alumina carrier. Weigh 74.0g of modified alumina carrier, ammonium metatungstate ((NH 4 ) 2 W 4 o 13 ·8H 2 O, 6.06g) and ammonium heptamolybdate ((NH 4 ) 6 Mo 7 o 24 4H 2 (22.05g) is formulated into a mixed aqueous solution of a certain concentration, the carrier is added to the above solution, immersed for 12 hours, dried at 110°C for 12 hours, and roasted at 450°C for 4 hours; according to the equal volume impregnation method, the above semi-finished catalyst Added to nickel nitrate (Ni(NO 3 ) 2 ·6H 2 (2, 11.67 g) was immersed in an aqueous solution for 1...

Embodiment 2

[0052] Weigh 100.0g of pseudo-boehmite (dry basis weight) and 3.0g of scallop powder and mix evenly, add 60ml of 4% dilute nitric acid, mix and shape in an extruder, dry at 110°C, and roast at 550°C After 8 hours, the alumina carrier was prepared; then the alumina carrier was impregnated with 1mol / L phosphoric acid solution, dried at 120°C, and calcined at 500°C for 8 hours to obtain the phosphoric acid-modified alumina carrier. Weigh 80.0 g of modified alumina carrier, nickel nitrate (Ni(NO 3 ) 2 ·6H 2 O, 46.68g) and ammonium heptamolybdate ((NH 4 ) 6 Mo 7 o 24 4H 2 (2, 3.68g) is formulated into a mixed aqueous solution with a certain concentration, the carrier is added to the above solution, immersed for 12 hours, dried at 110°C for 12 hours, and roasted at 450°C for 4 hours; according to the equal volume impregnation method, the above catalyst semi-finished product Added to cobalt nitrate (Co(NO 3 ) 2 ·6H 2 O, 10.88g) and lanthanum nitrate (La(NO 3 ) 3 .6H 2 (2...

Embodiment 3

[0055] Weigh 100.0g of pseudo-boehmite (dry basis weight) and 3.0g of scallop powder and mix evenly, add 60ml of 4% dilute nitric acid, mix and shape in an extruder, dry at 110°C, and roast at 550°C After 8 hours, the alumina carrier was prepared; then the alumina carrier was impregnated with 1mol / L oxalic acid solution, dried at 120°C, and calcined at 500°C for 8 hours to obtain the oxalic acid-modified alumina carrier. Weigh 74.0g of modified alumina carrier, ammonium metatungstate ((NH 4 ) 2 W4 o 13 ·8H 2 O, 6.06g) and ammonium heptamolybdate ((NH 4 ) 6 Mo 7 o 24 4H 2 (22.05g) is formulated into a mixed aqueous solution of a certain concentration, the carrier is added to the above solution, immersed for 12 hours, dried at 110°C for 12 hours, and roasted at 450°C for 4 hours; according to the equal volume impregnation method, the above semi-finished catalyst Added to cobalt nitrate (Co(NO 3 ) 2 ·6H 2 (2, 10.88g) was immersed in an aqueous solution for 12 hours, dr...

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Abstract

The invention discloses hydrodeoxygenation catalyst for Fischer Tropsch synthesis oil. The catalyst consists of one or more of Mo, W and Ni which are used as main catalytic reactive metal components, a carrier and IIIA-group, VA-group, VIII-group or lanthanide-series and other acid catalytic active components, wherein the carrier is an acid modified alumina carrier, a compounded carrier containing a molecular sieve and alumina or a solid acid carrier or a combination of more of the acid modified alumina carrier, the compounded containing the molecular sieve and alumina and the solid acid carrier. The invention also discloses a preparation method for the catalyst and the application of the catalyst to a hydrodeoxygenation process of the Fischer Tropsch synthesis oil; by using the catalyst, organic oxygenated chemicals in the Fischer Tropsch synthesis oil can be effectively subjected to hydro-conversion under the conditions that the reaction temperature is 150 to 350 DEG C, pressure is 2 to 10 MPa, weight hourly space velocity (WHSV) is 0.3 to 5.0h<-1>, and the volume ratio of hydrogen to oil is 300 to 2,000; the removal rate of the organic oxygenated chemicals is more than 96.0 percent, and a product is low in acid value and high in chromaticity; and compared with the conventional catalyst, the catalyst has the advantages of obviously reducing the reaction temperature and reducing energy consumption.

Description

technical field [0001] The invention relates to a catalyst for hydrodeoxygenation of Fischer-Tropsch synthetic oil, which is suitable for the hydrogenation conversion process of Fischer-Tropsch synthetic oil with a certain amount of organic oxygen-containing compounds, and is especially suitable for the hydrogenation conversion of Fischer-Tropsch synthetic oil to produce high-quality Naphtha, solvent oil, liquid paraffin, diesel fraction, lubricating oil base oil fraction and high-quality wax, etc. The invention also relates to the preparation method and application of the catalyst. Background technique [0002] With the increase in demand for petroleum-based liquid fuels, the dwindling of petroleum resources, and the continuous improvement of environmental protection requirements, the development of environmentally friendly alternative fuels has attracted widespread attention from various countries. Fischer-Tropsch synthetic oil technology has become the most One of the te...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/888B01J23/887B01J31/34B01J29/16B01J29/48B01J29/78B01J27/19B01J27/053C10G45/08C10G45/04C10G45/12
Inventor 任杰张怀科吕恩静李永旺
Owner SYNFUELS CHINA TECH CO LTD
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