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Application of transition metal carbide to biomass oil hydrodeoxygenation

A technology of transition metals and biomass oil, applied in hydrotreating process, physical/chemical process catalyst, hydrocarbon oil treatment, etc., can solve problems such as poor stability, unsatisfactory results, easy deactivation, etc., and achieve stability Good, quality improvement, low cost effect

Active Publication Date: 2012-07-25
山西中科化美科技有限责任公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although this type of catalyst also has high initial activity for hydrodeoxygenation (HDO), it has problems such as poor stability and easy deactivation.
Researchers have invested a lot of energy in the hope of improving the stability of this type of catalyst for HDO reactions, but the results are not satisfactory

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] Using the equal volume impregnation method, impregnate γ-Al with a certain concentration of ammonium molybdate 2 o 3 , dried at 100°C, and then calcined at 550°C for 5h to obtain a loading of 30 wt.%MoO in terms of metal oxides 3 / γ-Al 2 o 3 oxidation state catalyst. Put the oxidized catalyst into a stainless steel reaction tube, and pass through carbonization gas (20%CH 4 / 80%H 2 ) for temperature programmed reduction. Firstly, the temperature was raised from room temperature to 350°C at a rate of 10°C / min, then to 500°C at a rate of 0.5°C / min, and then to 700°C at a rate of 1°C / min, and kept at a constant temperature for 2 hours. To prevent carbides from spontaneously igniting in air, use 1% O 2 / Ar mixed gas to passivate it for 12h to obtain the passivated catalyst MoC / γ-Al 2 o 3 .

[0016] A fixed-bed reactor is used to carry out one-stage hydrorefining of biomass oil. The specific process is: take 5mL MoC / γ-Al 2 o 3 Put it into a reaction tube and fill...

Embodiment 2

[0018] Prepare passivation state catalyst MoC / γ-Al according to embodiment 1 2 o 3 And carry out one-stage hydrogenation to biomass oil according to the conditions given in Example 1. Then use a fixed-bed reactor to carry out two-stage hydrofining of the first-stage hydrogenation product of biomass oil, the reaction temperature is 400 ° C, the pressure is 6 MPa, and then the biomass oil is continuously introduced into the reaction tube by a high-pressure liquid phase pump, and the hydrogen-oil ratio is controlled to 1600 , the space velocity (LHSV) is 1 h -1 , the product is collected by the liquid collector after being cooled by the cold trap. The yield of biomass oil after two-stage hydrogenation is 63.1%, and the element composition is: C: 85.23%; H: 13.47%; O: 1.3%.

Embodiment 3

[0020] Using the equal volume impregnation method, impregnate γ-Al with a certain concentration of ammonium molybdate and nickel nitrate solution 2 o 3 , dried at 100 °C, and then calcined at 550 °C for 5 h to obtain a loading of 15 wt% MoO in terms of metal oxides 3 +4.5 wt% NiO / γ-Al 2 o 3 oxidation state catalyst. Put the oxidized catalyst into a stainless steel reaction tube, and pass through carbonization gas (20%CH 4 / 80%H 2 ) for temperature programmed reduction. Firstly, the temperature was raised from room temperature to 350°C at a rate of 10°C / min, then to 500°C at a rate of 0.5°C / min, and then to 700°C at a rate of 1°C / min, and kept at a constant temperature for 2 hours. To prevent carbides from spontaneously igniting in air, use 1% O 2 / Ar mixed gas to passivate it for 12h to obtain the passivated catalyst NiMoC / γ-Al 2 o 3 .

[0021]A fixed-bed reactor is used to carry out one-stage hydrorefining of biomass oil. The specific process is: Take 5mL NiMoC / γ-A...

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Abstract

The invention relates to application of transition metal carbide to biomass oil hydrodeoxygenation, which belongs to the technical field of transition metal carbide catalyst and aims to solve the technical problem about providing application and a preparation method of transition metal carbide catalyst which is high in activity and fine in stability. The preparation method includes: filling transition metal carbide catalyst into a reactor tube, reducing the transition metal carbide catalyst online under the atmosphere of H2, adjusting system pressure to be 1-10MPa when the temperature of the reactor tube is lowered to reaction temperature after reduction, introducing biomass oil into the reactor tube by a high-pressure liquid-phase pump, controlling liquid hourly space velocity (LHSV) to be 1-4h-1, hydrogen oil ratio to be 800-1600 and reaction temperature to be 200-500 DEG C, and collecting products cooled by a cold trap by a liquid collector. The transition metal carbide prepared is low in cost, high in activity, fine in stability, and suitable for industrialized production.

Description

technical field [0001] The invention belongs to the technical field of transition metal carbide catalysts. Background technique [0002] With the large-scale development and utilization of fossil energy, human society is facing a series of challenges, such as energy crisis and environmental degradation. In order to achieve the sustainable development of human society, all countries are actively committed to the development of environmentally friendly and renewable energy. Biomass oil is a liquid product obtained by rapid pyrolysis of biomass. Biomass oil has low sulfur and nitrogen content, and its utilization can avoid the formation of SO due to combustion 2 and NO 2 The resulting air pollution can also achieve CO 2 Recycling and reducing the greenhouse effect is an environmentally friendly alternative energy source with good application prospects. However, biomass oil is composed of hundreds of organic oxygen compounds, and its oxygen content is as high as about 50%. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G45/04C10G45/06C10G45/08C10G65/00B01J27/22
Inventor 张伟王桂云刘雪梅
Owner 山西中科化美科技有限责任公司
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