Catalytic pyrolysis method for preparing LGO

A catalytic pyrolysis and catalyst technology, applied in chemical instruments and methods, preparation of sugar derivatives, physical/chemical process catalysts, etc., can solve the problems of acid site loss, catalysts that cannot be recovered and regenerated, and difficult to exist stably, so as to promote Depolymerization, achieve high yield and high selectivity preparation, good adsorption effect

Pending Publication Date: 2022-08-05
NORTH CHINA ELECTRIC POWER UNIV (BAODING)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Chinese patent application 201110134871.9 discloses a method using sulfuric acid as the core to prepare a series of liquid acids or solid acids to catalyze the pyrolysis of cellulose or biomass to prepare LGO. Due to the existence of water vapor, the loss of acidic sites is prone to occur, and at the same time it will lead to the secondary reaction of LGO, making it difficult to exist stably
Chinese patent applications 201110430742.4 and 201110430778.2 respectively disclose a method for preparing LGO by catalyzing cellulose or biomass pyrolysis with solid phosphoric acid and magnetic solid phosphoric acid, using silica or alumina combined with a magnetic substrate as a carrier, and preparing it by equal volume impregnation The solid phosphoric acid catalyst not only solves the problems of strong acid catalysts polluting the environment and the secondary reaction of LGO, but also can rely on an external magnetic field to realize the recovery of the catalyst, but the catalyst needs to be further improved to improve the yield and selectivity of LGO
On this basis, Chinese patent application 201710092409.4 discloses a method for preparing LGO by biomass-based phosphoric acid-activated activated carbon catalyzed by pyrolysis of biomass. Biochar is used as a carrier and phosphoric acid is impregnated to prepare phosphoric acid-activated activated carbon catalyst. In the solution experiment, the yield of LGO was 10.4wt%. However, the catalyst cannot be recovered and regenerated due to the use of biochar carrier, and the economic performance is restricted.
In addition to traditional catalysts, Chinese invention patent 202011332857.9 discloses a method for preparing LGO by catalyzing cellulose pyrolysis with waste strong acidic macroporous resin Amberlyst-15. This method avoids the complicated catalyst preparation process and also provides a waste resin Reuse of resources, however, considering the output and acidity of waste resin is not stable, it cannot meet industrial needs

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Weigh 54g NbCl 5 The mixed gel was prepared with 10g CTAB, placed in a hydrothermal kettle for aging at 160°C for 24h, then washed with deionized water to pH=7, then dried in an oven at 80°C for 12h, and finally calcined at 450°C 6h to obtain mesoporous niobium oxide.

[0027] Take 10g of the mesoporous niobium oxide prepared above, and another 6.1g of NH 4 H 2 PO 4 Dissolved in a certain amount of deionized water to make a solution, and the NH 4 H 2 PO 4 Loaded on mesoporous niobium oxide, ultrasonicated for 30 min, then dried in an oven at 80 °C for 12 h, taken out and calcined at 450 °C for 4 h to obtain NH 4 H 2 PO 4 Modified mesoporous niobium oxide, in which phosphate accounts for 50% by mass.

[0028] Take 10 g of NH prepared above 4 H 2 PO 4 The modified mesoporous niobium oxide was ground to 0.2 mm, and commercial microcrystalline cellulose was used as the raw material (average particle size was 0.05 mm), and the cellulose and the catalyst were mixe...

Embodiment 2

[0030] Weigh 107g C 10 H 5 NbO 20 The mixed gel was prepared with 10g CTAB, placed in a hydrothermal kettle for aging at 150°C for 24h, then washed with deionized water to pH=7, then dried in an oven at 80°C for 12h, and finally calcined at 450°C 6h to obtain mesoporous niobium oxide.

[0031]Take 10g of the mesoporous niobium oxide prepared above, and another 5.5g (NH 4 ) 2 HPO 4 It was dissolved in a certain amount of deionized water to make a solution, and the (NH) 4 ) 2 HPO 4 Loaded on mesoporous niobium oxide, ultrasonicated for 30 min, then placed in an oven to dry at 80 °C for 12 h, taken out and calcined at 450 °C for 5 h to obtain (NH 4 ) 2 HPO 4 Modified mesoporous niobium oxide, in which phosphate accounts for 40% by mass.

[0032] Take 10 g of (NH) prepared above 4 ) 2 HPO 4 The modified mesoporous niobium oxide was ground to 0.2 mm, and commercial microcrystalline cellulose was used as the raw material (average particle size was 0.05 mm), and the cel...

Embodiment 3

[0034] Weigh 64g C 4 H 4 NNbO 9 ·nH 2 O and 10g CTAB were prepared as mixed gel, which was aged in a hydrothermal kettle at 180°C for 24h, then washed with deionized water to pH=7, then dried in an oven at 80°C for 12h, and finally at 450°C After calcination for 6h, mesoporous niobium oxide was obtained.

[0035] Take 10g of the mesoporous niobium oxide prepared above, and another 9.3g (NH 4 ) 3 PO 4 It was dissolved in a certain amount of deionized water to make a solution, and the (NH) 4 ) 3 PO 4 Loaded on mesoporous niobium oxide, ultrasonicated for 30 min, then placed in an oven to dry at 80 °C for 12 h, taken out and calcined at 450 °C for 3 h to obtain (NH4) 3 PO 4 Modified mesoporous niobium oxide, in which phosphate accounts for 60% by mass.

[0036] Take 10 g of (NH) prepared above 4 ) 3 PO 4 The modified mesoporous niobium oxide was ground to 0.2 mm, and commercial microcrystalline cellulose was used as the raw material (average particle size was 0.05 m...

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PUM

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Abstract

The invention belongs to the field of biomass energy utilization, and particularly relates to a catalytic pyrolysis method for preparing levoglucosenone (LGO, 1, 6-anhydro-3, 4-dideoxy-beta-D-pyranose alkene-2-ketone). According to the method, phosphate modified mesoporous niobium oxide is used as a catalyst, cellulose / biomass is used as a raw material, mechanical mixing is adopted, rapid pyrolysis is performed in an inert oxygen-free environment at 300-500 DEG C, and pyrolysis gas is rapidly condensed to obtain a liquid product rich in LGO. In addition, the catalyst is stable in performance, can be simply regenerated by roasting in an air atmosphere, and can be recycled for multiple times.

Description

technical field [0001] The invention belongs to the field of utilization of biomass energy, in particular to a catalytic pyrolysis method for preparing LGO. Background technique [0002] L-glucosone (LGO, 1,6-anhydro-3,4-dideoxy-β-D-pyranosyl-2-one) is a kind of dehydration reaction of cellulose and part of hemicellulose during biomass pyrolysis. An important anhydrosugar derivative formed. LGO has highly active ketone groups and acetal centers, and is an important raw material in chemical, medical and other fields, and has high commercial value. Generally, LGO can be generated by reactions such as depolymerization and dehydration that occur during the pyrolysis of cellulose. However, the conventional pyrolysis products of cellulose are very complex, and the yield and selectivity of LGO are extremely low, which makes further extraction and separation very difficult. Therefore, the pyrolysis process of cellulose or biomass must be regulated by suitable means to promote the...

Claims

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Application Information

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IPC IPC(8): C07D493/08C07H3/10C07H1/00B01J27/195
CPCC07D493/08C07H3/10C07H1/00B01J27/195C07B2200/07Y02E50/10
Inventor 刘吉胡斌陆强付浩李洋张镇西夏源谷陈浩泽
Owner NORTH CHINA ELECTRIC POWER UNIV (BAODING)
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